EP2066702A1 - Particules contenant un additif polymère - Google Patents

Particules contenant un additif polymère

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Publication number
EP2066702A1
EP2066702A1 EP07820277A EP07820277A EP2066702A1 EP 2066702 A1 EP2066702 A1 EP 2066702A1 EP 07820277 A EP07820277 A EP 07820277A EP 07820277 A EP07820277 A EP 07820277A EP 2066702 A1 EP2066702 A1 EP 2066702A1
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EP
European Patent Office
Prior art keywords
monomers
polymer
particles
polymer additives
additives
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
EP07820277A
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German (de)
English (en)
Inventor
Rainer Dyllick-Brenzinger
Alban Glaser
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BASF SE
Original Assignee
BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to EP07820277A priority Critical patent/EP2066702A1/fr
Publication of EP2066702A1 publication Critical patent/EP2066702A1/fr
Withdrawn legal-status Critical Current

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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
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to particles based on ethylenically unsaturated monomers containing polymer additives and the use of these particles to provide organic polymers, in particular for stabilization against the action of UV radiation. Furthermore, the invention relates to aqueous polymer dispersions which contain such particles, as well as processes for the preparation of these polymer dispersions.
  • the present invention encompasses polymer powders which are obtainable from the abovementioned polymer dispersions and also polymer dispersions obtainable by re-dispersing the polymer powders.
  • No. 4,419,471 describes polymer compositions having a core of styrene / butadiene and an alkyl acrylate / methacrylate shell.
  • the core of styrene / butadiene is used as a seed latex.
  • the core contains antioxidants and is at least partially surrounded by a closed shell.
  • the shell contains a copolymerized UV stabilizer.
  • WO 01/10936 describes polymeric particles having a core-shell structure whose core contains a UV absorber.
  • the UV absorber can either be chemically incorporated into the polymeric core or attached to the polymeric core or dispersed in the core.
  • the preparation of the polymeric particles disclosed in the Examples takes place without seed latex.
  • WO 05/102044 discloses aqueous, fungicidal active ingredient compositions and their use for controlling harmful microorganisms.
  • the compositions contain a finely divided polymer having a mean pond size of less than 300 nm.
  • the finely divided polymers are obtained by emulsion polymerization of ethylenically unsaturated monomers prepared, inter alia, also in the presence of a seed latex.
  • the active ingredient contained in the particles is released from the particles when used to control microorganisms.
  • the prior art teachings therefore offer the alternative of chemically incorporating the ingredients as comonomers into the polymers or attempting to encapsulate them in the core of core-shell particles ,
  • both measures either limit the choice of possible content substances, or sometimes lead to insufficient long-term effects.
  • TeN chen which are obtainable by aqueous emulsion polymerization of ethylenically unsaturated monomers M in the presence of polymer additives and seed latices, wherein the monomers M
  • the particles have an average particle size of at most 500 nm.
  • Terms of the form C 3 -Cb in the context of this invention designate chemical compounds or substituents with a certain number of carbon atoms. The number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a. Further specification of the chemical compounds or substituents is made by terms of the form C 3 -Cb-V. V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • the particles are prepared on the basis of ethylenically unsaturated monomers M.
  • the monomers M may all be the same or different. If all monomers M are the same, then the polymer prepared from them consists of homopolymers, while in the case of different monomers M, the polymer consists of copolymers.
  • the particles according to the invention comprise one or more polymers of the monomers M. The particles can thus also contain mixtures of identical or different homopolymers or copolymers.
  • Suitable monomers M are in principle all ethylenically unsaturated monomers which can be polymerized by the method of aqueous emulsion polymerization.
  • a subset of M are the neutral, ethylenically unsaturated and substantially water-insoluble monomers M1.
  • the monomers M1 are preferably monounsaturated with respect to the ethylenic group.
  • the monomers M1 may all be the same or different.
  • Monomers M suitable monomers M1 include vinyl aromatic monomers such as styrene, vinyl ethers, esters of monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 12 and in particular 3 or 4 carbon atoms with Ci-Ci2-alkanols or Cs-Cs-cycloalkanolen, in particular the esters of acrylic acid, of methacrylic acid, of crotonic acid, of the diesters of maleic acid, of fumaric acid or of itaconic acid and particularly preferably the esters of acrylic acid with C 2 -C 12 -alkanols, which are referred to as C 2 -C 12 -alkyl acrylates, such as Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, 3-propylheptyl acryl
  • Suitable monomers M1 are also vinyl or allyl esters of aliphatic carboxylic acids having 2 to 10 carbon atoms, for example vinyl acetate, vinyl propionate, and the vinyl esters of Versatic® acids (vinyl versatates), vinyl halides such as vinyl chloride or vinylidene chloride, conjugated diolefins such as butadiene or isoprene and C2-C6 olefins such as ethylene, propene, 1-butene or n-hexene.
  • vinyl halides such as vinyl chloride or vinylidene chloride
  • conjugated diolefins such as butadiene or isoprene
  • C2-C6 olefins such as ethylene, propene, 1-butene or n-hexene.
  • Preferred monomers M1 are vinylaromatic monomers, in particular styrene, C 2 -C 12 -alkyl acrylates, in particular C 2 -C 8 -alkyl acrylates or C 1 -C 12 -alkyl methacrylates, vinyl acetate, vinyl ethers and methacrylonitrile or acrylonitrile.
  • the particles are preferably composed of from 60 to 100% by weight, based on the total amount of monomers M, preferably from 70 to 100% by weight and more preferably from 80 to 100% by weight, of monomers M1.
  • the specified solubilities for example water solubilities, are measured under normal conditions, at a temperature of 25 ° C. and a pressure of 1013 mbar.
  • the solubilities of the monomers are determined, for example, by dropping monomer into deionized water until a visually apparent phase boundary is formed.
  • the monomers M1 are largely water-insoluble. Therefore, the monomers M1 preferably have a water solubility of not more than 30 g / l. In particular, the water solubility of the monomers M1 under these conditions is from 0.05 to 20 g / l.
  • the monomers M further comprise ethylenically unsaturated, at least partially water-soluble monomers M2.
  • the monomers M comprise from 0.01 to 40% by weight, based on the total amount, of the monomers M, preferably optionally from 0.01 to 30% by weight, optionally in particular from 0.01 to 20% by weight.
  • monomers M2 other than monomers M1.
  • the sum of the proportions of monomers M1 and M2 gives 100% by weight, based on the total amount of monomers M, if only monomers M1 and M2 are used for the monomers M.
  • the monomers M2 have a water solubility of at least 50 g / l and in particular at least 100 g / l.
  • the solubility of the monomers M2 in M1 can vary. In general, with low polarity of monomer M1, little monomer M2 will dissolve in M1, but this can be readily determined by simple solubility experiments.
  • the monomers M2 include, in particular, monoethylenically unsaturated monomers M2a which have a water solubility of at least 50 g / l and in particular at least 100 g / l and which have at least one acid group or at least one anionic group, in particular monomers M2a which contain a sulfonic acid group, a phosphonic acid group or one or two carboxylic acid groups, as well as the salts of the monomers M2a, in particular the alkali metal salts, for.
  • monomers M2a which contain a sulfonic acid group, a phosphonic acid group or one or two carboxylic acid groups, as well as the salts of the monomers M2a, in particular the alkali metal salts, for.
  • the sodium or potassium salts and ammonium salts as the sodium or potassium salts and ammonium salts.
  • ethylenically unsaturated sulfonic acids in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloxyethanesulfonic acid or 2-methacryloxyethanesulfonic acid, 3-acryloxy- or 3-methacryloxypropanesulfonic acid, vinylbenzenesulfonic acid or salts thereof, ethylenically unsaturated phosphonic acids, such as vinylphosphonic acid or vinylphosphonic acid.
