NO156493B - MARIN PAINTING comprising a film-forming acrylic polymer and an acrylic polymer for use in the paint - Google Patents
MARIN PAINTING comprising a film-forming acrylic polymer and an acrylic polymer for use in the paint Download PDFInfo
- Publication number
- NO156493B NO156493B NO840005A NO840005A NO156493B NO 156493 B NO156493 B NO 156493B NO 840005 A NO840005 A NO 840005A NO 840005 A NO840005 A NO 840005A NO 156493 B NO156493 B NO 156493B
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- Norway
- Prior art keywords
- units
- acrylic polymer
- monomer
- triorganotin
- paint
- Prior art date
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- 239000003973 paint Substances 0.000 title claims description 20
- 229920000058 polyacrylate Polymers 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims description 31
- 229920001897 terpolymer Polymers 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 6
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- LPUCKLOWOWADAC-UHFFFAOYSA-M tributylstannyl 2-methylprop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C(C)=C LPUCKLOWOWADAC-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 description 15
- 238000005498 polishing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 8
- 230000003115 biocidal effect Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 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 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940075894 denatured ethanol Drugs 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- MDPPJXJNOWFRRG-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.COCCOC(=O)C=C MDPPJXJNOWFRRG-UHFFFAOYSA-N 0.000 description 1
- PLDCQJBVJINWLF-UHFFFAOYSA-M C(C=C)(=O)OCCOC.C(C(=C)C)(=O)OC.C(C(=C)C)(=O)[O-].C(CCC)[Sn+](CCCC)CCCC Chemical compound C(C=C)(=O)OCCOC.C(C(=C)C)(=O)OC.C(C(=C)C)(=O)[O-].C(CCC)[Sn+](CCCC)CCCC PLDCQJBVJINWLF-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JNRFAGAIHOKUES-UHFFFAOYSA-M triphenylstannyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 JNRFAGAIHOKUES-UHFFFAOYSA-M 0.000 description 1
- GFHQVPZQABAPQR-UHFFFAOYSA-M tripropylstannyl 2-methylprop-2-enoate Chemical compound CCC[Sn](CCC)(CCC)OC(=O)C(C)=C GFHQVPZQABAPQR-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Description
Denne oppfinnelse angår nye marine malinger og visse nye terpolymerer som er nyttige komponenter deri. This invention relates to new marine paints and certain new terpolymers which are useful components therein.
Det er kjent marine malinger hvor en vesentlig komponent There are known marine paints where an essential component
er en kopolymer som inneholder enheter av alkylakrylater og -metakrylater og enheter av triorganotinnestere av akryl- og metakrylsyre. Alkylakrylat- og -metakrylat-enhetene tilfører hardhet til den film som oppnås når den marine maling påføres på et underlag, og triorganotinnester-enhetene tilfører biocid såvel som selvpolerende virkning. Under bruk avspaltes triorganotinn-enhetene fra polymeren ved hydrolyse og/eller ionebytting, hvorved filmen av den marine maling utøver en ønsket biocid virkning. Samtidig nedbrytes filmen, og dette resulterer i den selvpolerende virkning. is a copolymer containing units of alkyl acrylates and methacrylates and units of triorganotin esters of acrylic and methacrylic acid. The alkyl acrylate and methacrylate units add hardness to the film obtained when the marine paint is applied to a substrate, and the triorganotin ester units add biocide as well as self-polishing action. During use, the triorganotin units are split off from the polymer by hydrolysis and/or ion exchange, whereby the film of the marine paint exerts a desired biocidal effect. At the same time, the film breaks down, and this results in the self-polishing effect.
