CN112062921A - Zinc salt-containing acrylic polyurethane resin and preparation method and application thereof - Google Patents
Zinc salt-containing acrylic polyurethane resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN112062921A CN112062921A CN202010859221.XA CN202010859221A CN112062921A CN 112062921 A CN112062921 A CN 112062921A CN 202010859221 A CN202010859221 A CN 202010859221A CN 112062921 A CN112062921 A CN 112062921A
- Authority
- CN
- China
- Prior art keywords
- parts
- zinc salt
- antifouling
- solvent
- polyurethane resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000003751 zinc Chemical class 0.000 title claims abstract description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000003973 paint Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002519 antifouling agent Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 47
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000008096 xylene Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 15
- -1 hydroxyl acrylic ester Chemical class 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 12
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 7
- 229940112669 cuprous oxide Drugs 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 3
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 238000000034 method Methods 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- WJSXSXUHWBSPEP-UHFFFAOYSA-N pyridine;triphenylborane Chemical compound C1=CC=NC=C1.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 WJSXSXUHWBSPEP-UHFFFAOYSA-N 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- GCOZVVAFILCKBN-UHFFFAOYSA-N 3-(2,3,4-trichlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=C(Cl)C(Cl)=CC=C1C1=CC(=O)NC1=O GCOZVVAFILCKBN-UHFFFAOYSA-N 0.000 claims description 2
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- HDHLIWCXDDZUFH-UHFFFAOYSA-N irgarol 1051 Chemical compound CC(C)(C)NC1=NC(SC)=NC(NC2CC2)=N1 HDHLIWCXDDZUFH-UHFFFAOYSA-N 0.000 claims 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 30
- 238000000576 coating method Methods 0.000 abstract description 30
- 229920005989 resin Polymers 0.000 abstract description 29
- 239000011347 resin Substances 0.000 abstract description 29
- 239000013505 freshwater Substances 0.000 abstract description 10
- 238000002791 soaking Methods 0.000 abstract description 7
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000007667 floating Methods 0.000 abstract description 2
- 238000012423 maintenance Methods 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 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
- 239000013032 Hydrocarbon resin Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920006270 hydrocarbon resin Polymers 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229940043810 zinc pyrithione Drugs 0.000 description 3
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 3
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- UBPQITZLYDWRFS-UHFFFAOYSA-N 3,4-dihydro-1H-triazine-2,4-diamine Chemical compound NC1NN(N)NC=C1 UBPQITZLYDWRFS-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- QGDIJZMKEQCRBX-UHFFFAOYSA-N zinc;ethene Chemical group [Zn+2].[CH-]=C.[CH-]=C QGDIJZMKEQCRBX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
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Abstract
The invention relates to acrylic polyurethane resin containing zinc salt and a preparation method and application thereof. The resin is taken as a film forming material, and an environment-friendly antifouling paint is obtained by adding an environment-friendly antifouling agent, a pigment filler, an auxiliary agent, a solvent and the like. The antifouling paint has excellent physical and mechanical properties; the antifouling performance is excellent, and the antifouling period is long; the antifouling paint does not contain organic tin, dichlorodiphenyl trichloroethane and other antifouling agents, uses an antifouling agent compound system which meets the requirements of environmental laws and regulations, and is friendly to marine environment; the marine floating body has good fresh water soaking resistance, and can meet the use requirement of a ship entering a fresh water river; the single-component coating has low VOC content, simple and convenient construction and easy maintenance; expensive acrylate monomers are not used, so that the cost performance is very high, and the popularization and the application are facilitated.
Description
Technical Field
The invention relates to the technical field of antifouling paint, and particularly relates to acrylic polyurethane resin containing zinc salt, and a preparation method and application thereof.
Background
The marine fouling organisms mainly refer to the general term of animals, plants and microorganisms attached to the ship bottom, buoys and all artificial facilities, and are one of the important factors influencing the safety and the service life of marine facilities. For ships sailing in the ocean, marine fouling organisms are attached to the bottom surface of the ship, sailing resistance is obviously increased, fuel consumption is increased, and global greenhouse effect is increased; for a static marine facility which is in service in the sea, the gravity center of the static marine facility deviates due to the uneven attachment of marine fouling organisms, and the operation stability of the static marine facility is influenced; for sensing instruments such as sonar at sea, the attachment of marine fouling organisms can significantly reduce their sensitivity. Therefore, prevention of adhesion of marine fouling organisms to the surface of marine equipment has become a very important research topic. In the current antifouling technology, the most effective and economical means is to apply marine antifouling paint containing antifouling poison.
