NL8403606A - BIOCIDE POLYMERS, COMPOSITIONS CONTAINING THESE POLYMERS, PROCESSES FOR PREPARING THESE POLYMERS AND THE USE THEREOF AS ALGICIDES. - Google Patents

Description

ft. 0 N032838 1

The present invention relates to new polymers containing algicidally active groups and compositions containing these polymers. Methods for preparing these polymers and their use as algicides. contain; the invention furthermore relates to a process for the preparation of these substances as well as their use as algicides. The principle of attaching a biocidal active group to a polymer backbone is known. For example, U.S. Pat. No. 3,167,473 discloses polymers in which organic tin groups are attached as esters to a polymer backbone.

In J. Coatings Techn., 48, 31 (1976), Pittman et al. Describes a monoamine * s * triazine, which was incorporated into an polyacrylate via an amide group.

European 2,63749 discloses special 2,6-diamino-s-triazines as particularly active seawater algicides. It would be desirable to also bind these highly active compounds to a polymer to improve its compatibility with other substrate components and, in particular, reduce their tendency to recrystallize in lacquer formulations. Since two amino groups are present in the molecule of the active substance, it is expected that when incorporated into a polymer containing carboxyl groups, cross-links occur, and thus the compatibility with other lacquer raw materials or the water solubility of the functionalized polymer decreases. A double bond of the diaminotriazine to the polymer would further result in the release of the biocide triazine by hydrolytic cleavage of the amide bond in comparison to single coupled active groups, thereby delaying the effective concentration of free biocide. diaminotriazine drops.

Surprisingly, it has now been found that special diamino-s-trizines which carry at least a bulky group on an amino nitrogen can only be linked with an amino group to a carboxylic acid or to a reactive carboxylic acid derivative, so that no cross-links in the functionalized polymer occur. It is also surprising that even at high concentrations of triazine the good compatibility of functionalized polymers with other lacquer components is maintained.

40 It is hereby possible to use high concentrations of active substance 8403606 P * ï f »2 sen.

The present invention relates to organic polymers with a molecular weight between 1,000 and 150,000, which contain the structural unit of the formula I and / or the formula 2, wherein βΛ is hydrogen 5, r 2 represents hydrogen or -COOR 1 and R 1 represents hydrogen or methyl and wherein R * additionally represents methyl when R ^ -COOR ^ and when r3 is methyl, and wherein R ^ is additionally methyl, when R1 and R1 represent hydrogen, wherein n is 0 or 1 when R ^, R and r3 are hydrogen, wherein r4 is straight C2 "C8 alkyl or C3-10 C8 cycloalkyl, wherein R® represents branched C3" C5 alkyl, wherein A is -SR®, -OR® or Cl, wherein R * > C]> - is C3 alkyl, where R? hydrogen, C 1 -C 20 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, phenyl, C 5 -C 12 cycloalkyl, C 7 "C 4 .4" aralkyl, C 7 -C 14 alkaryl, with one or two hydroxyl groups substituted C 2 -C 20 alkyl or with one to 5-, 0-, -S- or -N (CH 3) -interrupted, optionally substituted C 3 -C 20 ”alkyl, optionally with a hydroxyl group, optionally having multiple hetero atoms with at least one methylene group should be separated; or copolymers thereof with at least one of a polymerizable double bond-containing compound, wherein the mol ratio of the component (s) of formula 1 and / or of formula 2 to the co-monomers component is up to 0.5: Can be 99.5.

R 2 represents C 2 -C 8 alkyl as, for example, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl. Ethyl is preferred.

R 3 represents as C 3 "C 5 cycloalkyl, for example, cyclopropyl, cydobutyl, cyclopentyl or cyclohexyl, particularly preferably, however, cyclopropyl.

r5 represents as branched C3 -C8 alkyl, for example, isopropyl, sec-butyl, tert-butyl, 1,2-dimethylpropyl, 1,3-T-dimethylpropyl, 2,3-di-30-methylpropyl, tert-pentyl, sec.heqrl or tert hexyl for. Preference is given to isopropyl, tert-butyl or 1,2-dimethylpropyl, especially tert-butyl in particular.

R® as C 1 -C 3 alkyl is methyl, ethyl, n-propyl or isopropyl.

Methyl is preferred. A represents -SR®, -OR® or Cl, preferably -SR® or Cl and particularly preferably -SR®, very particularly SCH3.

For example, R 1 as C 1 - “C 20“ alkyl represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopenyl, n-hexyl, 1,1- dimethylbutyl, n-heptyl, n-octyl, 2-ethylhexyl, n-no-40 nyl, n-decyl, 1,1,3,3-tetramethylbutyl, 1,1,3,3-tetramethylhexyl, n-un-8403606 3 decyl, n-dodecyl, 1,1,3,3,5,5-hexamethylhexyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl for. Preference is given to methyl-e7 as C2 -C12 -alkenyl, for example, vinyl, allyl, but-3-enyl, penten-4-enyl, hex-5-enyl, oct-7-enyl, dec-9-enyl or dodec- 5 11-enyl for. Preferred are venyl or allyl-R.7 as represents, for example, ethynyl, propargyl, but-3-ynyl, hex-5-ynyl, oct-7-ynyl, dec-9-ynyl or dodec-11-ynyl Propargyl is preferred.

