EP1858936A1 - Dispersions aqueuses a base de polymeres comportant des substances a effet, leurs procedes de preparation et leur utilisation - Google Patents

Dispersions aqueuses a base de polymeres comportant des substances a effet, leurs procedes de preparation et leur utilisation

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Publication number
EP1858936A1
EP1858936A1 EP05715913A EP05715913A EP1858936A1 EP 1858936 A1 EP1858936 A1 EP 1858936A1 EP 05715913 A EP05715913 A EP 05715913A EP 05715913 A EP05715913 A EP 05715913A EP 1858936 A1 EP1858936 A1 EP 1858936A1
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EP
European Patent Office
Prior art keywords
polymer
effect
molecular weight
butene
average molecular
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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Application number
EP05715913A
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German (de)
English (en)
Inventor
Rainer Dyllick-Brenzinger
Alban Glaser
Matthias Bratz
Christian Krüger
Felix Christian GÖRTH
Günter OETTER
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BASF SE
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BASF SE
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Publication of EP1858936A1 publication Critical patent/EP1858936A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins

Definitions

  • the invention relates to effect-containing aqueous polymer dispersions having an average particle diameter of the dispersed particles of ⁇ 1000 nm, process for preparing the aqueous polymer dispersions by miniemulsion polymerization, wherein a solution of at least one effect substance in at least one ethylenically unsaturated monomer and a hydrophobic organic compound in the presence emulsifying at least one surfactant in water to a miniemulsion having a mean droplet size ⁇ 500 nm and then radically polymerizing the miniemulsion, and using polymers containing effectants to stabilize polymers against the action of UV radiation, oxygen and / or heat cosmetic or pharmaceutical formulations, in lacquer coatings, in the manufacture of paper, leather or textiles, in formulations for animal nutrition and in formulations for agriculture and forestry chaft.
  • aqueous polymer dispersions which contain functional substances such as in particular UV absorbers or epoxy resins. They are prepared by dissolving the functional substances in an unsaturated monomer, emulsifying this solution in water in the presence of a surfactant to form a monomer emulsion with average particle sizes between 5 and 500 nm and polymerizing the miniemulsion in the presence of a free-radical initiator.
  • the aqueous dispersions containing the functional substances such as UV absorbers, epoxy resins, acrylic-based polymers, phenolic resins, unsaturated polyesters, phenol-based substances, and petroleum resins are used as a binder and as an additive for protective films.
  • WO 99/40123 discloses a process for the preparation of aqueous polymer dispersions whose dispersed polymer particles contain an organic dye homogeneously, ie distributed in a molecular dispersion.
  • aqueous dispersions are prepared by miniemulsion polymerization by polymerizing ethylenically unsaturated monomers containing an organic dye dissolved in the form of an oil-in-water emulsion in the presence of radical-forming polymerization initiators, the disperse phase of the emulsion substantially consisting of dye-containing monomer droplets is formed with a diameter ⁇ 500 nm.
  • monomer mixtures which contain crosslinking monomers are used in the polymerization.
  • the polymer dispersions are sedimentation-stable.
  • the dispersed particles have a mean particle diameter of 100 to 400 nm. They can be obtained from the aqueous dispersions using conventional drying methods.
  • the dye-containing For example, polymer dispersions are used for the pigmentation of high molecular weight organic and inorganic materials, for the pigmentation of printing inks and inks for ink-jet printing.
  • colorant-containing polymer dispersions whose colorant-containing polymer particles have an average particle diameter of less than 1000 nm are known from EP-A 1 191 041. Suitable colorants are, in addition to organic dyes, UV absorbers and optical brighteners.
  • They are prepared by dissolving a colorant in at least one ethylenically unsaturated monomer, emulsifying this solution in water to form a conventional macroemulsion, homogenizing the macroemulsion to form a miniemulsion having an average droplet size below 1000 nm, and polymerizing the miniemulsion in the presence of a radical Polymerization initiator, 0.1 to 20 wt .-% of at least one nonionic surface-active compound and 1 to 50 wt .-%, in each case based on the monomers used, at least one amphiphilic polymer produced.
  • the polymer particles contain 0.5 to 50 wt .-%, at least one organic dye, optical brightener or UV absorber homogeneously distributed, which is to be understood that the organic colorants are dissolved in the polymer matrix monomolecular or in the form of bi- or higher molecular weight Aggregates are present.
  • WO 01/10936 discloses particles having a core / shell structure are known, in which the core 9 from below 4O 0 C and a UV absorber comprises a polymer having a glass transition temperature T and the shell preferably consists of a polymer of methyl acrylate, ethyl acrylate, Ethyl methacrylate and / or methyl methacrylate.
  • the polymer that forms the core of the particle may optionally be crosslinked.
  • the polymer particles are prepared by emulsion polymerization.
  • the UV absorber-containing polymer particles are used to make UV-absorbing polymer compositions.
  • aqueous polymer dispersions containing alkyldiketenes are known, which are obtainable by miniemulsion polymerization of hydrophobic monoethylenically unsaturated monomers in the presence of alkyldiketenes.
  • This Dis- Persions are used as sizing agents for paper, as water repellents for leather, natural and / or synthetic fibers and textiles.
  • PCT / EP / 05/0308 relates to aqueous polymer dispersions containing alkyenylsuccinic anhydrides, which are prepared by miniemulsion polymerization of hydrophobic monoethylenically unsaturated monomers in the presence of alkylenylsuccinic anhydrides.
  • the dispersions are used as bulk and doctorsnlei- mungsstoff for paper and for the hydrophobization of leather, natural and / or synthetic fibers and textiles.
  • the polymer particles of the polymer powders have a particle size of 500 nm or below. They are preferably prepared by miniemulsion polymerization by methods which are known from the abovementioned publications
  • the polymer particles contain 0.5 to 50 wt .-% of at least one UV absorber, which is present either homogeneously distributed in molecular or nanocrystalline form or completely or even partially surrounded by the polymer matrix.
  • the prior application 10 2004 012 576.7 discloses aqueous polymer dispersions containing effect substances having an average particle diameter of the dispersed particles of ⁇ 500 nm, wherein the polymer particles comprise a polymer matrix composed of at least one ethylenically unsaturated monomer as the core, on the surface of which at least partially Effect substance is arranged, which is soluble in the monomers which form the polymer matrix of the particles.
  • These polymer dispersions are prepared by first preparing a miniemulsion by emulsifying ethylenically unsaturated monomers in water in the presence of at least one effect substance and a surface-active agent having an average particle size of the emulsified particles of ⁇ 500 nm and thus polymerizing them in a radical manner. initially polymerize only a maximum of 50% of the monomers which are in the polymerization zone and the effect substances migrate to the surface of the emulsified particles, and the polymerization only after substantially or complete accumulation of the effect substances on the surface of the resulting polymer. particles to an end.
  • the dispersions thus obtainable and the polymer powders resulting therefrom by evaporation of the volatile constituents are used, for example, for stabilizing polymers against the effects of UV radiation, oxygen and heat, in cosmetic and pharmaceutical formulations, in lacquer coatings, in the production of paper, leather and textiles and used in formulations for animal nutrition.
  • pesticides which have low solubility in water are often formulated in the form of aqueous suspensions or emulsions. While emulsions usually still contain organic solvents, suspensions are usually formulated solvent-free. In these suspensions, the active ingredient is in the form of fine particles with particle sizes in the micron range.
  • an aqueous active substance composition which comprises at least one fungicidal organic active substance having a water solubility of not more than 5 g / l at 25 ° C and 1013 mbar and a finely divided polymer having an average particle size of not has more than 300 nm, wherein the polymer particles contain the active ingredient.
  • the polymer is at least 60% by weight of at least one neutral, monoethylenically unsaturated monomer having a water solubility of not more than 30 g / l at 25 ° C and up to 40% by weight, based in each case on the total amount of monomers of another ethylenically unsaturated monomer.
  • Such active ingredient compositions are obtainable by free-radical aqueous emulsion polymerization of an oil-in-water emulsion of the ethylenically unsaturated monomers containing at least one fungicidal active ingredient and optionally an insecticidal active ingredient.
  • the stability of the aqueous dispersions however, still needs to be improved.
  • the present invention has for its object to provide more effect substances containing aqueous polymer dispersions available, the effect substances in the release the respective application controlled, or provide the effect substances migration stable and / or protect them from decomposition.
