GB2029831A - Triorganotin Salts and their use in Improved Ablative Antifouling Compositions - Google Patents
Triorganotin Salts and their use in Improved Ablative Antifouling Compositions Download PDFInfo
- Publication number
- GB2029831A GB2029831A GB7846632A GB7846632A GB2029831A GB 2029831 A GB2029831 A GB 2029831A GB 7846632 A GB7846632 A GB 7846632A GB 7846632 A GB7846632 A GB 7846632A GB 2029831 A GB2029831 A GB 2029831A
- Authority
- GB
- United Kingdom
- Prior art keywords
- triorganotin
- radical
- salt
- acid
- aliphatic
- 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.)
- Withdrawn
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 28
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000003115 biocidal effect Effects 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000000375 suspending agent Substances 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical group SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003566 thiocarboxylic acids Chemical group 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical group 0.000 claims 1
- 150000002484 inorganic compounds Chemical class 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 239000003139 biocide Substances 0.000 abstract description 11
- 239000007787 solid Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 6
- -1 Amine Iso-cyanate Chemical class 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
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- JWQFKVGACKJIAV-UHFFFAOYSA-N 5-[(3-carboxy-4-hydroxyphenyl)methyl]-2-hydroxybenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(CC=2C=C(C(O)=CC=2)C(O)=O)=C1 JWQFKVGACKJIAV-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- WCMMILVIRZAPLE-UHFFFAOYSA-M cyhexatin Chemical compound C1CCCCC1[Sn](C1CCCCC1)(O)C1CCCCC1 WCMMILVIRZAPLE-UHFFFAOYSA-M 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- HLJDOURGTRAFHE-UHFFFAOYSA-N isocyanic acid;3,5,5-trimethylcyclohex-2-en-1-one Chemical compound N=C=O.N=C=O.CC1=CC(=O)CC(C)(C)C1 HLJDOURGTRAFHE-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- DZWGKMVDRPKMPD-UHFFFAOYSA-N tripropyl(tripropylstannyloxy)stannane Chemical compound CCC[Sn](CCC)(CCC)O[Sn](CCC)(CCC)CCC DZWGKMVDRPKMPD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SDMIOFRAYIQSKO-UHFFFAOYSA-N 10-(5h-phenarsazinin-10-yloxy)-5h-phenarsazinine Chemical compound C12=CC=CC=C2NC2=CC=CC=C2[As]1O[As]1C2=CC=CC=C2NC2=CC=CC=C21 SDMIOFRAYIQSKO-UHFFFAOYSA-N 0.000 description 1
- YYWOZYUMEVQQCJ-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid 2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound C(C(O)C(O)C(=O)O)(=O)O.C(C(O)C(O)C(=O)O)(=O)O.C(CC(O)(C(=O)O)CC(=O)O)(=O)O YYWOZYUMEVQQCJ-UHFFFAOYSA-N 0.000 description 1
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-UHFFFAOYSA-N 0.000 description 1
- VHBSECWYEFJRNV-UHFFFAOYSA-N 2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O.OC(=O)C1=CC=CC=C1O VHBSECWYEFJRNV-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000005745 Captan Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- NNIVFXCKHNRSRL-VKHMYHEASA-N Hydroxyglutamic acid Chemical compound ON[C@H](C(O)=O)CCC(O)=O NNIVFXCKHNRSRL-VKHMYHEASA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 229940117949 captan Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- HKIOYBQGHSTUDB-UHFFFAOYSA-N folpet Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)Cl)C(=O)C2=C1 HKIOYBQGHSTUDB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- VGPBPWRBXBKGRE-UHFFFAOYSA-N n-(oxomethylidene)hydroxylamine Chemical compound ON=C=O VGPBPWRBXBKGRE-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- HTSABAUNNZLCMN-UHFFFAOYSA-F paris green Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.[O-][As]=O.CC([O-])=O.CC([O-])=O HTSABAUNNZLCMN-UHFFFAOYSA-F 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CXGOYWIFLADZKJ-UHFFFAOYSA-M tributylstannyl n,n-dimethylcarbamodithioate Chemical compound CCCC[Sn](CCCC)(CCCC)SC(=S)N(C)C CXGOYWIFLADZKJ-UHFFFAOYSA-M 0.000 description 1
- GQZXITZWLBSSOI-UHFFFAOYSA-M tributylstannyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)CCCC GQZXITZWLBSSOI-UHFFFAOYSA-M 0.000 description 1
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3897—Low-molecular-weight compounds having heteroatoms other than oxygen containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
- A01N55/04—Tin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
-
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/1643—Macromolecular compounds containing tin
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a monomeric or oligomeric triorganotin salt of a polyfunctional organic acid of the general formula: R(X)x(A)a where R represents an aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical; X represents an acid radical; A represent an active hydrogen- containing radical capable of reaction with an isocyanate; and x and a which may be the same or different, are each an integer of at least 1. The triorganotin salt optionally being pre-reacted with a low molecular weight polyol. Such a triorganotin salt is combined with a functional isocyanate and optionally a biocidal agent to provide an antifouling composition which releases biocide and ablates.
