GB2027711A - Bis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids and antifouling compositions containing same - Google Patents
Bis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids and antifouling compositions containing same Download PDFInfo
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- GB2027711A GB2027711A GB7908410A GB7908410A GB2027711A GB 2027711 A GB2027711 A GB 2027711A GB 7908410 A GB7908410 A GB 7908410A GB 7908410 A GB7908410 A GB 7908410A GB 2027711 A GB2027711 A GB 2027711A
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- formula
- bis
- compound
- trialkylstannyl
- toluene
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 24
- -1 derivatives of chlorinated polycyclic dicarboxylic acids Chemical class 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 17
- 235000014692 zinc oxide Nutrition 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 235000010215 titanium dioxide Nutrition 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims 1
- 229940117958 vinyl acetate Drugs 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 31
- 239000000047 product Substances 0.000 description 15
- 238000005452 bending Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 9
- 125000006414 CCl Chemical group ClC* 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- WYNGWCBQLDADES-UHFFFAOYSA-N 2-hex-4-enyl-3-propylbutanedioic acid Chemical compound CC=CCCCC(C(CCC)C(=O)O)C(=O)O WYNGWCBQLDADES-UHFFFAOYSA-N 0.000 description 5
- 229940093499 ethyl acetate Drugs 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical compound OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 description 5
- 229950000975 salicylanilide Drugs 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 3
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VIULBFHXDPUWIL-UHFFFAOYSA-N triethyl(triethylstannyloxy)stannane Chemical compound CC[Sn](CC)(CC)O[Sn](CC)(CC)CC VIULBFHXDPUWIL-UHFFFAOYSA-N 0.000 description 3
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910020813 Sn-C Inorganic materials 0.000 description 2
- 229910018732 Sn—C Inorganic materials 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000007858 starting material Substances 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
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- YYPMMAIWAOHDMY-UHFFFAOYSA-N 3-hex-4-enyl-4-propyloxolane-2,5-dione Chemical compound CC=CCCCC1C(CCC)C(=O)OC1=O YYPMMAIWAOHDMY-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- DJKGDNKYTKCJKD-UHFFFAOYSA-N chlorendic acid Chemical compound ClC1=C(Cl)C2(Cl)C(C(=O)O)C(C(O)=O)C1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- YPUBDZDOJVNIDZ-UHFFFAOYSA-N trimethyl(trimethylstannyloxy)stannane Chemical compound C[Sn](C)(C)O[Sn](C)(C)C YPUBDZDOJVNIDZ-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
- C09D5/1631—Organotin compounds
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Bis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids of formula I: <IMAGE> in which R is a lower alkyl group, R' is H or CH3 and n is 0 or 1, have good antifouling properties. These compounds are novel.
Description
SPECIFICATION
Bis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids and antifouling compositions containing same
The present invention is concerned with the protection of the surfaces of structures against marine fouling and, more particularly, with certain novel bis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids, with a method for their preparation, and with antifouling coating compositions containing them.
According to the invention, there are provided, as novel compounds, bis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids of formula I:
in which R is a lower alkyl group, R' is H or CH3, and n isO or 1.
We have found that compounds of formula I are biologically active and can be used as antifouling agents in protective polymer coatings. These compounds are more effective antifouling agents than those known in the prior art and suppress the growth of biomasses of both vegetal and animal origin.
This property is due to the presence in the molecule of the compounds of chlorinated cyclic portions with two organotin carboxyls. Another advantage of the compounds is the low rate at which they are leached out of coatings by seawater.
Preferred compounds according to the invention are those in which R is an n-butyl group because they show good compatibility with polymeric binders and other ingredients of coating compositions.
According to a further aspect of the invention, there is provided an antifouling coating composition, which comprises, as the active antifouling component, a bis-trialkylstannyl derivative according to the invention.
Such a composition preferably additionally comprises a polymeric binder, a filler, a pigment, additives, and a solvent and has the following composition, in parts by weight:
compound of formula 1 5-10 polymeric binder 7-30 filler 25-30 pigment 0.5-5.5 additives 0--5.5 solvent 1035.