For således å oppnå en tilfredsstillende selvpolerende Virkning, må en viss mengde av triorganotinn-enheter være til stede i kopolymeren som anvendes i den marine maling, eftersom den selvpolerende virkning er en følge av avspaltningen av nevnte enheter. På den annen side ønskes det å holde mengden av triorganotinnenheter så lav som mulig, under hensyntagen til den ønskede biocide og selvpolerende virkning, eftersom triorganotinnmonomerer er forholdsvis kostbare og også har en myknende virkning på kopolymeren. In order to thus achieve a satisfactory self-polishing effect, a certain amount of triorganotin units must be present in the copolymer used in the marine paint, since the self-polishing effect is a consequence of the splitting off of said units. On the other hand, it is desired to keep the amount of triorganotin units as low as possible, taking into account the desired biocidal and self-polishing effect, since triorganotin monomers are relatively expensive and also have a softening effect on the copolymer.
Kopolymerer av den ovenfor angitte type er beskrevet bl.a. Copolymers of the above-mentioned type have been described i.a.
i britisk patent 1.457.590. in British patent 1,457,590.
I norsk patentansøkning 81.3553 er det foreslått å erstatte noen av eller alle triorganotinnester-enhetene med metylakrylat-og/eller etylakrylat-enheter. Den marine maling kan inneholde noe ytterligere biocid, særlig hvis kopolymeren ikke inneholder noen triorganotinnester-enheter. Nevnte metylakrylat- og etylakrylat-enheter vil til en viss grad hydrolyseres i vann og vil gi det ferdige belegg en selvpolerende virkning. På grunn av den resulterende kopolymers lave hydrolysehastighet vil imidlertid den selvpolerende virkning ikke være helt tilfredsstillende. In Norwegian patent application 81.3553, it is proposed to replace some or all of the triorganotin ester units with methyl acrylate and/or ethyl acrylate units. The marine paint may contain some additional biocide, particularly if the copolymer does not contain any triorganotin ester units. Said methyl acrylate and ethyl acrylate units will be hydrolysed to a certain extent in water and will give the finished coating a self-polishing effect. However, due to the resulting copolymer's low hydrolysis rate, the self-polishing effect will not be completely satisfactory.
Ifølge foreliggende oppfinnelse tilveiebringes en marin maling, som i tillegg til vanlige malingkomponenter så som pigmenter, farvestoffer, oppløsningsmidler osv., omfatter en filmdannende akrylpolymer inneholdende enheter av monomerer med formelen According to the present invention, a marine paint is provided which, in addition to usual paint components such as pigments, dyes, solvents, etc., comprises a film-forming acrylic polymer containing units of monomers with the formula
hvor R<1> er C^_^-alkyl, og eventuelt også enheter av where R<1> is C^_^-alkyl, and optionally also units of
2. ett eller flere triorganotinnmetakrylater eller 2. one or more triorganotin methacrylates or
-akrylater. - acrylates.
Det karakteristiske ved oppfinnelsen er at kopolymeren også inneholder enheter av monomerer med formelen The characteristic feature of the invention is that the copolymer also contains units of monomers with the formula
hvor R=H eller CH3, R" = CH3 eller C2H5, n = 1 eller 2. where R=H or CH3, R" = CH3 or C2H5, n = 1 or 2.
Enhetene av monomer nr. 3 hydrolyseres lett for å danne frie karboksylgrupper, hvilket resulterer i en polymer som gradvis nedbrytes slik at det oppnås en selvpolerende virkning. The units of monomer No. 3 are readily hydrolyzed to form free carboxyl groups, resulting in a polymer that gradually degrades to achieve a self-polishing effect.
Monomer nr. 1 er til stede for å gjøre filmen tilstrekkelig hard. Monomer #1 is present to make the film sufficiently hard.
Når kopolymeren som anvendes i de marine malinger ifølge foreliggende oppfinnelse, bare består av enheter av monomerene 1 When the copolymer used in the marine paints according to the present invention only consists of units of the monomers 1
og 3, inneholder den vanligvis fra 15 til 80 vekt% av monomer nr. 3 og fra 20 til 85 vekt% av monomer nr. 1. and 3, it generally contains from 15 to 80% by weight of monomer No. 3 and from 20 to 85% by weight of monomer No. 1.