  • the object is achieved according to the invention by means of effect-containing, aqueous polymer dispersions having an average particle diameter of the dispersed particles of ⁇ 1000 nm, wherein the polymer particles comprise a polymer matrix composed of at least one ethylenically unsaturated monomer and at least one effect substance present in the ethylenically unsaturated monomers, from which the polymers are built, is soluble, when the dispersed polymer particles at least 0.1 wt .-% of at least one polymer from the group
  • Hexene-1 having an average molecular weight M w of 100 to 10,000, (ii) the copolymers of at least two of the monomers mentioned under (i) with an average molecular weight M w of 100 to 10,000 and / or
  • the invention furthermore relates to a process for the preparation of finely divided aqueous polymer dispersions containing effect substances having an average particle diameter of the dispersed particles of ⁇ 1000 nm by miniemulsion polymerization, wherein a solution of at least one effect substance in at least one ethylenically unsaturated monomer and a hydrophobic organic compound emulsified in the presence of at least one surfactant in water to a miniemulsion having a mean droplet size ⁇ 500 nm and then radically polymerizing the miniemulsion when, as a hydrophobic organic compound
  • the particle sizes of the finely divided polymer specified here are weight-average particle sizes, as can be determined by dynamic light scattering. Processes for this are familiar to the person skilled in the art, for example from H. Wiese in D.
  • the average particle size is preferably in the range of 10 to 250 nm, in particular in the range of 20 to 200 nm, more preferably in the range of 30 to 150 nm and most preferably in the range of 30 to 100 nm.
  • effect substances are to be understood as products which are selected, for example, from the group of UV absorbers, organic dyes which absorb light in the visible range, IR dyes, optical brighteners, stabilizers and auxiliaries for organic polymers, antioxidants for polymers , Antifogging agents for polymers, lubricants for polymers, antistatics for polymers, flame retardants for polymers, reactive sizing agents for paper, pharmaceutical agents, biocides and agroactive agents.
  • the candidate effect substances are soluble in the ethylenically unsaturated monomers which form the core of the polymer particles of the aqueous dispersion.
  • the solubility of the effect substances in the monomers is at a temperature of 25 ° C.
  • the amount of effect substances present in the dispersed polymer particles is, for example, 0.5 to 60% by weight, preferably 10 to 40% by weight, and most often in the range of 10 to 30% by weight, in each case on the polymer matrix.
  • mini-emulsion polymerization of ethylenically unsaturated monomers in the presence of oil-soluble dyes is known, for example, from WO 99/40123 cited in the prior art. Because of the details of this polymerization is particularly noted on page 3, line 30 to page 38, line 6 and page 69, line 11 to page 84, line 43 of WO 99/40123. This part of the WO
  • UV absorbers are commercial products. They are sold, for example, under the trademark Uvinul® by BASF Aktiengesellschaft, Ludwigshafen. Under UV absorbers are known to UV-absorbing compounds that disable the absorbed radiation without radiation. UV absorbers absorb light of wavelength ⁇ 400 nm and convert it into heat radiation. Such compounds are used, for example, in sunscreens and for stabilizing tion of organic polymers used.
  • UV absorbers are derivatives of p-aminobenzoic acid, in particular their esters, for example ethyl 4-aminobenzoate and ethoxylated ethyl 4-aminobenzoate, salicylates, substituted cinnamates (cinnamates) such as octyl p-methoxycinnamate or 4-isopentyl-4-methoxycinnamate, 2 Phenylbenzimidazole-5-sulfonic acid and its salts.
  • a particularly preferred UV absorber is 4-n-octyloxy-2-hydroxybenzophenone.
  • Further examples of UV absorbers are:
  • substituted acrylates e.g. Ethyl or isooctyl- ⁇ -cyano- ⁇ - ⁇ -diphenylacrylate (mainly 2-ethylhexyl- ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate), methyl- ⁇ -methoxycarbonyl- ⁇ -phenylacrylate, methyl- ⁇ -methoxycarbonyl- ⁇ -Cp-methoxyphenyl acrylate, methyl or butyl ⁇ -cyano- ⁇ -methyl- ⁇ - (p-methoxyphenyl) acrylate, N- ( ⁇ -methoxycarbonyl- ⁇ -cyanovinyl) -2-methylindoline, octyl-p-methoxycinnamate, isopentyl 4-methoxycinnamate, urocaninic acid and its salts and esters;
  • Ethyl or isooctyl- ⁇ -cyano- ⁇ - ⁇ -diphenylacrylate mainly 2-
  • 2-hydroxybenzophenone derivatives e.g. 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4,4' - dimethoxy-2-hydroxybenzophenone and 4-methoxy-2-hydroxybenzophenone-sulfonic acid sodium salt;
  • Esters of 4,4-diphenylbutadiene-1, 1-dicarboxylic acid e.g. the bis (2-ethylhexyl) ester;
  • benzotriazoles and 2- (2'-hydroxyphenyl) benzotriazoles such as 2- (2H-benztriazol-2-yl) -4-methyl-6- (2-methyl-3- ((1,1,3,3 tetramethyl- (trimethylsilyloxy) disiloxanyl) propyl) phenol, 2- (2'-hydroxy-5'-methylphenyl) benztriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benztriazole, 2- [2'-hydroxy-5 l - (1,1,3,3-tetramethylbutyl) phenyl] benztriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 I-hydroxy-5'-methylphenyi)
  • Benzylidene camphor and its derivatives as described, for. As mentioned in DE-A 38 36 630, e.g. 3-Benzylidene camphor, 3 (4'-methylbenzylidene) d-1-camphor;
  • Dibenzoylmethanes e.g. 4-tert-butyl-4'-methoxydibenzoylmethane
  • 2,4,6-triaryltriazine compounds such as 2,4,6-tris ⁇ N- [4- (2-ethylhex-1-yl) oxycarbonylphenyl] amino ⁇ -1,3,5-triazine, 4,4 ' - ((6- ((tert.
  • Suitable UV absorbers are also described in lines 14 to 30 on page 6 of EP-A 1 191 041.
  • organic dyes which absorb light in the visible range
  • optical brighteners which dissolve in ethylenically unsaturated monomers and which themselves are not polymerizable.
  • Such dyes and optical brighteners are described in detail in the state of the art WO 99/40123, page 10, line 14 to page 25, line 25, which is hereby expressly referred to again.
  • organic dyes have an absorption maximum in the wavelength range from 400 to 850 nm
  • optical brighteners have one or more absorption maxima in the range from 250 to 400 nm.
  • Optical brighteners emit fluorescence radiation in the visible range when irradiated with UV light.
  • optical brighteners are compounds from the classes of bisstyrylbenzenes, stilbenes, benzoxazoles, coumarins, pyrenes and naphthalenes.
  • Commercially available optical brighteners are sold under the trademarks Tinopal® (Ciba), Ultraphor® (BASF Aktiengesellschaft) and Blankophor® (Bayer).
  • Optical brighteners are also described in Römpp, 10th Ed., Vol. 4, 3028-3029 (1998) and in Ulimanns, Encyclopedia of Industrial Chemistry, Vol. 24, 363-386 (2003).
  • the stabilizers are compounds that stabilize polymers against degradation upon exposure to oxygen, light or heat. They are also referred to as antioxidants or as UV and light stabilizers, cf. Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 3, 629-650 (ISBN-3-527-30385-5) and EP-A 1 110 999, page 2, line 29 to page 38, line 29. Such stabilizers can be used in practice all organic polymers are stabilized, cf. EP-A 1 110 999, page 38, line 30 to page 41, line 35. This reference is also made by reference to the disclosure of the present invention.
  • the stabilizers described in the EP application belong to the compound class of the pyrazolones, the organic phosphites or phosphonites, the sterically hindered phenols and the sterically hindered amines (stabilizers of the so-called HALS type, see Römpp, 10th edition, Vol 5, pages 4206-4207
  • Auxiliary agents are, for example, substances which at least largely prevent the fogging of foils and molded parts made of plastics, so-called antifogging agents
  • Commercially customary stabilizers and auxiliaries are marketed under the trademarks Tinuvin® and Cysorb® from Ciba and Tenox® by Eastman Kodak Stabilizers and auxiliaries are described, for example, in Plastics Additives Handbook, 5th edition, Hanser publishing house, ISBN 1-56990-295-X.
  • the stabilizers and auxiliaries are soluble in ethylenically unsaturated monomers, with at least 1 g / l, preferably at least 10 g / l dissolving at a temperature of 25 ° C. and a pressure of 1013 mbar.
  • IR dyes which are sold, for example, by BASF Aktiengesellschaft as Lumogen® IR
  • flame retardants which are described, for example, in Römpp, 10th edition, pages 1352 and 1353 and in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 53-71.