Preferred compositions according to the invention are as follows, in parts by weight:
I. Compound of formula 1 10.0
Vinylchloride/vinyl acetate copolymer 17.0
Colophony 12.0
Titanium white 28.0
Toluene 33.0
II. Compound of formula I (preferably wherein R = n-C4Hg, R' = CH3, n = 1 ) 7.5
Postchlorinated polyvinyl chloride 8.0
Colophony 9.0
Zinc white 30.0
Dibutylphthalate 5.0
Salicylanilide 5.5
Ethylacetate/toluene (1:1 mixture) 35.0
III. Compound of formula I (preferably wherein
R = C2H5, R' = CH3, n = 1) 10.0
Epoxy resin 30.0
Polyethylene polyamine 5.0 Dibutylphthalate 7.5
Zinc white 30.0
Toluene 12.5
The binders, fillers, pigments, solvents and other additives inciuded in the coating compositions are commercially available products.
The coatings' compositions are formed by dispersion of the various components thereof in a ball mill to a particle size of 60 to 70 microns. It generally takes 2 to 8 hours for the coatings to dry following application to a surface.
According to a further aspect of the invention, there is provided a method of preparing a bistrialkylstannyl derivative according to the invention, which comprises condensing a chlorinated polycyclic dicarboxylic acid anhydride of formula II:
in which Rt and n have the above-stated meanings with a hexaalkyldistannoxane of the formula
R3SnOSnR3, in which R has the above-stated meaning, in the presence of an inert organic solvent.
The reaction is exothermic and occurs at room temperature, although at 60 to 800 C, it is more effective. The reactants may be used in stoichiometric proportions or with a slight excess of the anhydride. The resulting compounds are waxy or gummy products without any pungent odour and are readily soluble in organic solvents.
The starting materials, that is the anhydrides of formula II and the hexaalkyldistanoxanes are well known and readily available compounds.
Since the process according to the invention involves a single stage, can be conducted under mild conditions, does not require excessive power and additional reagent consumption, is simple and easy to carry out, and makes use of readily available starting materials, the commercial value of the novel compounds and antifouling compositions based thereon is clear.
In order that the invention may be more fully understood, the following examples, of which
Examples 1 to 9 describe the preparation of the compounds and Examples 10 to 27, compositions containing them, are given by way of illustration. All parts and percentages are by weight, unless otherwise indicated.
EXAMPLE 1
Bis-trimethylstannyl ester of 1,2,3,4,11,11 -hexachloro-6-methyltricyclo (4,2,1,05.10) undec-2-ene-7,8dicarboxylic acid
A four-necked flask provided with a mechanical stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen inlet tube was charged with 6.6 g (0.015 mol) of 1,2,3,4,1 1,1 1-hexachloro-6- methyltricyclo (4,2,1,05.10) undec-2-ene-7,8-dicarboxylic acid anhydride and 200 mi of benzene. The mixture was stirred and heated at 600C until complete dissolution of the anhydride, then 3.4 g (0.01 mol) of hexamethyldistannoxane dissolved in 10 ml of benzene were added to the mixture. The reaction was accompanied by the evolution of heat.
The reaction mixture was heated at 800C for 10 hours. The reaction product was isolated by extraction with heptane. At the same time, the excess unreacted anhydride precipitated and the precipitate was separated by filtration. After distilling off the solvent from the heptane extract, the product obtained was dried in a vacuum dessicator at 40 C. 6.0 g (76% of the theoretical) of the abovenamed product were obtained; m.p. 47.5-49 C; M.W. 783.6 (determined by cryoscopy in benzene).
Analysis, found, %: Cl 27.86, Sn 29.97; calculated for C20H28O4Cl6Sn2, %: CI 27.18, Sn 30.33.
IR spectra, cm-1: #C-Cl 680, #sn-cs 515, ##sn-cas 610, #c=0 1790, 1830, 1595 (Me3SnOOC-).
EXAMPLE 2
Bis-triethylstannyl ester of 1,2,3,4,11,11 -hexachloro-6-methyltricyclo [4,2,1 05.10] undec-2-ene-7,8
dicarboxylic acid
Under conditions similar to those of Example 1, but using 52.7 g (0.12 mol) of the anhydride of
Example 1 and 42.7 g (0.1 mol) of hexaethyldistannoxane, there were obtained 71.0 g (82% of the theoretical) of the above-named product as a yellowish syrup: #= 612.5 cS, M.W. 865.8, and d420= 1.4855. Analysis, found, %: Cl 24.75, Sn 27.26; calculated for C26H40O4Cl6Sn2, %: CI 24.54, Sn 27.39.