  • Cs-Cs mono- or C4-C8 dicarboxylic acids in particular acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid.
  • the optional proportion of mo- Mere M2a is often not more than 35 wt .-%, based on the total amount of the monomers M, preferably not more than 20 wt .-%, z. B. 0.01 to 20 wt .-% and in particular 0.01 to 15 wt .-% account.
  • Preferred monomers are acrylic and methacrylic, and itaconic acid and their alkali metal salts.
  • the monomers M2 furthermore include the monoethylenically unsaturated, neutral, at least partially water-soluble monomers M2b which have a water solubility of at least 50 g / l and in particular at least 100 g / l.
  • Examples of these are the amides of the abovementioned ethylenically unsaturated carboxylic acids, in particular acrylamide or methacrylamide, hydroxyalkyl esters of the abovementioned ⁇ , ⁇ -ethylenically unsaturated Cs-Cs monocarboxylic acids or C4-C8 dicarboxylic acids, in particular hydroxyethyl acrylate, hydroxyethyl methacrylate, 2- or 3- Hydroxypropyl acrylate, 2- or 3-hydroxypropyl methacrylate, esters of the abovementioned monoethylenically unsaturated mono- or dicarboxylic acids with C 2 -C 4 -polyalkylene glycols, in particular the esters of these carboxylic acids with polyethylene glycol or alkyl polyethylene glycols, where the (alkyl) polyethylene glycol Usually has a molecular weight in the range of 100 to 3000.
  • the monomers M2b also include N-vinylamides such as N-vinylformamide, N-vinylpyrrolidone, N-vinylimidazole or N-vinylcaprolactam.
  • Preferred monomers M2b are acrylamide, metacrylamide, vinyl laccetate or vinyl propionate.
  • the optional proportion of the monomers M2b is preferably not more than 20 wt .-%, based on the total amount of the monomers M, and in particular not more than 10 wt .-%, z. B. 0.01 to 10 and in particular 0.01 to 5 wt .-% make up.
  • the monomers M2 furthermore include monoethylenically unsaturated, at least partially water-soluble monomers M2c which have a water solubility of at least 50 g / l and in particular at least 100 g / l and which have at least one cationic group and / or at least one protonatable group in the aqueous ,
  • the monomers M2c include, in particular, those which have a protonatable amino group, a quaternary ammonium group, a protonatable imino group or a quaternized imino group. Examples of monomers having a protonatable imino group are N-vinylimidazole or vinylpyridines.
  • monomers having a quaternized imino group are N-alkylvinylpyridinium salts or N-alkyl-N'-vinylimidazolinium salts, such as N-methyl-N'-vinylimidazolinium chloride or monosulphate.
  • monomers M2c in particular the monomers of the general formula I are preferred wherein
  • R 1 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
  • R 2 , R 3 independently of one another are C 1 -C 4 -alkyl, in particular methyl, and
  • R 4 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
  • A is C 2 -C 8 alkylene, e.g. B. 1, 2-ethanediyl, 1, 2 or 1, 3-propanediyl,
  • X represents an anion equivalent, for example halides such as Ch, BF 4 ", HSO 4 ", / 4 SO 4 2" or CH 3 OSO 3 -,
  • Examples of such monomers are 2- (N, N-dimethylamino) ethyl acrylate, 2- (N 1 N-dimethylamino) ethyl acrylate methochloride, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-dimethylamino ) ethylacrylamide, 3- (N, N-dimethylamino) propylacrylamide, 3- (N, N-dimethylamino) propylmethacrylamide, 2- (N, N-dimethylamino) ethylmethacrylamide, 2- (N, N, N-trimethylammonium) ethyl methacrylate chloride, 2- (N, N, N, N trimethylammonium) ethyl methacrylamide chloride, 3- (N, N 1 NT rimethylammonium) propyl acrylamide chloride, 3- (N, N, N 1 NT rimethyl
  • the monomers M comprise at least one monomer M2c.
  • the proportion of the monomers M2c is then advantageously not more than 20 wt .-%, based on the total amount of the monomers M, in particular 0.01 to 10 wt .-%, and particularly preferably 0.01 to 7 wt .-%.
  • the monomers M as monomers M1, methyl methacrylate, acrylonitrile, or mixtures thereof, and optionally as monomers M2a acrylic acid, methacrylic acid, mixtures thereof, or their salts or salts of the mixtures, and optionally as monomers M2b acrylamide, Methacrylamide, or mixtures thereof, and optionally as monomers M2c 3- (N, N-dimethylamino) propylmethacrylamid, 2- (N, N-dimethylamino) - ethyl acrylate, mixtures thereof, or their acid adducts or the acid adducts of the mixtures.
  • the monomers M as monomers M1, methyl methacrylate, acrylonitrile, or mixtures thereof, and as monomers M2a acrylic acid, methacrylic acid, mixtures thereof, or also their salts or salts of the mixtures, and optionally as monomers M2b acrylamide, Methacrylamide, or mixtures thereof, and optionally as monomers M2c 3- (N, N-dimethylamino) propylmethacrylamid, 2- (N, N-dimethylamino) - ethyl acrylate, mixtures thereof, or their acid adducts or the acid adducts of the mixtures.
  • the monomers M include all ethylenically unsaturated monomers which can usually be used in an aqueous emulsion polymerization.
  • monomers having two or more non-conjugated ethylenically unsaturated double bonds can be used as monomers M.
  • the proportion of monomers M having two or more nonconjugated, ethylenically unsaturated double bonds usually makes up not more than 5% by weight, in particular not more than 2% by weight, eg. B. 0.01 to 2 wt .-% and in particular 0.05 to 1, 5 wt .-%, based on the total amount of the monomers M, from.
  • the amount of monomers M1 is 100% by weight, based on the total amount of monomers M.
  • the proportions of the monomers M1 to M2 are from 60 to 99.99% by weight to from 0.01 to 40 % By weight, in each case based on the total amount, of the monomers M.
  • the proportions of the monomers M1 to M2 are preferably from 70 to 99.99% by weight of
  • the amounts of the monomers M1 to M2 are particularly preferably from 80 to 99.99% by weight to from 0.01 to 20% by weight, in each case Of course, based on the total amount of monomers M.
  • the total amount of monomers M1 and M2 is 100% by weight, which corresponds to the total amount of monomers M.
  • the proportion of the monomers M2a and M2b and M2c is in each case not more than 20% by weight, and in total not more than 40% by weight, based on the total amount of the monomers M.
  • aqueous emulsion polymerization monomer mixtures which contain crosslinking monomers M, such as allyl acrylate, allyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate Trimethylolpropane trimethacrylate, butadiene, divinylbenzene, di-vinylurea or methylenebisacrylamide.
  • crosslinking monomers M such as allyl acrylate, allyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaeryth
  • crosslinkers sold by Sartomer under the following names: CN435, SR415, SR454, SR499, SR502: ethoxylated trimethylolpropane triacrylates; SR593: ethoxylated pentaerythritol triacrylate; SR9019: propoxylated glyceryl triacrylate; SR351M: trimethylolpropane triacrylate; SR9021: highly propoxylated glyceryl triacrylate; SR9020: propoxylated glyceryl triacrylate; SR492: propoxylated trimethylolpropane triacrylate; SR368: tris (2-hydroxyethyl) isocyanurate triacrylate; SR355: di-trimethylolpropane tetraacrylate; SR399, SR399 LV: dipentaerythritol pentaacrylate; SR494: ethoxylated
  • the particles of the invention have a glass transition temperature Tg of at least 10 0 C, preferably at least 20 0 C and in particular at least 30 0 C.
  • the glass transition temperature will not exceed a value of 180 ° C., and more preferably 130 ° C.