Description
SPECIFICATION
Improved Ablative Antifouling Compositione
This invention relates to improved ablative antifouling compositions comprising new triorganotin salts of polyfunctional organic acids. The invention is more particularly concerned with the wetted area of ships' hulls and other immersed structures for which long term protection against marine fouling is desired.
The reason for seeking antifouling protection on powered vessels and on static structures are different; in the case of vessels, the important factor is the roughening of the surface caused by the adherent fouling organisms, and indeed the roughness of the surfaces itself, which, acting so as to increase the frictional component of drag on the vessel, results in either a slowing of the vessel or an increase in power required to maintain speed.In the case of static structures two factors are of important: (i) increased drag on the structure due to the waves and currents increases the stresses on the structure and adversely affects its stability, and (ii) the presence of biological fouling on the surface makes it difficult to inspect, and difficult to measure corrosion and to detect defects in the structure.
This is obviously of particular importance in offshore oil and gas installations. In both cases however, long service of the system is being increasingiy demanded. Antifouling processes in the past have been designed for a maximum lifetime of up to two years; at present it is proposed to increase the permitted period between surveys on a vessel (for the purposes of insurance) to five years; and in the near future vessels may be designed and built with the invention of never docking. Fixed offshore structures clearly cannot be docked for repair and maintenance, in the conventional sense at least, and they must be built with an envisaged service life of 25-30 years.Not only is the present generation of antifouling processes inadequate for such long term duty, but there are several limitations, both in theory and practice, which make it both pointless and uneconomic to pursue conventional techniques further.
Almost all antifouling compositions in the current art come into the category of "non-convertible coatings" (O.C.C.A. Paint Tech. F'ianuai Volume 1 defines this term), i.e. they are solutions of polymers or mixtures of polymers, plasticisers, pigments and fillers, which dry by solvent evaporation and contain biocides or mixtures of biocides. 'vA/hen films of these materials, and structures coated with them are immersed in sea-water, the biocidal materials are leached from the film at a rate sufficient to kill and/or repel the larvea and spores of fouling organisms. Compositions of this sort suffer from several handicaps:
(i) Being based on high polymers (such as vinyl resins e.g.Vinyl VAGH (Trade Mark) manufactured by Union Carbide, or chlorinated rubber resins (e.g. Alloprene R10 (Trade Mark) manufactured by I.C.I.), they require large amounts of expensive and hazardous solvents to reduce their viscosity to a value suitable for application;
(ii) Because of the amount of solvent required in these compositions, the limit on the volume solids (i.e. the volume fraction of the material applied which remains after volatilisation of the solvent) is low. For example, a vinyl antifouling composition would have a solids volume e of only 30 to 35%, requiring a wet film thickness of 285-333 microns for every 100 microns of dry film required.
Similarly, for a.chlorinated rubber-based antifouling composition it would be unusual to achieve a volume solids content in excess of 50%, requiring 200 microns of wet film thickness for every 100 microns of dry film required:
(iii) Even the best of current "state of the art" antifouling compositions, however, have an intrinsic defect which iimits their potential as "long-life" compositions, and this is that water-insoluble resin and pigment components, such as vinyl and chlorinated rubber, persist on the surface of the antifouling composition of the biocides leach, and do in fact become the rate-determining step in the leaching.The process is thus self-limiting, and the application (beyond a certain point) of further coats of composition does not result in any increase in lifetime for the system.
Various proposals have been made for the amelioration of this state of affairs; the preferred current approaches can be conveniently summarised as follows:
I. The "reactivating" approach. This method recognises the selflimiting nature of the superficial matrix layer, and proposes, by scrubbing a vessel or installation underwater, to remove it at regular intervals. The defects from which the method suffers, however, are: (i) that it is only the antifouling system, known in which it is proposed to scrub the vessel even when clean, and (ii) the low volume solids of the coating (approximately 33%) requires a multiplicity of coats to achieve a long service life.
II. The controlled diffusion approach. This method proposes to extend the lifetime of an antifouling system by superimposing a hydrophilic diffusion membrane over a high performance antifouling system, so that the leaching of the biocides approaches linearity more closely than in the conventional materials. The limitations of this system are as before: (i) a low volume solids, (ii) a multiplicity of coats, and (iii) the problems associated either with the removal of the hydrophilic varnish or its overcoating.