IR spectra, cm-1: #C-Cl 680, #Sn-cs 505, #Sn-Cas 600, #c=0 1785, 1830, 1595 (Et3SnOOC-).
EXAMPLE 3 Bis-tri-n-propylstannyl ester of 1,2,3,4,11,11 1-hexachloro-6-methyltricyclo [4,2,1,05,1 0] undec-2-ene- 7,8-dicarboxylic acid
Under conditions similar to those of Example 1, but using 65.8 g (0.15 mol) of the anhydride of
Example 1 and 61.4 g (0.12 mol) of hexa-n-propyldistannoxane, there was obtained 97.5 g of the above-named product in the form of a gummy light yellow mass. The yield was 85.5% of theoretical, # = 457 cS, M.W. 950, d420 = 1.4220. Analysis, found, %: CI 22.67, Sn 25.18; calculated for C32H5204CI6Sn2, %: Cl 22.37, Sn 24.96.
IR spectra, cm-1: #C-Cl 685, #Sn-C 490, #Sn-Cas 600, #c=0 1790, 1825, 1595 N-Pr3SnOOC-).
EXAMPLE4 Bis-tri-n-butylstannyl ester of 1,2,3,4, 1 1,1 1 -hexachloro-6-methyltricyclo [4,2,1,05,10] undec-2-ene
7,8-dicarboxylic acid
Under conditions similar to those of Example 1, but using 43.9 g (0.1 mol) of the anhydride of
Example 1 and 65.6 g (0.1 1 mol) of hexa-n-butyldistannoxane, there were obtained 91.3 g of the above-named product as a viscous light yellow product. The yield was 88.2 of theoretical, 17 = 374.6 cS, d24 = 1.3689, M.W. 1,120. Analysis, found, %: Cl 20.85, Sn, 23.24; calculated for C38Hó404CI6Sn2, %: Cl 20.55, Sn 22.93.
IR spectra, cam : Pc-cl 680, PSn~C 490, PSSn~c 600, Pc=o 1790, 1820, 1590 (n-BusSnOOC-).
EXAMPLE 5
Bis-triethylstannyl ester of 1,2,3,4,11,11 -hexachlorotricyclo-[4,2, 1 ,05.1o] undec-2-ene-7,8-dicarboxylic
acid
Under conditions similar to those of Example 1, but using 42.5 g (0.1 mol) of hexachlorotricycloundecenedicarboxylic acid anhydride and 42.7 g (0.1 mol) of hexaethyl-distannoxane, there were obtained 65.4 g of the above-named product as a gummy light yellow product The yield was 76.8% of theoretical, #=680 cS, M.W. 850, d24 = 1.4905. Analysis, found, %: Cl 25.41, Sn 26.34; calculated for C25H3804CI6Sn2, %: Cl 24.97,Sn 27.83.
IR spectra, cm-1:#Sn-cs 510, #Sn-Cas 615, #C-Cl 680, #c=0 1785, 1835, 1590 (Et3SnOOC-), #c=0 1600.
EXAMPLE 6
Bis-tri-n-butylstannyl ester of 1,2,3,4,1 1,1 1 -hexachlorotricyclo 4,2,1 05.10-undec-2-ene-7,8-
dicarboxylic acid
Under conditions similar to those of Example 1, but using 44.5 g (0.12 mol) of chlorendic
Example 5 and 59.5 g (0.1 mol) of hexa-n-butyldistannoxane, there were obtained 84.2 of the abovenamed product as a gummy transparent mass. The yield was 82.5%, #=390 cS, d420 = 1 .3710,M.W.
1,015. Analysis, found, %: Cl 21.61, Sn 22.95; calculated for C39H62O4Cl6Sn2, %: Cl 21.09, Sn 23.50.
IR spectra, cm-1: #C-Cl 685, #Sn-CS 495, #Sn-Cas 605, #c=0 1790, 1815, 1505 (n-Bu3SnOOC-).