The existing marine antifouling paint mainly adopts tin-free self-polishing antifouling paint, wherein the antifouling paint taking (methyl) acrylic siloxane resin as a film forming matter has the advantages of long antifouling period (up to 60-90 months), stable antifouling performance and long fresh water soaking resistance, but the price is high, and the application range is limited. The antifouling paint using zinc acrylate/copper resin as film forming matter has antifouling period as long as 36-60 months, and has low cost, high cost performance and wide application foreground. However, the resin of this type has a significant technical drawback, namely that the molecular weight of the resin is relatively low. If the molecular weight of the resin is increased by means of reducing the dosage of the initiator, reducing the reaction temperature and the like in the resin synthesis process, the molecular structure of the resin is excessively crosslinked, so that the resin is easy to gel and fails to react, and meanwhile, the resin has overlarge steric hindrance effect, so that the difficulty of the ion exchange reaction between the organic zinc/copper salt functional group and metal ions in seawater is increased, and the antifouling coating fails. Therefore, the resin has a small molecular weight, which results in low physical and mechanical strength of the antifouling coating using the resin as a film-forming material, and the small molecular weight also facilitates penetration of moisture into the coating, resulting in a short time of the fresh water soaking resistance of the coating. Although there is no problem in marine service, sometimes the ship drives into inland river, if the time is too long, the anti-fouling coating generates bubbling phenomenon, thereby limiting the application of the anti-fouling coating.
In patent publication No. CN101981145A, application No. CN200980112451.1, entitled freshwater domain corresponding type antifouling paint composition, its coating film and antifouling method, the resin preparation method described is divided into two steps. A first step of preparing a monomer containing metal (magnesium, zinc or copper) and unsaturated double bonds; and a second step of preparing the acrylic ester resin containing metal (magnesium, zinc or copper) by adopting a free radical solution polymerization method. The subject matter described in this reference patent is essentially an acrylate resin containing a metal (magnesium, zinc or copper) salt. However, when the acrylate resin is used as a film-forming material of an antifouling paint, the prepared acrylate resin containing metal (magnesium, zinc or copper) and alicyclic hydrocarbon resin need to be physically cold-blended to improve the fresh water soaking resistance of the coating. It is also clear that the number average molecular weight of the alicyclic hydrocarbon resin is preferably 150-2000, more preferably 200-1000. If less than the above range, it may not contribute to the improvement in the strength of the paint film; if it is larger than the above range, the flatness at the time of paint film formation may be lowered. The problems are consistent with the invention, and the defects of low physical and mechanical strength and poor fresh water soaking resistance of the coating in the prior art are overcome. The comparison document needs to be physically cold-spliced with the alicyclic hydrocarbon resin instead of being chemically bonded when applied. Meanwhile, the alicyclic hydrocarbon resin used has a small molecular weight, and has a limited effect on enhancing the physical mechanical strength and the fresh water soaking resistance of the coating.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the acrylic polyurethane resin containing the zinc salt and the preparation method and the application thereof.
The technical scheme for realizing the purpose of the invention is as follows: an acrylic polyurethane resin containing zinc salt comprises the following components in parts by weight:
10-35 parts of organic zinc salt (a1) containing unsaturated double bond,
5-20 parts of hydroxyl acrylic ester (a2),
25-65 parts of soft monomer acrylic ester (a3),
5-40 parts of hard monomer acrylic ester (a4),
80-180 parts of solvent,
5-12 parts of initiator,
Isocyanate: 1-10 parts of (A) a solvent,
the structural formula of the organic zinc salt (a1) containing unsaturated double bonds is as follows:
CH2＝C(X1)-CO-O-Zn-O-CO-(X1)C＝CH2 (a1)
wherein, X1Represents H or CH3；
The structural formula of the hydroxyl acrylate (a2) is as follows:
CH2＝C(X1)-CO-O-R1-OH (a2)
wherein, X1Represents H or CH3；R1Represents an alkyl chain of C2-C4;
the soft monomer acrylate (a3) has the structural formula:
CH2＝CH-CO-O-R2 (a3)
wherein R is2Represents an alkyl chain of C2-C8
The hard monomer acrylate (a4) has the structural formula:
CH2＝C(X1)-CO-O-R3 (a4)
wherein, X1Represents H or CH3；R3Represents an alkyl chain of C1-C4, or a cycloalkyl, aryl or arylalkyl group.