Ill. The self-pollshing approach. In this proposal, the trialEnyl tin salts of polymeric vinyl carbolic resins have been claimed to give long life antifouling systems. They are based on the observation that
the tributyl tin copolymer resins hydrolyse in sea-water (pH 8-8.2) to give water-soluble components
and that films variously pigmented with biocides, under the influence of turbulent flow, are ablated or
polished at a steady rate.This overcomes the problem of matrix inhibition, but these compositions are
also non-convertible coatings of low volume solids content (approximately 37.5%), requiring multiple
coats to achieve adequate film thickness, with long drying periods, and are thus extremely expensive
processes.
In this invention we have sought to provide anti-fouling compositions which can be applied at
high volume solids and yet which have long service life.
The invention provides a monomeric oligomeric triorganotin salt of a polyfunctional organic acid
of the general formula: R(X)X(A)e where
R represents an aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical;
X represents an acid radical;
A represents an active hydrogen-containing radical capable of reaction with an isocyanate; and
x and a, which may be the same or different, are each an integer of at least 1,
The triorganotin salt optionally being pre-reacted with a low molecular weight polyol.
The monomeric or oligomeric triorganotin salt is preferably derived from a polyfunctional organic
acid of the general formula:
R(X)x(Y)y(Z)z where
R represents an aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical;
X represents a carboxylic, thiocarboxylic, dithiocarboxylic, sulphonic or phosphoric acid radical;
Y represents a hydroxy (OH) or mercaptan (SH) radical;
Z represents a primary amino (-NH2), secondary amino (-NHR' where R' is an alkyl or aryl grntlp) or amido (-CONH2) radical;
x is an integer of at least 1;
y and z are each 0 or an integer of at least 1, provided that y and z are not both 0.
The triorganotin salts according to the invention can be prepared, for example, by reacting a triorganotin compound (e.g. the oxide or hydroxide) with the organic acid, or by reacting a triorganotin halide with a metallic salt of the organic acid.
The invention also provides an antifouling composition comprising:
(i) a functional isocyanate, and
(ii) a triorganotin salt as defined above, the triorganotin salt optionally being pre-reacted with a low molecular weight polyol.
The isocyanate is preferably di-functional. This produces linear polymers, giving films which both leach biocide and ablate. Suitable di-functional isocyanates are, for example, isophorone di-isocyanate and diphenyl-methane-4,4'-di-isocyanate.
According to the invention, the antifouling composition is suitable for use in a finish coat for ships' hulls or submarine installations.
The antifouling composition preferably also comprises:
(iii) at least one biocidal, substantially water-insoluble compound which may be inorganic, organo-metallic or organic; and/or
(iv) at least one diluent resin, plasticiser, accelerator and/or suspending agent such as those normally used in the art to provide the necessary viscosity, stability and application properties.
The crosslinking of hydroxyl or amino groups of monomeric or oligomeric precursors by isocyanates of mono di- or polyfunctionality is a reaction well known in the art, and may be represented as follows:-
0 II R1OH + R2NCOo R1-O-N-C-R2 Hydroxy Isocyanate I H Urethane R,NH2 + R,NC6 R1--NN--CC-N-R, Amine Iso-cyanate I II I HOH Substituted Urea Where both components are polyfunctional, resinous or elastomeric products result, which are noted for their hardness, abrasion and chemical resistance.The tributyl tin salts of polycarboxylic polyhydroxyl acids can likewise be crosslinked with mono and polyfunctional isocyantes to produce tough, hard and adherent coatings; the general chemistry of the composition can be suitably exemplified by the reaction of, say, the tributyl tin salt of dl, or ditartaric acid,
and the commercial isocyanate Desmodur N (a Trade Mark of the Bayer Company), a trifunctional isocyanate with the formula:
Suitable functional acids for the production of the organotin salts are lactic acid, tartronic acid (hydroxy malonic acid), malic acid (hydroxysuccinic acid), tartaric acid (dihydroxy succinic acid) citric acid, salicylic acid (o-hydroxy-benzoic acid) and 5,5'-methylene disalicylic acid.
Suitable examples of amino acids are aspartic acid, (amino-succinic acid), glutamic acid and acids of mixed functionality such as hydroxyglutamic acid.
