Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • 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
  • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
• • 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
  • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
• • 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
  • C09D5/165—Macromolecular compounds containing hydrolysable groups

Definitions

• the present invention relates to anti-fouling compositions and the use thereof to coat solid surfaces.
• Anti-fouling coatings are useful when applied to surfaces which come into contact with aqueous media containing organisms which can attach themselves to such surfaces.
• anti-fouling coatings have become popular in marine environments to prevent animal and vegetable organisms such as algae and barnacles from attaching themselves to solid surfaces such as ship hulls.
• the presence of such organisms significantly increases the drag on ships thereby increasing the energy requirements to propel the ship through the water.
• the growth of micro-organisms in circulating water systems such as that found in cooling towers, recreational waters and industrial cutting fluids can also create problems when such micro-organisms attach themselves to surfaces, especially the inner walls of pipes and heat exchangers which restricts the flow of water and reduces the efficiency of heat exchangers.
• micro-organisms can result in the growth of symbiotic colonies of bacteria, fungi and yeasts which can generate an extemal protective envelope.
• the presence of such colonies attached to pipes etc not only reduces the water-flow but can also act as a reservoir of micro ⁇ organisms especially where a protective envelope is present.
• Such an envelope can prevent the micro-organisms within the protective biosphere from coming into contact with anti-microbial active agents. This can result in unhygienic water which is a particular problem with recreational circulating water systems such as swimming pools, spas and hot tubs.
• Micro-organisms are also found on solid surfaces in the food and health-care industries and can result in unhygienic conditions, especially in the preparation and packaging of foodstuffs.
• One of the more successful ways of preventing marine organisms from attaching to solid surfaces such as ship hulls is to coat the surface with a self-polishing anti-fouling paint, such as that disclosed in WO 91/09915.
• a self-polishing anti-fouling paint such as that disclosed in WO 91/09915.
• This discloses an anti-fouling coating composition comprising a marine biocide and a binder which is a hydrolysable film-forming seawater-erodible polymer, characterised in that the polymer contains sulphonic acid groups in quaternary ammonium salt form.
• These polymers have limitations and are not particularly effective against micro-organisms, especially those present in circulating water systems.
• a water-erodible organic polymer bearing anionic salt groups at least a proportion of which have as counter ions a biologically active heterocyclic cation having a delocalised positive charge.
• a composition for providing a water-erodible polymer- coating on a surface wherein said composition comprises a binder polymer as defined supra and an organic liquid.
• the coating composition may optionally contain a corrosion inhibitor, pigment, further microbiologically active compound or other adjuvant.
• water-erodible polymer coating refers to a coating where the outer layer of the coating is removed on contact with water and is further explained hereinafter.
• the anionic groups are, for example, derived from one or more of phosphoric, phosphonic and especially carboxylic and sulphonic acid groups.
• the heterocyclic ring of the heterocyclic cation contains two or more hetero atoms especially two or more nitrogen atoms.
• the heterocyclic ring preferably contains 5 atoms. Examples of such heterocyclic rings are pyrazolyl, triazolyl and especially imidazolyl rings.
• the heterocyclic cation may contain only the one heterocyclic ring but preferably contains two or more heterocyclic rings. More preferably the cation contains two heterocyclic rings.
• a cation containing two or more heterocyclic rings may form a salt linkage between each cationic ring and an anionic group in the same or different polymer chains. It is preferred, however, that at least one cationic ring of the cation containing two or more heterocyclic rings does not form a salt linkage with an anionic group of the polymer chain.
• the cation when it contains two heterocyclic rings it preferably forms only the one salt linkage with an anionic group in the polymer chain.
• the rings are preferably the same.
• heterocyclic cation is a an imidazolium cation having one ring it is preferably a cation of Formula 1
• R 1 is C ⁇ -alkyl or aralkyl
• R 2 is hydrogen or C ⁇ -alkyl
• R 3 is C ⁇ -alky! or aralkyl
• R 4 and R 5 are each, independently, hydrogen or C ⁇ -alkyl or R 4 and R 5 together with the carbon atoms to which they are attached form a phenyl ring.
• R 1 and R 3 may be linear or branched but are preferably linear. It is also preferred that R 1 and R 3 are each, independently, alkyl containing at least 6 carbon atoms and preferably at least 8 carbon atoms. Preferably R and R 3 each, independently, contain less than 18, more preferably less than 16 and especially less than 12 carbon atoms.
• R or R 3 is aralkyl, it is preferably benzyl or 2-phenylethyl.
• R 1 is the same as R 3 .
• R 4 and R 5 are hydrogen.
• R 2 is hydrogen, ethyl and especially methyl.