EXAMPLE 7
Bis-triethylstannyl ester of 1,2,3,4,7,7-hexachlorobicyclo-[2,2,1]hept-2-ene-5,6-dicarboxylic acid
Under conditions similar to those of Example 1, but using 44.5 g (0.12 mol) of chlorendic anhydride and 42.7 g (0.1 mol) of hexaethyldistannoxane, there were obtained 71.4 g of the abovenamed product as a waxy light yellow product. The yield was 89.5%, m.p. 74.5 C, M.W. 800. Analysis, found, %: Cl 27.08, Sn 30.19; calculated for C21H32O4Cl6Sn2, %: Cl 26.29, Sn 29.73.
IR spectra, cm-1: #C-Cl 680, #Sn-Cs 510 #Sn-C 610, #c=0 1780, 1840, 1595 (Et3SnOOC-).
EXAMPLE 8
Bis-tri-n-propylstannyl ester of 1,2,3,4,7,7-hexachlorocyclo-[2,2,1]hept-2-ene-5,6-dicarboxylic acid
Under conditons similar to those of Example 1, but using 44.5 g (0.12 mol) of chlorendic anhydride and 51.1 g (0.1 mol) of hexapropyldistannoxane, there were obtained 79.4 g of the abovenamed product as a gum. The yield was 90%, 17=810 cS, d420 = 1 4130, M.W. 885. Analysis, found, %:
CI 24.75, Sn 27.22; calculated for C27H4404CI6Sn2, %: Cl 24.15, Sn 26.98.
IR spectra, cm-1: #C-Cl 675, #Sn-Cs 500, #Sn-Cas 600, #c=0 1770, 1840, 1590 (Pr3SnOOC-), #c=c 1600.
EXAMPLE 9
Bis-tri-n-butylstannyl ester of chloroendic acid
Under conditions similar to those of Example 1, but using 89 g (0.24 mol) of chlorendic anhydride and 119 g (0.2 mol) of hexa-n-butyldistannoxane, there were obtained 178.7 g of the above-named product in the form of a viscous resinous mass. The yield was 92.5% #=720cS, d420=1,3926, n020= 1.5281. M.W. 970. Analysis, found, %: Cl 21.86, Sn 25.11; calculated for C33H56O4Cl6Sn2, %:CL 22.05,
Sn 24.56.
IR spectra, cm-1: #C-Cl 680, #Sn-Cs 490, #Sn-Cas 615, #c=0 1785, 1830m 1590 (n-Bu3SnOOC-).
EXAMPLE 10
10 parts of the compound of Example 4 (í, R=n-C4Hg, R' = CH2, n=1), 17.0 parts of a vinyl chloride/vinyl acetate copolymer, 12 parts of colophony, 28 parts of titanium white and 33 parts of toluene were charged into a ball mill. The charge was milled to a suspended particle size of 70 microns.
The resulting composition was ready for use to form antifouling coatings and could be applied by any conventional technique, such as spraying or application with a brush or roller.
A uniform, durable matte coating 40 to 50 microns thick was formed on a surface; it took 6 hours for the coating to dry. The properties of the coating are given in Table 1 below.
EXAMPLE 11
The following composition was prepared as described in Example 10:
compound of Example 6(1, R = n-C4H9, R' =H,n= 1) 10.0
vinyl chloride/vinyl acetate copolymer 17.0
colophony 12.0
titanium white 28.0
toluene 33.0
The properties of coatings prepared therefrom are given in Table 1.
EXAMPLE 12
The following composition was prepared as described in Example 10:
compound of Example 9(1, R = n-C4H9, n=0) 10.0
vinyl chloride/vinyl acetate copolymer 17.0
colophony 12.0
titanium white 28.0
toluene 33.0
The properties of coatings prepared from this composition are given in Table 1.
EXAMPLE 13
The following composition was prepared as described in Example 10:
compound of Example 4 (I, R = n-C4Hg, R'=CH3,n=1) 7.5 postch lorinated polyvinyl chloride 8.0
colophony 9.0
zing white 30.0
dibutylphthalate 5.0
salicylanilide 5.5
ethylacetate/toluene (1:1 mixture) 35.0
The properties of coatings obtained therefrom are given in Table 1.