  • the particles according to the invention are prepared by step polymerization and thus present as core-shell particles, or in the form of mixtures of different particles, the proportion of particles having a glass transition temperature of at least 10 ° C., preferably at least 20 ° C. and in particular at least 30 ° C, for example, at least 40 wt .-%.
  • the glass transition temperature Tg is understood here to be the midpoint temperature determined by differential thermal analysis (DSC) in accordance with ASTM D 3418-82 (compare Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A 21, VCH Weinheim 1992, p A. Zosel, color and paint 82 (1976), pp. 125-134, see also DIN 53765).
  • DSC differential thermal analysis
  • X 1 , X 2 , ..., X n is the mass fractions of the monomers 1, 2, ..., n and T 9 1 , T 9 2 , ..., T 9 "the glass transition temperatures of each of only one of Monomers 1, 2, ..., n of polymers (homopolymers) in degrees Kelvin, the latter being known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p Brandrup, EH Immergut, Polymer Handbook 3rd ed., J. Wiley, New York 1989.
  • the average particle size of the particles according to the invention is at most 500 nm.
  • the particle size distribution of the primary particles can be multi- but also monomodal. The distribution can be narrow or wide depending on the reaction conditions.
  • the average particle size is preferably in the range from 10 to 450 nm, in particular in the range from 20 to 400 nm, particularly preferably in the range from 30 to 350 nm and very particularly preferably in the range from 40 to 300 nm.
  • the particle sizes given here are weight-average particle sizes as they can be determined by dynamic light scattering. Methods for this purpose are familiar to the person skilled in the art, for example from H. Wiese in D.
  • polymer additives are not understood to mean active ingredients such as fungicides, herbicides, insecticides or pharmaceutical active ingredients.
  • the equipment of organic polymers also means the stabilization of organic polymers using the polymer additives.
  • the polymer additives contained in the particles according to the invention are either all the same or different.
  • polymer additives encompasses a single polymer additive and mixtures of polymer additives
  • the water solubility of the substantially water-insoluble polymer additives is typically not more than 5 g / l, often not more than 3 g / l and especially not more than 1 g / l 0.001 g / l to 1 g / l, in particular 0.002 to 0.5 g / l
  • the solubility of the polymer additives in the monomers M1 depends on the details of the chemical nature of the polymer additives and can therefore vary within wide limits
  • the polymer additives may be partly present in the monomers M1, preferably in a small proportion, even in dispersed form Polymer additives are usually soluble in the monomers M1 and slightly soluble in the monomers M2 a -c.
  • polymer additives are to be understood as meaning, in particular, UV absorbers, stabilizers, auxiliaries, dyes or reactive sizing agents for paper.
  • Stabilizers include UV, light stabilizers or antioxidants for organic polymers.
  • Adjuvants include antifogging agents for organic polymers, lubricants for organic polymers, antistatics for organic polymers, or flame retardants for organic polymers.
  • Dyes include organic dyes that absorb light in the visible range, IR dyes or optical brighteners. Classification of the polymer additives into one of the above groups is not exclusive, i. The individual polymer additives can definitely develop several effects, for example as a stabilizer and as an aid.
  • the suitable polymer additives are soluble according to the invention in the monomers M1.
  • the solubility of the polymer additives in the monomers M1 is, for example, at least 1 g / l, preferably at least 10 g / l.
  • the amount of polymer additives present in the 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, based in each case on the total weight of the particles.
  • UV absorbers are often commercial products. They are sold, for example, under the trademark Uvinul® by BASF Aktiengesellschaft, Ludwigshafen.
  • the Uvinul® sunscreens include compounds of the following classes: benzophenones, benzotriazoles, cyanoacrylates, monomeric or oligomeric hindered amines (HALS).
  • 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, alone or in mixtures with other light stabilizers in sunscreens and for the stabilization of organic polymers.
  • UV absorbers are derivatives of p-aminobenzoic acid, especially their esters, e.g. 4-aminobenzoic acid ethyl ester or ethoxylated ethyl 4-aminobenzoate, salicylates, substituted cinnamates (cinnamates) such as octyl-p-methoxycinnamate or 4-iso-pentyl-4-methoxycinnamate, 2-phenylbenzimidazole-5-sulfonic acid or its salts.
  • a particularly preferred UV absorber is 4-n-octyloxy-2-hydroxibenzo-phenone.
  • Further examples of UV absorbers are:
  • substituted acrylates such as, for example, ethyl or isooctyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate (mainly 2-ethylhexyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate), methyl ⁇ -methoxycarbonyl- ⁇ -phenylacrylate, methyl ⁇ -methoxycarbonyl- ⁇ - (p-methoxyphenyl) acrylate, methyl or butyl ⁇ -cyano- ⁇ -methyl- ⁇ - (p-methoxyphenyl) acrylate, N- ( ⁇ -methoxycarbonyl- ⁇ -cyanovinyl) -2-methylindoline, octyl-p-methoxycinnamate, isopentyl-4-methoxycinnamate, urocanic acid or salts thereof or esters;
  • 2-hydroxybenzophenone derivatives e.g. 4-hydroxy, 4-methoxy, 4-octyloxy, 4-deoxyloxy, 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;
  • Benzylidene camphor or its derivatives as described, for. B. in DE-A 38 36 630 are called, for example, 3-Benzylidencampher, 3 (4'-methylbenzylidene) d-1-camphor; ⁇ - (2-oxoborn-3-ylidene) toluene-4-sulfonic acid or its salts, N, N, N-trimethyl-4- (2-oxo-born-3-ylidenemethyl) anilinium monosulfate;
  • 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-butyl) aminocarbonyl) phenylamino) -1, 3,5-triazine-2,4-diyl) imino) bis (benzoic acid 2'-ethylhexyl ester);
  • UV absorbers can be found in the document Cosmetic Legislation, Vol. 1, Cosmetic Products, European Commission 1999, pp. 64-66, to which reference is hereby made.
  • Suitable UV absorbers are also described in lines 14 to 30 on page 6 of EP-A 1 191 041. These are incorporated by reference.
  • stabilizers for organic polymers are further considered.
  • the stabilizers are compounds that stabilize organic 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 1 10 999, page 2, line 29 to page 38, line 29. With such stabilizers virtually all organic polymers can be stabilized, cf.
  • the stabilizers described in the EP application belong to the class of compounds of pyrazolones, organic phosphites or phosphonites, sterically hindered phenols and sterically hindered amines (stabilizers of the so-called HALS type or HALS stabilizers, see Römpp, 10th edition, US Pat. Volume 5, pages 4206-4207.
  • auxiliaries for organic polymers are, for example, substances which at least largely prevent the fogging of films or molded parts made of plastics, so-called anti-fogging agents.
  • anti-fogging agents are also suitable as polymer additives. Such polymer additives are described, for example, by F. WyNn, in Plastics Additives Handbook, 5th Edition, Hanser, ISBN 1-56990-295-X, pages 609-626.
  • Suitable polymer additives are lubricants such as oxidized polyethylene waxes and antistatic agents for organic polymers. Examples of antistatic agents cf. the aforementioned reference F. WyNn, Plastics Additives Handbook, pp. 627-645.
  • polymer additives are flame retardants which are described, for example, in Römpp, 10th edition, pages 1352 and 1353 and in Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 14, 53-71.
  • stabilizers and adjuvants are sold, for example, under the trade names Tinuvin® and Cyasorb® by Ciba and Tenox® by Eastman Kodak. Stabilizers and auxiliaries are described, for example, in Plastics Additive Handbook, 5th Edition, Hanser Verlag, ISBN 1-56990-295-X.
  • the stabilizers and auxiliaries are soluble in the monomers M1, with at least 1 g / l, preferably at least 10 g / l dissolving.
  • organic dyes that absorb light in the visible range, or optical brighteners.