R5 as C5 "C1" 2 "cycloalkyl represents, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cydononyl, cyclodecyl, cycloundecyl or cydododecyl. Preference is given to C5 -C18 cycloalkyl and in particular cyclohexyl.

As C 1 -C 12 aralkyl, for example, benzyl, phenyl-ethyl, u, α-dimethylbenzyl, phenylbutyl, phenyl-a, α-dimethylpropyl, phenyl-hexyl, phenyl-a, α-dimethylbutyl, phenyloctyl or phenyl-a, α-dimethylhexyl for. Preferred is benzyl-R ^ if C7-C ^ 4 -alkaryl is, for example, o-, m- or p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4 -, 3,5- or 3,6-dimethylphenyl, o-, m- or p-ethylphenyl, o-, mr or p-propylphenyl, o-, m- or p-isopropylphenyl, o-, m-20 or p -butylphenyl, o-, m- or p-sec-butylphenyl, o-, m- or p-tert-butylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4 -, 3,5- or 3,6-dibutylphenyl resp. di-tert-butylphenyl or o-, m- or p-hexylphenyl or o-, a- or p-octylphenyl for. Preferred are o-, m- or p-tolyl.

For example, $ 7 as β-C20-alpha-substituted with one or two hydroxy groups, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydrobutyl, 2-hydroxyhexy 1,2-hydroxy-octyl, 2-hydrodecyl, 2-hydroxydode -cyl, 2-hydroxytetradecyl, 2-hydroxyhexadecyl, 2-hydroxyoctadecyl, 2-hydroxyeicosyl or 2,3-dihydroxypropyl for. Preference is given to C 2-30 C 1-6 alkyl which is substituted with one or two hydroxy groups.

Very particularly preferred are 2-hydroxyethyl, 2-hydroxypropyl or 2,3-dihydroxypropyl.

r7 as interrupted by one to five -0-, -S- or -N (CH3) -, optionally substituted with a hydroxyl group, C3 -C20 alkyl, for example, 3-oxabutyl, 3,6-dioxaheptyl, 3,6,9 -trioxadecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12,15-pentaoxahexadecyl, 3,6,9,12,15,18-hexa-oxanone decyl, 5-hydroxy-3-oxapentyl, 8 -hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 14-hydroxy-3,6,9,12-tetraoxatetradecyl, 3-thiabutyl, 5-hydroxy-3-azamethylpentyl, 5 -hydroxy-3-azaethylpentyl, 40 3-azamethyl-6-oxaheptyl or 3-azamethylbutyl for.

8403606 ____ i ^^ · - ^ -

a

i 4

If R? preference is given to C3 -C12 alkyl-O-interrupted radicals, which are optionally substituted with a hydroxyl group. Very particularly preferred are 5-hydroxy-3-oxapentyl or 3-oxabutyl.

Preferred are organic polymers or copolymers with a molecular weight between 1,000 and 150,000 which contain the structural unit of the formula 1 or the structural unit of the formula 2; very particularly preferred is the structural unit of the formula 1. Also of interest are polymers, as described above, which contain the structural unit of the formula 1, wherein is hydrogen, R 1 represents hydrogen or carboxy, R 1 represents hydrogen and, if R 1 hydrogen is also methyl, wherein n is 0, A represents -SR 1, wherein R 4 is cyclopropyl or ethyl, R 5 tert.bytyl or 1, 2-dimethyl-propyl, where R ^ is only then ethyl, wherein R ^ is 1,2-dimethyl-propyl and where R ^ is only cyclopropyl when R ^ is tert-butyl, and where R ^ is the has previously defined meaning.

Preference is given to homopolymers which contain the structural unit of the formula 1 or the formula 2.

Very particularly preferred are polymers containing the structural unit of the formula 1 or the formula 2, wherein R 1, R 2 and r 3 are hydrogen and wherein n represents 0; or wherein R ^, r2 and R ^ are hydrogen and wherein η is 1; or wherein R * and R 1 are hydrogen and represents methyl; or wherein R * and R 1 are hydrogen and R 1 is -C00H.

Of these preferred polymers, again very particularly preferred are those wherein R *, r 2 and R 2 represent hydrogen and n is 0 or wherein R 1 and R 2 are hydrogen and r 2 represents methyl.

Also preferred are polymers containing the structural unit of formula 1 or formula 2, wherein R 1 is ethyl and R 1 is tert-butyl; or wherein R 1 is ethyl or R 1 is isopropyl; or wherein R 1 is ethyl and R 1 is 1,2-dimethylpropyl; or wherein R 1 is cyclopropyl and R 5 is isopropyl; or wherein R 1 is cyclopropyl and R 5 is tert-butyl.