En foretrukket representant for monomer nr. 3 er 2-metoksyetylakrylat, og en foretrukket representant for monomer nr. 1 A preferred representative of monomer No. 3 is 2-methoxyethyl acrylate, and a preferred representative of monomer No. 1
er metylmetakrylat. is methyl methacrylate.
En marin maling som omfatter en kopolymer som inneholder A marine paint comprising a copolymer containing
enheter av de ovennevnte to monomerer nr. 1 og nr. 3, kan, som påpekt ovenfor, også inneholde biocide komponenter for å oppnå units of the above two monomers no. 1 and no. 3, may, as pointed out above, also contain biocidal components to achieve
den ønskede biocide virkning, så som kobber(I)oksyd, ditio-karbamater og triorganotinnfdrbindélser som er kjent innen teknikken. the desired biocidal effect, such as copper (I) oxide, dithiocarbamates and triorganotin compounds known in the art.
I tillegg til de to typer monomer som er angitt ovenfor, kan kopolymerene som anvendes i de marine malinger ifølge oppfinnelsen, også inneholde enheter av monomer nr. 2, dvs. triorganotinnakrylater og -metakrylater. Eksempler på slike triorganotinnmonomerer er tributyltinnmetakrylat og -akrylat, tripropyltinnmetakrylat og -akrylat og trifenyltinnmetakrylat og -akrylat. Triorganotinn-monomerene kan utgjøre opp til 60 vekt% av kopolymeren (terpolymer). In addition to the two types of monomer indicated above, the copolymers used in the marine paints according to the invention can also contain units of monomer no. 2, i.e. triorganotin acrylates and methacrylates. Examples of such triorganotin monomers are tributyltin methacrylate and acrylate, tripropyltin methacrylate and acrylate and triphenyltin methacrylate and acrylate. The triorganotin monomers can make up up to 60% by weight of the copolymer (terpolymer).
Slike terpolymerer er nye, og et ytterligere trekk ved oppfinnelsen er således akrylterpolymerer som inneholder enheter av de følgende monomerer Such terpolymers are new, and a further feature of the invention is thus acrylic terpolymers containing units of the following monomers
hvor R' = C^_4-alkyl, og where R' = C1-4-alkyl, and
2. triorganotinnmetakrylater eller -akrylater, 2. triorganotin methacrylates or acrylates,
hvor R = H eller CH3, R" er CH3 eller C2H5, n = 1 eller 2. where R = H or CH3, R" is CH3 or C2H5, n = 1 or 2.
Kopolymerene som inneholder monomerene nr. 1 og 3 kan frem-stilles ved vanlig polymerisasjon av egnede monomerer under anvendelse av egnede initiatorer og polymerisasjonsbetingelser. The copolymers containing the monomers no. 1 and 3 can be produced by ordinary polymerization of suitable monomers using suitable initiators and polymerization conditions.
Når det ønskes å fremstille en kopolymer (terpolymer) som også inneholder triorganotinn-metakrylat- eller -akrylatenheter (monomer 2), kan dette gjøres enten ved å polymerisere monomerene nr. 1 og 3 sammen med den ønskede triorganotinnmetakrylat- eller -akrylat-monomer, eller monomerene nr. 1 og 3 kan polymeriseres med met-akryl- eller akrylsyre, og karboksylgruppene på den resulterende polymer forestres derefter med triorganotinngrupper på i og for seg kjent måte. When it is desired to produce a copolymer (terpolymer) which also contains triorganotin methacrylate or acrylate units (monomer 2), this can be done either by polymerizing monomers no. 1 and 3 together with the desired triorganotin methacrylate or acrylate monomer, or the monomers no. 1 and 3 can be polymerized with methacrylic or acrylic acid, and the carboxyl groups on the resulting polymer are then esterified with triorganotin groups in a manner known per se.
