CN116855142A - Multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling paint and preparation method thereof - Google Patents
Multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling paint and preparation method thereof Download PDFInfo
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- CN116855142A CN116855142A CN202310754437.3A CN202310754437A CN116855142A CN 116855142 A CN116855142 A CN 116855142A CN 202310754437 A CN202310754437 A CN 202310754437A CN 116855142 A CN116855142 A CN 116855142A
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- Prior art keywords
- upy
- urushiol
- preparation
- antifouling paint
- acrylic ester
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Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 67
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 title claims abstract description 62
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003973 paint Substances 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000001404 mediated effect Effects 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 88
- 239000011248 coating agent Substances 0.000 claims abstract description 70
- 239000000178 monomer Substances 0.000 claims abstract description 31
- -1 hydroxy acrylic ester Chemical class 0.000 claims abstract description 25
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 8
- LCPNYLRZLNERIG-ZETCQYMHSA-N (2S)-6-amino-2-[2-(oxomethylidene)hydrazinyl]hexanoyl isocyanate Chemical compound NCCCC[C@H](NN=C=O)C(=O)N=C=O LCPNYLRZLNERIG-ZETCQYMHSA-N 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 7
- 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 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 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 4
- 238000003756 stirring Methods 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 229920001477 hydrophilic polymer Polymers 0.000 abstract description 10
- 230000036571 hydration Effects 0.000 abstract description 8
- 238000006703 hydration reaction Methods 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000008439 repair process Effects 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 21
- 239000000523 sample Substances 0.000 description 20
- 241000894006 Bacteria Species 0.000 description 15
- 230000000844 anti-bacterial effect Effects 0.000 description 13
- 235000018102 proteins Nutrition 0.000 description 12
- 108090000623 proteins and genes Proteins 0.000 description 12
- 102000004169 proteins and genes Human genes 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 241000193830 Bacillus <bacterium> Species 0.000 description 10
- 241000607594 Vibrio alginolyticus Species 0.000 description 10
- 230000001580 bacterial effect Effects 0.000 description 10
- 241000195493 Cryptophyta Species 0.000 description 9
- 241000191967 Staphylococcus aureus Species 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 241000588724 Escherichia coli Species 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 241001474374 Blennius Species 0.000 description 7
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 7
- 239000002953 phosphate buffered saline Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241000404165 Microcephala Species 0.000 description 5
- 241000208125 Nicotiana Species 0.000 description 5
- 241000206744 Phaeodactylum tricornutum Species 0.000 description 5
- 239000012496 blank sample Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940098773 bovine serum albumin Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000009010 Bradford assay Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 239000006137 Luria-Bertani broth Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 241000192125 Firmicutes Species 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 230000002532 anti-gammaglobulin Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 108010074605 gamma-Globulins Proteins 0.000 description 2
- 229920013747 hydroxypolyethylene Polymers 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000010069 protein adhesion Effects 0.000 description 2
- 239000012460 protein solution Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical class OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- INRQKLGGIVSJRR-UHFFFAOYSA-N 5-hydroxypentyl prop-2-enoate Chemical compound OCCCCCOC(=O)C=C INRQKLGGIVSJRR-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008366 buffered solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ARQRPTNYUOLOGH-UHFFFAOYSA-N chcl3 chloroform Chemical compound ClC(Cl)Cl.ClC(Cl)Cl ARQRPTNYUOLOGH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- UAJUXJSXCLUTNU-UHFFFAOYSA-N pranlukast Chemical compound C=1C=C(OCCCCC=2C=CC=CC=2)C=CC=1C(=O)NC(C=1)=CC=C(C(C=2)=O)C=1OC=2C=1N=NNN=1 UAJUXJSXCLUTNU-UHFFFAOYSA-N 0.000 description 1
- 229960004583 pranlukast Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 210000004021 protozoal spore Anatomy 0.000 description 1
- 238000007585 pull-off test Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the field of biomass coatings, in particular to a multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling coating and a preparation method thereof. Comprises (1) synthesizing UPy-NCO; (2) UPy-NCO reacts with hydroxy acrylic ester to obtain hydroxy acrylic ester monomer modified by UPy unit; (3) And (3) reacting urushiol, acrylic acid and the UPy unit modified hydroxy acrylic ester monomer prepared in the step (2), and preparing the antifouling paint by adopting one-step free radical polymerization. The invention solves the problems that the existing hydrophilic polymer hydration layer antifouling paint has poor adhesive force to the surface of a substrate and is difficult to repair after breakage. The technology is simple, easy for mass production, rich in raw material resources, green and environment-friendly, high in safety, and can be a new technology for constructing the marine antifouling paint with excellent performance, low carbon, long effect and environment friendliness.
Description
Technical Field
The invention relates to the field of biomass coatings, in particular to a multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling coating and a preparation method thereof.
Background
Marine biofouling refers to the undesirable phenomenon of the accumulation and growth of microorganisms, algae and animals in the ocean on artificial surfaces below the waterline. Marine biofouling is a major difficulty facing marine science, and can accelerate corrosion of marine equipment such as ships and the like, seriously threaten safe operation of the marine equipment, and bring huge economic loss and serious environmental hazard to marine industry.