• heterocyclic cation is an imidazolium cation containing two or more heterocyclic rings it is preferably a cation of Formula 2
• R 1 to R 5 are as defined in Formula 1;
• R 6 is C ⁇ -alkyl
• R 7 and R 8 are as defined in R 4 and R 5 ; n is 1 to 6; and
• X is a divalent linking group containing from 2 to 20 atoms.
• R 6 is the same as R 2 .
• R 7 and R 8 are the same as R 4 and R 5 , respectively.
• the group X may be alkylene optionally substituted by hydroxy, alkyleneoxyalkyleneoxyalkylene, alkylenecarbonylaminoalkyleneaminocarbonylalkylene, alkylenecarbonylaminoalkyleneoxyalkyleneaminocarbonylalkylene, alkylenearyienealkylene where arylene is phenylene or naphthylene or alkyleneoxyaryleneoxyalkylene.
• X is alkylene
• the number of carbon atoms is preferably at least 4 and especially at least 6. It is also preferred that the number of carbon atoms is less than 18, more preferably less than 16 and especially less than 14.
• R ⁇ R 5 , R 7 and R 8 are hydrogen or C ⁇ -alkyi and especially hydrogen.
• n is 1 in which case the cation of Formula 2 has two imidazolium rings.
• the preparation of suitable compounds for providing some cations of Formula 2 is described in GB 1 ,355,631.
• n is 2 or 3 wherein the cation of Formula 2 contains three or four imidazolium rings, respectively.
• the preparation of compounds providing some of the cations of this type are described in WO 94/08972.
• a still further preferred cation containing two or more imidazolium rings is that of Formula 3
• R 2 , R 4 and R 5 are defined as hereinbefore;
• R 9 is hydrogen or methyl
• Y is hydroxy or halogen; and p is an integer.
• Y is halogen, it is preferably chlorine or bromine.
• Y is preferably hydroxy.
• p is preferably at least 5, more preferably at least 10 and especially at least 20. It is preferred that p is less than 100, more preferably less than 70 and especially less than 50.
• Suitable counter ions are halogen such as chloride and bromide, methosulphate, bicarbonate, bisulphate, carbonate, sulphate and especially hydroxy. Halogen is less preferable since the presence of such counter ions can adversely affect metal surfaces to which the water-erodible polymer is applied. This is particularly true in the case of iron or steel surfaces, especially pipework, where the presence of halogen ions can promote corrosion.
• the water-erodible polymer preferably has a saturated aliphatic backbone with chain-pendant (i.e lateral) anionic groups which may be tactically or atactically disposed along the polymer chain.
• the heterocyclic salt of the polymer can be prepared by admixing the preformed polymer in which the anionic groups are in their free acid form or in the form of a salt of ammonia or alkali metal with a salt of the heterocycle, in which the counter ion is, for example, a halide, hydroxide, methosulphate, sulphate, carbonate or bicarbonate in a suitable liquid.
• the liquid is preferably organic and is preferably a solvent for the polymer and also the heterocyclic salt of the polymer since this facilitates the removal of inorganic salts formed during the reaction.
• the polymer is formed by (co)polymerisation of a reactive monomer containing an anionic group in the form of a heterocyclic salt as defined hereinbefore.
• Preferred reactive monomers contain an ethylenically unsaturated group.
• monomers which can be used in preparing the polymer containing anionic salt groups are acrylic acid, methacrylic acid, styrene sulphonic acid and preferably aliphatic sulphonic acid monomers such as 2-acrylamido-2-methyl- propane sulphonic acid (hereinafter AMPS), sulphoethyl methacrylate, vinyl sulphonic acid, methallyl sulphonic acid and propenesulphonic acid.
• AMPS 2-acrylamido-2-methyl- propane sulphonic acid
• Examples of phosphonic and phosphoric acid monomers are vinyl phosphonic acid, styrene phosphonic acid, 2- acrylamidopropane phosphonic acid, ethylidene-1 ,1 -diphosphonic acid and hydroxyethylacrylate monophosphate.
• the water-erodible polymer may in principle be a homopolymer or copolymer of anionic salt containing monomer(s) but is preferably a copolymer obtainable by reacting the monomer(s) containing an anionic salt group, or anionic group in its free acid form when the intention is to form the salt groups subsequent to polymerisation, with one or more ethylenically unsaturated co-monomers which are preferably devoid of ionic salt groups and more especially of Formula 4.
• CH 2 CR 10 COOR 11 wherein
• R 10 is hydrogen or C M -alkyl
• R 11 is optionally substituted C ⁇ -alkyl, aryl or C.-. 14 -cycloalkyl.