Of these compounds are particularly preferred, where in R 4 cyclopropyl and R 5 is t-butyl or wherein R * is ethyl and R 5 is 1,2-dimethylpropyl.

Also preferred are polymers having a molecular weight of between 1,000 and 5,000 which contain the structural unit of the formula 1 wherein n is O and R 1 is hydrogen, R 1 represents hydrogen or carboxyl; or 40 wherein n is O and R 4 is hydrogen or methyl 8403606 * 5 * 'and where tert-butyl, A -SR 4 and R® is methyl; or wherein R 1 is cyclopropyl, A -SR ** and R® is methyl.

R 1 is preferably cyclopropyl, while R 1 is preferably isopropyl or tert-butyl.

The homopolymers characterized by the above definition are good agents for combating green and brown algae or diatoms. Still, in many cases it is advantageous to modify these homopolymers by copolymerization with at least one compound having one or more polymerizable double bonds.

10 The comonomers are preferably 1-olefins with 2 to 6

Atoms, such as, for example, ethylene, propylene, X-butene, 1-pentene or 1-hexene, or around vinyl halides, such as, for example, vinyl fluoride, vinyl chloride or vinyl bromide, or around vinylidene halides, such as, for example, vinylidene chloride, to give nitriles of α, β-unsaturated acids, Such as, for example, acrylonitrile or methacrylonitrile, to include α, β-unsaturated acids, their esters or halo derivatives, such as, for example, aeryl acid, methacrylic acid, crotonic acid, maleic acid, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, propyl acrylate octyl acrylate, 2-ethylhexyl acrylate, isopropyl methacrylate, dimethylaminomethyl methacrylate, diethylaminoethyl acrylate, glycidyl methacrylate, glycidyl acrylate or chloromethyl methacrylate, α, β-unsaturated carboxylic acid amides, for example, acrylamide sulfides and their derivatives turn in turn in the form of Na, K, Cu or Zn salts; whether they are aromatic vinyl compounds, such as, for example, styrene, methyl styrene, vinyl toluene or α-chlorostyrene, or vinyl ketones, for example ethyl vinyl ketone, or vinyl esters, for example vinyl acetate, where vinyl ethers can be used in particular for the preparation of polyalcohols, whether they are heterocyclic vinyl compounds, such as, for example, vinyl pyridine, vinyl pyrrolidone or N-vinyl carbazole, or vinyl ethers or unsaturated phosphonates; whether it concerns those, for example butadiene, lsoprene or chloroprene. Particularly preferred comonomers are acrylic acid or methacrylic acid or derivatives of acrylic acid or methacrylic acid. Also preferred are maleic acid or derivatives thereof.

Very particularly preferred are comonomers which are hydrophilic or which can be converted into hydrophilic groups. These monomers include, for example, vinyl pyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Ν, Ν-dimethylacrylamide, acrylamide, vinyl methyl ether or vinyl (2-hydroxyethyl) ether. Preferred is 8403606 * 6 "vinyl acetate, which can be converted to vinyl alcohol" * in a subsequent hydrolysis step.

Another preferred class of coraonomers is derived from ethylenically unsaturated organotin compounds of formula III wherein R® is hydrogen or carboxy, is hydrogen, or, where R® represents hydrogen, is also methyl and wherein R 2 is O C3 -C8 alkyl or optionally substituted phenyl.

In addition, preference is given to comonomers derived from triorganotin-vinyl benzoates, the triorganotin residue being characterized by 10 -SnR 2.

r10 as C 1 -C 8 alkyl represents, for example, n-propyl, n-butyl, n-pentyl or n-hexyl.

As substituted phenyl, R 2 O represents, for example, tolyl or ethylphenyl, as well as p-chlorophenyl or p-bromophenyl. R 2 O is particularly preferred as n-butyl or as phenyl.

As already mentioned, the copolymerizable component may be completely missing or make up to 99.5 mol% of the polymer. Preference is given to copolymers or terpolymers, the total content of the comonomers being up to 95 mol%.

The molecular weight of the homo- or copolymers according to the invention is more than 1,000.

The molecular weight can be up to 150,000, but preferably can be up to 50,000. Furthermore, a molecular weight of 1000 to 10,000 is preferred, in particular a molecular weight of 1000 to 5,000. The monomers suitable as starting materials for the polymerization reaction correspond to the general formulas 4 and 5, wherein the radicals R 1, r 2, r 3, R 4 r 5 and 5 as well as the index n have the above defined meaning.

The starting materials of formulas 4 and 5 are new and are also subject of the present invention.

. In addition to their useful properties as starting materials for the biocide active polymers, which contain the structural unit of formula 1 and / or formula 2, the monomers themselves are biocides.