The marine biofouling process is complex and mainly comprises three stages: conditional membrane formation, small biofouling and large biofouling. Wherein, the condition film can be generated within a few minutes after the artificial surface is immersed in the seawater, and the main component of the film is composed of protein organic molecular substances, which is the material basis for the adhesion of the late fouling organisms. If the interference can be applied to the formation process of the conditional membrane, the adhesion of protein organic molecular substances on the artificial surface of the ship body and the like can be prevented, and soft organisms such as marine bacteria, diatom, microalgae, protozoan spores and the like at the later stage can not be settled on the surface of the ship body due to the lack of a suitable attached early-stage biological membrane, so that the aim of preventing the marine organisms is fulfilled.
The construction of dense hydrated layer barrier technology based on hydrophilic polymers on artificial surfaces is an emerging technology for protein adhesion resistance. The hydrophilic polymer combines water molecules through hydrogen bonding to form a compact hydration layer, thereby forming a physical barrier and an energy barrier which can effectively prevent protein from being adsorbed on the surface of the hydrophilic polymer. However, the inherent properties of hydrophilic polymer coatings make them less adherent to the substrate surface, and at the same time, they have low mechanical stability, and once broken, they are difficult to repair, limiting their application as coatings in the field of practical marine antifouling. Thus, it remains a challenge to design a hydrophilic polymer antifouling coating with high adhesion and which can improve the mechanical stability of the hydrophilic polymer coating by good self-healing properties.
The hydrogen bond has the advantage of dynamic reversibility, and can endow the polymer material with the advantages of high toughness, fatigue resistance, self-repairing and the like when being introduced into the polymer. The superposition of multiple hydrogen bonds such as double, triple or quadruple hydrogen bonds can obviously improve the binding energy, and the strength and network stability of the composite material can be enhanced by introducing multiple hydrogen bonds into the system. However, most of the self-repairing materials reported at present are structural materials, and the self-repairing characteristics of the self-repairing materials applied to the marine antifouling paint materials are rarely studied.
Raw lacquer is a good natural product resource with our country characteristics, and is a natural resin coating with good adhesive force, excellent film forming property, natural reproducibility and environmental friendliness. The urushiol is a main film forming substance of raw lacquer, has a catechol structure similar to dopamine, and the R side chain on the benzene ring is a linear alkane structure of C15-C17. The double-active hydroxyl and unsaturated double bond in the urushiol molecular structure enable the urushiol to have very high chemical activity and molecular modification, and are high-quality natural resources for constructing the green marine antifouling paint. The active phenolic hydroxyl in the urushiol molecular structure is easy to form stable interface combination with the surface of the substrate in a covalent bond or non-covalent bond mode, and an active site with high adhesive force is provided for the antifouling coating material. The urushiol has self-polymerization reaction of flexible unsaturated long side chain structure, and can provide a net-shaped polymer cross-linked network with good mechanical property for the polymer coating. The urushiol is introduced into the hydrophilic polymer coating structure, so that the technical problem of poor binding force between the current aqueous polymer coating and the substrate is hopefully solved.
Disclosure of Invention
The invention provides a high-adhesion urushiol-based supermolecule antifouling paint with multiple hydrogen bond mediated self-healing and a preparation method thereof, which are based on the problems that the existing hydrophilic polymer hydration layer antifouling paint has poor adhesion to the surface of a substrate and is difficult to repair after breakage occurs. The technical scheme adopted by the invention is as follows:
the invention firstly provides a preparation method of a multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling paint, which comprises the following steps:
(1) Synthesizing UPy-NCO;
(2) UPy-NCO reacts with hydroxy acrylic ester to obtain hydroxy acrylic ester monomer modified by UPy unit;
(3) And (3) reacting urushiol, acrylic acid and the UPy unit modified hydroxy acrylic ester monomer prepared in the step (2), and preparing the antifouling paint material by adopting one-step free radical polymerization.
The method specifically comprises the following steps:
(1) And (3) reacting 2-amino-4-hydroxy-6-methyl pyrimidine (UPy) with diisocyanate under nitrogen atmosphere at the reaction temperature of 100-120 ℃, adding n-hexane after the reaction is finished, filtering and separating UPy-NCO, and drying to obtain UPy-NCO powder.
(2) Mixing UPy-NCO synthesized in the step (1) with hydroxy acrylic ester, adding a proper amount of chloroform and dibutyltin dilaurate, and stirring at room temperature for reaction. After the reaction is finished, the solvent is removed under reduced pressure, the residue is washed by excessive acetone, and the UPy unit modified hydroxy acrylic ester monomer solid white product is obtained after drying.
(3) The antifouling paint material is prepared by adopting one-step free radical polymerization: and (3) dissolving urushiol, acrylic acid and the UPy unit modified hydroxy acrylic ester monomer prepared in the step (2) in an organic solvent under a nitrogen atmosphere, then adding N, N methylene bisacrylamide, ammonium persulfate and tetramethyl ethylenediamine, and reacting to obtain the high-adhesion urushiol-based supermolecule antifouling coating based on multi-hydrogen bond mediated self-healing.
Further:
the diisocyanate in the step (1) may be Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), L-Lysine Diisocyanate (LDI), or the like.
The molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) to diisocyanate in step (1) is 1: 3-1: 10.
the hydroxyacrylates described in step (2) include hydroxypolyethylene glycol acrylate (molecular weight may be 400, 600, 1000, 2000, 3500, 5000, 10000), 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methyl methacrylate, 6-hydroxyhexyl acrylate or 5-hydroxypentyl acrylate.