  • optical brighteners are described in detail in the prior art WO 99/40123, page 10, line 14 to page 25, line 25, which is incorporated herein by reference. While 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. Examples of optical brighteners are compounds from the classes of bisstyrylbenzenes, stilbenes, benzoxazoles, coumarins, pyrenes and naphthalenes.
  • 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 Ullmanns, Encyclopedia of Industrial Chemistry, Vol. 24, 363-386 (2003). Further suitable polymer additives are IR dyes, which are sold for example by BASF Aktiengesellschaft as Lumogen® IR. Lumogen® dyes include compounds of the classes of perylenes, naphthalimides, or quaterylenes.
  • Polymer additives are also to be understood as meaning reactive sizing agents for paper, such as alkyldiketenes and alkenylsuccinic anhydrides.
  • Alkyldiketenes are used as engine sizing agents in the manufacture of paper, board and board.
  • These polymer additives are essentially C 1 -C 22 -alkyldiketenes, such as stearyldiketene, palmityldiketene, behenyldiketene, oleyldiketene and mixtures of the diketenes.
  • 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 or n-hexadecenylsuccinic anhydride, cf. also C.E. Farley and R.B. Water, The Sizing of Paper, Second Edition, (3), Sizing With Alkenyl Succinic Anhydride, TAPPI PRESS, 1989, ISBN 0-89852-051-7, pages 51-62.
  • the polymer additives may be distributed in any manner in the particles of the invention or on their surface.
  • the polymer additives may be homogeneously distributed in the particles or present in the form of aggregates in the particle.
  • the polymer additives may be located primarily in the core or shell of the particles.
  • the polymer additives can form domains and can form different architectures as described for example in PCT / EP2005 / 002534.
  • the preparation of the particles according to the invention comprises an aqueous emulsion polymerization of an oil-in-water emulsion of the monomers M, in which the monomer droplets of the emulsion contain polymer additives.
  • aqueous emulsion polymerization and “emulsion polymerization” are used synonymously below.
  • the emulsion polymerization is carried out analogously to a conventional emulsion polymerization with the difference that the monomer emulsion to be polymerized contains the polymer additives dissolved in the monomer or partially dissolved.
  • the polymer additives may also be slightly soluble in the at least partially water-soluble monomers M2a-c, but they will preferably be dissolved in the largely water-insoluble monomers M1.
  • the monomers M2a-c react in the manner of a copolymerization with the monomers M1 to form the so-called Z-mers. It is conceivable that these Z-mers then polymerize as a hydrophobic radical initiator on the seed-swollen with monomer seed latex particles and cure them.
  • the mechanism of transfer of polymer additives and other The hydrophobic chemicals through the water phase are not fully understood, but the seed latex particles present may be helpful in this transfer.
  • the oil-in-water emulsion of the polymer additive monomer solution can be generated in-situ by adding a solution of the polymer additive in the monomers M to be polymerized to the polymerization vessel under polymerization conditions.
  • a solution of the polymer additive in the monomers M to be polymerized to the polymerization vessel under polymerization conditions.
  • one will dissolve polymer additives in the monomers M and convert the monomer solution thus obtained into an aqueous monomer emulsion, before feeding the monomer / polymer additive emulsion thus obtained to the polymerization reaction.
  • the emulsion polymerization is carried out in the presence of a seed polymer (seed latex, seed).
  • seed latex is a finely divided polymer latex whose mean particle size is usually not more than 100 nm, in particular not more than 80 nm and particularly preferably not more than 50 nm. In particular, the seed particle size is not more than 30 nm.
  • the seed latex monomers are preferably selected to be at least 90% by weight, especially at least 95% by weight and often more than 99% by weight among the monomers M1, wherein the seed latex for stabilization also small amounts, eg. B. from 0.1 to 10 wt .-%, in particular from 0.1 to
  • the seed latex has a glass transition temperature of at least 10, especially at least 50 and often at least 80 0 C.
  • the amount of seed latex is usually from 0.01 to 15 wt .-%, in particular from 1 to 10 wt .-%, based on the monomers M to be polymerized.
  • the major amount, and especially the total amount of seed latex is completely contained in the reaction vessel at the beginning of the emulsion polymerization.
  • the seed latex can also be generated in situ in the polymerization vessel by free-radical emulsion polymerization of the seed latex-forming monomers. The formation of the seed latex is completed in this case, however, before the production of the particles according to the invention begins. The delivery of additional seed latex during the emulsion polymerization is possible.
  • the desired particle size of the seed latex can be controlled in a manner known per se via the ratio of monomer to emulsifier.
  • the seed can be produced largely emulsifier-free with the aid of protective colloids.
  • the customary in the prior art methods for emulsion polymerizations are applicable.
  • the seed latex forming monomers from the group d- to Ci2-alkyl acrylates, d- to Ci2-alkyl methacrylates, styrene, acrylonitrile or methacrylonitrile are selected. Particularly preferred are styrene or methyl methacrylate.
  • the seed latex is preferably crosslinked.
  • One or more crosslinkers can be used. Allyl acrylate, allyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, butadiene, divinylbenzene, divinylurea or methylenebisacrylamide are suitable crosslinkers.
  • the emulsion polymerization for the preparation of the particles according to the invention takes place by a so-called monomer feed process, ie. H. the major amount, preferably at least 70% and especially at least 90% of the solution of the polymer additive in the monomers M or the major amount, preferably at least 70% and in particular at least 90% of the monomer / polymer additive solution or emulsion in the course of the polymerization reaction Polymerization vessel supplied already containing the seed latex.
  • monomer feed process ie. H. the major amount, preferably at least 70% and especially at least 90% of the solution of the polymer additive in the monomers M or the major amount, preferably at least 70% and in particular at least 90% of the monomer / polymer additive solution or emulsion in the course of the polymerization reaction Polymerization vessel supplied already containing the seed latex.
  • the period for the addition of the monomer / polymer additive solution or emulsion may vary over a wide range, depending on the composition.
  • the addition is over a period of at least 0.5 hours, preferably at least 1 hour, e.g. 1 to 10 hours and especially 2 to 5 hours.
  • the addition of the monomer / polymer additive solution or emulsion can be carried out at a constant or varying rate of addition, e.g. B. in intervals with constant rate of addition or variable rate of addition or continuously with variable rate of addition.
  • the composition of the monomer / polymer additive solution or emulsion can be kept constant or changed during the addition, wherein changes can be made both with respect to the monomer composition and with respect to the type of polymer additive or the concentration of the polymer additive.
  • particles are obtained which have a core-shell structure.
  • the seed forms the seed latex and the shell is formed from the monomers M.
  • different morphologies for the particles can be obtained. It may be one or more distinguishable, at least partially closed, shells, for example, 2 to 5 shells, arise, or a substantially continuous transition between polymer regions in a shell can be realized.
  • Such different polymer architectures of the dispersion particles are described in application PCT / EP2005 / 002534. This reference is made by reference to the disclosure of the present invention.
  • the monomer composition is changed in the course of the monomer addition in such a way that polymer regions having a different glass transition temperature are obtained in the shells of the particles.
  • step polymerization For this purpose, first, in the presence of the core (seed latex), a first monomer / polymer additive solution or emulsion whose monomer composition corresponds to a glass transition temperature Tg 1 is polymerized, followed by a second monomer / polymer additive solution or emulsion Emulsion whose monomer composition corresponds to a glass transition temperature T 9 2 (2nd stage) and optionally thereafter successively one or more further monomer / polymer additive solutions or emulsions whose monomer composition corresponds in each case to a glass transition temperature T g n , where n is the respective stage stands.
  • the respective glass transition temperatures in polymers obtained in successive polymerization stages differ by at least 10 K, in particular by at least 20 K, and more preferably by at least 30 K, for. B. 30 K to 200 K, in particular 40 K to 160 K.