Eksempel 1 Example 1
Metylmetakrylat (300 g, 3,00 mol) og 2-metoksyetylakrylat Methyl methacrylate (300 g, 3.00 mol) and 2-methoxyethyl acrylate
(200 g, 1,54 mol) ble oppløst i xylen (750 g). Azobisisobutyronitril (4 g, 0,024 mol) ble tilsatt, og oppløsningen ble opp-varmet til 7 5°C med omrøring og under nitrogen. (200 g, 1.54 mol) was dissolved in xylene (750 g). Azobisisobutyronitrile (4 g, 0.024 mol) was added and the solution was warmed to 75°C with stirring and under nitrogen.
Polymerisasjonen ble utført ved den ovenfor angitte tempera-tur i 5 timer og ble overvåket ved forandring i brytningsindeksen. The polymerization was carried out at the temperature indicated above for 5 hours and was monitored by changes in the refractive index.
Temperaturen ble hevet til 100°C i 30 minutter for å øde-legge eventuell gjenværende katalysatoraktivitet. The temperature was raised to 100°C for 30 minutes to destroy any remaining catalyst activity.
Det ble oppnådd en oppløsning av en kopolymer av metylmetakrylat - 2-metoksyetylakrylat (60:40 efter vekt). A solution of a copolymer of methyl methacrylate - 2-methoxyethyl acrylate (60:40 by weight) was obtained.
Eksempel 2 Example 2
Tributyltinnmetakrylat (150 g, 0,40 mol), metylmetakrylat Tributyltin methacrylate (150 g, 0.40 mol), methyl methacrylate
(250 g, 2,50 mol) og 2-metoksyetylakrylat (100 g, 0,77 mol) ble oppløst i xylen (750 g). Azobisisobutyronitril (4 g, 0,02 mol) ble tilsatt, og polymerisasjonen ble foretatt på lignende måte som i eksempel 1. (250 g, 2.50 mol) and 2-methoxyethyl acrylate (100 g, 0.77 mol) were dissolved in xylene (750 g). Azobisisobutyronitrile (4 g, 0.02 mol) was added and the polymerization was carried out in a similar manner to Example 1.
Det ble oppnådd en oppløsning av en terpolymer av tributyltinnmetakrylat - metylmetakrylat - 2-metoksyetylakrylat (30:50:20 A solution of a terpolymer of tributyltin methacrylate - methyl methacrylate - 2-methoxyethyl acrylate (30:50:20
efter vekt). by weight).
Eksempel 3 Example 3
409,2 g av kopolymeroppløsningen fra eksempel 1 ble blandet med kobber(I)oksyd (365,4 g) , sinkoksyd (151,2 g) , Aerosil® 409.2 g of the copolymer solution from example 1 was mixed with copper (I) oxide (365.4 g), zinc oxide (151.2 g), Aerosil®
(kolloidal kiselsyre) (4,0 g), Bentone® (fortykningsmiddel) (colloidal silicic acid) (4.0 g), Bentone® (thickener)
(8,0 g), denaturert etanol (4,8 g) og xylen (57,4 g) og ble malt natten over for å gi en maling med et forhold mellom kobber(I)oksyd og sinkoksyd på 70:30 efter volum. (8.0 g), denatured ethanol (4.8 g) and xylene (57.4 g) and was ground overnight to give a paint with a ratio of cupric oxide to zinc oxide of 70:30 by volume .
Eksempel 4 Example 4
409,2 g av terpolymeroppløsningen fra eksempel 2 ble blandet med kobber(I)oksyd (365,4 g), sinkoksyd (151,2 g), Aerosil® 409.2 g of the terpolymer solution from Example 2 was mixed with copper (I) oxide (365.4 g), zinc oxide (151.2 g), Aerosil®
(4,0 g), Bentone® (8,0 g), denaturert etanol (4,8 g) og xylen (57,4 g) og ble malt natten over for å gi en maling med et forhold mellom kobber(I)oksyd og sinkoksyd på 70:30 efter volum. (4.0 g), Bentone® (8.0 g), denatured ethanol (4.8 g) and xylene (57.4 g) and was ground overnight to give a paint with a ratio of copper(I) oxide and zinc oxide of 70:30 by volume.