In the step (2), the mol ratio of UPy-NCO to hydroxy acrylic ester is 1:1.1 to 1:1.3.
the adding amount of the dispersing agent chloroform (chloroform) in the step (2) is 50-100 times of the sum of the mass of UPy-NCO and the mass of the hydroxy acrylic ester.
The addition amount of the dibutyl tin dilaurate in the step (2) is 1-3% of the sum of the mass of UPy-NCO and the mass of the hydroxy acrylic ester.
The organic solvent in the step (3) may be 1,4 dioxane, N dimethylformamide, dimethyl sulfoxide and the like.
The mass fraction of the acrylic acid in the organic solvent in the step (3) is 5% -20%.
The addition amount of urushiol in the step (3) is 10-50% of the mass of the acrylic acid.
The adding amount of the UPy unit modified hydroxy acrylic ester monomer in the step (3) is 1-30% of the mass of the acrylic acid.
The addition amounts of the N, N methylene bisacrylamide, the ammonium persulfate and the tetramethyl ethylenediamine in the step (3) are respectively 0.1-1%, 0.1-0.5% and 0.5-1% of the mass of the acrylic acid.
The reaction temperature in the step (3) is 50-90 ℃ and the reaction time is 3-24h.
The invention further provides the antifouling paint prepared by the preparation method.
The invention has the following advantages:
(1) The invention provides a preparation method of a multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling paint, wherein catechol groups on urushiol functional monomers in the raw material components of the coating can form covalent bonds or non-covalent bonds with various surface functional groups on a substrate, so that the urushiol-based supermolecule antifouling paint prepared by the invention can be firmly attached to the surfaces of different substrates. Meanwhile, the self-polymerization reaction of the flexible unsaturated long side chain structure of urushiol can provide a reticular polymer cross-linked network with good mechanical properties for the polymer coating, the action mechanism is shown in figure 1, and the synthetic route is shown in figure 2.
(2) Compared with the prior art that catechol groups of dopamine which are expensive and difficult to synthesize are adopted to improve the coating adhesion, the urushiol in the raw material components of the invention is derived from natural plants, has abundant resources, is cheap and easy to obtain, and is a high-quality natural product resource of special resources in China. The 2-amino-4-hydroxy-6-methyl pyrimidine (UPy) unit on the acrylate functional monomer serving as a coating raw material component has self-complementary property through forming multiple hydrogen bonds, and can be associated again when being destroyed, so that when a material composed of macromolecules containing the UPy unit is destroyed to generate cracks, self-repairing can be completed without any repairing agent and other specific environmental conditions, and the coating is endowed with self-repairing property based on multiple hydrogen bonds. Meanwhile, the-COOH on the acrylic acid functional monomer in the coating raw material component has strong hydrophilicity, is extremely easy to combine water molecules through hydrogen bonds, and forms a compact hydration layer barrier which hardly interacts with protein, so that the protein is difficult to adsorb on the surface, fouling organisms are prevented from further settling on the artificial surface, and the aim of high-efficiency marine antifouling is achieved.
(3) Compared with the existing other antifouling paint for preventing attachment of fouling organisms, the antifouling paint provided by the invention starts from the source, and the adsorption of protein organic macromolecules is prevented by utilizing a dense hydration layer barrier technology based on hydrophilic polymers, so that the first step of the marine fouling process is prevented, and the antifouling effect is better. In addition, the invention has simple process, easy mass production, rich raw material resources, environmental protection and high safety, and can be a new technology of the marine antifouling paint with excellent construction performance, low carbon, long effect and environmental protection.
Drawings
The invention will be further described with reference to examples of embodiments with reference to the accompanying drawings.
FIG. 1 is a diagram showing the mechanism of action of the anti-fouling coating prepared according to the present invention.
FIG. 2 is a synthetic route diagram of the present invention, wherein: m: n: z=1 to 5:10:1 to 3
Is diisocyanate
Is hydroxy acrylic ester.
FIG. 3 is a 1H NMR spectrum of UPy-HDI-HBA monomer synthesized in example 1.
FIG. 4 is a FTIR spectrum of urushiol, UPy-HDI-HBA monomer and prepared urushiol-based supramolecular coating in example 1.
FIG. 5 (a) effect of UPy-HDI-APOH content of example 2 on coating self-healing efficiency (self-healing time 30 min); (b) When the UPy-HDI-APOH content is 40%, the change condition of the mechanical property of the coating along with the self-healing time is realized; (c) Is a micrograph of the self-healing effect of the sample in panel (b) at various times.
FIG. 6 is a graph showing the effect of urushiol level on substrate adhesion in example 1.
FIG. 7 shows the protein adsorption resistance of the urushiol based supramolecular antifouling coatings prepared in examples 1-4 and the control (glass slide).
FIG. 8 (a) is a digital photograph (24 hours of incubation) of examples 1-4 and blank samples for antimicrobial testing against typical gram negative bacteria, E.coli, gram positive bacteria, staphylococcus aureus, gram negative bacteria, vibrio alginolyticus, and gram positive bacteria, bacillus; (b) Examples 1-4 coatings were based on three parallel tests of antimicrobial efficacy against E.coli, staphylococcus aureus, vibrio alginolyticus, and Bacillus relative to a blank control coating.