Suitable biocidal organotin compounds with which the polyfunctional acids can be reacted are organotin compounds of the general formula R1R2R3SnX, in which R1, R2 and R3 may be the same or different and represent aliphatic or aromatic hydrocarbon radicals (preferably C1-C6 alkyl or phenyl) and X represents an oxide or hydroxide radical, for example:
tripropyl tin oxide, tributyl tin oxide, triphenyl tin hydroxide, tricyclohexyl tin hydroxide, and dibutyl cyclohexyl tin hydroxide.
An alternative method of forming the salts is to react together compounds of the general formula
R1R2R3SnX in which R1, R2 and R3 are as defined above, and X is a halogen, normally chlorine, with a metallic salt of the polyfunctional acid, for example R.COOM/n where M is a mono- di- or trivalent metal (n=valency), and which may conveniently, be sodium yielding the required salt and an organicinsoluble metallic halide.
The salts used in this invention have been found to be either liquid or low melting solids, readily mixable with, or soluble in, a wide range of hydrocarbon, ketone or ester solvents or mixtures of these, to yield low viscosity liquids, and also to be compatible with a wide range of plasticisers such as phthalates, phosphates, chlorinated paraffins, chlorinated diphenyls, citrates and the like.
It is also envisaged as part of the invention that the triorganotin salts can be premixed or prereacted with diluting resins with hydroxy functionality such as hydroxypolyethers (e.g. Lankro
Propylane D402, D702, D1002, D2002, D2122, or Desmophen 250U) or polyesters (e.g. Bayer
Desmophen 650 or Desmophen 850).
These modifications can be made to alter the cross-link density, improve adhesion and flexibility, and to alter the hydrophilic/hydrophobic balance of the polymer so as to control the rate of ablation of the coating. The rate of ablation may also be modified by changing the curing ratio from the 1:1 stoichiometry of OH:-N=C=O required for ideal curing, or by the choice of, or the amount of plasticiser. The molar ratio of active hydrogen atoms to isocyanate groups is preferably from 1:3 to 3:1, more preferably from 1:2 to 2:1, and especially from 1:1.5 to 1.5:1.
It is well known in the art that the biocidal properties of the organotin compounds, taken singly, do not generally provide efficiently the necessary complete spectrum of antifouling activity. Provision is therefore made in a preferred embodiment of the invention for the inclusion of either additional "free" or unbound organotin compounds, or the addition of suitable amounts of the customary antifouling biocides, such as tributyl tin oxide, tripropyl tin oxide, triphenyl tin hydroxide, triphenyl tin fluoride, tricyclohexyl tin hydroxide, tributyl tin stearate, tributyl tin dibromosuccinate, tributyl tin tetrachlorophthalate, tributyl tin dimethyldithiocarbamate, tetramethyl thiurium disulphide, trichloromethylthiophthalimide (Captan), D.D.T., cuprous thiocyanate, cuprous oxide, cupric hydroxide, basic copper carbonate, copper acetoarsenite, copper metal, alloys of copper and zinc (brass), alloys of copper and other metals such as Cu:Ni 90:10), zinc metal, zinc oxide, organometallic biocides such as
R.HgX where R is aliphatic, aromatic, alicyiic or substituted aliphatic, aromatic or alicylic, and X is a radical of an organic or inorganic acid; organic arsenical compounds such as 10.10' oxybis- phenoxarsine oxide, or phenarsazine oxide.
The invention also allows for the inclusion of such fillers, suspending agents, thixotropss or colouring pigments as are recuired to give the necessary application properties of the finished material.
The methods of application are those normal to the trade. Although it is recognised that application by brush and roller is unlikely, this is possible on small areas. The preferred method of application is by airless spray: 2-component airless spray in which the components are mixed immediately before atomisation, and hot airless spray, in which the two components are pre-hested to reduce application viscosity before atomisation. In this way the potential of the invention for providing a means for rapid curing of high-build antifouling coatings can be most readily exploited.
The following Examples illustrate the invention.
Example 1 A. hydroxy-functional triorganotin carboxylate is formed by heating together
Tributyl Tin Oxide 1 Mole 595 grams
5,5'-Methylene disalicyclic Acid 1 Mole 288 grams under reflux as a 75% solide in xylene, collecting the evolved water (1 mole, 18 grams), and drying the product ova calcium sulphate. The resulting solution has a viscosity of 1.00 poidse (determined on an I.C.I. cons and plats viscometer at 25 C).
Example 2 r'n antifouling paint was made by grinding the following ingredients in a ball mill:- Component A
Medium as in Example 1 10b grams
Cuprous Oxide 285 grams
Zinc Oxide 25 grams
Thixatrol (Trade Mark, Baker Castor Oil) 2.5 grams
Sylodex A24 (Trade Mark, Grace) 2.5 grams
Tributyl Tin Oxide 2.5 grams
Methyl isobutyl Ketone 20.5 grams followed by reacting with Component B
Isophorone Di-isocyanate 19.5 grams The above paint, when mixed in the above proportions, has a volume solids of 70% and a viscosity of 2 poise (determined on an l.C.I. cone and plate viscometer at 250C.