  • the flame retardants in question are soluble in ethylenically unsaturated monomers.
  • anti-fogging additives for polymers from which, in particular, sheets or films are produced are described, for example, by F. Wylin, in Plastics Additives Handbook, 5th Edition, Hanser, ISBN 1-56990-295-X, pages 609-626.
  • Suitable effect substances are lubricants for polymers such as oxidized polyethylene waxes and antistatics for polymers.
  • lubricants for polymers such as oxidized polyethylene waxes and antistatics for polymers.
  • antistatic agents cf. the aforementioned reference F. WyNn, Plastics Additives Handbook, pp. 627-645.
  • effect substances should also be understood to mean reactive sizing agents for paper, such as alkyldiketenes and alkenylsuccinic anhydrides.
  • Alkyl diketene is used as a mass sizing agent in the manufacture of paper, board and cardboard.
  • These effect substances are essentially Cu to C 22 alkyldiketenes such as stearyl diketene, palmityldiketene, behenyldiketene, oleyldiketene and mixtures of the diketones. They are soluble in ethylenically unsaturated monomers.
  • Alkenyl succinic anhydrides are also used in the manufacture of paper and paper products as engine sizing agents in the art.
  • sizing agents are the isomeric 4-, 5-, 6-, 7- and 8-hexadecenylsuccinic anhydrides, decenylsuccinic anhydride, octenylsuccinic anhydride, dodecenylsuccinic anhydride and n-hexadecenylsuccinic anhydride, cf. also CE. Farley and RB Water, The Sizing of Paper, Second Edition, (3), Sizing With Alkenyl Succinic Anhydride, TAPPI PRESS, 1989, ISBN 0-89852-051-7.
  • compositions which are soluble or else colloidally soluble in ethylenically unsaturated monomers can be used as effect substances.
  • pharmaceutical active substances should also be understood to mean vitamins. Vitamins are soluble in ethylenically unsaturated monomers. A summary of vitamins can be found for example in Römpp, 10th Edition, Volume 6, page 4877-4887 (1999) and Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 38, 109-294.
  • Other suitable effect substances are perfumes, cf. Ulimanns, Encyclopedia of Industrial Chemistry, Vol. 14, 73-199, and biocides, cf. Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 5, 269-280.
  • Pesticides are known to those skilled in the literature.
  • the term "pesticide” as used herein means at least one active ingredient selected from the group of insecticides, fungicides, herbicides, growth regulators and safeners (see Pesticide Manual, 13th Ed. (2003)).
  • the pesticide used as the active ingredient is an organic pesticide having a low water solubility of usually not more than 5 g / l, preferably not more than 3 g / l at 20 0 C and 1013 mbar.
  • the following list of insecticides shows, but is not limited to, possible drugs:
  • Organo (thio) phosphates such as acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyriphos-methyl, chlorfenvinphos, diazinon, dichlorophos, dicrotophos, dimethoate, disulfone, ethion, fenitrothion, fenthione, isoxathione, malathion, methamidophos, methidathion , Methyl parathion, mevinphos, monocrotophos, oxy-demeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet,
  • Carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbosulfan, fennoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
  • Pyrethroids such as allethrin, bifenthrin, cyfluthrin, cyphenothrin, cypermethrin, alpha, beta, theta and zeta isomers, deltamethrin, esfenvalerate, ethofenopx, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, imiprothrin, permethrin, prallethrin , Pyrethrin I, Pyrethrin II, Silafluofen, Tau Fluvalinate, Tefluthrin, Tetramethrin, Tralomethrin, Transfluthrin, Zeta
  • Arthropod growth regulators such as a) chitin synthesis inhibitors; z. B. benzoylureas such as chlorofluorazuron, cyromacin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists such as halofenozide, methoxyfenozide, tebufenozide; c) juvenoid such as pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors such as spirodiclofen;
  • Neonicotinoid such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiomethoxam, nitenpyram, nithiazine, acetamiprid, thiacloprid;
  • Pyrazole insecticides such as Acetoprol, Ethiprol, Fipronil, Tebufenpyrad, Tolfenpyrad and Vaniliprol; Furthermore, abamectin, acequinocyl, amitraz, azadirachtin, bifenazate, cartap, chlorfenapyr, chlordimeform, cyromazine, diafenthiuron, diofenolan, emamectin, endosulfan, fenazaquin, formetanate, formetanate hydrochloride, hydramethyl non, piperonyl butoxide, pyridaben, pymetrozine, spinosad, thiamethoxam, thio cyclam, pyridalyl, flonicamid, fluacypyrim, milbemectin, spiromesifen, flupyrazofos, NC 512, tolfenpyrad, flub
  • Acyl alanines e.g. Benalaxyl, Furalaxyl, Metalaxyl, Ofurace, Oxadixyl;
  • amine derivatives e.g. Aldimorph, dodin, dodemorph, fenpropimorph, fenpropidin; Guazatine, iminoctadine, spiroxamine, tridemorph;
  • Anilinopyrimidines e.g. Pyrimethanil, mepanipyrim or cyrodinyl;
  • antibiotics e.g. Cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin; or streptomycin, validamycin A;
  • Azoles e.g. Bitertanol, bromuconazole, cyazofamide, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, etridazole, fenbuconazole,
  • Fluquiconazole Fluquiconazole, flusilazole, flutriafol, fuberidazole, hexaconazole, hymexazole, imazalil, imibenconazole, metconazole, myclobutanil, penconazole, perfurazoate, propiconazole, prochlorazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, thiabendazole, triadimefon, triadimol, triflumizole, triticonazole, 5-chloro 7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluoro-phenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6 -iodo-3-propyl-chromen-4-one, 3- (3-bromo-6-fluoro-2-methylindole-1-sulfony
  • Dicarboximides e.g. Iprodione, mycelozolin, procymidone, vinclozolin;
  • Heterocyclic compounds e.g. Anilazine, Benomyl, Boscalid, Carbendazim, Carboxin, Oxycarboxin, Cyazofamide, Dazomet, Dithianone, Ethirimol,
  • Nitrophenyl Derivatives e.g. Binapacryl, dinocap, dinobutone, nitrophthaloisopropyl;
  • phenylpyrroles e.g. Fenpiclonil or fludioxonil;
  • Organic phosphorus compounds e.g. Edifenphos, Iprobenfos, Pyrazophos;
  • Other fungicides for example acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, dazomet, diclomethine, diclocymet, diethofencarb, ethaboxam, fenhexamide, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, Metrafenone, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozen, zoxamide, isoprothiolane, Probenfos, fluopicolide (picobenzamide); Carpropamide, mandipropamide, N-
  • R 1 and R 2 are independently halogen, methyl or halomethyl; stand
  • Strobilurins e.g. Azoxystrobin, Dimoxystrobin, Enestroburin, Fluoxastrobin,
  • Sulfenic acid derivatives e.g. Captafol, captan, dichlofluanid, folpet, tolylfluanid;
  • Cinnamic acid amides and analogs e.g. Dimethomorph, Flumetover or Flumorph
  • Amide Fungicides e.g. Cyclofenamide or (Z) -N- [ ⁇ - (cyclopropylmethoxyimino) -2,3-difluoro-
  • herbicides The following list of herbicides indicates, but is not limited to:
  • ALS inhibitors such as amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethoxysulfuron, flazasulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, lodosulfuron, mesosulfuron, metsulfuron, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, Pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, imazamethabenz, imazamox, imazapic, imazapyr
  • Protoporphyrinogen IX oxidase inhibitors such as acifluorfen, bifenox, chlomethoxyfen, chlornitrofen, ethoxyfen, fluorodifene, fluoroglycofen, fluoronitrofen, fomesafen, furyloxyfen, halosafen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen, fluazolates, pyrafluids, cinidon-ethyl, flumiclorac , Flumioxazine, flumipropyne, fluthiacet, thidiazimine, oxadiazon, oxadiargyl, azafenidine, carfentrazone, sulfentrazone, pentoxazone, benzfendzone, butafenacil, pyraclonil, profluazole, flufenpyr, flupropacil, nipyraclo
  • Herbicides such as metflurazon, norflurazon, flufenican, diflufenican, picolinafen, beflubutamide, fluridone, flurochloridone, flurtamone, mesotrione, sulcotrione, isoxachlorotol, isoaflutole, benzofenap, pyrazolynate, pyrazoxyfen, benzobicyclone, amitrole, clomazone, aclonifen, 4- (3 Trifluoromethylphenoxy) - 2- (4-trifluoromethylphenyl) pyrimidine and 4-heterocyclyl-substituted benzoyl derivatives of the formula (see WO 96/26202, WO 97/41116, WO 97/41117 and WO 97/41118)
  • R 8 to R 13 have the following meaning: R 8, R 10 is hydrogen, halogen, C 1 -C 6 -AIRyI, Ci-Ce-haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 - haloalkoxy, dC 6 -alkylthio, d-Ce-alkylsulfinyl or dC 6 alkylsulfonyl;
  • R 9 represents a heterocyclic radical selected from the group consisting of thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 4,5 - Dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl and 4,5-dihydroisoxazol-5-yl, wherein said radicals may carry one or more substituents, for example, mono-, di-, tri- or tetrasubstituiert by halogen, C 1 -C 4 -AIk ⁇ , C 1 -C 4 -alkoxy, C 1 -C 4 - haloalkyl, -C 4 -haloalkoxy or C 1 -C 4 -alkylthio;
  • R 11 hydrogen, halogen or C r C 6 alkyl
  • R 12 d-Ce-alkyl
  • R 13 hydrogen or C 1 -C 6 -A ⁇ yI.