The preparation of the carboxylic acid amides of the formulas 4 and 5 takes place in a manner known per se by reacting 2,6-diamino-4-alkylthio-s-triazine of the formula 6 with acrylic acid, methacrylic acid, malefic acid, fumaric acid, crotonic acid, citraconic acid, dimethylmalonic acid, vinyl acetic acid or their reactive derivatives such as, for example, esters, chlorides or anhydrides, but preferably with the carboxylic acid chlorides.

8403606 m 7

The conversion preferably takes place in an organic inert solvent *. Per mole of a compound of the formula 6, preferably 1 mole of the β-unsaturated carboxylic acid or a derivative thereof is used. work in the presence of a base, e.g., in the presence of a tertiary amine such as triethylamine, diisopropylethylamine, Ν, Ν-diethylaniline or pyridine or in the presence of anhydrous alkali or alkaline earth metal carbonate, or alkali hydrogen carbonate, such as M 10 Na2CO3 or K2CO resp. an alkali metal or alkaline earth metal hydride.

If an acid anhydride is used instead of the acid chloride, the base may optionally be omitted. Sodium hydride is particularly preferred.

The organic solvents used in the above-described process variants must be inert with respect to the reaction partners. Suitable are, for example, aliphatic hydrocarbons such as hexane or ligrophe, aromatic hydrocarbons such as benzene, toluene or xylene, chlorinated hydrocarbons such as dichloromethane or chloroform, amides such as hexamethylene phosphoric acid trlamide or ethers, such as dioxane, 1,2-dimethoxymethane, diethyl ether or tetrahydrofuran, in particular, however, dimethylformamide. The halogen-free solvents can also be used for the subsequent polymerization reaction of the monomers of the formulas 4 or 5. It is not unconditionally necessary to isolate the intermediates of the formulas 4 or 5, but the polymer or copolymer according to the invention can be further converted in one step immediately.

The s-triazines of the formula VI, in which the radicals rA, r5 and g have the above defined meaning, are known compounds.

The substances can be prepared analogously to the processes described in U.S. Pat. No. 3,799,925 by adding a 2,4-dichloro-6-alkylamino-s-triazine with a primary aliphatic amine to a 2-alkylkyino-4-chloro -6-alkylamino-s-triazine and optionally converts this product with alkyl mercaptan or alkyl alkoxide to the corresponding 4-alkylthio or 4-alkoxy derivatives.

The triazines of the formula VI are known as algicides. In particular, derivatives with A-SCH 3, R 1 -ethyl and R 5, 1,2-dimethylpropyl or A * -SCH 3, R 2 * cyclopropyl and tert-butyl are described in European Patent Specification 3749 as seawater algicides.

The polymers according to the invention can be prepared in two different ways. On the one hand, the functionalized monomers of the formulas 4 and / or 5 can be polymerized, or a polycarboxylic acid or a reactive derivative of the said polycarboxylic acid, for example a polycarboxylic acid chloride, is used, in particular polyacrylic acid chloride or a polycarboxylic anhydride, in particular co-5 or terpolymers of maleic anhydride, with the respective diamino-s-triazine of the formula 6 known per se to

The preparation of suitable polyacrylic acid chlorides is described, for example, in Chimia 19, 235 (1959)

The monomers of the formula 4 or 5 can be polymerized by known methods, which are described, for example, in Houben-Weyl 14 (1), 1010 (1962).

In particular, the radically and anionic homo- or. copolymerization known reactions suitable. The polymerization is controlled in a known manner by initiators and regulators or chain terminators. In addition, it is possible to arrive at polymers with the desired molecular weight. The poly-reaction can be carried out in bulk, in solution, in dispersion, in emulsion, in suspension, or as so-called pearl polymerization.

For the gay resp. copolymerization with free-radical formers are suitable, for example, azp compounds as well as reducing agents or initiators, particularly preferably azo compounds. Particularly suitable azo compounds are those in which the azo group is bound on both sides to tertiary C atoms which, in addition to alkyl groups, also bear nitrile or ester groups. For example, α, α'-azoisobo-25-acidic dinitrile is an important representative of this class of initiators. When the polymerization reaction is brought about by means of a reducing agent, either metal ions of low valency stage or metal-free compounds, which are readily oxidizable, such as, for example, Ag +, Fe ^ "1", Ti ^ +, hydrogen sulfite, are sulfite, thiosulfite, mercaptans, sulfines, amines, endiols (sugar) benzoin-Fe2 + or hydrogen sulfite / Fe2 + suitable. While, with the azo compounds, the nature of the initiator does not affect the polymerization rate, the average degree of polymerization, the nature of the terminal groups, or the number of branches, the polymerization is not suitable for every unsaturated compound. The molecular weight of the polymer is most easily controlled by means of a suitable control agent. Examples are mercaptans, such as n-butyl mercaptan or dodecyl mercaptan, and other organic sulfur bonds, such as diisopropyl xanthogenous disulfide, as well as aliphatic aldehydes and acetals or allyl compounds, such as 8403606 9- * 4 9. as allyl alcohol. The reaction temperatures are known to the person skilled in the art and / for the radical polymerization, depending on the component used, are -20 ° C to + 200eC, preferably + 20eC to 150eC.