• R 10 is C M -alkyl it is preferably methyl.
• R 1 is alkyl it may be linear or branched and is preferably C ⁇ -alkyl.
• R 11 is aryl it is preferably phenyl.
• R 11 is cycloalkyl it is preferably Ce. 10 -cycloalkyl such as cyclohexyl.
• R 11 is substituted C ⁇ -alkyl
• the substituent is preferably hydroxy or an acyloxy (i.e alkyl carbonyloxy) group which preferably contains not greater than a total of six carbon atoms.
• the acyloxy group may itself be substituted with, for example, an alkyl carbonyl group as in an acetoacetoxyethyl group.
• Preferred comonomers are aliphatic.
• co-monomers are (meth)acrylic acid esters and amides such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, acetoacetoxy ethyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, isobutyl (meth)acrylate, n-butyl (meth)acrylate, acrylonitrile, vinyl acetate, vinyl butyrate, and vinyl chloride.
• Aromatic ethylenically unsaturated monomers may also be used such as styrene, ⁇ -methyl styrene and vinyl pyridine.
• the water-erodible polymer may be a copolymer obtainable from the monomer containing an anionic salt group and more than one ethylenically unsaturated co ⁇ monomer or from the monomer containing an anionic group in the form of its free acid and more than one ethylenically unsaturated comonomer where the anionic salt group of the heterocyclic cation is formed subsequent to polymerisation.
• copolymers are those obtainable by polymerising a monomer containing an anionic group, or heterocyclic cation salt thereof, with methyl methacrylate and butyl acrylate or with ethyl methacrylate and 2-hydroxyethyl methacrylate.
• the copolymer generally contains not less than 1, preferably not less than 3, more preferably not less than 5 and especially not less than 10 weight % monomer units containing an anionic salt group. It is also preferred that the amount of monomer units containing an anionic salt group is not greater than 80 weight % and especially not greater than 70 weight %.
• the comonomers are preferably selected to give water-erodible polymers of desired glass transition temperatures (Tg) and also to control the rate of erosion of the polymer and release of the heterocydic cation in use.
• Tg glass transition temperatures
• the Tg is in the range from -20 to 100°C, preferably from -20 to 50°C and espedally from 5 to 50°C.
• the copolymer may additionally contain free carboxylic add groups.
• the water-erodible polymer bears anionic salt groups some of which have counter ions in the form of quaternary ammonium cations which are derivable from a quaternary ammonium compound (hereinafter OAC), and/or amine cations.
• OAC quaternary ammonium compound
• anionic salt groups with quaternary ammonium or amine cations are preferably not greater than 75%, more preferably not greater than 50%, even more preferably not greater than 30% and espedally not greater than 25% of the total number of anionic salt groups.
• the anionic salt groups with quaternary ammonium or amine cations when present, are preferably not less than 5%, more preferably not less than 10% and espedally not less than 15% of the total number of anionic groups in the polymer. When such anionic salt groups are present they are preferably amine salts.
• the OAC is preferably a tetra alkyl ammonium cation, or an alkyl ammonium cation which contains one or more cydoalkyl, aryl or aralkyl groups assodated with an anion which is preferably a halide, such as chloride or bromide, or a sulphate.
• the aralkyl group is preferably benzyl in which case the OAC is a benzalkonium compound.
• the OAC contains an aryl group it is preferably heteroaryl and especially pyridyl.
• the alkyl groups may be linear or branched, saturated or unsaturated, induding mixtures thereof.
• At least one of the alkyl groups contains at least 3, more preferably at least 6 and espedally at least 10 carbon atoms.
• Such QAC's contain an alkyl group preferably containing less than 30, more preferably less than 20 and espedally less than 18 carbon atoms. It is particularly preferred than such QAC's also contain a benzyl group.
• QAC's are those containing two alkyl groups containing from 3 to 30, more preferably from 6 to 20 and espedally from 10 to 18 carbon atoms.
• Examples of QAC's are diethyldodecylbenzyl ammonium chloride; dimethyloctadecyl- (dimethylbenzyl) ammonium chloride; dimethyldidecylammonium chloride; dimethyldidodecylammonium chloride; trimethyl-tetradecylammonium chloride; benzyldimethyl(C 12 -C 18 -alkyl)ammonium chloride; dichlorobenzyldimethyldodecylammonium chloride; hexadecylpyridinium chloride; hexadecylpyridinium bromide; hexadecyltrimethylammonium bromide; dodecylpyridinium chloride; dodecylpyridinium bis
• R 12 -N-R 14 5 wherein R 12 is a C ⁇ ao-hydrocarbyl group
• R 13 and R 14 is each, independently, hydrogen or C ⁇ o-hvdrocarbyl.