  • EPSP synthase inhibitors such as glyphosate
  • Glutamine synthase inhibitors such as glufosinate and bilanaphos
  • DHP synthase inhibitors such as asulam
  • Mitosis inhibitors such as Benfluralin, Butraline, Dinitramine, Ethalfluralin, Fluchloralin, i-Sopropalin, Methalpropalin, Nitralin, Oryzalin, Pendimethalin, Prodiamin, Profluralin, Trifluralin, Amiprofos-methyl, Butamifos, Dithiopyr, Thiazopyr, Propyzamide, Tebutam, Chlorthal, Carbetamide, Chlorobufam, Chlorpropham and Propham;
  • VLCFA inhibitors such as acetochlor, alachlor, butachlor, butenachlor, delachlor, diethyl, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prynachlor, terbuchlor, thenylchloride, xylachlor, Allidochlor, CDEA, epronaz, diphenamid, napropamide, naproanilide, pethoxamide, flufenacet, mefenacet, fentrazamide, anilofos, piperophos, cafenstrol, indanofan, and tridiphan;
  • Cellulose biosynthesis inhibitors such as dichlobenil, chlorthiamide, isoxaben and flupoxam;
  • Herbicides such as dinofenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, etinofen and medinoterb;
  • Auxin herbicides such as Clomeprop, 2,4-D, 2,4,5-T, MCPA, MCPA thioethyl, dichlorprop, dichlorprop-P, mecoprop, mecoprop-P, 2,4-DB 1 MCPB, Chloramben, Dicamba, 2 , 3,6- TBA, tricamba, quinclorac, quinmerac, clopyralid, fluroxypyr, picloram, triclopyr and benazoline;
  • Auxin transport inhibitors such as Naptalam, Diflufenzopyr;
  • safener has the following meaning: It is known that in some cases better herbicidal compatibility can be achieved by the combined application of specifically acting herbicides with organic active compounds, which themselves can have a herbicidal action. In these cases, these compounds act as antidote or antagonist and are referred to as “safeners” due to the fact that they reduce or prevent damage to crops.
  • a single effect substance or two or more effect substances are used for the production of the products according to the invention.
  • a mixture of a UV absorber and an organic dye which absorbs light in the visible range can be used in the process according to the invention, or - As already mentioned above - incorporate a fungicide and an insecticide in the polymers of the aqueous dispersion.
  • Suitable combinations of effect substances are: All organic effect substances which are destroyed by UV-Vis radiation, ie vitamins, agroactive substances, antioxidants, biocides, active pharmaceutical ingredients, etc., can be protected by a protective cover or simply by the proximity of a UV absorber become. Biocides, in combination with all organic effect substances, can protect them from infestation with microorganisms. The biocides can be protected by the wrapping with polymer before disintegration. Perfume in a polymer matrix can ensure that unpleasant odors are covered over a long period of time.
  • the polymer matrix of the dispersed particles is essentially made of a polymer
  • Hexene-1 having an average molecular weight M w of 100 to 10,000, (ii) the copolymers of at least two of the monomers mentioned under (i) with an average molecular weight of 100 to 10,000 and / or (iii) medium molecular weight polyisobutylene M w of at least 100
  • the water solubility of the monomers in each case refers to the solubility of the monomers in water at a temperature of 25 0 C and a pressure of 1013 mbar.
  • the dispersed polymer particles contain in most cases at least 80 wt .-% of a polymer
  • Hexene-1 having an average molecular weight M w of 100 to 10,000, (ii) the copolymers of at least two of the monomers mentioned under (i) with an average molecular weight of 100 to 10,000 and
  • the suitable monomers (a), (b) and (c) are described in detail in WO 99/40123, page 4, line 41 to page 10, line 12, to which reference is again made at this point.
  • individual monomers of groups (a) to (c) are to be mentioned, namely as monomers of group (a) styrene, ⁇ -methyl styrene, vinyl acetate, vinyl propionate, dimethyl maleate, maleic acid diethyl ester, esters of ethylenically unsaturated C 3 bis C 5 carboxylic acids and monohydric alcohols having 1 to 6 carbon atoms and allyl acetate.
  • the monomers (a) also include those monomers A ' which have an increased water solubility, ie> 60 g / l at 25 ° C. and 1013 mbar.
  • the monomers A ' are used to modify the polymers and are usually involved in amounts of from 0.1 to 20 wt .-%, preferably from 0.5 to 10 wt .-% in the construction of the polymer matrix.
  • Examples of these monomers are acrylic acid, methacrylic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and vinylphosphonic acid and cationizable monomers such as dimethylaminoethyl acrylate, dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide or 1-vinylimidazole and N-vinylformamide, acrylonitrile, methacrylonitrile, acrylamide, Methacrylamide and N-vinylpyrrolidone.
  • the basic monomers are used in the form of the free bases, as a salt or in quaternized form in the polymerization.
  • the acid group-having monomers can be used in the form of the free acids or in the partially or completely neutralized with alkali metal bases or ammonium bases in the polymerization.
  • Suitable monomers of group (b) are, for example, 2- and 4-methylstyrene, p-tert-butylstyrene, esters of ethylenically unsaturated C 3 - to C 5 -carboxylic acids and alcohols having more than 12 C atoms in the molecule, vinyl laurate, Vinyl stearate and macromonomers such as oligopropene acrylate.
  • Examples of monomers of group (c) are glycol diacrylate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrytate, pentaerythritol tetraacrylate, butanediol diacrylate, divinylbenzene, divinylurea and methylenebisacrylamide.
  • the polymer matrix of the dispersed polymer particles may be a polymer
  • Hexene-1 having an average molecular weight M w of 100 to 10,000, (ii) the copolymers of at least two of the monomers mentioned under (i) with an average molecular weight of 100 to 10,000 and
  • the polymer matrix consists of a polymer
  • Hexene-1 having an average molecular weight M w of 100 to 10,000, (ii) the copolymers of at least two of the monomers mentioned under (i) with an average molecular weight of 100 to 10,000 and (iii) polyisobutylene having an average molecular weight M w of at least 100.
  • the polymer of the monomers (a) and (c) is then included in the polymer particles, for example, in an amount of 99.8 to 80 wt .-%, while the polymers (i), (ii) and (iii) to 0, 2 to 20 wt .-% are contained in the polymer particles.
  • the polymer matrix of the water-dispersed particles preferably contains at least 80% by weight of a copolymer obtained by polymerizing
  • polyisobutylene having an average molecular weight M w of at least 100 is obtainable.
  • the polymer particles then contain the polymer of the monomers (a) and (c) in an amount of 99.8 to 80, preferably 99.5 to 90 wt .-%.
  • the aqueous polymer dispersions according to the invention contain dispersed particles having an average particle diameter ⁇ 1000 nm, usually ⁇ 500 nm, for example 5 to 450 nm, preferably 10 to 300 nm and in particular 50 to 250 nm.
  • the polymer particles consist essentially of a polymer matrix and at least one effect substance.
  • the effect substance can for example be distributed homogeneously in the polymer matrix or be present in the form of domains in the polymer particle.
  • the particles according to the invention may also be composed of a core and a shell, wherein the core of the particles contains at least one effect substance which is enveloped by a shell of a polymer matrix.
  • FIG. This is an electron micrograph of a section on a powder sample obtained from an aqueous polymer dispersion by distilling off the water.