FIG. 9 is an FE-SEM image of E.coli, staphylococcus aureus, vibrio alginolyticus, bacillus after 24 hours incubation period of examples 1-4 and blank coated surfaces.
FIG. 10 (a) is a digital photograph of inhibition of algae from Nicotiana microcephala, phaeodactylum tricornutum, in f/2 medium, with example 1-4 and the control coating for 1 day and 7 days; (b) The statistical graph of the algae cell concentration of the Nicotiana microcephala and Phaeodactylum tricornutum after 7 days of culture is based on the statistical results of three parallel experiments.
FIG. 11 (a) is a fluorescence photograph of a 7 day-old Nicotiana microcephala, phaeodactylum tricornutum, after incubation on the coatings of examples 1-4 and the control; (d) Algae density statistics of the examined area based on five random areas (40-fold magnification, 0.156 mm) were displayed by ImageJ software 2 Each region).
Detailed Description
Example 1
(1) 5.0g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) was added to a high temperature dried round bottom flask and dried under high vacuum at 110℃for about 4 hours to remove traces of moisture. After cooling to room temperature, 40mL of Hexamethylene Diisocyanate (HDI) was added to the flask and the reaction mixture was stirred under nitrogen atmosphere at 110 ℃ for 16h, after the completion of the reaction the flask was cooled to room temperature and the reaction mixture was poured into a large excess of n-hexane to isolate HDI modified UPy white powder (UPy-HDI). The UPy-HDI was filtered, washed with a large excess of n-hexane to remove traces of HDI, and dried under vacuum at 50℃for 12 hours to give UPy-HDI powder.
(2) 3.0g of UPy-HDI synthesized in the step (1) and 1.62g of 4-hydroxybutyl acrylate (HBA) are placed in a round-bottomed flask, an appropriate amount of 200mL of chloroform and 80. Mu.L of dibutyltin dilaurate are added, and the reaction is stirred at room temperature for 24 hours. Then, the solvent chloroform was removed under reduced pressure and the residue was washed 5 times with an excess of acetone. After vacuum drying, a solid white product of 4-hydroxybutyl acrylate monomer (UPy-HDI-HBA) containing UPy units is obtained, and a 1HNMR chart is shown in FIG. 2, which shows successful synthesis of UPy-HDI-HBA monomer.
(3) The antifouling paint is prepared by adopting one-step free radical polymerization: 1.0g of urushiol, 10.0g of acrylic acid and 0.5g of UPy-HDI-HBA monomer prepared in the step (2) are dissolved in 100ml of 1,4 dioxane under nitrogen atmosphere, then 0.05g of N, N methylene bisacrylamide, 0.1g of ammonium persulfate and 50 mu L of tetramethyl ethylenediamine are added, and the reaction is carried out for 8 hours at 70 ℃ to obtain the high-adhesion urushiol-based supermolecule antifouling paint based on multi-hydrogen bond mediated self-healing.
Example 2
(1) 4.0g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) was added to a high temperature dried round bottom flask and dried under high vacuum at 110℃for about 4 hours to remove traces of moisture. After cooling to room temperature, 60mL of isophorone diisocyanate (IPDI) was added to the flask and the reaction mixture was stirred under nitrogen atmosphere at 110 ℃ for 16h, after the reaction was completed, the flask was cooled to room temperature and the reaction mixture was poured into a large excess of n-hexane to isolate IPDI-modified UPy white powder (UPy-IPDI). UPy-IPDI was filtered, washed with a large excess of n-hexane to remove traces of HDI, and dried under vacuum at 50℃for 12h to give UPy-IPDI powder.
(2) 3.0g of UPy-IPDI synthesized in the step (1) and 4.48g of hydroxy polyethylene glycol Acrylate (APOH) (molecular weight 400) are placed in a round-bottomed flask, an appropriate amount of 300mL of chloroform and 90. Mu.L of dibutyltin dilaurate are added, and the mixture is stirred at room temperature for reaction for 24 hours. Then, the solvent chloroform was removed under reduced pressure and the residue was washed 5 times with an excess of acetone. After vacuum drying, a solid white product of the hydroxyl polyethylene glycol acrylate monomer (UPy-HDI-APOH) containing UPy units is obtained.
(3) The antifouling paint is prepared by adopting one-step free radical polymerization: 2.0g of urushiol, 12.0g of acrylic acid and 1.5g of UPy-HDI-APOH monomer prepared in the step (2) are dissolved in 90mL of N, N-dimethylformamide under nitrogen atmosphere, then 0.072g of N, N-methylenebisacrylamide, 0.036g of ammonium persulfate and 70 mu L of tetramethyl ethylenediamine are added, and the reaction is carried out for 12 hours at 65 ℃ to obtain the high-adhesion urushiol-based supermolecule antifouling paint based on multi-hydrogen bond mediated self-healing.
Example 3
(1) 6.0g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) was added to a high temperature dried round bottom flask and dried under high vacuum at 110℃for about 4 hours to remove traces of moisture. After cooling to room temperature, 50mL of Toluene Diisocyanate (TDI) was added to the flask and the reaction mixture was stirred under nitrogen atmosphere at 110 ℃ for 16 hours, after the completion of the reaction, the flask was cooled to room temperature and the reaction mixture was poured into a large excess of n-hexane to isolate TDI modified UPy white powder (UPy-TDI). The UPy-TDI was filtered, washed with a large excess of n-hexane to remove traces of TDI, and dried under vacuum at 50deg.C for 12h to give UPy-TDI powder.