  • the polymerized in one stage amount of monomer at least 5 wt .-%, preferably at least 10 wt .-%, z. B.
  • crosslinked polymers are to be prepared, it is possible, for example, to proceed by metering at least one crosslinker continuously into the reaction zone, either separately from the other monomers or in mixture with the other monomers. Another variant is to gradually add the crosslinker to the reaction zone.
  • the starters which are suitable for the emulsion polymerization according to the invention are the polymerization initiators which are suitable and usually used for emulsion polymerization and which initiate a free-radical polymerization of the monomers M.
  • these include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N - (- 2-hydroxyethyl) propionamide, 1, 1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, or 2,2'-azobis Azobis (2-amidinopropane) dihydrochloride, organic or inorganic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamylpeoxide, dio
  • cationic azo compounds such as azobis (dimethylamidinopropane), salts of peroxodisulfuric, in particular the sodium, potassium or ammonium salts or a redox initiator system containing as oxidizing agent a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide.
  • a sulfur compound which is especially selected from sodium hydrogen sulfite, sodium hydroxymethanesulfinate or the bisulfite adduct of acetone.
  • reducing agents are phosphorus-containing compounds such as phosphorous acid, hypophosphites or phosphinates, as well as hydrazine or hydrazine hydrate or ascorbic acid.
  • redox initiator systems may contain addition of small amounts of redox metal salts, such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.
  • the initiator is usually employed in an amount of 0.02 to 2% by weight and in particular 0.05 to 1.5% by weight, based on the amount of the monomers M.
  • the optimum amount of initiator naturally depends on the initiator system used and consequently can also be below or above the stated amount and can be determined by the person skilled in the art in routine experiments.
  • the initiator may be partially or completely charged in the reaction vessel.
  • the main amount of the initiator in particular at least 80 wt .-%, z. B. 80 to 99.5 wt .-% of the initiator in the course of emulsion polymerization in the polymerization reactor.
  • Pressure and temperature are of minor importance for the preparation of the polymer additive compositions of the invention.
  • the temperature naturally depends on the initiator system used and an optimum polymerization temperature can be determined by a person skilled in the art by routine experimentation.
  • the polymerization temperature is in the range of 10 to 110 0 C, often in the range of 50 to 95 0 C.
  • the emulsion polymerization is usually carried out at atmospheric pressure or ambient pressure. However, it can also be carried out in the pressure range from 800 mbar to 3 bar.
  • one or more surface-active substances are usually used to stabilize the particles in the aqueous medium.
  • These include protective colloids or low molecular weight emulsifiers, the latter, in contrast to the protective colloids usually a molecular weight below 2000 g / mol, in particular below 1000 g / mol (mass average).
  • the protective colloids or emulsifiers may be anionic, nonionic, cationic or zwitterionic in nature.
  • anionic surface-active substances are anionic emulsifiers, such as alkylphenylsulfonates, phenylsulfonates, alkylsulfates, alkylsulfonates, alkylethersulfates, alkylphenol ether sulfates, alkylpolyglycol ether phosphates, alkyldiphenyl ether sulfonates, polyarylphenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates, paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fatty acids, alkylnaphthalenesulfonic acids, Naphthalenesulfonic acids, including their alkali, alkaline earth, ammonium or amine salts.
  • anionic emulsifiers such as alkylphenylsulfonates, phenylsulf
  • anionic protective colloids examples include lignosulfonic acids, condensation products of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and optionally urea and condensation products of phenolsulfonic acid, formaldehyde and urea, lignin-sulfite waste liquor and lignosulfonates and polycarboxylates such as polyacrylates, maleic anhydride / olefin copolymers (eg B. Sokalan® CP9, BASF Aktiengesellschaft) and the alkali, alkaline earth, ammonium and amine salts of the aforementioned protective colloids.
  • lignosulfonic acids condensation products of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and optionally urea and condensation products of phenolsulfonic acid, formaldehyde and urea, lignin-sulfite waste liquor and lignosul
  • Further protective colloids are synthetic polymers or copolymers which contain as monomers the monomers listed under M2a, M2b or M2c, or mixtures thereof, and which are added as polymers or copolymers to the emulsion polymerization. Also, polysaccharides which carry anionic, nonionic or cationic groups are suitable as protective colloids. These polysaccharides may optionally be degraded in the reaction mixture.
  • Nonionic emulsifiers are, for example, alkylphenol alkoxylates, alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty acid polyalkoxylates, fatty acid polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isotridecyl alcohol, fatty acid amides, methyl cellulose, fatty acid esters, silicone oils, alkyl polyglycosides or glycerol fatty acid esters.
  • nonionic surfactants are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C3-C12) and ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: C8-C36).
  • fatty alcohols are the brands Lutensol® from BASF Aktiengesellschaft or the brands Triton® from Union Carbide.
  • Particularly preferred are ethoxylated linear fatty alcohols of the general formula
  • x are integers in the range of 10 to 24, preferably in the range of 12 to 20.
  • the variable y preferably stands for integers in the range of 5 to 50, more preferably 8 to 40.
  • Ethoxylated linear fatty alcohols are usually as Mixture of different ethoxylated fatty alcohols with different degree of ethoxylation ago.
  • the variable y in the context of the present invention stands for the mean value (number average).
  • Suitable nonionic surface-active substances are also copolymers, in particular block copolymers of ethylene oxide and at least one C3-C10-alkylene oxide, eg. B. triblock copolymers of the formula
  • A is a radical derived from an aliphatic, cycloaliphatic or aromatic diol, e.g.
  • B and B ' are independently propane-1, 2-diyl, butane-1, 2-diyl or phenethylethany4 independently of one another from 2 to 100 and Y 2, Y 3 independently of one another is a number from 2 to 100, wherein the sum of y1 + y2 + y3 + y4 is preferably in the range of 20 to 400, which corresponds to a number average molecular weight in the range of 1000 to 20,000.
  • A is ethane-1, 2-diyl, propane-1
  • nonionic protective colloids are polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymers, polyethyleneglycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol-polypropylene glycol ether block copolymers and mixtures thereof. Further preferred nonionic protective colloids are polysaccharides or their degradation products.
  • cationic emulsifiers are quaternary ammonium salts, e.g. B. trimethyl or triethyl-C6-C3o-alkylammonium salts such as cocotrimethylammonium salts, trimethylcetylammonium salts, dimethyl or diethyl-di-C4-C2o-alkylammonium salts such as Didecyldimethylammoniumsalze or Dicocodimethylammoniumsalze, methyl or ethyl-tri-C4-C2o-alkylammonium salts such as methyltrioctylammonium salts C 1 -C 20 -alkyl-di-C 1 -C 4 -alkylbenzylammonium salts such as triethylbenzylammonium salts or cocobenzyldimethylammonium salts, methyl or ethyl-C 1 -C 4 -alkylam
  • N-C6-C2o-alkylpyridinium salts e.g. N-Laurylpyridiniumsalze, N-methyl or N-ethyl-N-C6-C2o-alkylmorpholiniumsalze, and N-methyl or N-ethyl-N'-C6-C2o-al kylimidazoliniumsalze, in particular the halides, borates, Carbonates, formates, acetates, propionates, bicarbonates, sulfates or methosulfates.
  • N-C6-C2o-alkylpyridinium salts e.g. N-Laurylpyridiniumsalze, N-methyl or N-ethyl-N-C6-C2o-alkylmorpholiniumsalze, and N-methyl or N-ethyl-N'-C6-C2o-al kylimidazoliniumsalze, in particular the halides
  • cationic protective colloids are homopolymers and copolymers of the abovementioned monomers M2c, which are added as homopolymers or copolymers of emulsion polymerization, with a content of monomers M2c of at least 20% by weight, in particular at least 30% by weight, of monomers M2c
  • monomers M2c for example, homopolymers of N-vinyl-N-methylimidazolinium salts or of N-alkylvinylpyridinium salts and copolymers of polymers of these monomers with neutral, preferably water-miscible monomers M2b.
