EP2440043A1 - Supports inorganiques contenant des composés hétérocycliques à 3 cycles - Google Patents

Supports inorganiques contenant des composés hétérocycliques à 3 cycles

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Publication number
EP2440043A1
EP2440043A1 EP10725150A EP10725150A EP2440043A1 EP 2440043 A1 EP2440043 A1 EP 2440043A1 EP 10725150 A EP10725150 A EP 10725150A EP 10725150 A EP10725150 A EP 10725150A EP 2440043 A1 EP2440043 A1 EP 2440043A1
Authority
EP
European Patent Office
Prior art keywords
iodo
propynyl
heterocyclic
iodine
inorganic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP10725150A
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German (de)
English (en)
Inventor
Andreas Böttcher
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP10725150A priority Critical patent/EP2440043A1/fr
Publication of EP2440043A1 publication Critical patent/EP2440043A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/08—Separation; Purification; Stabilisation; Use of additives
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring

Definitions

  • the invention relates to heterocyclic 3-ring compounds containing inorganic support materials, their preparation and their use for the stabilization of iodine-containing compounds, as well as these binder formulations and their use for the protection of industrial materials
  • Iodine-containing biocides are used to protect engineering materials (e.g., paints) from infestation, decomposition, destruction, and optical change by fungi, bacteria, and algae, preferably fungi.
  • iodine-containing biocides also in combination with biocides of other classes of active ingredients, are used as components of biocidal active material protection agents such as wood preservatives.
  • active substances are also used here in which one or more iodine atoms are bound to double bond systems, but also to singly bonded carbon atoms.
  • iodine-containing biocides have in common that, when exposed to light, even in bulk or as a component of a technical material (e.g., paints), they lead to yellowing with drug degradation. This feature impedes or prevents the use of iodine-containing biocides in correspondingly sensitive materials, e.g. in light or white paints. Described are these destabilizing properties for the IPBC, for example in WO00 / 16628.
  • transition metal compounds e.g. Cobalt, lead, manganese and Vanadiumoctoate, as a dryer (desiccant) of the alkyd resin-containing binder system.
  • transition metal compounds are also used as pigments, some of which have comparable destructive properties with the siccatives.
  • iodine-containing biocides in certain water-based engineering materials (e.g., paints and preservatives such as wood preservatives and primers) is also problematic.
  • certain water-based engineering materials e.g., paints and preservatives such as wood preservatives and primers
  • transition metal compounds are used as siccatives, which is accompanied by destruction of the contained iodine-containing biocides.
  • WO 98/22543 describes the addition of chelating reagents.
  • transition metal-containing, solvent-based alkyd resin paints are known in which halopropargyl compounds are stabilized by organic epoxides (see WO 00/16628).
  • iodine-containing biocides are stabilized with 2- (2-hydroxyphenyl) benzotriazoles.
  • epoxy compounds is said to reduce the discoloration of iodoalkyne compounds such as IPBC (see US-A 4,276,211 and US-A 4,297,258).
  • the stabilizing effect of the abovementioned stabilizers is not always sufficient and has disadvantages in terms of performance.
  • the drying times of the colors are significantly extended, which in many cases is not acceptable to the user.
  • the inhibition of discoloration is not always sufficient. - -
  • Aziridine compounds are used for example in US2004 / 0077783 A1 constituent of polymerization initiators, which contain as further constituents organoborane compounds, support materials and optionally fillers. The latter are due to the production but as mixtures with the other components and not as with aziridine surface-modified support materials.
  • liquid iodine-containing formulations e.g. Solutions and dispersions, such as, for example, low concentration and thus unnecessary transport of solvent even further improved.
  • this form has stability advantages over iodine-containing solutions, in particular during storage, preferably at elevated temperatures.
  • the invention therefore relates to an inorganic carrier material comprising at least one adsorptively or covalently bonded heterocyclic 3-ring compound.
  • the support material according to the invention is preferably solid at room temperature.
  • silicas such as precipitated silicas, such as silica gels, mesoporous silicates, xerogels, aerogels, fumed silicas, silicic acids modified with inorganic, organic or organometallic radicals, for example silicic acids modified with dichlorodialkylsilanes, kieselguhr, porosils, for example zeosils, clathrasils or dealuminated zeolites, aluminosilicates, zeolites, natural or synthetic tectosilicates, natural silicates such as, vermiculite, mica or pyrogenic metal oxides for example.
  • TiÜ 2 including fumed metal mixed oxides.
  • pyrogenic silicic acids in particular hydrophilic or hydrophobic, for example those which are commercially available under the name Aerosil from Evonik-Degussa, the product Aerosil 200 being particularly preferred.
  • the inorganic carrier material does not contain organoborane in the case where the heterocyclic 3-ring compound is an aziridine.
  • hydrophilic or hydrophobic precipitated silicas in particular hydrophilic or hydrophobic, for example, under the name Sipernat ® from Evonik-Degussa are commercially available.
  • Sipernat ® 22S and Sipernat ® 50S are particularly preferred.
  • the support materials according to the invention preferably have a particle size of 0.001 to 1000 .mu.m, in particular from 0.005 to 500 microns.
  • DBP dibutyl phthalate, see DIN 53601 or ISO 4656
  • the DBP absorption capacity of the support materials according to the invention is preferably 0.1 to 800 g / 100 g, more preferably 1 to 500 g / 100 g of support material.
  • the support materials according to the invention preferably have a specific surface [m 2 / g], determined on the basis of the method of Brunauer, Emmett and Teller (BET surface, J. Am. Chem. Soc., 60, 309 (1938)) according to ISO 5794/1 (Annex D) from 1 to 1200 m 2 / g, particularly preferably from 50 to 900 m 2 / g.
  • BET surface Brunauer, Emmett and Teller
  • the coating or impregnation of the carrier material with the heterocyclic 3-ring compound was carried out adsorptively or by forming covalent bonds.
  • the proof that a heterocyclic 3-ring compound is adsorbed or bound to the inorganic support material in accordance with the invention is generally determined by the analytical determination of the heterocyclic 3-ring groups, for example the aziridine groups, by suitable methods, for example solid-state NMR (MAS - NMR). If a heterocyclic 3-ring compound can e.g. in the MAS-NMR determination of the inorganic support material, it is an inventive inorganic support material according to the present invention.
  • Preferred heterocyclic 3-ring compounds are those having a 3-ring function which have, as the heteroatom in the 3-membered ring, O, NR, S or Se, where R is hydrogen or a organic residue stands.