  • the effect substance is arranged therein in the core of the dispersed particles.
  • aqueous polymer dispersions whose dispersed polymer particles are obtained by miniemulsion polymerization of (a) methyl methacrylate, ethyl acrylate, and / or acrylic acid
  • Hexene-1 having an average molecular weight M w of 100 to 1000
  • polyisobutylene having an average molecular weight M w of at least 100 and at least one UV absorber, in particular 4-n-octyloxy-2-hydroxybenzophenone, are obtainable.
  • the monomers are used in the polymerization, for example in amounts such that the resulting dispersed polymer particles
  • the polymers may also contain a monomer (c) in copolymerized form. If it is used, it is used, for example, in an amount of 0.1 to 30 wt .-%, in particular 0.5 to 20, usually 1 to 10 wt .-%, based on the total monomers used in the polymerization.
  • polymers of group (i) are low molecular weight homopolymers of ethylene, propylene, butene-1, pentene-1 and hexene-1.
  • polymers of group (i) are low molecular weight homopolymers of ethylene, propylene, butene-1, pentene-1 and hexene-1.
  • oligomers of ethylene such as, in particular, polymers containing 8 or 12 carbon atoms per molecule, for example from Shell under the trademark Neodene® and from BP as alpha-olefin, for example AO 2026, and from Chevron-Phillips Corporation.
  • Compound (i) also comes from the company Exxon-Mobil tetramer propene and offered by the company Oxeno tetra-butene into consideration.
  • the compounds (i) contain a double bond. They have an average molecular weight M w of 100 to 10,000, preferably 150 to 2,000.
  • Examples of compounds (ii) are copolymers of ethylene and propylene, copolymers of ethylene and butene-1, copolymers of ethylene and butene-2, copolymers of ethylene and hexene-1, copolymers of propylene and butene-1 and copolymers of propylene , Butene-1 and butene-2 and other combinations. These copolymers also contain an ethylenically unsaturated double bond. They have, for example, average molecular weights M w of 100 to 10,000, preferably 150 to 2,000.
  • the compounds of group (iii) are preferably used in the preparation of the polymer dispersions of the invention.
  • the suitable polyisobutylene for example, has an average molecular weight M w of at least 100, preferably at least 150.
  • the average molar masses M w are, for. Most often, the average molecular weight M w of the contemplated polyisobutylenes is at least 400, and is preferably in the range of 500 to 4,000.
  • polymer particles of the invention are at least two containing various polymers, namely at least one polymer of the abovementioned monomers (a) and optionally (b) and optionally (c) and at least one polyisobutylene in an amount of at least 0.1 wt .-%, usually 0.2 to 20 and preferably 0.5 to 10 wt .-%.
  • Suitable polyisobutylenes are commercially available. Examples include the Glissopal® brands and Oppanol® grades from BASF Aktiengesellschaft, such as Glissopal® 550, Glissopal® 1000, Glissopal® 1300, Glissopal® 2300, Oppanol B10 and B12. Polyisobutylene is produced, for example, by cationic polymerization of isobutene under BF 3 catalysis. These polyisobutylenes have a high content of ⁇ -olefin groups, which is for example at least 80%, preferably at least 85%.
  • the polydispersity index (PDI), ie the ratio of weight-average and number-average molecular weight, is in the range from 1.05 to 10, preferably in the range of 1.05 to 5, and more preferably in the range of 1.05 to 2.0.
  • the method of determination of the polydispersity (PDI) and the number and weight average molecular weight is described for example in the Analytical Paperback, Volume 4, pages 433 to 442, Berlin 1984.
  • aqueous dispersions which are, for example, at least one polymer from the group
  • novel aqueous polymer dispersions having an average particle diameter of the dispersed polymer particles of ⁇ 1000 nm are prepared by miniemulsion polymerization of ethylenically unsaturated monomers.
  • one proceeds by first dissolving at least one effect substance in at least one monomer.
  • the effect substances are dissolved in most cases monomolecular, but can also be dissolved colloidally dispersed.
  • the monomer solutions containing effect substances are then emulsified in water in the presence of at least one surface-active agent.
  • insoluble microparticles or nanoparticles may also be used as stabilizers for the emulsion in water and / or the monomers.
  • Stabilizers of this type are, for example, nanoscale silica, alumina and magnesium sulfate. A miniemulsion with an average droplet size of the emulsified droplets of ⁇ 500 nm is obtained.
  • Emulsification is carried out by methods described in detail in WO 99/40123, page 26, line 11 to page 32, line 4.
  • high-pressure homogenizers of different types are used for emulsifying, or ultrasound is allowed to act on a macroemulsion containing as essential constituents at least one effect substance dissolved in at least one monomer and water, cf. EP-A-0 765 896, EP-A-1 008 380.
  • the mixture is emulsified in the presence of a surfactant.
  • they are, as described above, first dissolved in at least one monomer and emulsified in dissolved or colloidally dissolved form in water.
  • the aqueous phase used to prepare the miniemulsions consists of water and optionally contains a surface-active agent which stabilizes the finely divided monomer droplets formed in the emulsion of the organic phase in the aqueous phase.
  • the surface-active agent is used, for example, in amounts of up to 15% by weight, for example from 0.05 to 15% by weight, preferably from 0.05 to 5% by weight and in particular from 0.1 to 2% by weight. , in each case based on the total dispersion used. It is found either in the aqueous phase, the organic phase or in both phases. It is preferably added to the aqueous phase prior to emulsification. In principle, all surface-active agents can be used.
  • Preferred surface-active agents are anionic and / or nonionic surfactants and amphiphilic polymers having average molecular weights M.sub.w of, for example, 1000 to 100,000.
  • suitable surface-active agents are sodium lauryl sulfate, sodium dodecylsulfate, sodium hexadecylsulfate, sodium dioctylsulfosuccinate and / or addition products of from 15 to 50 mol Ethylene oxide and / or Propyle- noxid to 1 mole of a Ci 2 - to C 22 -alcohol.
  • the miniemulsion can be stabilized with the aid of amphiphilic polymers, which are optionally used.
  • amphiphilic polymers are used, they are used in amounts of, for example, from 0.05 to 15% by weight, preferably from 0.5 to 5% by weight, based on the monomers used in the polymerization.
  • amphiphilic polymers are copolymers comprising units of
  • (a) are, for example, styrene, methylstyrene, ethylstyrene, acrylonitrile, methacrylonitrile, C 2 - to C 18 -olefins, esters of monoethylenically unsaturated C 3 - to C 5 - carboxylic acids and monohydric alcohols, vinyl alkyl ethers, vinyl esters or their
  • Isobutene, diisobutene, styrene and acrylic esters such as ethyl acrylate, isopropyl acrylate, n-butyl acrylate and sec-butyl acrylate are preferably used from this group of monomers.
  • amphiphilic copolymers contain as hydrophilic monomers
  • the acidic monomers may be in the form of the free acids or in partially or completely neutralized form.
  • hydrophilic monomers are basic monomers. They can be polymerized with the hydrophobic monomers (a) alone or in admixture with the acidic monomers mentioned above. When mixtures of basic and acidic monomers are used, amphoteric copolymers are formed, which are anionically or cationically charged, depending on the molar ratio of the copolymerized acidic to basic monomers.
  • Basic monomers are, for example, di-C 1 to C 2 -alkylamino-C 2 to C 4 -alkyl (meth) acrylates or diallyldimethylammonium chloride.
  • the basic monomers may be in the form of the free bases, the salts with organic or inorganic acids, or in the form quaternized with alkyl halides.
  • the salt formation or the quaternization, at which the basic monomers become cationic, can be partial or complete.
  • Examples of such compounds are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, diethylaminopropyl methacrylate, diethylaminopropyl acrylate and / or dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and / or diallyldimethylammonium chloride.
  • amphiphilic copolymers in the form of the free acid are not sufficiently water-soluble, they are used in the form of water-soluble salts, for example using the corresponding alkali metal, alkaline earth metal and ammonium salts.
  • These salts are prepared, for example, by partial or complete neutralization of the free acid groups of the amphiphilic copolymers with bases, eg For neutralization, sodium hydroxide solution, potassium hydroxide solution, magnesium oxide, ammonia or amines such as triethanolamine, ethanolamine, morpholine, triethylamine or butylamine are used.
  • the acid groups of the amphiphilic copolymers are neutralized with ammonia or sodium hydroxide solution.
  • the water solubility of basic monomers or of copolymers which contain such monomers in copolymerized form can be increased by partial or complete neutralization with a mineral acid such as hydrochloric acid or sulfuric acid or by addition of an organic acid such as acetic acid or p-toluenesulfonic acid.