• R 12 to R 14 is hydrocarbyl it is saturated or unsaturated and can be aliphatic, aryl, aralkyl or heterocydic.
• the hydrocarbyl group or groups is aliphatic.
• R 12 to R 14 is aliphatic it may be linear or branched but is preferably linear.
• Preferred amines are those wherein at least one of R 12 to R 14 is alkyl. It is also preferred that at least one of the alkyl groups represented by R 12 to R 14 contains at least 6, more preferably at least 8 and especially at least 12 carbon atoms. The alkyl group preferably contains less than 25, more preferably less than 20 and especially 18 or fewer carbon atoms.
• Suitable amines are dodecylamine, hexadecylamine, octadecyl amine, oleylamine, tallow amine, hydrogenated tallow amine, coconutamine induding their benzyl, N-(C M -alkyl) and N,N-di(C lJr alkyl) derivatives. It is particularly preferred that R 3 and R 14 are both C ⁇ -hydrocarbyl when the amine of Formula 5 is a tertiary amine such as methyl ditallowamine.
• R 12 , R 13 and R 14 are the same and it is particulariy preferred that R 12 , R 13 and R 14 are all alkyl and espedally where the total number of carbon atoms is between 12 and 54.
• Examples of such tertiary amines are tributylamine and trihexylamine.
• the polymer is preferably devoid of anionic groups having OAC and amine counter ions.
• Polymerisation of the monomer containing an anionic group either in the form of a free add or as its salt with a biologically adive heterocydic cation can be ca ⁇ ied out by any method known to the art but is preferably ca ⁇ ied out in water or more preferably in a polar organic liquid using a free radical initiator.
• Preferred initiators are azo compounds such as azo-bis-iso-butyronitrile (hereinafter AIBN) and peroxides such as hydrogen peroxide and benzoyl peroxide.
• Other free radical initiators are cobalt chelate complexes and particularly Co(ll) and Co(III) complexes of porphyrins, dioximes and benzildioxime diboron compounds.
• the organic liquid is preferably a polar liquid and may be a ketone, alcohol or an ether.
• suitable polar liquids are methyl ethyl ketone, acetone, methyl isobutylketone, methylisoamylketone, butyl acetate, methoxypropylacetate, ethoxyethylacetate, n-propanol, iso-propanol, n-butanol, iso-butanol, amyl alcohol, ethanol, diethylglycol mono-n-butyl ether and butoxyethanol.
• the polar organic liquid may also be used in admixture with a non-polar organic liquid.
• Preferred non-polar liquids are aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons and espedally aromatic hydrocarbons.
• suitable non-polar organic liquids are heptane, hexane, methylene dichloride, chloroform, carbon tetrachloride, tri- and per- chloroethylene, trichloroethane, toluene and xylene.
• the number average molecular weight (Mn) of the water-erodible polymer is typically in the range 1,000 to 100,000.
• Mn is not less than 5,000 and more preferably not less than 10,000.
• Mn is not greater than 50,000 and espedally not greater than 25,000.
• the low molecular weight polymers having a Mn in the range 1,000 to 10,000 have been found espedally useful in high solids coatings.
• the water-erodible polymer can also be made by aqueous emulsion or suspension polymerisation in which case Mn is much higher and is preferably in the range from 20,000 to 500,000.
• the molecular weight can be controlled by the amount of initiator used or, more usually, by the use of appropriate chain transfer agents such as mercaptans, certain halohydrocarbons or cobalt complexes.
• anionic monomer containing an anionic group in the form of its free add exhibits very limited solubility in the organic liquid, as in the case of AMPS, polymerisation can be canied out in water but it is preferred to form the salt with the biologically-active heterocydic cation and to co-polymerise this salt in a polar organic liquid.
• the polymers according to the invention are water- erodible.
• the salt linkages between the anionic groups of the polymer and the biologically-active heterocydic cations in the outer layer of a polymeric cation coating obtainable by application of the defined coating composition to a substrate are believed to slowly dissodate in water, so releasing the heterocycle as an inorganic salt.
• the heterocycle In seawater, the heterocycle is probably released with one or more chloride counter-ions whereas in fresh water systems the heterocyde is more likely released as a hydroxide, carbonate or bicarbonate depending on the degree of hardness of the water.
• the outer layer of the polymer coating may also be released with the ionically attached heterocycle.
• a coating composition containing the water-erodible polymer may optionally contain a further biologically adive material or compound depending on its end use.
• a coating composition comprising a water-erodible polymer bearing anionic salt groups as defined hereinbefore and a further biologically material or compound.