(2) 4.0g of UPy-TDI synthesized in step (1) and 1.85g of 2-hydroxyethyl acrylate (HEA) were placed in a round-bottomed flask, and an appropriate amount of 250mL of chloroform and 60. Mu.L of dibutyltin dilaurate were added thereto, and the reaction was stirred at room temperature for 15 hours. Then, the solvent chloroform was removed under reduced pressure and the residue was washed 5 times with an excess of acetone. After vacuum drying, a 2-hydroxyethyl acrylate monomer containing UPy units (UPy-TDI-HEA) was obtained as a solid white product.
(3) The antifouling paint is prepared by adopting one-step free radical polymerization: 1.5g of urushiol, 9.0g of acrylic acid and 2.0g of UPy-TDI-HEA monomer prepared in the step (2) are dissolved in 120mL of dimethyl sulfoxide under nitrogen atmosphere, then a certain amount of 0.09g of N, N methylene bisacrylamide, 0.045g of ammonium persulfate and 60 mu L of tetramethyl ethylenediamine are added, and the reaction is carried out for 20 hours at 60 ℃ to obtain the high-adhesion urushiol-based supermolecule antifouling paint based on multi-hydrogen bond mediated self-healing.
Example 4
(1) 7.0g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) was added to a high temperature dried round bottom flask and dried under high vacuum at 110℃for about 4 hours to remove traces of moisture. After cooling to room temperature, 80mL of L-Lysine Diisocyanate (LDI) was added to the flask and the reaction mixture was stirred under nitrogen atmosphere at 110 ℃ for 16h, after the completion of the reaction the flask was cooled to room temperature and the reaction mixture was poured into a large excess of n-hexane to isolate LDI modified UPy white powder (UPy-LDI). The UPy-LDI was filtered, washed with a large excess of n-hexane to remove traces of LDI, and dried under vacuum at 50℃for 12h to give UPy-LDI powder.
(2) 6.0g of UPy-LDI synthesized in the step (1) and 3.2g of 2-hydroxypropyl methyl methacrylate (HPMA) are placed in a round-bottomed flask, and an appropriate amount of 350mL of chloroform and 90. Mu.L of dibutyltin dilaurate are added thereto to stir and react for 15 hours at room temperature. Then, the solvent chloroform was removed under reduced pressure and the residue was washed 5 times with an excess of acetone. After vacuum drying, a solid white product of UPy unit-containing 2-hydroxypropyl methyl methacrylate monomer (UPy-LDI-HPMA) was obtained.
(3) The antifouling paint is prepared by adopting one-step free radical polymerization: 3.0g of urushiol, 12.0g of acrylic acid and 2.4g of UPy-LDI-HPMA monomer prepared in the step (2) are dissolved in 90mL of dimethyl sulfoxide under nitrogen atmosphere, then a certain amount of 0.06g of N, N methylene bisacrylamide, 0.05g of ammonium persulfate and 80 mu L of tetramethyl ethylenediamine are added, and the reaction is carried out for 18 hours at 85 ℃ to obtain the high-adhesion urushiol-based supermolecule antifouling paint based on multi-hydrogen bond mediated self-healing.
Comparative example 1
The preparation method of the multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling paint is different from that of example 2: the UPy-HDI-APOH synthesized in the step (1-2) is not added in the preparation process of the antifouling paint.
Comparative example 2
The preparation method of the multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling paint is different from that of example 2: no urushiol is added in the preparation process of the antifouling paint.
The chemical structures of urushiol, UPy-HDI-HBA monomer and the prepared urushiol-based supermolecular coating in example 1 are characterized by adopting a Fourier infrared spectrogram. As shown in FIG. 4, the wave number is 2873.2cm -1 、1728.6cm -1 For the c=o characteristic vibration absorption peak, it was observed on FTIR spectra of UPy-HDI-HBA monomer and urushiol based supramolecular coating, which was derived not only from UPy groups but also from polyacrylic acid. Urushiol-based supermolecule coating at 3473.2cm -1 、2929.1cm -1 And 1596.4cm -1 The absorption peak at the position is the vibration absorption peak of phenolic hydroxyl and C-H in urushiol. Meanwhile, the urushiol-based supermolecule coating is 2957.4cm -1 、1258.3cm -1 、1728.6cm -1 The vibration absorption peaks of N-H, C-O-C and C-N in the UPy-HDI-HBA are shown. In addition, UPy-HDI-HBA monomer was measured at 1563.7cm -1 Characteristic vibration absorption peak at c=c and urushiol at 991.4cm -1 The c=c characteristic vibration absorption peak at the spot, none appear on the FTIR spectrum of the urushiol-based supramolecular coating. The result shows that functional monomers UPy-HDI-HBA containing quadruple hydrogen bonds UPy and urushiol containing phenolic hydroxyl groups are successfully polymerized into the supermolecule coating through free radical copolymerization reaction, and a material structure foundation is provided for realizing self-healing performance and high adhesive force.