The schematic structure of the acrylic polyurethane resin containing zinc salt in the technical scheme is as follows:
wherein R4 represents the molecular segment remaining after the reaction of the isocyanate groups contained in the isocyanate. If the isocyanate is chosen to be a diisocyanate, the structure within the dashed frame is absent. Because the hydroxyl is excessive and the isocyanate is insufficient, the resin structure contains unreacted hydroxyl, thereby providing certain hydrophilicity for the resin, and being beneficial to the ion exchange reaction between the organic zinc salt functional group and metal ions in seawater. The resin has a network structure with higher branching degree, and the molecular weight of the resin is obviously improved, so that the resin can provide good physical and mechanical properties for a coating, and has the characteristics of high solid and low viscosity, thereby being beneficial to reducing the VOC content of the prepared coating.
The solvent in the technical scheme is one or more of toluene, xylene, trimethylbenzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol methyl ether acetate, ethyl acetate and butyl acetate.
The initiator in the technical scheme is one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, benzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
The isocyanate in the technical scheme is Hexamethylene Diisocyanate (HDI) trimer, biuret triisocyanate, isophorone diisocyanate (IPDI) and hydrogenated xylylene diisocyanate (H)6XDI), 4' -dicyclohexylmethane diisocyanate (H)12MDI).
The invention also provides a preparation method of the acrylic polyurethane resin containing zinc salt, which comprises the following steps:
s1, dissolving organic zinc salt containing unsaturated double bonds in a solvent, and then mixing and stirring the organic zinc salt with hydroxyl acrylate, soft monomer acrylate, hard monomer acrylate, an initiator and the like which are weighed according to parts by weight to form a mixed monomer solution;
s2, adding a mixed solvent into a reaction container provided with a stirring device, a condenser, a dropping device and a thermometer, heating to 70-110 ℃, dropping the mixed monomer solution into the reaction container at a constant speed within 2-8h, and then keeping the reaction temperature for 1-2 h;
s3, dropwise adding the mixed solution of the initiator and the solvent at a constant speed for 0.5-1h, keeping the reaction temperature for 2-4h, and cooling to room temperature;
s4, dropwise adding the mixed solution of isocyanate and solvent at a constant speed for 1-3h, heating to 60-90 ℃, keeping the temperature for 2-4h, and cooling to room temperature to finish the reaction.
The acrylic polyurethane resin containing zinc salt is used as a film forming material for preparing the antifouling paint, and the antifouling paint comprises the following components in parts by weight:
10-55 parts of acrylic polyurethane resin containing zinc salt,
12-60 parts of antifouling agent (B),
8-45 parts of pigment and filler (C),
1-25 parts of assistant (D),
2-22 parts of a solvent (E).
The invention also provides application of the acrylic polyurethane resin containing the zinc salt, and the antifouling paint comprises the following preparation steps:
firstly, adding acrylic polyurethane resin containing zinc salt, an auxiliary agent (D) and a solvent (E) into a mixing container according to the formula amount, and uniformly dispersing and stirring at a high speed;
then, adding the antifouling agent (B) and the pigment filler (C), and dispersing and stirring uniformly at a high speed again to form a pre-mixed material;
finally, the premix fineness is dispersed to less than 60 μm using a grind dispersing apparatus.
The antifouling agent (B) in the technical scheme is a copper inorganic compound and an organic compound which are used singly or in a compound way, and the copper inorganic compound is one or two of copper powder and cuprous oxide which are used in a compound way; the organic compound is pyridine triphenylborane, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, cuprous thiocyanate, copper pyrithione, zinc ethylene bis (disulfuric) carbamate, trichlorophenylmaleimide, tetramethylthiuram disulfide, N-dimethyl-N '-dichlorofluoromethylthio-N' -phenylsulfamide, N-dimethyl-N '- (4-tolyl) -N' - (dichlorofluoromethylthio) sulfonamide, N '- (3, 4-dichlorophenyl) -N, N-dimethylurea, N-cyclopropyl-N' - (1, 1-dimethylethyl) -6- (methylthio) -1,3, one or more of 5-triazine-2, 4-diamine, 2- (p-chlorphenyl) -3-cyano-4-bromo-5-trifluoromethyl-pyrrole, 2,4, 5, 6-tetrachloroisophthalonitrile and metopyhmidine hydrochloride.