  • Preferred heterocyclic 3-ring compounds are epoxides or azirindines, in particular aziridines.
  • Suitable aziridines are those which contain one or more aziridine groups.
  • aziridine compounds of the formula (I) are preferred.
  • R 1 is hydrogen, alkyl or cycloalkyl, which are each unsubstituted or substituted and / or mono- or polyethylenically unsaturated, in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl, arylcarbonyl, alkanoyl, carbamoyl or oxomethylene,
  • R 2 , R 3 , R 4 and R 5 independently of one another have the same meaning as R 1 and additionally independently halogen, hydroxyl, carboxyl, alkylsulfonyl, arylsulfonyl, nitrile, isonitrile or the radicals
  • R 2 and R 4 or R 3 and R 5 together with the carbon atoms to which they are attached form a 5- to 10-membered carbocyclic ring which is unsubstituted or substituted and / or mono- or polyethylenically unsaturated.
  • Suitable monofunctional aziridines of the formula (I) are those in which R 2 and R 4 or R 3 and R 5 together with the carbon atoms to which they are attached form a 5- to 10-membered carbocyclic ring which is unsubstituted or substituted and / or mono- or polyethylenically unsaturated.
  • carbocyclic ring is unsubstituted or substituted by one or more substituents selected from the group halogen, hydroxyl, oxo, carboxyl, alkylsulfonyl, arylsulfonyl, nitrile, isonitrile, alkyl or cycloalkyl, each unsubstituted or substituted and / or singly or multiply ethylenically unsaturated, substituted or unsubstituted fullerenyl, aryl, alkoxy, alkoxycarbonyl or alkanoyl, and
  • n is a number from 0 to 6, preferably 0 to 1.
  • R 24 is -H or alkyl, preferably -H, -CH 3 , -C 2 H 5 , particularly preferably -CH 3 , -C 2 H 5 ,
  • g is a number from 1 to 4, preferably 1 to 3, particularly preferably 1 to 2,
  • h is a number from 1 to 11, preferably 1 to 5 and particularly preferably 1 to 3
  • R is -H or alkyl, preferably -H or -CH 3 , particularly preferably -CH 3 ,
  • R ⁇ 25 is -H or alkyl, preferably -H or -CH 3 , more preferably -CH 3 and the remaining radicals have the above significance.
  • aziridines which have two or more aziridine functions.
  • compounds of formula (V) are mentioned.
  • A is an m-valent aliphatic, cycloaliphatic or aromatic radical which is optionally substituted,
  • n is a number from 2 to 5, in particular 2 to 3, and
  • Each R 30 is independently hydrogen or C 1 -C 4 -alkyl, in particular CH 3 or CH 2 CH 3 .
  • A is preferably C 2 -C 10 -alkylene
  • A is preferably the trivalent radical of the formula
  • Suitable alcohol components are, for example, trimethylolpropane, neopentyl glycol, glycerol, pentaerythritol, 4,4'-isopropylidenediphenol, 4,4'-methylenediphenol and polyvinyl alcohols.
  • ß- unsaturated carboxylic acids are, for example, acrylic and methacrylic acid, crotonic acid and cinnamic acid in question. Particularly preferred is acrylic acid.
  • the corresponding polyhydric alcohols of the .alpha.,. Beta.-unsaturated carboxylic acid esters may optionally be alcohols which, in their OH functions, are partly or completely extended with alkylene oxides.
  • alkylene oxides are ethylene oxide and propylene oxide.
  • aziridines suitable according to the invention are those on S. 3, lines 29-34 of WO2004 / 050617 mentioned.
  • aziridines as described for example in US 3,225,013 (Fram), US 4,490,505 (Pendergrass) and US 5,534,391 (Wang).
  • aziridines of the formula (I) which have at least three aziridine groups, for example trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate] , Trimethylolpropane tris [2-aziridinyl butyrate], tris (1-aziridinyl) phosphine oxide, tris (2-methyl-1-aziridinyl) phosphine oxide, pentaerythritol tris [3- (1-aziridinyl) propionate] and pentaerythritol tetrakis [ 3 - (1-aziridinyl) propionate].
  • trimethylolpropane tris [3- (1-aziridinyl) propionate]
  • trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate]
  • trimethylolpropane tris [2-aziridinyl butyrate]
  • pentaerythritol tris- [3 - (1-aziridinyl) propionate]
  • pentaerythritol tetrakis [3 - (1-aziridinyl) propionate].
  • trimethylolpropane tris [3- (1-aziridinyl) propionate]
  • trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate]
  • pentaerythritol tetrakis [3- (1-aziridinyl) propionate].
  • B is the residue of an aliphatic polyol having at least x OH functions, where x
  • f is a number from 0 to 6, in particular from 1 to 3,
  • x is a number greater than or equal to 2, in particular represents 2 to 500,000 and
  • R 38 , R 39 , R 40 and R 41 have the identical meaning as the radicals R 2 - R 5 in the formula (I).
  • R 38 is hydrogen or CH 3 .
  • the aziridine compound of the formula (VIa), also known as DSM crosslinker CX-100, with R 38 methyl and also the product "Corial Hardener AN" from BASF, which is the aziridine of the formula (VIa) where R 38 is hydrogen, is particularly preferred contains.
  • Epoxides are all compounds which contain one or more oxirane rings.
  • R 43 , R 44 , R 45 and R 46 independently of one another are hydrogen, alkyl or cycloalkyl, which are each unsubstituted or substituted and / or mono- or polyethylenically unsaturated, in each case substituted or unsubstituted fullerenyl, aryl, alkoxy, aryloxy, alkanoyl, alkoxycarbonyl , Arylcarbonyl, alkanoyl, carbamoyl or oxomethylene, halogen, hydroxyl, carboxyl, alkylsulfonyl, arylsulfonyl, nitrile, isonitrile
  • R 43 and R 44 or R 45 and R 46 together with the carbon atoms to which they are attached form a 5- to 10-membered carbocyclic ring which is unsubstituted or substituted and / or mono- or polyethylenically unsaturated.
  • alkyl is a linear or branched alkyl radical having 1 to 20, preferably 1 to 12 carbon atoms
  • alkyl radicals according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Pentyl, iso-amyl, hexyl, octyl, etc.