Organometallic compounds such as diethyl zinc or di-sobutyl zinc, naphthalene sodium n-amyl sodium, cyclopentadienyl sodium, n-butyl lithium or triethyl aluminum, such as alkali metal alkali metals, such as alkali metal alkali metals, are suitable as initiators in anionic polymerization. alkanolates, amides and hydrides. Particular preference is given to initiating alkali metal or alkaline earth metal hydrides, in particular NaH. Instead of the control agents used in the radical polymerization, the anionic polymerization uses substances which react with the growing chain end; these include, for example, water, alcohols, acids and amines. The temperature in this reaction variant is from -100eC to + 200eC, preferably -20eC to + 150eC and is known to the person skilled in the art for the desired type of polymerization.

It is further also possible to use as initiating means for the polymerization heat, light or energy-rich radiation. The reaction proceeds according to the radical mechanism. In the light-initiated polymerization, suitable catalysts are, for example, benzoinethers, benzyl ketals, dialkoxyacetophenone derivatives or aromatic ketone-amine combinations.

The described methods are in principle suitable for both the homo and the copolymerization reactions. Depending on the choice of the copolymerization parameters, statistical copolymers or block copolymers are thus obtained.

The present invention also relates to a process for preparing a polymer containing the structural unit of the formula 1 and / or the formula 2, characterized in that monomers of the formula 4 and / or 5 are used alone or together with other ethylenically unsaturated monomers polymerizes.

The present invention also relates to an organic polymer, which is obtainable by homo- or copolymerizing a functionalized monomer of the formula 4 and / or 5.

Furthermore, the present invention relates to a process of a polymer containing the structural unit of the formula 1, characterized in that polyacrylic acid chloride, polymethacrylic acid chloride, polymalic anhydride or co- or terpolymers of maleic anhydride with one or two 2,6 diamino-2-triazines of the formula 6, but preferably 40 with 2-cyclopropylamino-4-methylthio-6-tert-butylamino-s-triazine.

8403605 10.

The present invention also relates to an organic polymer, which can be obtained by reacting an s-triazine of the formula 6 and a polyacrylic acid chloride, a polymethacrylic acid chloride, or a co-or terpolymer of maleic anhydride.

The compounds according to the invention are used everywhere where objects to be protected against the growth of algae or diatoms are exposed to water, in particular seawater. This particularly concerns ship hulls, hydraulic engineering works, buoys and fishing nets. The protective effect of the compounds according to the invention extends to cooling or pipe systems, which flow through water, as well as to structures that come into contact with water, to swimming pools and water reservoirs. In general, the mentioned functionalized polymers protect all materials that come into contact with water against algae growth, e.g. wood, cellulose, textile materials and leather, paints, lacquers, e.g. anti-fouling paints, dispersion paints, dispersion plasters and similar coatings, optical and other glasses, plastics, rubber and adhesives as well as other materials.

Depending on the application purpose, the compounds are used within the concentration ranges known to the person skilled in the art. The limits of the usual concentrations are given by the following values: while in cooling water concentrations in the ppm range are already sufficient, anti-fouling recipes concentrations of up to 60% by weight are usual.

The compounds can be applied in pure form. They can also be dissolved or suspended in liquid mediums, optionally for the formation of uniform dispersions of humectants or emulsifiers to promote the uniform distribution of the active substance. Other biocides can preferably be added. In cooling water applications, the polymer can also be used in tablet form, optionally also in combination with other water treatment agents.

A particularly preferred field of application are agents for applying a protective layer, in particular anti-fouling paints, as well as dispersion paints or dispersion plaster layers, which, in addition to the usual raw materials and additives, are 0.5-60% by weight, preferably 3 up to 25% by weight, based on the total mixture of a polymer according to the invention or a mixture of these polymers. The polymers according to the invention or mixtures thereof are also suitable for the preparation of so-called self-polishing anti-tar 8403606 gp 11 Ψ growth paints.

Common starting materials for anti-fouling paints are the lacquer raw materials known as binders and known to the person skilled in the art, such as natural and synthetic resins, homo- and copolymer products with the monomers vinyl chloride, vinylidene chloride, styrene, vinyl toluene, vinyl esters, acrylic acid and methacrylic acid, as well as the esters furthermore chlorine rubber, natural and synthetic rubber, optionally chlorinated or cyclized, also reaction resins such as epoxy resins, polyurethanes or unsaturated polyesters, which can optionally be converted into film-forming, high-molecular-weight products by adding 10 hardeners. The polymers according to the invention can also be used as a binder.