Malingene beskrevet i eksemplene 3 og 4 ble undersøkt med hensyn til polering under anvendelse av et rotorapparat med en periferihastighet på 17 knop (ca. 31 km/t) i sjøvann ved en gjennomsnittstemperatur på 23°C. The paints described in Examples 3 and 4 were examined for polishing using a rotor apparatus with a peripheral speed of 17 knots (about 31 km/h) in sea water at an average temperature of 23°C.
En kommesielt vellykket selvpolerende maling inneholdende organotinnpolymer (X) ble anvendt som referanse. Prøvene ble utført over en periode på 90 dager, og malinglagets tykkelse ble bestemt ved elektromagnetisk induksjon. A commercially successful self-polishing paint containing organotin polymer (X) was used as a reference. The tests were carried out over a period of 90 days, and the thickness of the paint layer was determined by electromagnetic induction.
Claims (6)
Priority Applications (19)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO840005A NO156493C (en) | 1984-01-02 | 1984-01-02 | MARIN PAINTING INCLUDING A MOVIE-forming ACRYLIC POLYMER AND AN ACRYLIC POLYMER FOR USE IN THE PAINTING. |
DK610484A DK172317B1 (en) | 1984-01-02 | 1984-12-19 | Marine paints and acrylic polymers for use in marine paints |
GB08432163A GB2152947B (en) | 1984-01-02 | 1984-12-20 | Marine coating and certain new terpolymers for use therein |
NL8403867A NL192114C (en) | 1984-01-02 | 1984-12-20 | Method for coating ships and the like with an acrylic polymer-containing coating. |
IT49342/84A IT1178318B (en) | 1984-01-02 | 1984-12-21 | COMPOSITION FOR MARINE COATINGS AND ACRYLIC TERPOLYMERS TO BE USED IN THEM |
DE3446971A DE3446971C2 (en) | 1984-01-02 | 1984-12-21 | Use of a film-forming acrylic polymer as a ship's paint |
FR8419796A FR2557585B1 (en) | 1984-01-02 | 1984-12-26 | UNDERWATER PAINTS AND NEW TRIPOLYMERS INCLUDING THEIR COMPOSITION |
AU37147/84A AU570530B2 (en) | 1984-01-02 | 1984-12-27 | Acrylic anti-fouling marine coatings |
ES539165A ES539165A0 (en) | 1984-01-02 | 1984-12-28 | A PROCEDURE FOR PRODUCING A MARINE COATING INCLUDING A FILM FORMING ACRYLIC POLYMER |
SE8406666A SE465574B (en) | 1984-01-02 | 1984-12-28 | MARIN FAERG AND ACRYLIC POLYMER BEFORE USING THERE |
CA000471098A CA1260186A (en) | 1984-01-02 | 1984-12-28 | Marine coating and certain new terpolymers for use therein |
JP59274997A JPS60158211A (en) | 1984-01-02 | 1984-12-28 | Paint for boat and ship |
BR8406783A BR8406783A (en) | 1984-01-02 | 1984-12-28 | COATING FOR MARITIME MATERIAL AND ACRYLIC TERPOLYMER |
GR82615A GR82615B (en) | 1984-01-02 | 1984-12-28 | Marine coating and certain new terpolymers for use therein |
PT79776A PT79776B (en) | 1984-01-02 | 1984-12-28 | Process for preparing marine coating and certain new terpolymers for use therein |
BE0/214280A BE901426A (en) | 1984-01-02 | 1984-12-28 | MARINE PAINT AND NEW TERPOLYMERS FOR USE THEREIN. |