• the further biologically adive material or compound is preferably one which broadens the spedrum of adivity of the polymer relative to those micro-organisms which cause problems in such waters.
• urea derivatives such as 1 ,3-bis(hydroxymethyl)-5,5-dimethylhydantoin; bis(hydroxymethyl)urea; tetrakis(hydroxymethyl)acetylene diurea; 3-(3,4-dichlorophenyl)-1,1 -dimethylurea; 3-(4- isopropylphenyl)-1,1 -dimethylurea; 1-(hydroxymethyl)-5,5-dimethylhydantoin and imidazolidinyl urea; amino compounds such as 1,3-bis(2-ethylhexyl)-5-methyl-5- aminohexahydropyrimidine; hexamethylene tetra amine;
• imidazole derivatives such as 1[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)ethyl]-1H-imidazole; 2-(methoxycarbonylamino)-benzimidazole; nitrile compounds such as 2-bromo-2- bromomethylglutaronitrile, 2-chloro-2-chloromethylglutaronitrile, 2,4,5,6-tetra- chloroisophthalodinitrile; isothiazolin-3-ones such as 4,5-trimethylene-4-isothiazolin-3- one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-methylisothiazolin-3-one, 5-chloro- 2-methylisothiazolin-3-one, benzisothiazolin-3-one, 2-methylbenzisothiazolin-3-one, 2-methylbenzisothiazolin-3-one, 2-methylbenzisothiazolin-3-one, 2-methyl
• the further biologically adive compound or material may also be a peroxide such as hydrogen peroxide, a perborate such as sodium perborate, halogen such as chlorine or bromine, ozone or a chlorine release compound such as sodium or caldum isocyanurate.
• a peroxide such as hydrogen peroxide
• a perborate such as sodium perborate
• halogen such as chlorine or bromine
• ozone a chlorine release compound such as sodium or caldum isocyanurate.
• the further biologically adive material or compound is preferably a marine biodde which is preferably sparingly soluble in water.
• a preferred marine biodde is a metalliferous pigment, particularly a copper, tin or zinc compound, which may be inorganic or organic. Examples of such compounds are cuprous oxide, cuprous thiocyanate, zinc oxide, zinc ethylene bis(dithiocarbamate), zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, cuprous ethylene bis(dithiocarbamate) and alkyl tin oxides such as tert butyltinoxide, induding mixtures thereof.
• non-metalliferous marine biocides are tetramethyl thiuram disulphide, methylene bis(thiocyanate) and captan.
• the water-erodible polymer may also be used with, or the coating composition may also contain, a corrosion inhibitor espedally one which has no significant effed on the biological adivity of the heterocydic cation.
• a corrosion inhibitor espedally one which has no significant effed on the biological adivity of the heterocydic cation.
• Preferred corrosion inhibitors are acrylates, borates, molybdates, polyethyleneimine, benztriazoles, nitrates, phosphates, complex inorganic phosphates and especially organic compounds containing one or more aminomethylene phosphate groups and organic aromatic compounds containing at least one 2-hydroxy-, 2-amino- or 2-mercapto-alkyl amino methylene group adjacent a phenolic hydroxyl group.
• Examples of specific corrosion inhibitors are aminomethylene phosphonic acid, 1 -hydroxy ethylidene di phosphonic add, sodium molybdate, sodium polyacrylate, sodium metaborate, sodium hexametaphosphate, 1,6-hexylenediamine-N,N,N',N'- tetra(methylenephosphonic acid), 2-(N-methyl-N-(2-hydroxy ethyl)amino methyl)phenol, and 2,3,5-tris-(N-methyl-N-(2-hydroxyethylaminomethyl)phenol.
• one of the prindpal uses of the polymer according to the invention is for applying to a solid surface as a coating or paint or dear varnish.
• the polymer may be applied to the solid surface by any means known to the industry.
• the polymer has been prepared by aqueous emulsion polymerisation it is preferable to apply the polymer as an aqueous formulation.
• the polymer is prepared in a polar liquid, especially a water-misdble polar liquid
• the polymer is preferably applied as a formulation containing a mixture of water and the polar liquid.
• the polymer is prepared in a non-polar organic liquid it is preferably applied to the solid surface as an aqueous emulsion of the non-polar organic liquid containing the polymer.
• a coating composition comprising a polymer bearing anionic salt groups as defined hereinbefore and an organic liquid.
• the organic liquid is a solvent for the polymer.