In the technical scheme, the pigment and filler (C) is one or more of titanium dioxide, black iron oxide, red iron oxide, zinc oxide, talcum powder, silica micropowder, barium sulfate, calcium sulfate hemihydrate, calcium carbonate and mica powder; wherein, titanium dioxide, iron oxide black, iron oxide red and zinc oxide are used as pigments; talcum powder, silicon micropowder, barium sulfate, calcium sulfate hemihydrate, calcium carbonate and mica powder are used as fillers.
The auxiliary agent (D) is one or more of 52# chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, epoxidized soybean oil, tricresyl phosphate, gum rosin, hydrogenated rosin, organic bentonite, polyamide wax slurry, fumed silica, ethyl orthosilicate and a molecular sieve; 52# chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, epoxidized soybean oil and tricresyl phosphate are used as plasticizers; the gum rosin and the hydrogenated rosin are used as auxiliary film forming and antifouling agent exudation auxiliary agents; organic bentonite, polyamide wax slurry and fumed silica are used as rheological additives; tetraethoxysilane and molecular sieves are used as water absorbents.
The solvent (E) is one or more of dimethylbenzene, trimethylbenzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, n-butanol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate and butyl acetate.
After the technical scheme is adopted, the invention has the following positive effects:
the invention provides zinc salt-containing acrylic polyurethane resin and a preparation method and application thereof. Simultaneously introducing hydroxyl acrylic acid functional monomers and organic zinc salt into an acrylate resin structure, and then reacting isocyanate with hydroxyl in the acrylate resin structure to form acrylic polyurethane resin containing zinc salt. The resin is taken as a film forming material, and an environment-friendly antifouling paint is obtained by adding an environment-friendly antifouling agent, a pigment filler, an auxiliary agent, a solvent and the like. The marine antifouling paint taking the resin as a film forming matter has excellent physical and mechanical properties; the antifouling performance is excellent, and the antifouling period is long; the antifouling paint does not contain organic tin, dichlorodiphenyl trichloroethane and other antifouling agents, uses an antifouling agent compound system which meets the requirements of environmental laws and regulations, and is friendly to marine environment; the marine floating body has good fresh water soaking resistance, and can meet the use requirement of a ship entering a fresh water river; the single-component coating has low VOC content, simple and convenient construction and easy maintenance; expensive acrylate monomers are not used, so that the cost performance is very high, and the popularization and the application are facilitated.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.
Synthesis of acrylic polyurethane resin containing zinc salt:
example 1 (resin R-1)
In a compounding vessel, 17 parts of zinc acrylate (ZDAA) was dissolved in 17 parts of propylene glycol methyl ether acetate, and then 8 parts of 2-hydroxyethyl acrylate, 56 parts of ethyl acrylate, 19 parts of methyl methacrylate, 8 parts of xylene and 7 parts of azobisisoheptonitrile were added and stirred uniformly to form a mixed monomer solution. 60 parts of xylene and 20 parts of propylene glycol monomethyl ether acetate are added to a reaction vessel equipped with a stirring device, a condenser, a dropping device and a thermometer, and heated to 100 ℃. Maintaining the reaction temperature at 100 ℃, dropwise adding the mixed monomer solution into the reaction vessel at a constant speed within 5h, and then maintaining the reaction temperature for 1 h. 0.5 part of azobisisovaleronitrile is dissolved in 10 parts of dimethylbenzene and is dripped into a reaction vessel at a constant speed within 0.5 h. Keeping the reaction temperature for 2h, and cooling to room temperature. 5 parts of Hexamethylene Diisocyanate (HDI) trimer are uniformly dissolved in a mixed solvent formed by 5 parts of dimethylbenzene and 5 parts of butyl acetate, and the mixed solvent is uniformly dripped into a reaction vessel within 1.5 h. And (3) heating to 80 ℃, keeping the temperature for 2h, cooling to room temperature, and finishing the reaction to obtain the yellowish, clear and transparent zinc salt-containing acrylic polyurethane resin R-1, wherein the solid content of the resin R-1 is 45.6%, and the viscosity of the resin R-1 is 575 cP.