The above paint was mixed in the above proportions to give a product which was applied to a rotor disc and cured for 36 hours. After immersion in running sea water for 1 month it gave a film which both leached biocide and in which ablation of the film took place.
Claims (10)
1. A monomeric or oligomeric triorganotin salt of a polyfunctional organic acid of the general formula:
R(X)g(A)a where
R represents an aiiphatic, aromatic or aliphatic-aromatic hydrocarbon radical;
X represents an acid radical;
A represents an active hydrogen-containing radical capable of reaction with an isocyanate: and ;:'and a, which may be the same or different, are each an integer of ar least 1,
The triorganotin salt optionally being pre-reacked with a low molecular weight polyol.
2. A triorganotin salt as claimed in Claim 1, wherein the polyfunctional organic acid has the general formula:
R(X)x(Y)y(Z)z where
R represents an aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical:
X represents a carboxylic, thiocarboxylic, dithio-carboxylic, sulphonic or phosphoric acid radical;
V represents a hydroxy (OH) or mercaptan (SH) radical;
Z represents a primary amino (-NH2), secondary amino (-NHR' where R' is an alkyl or aryl group) or amido (-CONH2) radical; xis an integer of at least 1; and
y and z are each 0 or an integer of at least 1, provided that y and z are not both 0.
3. A triorganotin salt as claimed in Claim 1 or 2, wherein the triorganotin radical has the formula R1R2R3Sn, in which each of R1, R2 and R3 independently is a C1-C6 alkyl or a phenyl radical.
4. A triorganotin salt as claimed in Claim 1, substantially as hereinbefore described with reference to any of the Examples.
5. A process for preparing a triorganotin salt as claimed in Claim 1, which comprises reacting a triorganotin compound with the organic acid, or reacting a triorganotin halide with a metallic salt of the organic acid.
6. A process as claimed in Claim 5, substantially as hereinbefore described with reference to any of the Examples.
7. A triorganotin salt when prepared by a process as claimed in Claim 5 or 6.
8. An antifouling composition, comprising:
(i) a functional isocyanate, and
(ii) a triorganotin salt as claimed in any one of Claims 1 to 4 and 7, the triorganotin salt optionally being pre-reacted with a low molecular weight polyol.
9. An antifouling composition as claimed in Claim 8, also comprising:
(iii) at least one biocidal, substantially water-insoluble, inorganic, organo-metallic or organic compound; and/or
(iv) at least one diluent resin, plasticiser, accelerator and/or suspending agent.
10. An antifouling composition substantially as hereinbefore described with reference to any of the Examples.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7846632A GB2029831A (en) | 1977-12-06 | 1978-11-30 | Triorganotin Salts and their use in Improved Ablative Antifouling Compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB5073577 | 1977-12-06 | ||
GB7846632A GB2029831A (en) | 1977-12-06 | 1978-11-30 | Triorganotin Salts and their use in Improved Ablative Antifouling Compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
GB2029831A true GB2029831A (en) | 1980-03-26 |
Family
ID=26266726
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7846632A Withdrawn GB2029831A (en) | 1977-12-06 | 1978-11-30 | Triorganotin Salts and their use in Improved Ablative Antifouling Compositions |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2029831A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2188327A (en) * | 1986-03-27 | 1987-09-30 | Ashland Oil Inc | Tin or bismuth complex catalysts and trigger cure of coatings therewith |
US5670215A (en) * | 1993-03-08 | 1997-09-23 | Oakes; Thomas W. | Composition and method for protective coating |
US7231128B2 (en) | 2001-09-18 | 2007-06-12 | Ut-Battelle, Llc | Hybrid solar lighting systems and components |
-
1978
- 1978-11-30 GB GB7846632A patent/GB2029831A/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2188327A (en) * | 1986-03-27 | 1987-09-30 | Ashland Oil Inc | Tin or bismuth complex catalysts and trigger cure of coatings therewith |
GB2188327B (en) * | 1986-03-27 | 1990-07-04 | Ashland Oil Inc | Tin or bismuth complex catalysts and the curing of polyol/polyisocyanate coatings therewith |
US5670215A (en) * | 1993-03-08 | 1997-09-23 | Oakes; Thomas W. | Composition and method for protective coating |
US7231128B2 (en) | 2001-09-18 | 2007-06-12 | Ut-Battelle, Llc | Hybrid solar lighting systems and components |
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