  • alkyl radicals may be preferably substituted by the following radicals; alkoxy, - - preferably Ci-C 2 alkoxy, nitro, monoalkylamino, preferably Dialkylamino, preferably di [Ci-Ci 2 -] alkylamino, cyano, halo, haloalkyl, preferably trifluoromethyl, alkanoyl, aminocarbonyl, monoalkylaminocarbonyl, dialkylaminocarbonyl, alkylamido, preferably Ci-Ci 2 -Alkylamido, alkoxycarbonyl, preferably C 1 -C 12 - alkoxycarbonyl , Alkylcarbonyloxy, preferably Ci-Ci 2 -alkylcarbonyloxy, aryl, preferably phenyl or by halogen, Ci-Ci 2 alkyl or Ci-Ci 2- Alkoxy substituted aryl, heterocyclic 3-ring groups, in particular Azirid
  • the radicals R 43 , R 44 , R 45 and R 46 are each independently hydrogen or aralkyl, aryloxyalkyl, alkoxyalkyl such as epoxy-di-alkoxyalkyl, for example, 2,3-epoxy-l-propoxyethoxymethyl, 2,3-epoxy-1 Butoxyethoxyethyl or 3,4-epoxy-l-butoxyethoxyethyl, for the rest of the formula
  • Z is a straight or branched Ci-Cio alkylene, preferably propylene, butylene, pentylene, hexylene, or heptylenes, halogenated straight or branched C 1 -C 1 0-alkylene such as, 2,2-Dichloromethylpropylen is
  • Q is Ci-C / pAlkylen, Carbonylarylcarboxy such as. Carbonylphenylcarboxy.
  • Preferred epoxides include the compounds in which
  • R 46 is hydrogen, alkoxy, alkyl or 2,3-epoxy-1-propoxyethoxymethyl
  • R 43 is hydrogen or alkyl
  • R 44 and R 45 is hydrogen, and additionally R 43 and R 44 or R 45 and R 46 together with the carbon atoms to which they are attached form a 5- to 10-membered carbocyclic ring which is unsubstituted or substituted and / or mono- or polyethylenically unsaturated ,
  • epoxides include glycidyl ethers. These compounds are characterized in that they contain one or more 2,3-epoxypropanoxy groups and can be represented by the general formula (VIII):
  • R 47 has the same meaning as R 43 , R 44 , R 45 or R 46 .
  • glycidyl ethers are commercially available. In principle, all glycidyl ethers are suitable, in particular those obtained by reaction of 1-chloro-2,3-epoxypropane with alcohols, or by reaction of glycidyl alcohol with suitable electrophiles, e.g. Halides, can be produced.
  • epoxy-containing products obtainable by reaction of epichlorohydrin (1-chloro-2,3-epoxypropane) with polyhydric alcohols, in particular polyhydric phenols such as BSW.
  • polyhydric phenols such as BSW.
  • Bisphenol A including oligomeric and polymeric reaction products.
  • Particularly preferred are those having an average molecular weight of less than 2000 g / mol, in particular less than 1000 g / mol.
  • the preferred epoxides also include the following compounds:
  • R 48 is C 1 -C 20 -alkyl
  • R 51 is C 1 -C 20 -alkyl
  • R is C 1 -C 20 -alkyl, preferably methyl or ethyl. - 5 -
  • the inorganic support material according to the invention may additionally contain other compounds, for example solvents such as esters of mono- or polybasic carboxylic acids (eg mixtures containing diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate), preferably VOC-free or low-VOC solvents, VOC (volatile organic compounds ) volatile organic compounds having a boiling point of less than 250 0 C is understood, emulsifiers such as castor oil ethoxylates, dispersants such as polyvinyl alcohols, Chelathnesreagentien such as in WO 98/22543 mentioned, one or more stabilizers from the series of antioxidants, radical scavenger , UV stabilizers and / or UV absorbers (examples see below). In many cases, synergistic effects are observed here.
  • solvents such as esters of mono- or polybasic carboxylic acids (eg mixtures containing diisobutyl adipate,
  • the support materials according to the invention preferably contain
  • the inorganic support material according to the invention contains from 0.0001 to 8% by weight, preferably from 0.0005 to 6% by weight, in particular from 0.001 to 5% by weight, of emulsifiers.
  • the inorganic support material according to the invention may contain from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 6% by weight, of a dispersing assistant.
  • the invention further relates to the use of azirdines for the preparation of aziridine-containing inorganic support materials.
  • the invention further relates to a process for the preparation of the inorganic support materials according to the invention, which is characterized in that
  • an emulsion containing at least one heterocyclic 3-ring compound in particular aziridines, water, at least one organic solvent and optionally emulsifiers mixed with an inorganic support material and the with at least one heterocyclic 3-ring
  • isolation of the loaded carrier material, obtained after steps b) to d) is preferably carried out by complete or partial removal of the solvent, in particular by
  • Spray drying is a gentle process where the temperatures occurring only act swiftly on the slurry and also not directly burden the scale Inlettemperaturen of about 160 0 C due to the heat of evaporation of water the product.
  • the drying is a spray drying, available inorganic support materials, as described above.
  • nonionic and anionic emulsifiers are suitable as preferred dispersants.
  • a dispersant preferably Anionic emulsifiers such as, for example, alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, in particular the alkali metal and alkaline earth metal salts, for example sodium, potassium, magnesium , Calcium, and ammonium and triethanolamine salts or ionic emulsifiers such as alkylaryl polyglycol ethers such as Polyoxyethylenoctylphenolether, ethoxylated
  • a dispersion of the inorganic carrier material in water is first produced using preferably low shear energy, for example by using a vane blade stirrer.
  • the preparation of the O / W emulsion of the heterocyclic 3-ring compound, in particular an aziridine, dissolved in a suitable, inert organic solvent is optionally carried out with the addition of suitable emulsifiers and preferably using high shear forces (for example Ultraturrax).
  • suitable emulsifiers for example Ultraturrax.
  • the addition of the O / W emulsion of the heterocyclic 3-ring compound, especially the aziridine, to the dispersion of the inorganic carrier is preferably carried out under a low shear force (e.g., blade agitator).
  • the loading of the inorganic support with the heterocyclic 3-ring compound, in particular with an aziridine is preferably carried out by stirring the resulting low shear shear suspoemulsion (e.g., blade agitator) for at least 12 hours.
  • the subsequent isolation of the heterocyclic 3-ring compound, in particular aziridines and optionally solvent-loaded inorganic support material is preferably carried out by fluidized bed drying or spray drying. If appropriate, the inorganic support material according to the invention thus obtained may be further deaggregated by using a screen sieve mill and then converted into a homogeneous solid mixture using a mixer, for example a Lödige mixer.