• the organic liquid is preferably the same as that used to prepare the monomer containing the anionic group which is in the form of a salt of a cation of the microbiologically active heterocydic cation. This may be diluted by a further organic liquid which is preferably an aromatic hydrocarbon. Examples of such aromatic hydrocarbons are xylene, toluene and trimethylbenzene.
• the coating composition may also contain a pigment which may be any pigment commonly used in the paint or coating industry.
• a pigment which may be any pigment commonly used in the paint or coating industry.
• suitable pigments are iron oxide, titanium dioxide and coloured pigments such as phthalocyanines espedally copper and nickel phthalocyanines.
• the coating composition may also contain other adjuvants which are commonly used in the paint industry such as plastidsers, cross-linking agents, dispersants, defoamers, thickening and anti-settling agents, auxiliary film-forming resins and stabilisers against light and heat.
• the composition may also contain dyestuffs and particularly solvent-soluble dyestuffs.
• the organic liquid is preferably present in at least 20% and espedally at least 30% by weight of the composition. It is also preferred that the amount of organic liquid is less than 90%, and espedally less than 70% by weight of the composition.
• the further microbiologically adive material or compound, if used, is present in an amount which is just suffident to inhibit the growth of micro-organisms.
• the amount of the further microbiologically-active material or compound is not less than 1%, more preferably not less than 5% and espedally not less than 10% of the total weight of the composition.
• the amount of the further microbiologically-adive material or compound is not greater than 60%, more preferably not greater than 50% and espedally not greater than 40% by weight of the composition.
• the amount of corrosion inhibitor is preferably not less than 0.1%, more preferably not less than 1% and especially not less than 5% by weight of the composition. It is also preferred that the amount of corrosion inhibitor is not greater than 25%, more preferably not greater than 20% and espedally not greater than 15% by weight of the composition.
• the water-erodible polymer according to the invention can be used in any application where it is desirable to protect a surface from microbiological degradation and espedally where it is desirable to prevent organisms, and especially micro-organisms becoming attached to a surface.
• the water-erodible polymer according to the invention can be used in water treatment applications such as industrial cooling water, air conditioning units, central heating units, (de) humidifiers, heat exchangers, automobiles, swimming pools, spas and in pulp and paper mill liquors.
• the polymer may also be used as a coating for solid surfaces to provide solid surface disinfedion/sterilisation and can also be used in food processing outlets such as tunnel pasteurisers. It may also be used to coat medical items such as urinary catheters.
• the polymer can be used as a marine antifouling coating. It can, however, also be used to coat timber and metal in general and also architedural strudures, especially those made of concrete and stone.
• the monomer containing an anionic salt group in which the counter ion is in the form of a salt of a biologically adive heterocydic cation is novel.
• an ethylenically readive monomer containing an anionic salt group which is in the form of a salt of a biologically- adive heterocydic cation.
• the anionic group is a carboxylic or sulphonic add anion. It is preferred that the number of carbon atoms in the ethylenically readive monomer is not greater than 20, more preferably not greater than 12 and especially not greater than 10. It is especially preferred that the monomer is AMPS or (meth)acrylic add.
• heterocydic cation contains one or more imidazolium rings.
• the invention is further illustrated by the following examples wherein all references are to parts by weight unless expressed to the contrary.
• Biodde 1 (89.9 parts; 0.0485 mol) was stirred with 2-acrylamido-2- methylpropane sulphonic add (AMPS 10.1 parts; 0.0485 mol ex Lubrizol) to give a solution of a 1:1 monomer wherein the sulphonic add group of AMPS is in the form of an imidazolium salt and the unbound cationic centre is present as a hydroxide.
• This solution is Monomer 1 (Mw of 835).
• Biodde 1 (74.1 parts; 0.04 mol) was stirred with 2-acrylamido-2methylpropane sulphonic add (AMPS 16.56 parts; 0.08 mol ex Lubrizol) to give a solution of a 2:1 monomer wherein the sulphonic add group of AMPS is in the form of an imidazolium salt.
• AMPS 2-acrylamido-2methylpropane sulphonic add
• Tri-(2-ethylhexyl) amine (16.7 parts; 0.047 mol ex BASF) was dissolved in butanol (30 parts) and AMPS (9.8 parts; 0.047 mol) was added portionwise with sti ⁇ ing at 20-25°C. The AMPS slowly dissolved on formation of the salt. This solution is Monomer 3 (MW561).
• Methylditallow amine (Armeen M2HT 26.2 parts; 0.05 mol ex AKZO) was dissolved in butanol (30 parts) and AMPS (10.35 parts; 0.05 mol) was added portionwise with stirring at 20-25°C. The AMPS slowly dissolved on formation of the salt. This solution is Monomer 4 (MW 731).