Example 2 (resin R-2)
28 parts of zinc acrylate (ZDAA) is dissolved in 28 parts of propylene glycol methyl ether acetate in a mixing container, 10 parts of 2-hydroxyethyl acrylate, 32 parts of n-butyl acrylate, 30 parts of methyl methacrylate, 8 parts of xylene and 9 parts of azobisisoheptonitrile are added, and the mixture is stirred uniformly to form a mixed monomer solution. 50 parts of xylene and 20 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a stirring device, a condenser, a dropping device and a thermometer, and heated to 90 ℃. Maintaining the reaction temperature at 90 ℃, dropwise adding the mixed monomer solution into the reaction vessel at a constant speed within 5h, and then maintaining the reaction temperature for 1 h. 0.5 part of tert-butyl peroxy-2-ethylhexanoate is dissolved in 6 parts of xylene and added dropwise to the reaction vessel at a constant speed within 0.5 h. Keeping the reaction temperature for 2h, and cooling to room temperature. 4 parts of 4, 4' -dicyclohexylmethane diisocyanate (H)12MDI) is uniformly dissolved in a mixed solvent formed by 4 parts of dimethylbenzene and 4 parts of butyl acetate, and the mixed solvent is dropwise added into a reaction vessel at a constant speed within 1 hour. And (3) heating to 80 ℃, keeping the temperature for 2h, cooling to room temperature, and finishing the reaction to obtain a light yellow, clear and transparent zinc salt-containing acrylic polyurethane resin R-2, wherein the solid content of the resin R-2 is 46.9%, and the viscosity of the resin R-2 is 557 cP.
Example 3 (resin R-3)
In a mixing container, 23 parts of zinc methacrylate (ZDMA) was dissolved in 23 parts of propylene glycol methyl ether acetate, and then 10 parts of 2-hydroxyethyl acrylate, 59 parts of ethyl acrylate, 8 parts of methyl methacrylate, 8 parts of xylene, and 7 parts of azobisisoheptonitrile were added and stirred uniformly to form a mixed monomer solution. 55 parts of toluene and 20 parts of propylene glycol monomethyl ether acetate were placed in a reaction vessel equipped with a stirrer, a condenser, a dropping device and a thermometer, and heated to 100 ℃. Maintaining the reaction temperature at 100 ℃, dropwise adding the mixed monomer solution into the reaction vessel at a constant speed within 5h, and then maintaining the reaction temperature for 1 h. 0.5 part of tert-butyl peroxy-2-ethylhexanoate is dissolved in 6 parts of xylene and added dropwise to the reaction vessel at a constant speed within 0.5 h. Keeping the reaction temperature for 2h, and cooling to room temperature. 4 parts of isophorone diisocyanate (IPDI) is uniformly dissolved in a mixed solvent formed by 4 parts of dimethylbenzene and 4 parts of butyl acetate, and the mixed solvent is dropwise added into a reaction vessel at a constant speed within 1 hour. And (3) heating to 80 ℃, preserving the heat for 2h, cooling to room temperature, and then finishing the reaction to obtain a light yellow, clear and transparent zinc salt-containing acrylic polyurethane resin R-3 with the solid content of 46.4% and the viscosity of 423 cP.
Example 4 (resin R-4)
In a mixing vessel, 12 parts of zinc acrylate (ZDAA) and 12 parts of zinc methacrylate (ZDMA) were dissolved in 24 parts of propylene glycol methyl ether acetate, and then 10 parts of 2-hydroxyethyl acrylate, 56 parts of ethyl acrylate, 10 parts of methyl methacrylate, 8 parts of xylene, and 7 parts of azobisisoheptonitrile were added and stirred uniformly to form a mixed monomer solution. 55 parts of xylene and 20 parts of propylene glycol monomethyl ether acetate are added into a reaction vessel provided with a stirring device, a condenser, a dropping device and a thermometer, and heated to 100 ℃. Maintaining the reaction temperature at 100 ℃, dropwise adding the mixed monomer solution into the reaction vessel at a constant speed within 5h, and then maintaining the reaction temperature for 1 h. 0.5 part of tert-butyl peroxy-2-ethylhexanoate is dissolved in 6 parts of dimethylbenzene and is added dropwise into the reaction vessel at a constant speed within 0.5 h. Keeping the reaction temperature for 2h, and cooling to room temperature. 5 parts of biuret triisocyanate are uniformly dissolved in a mixed solvent formed by 5 parts of dimethylbenzene and 5 parts of butyl acetate, and the solution is dropwise added into a reaction vessel at a constant speed within 1.5 h. And (3) heating to 80 ℃, keeping the temperature for 2h, cooling to room temperature, and finishing the reaction to obtain a light yellow, clear and transparent zinc salt-containing acrylic polyurethane resin R-4 with the solid content of 46.1% and the viscosity of 497 cP.