By using the antifouling paints of examples 1 to 4 and comparative examples 1 to 2 according to the present invention, an antifouling coating was prepared and the following performance test was performed:
the antifouling coating is also easily damaged by external force in the process of protecting equipment, and the surface of the substrate is exposed, so that fouling organisms adhere and proliferate at the damaged part of the coating, and the integral antifouling effect of the coating is weakened. Thus, the synthesis of marine antifouling coatings with self-healing capabilities is crucial to improving the stability of the antifouling coating and to extend the service life. Based on the intermolecular reversible interaction force and the molecular fluidity, the invention examines the influence of UPy content on the self-healing performance of the supermolecule antifouling coating. Taking the coating prepared in example 2 (the antifouling paint is brushed on the surface of the substrate), as shown in fig. 5, the effect on the self-healing ability of the supermolecule coating when the additive amount of UPy-HDI-APOH (the amount of acrylic acid) in the supermolecule coating is 0% (comparative example 1), 10%,20%,30%,40%,50% is examined respectively. The self-healing performance test method of the supermolecule coating comprises the following steps: the coating film sample (50 mm×10mm×0.5 mm) was scratched with a scalpel to break the same depth and length, then the sample was immersed in an aqueous solution for a certain period of time, and then taken out, and the sample was loaded into a universal mechanical tester for tensile test to evaluate the self-healing properties of the coating. The self-healing efficiency of the coating is the ratio of the original fracture stress to the fracture stress after healing. As shown in fig. 5 a, the self-healing property of the supramolecular coating increases with the increase of the UPy-HDI-APOH content within a certain range, and the self-healing efficiency of the supramolecular coating reaches 95% when the UPy-HDI-APOH addition amount is 40%. The UPy-HDI-APOH content is continuously increased, and the self-healing efficiency is reduced. Therefore, the preferable UPy-HDI-APOH addition amount is 40%. In FIG. 5 b, the effect of time on the self-healing efficiency was shown at 40% UPy-HDI-APOH. From the graph, the mechanical property of the coating gradually returns to the initial value along with the extension of time, when the self-healing time is 30min, the self-healing stress is 31.9MPa, the self-healing efficiency is 96.3%, and the coating has good self-healing performance. In fig. 5c is a photomicrograph of the self-healing process of the coating, which shows that the coating can fully achieve self-healing within 30 minutes.
The invention further examines the influence of urushiol content on the adhesive force performance of the supermolecule antifouling paint. Taking the coating prepared in example 1 as an example, the effect of the addition of urushiol (accounting for the amount of acrylic acid) in the coating at 0% (comparative example 2), 10%,20%,30%,40% and 50% on the adhesion of the supramolecular coating (GB/T5210-2006 paint and varnish pull-off test) was examined respectively. As shown in fig. 6, the results showed that the adhesion of the supramolecular coating increased with the increase of the urushiol content within a certain range, and when the urushiol addition amount increased from 0% to 30%, the adhesion of the supramolecular coating increased from 0.8MPa to 9.1MPa. The urushiol content is continuously increased, and the adhesive force is reduced to some extent. Therefore, the preferable addition amount of urushiol is 30%.
Evaluation of protein adhesion resistance of urushiol-based supramolecular antifouling paint: the Bradford method (document Bradford Assay for Determining Protein Concentration) was used to test the anti-protein (including Bovine Serum Albumin (BSA) and gamma globulin) anti-fouling properties of the coatings of examples 1-4. The coated samples (2 cm. Times.2 cm) and slides (control) prepared in examples 1-4 were first sterilized under ultraviolet light for 30min, then equilibrated in sterilized 30mL phosphate buffered solution (PBS, pH=7.4) for 2h, and then the samples were immersed in 50mL of protein solution at a concentration of 2 mg/mL. After incubation for 24h at 25 ℃, the samples were gently rinsed with 30mL PBS (ph=7.4) to remove BSA that did not adhere to the coated surface. The above washing solution and the BSA-soaking solution were mixed, and the concentration of BSA in the mixed solution was measured by Bradford method. The anti-gamma-globulin stain resistance test was similar. The protein adsorption resistance (P%) was calculated from the following formula:
wherein: c (C) 0 Initial solubility for protein solution; c is the protein concentration in the solution of the coatings of examples 1-4 after soaking adsorption.
The results of the anti-protein adsorption performance test are shown in FIG. 7, and the adsorption rates (both greater than 80%) of the anti-BSA and gamma-globulin on the surfaces of the coating samples of examples 1-4 are obviously higher than those of the control group (41% and 53%), wherein the adsorption rate of the anti-BSA of example 4 is 93%, and the adsorption rate of the anti-gamma-globulin of example 1 is 87%, which indicates that the anti-fouling coating material prepared by the invention has obviously excellent anti-protein adsorption performance. The high-efficiency anti-protein anti-fouling coating is mainly characterized in that-COOH on an acrylic acid functional monomer in the coating component has strong hydrophilicity, and water molecules are combined through hydrogen bonds to form a dense hydration layer barrier, so that proteins are difficult to adsorb on the surface, and the proteins are prevented from settling on the surface of the coating, so that the high-efficiency anti-protein anti-fouling purpose is achieved.