  • a mineral acid such as hydrochloric acid or sulfuric acid
  • an organic acid such as acetic acid or p-toluenesulfonic acid.
  • the molecular weight of the amphiphilic copolymers is for example 1000 to 100,000 and is preferably in the range of 1500 to 10,000.
  • the acid numbers of the amphiphilic copolymers are, for example, 50 to 500, preferably 150 to 350 mg KOH / g of polymer.
  • Copolymers are particularly preferably used as stabilizer for the miniemulsion, which
  • the copolymers may contain polymerized units of maleic monoesters as further monomers (c).
  • Such copolymers are obtainable, for example, by copolymerizing copolymers of styrene, diisobutene or isobutene or mixtures thereof with maleic anhydride in the absence of water and reacting the copolymers with alcohols after the polymerization, with from 5 to 50 per mole of anhydride groups in the copolymer Mol% of a monohydric alcohol.
  • Suitable alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol.
  • polyhydric alcohols such as glycol or glycerol.
  • the reaction is carried out only to the extent that only one OH group of the polyhydric alcohol reacts with the anhydride group. If the anhydride groups of the copolymers are not completely reacted with alcohols, the ring opening of the non-reacted with alcohols anhydride groups by addition of water.
  • Suitable stabilizers for miniemulsions compounds are, for example, commercially available polymers of monoethylenically unsaturated acids and Graft polymers of N-vinylformamide on polyalkylene glycols, which are described for example in WO 96/34903.
  • the grafted vinylformamide units may optionally be up to 10% hydrolyzed.
  • the proportion of grafted vinylformamide units is preferably from 20 to 40% by weight, based on polyalkylene glycol. Polyethylene glycols having molecular weights of 2,000 to 10,000 are preferably used.
  • zwitterionic polyalkylenepolyamines and zwitterionic polyethyleneimines are suitable for stabilizing miniemulsions.
  • Such compounds are known, for example, from EP-B-0 112 592. They are obtainable, for example, by first alkoxylating a polyalkylene polyamine or polyethyleneimine, e.g. with ethylene oxide, propylene oxide and / or butylene oxide and the alkoxylation products are then quaternized, e.g. with methyl bromide or dimethyl sulfate and the quaternized, alkoxylated products then sulfatiert with chlorosulfonic acid or sulfur trioxide.
  • the molecular weight of the zwitterionic polyalkylenepolyamines is, for example, 1000 to 9000, preferably 1500 to 7500.
  • the zwitterionic polyethyleneimines preferably have molecular weights in the range from 1500 to 7500 daltons.
  • the other stabilizers mentioned above are optionally used except for a surfactant to stabilize the miniemulsion. If used, they are used, for example, in amounts of 0.05 to 15 wt .-%, preferably 0.5 to 5 wt .-%, based on the monomers.
  • a nonpolymerizable hydrophobic compound eg a hydrocarbon
  • an alcohol of 10 to 24 carbon atoms e.g. 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol, 1,3-butanediolstylstylstylsilanes and / or mixtures of the compounds mentioned.
  • Such stabilizers are hexadecane, Dekahydronaphtha- lin, olive oil, polystyrene having an average molecular weight M w of 500 to 50,000, siloxanes having a molecular weight M w of 500 to 5000, poly-n-butyl acrylate such as Acronal® A 150 F, cetyl alcohol , Stearyl alcohol, palmityl alcohol and / or behenyl alcohol.
  • the hydrophobic, nonpolymerizable compounds are optionally used. They have a water solubility of ⁇ 0.1 g / l at 25 ° C and 1013 mbar. If used, they are used in amounts of 1 to 10, preferably 2 to 6 wt .-%, based on the monomers used in the polymerization.
  • the polymerization can optionally additionally be carried out in the presence of protective colloids.
  • protective colloids are polyvinyl alcohols, cellulose derivatives such as carboxymethylcellulose, polyvinylpyrrolidone, polyethylene glycols, graft polymers of vinyl acetate and / or vinyl propionate on polyethylene glycols, one or both sides polyethylene glycols which are end-capped with alkyl, carboxyl or amino groups, polydiallyldimethylammonium chlorides and / or polysaccharides, in particular water-soluble starches, starch derivatives and proteins.
  • starch e.g. both amylose and a mylopectin, native starches, hydrophobically or hydrophilically modified starches, anionic starches, cationically modified starches, degraded starches, wherein the starch degradation can be carried out, for example, oxidatively, thermally, hydrolytically or enzymatically, and wherein for the degradation of starch both native and modified starches can be used.
  • suitable protective colloids are dextrins and crosslinked water-soluble starches which are water-swellable.
  • the average molecular weight M w of the degraded starches is, for example, 500 to 100,000, preferably 1,000 to 30,000.
  • the degraded starches have, for example, an intrinsic viscosity [ ⁇ ] of 0.04 to 0.5 dl / g.
  • Such starches are described, for example, in EP-B-257 412 and EP-B 276 770.
  • protective colloids are used in the polymerization, the amounts used are, for example, from 0.5 to 50, in particular from 5 to 40, preferably from 10 to 30,% by weight, based on the monomers used in the polymerization.
  • the polymerization can optionally be carried out in the presence of at least one polymerization regulator.
  • polymerization regulators are organic compounds which contain sulfur in bonded form, such as dodecyl mercaptan, thiodiglycol, ethylthioethanol, di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropan.
  • the miniemulsion is radically polymerized.
  • the polymerization usually takes place in the presence of at least one free-radical polymerization initiator.
  • Suitable polymerization initiators are all compounds which can initiate a polymerization. These are essentially peroxides, hydroperoxides, azo compounds and redox catalysts. Examples of initiators can be found in WO-A-99/40123, page 32, line 45 to page 34, line 9.
  • the polymerization can also be triggered by the action of high-energy radiation such as UV or actinic or radioactive radiation, optionally working in the presence of at least one sensitizer.
  • the polymerization of the monomers in the miniemulsion can also be carried out electrochemically, by means of microwave radiation and / or by the action of ultrasound.
  • the polymerization temperature is, for example, 0 to 120 ° C., where it is carried out at temperatures above 100 ° C. under elevated pressure in pressure-tight apparatus. In most cases, polymerizing the mini-emulsion in the temperature range from 0 to 95 0 C.
  • the polymerization can be carried out, for example, so that initially only a maximum of 50% of the monomers which are in the polymerization zone are polymerized. If, during the polymerization, incompatibility occurs between the effect substances and the forming polymer, i. the effect substances are not soluble in the resulting polymer or the mixture of monomer, at least one compound (i), (ii) and / or (iii), in particular polyisobutylene and the polymer being formed, it may happen that the effect substances collect in the core of the resulting polymer particle and be enveloped by a shell of a polymer. One then only has to give the polymerizing system sufficient time for a separation of the effect substances to take place.
  • the polymerization is then brought to completion only after extensive or complete accumulation of the effect substances in the core of the resulting polymer particles.
  • the effect substances may optionally partly enter the aqueous phase, form domains in the polymer particle, migrate to the surface of the polymer particles or otherwise accumulate in the polymer.
  • the polymerization of the miniemulsion can also be carried out continuously, for example by introducing 5 to 30% of the miniemulsion to be polymerized, the polymerization starts and the remaining miniemulsion is metered in continuously or in portions under polymerization conditions.
  • (B) optionally at least one ethylenically unsaturated monomer B having a water solubility of ⁇ 0.01 g / l (at 25 ° C and 1013 mbar) and
  • crosslinkers according to (c), which can be used optionally, are either added in bulk, wherein the dosage can be done at the very beginning in the template - before the actual polymerization begins - in one go or else in the feed process. If at least two crosslinkers are used, these can be metered either as a mixture or separately from one another synchronously or else with a time delay.
  • the crosslinker can also be introduced into the miniemulsion together with the monomers. But it can also be emulsified in water and overall metered as emulsion feed or in feed mode. It is advantageous if at least one surfactant ensures the stability of the crosslinker emulsion.
  • the solids concentration of these aqueous dispersions is for example 10 to 60, preferably 20 to 45 wt .-%.
  • the aqueous polymer dispersions contain dispersed particles having an average particle diameter ⁇ 1000 nm, usually ⁇ 500 nm, for example 5 to 450 nm, preferably 10 to 300 nm and in particular 50 to 250 nm.