The usual binders can be liquid or in dissolved form. With dissolved binders, also thermoplastics, a protective layer can also be formed by evaporation of the solvent. Solid coatings can, for example, be applied to articles according to the powder coating process. Other common raw materials are, for example, tar, modifiers, dyes, inorganic pigments, fillers and hardeners.

Finally, the compounds according to the invention can also be used in elastomeric coatings, or can also be used in plastics.

Another field of application of the polymers according to the invention relates to their use in dispersion paints, in dispersion plaster layers and in cooling water. In the latter, they are preferably used in combination with scale inhibitors and / or corrosion inhibitors, for example in combination with polyacrylic acid, polymethacrylic acid, hydrolysed polymelphic anhydride or hydrolysed copolymers of maleic anhydride and ethylenically unsaturated monomers. Also combinations with polyphosphates can be used.

In practice, algicidal active substances are often used with other biocides. Anti-fouling paints prove to be advantageous in combination with a biocide that works against animal growth organisms. For example, metallic copper, for example in powder form, as well as CU2O, zinc oxide, triorganotin compounds such as tributyltin oxide, dibutyltin fluoride or triphenyltin chloride, or such substances which are known to those skilled in the art as active against animal growth, are suitable. in particular, it is also possible to charge the homo- or copolymers according to the invention, which contain free carboxyl groups, by salt formation with metal ions, preferably using Cu * "- t Cu ^ + - or 8403506. Zn ^ + ions. In the case of dispersion paints and .r plaster layers, the combination with a fungicide is appropriate. The water treatment preferably combines with a bactericide to combat mucus-forming bacteria, while the polymer according to the invention acts in particular against mucus-forming algae. In many cases, the combination with other algicides is also advantageous.

The invention therefore also relates to an algicidal composition, which contains a functionalized polymer with the structural unit of the formula 1 and / or the formula 2 and optionally contains other biocides. This is preferably a means for applying a protective layer, in particular an anti-fouling paint, a dispersion paint, a dispersion plaster layer or a dispersion lacquer.

The polymer according to the invention or mixtures of these polymers are in particular active agents against algae or diatoms living in fresh and salt water, in particular, however, against algae occurring in sea water. The Eneromorpha and Amphora can be mentioned here as the most important and numerous species. The following examples illustrate the invention without limiting it.

Preparation Examples 20 I. Preparation of polyacrylic acid fixed 2-cydopropylamine-4-methylthio-6-tert-butylamino-s-triazine by reacting the triazine with acrylic acid chloride.

To a solution of 400 g (1.58 mol) of the triazine derivative in 1800 ml of dimethylformamide cooled with jLs, a suspension of 37.9 g (1.58 mol) of NaH (purified in hexane) in 400 ml of dimethylformamide is added dropwise under nitrogen. added. The reaction mixture is stirred at 0 ° C for 30 minutes and then at room temperature for 2 hours. The solution is cooled again to 0 ° C and 144.5 g (1.58 mol) of freshly distilled acrylic acid chloride in 130 ml of dimethylformamide are slowly added dropwise. It is stirred at 0 ° C for 30 minutes and then at 50 ° C for 2 hours. After concentrating at 70 ° C (bath temperature) under reduced pressure, the about 40 to 50 percent solution is poured into water. The precipitated product is filtered quickly, washed with water, dried and redissolved in ethyl acetate. The organic solution is dried with Na 2 SO 4, filtered and concentrated to about 800 ml under reduced pressure at 60 to 70 ° C (bath temperature). After precipitating this concentrated solution in hexane, the resulting polymer is stirred in hexane-ethyl acetate (955) and then in hexane, then filtered and dried.

8403606β '13

Yield: 331 g (68.1% of theory, Mq: 2450 * '(vapor pressure cosmometrically determined). II. Preparation of polyacrylic acid-fixed 2-cyclopropylamino-4-methylthio-6-tert-butylamino-s-triazine by reacting the triazine 5 with polyacrylic acid chloride.

To a ice-cooled solution of 12.65 g (0.05 mol) of the triazine derivative in 100 ml dimethylformamide, a suspension of 1.2 g (0.05 mol) NaH (purified with hexane) in 40 ml dimethylformamide is added under nitrogen. added dropwise * The reaction mixture is stirred at 0 ° C for 0.5 hours and then at room temperature for 2 hours. The solution is cooled again to Q ° C and 4.53 g (0.05 mol) of polyacrylic acid chloride (50% in dioxane) are slowly added dropwise. After 30 minutes at 0 ° C, the solution is stirred at room temperature for an additional 16 hours. The mixture is precipitated in water. The solid 15 'product is dried, dissolved in 50 ml CH 2 Cl 2 and precipitated again in methanol. After filtration and drying, a fraction A is obtained: 3.33 g (21%) of Mj / w / v7700. The filtrate is concentrated to half its volume and the residue is precipitated in pentane. A second fraction is obtained in this way. Fraction B: 2.9 g 20 (18%) Möï 2250 (determined by vapor pressure cosmometrically).