EXAMPLE 14
The following composition was prepared as described in Example 10:
compound of Example 6(1, R = n-C4Hg, R'=H,n=1) 7.5
postchlorinated polyvinyl chloride 8.0
colophony 9.0
zinc white 30.0
dibutylphthalate 5.0
salicyclanilide 5.5
ethylacetate/toluene (1:1 mixture) 35.0
The properties of coatings obtained therefrom are given in Table 1.
EXAMPLE 15
The following composition was prepared as described in Example 10:
compound of Example 9(1, R = n-C4H2, n=0) 7.5
postchlorinated polyvinyl chloride 8.0
colophony 9.0
zinc white 30.0
dibutylphthalate 5.0
salicyclanilide 5.5
ethylacetate/toluene(1:1 mixture) 35.0
The properties of coatings obtained therefrom are given in Table 1.
EXAMPLE 16
The following composition was prepared as described in Example 10:
compound of Example 4(1, R = n-C4Hg, R'=CH3,n=1) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.0
The properties of coatings obtained therefrom are given in Table 1.
EXAMPLE 17
The following composition was prepared as described in Example 10:
compound of Example 9 (1, R = n-C4Hg, n=0) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
The properties of coatings obtained therefrom are given in Table 1.
EXAMPLE 18
The following composition was prepared as described in Example 10:
compound of Example 1 (I, R = CH3, R'=CH3, n = 1) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
The properties of coatings obtained therefrom were as follows: impact strength, 70 kg/cm; bending strength, 1 mm; pendulum hardness, 0.35; weathering stability, 8 points; duration of antifouling action, 1 8 months.
EXAMPLE 19
The following composition was prepared as described in Example 10:
compound of Example 2 (I, R = C2H5, R'=CH3, n=1) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
The properties of coatings obtained therefrom were as follows: impact strength, 75 kg/cm; bending strength, 1 mm; hardness, 0.25; weathering stability, 7 points; duration of antifouling action, 20 months.
EXAMPLE 20
The following composition was prepared as described in Example 10:
compound of Example 3, (1, R = n-C3H7, R' =CH3, n = 1 ) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
The properties of coatings obtained therefrom were as follows: impact strength, 80 kg/cm; bending strength, 1 mm; hardness, 0.3; weathering stability, 8 points, duration of antifouling action, 20 months.
EXAMPLE 21
The following composition was prepared as described in Example 10:
compound of Example 5(1, R = C2Hs, R' = H,
n=1) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
The properties of coatings obtained therefrom were as follows: impact strength, 65 kg/cm; bending strength, 1 mm; hardness, 0.18; weathering stability, 7 points; duration of antifouling action, 1 8 months.
EXAMPLE 22
The following composition was prepared as described in Example 1 0:
compound of Example 7 (1, R = C2H5, n=0) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
The properties of coatings obtained therefrom were as follows: impact strength, 80 kg/cm; bending strength, 1 mm; hardness, 0.1 5; weathering stability, 7 points, duration of antifouling action,' 20 months.
EXAMPLE 23
The following composition was prepared as described in Example 10:
compound of Example 8 (I, R = C3H7,
n =0) 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
The properties of coatings obtained therefrom were as follows: impact strength, 70 kg/cm; bending strength, 1 mm; hardness, 0.25; weathering stability, 8 points; duration of antifouling action, 20 months.
EXAMPLE 24
The following composition was prepared as described in Example 10:
compound of Example 2 (I, R = C2H5, R'=CH3, n=1) 7.5
postchlorinated polyvinyl chloride 8.0
colophony 9.0
zinc white 30.0
dibutylphthalate 5.0
salicylanilide 5.5
ethylacetate/toluene (1:1 mixture) 35.0
The properties of coatings obtained therefrom were as follows: impact strength, 50 kg/cm; bending strength, 1 mm; hardness, 0.15; weathering stability, 7 points; duration of antifouling action, 18 months.