Antibacterial evaluation of urushiol-based supramolecular antifouling paint: the antibacterial properties of the urushiol-based supramolecular antifouling coatings of examples 1-4 were examined using four typical bacteria, gram-negative E.coli BW 25113 and Vibrio alginolyticus ATCC 33787 and gram-positive Staphylococcus aureus ATCC25923 and Bacillus MCCC 1B 00342. Coli and staphylococcus aureus strains were placed in a mixed solution of Luria-Bertani (LB) broth and 40% (v/v) glycerol at a ratio of 1:1 and stored frozen at-80 ℃. The marine vibrio alginolyticus and bacillus strain are put into 2216E culture solution and 40% (v/v) glycerol mixed solution with the proportion of 1:1, and frozen and preserved at-80 ℃. Before use in the antibacterial test, the bacterial strain was cultured with fresh LB broth (2216E broth for marine bacteria) at 37℃C (Vibrio alginolyticus culture temperature at 30℃and Bacillus at 28 ℃) with shaking at 170rpm for 20 hours until O.D.600nm reached 1.8-2.0. The samples of the anti-fouling coatings of examples 1-4 were then wiped with absolute ethanol (the anti-fouling coatings were brushed onOn the surface of the glass substrate, the size was 2.5 cm. Times.2.5 cm, and the glass substrate was sterilized by irradiation with ultraviolet rays for 30 minutes and placed in a plastic petri dish. Diluting the bacterial suspension with fresh LB broth (2216E nutrient solution for marine bacteria) to about 10 5 -10 6 After CFU/mL, 100. Mu.L of diluted bacterial suspension was inoculated on each of the above coatings and covered with a preservative film, and incubated in an environment at 37℃for 24 hours (marine bacteria were cultured at the above temperatures). Subsequently, the surface of the sample was gently rinsed with 10mL of sterilized Phosphate Buffered Saline (PBS) to wash away the non-adherent bacteria. Antibacterial ratio of coating (a.r.) by counting the number of colonies of PBS rinse present on the agar plates, according to the formula:
A.R.＝(N control -N sample )/N control ×100％
wherein N is control Colony count (CFU/mL) on BG plate, N sample Is the bacterial colony count (CFU/mL) on the PUBz and PUBz-SB coatings. Each sample was measured three times to obtain the mean and standard deviation.
Fixing the coating sample washed by the PBS with 2.5% glutaraldehyde, dehydrating the coating sample by using ethanol solutions with different concentrations, and performing metal spraying treatment after freeze drying. The surface morphology of the coating and the adhesion of bacteria to the surface were observed by FE-SEM.
The ability to kill bacteria was quantified by calculating the bacterial colony count of the bacterial culture on the agar plates from the different samples relative to the bacterial colony count of the control samples. As shown in FIG. 8, a large number of bacterial colonies were observed on the agar plates cultured in the bacterial culture isolated from the blank control group samples, whereas there were almost no colonies on the agar plates cultured in the bacterial culture isolated from the samples of example 1, example 2, example 3 and example 4. By calculation, the antibacterial rates of the sample of example 1 on E.coli, staphylococcus aureus, vibrio alginolyticus and Bacillus were 99.5%, 98.2% and 96.3%, respectively; the antibacterial rates of the samples of example 2 against E.coli, staphylococcus aureus, vibrio alginolyticus and Bacillus were 98.3%, 98.8% and 99.4%, respectively; example 3 samples were 98.8%, 96.8%, 99.5% and 97.1% antimicrobial against E.coli, staphylococcus aureus, vibrio alginolyticus and Bacillus respectively; example 4 samples showed good bactericidal performance against E.coli, staphylococcus aureus, vibrio alginolyticus and Bacillus at antibacterial rates of 96.8%, 96.2%, 97.1% and 99.1%, respectively. Further, as shown in fig. 9, a large amount of bacteria are adhered to the surfaces of the blank samples, while only a small amount of bacteria are adhered to the surfaces of the four samples, which indicates that the four samples have good antibacterial adhesion performance, and the four samples mainly have antibacterial effect on the surfaces of the coatings, inhibit the growth and propagation of bacteria, kill the bacteria adhered to the surfaces of the coatings, are easily stripped by hydraulic turbulence, form a hydration layer on the surfaces, prevent the adhesion of the bacteria, and show good antibacterial performance.
Evaluation of algae inhibition performance of urushiol-based supramolecular antifouling coating: the inhibition performance of the urushiol-based supramolecular antifouling coatings of examples 1-4 on algae was evaluated using the same species as that of the Nicotiana microcephala and Phaeodactylum tricornutum. Microalgae cells are cultured in an f/2 culture medium of artificial seawater ASW, wherein the culture temperature is 22+/-2 ℃, and the growth cycle period is 12h to 12h of illumination/darkness. After 7 days of culture, the microalgae cells were diluted to 10 in concentration with fresh culture medium 5 -10 6 cell/mL for microalgae cell reproduction and adhesion experiments. The coated samples of examples 1-4 sterilized by irradiation with ultraviolet light for 30min were immersed in 30mL of a culture solution containing microalgae cells, after 7 days of immersion, the concentration of microalgae cells was measured with a hemocytometer, and photographs of the growth process of algae were recorded. After the incubation period was completed, each coating was removed from the test medium and all microalgae cells not adhered to the surface of the coating were rinsed off with 20mL of sterile PBS solution. Subsequently, the coating surface was observed using a fluorescence microscope (Axio ImagerA2, zeiss, germany) and five random areas (40-fold magnification, 0.156 mm) were recorded for each sample 2 /field of view). The algae coverage on the coating surfaces of examples 1-4 was determined by analyzing fluorescence microscopy images using ImageJ software. All results and standard deviations were based on three parallel experiments.