KR1019840008526A KR930008744B1 (en) | 1984-01-02 | 1984-12-29 | Acrylic anti-fouling marine coatings |
SG799/90A SG79990G (en) | 1984-01-02 | 1990-09-29 | Marine coatings,production and use thereof |
HK948/92A HK94892A (en) | 1984-01-02 | 1992-11-26 | Marine coatings production and use thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NO840005A NO156493C (en) | 1984-01-02 | 1984-01-02 | MARIN PAINTING INCLUDING A MOVIE-forming ACRYLIC POLYMER AND AN ACRYLIC POLYMER FOR USE IN THE PAINTING. |
Publications (3)
Publication Number | Publication Date |
---|---|
NO840005L NO840005L (en) | 1985-07-03 |
NO156493B true NO156493B (en) | 1987-06-22 |
NO156493C NO156493C (en) | 1987-09-30 |
Family
ID=19887419
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO840005A NO156493C (en) | 1984-01-02 | 1984-01-02 | MARIN PAINTING INCLUDING A MOVIE-forming ACRYLIC POLYMER AND AN ACRYLIC POLYMER FOR USE IN THE PAINTING. |
Country Status (19)
Country | Link |
---|---|
JP (1) | JPS60158211A (en) |
KR (1) | KR930008744B1 (en) |
AU (1) | AU570530B2 (en) |
BE (1) | BE901426A (en) |
BR (1) | BR8406783A (en) |
CA (1) | CA1260186A (en) |
DE (1) | DE3446971C2 (en) |
DK (1) | DK172317B1 (en) |
ES (1) | ES539165A0 (en) |
FR (1) | FR2557585B1 (en) |
GB (1) | GB2152947B (en) |
GR (1) | GR82615B (en) |
HK (1) | HK94892A (en) |
IT (1) | IT1178318B (en) |
NL (1) | NL192114C (en) |
NO (1) | NO156493C (en) |
PT (1) | PT79776B (en) |
SE (1) | SE465574B (en) |
SG (1) | SG79990G (en) |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4121811A1 (en) * | 1991-07-02 | 1993-01-07 | Roehm Gmbh | METHOD FOR PRODUCING POLYALKYL METHACRYLATE MACROMONOMERS AND THE USE THEREOF FOR PRODUCING COMB POLYMERS |
DK137491D0 (en) * | 1991-07-19 | 1991-07-19 | Hempel Skibsfarve Fab S J | PAINT COMPOSITION |
JP3196361B2 (en) * | 1991-12-25 | 2001-08-06 | 日立化成工業株式会社 | Resin composition for paint and antifouling paint for underwater structures |
US5288828A (en) * | 1993-03-08 | 1994-02-22 | The Sherwin-Williams Company | Dispersant polymers |
FR2729965B1 (en) * | 1995-01-26 | 2000-05-19 | France Etat | SELF-POLISHING ANTI-FOULING PAINTS |
DK0841380T3 (en) * | 1996-11-07 | 2000-02-21 | Witco Gmbh | Process for the preparation of polymeric binders and their use in antifouling dye systems |
EP0841353A1 (en) * | 1996-11-07 | 1998-05-13 | Witco GmbH | Process for the preparation of polymeric binders and their application as antifouling paint |
EP1308484A1 (en) | 2001-10-30 | 2003-05-07 | Sigma Coatings B.V. | Use of silylesters of rosin in self-polishing antifouling paints |
EP1475415A1 (en) | 2003-05-07 | 2004-11-10 | SigmaKalon Services B.V. | Silyl esters, their use in binder systems and paint compositions and a process of production thereof |
FR2930778A1 (en) | 2008-04-30 | 2009-11-06 | Bluestar Silicones France Soc | ARTICLE HAVING ANTIFOULING PROPERTIES AND INTENDED FOR USE IN AQUATIC APPLICATIONS, IN PARTICULAR MARINE |