III. Preparation of 2-Cydopropylamino-4-methylthio-6- (N-tert-butylmethacrylamido) -s-triazine.

In a three-necked flask with reflux condenser, KPG stirrer, internal thermometer and dropping funnel, a solution of 25.35 g (0.1 mol) of 2-cydopropylamino-4-methyl-thio-6- (N) is added with sealing of moisture from the air. tert-butylamino) -s-triazine in 250 ml of dry dichloromethane in an ice bath cooled to Q-5eC and 10.5 g (0.1 mol) of triethylamine are added. A solution of 10.46 g (0.1 mol) of methacrylic acid chloride (distilled and stabilized with 0.01% by weight of 2,6-di-tert-butyl-p-cresol) at 0-3 ° C is then stirred with vigorous stirring. ) in 40 ml of dry dichloromethane was added dropwise over 60 minutes.

The mixture is stirred for an additional 5 hours in an ice bath and then at room temperature for 10 hours. The resulting suspension of triethyl-35 amine hydrochloride is filtered, the filtrate is evaporated on a rotary evaporator and the solution of the residue in diethyl ether is filtered through silica gel. After evaporation of the diethyl ether and recrystallization from hexane / diethyl ether, a crystalline product at a melting point of 115-177 ° C is obtained (yield 20.5 g * 64% of the theory).

/ 8403606 14

The structure of the product is confirmed by IR as well as H-H and F-C NMR spectroscopy.

IV. Preparation of 2-cyclopropylamino-4-methylthio-6- (N-tert-butyl-acrylamido) -s-triazine.

Analogously to the method described in Example III, 2-cyclopropylamino-4-methylthio-6- (N-tert-butylamino) -s-triazine is converted into dichloromethane with triethylamine and acrylic acid chloride. The resulting product melts at 119 DEG-121 DEG C. and has the structure indicated by IR as well as 1 H or 1 C NMR spectroscopic findings.

10 V. Polymerization of 2-cyclopropylamino-4-methylthio-6- (N-tert-butyl-methacrylamido) -s-triazine.

11.2 g of 2-cyclopropylamino-4-methyl-thio-6- (N-tert-butylmethacrylamido) -silazine prepared in Example 3 in a refluxed three-necked flask, KPG stirrer, internal thermometer and gas inlet tube. dissolved in 200 ml of absolutely dry distilled tetrahydrofuran. This solution is purged with dry nitrogen to displace the oxygen from the air and cooled to 0-3 ° C. 1.5 ml of a 1.6 molar solution of n-butyl lithium in hexane are added at this temperature and the orange-colored solution is stirred at 0-3 ° C for 3 hours and at 25 ° C for 12 hours.

After adding an additional 0.5 ml of n-butyl lithium solution, the reaction mixture is heated to 65 ° C for 1 hour, cooled, filtered and the dissolved polymer is isolated by precipitation in a mixture of the hexane / diethyl ether (9; 1).

After recrystallization from ethyl acetate / hexane / diethyl ether, the polymer is free from monomers and oligomers and has a molecular weight of 3000 (determined by atmospheric pressure, concentration 0.72% in CHCl3).

The yield is 7.9 g, corresponding to 70.5% of the theory.

Application examples

An anti-fouling paint is prepared in which a mixture of polymers according to the invention is used as a binder (without the use of a conventional binder), according to reaction A: @ 403606 1 15 * fixed on polyacrylic acid 2-cyclopropylamino below. -4-methylthio-6-tert-butylamino-s-triazine with an average molecular weight of 4000 (obtained by reacting the triazine with polyacrylic acid chloride) 3.80 g of polyacrylic acid fixed 2-cyclopropylamino-4-methylthio-6- tert.butylamino-s-triazine with an average molecular weight of 2000 (obtained by reacting the triazine with polyacrylic acid chloride) 5.20 g (the triazine content in these polymers is about 652) phosphate plasticizer (REOFOS & 65) 0.45 g epoxidized soybean oil (IRGAROllS · SA 39) 0.45 g talc. 3.36 g iron oxide red 5.76 g heavy spar 5.28 g tributyltin fluoride 4.2 g 20 aromatics rich solvent (Shell Sol A) 22.5 g xylene 11.2 g methyl isobutyl ketone 22.5 g

The anti-fouling paint A is coated by sandblasting, treatment with primer and with a Menninge paint based on vinyl chloride copolymer plates of 10 by 15 cm. The paint gives a paint-technically under-flawless coating. After storage for about 4 weeks, the plates coated in this way are placed horizontally in a wooden window at a water depth of about 30 cm on a float in the Mediterranean Sea and examined for algae growth according to the following schedule: 10 * completely free of growth 0 * totally grown there between lying figures represent the degree of growth 35.

After 8, 12 and 16 months, the following growth results with algae can be observed.