  • novel process alternatives are preferably carried out at a temperature of 0 to 35 0 C, in particular at room temperature (22 ° C).
  • the invention further relates to the use of the support materials according to the invention for the stabilization of iodine-containing compounds, in particular biocides.
  • iodine-containing compounds are preferably iodoalkynyl compounds or compounds in question, in which one or more iodine atoms are bonded to double bonds or in which one or more iodine atoms are bonded to single bonded carbon atoms.
  • the iodine-containing compounds are, for example, diiodomethyl-p-tolylsulfone, diiodomethyl-p-chlorophenylsulfone, 3-bromo-2,3-diiodo-2-propenyl alcohol, 2,3,3-triiodoallyl alcohol, 4-chloro 2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone (CAS-RN: 120955-77-3) iodoffen, 3-iodo 2-propynyl-2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenylformal (IPCF), N-iodopropargyloxycarbonyl- ⁇ 1 -in, N-iodopropargyloxycarbonyl-alanine
  • the iodine-containing compounds are preferably 3-iodo-2-propynyl-2,4,5-trichlorophenyl ether, 3-iodo-2-propynyl-4-chlorophenyl phosphate (IP CF), N-iodopropargyloxycarbonyl-alanine, N-iodopropargyloxycarbonyl-alanine ethyl ester, 3- (3-iodopropargyl) -benzoxazol-2-one, 3- (3-iodopropargyl) -6-chlorobenzoxazol-2-one, 3-iodo-2- propynyl alcohol, 4-chlorophenyl-3-iodopropargylformal, 3-iodo-2-propynyl-propyl carbamate, 3-iodo-2-propynyl-butyl-carbamate (IPBC), 3-iodo-2-propy
  • the iodine-containing compounds are more preferably 3-iodo-2-propynyl-propyl-carbamate, 3-iodo-2-propynyl-butyl-carbamate (IPBC), 3-iodo-2-propynyl m-chlorophenyl c arb amate, 3-iodo-2-propynylphenyl c arb amate, di- (3-iodo-2-propynyl) hexyl dicarbamate, - -
  • the particularly preferred iodine-containing compounds are N-alkyl-iodotetrazoles, N-aryl-iodo-terazoles and N-aralkyl-iodo-terazoles, as described, for example, in (EP 1773125).
  • the iodine-containing compounds in particular biocides, can be used individually or in mixtures together with a plurality of iodine-containing compounds, in particular biocides. Particularly preferred is IPBC.
  • the carrier materials according to the invention to be used according to the invention are preferably suitable for stabilizing iodine-containing compounds, in particular biocides in binder formulations, for example in alkyd resin-based systems such as paints containing transition metal dryers, especially in the presence of transition metal dryers.
  • binder formulations and transition metal driers are described in more detail below.
  • stabilization is preferably understood to mean the stabilization of iodine-containing compounds both from chemical and light-induced degradation, in particular from chemical degradation.
  • the support materials according to the invention can be used to suppress or at least slow down the chemical degradation of compounds containing iodine, in particular biocides in active ingredient formulations, in particular paints such as paints, lacquers, primers, impregnations, glazes and other technical materials.
  • the support materials according to the invention which can be used according to the invention for stabilizing iodine-containing compounds, in particular biocides have a good stabilizing action, especially in alkyd resin-based systems such as paints containing transition metal dryers.
  • the stabilization is preferably realized by the fact that the iodine-containing compounds, in particular biocides and the support materials according to the invention are present together in a mixture or in a medium.
  • composition is used, containing
  • composition is also an object of the present invention.
  • compositions contain:
  • compositions according to the invention generally contain 0.01-70% by weight, preferably 0.05-60% by weight, more preferably 0.1-50% by weight of at least one iodine-containing biocide and at least one support material according to the invention, such that the content of all heterocyclic 3-ring compounds present in the composition according to the invention, in particular aziridine compounds, is 0.001-50% by weight, preferably 0.005-40% by weight, particularly preferably 0.01-30% by weight.
  • composition according to the invention preferably contains the iodine-containing biocide and an aziridine compound in the total amount of from 40 to 99% by weight.
  • the carrier material according to the invention is used so that the content of all heterocyclic 3-ring compounds present in the composition according to the invention, in particular aziridines, is generally 1 to 280% by weight, preferably 2 to 225% by weight, in particular 5 to 110 wt .-%, based on the iodine-containing biocide.
  • 0.05 to 5 preferably 0.1 to 4, in particular 0.25 to 2 equivalents of the heterocyclic 3-ring functions present in the inventive carrier material, in particular aziridine functions.
  • the erfmdungswashe composition may be in various forms, for example.
  • a solvent-based dispersion water-based dispersion, solid mixture, etc. are present. - -
  • composition according to the invention is particularly preferably present as a solid mixture, for example as a powder, granules, in particular with an average particle size of 50 to 2000 ⁇ m, or as a compact, such as, for example, compacted powder such as pellets, tablets, etc.
  • the composition according to the invention is in the form of a solvent-based dispersion, it being possible to add, for example, alkyd resins, modified alkyd resins, thixotropic resins, etc., and other additives, such as skin inhibitors (antioxidants), pigments, crystallization stabilizers, etc., to adjust the rheological properties of the dispersion.
  • alkyd resins modified alkyd resins, thixotropic resins, etc.
  • other additives such as skin inhibitors (antioxidants), pigments, crystallization stabilizers, etc.
  • composition according to the invention can be used as further ingredients adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids and mineral and vegetable oils.
  • adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids and mineral and vegetable oils.
  • adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids and mineral and vegetable oils.
  • dyes such
  • Stabilizers for example tetramethylethylenediamine (TMEDA), triethylenediamine and the known from WO2004 / 050617 1,4-diazabicyclo [2.2.2] octane (DABCO) included.
  • TEDA tetramethylethylenediamine
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • the invention further relates to a process for the preparation of the composition according to the invention.
  • composition according to the invention can be prepared, for example, by mixing the individual components, ie the support material according to the invention and the iodine-containing compound optionally with extenders and optionally using further additives such as flow improvers, additives for increasing the electrical conductivity, additives for adjusting the dusting behavior, etc. ,
  • suitable solid mixers such as Lödige mixers, paddle mixers, tumble mixers, drum mixers with disruptive bodies, etc. are used here, optionally after pretreatment of the components to be mixed with, for example, screen mills such as the Bauerffle mill
  • the transfer of thus prepared solid mixtures in other embodiments, such as. Granules, compacts such as pillows, tablets, etc. is using fluidized bed granulation, use mechanical compaction, possibly with the addition of other additives such as. Binder, possible. - -
  • composition according to the invention is a solvent-based dispersion comprising an iodine-containing compound, in particular IPBC, and at least one excipient according to the invention, in particular one in which the heterocyclic-3-ring compound is at least one aziridine compound.