  • Cationic protective colloids may also be natural polymers such as chitosan or cationically modified polysaccharides.
  • Zwitterionic emulsifiers are those with betainic structures. Such substances are known to the person skilled in the art and can be taken from the relevant prior art (see, for example, R. Heusch, Ullmanns Encylopedia of Industrial Chemistry, 5th Ed. On CD-ROM, Wiley-VCH 1997, “Emulsions", Chapter 7, Table 4) Gemini surfactants are also known to the person skilled in the art.
  • protective colloids are polyvinyl alcohols, cellulose derivatives such as carboxymethylcellulose, polyvinylpyrrolidone, graft polymers of vinyl acetate and / or vinyl propionate on polyethylene glycols, polyethylene glycols terminated on one or both sides with alkyl, carboxyl or amino groups, polydiallyldimethylammonium chlorides and / or polysaccharides such as, in particular, water-soluble Starches, starch derivatives or proteins.
  • Such products are described, for example, in Römpp, Chemie Lexikon 9th Edition, Volume 5, page 3569 or in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/2 Chapter IV conversion of cellulose and starch of E. Husemann and R. Werner, pages 862-915 and in Ullmann's Encyclopedia for Industrial Chemistry, 6th edition, volume 28, pages 533 ff under polysaccharides.
  • starch e.g. both amylose and amylopectin, 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 starch degradation both native and modified starches can be used.
  • suitable protective colloids are dextrins or crosslinked water-soluble starches which are water-swellable.
  • the molecular weight reduction is preferably carried out enzymatically but can also be carried out hydrolytically or oxidatively.
  • 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.
  • maltodextrin (CAS # 9050-36-6) is suitable as a protective colloid, a water-soluble carbohydrate mixture which can be prepared by hydrolytic, enzymatic or oxidative degradation of starch or variants of the three processes.
  • maltodextrin C * Pur 01915 from Cerestar is used.
  • protective colloids are used in the emulsion polymerization
  • the amounts used are, for example, from 0.5 to 50, in particular from 5 to 40,%, usually from 10 to 30,% by weight, based on the monomers M. used in the emulsion polymerization.
  • the polymer dispersions according to the invention usually comprise at least one emulsifier, preferably at least one ionic emulsifier and optionally one or more nonionic emulsifiers.
  • the amount of emulsifier is usually in the range of 0.1 to 15 wt .-%, in particular in the range of 0.2 to 12 wt .-%, and particularly preferably 0.7 to 10 wt .-%, based on the monomers M.
  • the amount of ionic emulsifier is preferably 0.3 to 10 wt .-% and in particular 0.5 to 8 wt .-%, based on the monomers M.
  • the amount of nonionic emulsifier is preferably in the range of 0.2 to 12% by weight, in particular from 0.5 to 10% by weight, based on the monomers M. which constitute the polymer.
  • the amounts of surface-active substances customarily used for emulsion polymerization are usually in the abovementioned ranges, so that all or some of the surface-active substances are supplied via the emulsion polymerization. However, it is also possible only a part, for. B. 10 to 90 wt .-%, in particular 20 to 80 wt .-% of the surface-active substances in the emulsion and to add the remaining amount of surface-active substance following the emulsion polymerization, before or after an optionally be performed deodorization of the emulsion (post-soaps) ,
  • the molecular weight of the polymers can be reduced by adding regulators in a small amount, e.g. B. 0.01 to 2 wt .-%, based on the polymerizing monomers M, be adjusted.
  • Suitable regulators are, in particular, organic thio compounds, furthermore allyl alcohols or aldehydes.
  • Polymerization regulators and crosslinkers can be used together in the emulsion polymerization. This can be used, for example, to control the rheology of the resulting polymer dispersions.
  • aqueous polymer dispersions Following the actual polymerization reaction, it may be necessary to substantially free the aqueous polymer dispersions according to the invention from Odorants, such as residual monomers and other organic volatile constituents. This can be achieved physically in a manner known per se by distillative removal (in particular via steam distillation) or by stripping with an inert gas.
  • the lowering of the residual monomers can continue chemically by free radical postpolymerization, in particular under the action of redox initiator systems, as z. For example, in DE-A 44 35 423, DE-A 44 19 518 and in DE-A 44 35 422 listed, carried out.
  • the postpolymerization is preferably carried out with a redox initiator system comprising at least one organic peroxide and one organic sulfite.
  • the polymer dispersions thus obtained are frequently made alkaline, preferably to pH values in the range from 7 to 10, before they are used according to the invention.
  • alkaline preferably to pH values in the range from 7 to 10.
  • ammonia or organic amines can be used, and preferably hydroxides, such as sodium hydroxide, potassium hydroxide or calcium hydroxide can be used.
  • novel polymer dispersions are distinguished by high stability and a low content of volatile organic compounds, which are usually not more than 1% by weight, often not more than 0.1% by weight and in particular not more than 100 ppm , based on the total weight of the polymer dispersion.
  • Volatile compounds are all organic compounds having a boiling point below 200 0 C at atmospheric pressure here and in the constricting folic.
  • the polymer additives are at least partially enveloped by the water-insoluble polymers formed from the monomers M, ie, the particles according to the invention contain the polymer additives. It is often observed no measurable or very low levels of agglomerates or coagulants, which usually account for less than 2 wt .-%, preferably less than 0.2 wt .-%, based on the solids contained in the polymer dispersion.
  • the solids content of the polymer dispersions according to the invention is determined to a first approximation by the particles according to the invention and is generally in the range from 10 to 60% by weight and in particular in the range from 20 to 50% by weight.
  • Preferred particles according to the invention are those particles in which all features take on their preferred meaning.
  • particles which, as monomers M1 are methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile, methacrylonitrile or mixtures of these monomers.
  • ren and whose seed latex is based on polystyrene and / or polymethyl methacrylate or copolymers of polystyrene and polymethyl methacrylate.
  • particles which contain, as monomers M1, methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile or mixtures of these monomers and whose seed latex is based on polystyrene and / or polymethyl methacrylate or copolymers of styrene and methyl methacrylate and which have been prepared with the aid of protective colloids
  • Protective colloids in particular polyvinyl alcohol, or polyvinyl acetate or polysaccharides which have been further cured by means of crosslinkers such as glyoxal or glutaric dialdehyde.
  • particles which comprise methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile or mixtures of these monomers as monomers M1 and whose seed latex is based on polystyrene and / or polymethyl methacrylate or copolymers of styrene and methyl methacrylate and which have been prepared with the aid of emulsifiers Emulsifiers in particular Dowfax® 2 A1, sodium lauryl sulfate, or sulfosuccinic come into consideration.
  • Dowfax® 2A1 contains a 45% aqueous solution of 28-36% disodium dodecyl (sulfonatophenoxy) benzenesulfonate (CAS # 28519-02-0, EC No 249-063-8) and 8-15% disodium (oxybis) dodecylbenzenesulfonate (CAS # 25167-32-2, EC No. 246-688-8).
  • the seed may contain the same or different surfactants as used for emulsion polymerization.
  • particles which contain as monomers M1 methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile or mixtures of these monomers and whose seed latex is based on polystyrene and / or polymethyl methacrylate or copolymers of styrene and methyl methacrylate and which have been prepared with the aid of emulsifiers, mixtures of nonionic surfactants and anionic surfactants, such as, for example, the Lutensol® grades from BASF in combination with the abovementioned anionic surfactants, are particularly suitable as emulsifiers.