  • the polymer particles consist essentially of a polymer matrix and contain at least an effect substance, for example, a UV absorber or as active ingredient, a pesticide in an amount of 0.5 to 60 wt .-%. This amount corresponds to the amounts used in the oil phase of the miniemulsion.
  • the effect substances can, as already described above, for example be distributed homogeneously in the polymer matrix or be present in the form of domains in the polymer particles.
  • the dispersed particles may also be composed of a core and a shell, wherein the core of the particles contains at least one pesticide which is enveloped by a shell of a polymer matrix.
  • the effect substances can also partially or almost completely emerge from the polymer matrix. They are then in the form of particles with an average diameter of about 40 to 400 nm, which are stabilized with the aid of surfactants, in the aqueous phase.
  • the dispersions according to the invention and the polymer powders obtainable therefrom by evaporation of the liquid phase have the advantage that they release the effect substances in a controlled manner, ie the effect substances are released continuously over a relatively long period of time.
  • the effect substances are thus present in a matrix which is particularly advantageous for their application.
  • This fact applies in particular to those dispersions and polymer powders which contain a UV absorber, preferably 4-n-octyloxy-2-hydroxybenzophenone, or a pesticide, for example a fungicide, such as epoxiconazole.
  • polymer powders which contain as effect substance at least one antistat for polymers or an antifogging agent for polymers or at least one pesticide or at least one reactive sizing agent are also of interest.
  • aqueous polymer dispersions or the polymer particles containing them are used, for example, to stabilize polymers against the action of UV radiation, oxygen and heat, in cosmetic and pharmaceutical formulations, in enamel coatings, in the production of paper, Leather and textiles, in formulations for animal nutrition and in agrochemicals, eg used as part of pesticide-containing formulations for agriculture and forestry.
  • the aqueous dispersions or the polymer powders obtainable therefrom by evaporation of the volatile fractions and containing at least one pesticide are, for example, plant growth which is undesirable for controlling harmful microorganisms and / or regulating the growth of plants and / or controlling them and / or for controlling unwanted insect or mite infestation on plants and / or for controlling phytopathogenic fungi and / or for treating seed.
  • the aqueous dispersions or the polymer powders obtainable therefrom are preferably used in the form of the pesticide formulations customary for this application.
  • aqueous dispersions prepared according to the invention e.g. obtained by spray drying polymer powder containing as active ingredient at least one pesticide.
  • use is made of an aqueous dispersion for crop protection obtainable by polymerizing a miniemulsion containing at least one pesticide.
  • the method for controlling harmful microorganisms and / or for regulating the growth of plants and / or for controlling unwanted plant growth and / or for controlling undesirable insect or mite infestation on plants and / or for controlling phytopathogenic fungi and / or Treatment of seeds is characterized in that the fungi / insects, their habitat or the plants to be protected against fungal or insect infestation, the soil or seeds of crops or the undesirable plants are treated with an effective amount of the dispersions prepared by the process according to the invention , Controlling undesired plant growth means controlling / destroying plants that grow in places where they are undesirable, eg
  • Lepidoptera for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anti- carsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cececia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis
  • Beetles for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Coderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasi
  • Diptera for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomia bezziana, Chrysomya hominivorax, Chrysosomia macellaria, Contarina sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis , Gasterophilus intestinalis, Glossina morsitans, Haematobia irritants, Haplodiplosis equestris, Hyemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor
  • Thysanoptera for example, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, and Thrips tabaci;
  • Hymenoptera for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta;
  • Heteroptera for example Acrostemum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
  • Homoptera for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis cut, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachy- caudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia picaeae, Dysaphis radicola, Dys
  • Termites e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis;
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina Stauronotus maroccanus and Tachycines asynamorus;
  • Arachnoid for example Acarina, e.g. from the families Argasidae, Ixodidae and Sarcoptidae, e.g. Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • Acarina e.g. from the families Argasidae, Ixodidae and Sarcoptidae, e.g. Amb
  • Nematodes especially plant parasitic nematodes, egplant root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Star and foliar nematodes, Aphelenchoides species; Sting nematodes, Longolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursa- phelenchus xylophilus and other Bursaphelenchus species; Ring Nematodes, Criconema Species
  • rice pathogens such as e.g. rice water weevil (Lissorhoptrus oryzaphilus), rice stem borer (Chilo suppresalis), rice leaf roller, rice leaf beetle, rice leaf miner (Agromyca oryzae), leafhoppers (Nephotettix spp., green rice leafhopper), planthoppers ( Delphacidae; especially white backed plant hopper, brown rice planthopper), stinkbugs;
  • phytopathogenic fungi describes, but is not limited to, the following species:
  • the aqueous dispersions containing pesticidal compositions usually contain the active ingredient in the polymer particles in an amount of 5 to 50% by weight, in the case of a fungicide or herbicide / safener or growth regulator, or in an amount of 0.01 to 60% by weight .-%, if it is an insecticide.
  • pesticidal aqueous polymer dispersions obtainable by the process according to the invention may optionally contain further for the formulation contain suitable adjuvants, such as surfactants such as wetting agents, adhesives or dispersants, foam control agents, thickeners, carriers, antifreeze and bactericides.
  • suitable adjuvants such as surfactants such as wetting agents, adhesives or dispersants, foam control agents, thickeners, carriers, antifreeze and bactericides.
  • carriers are used, in particular in solid formulations, they are usually present in an amount of 0.1 to 99% by weight, preferably 10 to 80% by weight, in the formulations.
  • the amount of other auxiliaries in the formulations, if used, is, for example, from 0.1 to 40% by weight.
  • thickeners ie compounds which impart a pseudoplastic flow behavior to the formulation, ie high viscosity at rest and low viscosity in the agitated state
  • thickeners are, for example, polysaccharides or organic layer minerals such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (US Pat. Rhone Poulenc) or Veegum® (RT Vanderbilt) or Attaclay® (Engelhardt).
  • Suitable defoamers are, for example, silicone emulsions (for example Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides can be used, for example, for stabilizing aqueous pesticide formulations.
  • Suitable bactericides are, for example, Proxel® from the company ICI or Acticid® RS from Thor Chemie and Kathon® MK from Rohm & Haas.
  • Suitable antifreeze agents are e.g. Ethylene glycol, propylene glycol or glycerin.
  • Examples of carriers are ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg finely divided silica, silicates).
  • Examples of emulsifiers are nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and Dispersant as mentioned below.
  • surfactants are alkali, alkaline earth, ammonium salts of
  • formulation types include emulsifiable concentrates, suspensions, soluble concentrates, dispersible concentrates, pastes, pastilles, wettable powders, dusts (DP) or granules (GR, FG, GG, MG), which may be either water-soluble or dispersible .
  • Common formulation types for seed treatment are FS (flowable concentrates), LS (solutions), DS (powders for dry treat- ment), WS (water dispersible powders for slurry treatment), SS (water-soluble powders SS) and ES (emulsion).
  • granules are finely ground and combined with 95.5% excipients.
  • Common processes are extrusion, spray drying or fluidized bed. This gives granules for direct application.
  • emulsions, pastes or oil dispersions come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthal
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the aqueous polymer dispersions containing the active ingredients or the powder obtainable therefrom, for example by spray-drying, with a solid carrier.
  • Granules for example coated, impregnated and homogeneous granules, can be prepared by binding the products produced according to the invention to solid carriers become.
  • Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate , Ammonium nitrate, ureas and vegetable products such as cereal flour, bark, wood and nutshell flour, cellulose powder and other solid carriers. If necessary, the final product obtained can be dried before further processing.
  • mineral earths such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth
  • the present invention also includes seed treated with pesticidal aqueous polymer dispersions.
  • pesticide application rates of 0.1 to 10 kg / 100 kg of seed, preferably 1 to 5 kg / 100 kg, in particular 1 to 2.5 kg / 100 kg, are generally used.
  • aqueous dispersions comprising UV absorbers or the powders obtained therefrom are used in cosmetic formulations or for the stabilization of polymers, in particular films or shaped bodies of any shape from polymers such as polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyamide or polyester, against the action of UV radiation.
  • the stabilization of films against the action of UV radiation is particularly important for films used for greenhouses.
  • the products according to the invention which comprise a UV absorber can also be used for the stabilization of polymers from which shaped bodies of arbitrary shape are produced.
  • polymers are in particular polyethylene, polypropylene, acrylonitrile-butadiene-styrene polymers (ABS) and PVC.
  • ABS acrylonitrile-butadiene-styrene polymers
  • PVC polyvinyl-styrene polymers
  • Aqueous dispersions containing UV absorbers or the polymer powders obtained therefrom can also be used together with other dispersions according to the invention which contain, for example, stabilizers for polymers such as antioxidants for stabilizing polymers and lacquer layers.