  • the iodine-containing compound, in particular IPBC and erfmdungswashe carrier material are preferably under high shear in an inert organic solvent as a continuous phase (eg isoparaffins such as Isopar "L (isoparaffin from Exxon) or so-called.”
  • an inert organic solvent eg isoparaffins such as Isopar "L (isoparaffin from Exxon) or so-called.”
  • White spirits “such as” Shellsol " ground D60) optionally with the addition of processing aids and stabilizers, such as, rheological additives (thixotropic resins such as. WORLÉETHIX S6358, a thixotropic alkyd resin from. Worlee) and optionally anti-skinning agents such as.
  • Antiskin ® 444 Fa. Borchers
  • disp added eg bead mill.
  • compositions according to the invention or of the iodine-containing compound used can be increased if, if appropriate, further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients are added or used to increase the spectrum of action or to achieve particular effects become. These mixtures can have an even broader spectrum of activity.
  • Triazoles such as:
  • Succinate dehydrogenase inhibitors such as:
  • Naphthalene derivatives such as:
  • Benzimidazoles such as:
  • Morpholine derivatives such as:
  • Benzothiazoles such as:
  • Benzothiophene dioxides such as:
  • Formaldehyde and formaldehyde-releasing compounds such as:
  • Isothiazolinones such as:
  • Aldehydes such as:
  • Cinnamaldehyde formaldehyde, glutardialdehyde, ⁇ -bromocinnamaldehyde, o-phthaldialdehyde;
  • Benzalkonium chloride benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, dichlorobenzyldimethylalkylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, N-hexadecyltrimethylammonium chloride, 1-hexadecylpyridinium chloride, iminoctadine tris (albesilate);
  • Microbicides with activated halogen group such as:
  • Methoxyacrylates or similar such as:
  • Azoxystrobin Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, 2,4-dihydro-5-methoxy-2-methyl-4- [2 - [[[[l- [3- (trifluoromethyl ) phenyl] ethylidenes] amino] oxy] methyl] phenyl] -3H-l, 2,4-triazol-3-ones (CA S No. 185336-79-2);
  • Salts of the metals tin, copper and zinc with higher fatty, resinous, naphthenic and phosphoric acid e.g. Tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
  • Salts of the metals tin, copper, zinc, as well as chromates and dichromates such. Copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;
  • Oxides of the metals tin, copper and zinc e.g. Tributyltin oxide, CU2O, CuO, ZnO;
  • Oxidizing agents such as:
  • K-salts bis-N- (cyclohexyldiazenium-dioxy) -copper, iprovalicarb, fenhexamide, spiroxamine,
  • Bacillus thuringiensis barthrin, 4-bromo-2 (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, bioresmethrin, bioallethrin, Bistrifluron, Bromophos A, Bromophos M, Bufencarb, Buprofezin, Butathiophos, Butocarboxine, Butoxycarboxime,
  • Fenamiphos fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fensulfothion, fenthione, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flupyrazofos, fluffine, flumethrin flufenprox , Fluvalinate, Fonophos, Formethanates, Formothion, Fosmethilan Fosthiazat, Fubfenprox, Furathiocarb,
  • Halo fenocid, HCH (CA S RN: 58-89-9), heptenophos, hexaflumuron, hexythiazox, hydramethylnone, hydroprene, - -
  • Imidacloprid Imiprothrin, Indoxycarb, Iprinomectin, Iprobenfos, Isazophos, Isoamidophos, Isofenphos, Isoprocarb, Isoprothiolane, Isoxathion, Ivermectin,
  • Parathion A parathion M, penfluron, permethrin, 2- (4-phenoxyphenoxy) ethyl-ethylcarbamate, phenthoate, phorate, phosalone, phosmet, phosphamidone, phoxim, pirimicarb, pirimiphos M, pirimiphos A, prallethrin, profenophos, promecarb, propaphos, Propoxur, Prothiophos, Prothoate, Pymetrozine, Pyrachlophos, Pyridaphenthione, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyrimidifen, Pyriproxifen, Pyrithiobac Sodium
  • Herbicides and algicides - -
  • ketospiradox - -
  • MCPA MCPA hydrazide, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron, metam, metamifop, metamitron, metazachlor, methabenzthiazuron, methazole, methopyrone, methyldymrone, methylisothiocyanate, metobromuron, metoxuron, metribuzin, metsulfuron, Molinate, Monalid, Monolinuron, MSMA, Metolachlor, Metosulam, Metobenzuron,
  • the invention further relates to a binder formulation containing
  • At least one iodine-containing compound in particular biocide and - at least one inventive carrier material.
  • the binder formulation preferably contains the components iodine-containing compound, in particular biocide and, according to the invention, carrier material in the form of the composition according to the invention.
  • Preferred binders include oxidatively drying binders, - - Preferably alkyd resin-based binder or by coalescing agent filming binder, in particular latices in question.
  • alkyd resin-based binders are preferably alkyd resins and modified alkyd resins in question.
  • the alkyd resins are generally polycondensation resins of polyols and polybasic carboxylic acids or their anhydrides and fats, oils or free natural and / or synthetic fatty acids. If appropriate, the alkyd resins may also be chemically modified with hydrophilic groups, in particular water-soluble groups, in order to be usable, for example, as an emulsifiable or water-soluble alkyd resin.
  • the polyols mentioned are preferably glycerol, pentaerythritol, trimethylolethane, trimethylolpropane and various diols, such as ethane / propanediol, diethylene glycol and neopentyl glycol.
  • the polybasic carboxylic acids or their anhydrides mentioned are preferably phthalic acid, phthalic anhydride, maleic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, adipic acid, azelaic acid or sebacic acid.
  • oils or fatty acids mentioned are generally linseed oil, oiticia oil, wood oil, soybean oil, sunflower oil, safflower oil, ricinole oil, tall oil, castor oil, coconut oil, peanut oil, their fatty acids and also synthetic saturated, unsaturated or polyunsaturated monocarboxylic acids or mixtures of these components ,
  • the alkyd resins may optionally be modified, for example, with natural resins, phenolic resins, acrylic resins, styrene, epoxy resins, silicone resins, isocyanates, polyamides or aluminum alcoholates.