  • the seed may contain the same or different surfactants as used for emulsion polymerization.
  • particles which contain, as monomers M1, methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile or mixtures of these monomers and whose seed latex is based on polystyrene and / or polymethyl methacrylate or copolymers of styrene and methyl methacrylate and which have been prepared with the aid of protective colloids, wherein the protective colloids are in particular polyvinyl alcohol, or polyvinyl acetate or polysaccharides which have been further cured by means of crosslinkers such as glyoxal or glutaric dialdehyde and which have been further prepared with the aid of emulsifiers, wherein as emulsifiers in particular Dowfax 2 A1, sodium lauryl sulfate, or Sulfobernsteinklander in To consider.
  • monomers M1 methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile or mixtures of
  • the seed may contain the same or different surfactants as used for emulsion polymerization. Furthermore, preference is given to particles which comprise methyl methacrylate, methyl acrylate, ethyl acrylate, acrylonitrile or mixtures of these monomers as monomers M1 and whose seed latex is based on polystyrene and / or polymethyl methacrylate or copolymers of styrene and methyl methacrylate and which have been prepared with the aid of protective colloids
  • Protective colloids represent synthetic polymers which contain 3- (N 1 N-dimethylamino) propyl methacrylamide monomers and which were furthermore prepared with the aid of emulsifiers, suitable emulsifiers being, in particular, Dowfax 2 Al, sodium lauryl sulfate or sulfosuccinic acid esters.
  • the seed may contain the same or different surfactants as are used for emulsion polymerization.
  • the polymer dispersions according to the invention can be used directly as such or after dilution.
  • the polymer dispersions of the invention may contain conventional additives (additives), for.
  • additives for.
  • thickener thickener
  • anti-foaming agents for.
  • bactericides for.
  • antifreeze for.
  • Suitable thickeners are compounds which impart a pseudoplastic flow behavior to the formulation, i. H. high viscosity at rest and low viscosity when in motion.
  • Suitable thickeners are compounds which impart a pseudoplastic flow behavior to the formulation, i. H. high viscosity at rest and low viscosity when in motion.
  • polysaccharides or organic acids for example, polysaccharides or organic acids
  • Layered minerals such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (company RT Vanderbilt) or Attaclay® (Engelhardt, magnesium aluminum silicate, Palygorskite), where xanthan gum Gum is preferably used.
  • Suitable antifoams for the polymer dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides can be added to stabilize the polymer dispersions according to the invention against attack by microorganisms.
  • Suitable bactericides are, for example, Proxel® from Avecia (or Fa. Arch) or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas.
  • Suitable antifreeze are organic polyols, eg. As ethylene glycol, propylene glycol or glycerol. These are usually used in amounts of not more than 10% by weight, based on the total weight of the polymer dispersion.
  • the polymer dispersions of the invention may contain 1 to 5 wt .-% buffer, based on the total amount of the formulation prepared for pH regulation, wherein the amount and type of buffer used according to the chemical properties of the polymer additives or polymers.
  • buffers are alkali salts of weak inorganic or organic acids such. For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • novel aqueous polymer dispersions can be formulated with conventional binders, for example aqueous polymer dispersions, water-soluble resins, for example water-soluble alkyd resins, or with waxes.
  • the particles according to the invention are contained in the polymer dispersions and can be obtained from these polymer dispersions by removing the volatile constituents of the liquid phase in powder form.
  • the particles according to the invention can be present either singly, in agglomerated form, or else partially in film form.
  • the polymer powders according to the invention are accessible, for example, by evaporation of the liquid phase, freeze drying or by spray drying.
  • polymer dispersions according to the invention are obtainable by redispersing the polymer powders according to the invention.
  • the polymer dispersions according to the invention and the polymer powders obtainable therefrom by evaporation of the liquid phase have the advantage that they contain the polymer additives in a controlled migration-stable manner over a long period of time, ie. the polymer additives are associated with the particles for an extended period of time and are not released to the environment outside the particles.
  • the polymer additives are thus present in a matrix which is particularly advantageous for their application. This fact applies in particular to those polymer dispersions or polymer powders which contain a UV absorber.
  • the migration stability can be measured, for example, by spray drying the polymer dispersion according to the invention and subsequent extraction of the powder with tetrahydrofuran (THF) or other suitable liquids by determining the fraction of polymer additives recovered by extraction.
  • the polymer additives are at least 80 wt .-% in the polymeric matrix, more preferably the proportion of polymer additives, which can be found in the matrix is at least 85 wt .-%, based on the total amount of polymer additive.
  • the proportion of polymer additive that is not in the matrix often crystallizes out and can be separated off, for example by filtration.
  • the particles according to the invention in the form of their polymer dispersions or polymer powders are preferably used for finishing, for example for stabilizing, organic polymers.
  • the particles can be used for this purpose both as Polymer dispersion and as a powder by the usual methods incorporated into the organic polymers. Mention may be made, for example, of the mixture of the particles with the organic polymers before or during an extrusion step.
  • Organic polymers here are to be understood as meaning any plastics, preferably thermoplastics, in particular films, fibers or shaped bodies of any desired shape.
  • the organic polymers are, for example, polyethylene, polypropylene, polyamide, polyacrylonitrile, polycarbonate, acrylonitrile-butadiene-styrene (ABS), polyvinyl chloride, or polyester. Further examples of the equipment or stabilization of organic polymers with polymer additives can be found in the Plastics Additives Handbook, 5th edition, Hanser Verlag, ISBN 1-56990-295-X.
  • thermoplastic polymer In order to stabilize a thermoplastic polymer against UV exposure, it is possible, for example, to melt the polymer first in an extruder, to incorporate a powder produced according to the invention into the polymer melt at a temperature of, for example, 180 to 200 ° C. and UV absorber from it produces a granulate from which then films, fibers, or moldings are prepared by known methods, which are stabilized against the action of UV radiation.
  • particles according to the invention may have the same or different compositions and size distributions.
  • particles containing UV absorbers can also be used together with other particles according to the invention which comprise, for example, stabilizers for organic polymers such as antioxidants for stabilizing organic polymers and lacquer layers.
  • aqueous polymer dispersions of the invention or those thereof e.g. obtained by spray drying polymer powder containing particles of the invention containing at least one antioxidant, for example phenolic compounds.
  • polymer powders which contain as effect substance at least one antistatic agent for organic polymers or an antifogging agent for organic polymers or a colorant for organic polymers or at least one reactive sizing agent for paper.
  • the particles of the present invention may also be used in conjunction with classical additive systems to improve overall efficiency.
  • classical additive systems for example, with conventional emulsion concentrates, suspension concentrates, suspoemulsion concentrates of polymer additives.
  • conventional aqueous preparations of the abovementioned polymer additives By mixing the particles according to the invention with conventional aqueous preparations of the abovementioned polymer additives, on the one hand a broadening of the spectrum of action is achieved, when the conventional preparation contains polymer additives other than the particles of the invention.
  • the advantages of the particles according to the invention are not lost by formulating with conventional aqueous polymer additive preparations, in particular the improved migration stability. Consequently, one can improve the performance of a conventional aqueous polymer additive formulation by formulation with particles of the invention containing the same polymer additives.
  • the polymer dispersions according to the invention are associated with a number of further advantages.
  • these are stable aqueous formulations of polymer additives which are not or only slightly soluble in water.
  • the phase separation problems and settling of the polymer additive observed in conventional formulations and in micro- or nano-dispersions of the polymer additives are not observed, even when drastic conditions are used, such as occur in the case of finishing organic polymers with polymer additives.
  • the content of organic volatile compounds is less with conventional additives than with comparable conventional formulations and in comparison with microdispersions or nanodispersions of polymer additives.