WO2009156609A2 (en) | 2008-05-29 | 2009-12-30 | Bluestar Silicones France | Article having antifouling properties for aquatic and particularly sea use |
US9744527B2 (en) | 2008-05-29 | 2017-08-29 | Bluestar Silicones France Sas | Article having antifouling properties for aquatic and particularly sea use |
EP2348077B1 (en) | 2010-01-26 | 2013-04-03 | Jotun A/S | Antifouling composition |
KR20130131277A (en) | 2010-06-04 | 2013-12-03 | 요툰 에이/에스 | Antifouling coating |
EP2708594A1 (en) | 2012-09-18 | 2014-03-19 | Jotun A/S | Cleaning process |
WO2014064048A1 (en) | 2012-10-23 | 2014-05-01 | Jotun A/S | Antifouling coating composition |
EP2725073B1 (en) | 2012-10-23 | 2016-08-03 | Jotun A/S | Antifouling coating composition |
CN104955828A (en) | 2012-12-19 | 2015-09-30 | 佐敦集团 | Silyl ester copolymer |
FR2999980A1 (en) | 2012-12-20 | 2014-06-27 | Bluestar Silicones France | ARTICLE HAVING ANTIFOULING PROPERTIES AND INTENDED FOR USE IN AQUATIC APPLICATIONS, IN PARTICULAR MARINE |
KR101779681B1 (en) | 2012-12-20 | 2017-09-18 | 블루스타 실리콘즈 프랑스 에스에이에스 | Article with antifouling properties, intended for aquatic uses and, in particular, for marine uses |
FR3014107A1 (en) | 2013-12-03 | 2015-06-05 | Bluestar Silicones France | ARTICLE HAVING ANTIFOULING PROPERTIES AND INTENDED FOR USE IN AQUATIC APPLICATIONS, IN PARTICULAR MARINE |
EP2902452A1 (en) | 2014-01-31 | 2015-08-05 | Jotun A/S | Antifouling composition |
EP2902453A1 (en) | 2014-01-31 | 2015-08-05 | Jotun A/S | Antifouling Composition |
SG10201602858XA (en) | 2015-04-09 | 2016-11-29 | Jotun As | Antifouling Composition |
WO2018087287A1 (en) | 2016-11-11 | 2018-05-17 | Jotun A/S | Antifouling composition |
DE102017126336A1 (en) | 2016-11-11 | 2018-05-17 | Jotun A/S | Antifouling composition |
JP7178167B2 (en) | 2016-11-11 | 2022-11-25 | ヨトゥン アーエス | antifouling composition |
GB201718891D0 (en) * | 2017-11-15 | 2017-12-27 | Jotun As | Antifouling composition |
CN112771090A (en) * | 2018-09-26 | 2021-05-07 | 三菱化学株式会社 | Copolymer for inhibiting protein adhesion, method for producing copolymer, resin modifier, molding material, composition containing copolymer, coating film, and article |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB988171A (en) * | 1960-04-14 | 1965-04-07 | Vinyl Products Ltd | Improvements in or relating to thermosetting resin compositions |
DE1952721A1 (en) * | 1968-10-22 | 1970-09-10 | Hydron Ltd | Coating agent for use on humans or animals |
GB1292953A (en) * | 1968-10-22 | 1972-10-18 | Hydron Ltd | Coating compositions based on acrylate and/or methacrylate copolymers |
GB1457590A (en) * | 1974-04-03 | 1976-12-08 | Int Paint Co | Marine paint |
JPS55164261A (en) * | 1979-06-08 | 1980-12-20 | Chugoku Toryo Kk | Antifouling coating material |
DE3170163D1 (en) * | 1980-10-30 | 1985-05-30 | Int Paint Plc | Marine paint |