/ 8403606 *, 16 • V '-¾ f

* i Anti-fouling paint A

valuation after 8 months 10 valuation after 12 months 10 5 valuation after 16 months 10

The paint A shows no defects after 8, 12 or 16 months such as blistering, flattening, loss of color or the like.

8403606

Claims (22)

1. Organic polymers with a molecular weight between 1,000 and 150,000, which contain the structural unit of the formula 1 and / or the formula 1, wherein βΛ is hydrogen, R ^ is hydrogen or -COOR ^ 5 and R ^ is hydrogen or methyl and in which R * additionally represents methyl when R ^ -C00R ^ and when R ^ is methyl, and where R ^ is additionally methyl, when R ^ and R ^ represent hydrogen, where n is 0 or 1 when R ^ s R and are hydrogen, wherein R 1 is straight C 2 "C 6" alkyl or C 1 -C 8 cycloalkyl, wherein R 1 represents branched C 3 -C 8 alkyl, wherein A is -SR®, -OR® or Cl, wherein R® is C 1 -C 3 alkyl, wherein R 1 is hydrogen, C 2 -C 20 alkyl, C 2 “C 12 alkenyl, C 2“ C]> 2 ”alkynyl, phenyl, C 5 -C 12 alkyl, C 1 -C 6 aralkyl, C 1 -C 7 -alkaryl, C 2 "C 20" alkyl substituted with one or two hydroxy groups or interrupted by 1 to 5 0-, -S- or -N (CH 3) -, optionally substituted with a hydroxyl group C 3 "C20" represents alkyl, optionally containing multiple heteroatoms by at least one methyl and group should be separated; or its copolymers with at least one polymerizable double. A bond-containing compound, wherein the molar ratio of the component (s) of formula 1 and / or of formula 2 to the e-monomer component may be up to 0.5: 99.5. Organic homopolymers containing the structural unit of the formula 1 according to claim 1. Organic homopolymers containing the structural unit of the formula 2 according to claim 1. Organic copolymers or terpolymers containing the structural unit of the formula 1 according to claim 1. 5. Organic copolymers or terpolymers containing the structural unit of the formula 2 according to claim 1. Organic polymers or copolymers according to claim 1 having a molecular weight between 1000 and 50,000, containing the structural unit of the formula 1, wherein R 1 is hydrogen, R 2 is hydrogen or carboxy, R 1 is hydrogen and, if R 1 is hydrogen, also methyl represents where n is zero, A represents -SR®, wherein R 1 is cyclopropyl or ethyl, R 1 is tert-butyl or 1,2-dimethylpropyl, where R 1 is only ethyl when R 1 is, Is 2-dimethylpropyl, and wherein R 1 is only then cyclopropyl when R 1 represents t-butyl, and wherein R 3 is finally C 1 -C 3 alkyl. Organic copolymers according to claim 4, which are as monomers / 8403606 5 e *. » 18 contain acrylic acid or derivatives thereof or methacry Izmir or derivatives thereof. Organic copolymers according to claim 4, which contain as comonomers maleic acid or derivatives thereof. Organic polymers according to claim 1, wherein R.1 and R3 represent hydrogen and wherein n is 0. Organic polymers according to claim 1, wherein R 1 and R 3 are hydrogen and wherein R 1 represents carboxy. Organic polymers according to claim 1, wherein n is 0 and R3 represents hydrogen. Organic polymers according to claim 1, wherein R 3 represents methyl. Organic polymers according to claim 1, wherein A represents -SCH3. Organic polymers according to claim 1, wherein R 3 represents tert-butyl and A-SCH 3. Organic polymers according to claim 1, wherein R 1 represents cyclo-propyl and A-SCH 3. Organic polymers according to claim 1, wherein the content of the structural unit of the formula 1 and / or the formula 2 is between 5 and 100 mol. 2. 17. Ethenically unsaturated monomer of the formula 4 or 5, wherein the radicals R 1, R 3, r 3, R 4, r 5 and A and the index n have the meaning as defined in claim » A substance composition containing at least one polymer having the structural unit of the formula 1 and / or the formula 2 according to claim 1. 19. Process for preparing polymers, characterized in that the monomer of the formula 4 and / or 5 according to claim 17 is polymerized. Process for preparing polymers according to claim 19, characterized in that the monomer of the formula 4 and / or 5 is polymerized together with other ethylenically unsaturated monomers. 21. A process for preparing a functionalized polymer according to claim 1, characterized in that a triazine of the formula 6 is reacted with polyacrylic acid chloride, with polymethacrylic acid chloride, with polymalic anhydride or with co- or terpolymers of maleic anhydride, wherein R 1, R3 and A have the meaning defined in claim 1. 22. Use of the polymer according to claim 6 as algicide 8403606 "= - 19" in anti-fouling paints. (23. Use of the polymer according to claim 1 as an algicide in dispersion paints and in dispersion plaster layers. Use of the polymer according to claim 1 as algicide 5 in refrigeration cycles. 8403606