  • the amount of emulsifier is lower, based on the polymer additive used.
  • the leaching of the polymer additive from the treated organic polymer when exposed to water is significantly reduced compared to other formulations. Furthermore, interactions of the polymer additives with other formulation ingredients or co-polymer additives, as commonly encountered in conventional formulation, are not observed. In addition, the degradation of the polymer additives by substrate or environmental influences, such as pH of the environment or UV radiation is slowed down or even completely prevented. Surprisingly, a reduced effectiveness of the polymer additives by incorporation into a polymer matrix is generally not observed.
  • the production process of the particles according to the invention by aqueous emulsion polymerization using a seed latex allows very efficient access to the particles.
  • the particles according to the invention are present, for example, as constituents of polymer dispersions or of polymer powders and can easily be incorporated into organic polymers.
  • the particles of the invention are particularly suitable for the equipment, for example against static charge or fogging and / or stabilization, for example against oxidation, exposure to UV rays, heat and / or light, of organic polymers.
  • the following examples are intended to illustrate the invention without, however, limiting it.
  • the particle sizes were measured by light scattering with a Coulter N4 Plus laser diffuser or alternatively with a Coulter 230 LS. It was always measured in about 0.1% aqueous preparations.
  • Rongalite C sodium salt of a sulfinic acid derivative
  • Lipamin® OK ethoxylated stearylamine, which with
  • Example 1 154 g of deionized water, 33.33 g of polystyrene seed (33%) with a particle size of about 30 nm and 55 g of maltodextrin C * Pur 01915 were placed in a nitrogen-purged reactor. While stirring, the internal temperature was brought to 80 0 C. Then, at a time, 13.63 g of a mixture of 9.53 g of deionized water and 33 g of a 2% sodium peroxodisulfate solution (feed 2) were added.
  • the mixture was then allowed to cool to room temperature (20 ° C.) and the polymer dispersion was filtered through a 500 ⁇ m filter and then through a 125 ⁇ m filter to remove residual coagulum.
  • the separated coagulum was 27.4 g in total and the solids content was found to be 28.5%.
  • the mean particle size (bimodal) was 121 nm after centrifugation 106 nm (monomodal) determined with the Beckman Coulter 230 LS.
  • Example 3 147 g of deionized water, 31, 82 g of polystyrene seed (33%) with a particle size of about 30 nm and 52.5 g of maltodextrin C * Pur 01915 were placed in a nitrogen-purged reactor. While stirring, the internal temperature is raised to 80 ° C. introduced. Then, 10.17 g of a mixture of 9.2 g of deionized water and 31.5 g of a 2% sodium peroxodisulfate solution (feed 2) were added all at once.
  • feed 2 was metered in over the course of 1.5 hours, and the remaining feed 3 was added simultaneously in 3.5 hours.
  • feed 1 a mixture of 195.5 g of deionized water, 20.7 g of lipamine OK, 1.84 g of a 50% strength aqueous sulfuric acid, 6.90 g of dimethylaminoethyl methacrylate and 131.1 g of methyl methacrylate (feed 2) was then added. dosed in 2 hours. Then allowed to polymerize for a further 30 minutes.
  • the separated coagulum was a total of 2.1 g, the solids content was determined to be 28.7%.
  • the average particle size was 120 nm.
  • Example 2 When Example 2 was repeated without the use of the polystyrene seed, no suitable dispersions were obtained.
  • the Uvinul® 3008 was found largely unencapsulated on the stirrer and on the wall of the reactor.
  • the dispersion had a solids content of 22%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Paper (AREA)

Abstract

L'invention concerne des particules, pouvant être obtenues par polymérisation en émulsion aqueuse de monomères M à insaturation éthylénique en présence d'additifs polymères et de semences. Selon l'invention, les monomères M comprennent les monomères M1 en grande partie insolubles dans l'eau et éventuellement les monomères M2, au moins en partie solubles dans l'eau, et les additifs polymères sont sensiblement insolubles dans l'eau et solubles dans les monomères M1, et ne sont pas polymérisables dans les conditions de formation des particules. Les particules présentent une taille moyenne inférieure ou égale à 500 nm.
EP07820277A 2006-09-20 2007-09-18 Particules contenant un additif polymère Withdrawn EP2066702A1 (fr)

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EP06120954 2006-09-20
PCT/EP2007/059812 WO2008034813A1 (fr) 2006-09-20 2007-09-18 Particules contenant un additif polymère
EP07820277A EP2066702A1 (fr) 2006-09-20 2007-09-18 Particules contenant un additif polymère

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CN101668586A (zh) * 2007-04-26 2010-03-10 巴斯夫欧洲公司 制备微胶囊的酶催方法
US20110230343A1 (en) * 2008-10-24 2011-09-22 Basf Se Method for the Manufacture of Microparticles Comprising an Effect Substance
TR201908012T4 (tr) * 2008-12-03 2019-06-21 Omya Int Ag İnce taneli dolgu maddelerinin sulu bulamaçları, bunun üretimine yönelik yöntem ve dolgu maddesi içeren kağıtların üretilmesine yönelik kullanım.
GB2489420B (en) * 2011-03-25 2013-02-13 Renolit Cramlington Ltd Flexible laminate film
JP2015508837A (ja) * 2012-02-14 2015-03-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ リグノスルホン酸塩の存在下でのラジカル開始乳化重合により得ることができる水性ポリマー分散液
JP7267260B2 (ja) * 2017-09-01 2023-05-01 ビーエーエスエフ ソシエタス・ヨーロピア 油溶性有機ｕｖ吸収剤の水性濃縮生成物形態
KR102492405B1 (ko) * 2019-10-07 2023-01-27 주식회사 엘지화학 카르본산 변성 니트릴계 공중합체 라텍스의 제조방법

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3400093A (en) * 1966-03-11 1968-09-03 Feinberg Irving Process for preparing a stable polymer latex containing an insecticide
US4419471A (en) * 1981-09-04 1983-12-06 Gaf Corporation Core-shell polymers
US6080802A (en) * 1991-12-03 2000-06-27 Rohm And Haas Company Process for preparing an aqueous dispersion of composite particles including polymeric latex adsorbed to titanium dioxide
DE19649331A1 (de) * 1996-02-29 1997-09-04 Bayer Ag Verfahren zur Herstellung von Lacites auf Basis von konjugierten Dienen mittels Emulsionspolymerisation
DE19729652A1 (de) * 1997-07-11 1999-01-14 Basf Ag Acrylesterkautschukpartikel
DE10013733A1 (de) * 2000-03-21 2001-09-27 Basf Ag Verfahren zur Herstellung von Kautschukteilchen
EP1317505B1 (fr) * 2000-09-14 2008-09-03 Rohm And Haas Company Copolymeres segmentaires et dispersions aqueuses et films a base de ceux-ci
DE102004018546A1 (de) * 2004-04-14 2005-11-03 Basf Ag Strahlungshärtbare 1,3,5-Triazincarbamate und -harnstoffe
PT1742531E (pt) * 2004-04-26 2014-10-29 Basf Se Composição aquosa fungicida e a utilização da mesma para o combate de microrganismos prejudiciais
CN101170903A (zh) * 2005-03-10 2008-04-30 巴斯福股份公司 含农药的聚合物水分散体的制备方法及其用途
US20080146448A1 (en) * 2005-03-10 2008-06-19 Basf Aktiengesellschaft Aqueous Polymer Dispersions Comprising Effect Substances, Processes For Preparing Them And Their Use
WO2007118111A1 (fr) * 2006-04-07 2007-10-18 Basf Se Dispersions electriquement neutres et leur procede de preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008034813A1 *

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US20090318605A1 (en) 2009-12-24
JP2010504385A (ja) 2010-02-12
US20120053283A1 (en) 2012-03-01

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