  • Aqueous polymer dispersions containing alkyldiketenes and / or alkenylsuccinic anhydrides, which are obtainable according to the invention, or the polymer powder obtainable therefrom by drying, are used in the production of paper in the paper industry. added as a sizing agent.
  • Alkyldiketenes containing aqueous polymer dispersions are also used as surface sizing agents, wherein they are applied by means of a film or size press or a gate roll.
  • the percentages in the examples are by weight.
  • the droplet size of the miniemulsion was determined using a Coulter N4 Plus Particle Analyzer on 0.01% by weight samples of the emulsion.
  • the mean particle size of the dispersed polymer particles was determined with the aid of a Coulter LS 230 on 0.01% by weight samples of the aqueous dispersions.
  • This solution was then added to a solution of 4.8 g of a 15% aqueous sodium lauryl sulfate solution and 555.8 g of water and emulsified therein.
  • the macroemulsion thus prepared was then brought to a droplet size of about 200 nm by passing three times through an APV-Gaulin high pressure homogenizer (150 bar). This miniemulsion was storage stable.
  • This solution was then added to a solution of 6.8 g of a 15% aqueous sodium lauryl sulfate solution and 437.8 g of demineralized water and emulsified.
  • the macroemulsion thus prepared was then brought to a droplet size of about 200 nm by passing three times through an APV-Gaulin high pressure homogenizer (150 bar). This miniemulsion was storage stable.
  • aqueous polymer dispersion having an average particle diameter of the polymer particles of 61 nm was obtained.
  • the polymer particles enveloped the UV absorber. These were core-shell particles with the UV absorber in the core and the polymer in the shell.
  • This solution was then added to 4.6 g of a 15% aqueous solution of sodium lauryl sulfate in 537.62 g of demineralized water and emulsified.
  • the macroemulsion thus prepared was then brought to a droplet size of about 182 nm by means of ultrasound for 10 minutes. This miniemulsion was storage stable.
  • 196.34 g (24% of the total) of the miniemulsion were placed in a reactor and heated to 80 0 C. At 80 0 C then 6.9 g of a 2% aqueous solution of sodium persulfate were added all at once. Subsequently, 621, 8 g (76% of the total) of the miniemulsion and simultaneously 35.65 g of an aqueous emulsion consisting of 23 g of demineralized water, 1.15 g of a 15% aqueous sodium lauryl sulfate and 11, 5 g of pentaerythritol tetraacrylate within 60 minutes each.
  • reaction mixture was stirred for 30 minutes at 80 0 C, and then metered 108.1 g of a 2% aqueous solution of sodium persulfate for 60 minutes, stirred for a further 60 minutes at 80 0 C and then allowed to cool the dispersion to 25 ° C. , filtered through a 500 ⁇ m and a 125 ⁇ m mesh screen to remove the coagulum (about 0.3g).
  • This gave an aqueous polymer dispersion having an average particle diameter of the polymer particles of 178 nm.
  • the dispersion was storage-stable.
  • This solution was then added to 5.2 g of an aqueous 15% aqueous sodium lauryl sulfate solution in 711, 62 g of deionized water and emulsified.
  • the macroemulsion prepared in this way was then brought to a droplet size of about 194 nm in 10 minutes by means of ultrasound. This miniemulsion was storage stable.
  • aqueous polymer dispersion having an average particle diameter of the polymer particles of 176 nm was thus obtained.
  • Elmi images of pulverulent polymer particles obtained by drying the aqueous dispersion show that these are core-shell particles in which the antioxidant ( Irganox) in the nucleus and the polymer in the shell.
  • the dispersion was storage stable and had a good antioxidant effect. The migration of these particles into polymers was significantly lower than that of Irganox 1076 FF itself.
  • the aqueous polymer dispersion prepared according to Example 1 was dried to a powder (spray-drying). In a twin-screw extruder is then com- poundiert at a temperature of 200 0 C 96.88 parts of polyethylene (Lupolen® 1840 D) with 3.12 parts of the powder obtained in each case from the dispersions and then the granules are processed into a film having a thickness of 100 ⁇ m. The zero UV vis spectrum between 200 and 800 nm was first measured on this film. The film was then weathered according to ISO 4892-2. After the times indicated in the table, the transmission was measured at ⁇ max 265 nm. The results are given in the table.
  • Example 5 Analogously to Example 5, the aqueous dispersion prepared according to Example 2 was spray-dried and then incorporated into Lupolen® 1840 D. The results of the exposures of the film are shown in the table.
  • Example 5 was repeated with the exception that instead of the polymer powder, which was obtained from the aqueous dispersion prepared according to Example 5, now 0.5% of the powdered UV absorber 4-n-octyloxy-2-hydroxybenzophenone in Polyethylene, made a film therefrom, also weathered it to ISO 4892-2 and tested for transmission times given in the table.
  • the polymer powder which was obtained from the aqueous dispersion prepared according to Example 5
  • 0.5% of the powdered UV absorber 4-n-octyloxy-2-hydroxybenzophenone in Polyethylene made a film therefrom, also weathered it to ISO 4892-2 and tested for transmission times given in the table.
  • This solution was then added to a solution of 16 g of a 15% aqueous solution of sodium lauryl sulfate and 707.8 g of demineralized water and emulsified.
  • the macroemulsion thus prepared was then brought to a droplet size of about 200 nm by passing three times through an APV-Gaulin high pressure homogenizer (150 bar). This miniemulsion was storage stable.
  • This solution was then introduced into a 80 0 C hot solution of 20 g of a 15% aqueous sodium lauryl sulfate and 844.7 g of deionized water and emulsified.
  • the macro-emulsion thus prepared was then (150 bar) at 80 0 C to a droplet size by three times through an APV-Gaulin Hochdruckhomogeni-sator of about 200 nm accommodated. This miniemulsion was storage stable for only a short time.
  • aqueous polymer dispersion having a mean particle diameter of the polymer particles of 134 nm was obtained.
  • the dispersed particles contained virtually all of the epoxiconazole used in the polymerization.
  • the dispersion was storage stable.

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Abstract

La présente invention a trait à des dispersions aqueuses à base de polymères comportant des substances à effet, et ayant un diamètre moyen de particules inférieure à 1000 nm, les particules de polymère comportant une matrice polymérique comprenant au moins un monomère à insaturation éthylénique, au moins 0,1 % en poids d'un polymère choisi parmi le groupe (i) d'au moins un homopolymère d'éthylène, propylène, butène-1, butène-2, pentène-1 ou hexène-1, ayant une masse molaire moyenne Mw de 100 à 10,000, (ii) d'au moins un copolymère d'au moins deux des monomères spécifiés sous (i), ayant une masse molaire moyenne de 100 à 10,000, et/ou (iii) d'au moins polyisobutylène ayant une masse molaire moyenne égale ou supérieure à 100, et au moins une substance à effet qui est soluble dans les monomères à insaturation éthylénique à partir desquels les polymères sont synthétisés. L'invention a également trait à un procédé pour la préparation de telles dispersions à l'aide d'une polymérisation en miniémulsion, une solution d'au moins une substance à effet dans au moins un monomère à insaturation éthylénique et au moins un polymère selon (i), (ii) et/ou (iii) étant émulsionnée en présence d'au moins un tensioactif dans l'eau pour l'obtention d'une miniémulsion ayant une taille de gouttelettes moyenne inférieure à 500 nm, et la miniémulsion étant ensuite soumise à une polymérisation radicalaire. L'invention a trait en outre à l'utilisation des dispersions aqueuses à base de polymères susceptibles d'être ainsi obtenues ou des poudres à base de polymères obtenues à partir de celles-ci en vue de la stabilisation de polymères contre l'exposition au rayonnement ultraviolet, à l'oxygène ou à la chaleur, en tant que lubrifiants pour des polymères, dans des formulations cosmétiques ou pharmaceutiques, dans des enduits, dans la production de papier, de cuir ou de textiles, dans des formulations pour l'alimentation d'animaux, et dans des formulations pour l'agriculture et la sylviculture.
EP05715913A 2005-03-10 2005-03-10 Dispersions aqueuses a base de polymeres comportant des substances a effet, leurs procedes de preparation et leur utilisation Withdrawn EP1858936A1 (fr)

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US20080146448A1 (en) 2008-06-19
JP2008533222A (ja) 2008-08-21
CN101142242A (zh) 2008-03-12

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