JPS5776012A (en) * | 1980-10-31 | 1982-05-12 | Mitsubishi Rayon Co Ltd | Preparation of high polymeric acrylic resin containing triorganotin |
JPS58118868A (en) * | 1982-01-07 | 1983-07-15 | Nippon Paint Co Ltd | Resin composition for antifouling paint |
JPS58180565A (en) * | 1982-04-16 | 1983-10-22 | Nippon Oil & Fats Co Ltd | Antifouling coating |
-
1984
- 1984-01-02 NO NO840005A patent/NO156493C/en not_active IP Right Cessation
- 1984-12-19 DK DK610484A patent/DK172317B1/en not_active IP Right Cessation
- 1984-12-20 GB GB08432163A patent/GB2152947B/en not_active Expired
- 1984-12-20 NL NL8403867A patent/NL192114C/en not_active IP Right Cessation
- 1984-12-21 IT IT49342/84A patent/IT1178318B/en active
- 1984-12-21 DE DE3446971A patent/DE3446971C2/en not_active Expired - Fee Related
- 1984-12-26 FR FR8419796A patent/FR2557585B1/en not_active Expired - Fee Related
- 1984-12-27 AU AU37147/84A patent/AU570530B2/en not_active Ceased
- 1984-12-28 CA CA000471098A patent/CA1260186A/en not_active Expired
- 1984-12-28 BE BE0/214280A patent/BE901426A/en not_active IP Right Cessation
- 1984-12-28 PT PT79776A patent/PT79776B/en not_active IP Right Cessation
- 1984-12-28 ES ES539165A patent/ES539165A0/en active Granted
- 1984-12-28 SE SE8406666A patent/SE465574B/en not_active IP Right Cessation
- 1984-12-28 GR GR82615A patent/GR82615B/en unknown
- 1984-12-28 BR BR8406783A patent/BR8406783A/en not_active IP Right Cessation
- 1984-12-28 JP JP59274997A patent/JPS60158211A/en active Pending
- 1984-12-29 KR KR1019840008526A patent/KR930008744B1/en not_active IP Right Cessation
-
1990
- 1990-09-29 SG SG799/90A patent/SG79990G/en unknown
-
1992
- 1992-11-26 HK HK948/92A patent/HK94892A/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
IT8449342A0 (en) | 1984-12-21 |
NO840005L (en) | 1985-07-03 |
IT1178318B (en) | 1987-09-09 |
SE8406666D0 (en) | 1984-12-28 |
SG79990G (en) | 1990-11-23 |
GB2152947A (en) | 1985-08-14 |
GR82615B (en) | 1985-05-02 |
DE3446971C2 (en) | 1995-09-28 |
GB2152947B (en) | 1987-09-30 |
NL192114C (en) | 1997-02-04 |
DK610484D0 (en) | 1984-12-19 |
ES8607995A1 (en) | 1986-01-01 |
KR850004976A (en) | 1985-08-19 |
AU3714784A (en) | 1985-07-11 |
DK172317B1 (en) | 1998-03-16 |
PT79776B (en) | 1987-01-05 |
NL192114B (en) | 1996-10-01 |
CA1260186A (en) | 1989-09-26 |
NO156493C (en) | 1987-09-30 |
HK94892A (en) | 1992-12-04 |
NL8403867A (en) | 1985-08-01 |
JPS60158211A (en) | 1985-08-19 |
FR2557585B1 (en) | 1993-10-08 |
GB8432163D0 (en) | 1985-01-30 |
DE3446971A1 (en) | 1985-07-11 |
PT79776A (en) | 1985-01-01 |
BE901426A (en) | 1985-06-28 |
KR930008744B1 (en) | 1993-09-13 |
SE8406666L (en) | 1985-07-03 |
ES539165A0 (en) | 1986-01-01 |
FR2557585A1 (en) | 1985-07-05 |
SE465574B (en) | 1991-09-30 |
AU570530B2 (en) | 1988-03-17 |
BR8406783A (en) | 1985-10-22 |
DK610484A (en) | 1985-07-03 |
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