Preparation of the antifouling paint:
example 5
15 parts of zinc salt-containing acrylic urethane resin R-1 prepared in example 1, 8 parts of gum rosin, 1 part of organobentonite, 2 parts of fumed silica and 12 parts of xylene are added to a mixing vessel, and the mixture is dispersed and stirred uniformly at a high speed. Then adding 39 parts of cuprous oxide, 5 parts of copper pyrithione, 6 parts of zinc oxide, 4 parts of iron oxide red, 5 parts of talcum powder and 3 parts of No. 52 chlorinated paraffin, and dispersing and stirring uniformly at high speed to form the premix. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-1.
Example 6
46 parts of zinc salt-containing acrylic urethane resin R-1 prepared in example 1,1 part of organic bentonite, 2 parts of polyamide wax slurry and 4 parts of xylene are added into a mixing container, and dispersed and stirred uniformly at a high speed. Then 11 parts of 2- (p-chlorphenyl) -3-cyano-4-bromo-5-trifluoromethyl-pyrrole, 6 parts of zinc pyrithione, 16 parts of zinc oxide, 4 parts of iron oxide red, 7 parts of talcum powder and 3 parts of tricresyl phosphate are added, and the mixture is dispersed and stirred uniformly at high speed again to form the premix. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-2.
Example 7
19 parts of zinc salt-containing acrylic urethane resin R-2 prepared in example 2, 6 parts of gum rosin, 1 part of organobentonite, 2 parts of polyamide wax slurry, 8 parts of xylene and 2 parts of methyl isobutyl ketone are added into a mixing vessel, and dispersed and stirred uniformly at a high speed. Then adding 40 parts of cuprous oxide, 6 parts of ethylene bis (carbamic acid disulfide) zinc, 5 parts of zinc oxide, 4 parts of iron oxide red, 5 parts of talcum powder and 2 parts of No. 52 chlorinated paraffin, and dispersing and stirring uniformly at high speed to form the premix. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-3.
Example 8
24 parts of zinc salt-containing acrylic urethane resin R-2 prepared in example 2,4 parts of gum rosin, 1 part of organobentonite, 2 parts of fumed silica and 8 parts of xylene are added to a mixing vessel, and the mixture is dispersed at a high speed and stirred uniformly. Then adding 35 parts of cuprous oxide, 3 parts of copper pyrithione, 3 parts of 4, 5-dichloro-2-n-octyl-4-isothiazoline-3-ketone, 4 parts of zinc oxide, 4 parts of iron oxide red, 5 parts of talcum powder, 4 parts of silicon micropowder and 3 parts of tricresyl phosphate, and dispersing and stirring uniformly at high speed again to form the premix. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-4.
Example 9
34 parts of zinc salt-containing acrylic urethane resin R-3 prepared in example 3, 1 part of organic bentonite, 2 parts of fumed silica and 8 parts of xylene are added into a mixing container, and the mixture is dispersed at a high speed and stirred uniformly. Then adding 29 parts of cuprous oxide, 5 parts of zinc pyrithione, 6 parts of zinc oxide, 4 parts of iron oxide red, 8 parts of talcum powder and 3 parts of tricresyl phosphate, and dispersing and stirring uniformly at high speed to form the premix. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-5.
Example 10
30 parts of zinc salt-containing acrylic urethane resin R-3 prepared in example 3, 1 part of organic bentonite, 2 parts of fumed silica and 8 parts of xylene are added into a mixing container, and the mixture is dispersed at a high speed and stirred uniformly. Then adding 30 parts of cuprous thiocyanate, 6 parts of N' - (3, 4-dichlorophenyl) -N, N-dimethyl urea, 3 parts of 4, 5-dichloro-2-N-octyl-4-isothiazoline-3-ketone, 5 parts of zinc oxide, 4 parts of iron oxide red, 8 parts of talcum powder and 3 parts of tricresyl phosphate, and dispersing at high speed and stirring uniformly to form a pre-mixed material. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-6.