  • the alkyd resins generally have a molecular weight of from 500 to 100,000 g / mol, preferably from 1,000 to 50,000 g / mol, in particular from 1,500 to 20,000 g / mol (determined by laser light scattering, see, for example, "Static Light Scattering of Polystyrene Reference Materials : Round Robin Test ", U. Just, B. Werthmann International Journal of Polymer Analysis and Characterization, 1999 Vol.5, pages 195-207).
  • the binder formulations of the invention preferably contain 1 to 80 wt .-%, preferably 2 to 70 wt .-% and particularly preferably 3 to 60 wt .-% of alkyd resin. - -
  • the binder formulation according to the invention preferably contains an alkyd resin-based binder and, for oxidative drying, a transition metal dryer.
  • transition metal dryers are understood in particular to mean transition metal compounds which accelerate the drying and hardening of the alkyd resin-based binder.
  • the salts of transition metals of groups Vb, VIb, VIIb, VIII and Ib of the Periodic Table is the salts of cobalt, manganese, vanadium, nickel, copper and iron, more preferably cobalt, manganese, iron and vanadium. They do not necessarily have to be used alone, but can also be used in combination with non-transition metal salts, such as lead, calcium or zirconium.
  • the preferred transition metal salts are soluble in organic solvents, for example.
  • White spirit at 20 0 C in an amount of more than 10 g / l.
  • it is the salts of carboxylic acids, which have a good compatibility with the alkyd resin binders and at the same time ensure sufficient solubility of the metal salt.
  • Transition metal salts of fatty acids such as oleates or linoleates, resin acids such as resinates or salts of 2-ethylhexanoic acid (octoates) are preferably used.
  • Preferred transition metal driers are cobalt octoate and cobalt naphthenate example Octasoligen -cobalt ® 12 from Borchers.
  • the binder formulations according to the invention preferably contain the transition metal dryers in an amount of 0.001 to 1 wt .-%, preferably 0.005 to 0.5 wt .-% and most preferably 0.01 to 0.1 wt .-%, each based on binder.
  • the binder formulations in a preferred embodiment contain at least one polar organic solvent, preferably a polar aprotic solvent.
  • polar organic solvent preferably a polar aprotic solvent.
  • polar protic and dipropylene glycol monomethyl ethers for example Dowanol DPM from Dow Chemical
  • polar aprotic solvents such as dimethylformamide and dimethyl sulfoxide
  • etherified glycols, oligoglycols and polyglycols etherified polyols and esterified polyols, esters of mono- and polybasic carboxylic acids, e.g. Adipic diisobutyl ester, diisobutyl maleate (e.g., Rhodiasolv DIB).
  • iodine-containing compound in particular biocide
  • heterocyclic 3-ring compound in particular aziridine compounds
  • solvent in particular nonpolar or polar solvents, preferably up to 10% by weight, in particular from 0.01 to 7.5% by weight, based on the binder preparation of polar aprotic solvents, and
  • binder formulations according to the invention comprising at least one alkyd resin, at least one transition metal dryer, IPBC, at least one solvent and at least one support material according to the invention containing at least one adsorptively or covalently bonded aziridine compound.
  • the binder formulation may also contain fillers, skin preventatives, rheology additives such as anti-settling agents and thixotropic agents, other biocides such as fungicides, bactericides, antifoulants and algicides, solvents, process additives, plasticizers, UV and heat stabilizers, and corrosion inhibitors in conventional amounts.
  • rheology additives such as anti-settling agents and thixotropic agents
  • other biocides such as fungicides, bactericides, antifoulants and algicides
  • solvents process additives
  • plasticizers plasticizers
  • UV and heat stabilizers UV and heat stabilizers
  • corrosion inhibitors in conventional amounts.
  • further stabilizers may be added to the binder formulations, such as the chelating reagents mentioned in WO 98/22543 or other heterocyclic 3-ring compounds, in particular those having a heteroatom other than what was used in the loaded 3-membered ring compound on the inorganic support.
  • these are preferably the organic epoxides mentioned in WO 00/16628. In many cases, synergistic effects are observed here.
  • one or more stabilizers from the series of antioxidants, free-radical scavengers, UV stabilizers, chelators and UV absorbers can also be added in the inventive use, which have partially synergistic effects.
  • UV stabilizers may be mentioned:
  • hindered phenols such as - -
  • butyl-4-hydroxybenzylphosphonic acid monoethyl ester calcination salt N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylenediamine, N, N'-di- (3 , 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine,
  • Esters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono- or polyhydric alcohols such as, for example, with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, - 5 -
  • Thiodiethylenglycol diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate or di-hydroxyethyl-oxalklarediamid.
  • N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) isophthalamides 4-hydroxy-2,2,6,6-tetramethylpiperidines, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy-2,2,6,6- tetramethylpiperidines, 1 - (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 1-ethyl
  • Tri (nonylphenyl) phosphites tris (2,4-di-tert-butylphenyl) phosphites, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphites, bis (2,6-di-tert-butyl-4-methylphenyl ) pentaerythritol diphosphites, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphites, tetrakis (2,4-di-tert-butylphenyl) [l, 1'-biphenyl] -4,4'- diyl bisphosphonites, 2,2'-ethylidene bis (4,6-di-tert-butylphenyl) fluorophosphites, dioctadecyl pentaerythritol diphosphonites, 2 -
  • N- (2-naphthyl) -N-phenylamines, 2,2,4-trimethyl-1,2-dihydroquinoline polymer (CAS No: 26780-96-1), N-2-propyl-N'-phenyl-p phenylenediamines, N- (1-naphthyl) -N-phenylamines, (benzeneamines, N-phenyl-, reaction products with 2,4,4-trimethylpentenes) (CAS No. 68411-46-1) or 4- (l -Methyl-1-phenylethyl) -N- [4- (1-methyl-1-phenylethyl) phenyl] anüine.
  • UV absorbers like,
  • Ethylenediaminetetraacetate ethylenediamine, acetylacetone, nitrilotriacetic acid, ethylene glycol bis ( ⁇ -aminoethyl ether) -N, N-tetraacetic acid, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 2, 2 ', 6', 2 "-terpyridine, 4,4'-diphenyl-2,2'-bipyridine, 2,2'-bipyridine-3,3'-diol, 1,10-phenanthroline, 4-methyl-1 , 10-phenanthrolines, 5-methyl-1, 10-phenanthrolines, 4,7-dimethyl-1, 10-phenanthrolines, 5,6-dimethyl-1, 10-phenanthrolines, 3,4,7,8-tetramethyl-1 , 10-phenanthrolines, 4,7-diphenyl-l, 10-phenanthrolines, 2,4,7,9-tetramethyl-l, 10-phen
  • Iodine-containing compounds in particular biocides, are broken down, especially in the presence of the dryers described in more detail above. Although the strongest effects are observed in the presence of these dryers, a number of other color components also have a destabilizing effect
  • Anti-settling and thixotropic agents other compounds, especially biocides such as fungicides, bactericides, antifouling agents and algicides, solvents, process additives, plasticizers, UV and
  • the support materials of the invention also show a strong stabilizing effect here.