• Example 6 Methylditallow amine (Armeen M2HT 26.2 parts; 0.05 mol ex AKZO) was dissolved in butanol (30 parts) and AMPS (10.35 parts; 0.05 mol) was added portionwise with stirring at 20-25°C. The AMPS slowly dissolved on formation of the salt. This solution is Monomer 4 (MW 731).
• N-Benzyl-N,N-dimethyl-N-(C 12 . 24 -alkyl) ammonium chloride (28.3 parts; 0.08 mol. Vantoc CL ex Zeneca Ltd) was converted into its hydroxide using sodium hydroxide (3.2 parts; 0.08 mol) in butanol (40 parts). Sodium chloride predpitated and was filtered out, leaving a solution of the hydroxy analogue (26.7 parts; 0.08 mol) as a 40% solution in butanol.
• the AMPS salt of this ammonium hydroxide was prepared by adding AMPS (16.56 parts; 0.08 mol) to Biodde 2 solution (66.7 parts of solution; 0.08 mol).
• Methylditallow amine (Aimeen M2HT 20.9 parts; 0.04 mol ex AKZO) was added to Biodde 1 (74.1 parts of solution 0.04 mol).
• AMPS (16.56 parts; 0.08 mol) were added with sti ⁇ ing at 20-25°C whereupon the solution gradually deared as the amine salt of the AMPS formed.
• Monomer 1 (100 parts of solution 0.0485 mol ex Example 2), ethyl methacrylate (EMA 17.96 parts; 0.1575 mol), 2-hydroxyethyl methacrylate (2-HEMA 4.73 parts; 0.0364 mol) and 1-dodeca ⁇ thiol (0.98 parts; 0.0049 mol) was stirred together under nitrogen. The temperature was then raised to about 80°C and azoisobutyronitrile (AIBN 0.27 parts; 0.00162 mol) in butanol (6 parts) was added with sti ⁇ ing under nitrogen. After 30 mins a further aliquot of AIBN (0.53 parts; 0.00323 mol) in butanol (8.2 parts) was added and the readion continued at about 80°C.
• AIBN azoisobutyronitrile
• Polymer 2 which contains a 2:1 ratio of bis imidazolium cation for each sulphonic add group, such that both cationic centres are present as the sulphonate salt. (Molar ratio of monomers 27.1:60.5:12.4).
• the AMPS salt was prepared in an analogous manner to that described in
• Example 2 except that 1 ,3-didecyl-2-methyl imidazolium hydroxide was used in place of the dimeric imidazolium hydroxide.
• This AMPS salt was then copolymerised with EMA and HEMA to give a copolymer of AMPS EMA HEMA in a mole % ratio of 20:65:15 using an analogous process to that described in example 8.
• This copolymer is hereinafter referred to as Polymer 3.
• Example 11 Example 11
• Example 1 was repeated except that Monomer 1 was replaced by Monomer 4 to give a copolymer of AMPS/EMA/HEMA in the mole % ratio of 20:65:15.
• This polymer is hereinafter referred to as Polymer 4.
• Example 1 was again repeated except that Monomer 1 was replaced by Monomer 5 to give a copolymer of AMPS EMA/HEMA in the mole % ratio of 20:65:15.
• the polymer is hereinafter referred to as Polymer 5.
• the Molar ratio of monomers is 6.0:2.7:56.2:35.1 (AMPSBiodde:AMPS/M2KT:BMA:IBMA).
• DD1, DB1, BZ and E are as in footnote to Table 1.
• Polymers 1,3 and 5 where each coated onto one surface of a PVC coupon (6 x 4 ins) from a 0.2ml solution in butanol.
• the coupons were then dried at 25°C for 4 hours and then individually supported vertically in 2.5 litres tap water which had been incubated with 2ml Pseudomonas fluorescens NC1B 9046 broth culture.
• each coupon was then transferred into 2 litres fresh tap water containing 2 ml glucose solution.
• the coupons were then incubated for a further period of 16 and 23 days at 20- 25°C and were then placed in 2 litres distilled water containing 20 ml nutrient broth and 5ml glucose.
• DB1 ,M2KT, BZ and E are as in the footnote to Table 1. - no growth +++ heavy growth ++++ very heavy growth Example 20
• Example 1c was repeated except that the n-butanol was replaced by the same amount of methylated spirits (95/5, ethanol/methanol).
• the dodecyl bis (1-decyl-2-methyl imidazolium)dihydroxide so obtained was readed with AMPS as described in Example 2 to give a AMPS/Biodde monomer (1:1).
• the solvent was finally evaporated. This is Monomer 7 and was used to prepare the following copolymer.