Example 11
20 parts of zinc salt-containing acrylic urethane resin R-4 prepared in example 4, 7 parts of gum rosin, 1 part of organobentonite, 2 parts of fumed silica and 10 parts of xylene are added into a mixing vessel, and the mixture is dispersed and stirred uniformly at a high speed. Then 38 parts of cuprous oxide, 6 parts of N' - (3, 4-dichlorophenyl) -N, N-dimethyl urea, 5 parts of zinc oxide, 4 parts of iron oxide red, 4 parts of talcum powder and 3 parts of No. 52 chlorinated paraffin are added, and the mixture is dispersed and stirred uniformly at high speed to form the premix. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-7.
Example 12
42 parts of zinc salt-containing acrylic urethane resin R-4 prepared in example 4, 1 part of organic bentonite, 2 parts of polyamide wax slurry and 5 parts of xylene are added into a mixing container, and dispersed and stirred uniformly at a high speed. Then adding 12 parts of pyridine triphenylborane, 5 parts of zinc pyrithione, 3 parts of 4, 5-dichloro-2-n-octyl-4-isothiazoline-3-ketone, 16 parts of zinc oxide, 4 parts of iron oxide black, 7 parts of talcum powder and 3 parts of tricresyl phosphate, and dispersing and stirring uniformly at high speed again to form the premix. And (3) dispersing the fineness of the coating to be less than 60 mu m by using grinding dispersion equipment to obtain the antifouling coating P-8.
The antifouling paints obtained in examples 5 to 12 were subjected to performance tests according to the national standards, and the results are shown in the following table:
remarking: 1. the blank sample plate is a sample plate only coated with epoxy anti-corrosion primer; 2. antifouling performance the data reported are percent area of fouling marine organisms attached and the panel was counted to remove 20mm of the edge of the panel to eliminate edge effects.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The acrylic polyurethane resin containing zinc salt is characterized by comprising the following components in parts by weight:
10-35 parts of organic zinc salt (a1) containing unsaturated double bond,
5-20 parts of hydroxyl acrylic ester (a2),
25-65 parts of soft monomer acrylic ester (a3),
5-40 parts of hard monomer acrylic ester (a4),
80-180 parts of solvent,
5-12 parts of initiator,
Isocyanate: 1-10 parts of (A) a solvent,
the structural formula of the organic zinc salt (a1) containing unsaturated double bonds is as follows:
CH2＝C(X1)-CO-O-Zn-O-CO-(X1)C＝CH2 (a1)
wherein, X1Represents H or CH3；
The structural formula of the hydroxyl acrylate (a2) is as follows:
CH2＝C(X1)-CO-O-R1-OH (a2)
wherein, X1Represents H or CH3；R1Represents an alkyl chain of C2-C4;
the soft monomer acrylate (a3) has the structural formula:
CH2＝CH-CO-O-R2 (a3)
wherein R is2Represents an alkyl chain of C2-C8
The hard monomer acrylate (a4) has the structural formula:
CH2＝C(X1)-CO-O-R3 (a4)
wherein, X1Represents H or CH3；R3Represents an alkyl chain of C1-C4, or a cycloalkyl, aryl or aralkyl group.
2. The zinc salt-containing acrylic polyurethane resin according to claim 1, wherein the schematic structure of the zinc salt-containing acrylic polyurethane resin is as follows:
wherein R4 represents the molecular segment remaining after reaction of the isocyanate groups contained in the isocyanate, if the isocyanate is selected to be a diisocyanate, the structure within the framework of the dotted line is absent.
3. The zinc salt-containing acrylic urethane resin according to claim 1, wherein: the solvent is one or more of toluene, xylene, trimethylbenzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol methyl ether acetate, ethyl acetate and butyl acetate.
4. The zinc salt-containing acrylic urethane resin according to claim 1, wherein: the initiator is one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, benzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
5. The zinc salt-containing acrylic urethane resin according to claim 1, wherein: the isocyanate is Hexamethylene Diisocyanate (HDI) trimer, biuret triisocyanate, isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate (H)6XDI), 4' -dicyclohexylmethane diisocyanate (H)12MDI).