Blank samples and four runsThe samples were immersed in the marine microalgae cell solution diluted in the f/2 medium for co-cultivation. As is evident from the photograph a in FIG. 10, after soaking for 7 days, a large amount of yellow-green precipitate appears at the bottom of the culture solution of the blank sample, which indicates that the culture medium of the three samples of the Nicotiana microcephala and Phaeodactylum tricornutum grow and reproduce in large quantities, and the cell concentration is 104.5X10 respectively 5 cell/mL and 96.5X10 5 cell/mL (b in FIG. 10). Compared with the blank samples, no obvious yellow-green precipitate appears in the culture solution of the four example samples, which indicates that no obvious seaweed cell proliferation exists, and no obvious difference exists in the cell concentration statistical result, which indicates that the four example samples have the effect of inhibiting the growth and proliferation of the seaweed cells, which is consistent with the antibacterial result. And further observing the adhesion condition of the two marine microalgae cells on the surface of the sample by adopting a forward fluorescence microscope, and calculating the adhesion rate of the seaweed cells on the surface of the sample by using Image software. As shown in FIG. 11, the control sample had a large number of algal cells adhered to the surface, and the surface adhesion rates were 32.9.+ -. 4.4% and 32.7.+ -. 2.9%, respectively. Compared with the blank control sample, the surface of the sample has large-area green fluorescence, the fluorescence intensity of the surface of the sample of the four embodiments is obviously weaker, which indicates that the adhesion amount of seaweed cells is very low, the adhesion rate of the surface of the sample is lower than 3%, which indicates that the sample of the four embodiments has good anti-adhesion performance to seaweed cells, and the experimental results are consistent with the antibacterial experimental results, which indicate that the sample of the four embodiments inhibits the propagation of seaweed cells, kills algae adhered to the surface of the coating, and the hydration layer formed on the surface prevents the seaweed cells from adhering to the surface of the coating, so that the sample can be used as an anti-fouling coating with good anti-fouling performance.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that the specific embodiments described are illustrative only and not intended to limit the scope of the invention, and that equivalent modifications and variations of the invention in light of the spirit of the invention will be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a multi-hydrogen bond mediated self-healing high-adhesion urushiol-based supermolecule antifouling paint is characterized by comprising the following steps of: the method comprises the following steps:
(1) Synthesizing UPy-NCO;
(2) UPy-NCO reacts with hydroxy acrylic ester to obtain hydroxy acrylic ester monomer modified by UPy unit;
(3) And (3) reacting urushiol, acrylic acid and the UPy unit modified hydroxy acrylic ester monomer prepared in the step (2), and preparing the antifouling paint by adopting one-step free radical polymerization.
2. The method of manufacturing according to claim 1, characterized in that: the method specifically comprises the following steps:
(1) Reacting 2-amino-4-hydroxy-6-methylpyrimidine with diisocyanate in a nitrogen atmosphere at a reaction temperature of 100-120 ℃, adding n-hexane after the reaction is finished, filtering and separating UPy-NCO, and drying to obtain UPy-NCO powder;
(2) Mixing UPy-NCO synthesized in the step (1) with hydroxy acrylic ester, adding chloroform and dibutyl tin dilaurate, stirring at room temperature for reaction, removing solvent under reduced pressure after the reaction is finished, washing residues with excessive acetone, and drying to obtain a UPy unit modified hydroxy acrylic ester monomer solid white product;
(3) The antifouling paint material is prepared by adopting one-step free radical polymerization: and (3) dissolving urushiol, acrylic acid and the UPy unit modified hydroxy acrylic ester monomer prepared in the step (2) in an organic solvent under a nitrogen atmosphere, then adding N, N methylene bisacrylamide, ammonium persulfate and tetramethyl ethylenediamine, and reacting to obtain the high-adhesion urushiol-based supermolecule antifouling coating based on multi-hydrogen bond mediated self-healing.
3. The preparation method according to claim 2, characterized in that: the diisocyanate in the step (1) comprises toluene diisocyanate TDI, isophorone diisocyanate IPDI, diphenylmethane diisocyanate MDI, dicyclohexylmethane diisocyanate HMDI, hexamethylene diisocyanate HDI or L-lysine diisocyanate LDI.
4. The preparation method according to claim 2, characterized in that: the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to diisocyanate in step (1) is 1: 3-1: 10.
5. the preparation method according to claim 2, characterized in that: in the step (2), the mol ratio of UPy-NCO to hydroxy acrylic ester is 1:1.1 to 1:1.3.
6. the preparation method according to claim 2, characterized in that: the mass fraction of the acrylic acid in the organic solvent in the step (3) is 5% -20%.
7. The preparation method according to claim 2, characterized in that: the addition amount of urushiol in the step (3) is 10-50% of the mass of the acrylic acid.
8. The preparation method according to claim 2, characterized in that: the adding amount of the UPy unit modified hydroxy acrylic ester monomer in the step (3) is 1-30% of the mass of the acrylic acid.
9. The preparation method according to claim 2, characterized in that: the reaction temperature in the step (3) is 50-90 ℃ and the reaction time is 3-24h.
10. An antifouling paint prepared by the preparation method as claimed in any one of claims 1 to 9.
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