• Ethomeen T12 (Surfadant) 1.32 parts Monomer 7 3.81 parts Seed iso-butylmethacrylate 1.46 parts
• the reador reagents were stirred under nitrogen and the temperature was raised to 60°C. The seed was then added, followed by an aliquot of the initiator mixture (0.67 parts). The pH was measured at 3.0. After 30 minutes the monomer mixture was added drop-wise over approximately 2 hours; every 15 minutes a further aliquot of initiator mixture (0.67 parts) was added to the reador. The pH was monitored and if necessary adjusted to pH 3.0. On completion of the feed and inrtiator the polymerisation was left at 60°C for a further 30 minutes, before the burn-up mixture was added. The polymerisation was then left for a further 60 minutes at 60°C.
• the resulting emulsion was free of residual monomers and had a solids content of 30% (wt wt); average particle size of 250nm and a minimum film forming temperature of 42°C. This is Polymer 7. Examples 21-28
• MAA methacrylic add
• Biodde is dodecyl bis(1-decyl-2-methylimidazolium) cation
• BMA is n-butylmethacrylate
• Polymers were coated onto polyester strips (6 by 2 inches) to give a dry coat thickness of one micron.
• the strips were inoculated by spraying with 2ml of a suspension of spores (10 6 /ml) of Aspergillus niger, Aureobasidium pullulans, Altrenariaretemata, Cladiosporium herbarum and Phoma violacea prepared in distilled water supplemented with 10% (wv) malt broth and 10% (w/v) Czapek Dox broth.
• the strips were then incubated for 3 days at 20°C in a humidity chamber and then inspeded for fungal growth.
• Coatings (approx 25 micron) of polymer were applied to aluminium test-piece surfaces.
• An inoculum of airborne microorganisms (unidentified airborne baderia and fungi) was prepared in an inorganic nutrient medium solution containing glucose as carbon source.
• the coated aluminium was dipped into the inoculum and allowed to drain.
• the aluminium substrates were cooled to approximately 7°C and the aluminium test pieces placed within a humidity chamber. Condensation dripping from the test- pieces was colleded in a container under each sample.
• the temperature of the samples was cyded daily between 25°C and 7°C.
• the condensate under each sample was removed after 7 days and plated out to test for microorganisms.
• the coated aluminium samples were then dipped in fresh inoculum, allowed to drain, replaced in the humidity chamber for a further 7 days. This cyde of sampling, re-inoculation and incubation was repeated.
• the control for the mould growth test was uncoated polyester film, filled PVC for the drculatory water test and an acrylic coating not containing any biocide for the condensation test.
• Example 29 was repeated except that 50% of the imidazolium salt was used.
• the resultant co-polymer contains a 1:2 molar ratio of biodde to sulphonic acid groups in the polymer i.e. both imidazolium units form a salt link with the copolymer.
• Dodecyl bis(1-decyl-2-methylimidazolium)dichloride (0.56 parts) was dissolved in ethanol (2 parts).
• a solution of sodium hydroxide (1 ml of a solution containing 4 parts NaOH in 103.5 parts ethanol; 0.0008M NaOH) was added and the sodium chloride removed by filtration.
• the biodde solution was added to a copolymer of MMA and BMA (10% w/w MMA; 0.07 parts dissolved in 2.14 parts ethanol).
• the resulting copolymer contained a 1:1 molar ratio of biodde to carboxylic add groups in the copolymer.
• Example 32 Example 31 was repeated using 50% of the biodde to give a polymer having a
• Biodde, AMPS, MMA and BMA are as described in the footnote of Table 4.
• Biodde copolymers were prepared by repeating Example 29 but repladng the biocide with the equivalent molar amount of the following heterocydic biodde molecules.

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)
• Plant Pathology (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
• Medicinal Preparation (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=10778560

Family Applications (1)

Country Status (6)

Cited By (16)

Citations (5)

• 1995
  • 1995-08-01 GB GBGB9515720.2A patent/GB9515720D0/en active Pending
• 1996
  • 1996-07-08 WO PCT/GB1996/001617 patent/WO1997005182A1/en active Application Filing
  • 1996-07-08 AU AU63643/96A patent/AU6364396A/en not_active Abandoned
  • 1996-07-08 GB GBGB9615244.2A patent/GB9615244D0/en active Pending
  • 1996-07-12 ZA ZA9605967A patent/ZA965967B/xx unknown
  • 1996-07-22 AR ARP960103693A patent/AR002917A1/es unknown
  • 1996-08-01 UY UY24301A patent/UY24301A1/es unknown

Patent Citations (5)

Also Published As

Similar Documents

Legal Events