6. The method for preparing acrylic urethane resin containing zinc salt according to claim 1, comprising the steps of:
s1, dissolving organic zinc salt containing unsaturated double bonds in a solvent, and then mixing and stirring the organic zinc salt with hydroxyl acrylate, soft monomer acrylate, hard monomer acrylate, an initiator and the like which are weighed according to parts by weight to form a mixed monomer solution;
s2, adding the mixed solvent into a reaction container provided with a stirring device, a condenser, a dropping device and a thermometer, heating to 70-110 ℃, dropping the mixed monomer solution into the reaction container at a constant speed within 2-8h, and then keeping the reaction temperature for 1-2 h;
s3, dropwise adding the mixed solution of the initiator and the solvent at a constant speed for 0.5-1h, keeping the reaction temperature for 2-4h, and cooling to room temperature;
s4, dropwise adding the mixed solution of isocyanate and solvent at a constant speed for 1-3h, heating to 60-90 ℃, keeping the temperature for 2-4h, and cooling to room temperature to finish the reaction.
7. The use of the zinc salt-containing acrylic polyurethane resin according to claim 1, wherein the zinc salt-containing acrylic polyurethane resin is used as a film forming material for preparing an antifouling paint, and the antifouling paint comprises the following components in parts by weight:
10-55 parts of acrylic polyurethane resin containing zinc salt,
12-60 parts of antifouling agent (B),
8-45 parts of pigment and filler (C),
1-25 parts of assistant (D),
2-22 parts of a solvent (E).
8. The use of the acrylic urethane resin containing zinc salt according to claim 7, wherein the antifouling paint has the following preparation steps:
firstly, adding acrylic polyurethane resin containing zinc salt, an auxiliary agent (D) and a solvent (E) into a mixing container according to the formula amount, and uniformly dispersing and stirring at a high speed;
then, adding the antifouling agent (B) and the pigment filler (C), and dispersing and stirring uniformly at a high speed again to form a premix;
finally, the premix fineness is dispersed to less than 60 μm using a grind dispersing apparatus.
9. Use of an acrylic urethane resin containing zinc salt according to claim 7, characterized in that: the antifouling agent (B) is a copper inorganic compound and an organic compound which are used singly or in a compound way, and the copper inorganic compound is one or two of copper powder and cuprous oxide which are used in a compound way; the organic compound is pyridine triphenylborane, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, cuprous thiocyanate, copper pyrithione, zinc ethylene bis (dithiocarbamate), trichlorophenylmaleimide, tetramethylthiuram disulfide, N-dimethyl-N '-dichlorofluoromethylthio-N' -phenylsulfamide, N-dimethyl-N '- (4-tolyl) -N' - (dichlorofluoromethylthio) sulfonamide, N '- (3, 4-dichlorophenyl) -N, N-dimethylurea, N-cyclopropyl-N' - (1, 1-dimethylethyl) -6- (methylthio) -1,3, 5-triazine-2, 4-diamine, 2- (p-chlorphenyl) -3-cyano-4-bromo-5-trifluoromethyl-pyrrole, 2,4, 5, 6-tetrachloroisophthalonitrile and metopyhmidine hydrochloride.
10. Use of an acrylic urethane resin containing zinc salt according to claim 7, characterized in that: the pigment and filler (C) is one or more of titanium dioxide, black iron oxide, red iron oxide, zinc oxide, talcum powder, silica micropowder, barium sulfate, calcium sulfate hemihydrate, calcium carbonate and mica powder; the auxiliary agent (D) is one or more of 52# chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, epoxidized soybean oil, tricresyl phosphate, gum rosin, hydrogenated rosin, organic bentonite, polyamide wax slurry, fumed silica, ethyl orthosilicate and a molecular sieve; the solvent (E) is one or more of dimethylbenzene, trimethylbenzene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, n-butanol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate and butyl acetate.
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Cited By (3)
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| CN112680012A (en) * | 2020-12-24 | 2021-04-20 | 海南大学 | Degradable antifouling coating containing basalt fiber, flake powder and copper metal powder and preparation process thereof |
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| CN116285336A (en) * | 2023-04-06 | 2023-06-23 | 济南际通智能制造有限公司 | Long-term cold-resistant ribbon material and preparation method thereof |
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