  • compositions according to the invention used in oxidatively drying binder preparations or the binder preparations according to the invention themselves show a marked reduction in the drying time or no lengthening of the drying time compared to the systems not equipped with IPBC compared to unstabilized iodine-containing systems, in particular IPBC-containing systems (so-called Blank formulations).
  • novel binder formulations are preferably used as paints, in particular as paints, lacquers, primers, impregnations and glazes. Accordingly, the invention also relates to the use of the binder formulations according to the invention as paints.
  • the invention further relates to the use of the inventive composition for the protection of industrial materials against destruction or infestation by microorganisms.
  • inventive compositions are suitable for the protection of industrial materials.
  • Technical materials as used herein mean non-living materials prepared for use in the art.
  • it is - - technical materials include adhesives, glues, paper and cardboard, textiles, leather, wood, wood-based materials, paints and plastics, coolants and other materials that may be attacked or decomposed by microorganisms.
  • microorganisms that can cause degradation or a change in the technical materials
  • bacteria, fungi, yeasts, algae and mucus organisms may be mentioned.
  • the active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and bacteria.
  • microorganisms of the following genus are mentioned:
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Aspergillus niger
  • Chaetomium such as Chaetomium globosum
  • Coniophora like Coniophora puetana,
  • Lentinus like Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma like Trichoderma viride
  • Escherichia like Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the invention further relates to technical materials containing at least one iodine-containing compound, in particular biocide and at least one inorganic support material according to the invention. - -
  • accelerated stability tests are performed by storage at elevated temperature.
  • the content of the IPBC was in all cases by HPLC.
  • Examples 1 to 5 describe the preparation of inorganic support materials according to the invention with adsorbed or covalently bonded aziridine compounds and compositions according to the invention comprising IPBC and such support materials.
  • the oil phase consisting of 9.0 g CX-100 crosslinker from DSM (trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate] and 2.5 g Rhodiasolv "DIB from Rhodia (mixture consisting of
  • Emulsion was added to a dispersion of 27.0 g Aerosil "200 from Evonik (fumed silica having a BET surface area of 200 m 2 / g and a DBP absorption capacity of 300 g / 100 g)
  • Aerosil loaded with the aziridine and Rhodiasolv DIB was isolated from the resulting dispersion by spray drying (Büchi B-290 spray drier, pump power 45%, N 2 flow 35 l-TnUi 1 , Inlet 160 0 C, outlet 73 ° C). 33 g of a very fine, colorless solid were obtained (84% of theory).
  • Example 2 inorganic carrier material with aziridines II
  • the oil phase consisting of 18.0 g CX-100 crosslinker from DSM (trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate] and 5.0 g Rhodiasolv "DIB from Rhodia (mixture consisting of Diisobutyl adipate, diisobutyl glutarate, diisobutyl succinate) was treated with a solution of the emulsifier of 1.15 g Tanemul "KS from Tanatex (castor oil ethoxylate with 30 eq. EO) in 50 g water under the action of an Ultraturrax (24,000 rpm * 1 ). emulsified for 10 minutes.
  • the colorless emulsion was added to a dispersion of 54.0 g of Aerosil "200 from. Evonik (fumed silica) in 600 g of a solution of 24 g of the dispersing Mowiol ® 3-85 (polyvinyl alcohol of the company. Kuraray) metered into 576 g of water under wing blade stirring, added 600 g of water and then stirred for 24 hours.
  • Aerosil "200 from. Evonik fumed silica
  • Mowiol ® 3-85 polyvinyl alcohol of the company. Kuraray
  • IPBC IP-content 41%).
  • IPBC 90.0 g of IPBC are homogenized with 96.9 g of the aziridine formulation from Example 2 (containing 23.2% of aziridine, which means the weight ratio of IPBC to aziridine is 3: 1) with the addition of ceramic balls (0 40 mm) to the drum mixer. A fine, colorless and homogeneous powder is obtained (IPBC content 48%).
  • IPBC 90.0 g of IPBC are homogenized with 128.4 g of the aziridine formulation from Example 1 (containing 23.03% of aziridine, the weight ratio of IPBC to azirides being 4: 1) with the addition of ceramic balls (0 40 mm) to the drum mixer. It is a fine, colorless and homogeneous powder obtained (IPBC content 41%).
  • IPBC compositions of Examples 3 and 4 are incorporated in a typical alkyd-based paint system (Alkydlasur A) in the presence of a transition metal drier (Co) and a metal oxide pigment (iron oxide).
  • Alkydlasur A alkyd-based paint system
  • a transition metal drier Co
  • a metal oxide pigment iron oxide
  • IPBC composition of Examples 3, 4 and 5 are incorporated in a commercial wood thick-layer varnish "Alkydlasur B" (containing alkyd resin, white spirit, iron oxide pigment, dryer, butanone oxime, UV absorber and additives) to equip the paint system with each 0 , 7% IPBC, based on the glaze, the compositions of Examples 3, 4, 5 and unstabilized IPBC are used in each case (see Table 4):
  • IPBC thick-film glazes Alkydlasur B-I to Alkydlasur B-IV were prepared by mixing the weight percentages of Alkydlasur B shown in Table 4 and said IPBC-containing compositions.

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Abstract

L'invention concerne des supports inorganiques contenant au moins un composé hétérocyclique à 3 cycles lié par covalence ou adsorption.