EXAMPLE 25
The following composition was prepared as described in Example 10:
compound of Example 7 (I, R = C2H5,
n=0) 7.5 postch lorinated polyvinyl chloride 8.0
colophony 9.0
zinc white 30.0
dibutylphthalate 5.0
salicylanilide 5.5
acetone/toluene (1:1 mixture) 35.0
The properties of coatings obtained therefrom were as follows: impact strength, 55 kg/cm; bending strength, 1 mm; hardness, 0.1 6; weathering stability, 7 points; duration of antifouling action, 22 months.
EXAMPLE 26
The following composition was prepared as described in Example 10:
compound of Example 7 (í, R = C2H6, n=0) 10.0
vinylchloride/vinyl acetate copolymer 17.0
colophony 12.0
titanium white 28.0
toluene 33.0
The properties of coatings obtained therefrom were as follows: impact strength, 50 kg/cm; bending strength, 1 mm; hardness, 0.2; weathering stability, 8 points; duration of antifouling action, 24 months.
EXAMPLE 27
The following composition was prepared as described in Example 10:
compound of Example 2 (I, R = C2H5, R' =CH3,n=1) 7.5
postchlorinated polyvinyl chloride 8.0
colophony 9.0
zinc white 30.0
dibutylphthalate 5.0
salicylanilide 5.5
acetone/toluene (1:1 mixture) 35.0
The properties of coatings obtained therefrom were as follows: impact strength, 55 kg/cm; bending strength, 1 mm; hardness, 0.1 5; weathering stability, 7 points; duration of antifouling action, 1 8 months.
The properties of coatings formed from the compositions described in Examples 10 to 17 are given in Table 1. For comparison, there are also given corresponding data for a prior art composition having (C4Hg)3SnOSn(C4H9)3 as its active component. As can be seen from Table 1, coatings obtained from the compositions according to the invention have excellent performance characteristics.
Coatings containing compounds according to the invention, applied to steel and aluminium plates 40 x 60 cm in size, have been tested in seawater under natural conditions in a region of Intensive fouling at a depth of 4 to 5 m. The test results are summarized in Table 2.
TABLE 1
Antifouling coating composition of Example Prior art coating with Properties of Coating 10 11 12 13 14 15 16 17 (C4H9)3SnOSn(C4H9)3 1. Impact strength kg/cm 50 50 55 50 55 55 70 70 50 2. Bending strength, mm 1 1 1 1 1 1 1 1 2 3. Hardness, kg/sq. m 0.15 0.15 0.17 0.16 0.18 0.25 0.15 0.25 0.35 4. Cross-cut adhesion 1 1 1 1 1 1 0.0 0.0 2 5. Particle size, microns 70 60 65 70 70 70 70 65 50 6. Weathering stability, points 7 7 7 8 7 8 8 8 2 7. Duration of antifouling action, months 18 18 22 18 20 24 20 18 8. Drying time, hrs 6 7 8 2 3 2 2 2 8 TABLE 2
Degree of fouling, kg/sq. m test duration, months
Leaching rate,
R R' n mg/sq cm per day 6 12 18 24 Note
CH3 CH3 1 0.067 0.011 0.018 0.115 0.215 On test specimens
C2H5 CH3 1 0.051 0.009 0.015 0.095 0.155 without antifouling
C2H5 H 1 0.049 0.009 0.016 0.105 0.165 coating, a large
C2H5 - 0 0.031 0.01 0.105 0.165 0.205 amount of biomass, n-C3H7 CH3 1 0.038 0.008 0.014 0.095 0.18 10 to 15 kg/sq. m, n-C4H9 CH3 1 0.027 0.005 0.09 0.11 0.145 was accumulated n-C4H9 H 1 0.025 0.005 0.08 0.12 0.135 over 6 to 8 months n-C4H9 - 0 0.028 0.003 0.06 0.095 0.125 (C4H9)3SnOSn(C4H9)3 0.68 0.125 0.75 1.15 1.86 (prior art)
Claims (12)
1. Bis-trialkylstannyl derivatives of chlorinated polycyclic dicarboxylic acids of formula I:
in which R is a lower alkyl group, R' is H orCH3, and n is O or 1.