EP10725150A 2009-06-12 2010-06-11 Supports inorganiques contenant des composés hétérocycliques à 3 cycles Withdrawn EP2440043A1 (fr)

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EP09162601 2009-06-12
PCT/EP2010/058242 WO2010142790A1 (fr) 2009-06-12 2010-06-11 Supports inorganiques contenant des composés hétérocycliques à 3 cycles
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Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
EP2594132A1 (fr) 2011-11-16 2013-05-22 Lanxess Deutschland GmbH Stabilisation de composés contenant de l'iode avec des polymères contenant de l'azote
DE102012203003A1 (de) 2012-02-28 2013-08-29 Schülke & Mayr GmbH Flüssige Zubereitung für die Reduktion von freiem Sauerstoff und die Konservierung von Wasser
CN104204057B (zh) * 2012-03-28 2016-10-05 朗盛德国有限责任公司 噻苯咪唑和含碘杀真菌剂的稳定组合物
EP3435767A1 (fr) * 2016-03-31 2019-02-06 Dow Global Technologies, LLC Combinaison synergique constituée d'un composé de lénacil et de diiodométhyl p-tolyl sulfone pour protection sous forme de film sec
WO2020020714A1 (fr) 2018-07-23 2020-01-30 Dsm Ip Assets B.V. Composé à plusieurs motifs aziridine
WO2021148561A1 (fr) 2020-01-22 2021-07-29 Covestro (Netherlands) B.V. Composé fonctionnel aziridine
CN112619593B (zh) * 2020-12-16 2022-08-02 吉林建筑大学 一种污水中磺胺类抗生素的吸附材料及其制备方法
US11685856B2 (en) * 2021-05-21 2023-06-27 Baker Hughes Oilfield Operations Llc Branched polyethyleneimine (B-PE) as oilfield metal naphthenate inhibitors
CN116515371B (zh) * 2023-02-13 2024-01-05 湖南坤灵涂料有限公司 一种高性能水性无机富锌涂料及其制备方法和应用
CN117718033B (zh) * 2023-10-17 2024-06-07 江苏大学 一种SiO2-Al2O3气凝胶负载CeO2/TiO2复合催化剂及其制备方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3225013A (en) 1964-10-12 1965-12-21 Minnesota Mining & Mfg Curable compositions of an organic acid anhydride and an alkylenimine derivative
US4276211A (en) 1980-03-10 1981-06-30 Troy Chemical Corporation Stabilization composition for coating composition
US4490505A (en) 1980-04-17 1984-12-25 Minnesota Mining And Manufacturing Company Polyfunctional aziridine crosslinking agents for aqueous magnetic recording media binder
US4297258A (en) 1980-04-28 1981-10-27 Ici Americas Inc. Non-yellowing paint formulations containing iodo substituted alkynyl urethanes as fungicides
EP0083308B2 (fr) 1981-12-24 1990-10-24 Ciba-Geigy Ag Procédé pour la stabilisation de fongicides
US4605698A (en) 1983-07-13 1986-08-12 Diamond Shamrock Chemicals Company Polyfunctional aziridines for use in crosslinking applications
JPH02164803A (ja) * 1988-12-15 1990-06-25 Takeda Chem Ind Ltd 安定な殺菌組成物
DE4337433A1 (de) * 1993-11-03 1995-05-04 Bayer Ag Stabilisierung von Iodverbindungen mit Hilfe anorganischer Trägermaterialien zur Verwendung im Materialschutz
US5534391A (en) 1994-01-28 1996-07-09 Minnesota Mining And Manufacturing Company Aziridine primer for flexographic printing plates
DE19627909A1 (de) * 1996-07-11 1998-01-15 Basf Ag Verfahren zur Herstellung von feinteiligen, wasserunlöslichen Polymerisaten von Aziridinen sowie von modifizierten, wasserunlöslichen Polymerisaten von Aziridinen sowie von modifizierten, wasserunlöslichen Polymerisaten von Aziridinen und ihre Verwendung
US5916930A (en) 1996-11-20 1999-06-29 Troy Corporation Stabilization of biocidal activity in air drying alkyds
US6059991A (en) * 1997-12-12 2000-05-09 Troy Technology Corporation, Inc. Stabilized composition containing halopropynyl compounds
US6140370A (en) * 1998-09-21 2000-10-31 Troy Technology Corporation, Inc. Stabilized alkyd based compositions containing halopropynl compounds
US6472424B1 (en) 2000-06-07 2002-10-29 Troy Technology Corporation, Inc. Stabilized antimicrobial compositions containing halopropynyl compounds and benzylidene camphors
US6616740B2 (en) * 2001-12-12 2003-09-09 Isp Investments Inc. Liquid compositions of IPBC in polyethylene glycol, polypropylene glycol or polypropylene glycol glyceryl esters
US7083801B2 (en) * 2002-07-18 2006-08-01 Rohm And Haas Company Stabilized haloalkynyl microbicide compositions
US7098279B2 (en) * 2002-10-22 2006-08-29 Loctite (R&D) Limited Non-flammable and non-combustible adhesive bonding systems having adherence to low energy surfaces
DE10256494A1 (de) 2002-12-03 2004-06-24 Basf Ag Stabilisierte Zusammensetzungen, enthaltend polyfunktionelle Aziridinverbindungen
CA2539185A1 (fr) * 2003-09-19 2005-03-31 Arch Chemicals, Inc. Compositions d'halopropynyle stabilisees en tant qu'agents de conservation
JP2005200612A (ja) * 2004-01-19 2005-07-28 National Institute Of Advanced Industrial & Technology 抗菌性樹脂成形品
DE102004037366A1 (de) 2004-07-30 2006-03-23 Lanxess Deutschland Gmbh 5-Iodtetrazole
DE102005042433A1 (de) 2005-09-07 2007-03-08 Lanxess Deutschland Gmbh Stabilisierung Iod haltiger Biozide
DE102006010199A1 (de) 2006-03-06 2007-09-13 Lanxess Deutschland Gmbh Stabilisierung Iod-haltiger Biozide durch spezielle Azolverbindungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010142790A1 *

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EP2440044A2 (fr) 2012-04-18
MX2011013350A (es) 2012-04-10
JP5619153B2 (ja) 2014-11-05
JP2012529473A (ja) 2012-11-22
AU2010258635A1 (en) 2012-02-02
CN102497776A (zh) 2012-06-13
BRPI1013119A2 (pt) 2015-09-15
US9328065B2 (en) 2016-05-03
WO2010142795A3 (fr) 2012-04-26
AU2010258560A1 (en) 2012-02-02
CN102497776B (zh) 2015-02-11
WO2010142795A2 (fr) 2010-12-16
WO2010142790A1 (fr) 2010-12-16
BRPI1013118A2 (pt) 2015-09-15
US20120178804A1 (en) 2012-07-12
RU2012100242A (ru) 2013-07-20
US20150087700A1 (en) 2015-03-26
CN102458106A (zh) 2012-05-16
MX2011013351A (es) 2012-04-10
JP2012529474A (ja) 2012-11-22

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