2. A bis-trialkylstannyl derivative as claimed in claim 1, in which R is n-C4Hg and n is 0.
3. A bis-trialkylstannyl derivative as claimed in claim 1, in which R is n-C4Hg, R' is CH3, and n is 1.
4. A method of preparing a bis-trialkylstannyl derivative of formula I specified in claim 1, which comprises condensing a chlorinated polycyclic dicarboxylic acid anhydride of formula II:
in which R' and n have the meanings specified in claim 1, with a hexaalkyldistannoxane of the formula R3SnOSnRa, in which R has the meaning specified in claim 1, in the presence of an inert organic solvent.
5. A method as claimed in claim 4, in which the condensation reaction is carried out at a temperature of 60 to 800 C.
6. An antifouling coating composition which comprises as the active antifouling component, a bistrialkylstannyl derivative as claimed in any of claims 1 to 3.
7. A composition according to claim 6, which additionally comprises a polymeric binder, a filler, a pigment, additives and a solvent and has the following composition, in parts by weight,
compound of formula I 5 to 10
polymeric binder 7 to 30
filler 25 to 30 pigment 0.5 to 5.5
additives 0to5.5 solvent 10 to 35.
8. A composition according to claim 7, which comprises, in parts by weight,
compound of formula 1 10.0
vinyl chloride/vinylacetate copolymer 17.0
colophony 12.0
titanium white 28.0
toluene 33.0
9. A composition according to claim 7, which comprises, in parts by weight,
compound of formula 1 7.5
postchlorinated polyvinyl chloride 8.0
colophony 9.0
zinc white 30.0
dibutylphthalate 5.0
salicylamilide 5.5
ethyl acetate/toluene (1:1 mixture) 35.0
10. A composition according to claim 7, which comprises, in parts by weight,
compound of formula 1 10.0
epoxy resin 30.0
polyethylene polyamine 5.0
dibutylphthalate 7.5
zinc white 30.0
toluene 12.5
11. A method of preparing a bis-trialkylstannyl derivative of formula I specified in claim 1, substantially as herein described in any of Examples 1 to 9.
12. An antifouling coating composition substantially as herein described in any of Examples 10 to 27.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU782640255A SU876647A1 (en) | 1978-08-08 | 1978-08-08 | Bistrialkylstannyl esters of chloroendic acid as antiovergrowing agent of polymeric coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2027711A true GB2027711A (en) | 1980-02-27 |
| GB2027711B GB2027711B (en) | 1982-11-17 |
Family
ID=20775150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7908410A Expired GB2027711B (en) | 1978-08-08 | 1979-03-09 | Bis - trialkylstannyl derivatives of chloroinated polycyclic dicarboxylic acids and antifouling compositions containing same |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5940398B2 (en) |
| DE (1) | DE2902646C2 (en) |
| ES (1) | ES477519A1 (en) |
| FR (1) | FR2433025B1 (en) |
| GB (1) | GB2027711B (en) |
| SU (1) | SU876647A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56148398A (en) * | 1980-04-21 | 1981-11-17 | Mitsubishi Heavy Ind Ltd | Cleaning device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3517104A (en) * | 1969-05-28 | 1970-06-23 | Pasquale P Minieri | Fungicidal compositions and methods employing dialkyltin,1,4-endoalkylene - 2,3 - dihydrophthages and -1,2,3,6-tetrahydrophthalates |
-
1978
- 1978-08-08 SU SU782640255A patent/SU876647A1/en active
-
1979
- 1979-01-24 DE DE2902646A patent/DE2902646C2/en not_active Expired
- 1979-01-30 JP JP54008827A patent/JPS5940398B2/en not_active Expired
- 1979-02-07 ES ES477519A patent/ES477519A1/en not_active Expired
- 1979-02-28 FR FR7905258A patent/FR2433025B1/en not_active Expired
- 1979-03-09 GB GB7908410A patent/GB2027711B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2902646C2 (en) | 1982-04-08 |
| SU876647A1 (en) | 1981-10-30 |
| JPS5524159A (en) | 1980-02-21 |
| GB2027711B (en) | 1982-11-17 |
| FR2433025B1 (en) | 1983-05-13 |
| DE2902646A1 (en) | 1980-02-14 |
| JPS5940398B2 (en) | 1984-09-29 |
| FR2433025A1 (en) | 1980-03-07 |
| ES477519A1 (en) | 1980-04-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |