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WO2012004160A1 - Composition pour la préparation de polymères, (méth)acryl-polymère, agent de revêtement et revêtement - Google Patents

Composition pour la préparation de polymères, (méth)acryl-polymère, agent de revêtement et revêtement Download PDF

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Publication number
WO2012004160A1
WO2012004160A1 PCT/EP2011/060831 EP2011060831W WO2012004160A1 WO 2012004160 A1 WO2012004160 A1 WO 2012004160A1 EP 2011060831 W EP2011060831 W EP 2011060831W WO 2012004160 A1 WO2012004160 A1 WO 2012004160A1
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WIPO (PCT)
Prior art keywords
meth
radical
carbon atoms
group
acrylate
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PCT/EP2011/060831
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German (de)
English (en)
Inventor
Christine Maria BREINER
Thorben SCHÜTZ
Ina Zwierzchowski
Mario Gomez Andreu
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Evonik Röhm Gmbh
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Publication of WO2012004160A1 publication Critical patent/WO2012004160A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate

Definitions

  • composition for the production of polymers (meth) acrylic polymer, coating agent and coating
  • the present invention relates to a composition for producing polymers and a (meth) acrylic polymer obtainable from the composition.
  • the present invention is directed to a
  • Coating agents in particular paints, have been produced synthetically for a long time.
  • An important group of these agents is based on aqueous dispersions, many times
  • the mixtures to be polymerized include (meth) acrylates which have been modified by unsaturated fatty acids.
  • An essential aspect of this solution is the use of polymers which are particularly broad
  • Dispersions comprising particles based on (meth) acrylates. The ones used to make the particles
  • Monomer mixtures include (meth) acrylates which are characterized by
  • Coating compositions have a very high
  • Minimum film forming temperature based on the hardness of the coatings that can be obtained from these coating compositions.
  • Process properties include in particular features caused by coating agents and coatings consisting of the coating agents
  • compositions should become
  • Dispersions or polymers for example
  • Emulsion polymers which can process a
  • the Invention to provide a coating agent which has a particularly long shelf life and durability. Furthermore, the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range. In particular, should
  • Another object is to see polymers for
  • Coating agents without volatile organic solvents are available. The from the aqueous dispersions
  • Weathering resistance in particular have a high UV resistance.
  • the films obtainable from the aqueous dispersions should have a low tackiness after a short time.
  • MIBK methyl isobutyl ketone
  • compositions should in particular be a good one
  • compositions for the production of polymers (meth) polymers and coating compositions, which can be obtained very inexpensively and on an industrial scale.
  • compositions are provided in subclaims under protection.
  • a (meth) acrylic polymer a process for producing polymers, a
  • Coating agent and a coating provide the claims 10, 12, 13 and 15, a solution to the underlying problems.
  • the subject of the present invention is a composition for the preparation of polymers at least one monomer and at least one radical initiator, which is characterized in that the radical initiator is an azo compound, at least one monomer is an amide or an amine monomer, and at least one monomer
  • Is (meth) acrylic monomer having in the alkyl group at least one C-C double bond and 8 to 40 carbon atoms.
  • compositions according to the invention can be added
  • Coating agents are available, which in turn are based on the polymers or compositions can be varied over a wide range. Surprisingly
  • mechanically stable coatings are obtained, which are characterized by a high elongation at break and / or a high tensile strength.
  • coating compositions according to the invention are available, based on the hardness and chemical resistance, a relatively low brittleness.
  • the coating agents of the present invention can be obtained according to the invention. From the coating agents of the The present invention obtainable coatings show a surprisingly high solvent resistance, which is particularly evident in experiments with methyl isobutyl ketone (MIBK), ammonia solutions or ethanol. Thus, the coatings obtained, in particular in tests according to the furniture test DIN 68861-1 an excellent classification.
  • MIBK methyl isobutyl ketone
  • Coating agents show in particular a good
  • Minimum film-forming temperature is clear, without affecting the mechanical properties or the
  • Minimum film-forming temperature of the coating compositions show the coatings obtainable from these improved chemical resistance and increased pendulum hardness.
  • compositions according to the invention are obtainable,
  • Coating agents a high storage stability, a high durability and a very good shelf life.
  • Coating an improved environmental impact Preferred embodiments hardly show any release of organic compounds, in particular solvents, into the atmosphere. Furthermore, the coating compositions have an extremely low residual monomer content.
  • Coating agents can be inexpensively in large
  • the coating compositions of the invention are environmentally friendly and safe and without large
  • the coating compositions of the invention show a very high shear stability.
  • composition according to the invention for the preparation of polymers comprises at least one (meth) acrylic monomer which has at least one double bond in the alkyl radical and 8 to 40
  • esters or amides of (meth) acrylic acid whose alkyl radical has at least one carbon-carbon double bond and 8 to 40 carbon atoms.
  • the spelling (Meth) acrylic acid means methacrylic acid and acrylic acid and mixtures thereof.
  • the alkyl or alcohol or amide radical may preferably have 10 to 30 and more preferably 12 to 20 carbon atoms, this radical may include heteroatoms, in particular oxygen, nitrogen or sulfur atoms.
  • the alkyl group may have one, two, three or more carbon-carbon double bonds.
  • Polymerization conditions in which the (meth) acrylate polymer is prepared are preferably chosen so that the largest possible proportion of the double bonds of the alkyl radical is maintained in the polymerization. This can be done for example by steric hindrance of the double bonds contained in the alcohol radical.
  • radical polymerization as a (meth) acrylic group, so that in the alkyl radical preferably no further
  • Such (meth) acrylic monomers generally correspond to the formula (I)
  • R' is hydrogen or a radical having 1 to 6 carbon atoms
  • R 1 denotes a linear or branched radical having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms, which has at least one CC double bond.
  • (meth) acrylamides can be obtained by reaction with an amine.
  • Suitable alcohols include octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, among others
  • Nonadeca-dien-ol, icosadien-ol and / or docosa-dien-ol are examples of compounds that are present in the hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic hydrophilic acid, osadien-ol and / or docosa-dien-ol.
  • fatty alcohols are partly commercially available or can be obtained from fatty acids, this reaction being carried out, for example, in F.-B. Chen, G. Bufkin, Journal of Applied Polymer Science, Vol. 30, 4571-4582
  • (meth) acrylates which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can also be obtained by reacting unsaturated fatty acids with (meth) acrylates which are present in the alkyl radical, in particular
  • Alcohol radical reactive groups can be obtained.
  • the reactive groups include in particular hydroxy groups and epoxy groups. Accordingly, for example, hydroxyalkyl (meth) acrylates, such as
  • hexanediol (meth) acrylate 1, 10-decanediol (meth) acrylate; or epoxy group-containing (meth) acrylates, for example
  • Glycidyl (meth) acrylate can be used as starting materials for the preparation of the aforementioned (meth) acrylates.
  • Suitable fatty acids for reaction with the abovementioned (meth) acrylates are often commercially available and are obtained from natural sources. These include undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid,
  • Methods available include, in particular
  • R is hydrogen or a methyl group
  • R is hydrogen or a methyl group
  • X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a
  • R ' is hydrogen or a radical having 1 to 6 carbon atoms and R 2 is an unsaturated radical having 9 to 25 carbon atoms, achieve.
  • radical having 1 to 6 carbon atoms represents a group having 1 to 6 carbon atoms and includes aromatic and heteroaromatic groups as well as
  • Alkanoyl, alkoxycarbonyl and heteroaliphatic groups Alkanoyl, alkoxycarbonyl and heteroaliphatic groups.
  • the groups mentioned can be branched or unbranched. Furthermore, these groups can be
  • the radicals R ' are preferably alkyl groups.
  • Preferred alkyl groups include methyl, ethyl,
  • the group Z preferably represents a linking group comprising 1 to 10, preferably 1 to 5 and most preferably 2 to 3 carbon atoms. These include in particular linear or branched, aliphatic or cycloaliphatic radicals, such as, for example, a methylene, ethylene,
  • the group R in formula (II) represents an unsaturated radical having 9 to 25 carbon atoms.
  • These groups include in particular alkenyl, cycloalkenyl, alkenoxy,
  • these groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • particularly preferred groups include alkenyl groups such as the nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl,
  • Tricosa-dien-yl and / or heptadeca-triene-yl group Tricosa-dien-yl and / or heptadeca-triene-yl group.
  • the preferred (meth) acrylic monomers of the formula (II) or (III) include heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecadienyloxy-2-ethyl (meth) acrylamide, heptadeca- trienyloxy-2-ethyl (meth) acrylamide, heptadecenyloyloxy-2-ethyl- (meth) acrylamide, (meth) acryloyloxy-2-ethyl- palmitoleic acid amide, (meth) acryloyloxy-2-ethyl oleic acid amide, (meth) acryloyloxy-2-ethyl-icosenoic acid amide, (meth) acryloyloxy-2-ethyl-cetoleic acid amide,
  • the notation (meth) acryl stands for acrylic and
  • Methacryl radicals with methacrylic radicals are preferred.
  • Particularly preferred monomers of the formula (II) or (III) are methacryloyloxy-2-ethyl-oleic acid amide, methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide.
  • the (meth) acrylic monomers of the formula (II) or (III) can be obtained in particular by multistage processes.
  • a first step for example, one or more unsaturated fatty acids or fatty acid esters can be reacted with an amine, for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine, to form an amide.
  • an amine for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine
  • the hydroxy group or amine group of the amide is reacted with a (meth) acrylate, for example
  • Alkyl (meth) acrylate for example methyl (meth) acrylate, with one of the aforementioned amines to a (meth) acrylamide with a hydroxy group in the alkyl radical are reacted, which is then reacted with an unsaturated fatty acid to a
  • Carboxylic acid amides which have hydroxy groups in the alkyl radical to be purified. According to a particular embodiment of the present invention, intermediates obtained can be reacted without expensive purification to the (meth) acrylic monomers of formula (II) or (III).
  • the (meth) acrylic monomers having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms and at least one double bond in the
  • Alkyl radical in particular monomers of the general formula (IV)
  • R is hydrogen or a methyl group
  • X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 3 is an alkylene group with 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of the formula NR ", where R" is hydrogen or a radical having 1 to 6 carbon atoms, and R 4 is an unsaturated radical having at least 8 carbon atoms and at least two double bonds ,
  • the radical R is an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10,
  • radical R 3 is particularly preferably having 2 to 6 carbon atoms.
  • Alkylene groups having 1 to 22 carbon atoms having 1 to 22 carbon atoms
  • Cyclohexylene group wherein the ethylene group is particularly preferred.
  • the radical R 4 comprises at least two CC double bonds which are not part of an aromatic system.
  • the radical R 4 represents a group with exactly 8 carbon atoms, which has exactly two double bonds.
  • the radical R 4 preferably represents a linear hydrocarbon radical which has no heteroatoms. According to a special
  • the radical R 4 in formula (IV) may comprise a terminal double bond.
  • the radical R 4 in formula (IV) can not comprise a terminal double bond.
  • the double bonds contained in the radical R 4 can
  • the double bonds contained in the radical R 4 are not conjugated.
  • the at least two radicals R 4 the at least two
  • Include double bonds include the octa-2, 7-dienyl group, octa-3, 7-dienyl group, Octa-4,7-dienyl, octa-5, 7-dienyl, octa-2, 4-dienyl, octa-2, 5-dienyl, octa-2, 6-dienyl, octa-3, 5-dienyl, octa 3, 6-dienyl group and octa-4, 6-dienyl group.
  • the (meth) acrylic monomers of the general formula (IV) include, inter alia, 2- [((2-E) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [( (2-Z) octa-2,7-dienyl) methylamino] ethyl-2-methylprop-2-enoate,
  • the (meth) acrylic monomers of the formula (IV) set out above can be obtained in particular by processes in which (meth) acrylic acid or a (meth) acrylate, in particular
  • Methyl (meth) acrylate or ethyl (meth) acrylate is reacted with an alcohol and / or an amine. These reactions have been previously stated.
  • Reacted reactant can advantageously of the formula (V)
  • HX-R-YR (V), wherein X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 3 is an alkylene group having 1 to 22 carbon atoms, Y
  • telomerization means the reaction of compounds with conjugated double bonds in the presence of nucleophiles, as set forth in the publications WO 2004/002931, WO 03/031379 and WO 02/100803
  • Catalysts and the reaction conditions are included in the present application for disclosure purposes.
  • telomerization of 1,3-butadiene using metal compounds comprising metals of the 8th to 10th group of the Periodic Table of the Elements, as
  • Palladiumcarbenkomplexe which are set forth in more detail in the above-mentioned documents, can be particularly preferably used.
  • dialcohols such as
  • Ethylene glycol 1, 2-propanediol, 1, 3-propanediol; Diamines, like Ethylenediamine, N-methylethylenediamine, ⁇ , ⁇ '-dimethylethylenediamine or hexamethylenediamine; or
  • Aminoalkanols such as aminoethanol, N-methylaminoethanol, ethylaminoethanol, aminopropanol, N-methylaminopropanol N-ethylaminopropanol can be used.
  • Carbon atoms are suitable.
  • reaction pressure is 1 to 300 bar, preferably up to 120 bar, more preferably 1 to 64 bar and most preferably 1 to 20 bar.
  • the preparation of isomers from compounds having an octa-2,7-dienyl group can be accomplished by isomerization of the double bonds contained in the compounds having an octa-2,7-dienyl group.
  • the above-mentioned (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group may be used singly or as a mixture of two or more monomers.
  • At least one double bond and having from 8 to 40 carbon atoms, in a composition according to the invention can vary over a wide range, wherein this proportion is preferably in the range of 0.1 to 60 wt .-%, more preferably 1 to 40 wt .-% and most preferably in the range of 2 to 20 wt .-%, based on the weight of the monomers.
  • compositions of the invention comprise at least one amide or one amine monomer, wherein amine monomers
  • an amide or an amine monomer is an organic compound having at least one C-C double bond which additionally has an amine or an amide group.
  • olefinic compounds having an amine or amide group such as N-allyl-N-methylacetamide or allylamine (3-amino-1-propene)
  • these compounds include in particular unsaturated esters and ethers having an amine and / or amide group.
  • amides of (meth) acrylic acid are preferred. These include, inter alia, (meth) acrylamide, N-methylol (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide.
  • (meth) acrylates which are derived from saturated fatty acid amides, such as
  • (meth) acrylic monomers which are an amide or an amine and in the alkyl radical at least one
  • These monomers include, but are not limited to, monomers of the formulas (II), (III) and (IV) set forth above
  • At least one of X 1 , X 2 , X or Y is a
  • compositions for the preparation of polymers preferably comprise (meth) acrylic monomers of the general formula (IV) in which the radical Y denotes a group of the formula NR '', where R ''
  • composition for the production of polymers is a particular aspect of the present invention.
  • composition according to the invention other monomers
  • copolymerizable monomers include, but are not limited to, monomers having an acid group, monomers A comprising ester groups, and styrenic monomers.
  • Acid group-containing monomers are compounds which are preferably free-radical with those set forth above
  • Copolymerize photoinitiator monomers include, for example, monomers having a sulfonic acid group, such as vinylsulfonic acid; Monomers with a
  • Phosphonic acid group such as vinylphosphonic acid and unsaturated carboxylic acids, such as methacrylic acid, acrylic acid, fumaric acid and maleic acid. Particularly preferred are methacrylic acid and acrylic acid.
  • the acid group-containing monomers can be used individually or as a mixture of two, three or more acid group-containing monomers.
  • the preferred ester groups comprising monomers A include in particular (meth) acrylates which differ from the monomers described above, fumarates, maleates and / or vinyl acetate.
  • the term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • the comonomers mentioned include, among others
  • the (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical include, inter alia, (meth) acrylates having a linear or branched alkyl radical, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
  • n-propyl (meth) acrylate iso-propyl (meth) acrylate
  • Decyl (meth) acrylate and cycloalkyl (meth) acrylates, such as
  • Isobornyl (meth) acrylate Isobornyl (meth) acrylate.
  • the above-described (meth) acrylates having 1 to 10 carbon atoms in the alkyl group may be used singly or as a mixture.
  • Another class of comonomers are (meth) acrylates having at least 11 carbon atoms in the alkyl radical, which are derived from saturated alcohols and no heteroatoms in the
  • Alkyl radical such as undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate,
  • Cycloalkyl (meth) acrylates such as 2, 4, 5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate;
  • heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-
  • Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as N- (methacryloyloxyethyl) diisobutylketimine, N- (methacryloyloxyethyl) dihexadecylketimine,
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or
  • HEMA Hydroxyethyl methacrylate
  • Hydroxypropyl (meth) acrylate for example 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, preferably hydroxypropyl methacrylate (HPMA),
  • polyalkoxylated derivatives of (meth) acrylic acid in particular polypropylene glycol mono (meth) acrylate with 2 to 10,
  • propylene oxide units preferably 3 to 6 propylene oxide units, preferably polypropylene glycol monomethacrylate with about 5
  • PPM5 Propylene oxide units
  • polyethylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6
  • Ethylene oxide units preferably polyethylene glycol monomethacrylate with about 5 ethylene oxide units (PEM5),
  • (Meth) acrylamides in particular N-methylol (meth) acrylamide, N, -dimethylaminopropyl (meth) acrylamide, tert. Butylaminoethyl methacrylate, methacrylamide and acrylamide;
  • Monomers These monomers have at least two
  • Glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate,
  • Diurethane dimethacrylate (Meth) acrylates having three or more double bonds, e.g. Glycerol tri (meth) acrylate,
  • the comonomers also include vinyl esters such as vinyl acetate, vinyl chloride, vinyl versatate, ethylene vinyl acetate, ethylene vinyl chloride;
  • maleic acid derivatives such as maleic anhydride, esters of maleic acid, for example
  • styrenic monomers such as styrene, substituted styrenes with a
  • Alkyl substituents in the side chain such as. B.
  • Methylstyrene and ethylstyrene substituted styrenes with an alkyl substituent on the ring, such as vinyltoluene and p-butylstyrene.
  • Methylstyrene, halogenated styrenes such as
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane,
  • Vinyl fluoride, vinylidene chloride and vinylidene fluoride are further examples of comonomers.
  • compositions which preferably contain 1% by weight to 99% by weight, preferably 10% by weight to 95% by weight and very particularly preferably 20% by weight to 90% by weight of units.
  • (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical, based on the weight of the monomers in the composition for the preparation of polymers.
  • compositions containing from 0 to 10% by weight, preferably from 0.5 to 8% by weight and more preferably from 1 to 5% by weight, of units derived from acid group-containing monomers on the weight of the monomers in the composition
  • the composition according to the invention may comprise from 0 to 60% by weight, more preferably from 5 to 50% by weight and most preferably from 10 to 40% by weight of units derived from styrenic monomers, in particular from styrene , substituted styrenes having an alkyl substituent in the side chain, substituted styrenes having an alkyl substituent on the ring and / or halogenated styrenes are derived, based on the weight of the monomers in the composition of
  • compositions are preferred for the preparation of polymers which are a very small proportion of
  • (Meth) acrylates having two or more carbon-carbon double bonds having a reactivity identical to a (meth) acrylate group According to a particular modification of the present invention the proportion of compounds having two or more (meth) acrylate groups is preferably at most 5% by weight, especially at most 2% by weight, particularly preferably at most
  • the amount of monomers in the composition for producing the polymers can be in a wide range.
  • the composition comprises at least 10% by weight of monomers, preferably at least 20% by weight of monomers and most preferably at least 30% by weight of monomers.
  • the upper limit results from the method with the
  • Composition is polymerized. At a
  • composition may consist of the said components, that is the
  • Composition consists of the monomers and the
  • the composition comprises a solvent or suspending agent.
  • Composition of the present invention at least one azo compound which can serve as a radical initiator, in particular for a radical polymerization.
  • R 5 and R 6 are independently a group of 1 to 20 carbon atoms.
  • the radicals having 1 to 20 carbon atoms include, but are not limited to, (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, aryl or heterocyclyl, wherein the aryl - or heterocyclyl radicals may be unsubstituted or substituted and in said alkyl, alkenyl or alkynyl radicals one or more, preferably up to three non-adjacent
  • saturated carbon units may be replaced by heteroatom units, such as oxygen or sulfur, and further wherein 3 to 6 atoms of these optionally modified as above hydrocarbon radicals can form a cycle and these hydrocarbon radicals with or without the specified variations, optionally with a or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series hydroxy (-OH), carboxy (-COOH), formyl, cyano (- CN), sulfonate (SO 3 H), Halogen, preferably fluorine, aryl,
  • Aryloxy, arylthio, (C3-C8) -cycloalkoxy, (C3-C8) -cycloalkylthio, heterocyclyl, heterocyclyloxy or (C1-C2) - alkoxycarbonyl may be substituted, wherein the
  • (C 1 -C 20) -alkyl means an unbranched or branched hydrocarbon radical having 1 to 20 carbon atoms, such as.
  • methyl, ethyl, propyl isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert.
  • Butyl radical; as well as B. the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl, or the 1,1, 3, 3-tetramethylbutyl radical; , as well as z.
  • aryloxy is meant, for.
  • heterocyclyl is meant a
  • heteromatic ring system means an aryl radical in which at least one CH group is replaced by N and 1 or at least two adjacent CH groups are replaced by S, NH or O, is understood, for.
  • heteroaliphatic ring system is replaced by a cycloalkyl radical in which at least one carbon unit is replaced by 0, S or a group NR "and R"
  • preferred azo compounds include
  • 2,2'-azobisisobutyronitrile (2,2'-azobis (isobutyronitrile)), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2, 2 'azobis (2, 4, 4 trimethylvaleronitrile), 1,1'-azobis (cyclooctanecarbonitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (N, N'-dimethyleneisobutyramidine) and / or 2,2'-azobis (isobutyric acid methyl ester) ,
  • azo compounds Particularly preferably used as azo compounds are: 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and / or 2,2'-azobis (isobutyronitrile) ,
  • water-soluble azo compounds can preferably be used, such as
  • azobiscyanovaleric acid for example, azobiscyanovaleric acid, 4- (phenylazo) benzoic acid, 2 (4-hydroxyphenylazo) benzoic acid, 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis [2- (5-methyl-2 - imidazolin-2-yl) propane] dihydrochloride.
  • azobis-cyanovaleric acid 4- (phenylazo) benzoic acid, 2 (4-hydroxyphenylazo) benzoic acid, 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride, 2,2'-azobis (2-
  • Azo compounds having an acid group such as azobiscyanovaleric acid, 4- (phenylazo) benzoic acid,
  • Sodium salt can be used.
  • Azomethine compounds to the usable as radical starter compounds include the formula
  • Free radical initiators include, in particular, 4-hydroxy-5- (2-hydroxybenzylideneamino) -naphthalene-2, 7-disulfonic acid (azomethine-H), said compound
  • radical initiators mentioned can be used individually or as a mixture. Further details may be found in the specialist literature, in particular H. Rauch-Puntigam, Th. Völker, "Acrylic and
  • the proportion of radical initiator in the composition is preferably in the range of 0.05 to 10 wt .-%, in particular 0.1 to 5 wt .-% and most preferably 1 to 3 wt .-%, based on the weight of the monomers in the composition for the production of polymers.
  • Composition comprise further ingredients. These include in particular solvents or water.
  • solvents include in particular aromatic hydrocarbons, such as toluene, xylene; Esters, in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone; Alcohols, especially isopropanol, n-butanol, isobutanol; Ether, in particular
  • glycol monomethyl ether glycol monoethyl ether
  • Glycol monobutyl ether Aliphatic, preferably pentane, hexane, cycloalkane and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gasoline, biodiesel; but also
  • Plasticizers such as low molecular weight polypropylene glycols or phthalates.
  • the composition of the invention is an emulsion.
  • the emulsion is stabilized by emulsifiers to obtain a low dispersion viscosity.
  • the total amount of emulsifier is preferably 0.1 to 15 wt .-%,
  • emulsifiers may be used during the
  • Particularly suitable emulsifiers are anionic or
  • nonionic emulsifiers or mixtures thereof in particular
  • Alkyl sulfates preferably those having 8 to 18
  • Alkylaryl ether sulfates having 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units; Sulfonates, preferably alkyl sulfonates with 8 to 18
  • Carbon atoms in the alkyl radical can also be from 1 to 40
  • Ammonium salts preferably alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the alkyl or
  • Alkyl polyglycol ethers preferably with 8 to 20
  • Alkylaryl polyglycol ethers preferably with 8 to 20
  • Block copolymers desirably with 8 to 40 ethylene oxide or propylene oxide units.
  • anionic emulsifiers include, in particular, fatty alcohol ether sulfates,
  • Nonionic emulsifiers include tert-octyl phenol ethoxylate with 30 ethylene oxide units and Fettalkoholpolyethylenglykolether which preferably 8 to 20 carbon atoms in the alkyl group and 8 to 40 have Ethyleno ⁇ oxide units.
  • These emulsifiers are commercially available under the trade names Triton® X 305 (Fluka), Tergitol® 15-S (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and Marlipal® 0 13/400 (Sasol Germany) ,
  • nonionic emulsifier in the range from 20: 1 to 1:20, preferably 2: 1 to 1:10 and particularly preferably 1: 1 to 1: 5.
  • a fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate in particular a diisooctyl sulfosuccinate or a paraffin sulfonate as anionic emulsifier and an alkylphenol ethoxylate or a
  • the emulsifiers can also be used in admixture with protective colloids.
  • Suitable protective colloids include u. a. partially hydrolyzed polyvinyl acetates,
  • Polyvinyl pyrrolidones carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins,
  • Vinyl ether maleic acid copolymers If protective colloids are used, this is preferably done in an amount from 0.01 to 1.0 wt .-%, based on the total amount of the monomers.
  • Emulsion can be achieved whose aqueous phase has a pH in the range of 4 to 9.5, particularly preferably 5 to 8.
  • the pH value in this context is defined as the negative decadic logarithm of the activity of the oxonium ions (HsO + ).
  • the pH can be determined at a temperature of 25 ° C by conventional titration, where it often sufficient to determine this size with electrical meters (pH meters).
  • compositions comprising a buffer Preference is therefore given in particular to compositions comprising a buffer.
  • the preferred buffers include, in particular, carbonic acid or carbonate buffers, which preferably have a buffer range of from pH 6.2 to pH 8.6.
  • phosphate buffers with a preferred
  • Buffer range from pH 5.4 to pH 7.8, for example, buffers containing KH2 PO4 + Na2HPC> 4 can be used. Furthermore, buffers are preferred, the ammonia / ammonium and / or
  • compositions comprising an electrolyte are preferred.
  • electrolyte denotes a salt, which is preferably derived from the buffers set forth above is, so in particular compositions are preferred which contain, for example, bicarbonates, acetates or phosphates.
  • the concentration of buffer and / or of electrolyte can be in a wide range. This should be the concentration
  • compositions according to the invention can be polymerized in particular by solution polymerizations, bulk polymerizations or emulsion polymerizations, with surprising advantages being achieved by a free-radical polymerization
  • Emulsion polymerizations can be achieved. These are set forth in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition.
  • emulsion polymerization an aqueous phase is prepared which is customary in addition to water Additives, in particular emulsifiers and protective colloids for stabilizing the emulsion may include. Especially preferred are emulsions comprising buffers and / or electrolytes.
  • Monomers are then added to this aqueous phase and polymerized in the aqueous phase.
  • Production of homogeneous polymer particles can in this case a
  • Monomermischung be added over a time interval continuously or batchwise.
  • the emulsion polymerization can be carried out, for example, as a micro-emulsion, which is closer in
  • a miniemulsion is commonly characterized by the use of costabilizers or swelling agents, often long-chain ones
  • Alkanes or alkanols are used.
  • the droplet size for miniemulsions is preferably in the range of 0.05 to 20 ⁇ m.
  • the droplet size in the case of microemulsions is preferably in the range below 1 ⁇ m, in which case particles below a size of 50 nm can be obtained. In microemulsions are often additional
  • Surfactants for example hexanol or similar compounds used.
  • the dispersing of the monomer-containing phase in the aqueous phase can be carried out by known means. These include in particular mechanical methods and the use of ultrasound.
  • core-shell polymers can also be prepared.
  • the composition of the monomer mixture can be changed stepwise, wherein prior to changing the composition, the polymerization is preferably up to a conversion of at least 80 wt .-%, particularly preferably at least 95 wt .-%, each based on the
  • Core-shell polymer here stands for a polymer which is prepared by a two- or multi-stage emulsion polymerization
  • the monomer composition for producing the core preferably comprises 50 to 100% by weight of (meth) acrylates, wherein
  • Methacrylates is used. According to a particular aspect of the present invention, the weight ratio of acrylates to methacrylates in the core may be greater than or equal to 1, more preferably greater than or equal to 2. After the production of the core may be on these preferably a
  • Monomers includes.
  • the emulsion polymerization is preferably carried out at a
  • Radical starters also called initiators, the one
  • the initiators mentioned can be used both individually and in mixtures. They are preferably used in an amount of 0.05 to 3.0 wt .-%, based on the total weight of the monomers of each stage. It is also possible to carry out the polymerization with a mixture of different polymerization initiators having a different half-life, in order to control the free radical flow in the course of the polymerization and at different temperatures
  • the stabilization of the approach is preferably carried out by means of emulsifiers and / or protective colloids.
  • the protective colloids can be initially charged or added before the start of the polymerization.
  • the initiator can be initially charged or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.
  • the polymerization is preferably carried out by heating the batch to the polymerization temperature and template and / or
  • the feed may be interrupted for a few minutes after e.g. 1 - 5% of
  • Monomers are added.
  • the dosages of emulsifier and monomers can be carried out separately or
  • the emulsion polymerization can be carried out in a wide pH range. Preferably, it is between 5 and 9.5. In a particular embodiment, the
  • the range is generally 8 - 9 or above.
  • compositions available polymers are new and therefore also subject of the present invention.
  • Polymers are distinguished in particular by an extremely high proportion of carbon-carbon double bonds in the polymer, based on the amount of (meth) acrylic monomers used, which have at least one C-C double bond and 8 to 40 carbon atoms in the alkyl radical.
  • the molecular weight of (meth) acrylic polymers according to the invention can be within a wide range.
  • the weight average molecular weight is usually at least 1000 g / mol, preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol.
  • the weight average molecular weight is usually at least 1000 g / mol, preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol.
  • (Meth) acrylic polymers are used which have a relatively high molecular weight. These (meth) acrylic polymers can be obtained in particular by emulsion polymerization, these (meth) acrylic polymers, for example, a
  • Emulsionspolymere are characterized in particular by a high environmental impact, since these often no
  • low molecular weight (meth) acrylic polymers may also be used. These (meth) acrylic polymers can be used.
  • a weight average molecular weight in the range of 1000 to 150000 g / mol, in particular 4000 to 100000 g / mol, particularly preferably in the range of 5000 to 50,000 g / mol.
  • Coating compositions used with organic solvents exhibit good processability over a wide temperature and humidity range. In relation to the performance show
  • Coating compositions with these (meth) acrylic polymers improved environmental compatibility.
  • extremely small amounts of organic solvents are released into the environment through evaporation, as the
  • Solvent content can be selected relatively low for a given workability.
  • (meth) acrylic polymers which have a polydispersity index M w / M n in the range from 1 to 5, particularly preferably in the range from 2 to 3.
  • the molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.
  • the glass transition temperature of the polymer (s) to be used according to the invention is preferably in the range from -30 ° C. to 70 ° C., more preferably in the range from -20 to 40 ° C. and very particularly preferably in the range from 0 to 25 ° C.
  • the glass transition temperature can be influenced by the type and proportion of monomers used to make the polymer.
  • the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC), for example according to DIN 53765.
  • DSC differential scanning calorimetry
  • Tg Tgl Tg 2 Tg n Tg n
  • x n is the mass fraction (% by weight / 100) of the monomer n
  • Tg n is the glass transition temperature in Kelvin
  • the polymer may have one or more different
  • Mixture comprising at least one (meth) acrylic monomer having at least one double bond in the alkyl radical and 8 to 40
  • Monomer mixture according to the invention is available.
  • the architecture of the (meth) acrylic polymer is for many reasons.
  • the polymers in particular the emulsion polymers, can be random copolymers, gradient copolymers,
  • Block copolymers and / or graft copolymers are Block copolymers and / or graft copolymers.
  • Block copolymers or gradient copolymers can be any suitable copolymers or gradient copolymers.
  • the emulsion polymer
  • the (meth) acrylic polymer is a statistical
  • a copolymer in which the monomer composition is substantially constant throughout the polymerization may vary across the polymer chain of the polymer.
  • the polymer may be a homogeneous polymer which, for example, forms particles with a constant composition in an aqueous dispersion.
  • the polymer which is preferably an emulsion polymer, may consist of one or more segments obtainable by polymerization of a monomer mixture.
  • the polymer may be a core-shell polymer which may have one, two, three, or more shells.
  • the shell may be connected to the core or inner shells via covalent bonds.
  • the shell can also be polymerized on the core or an inner shell.
  • the outermost shell of preferred emulsion polymers may preferably comprise from 10 to 40% by weight, more preferably from 15 to% by weight, of (meth) acrylic monomers
  • Double bond and having from 8 to 40 carbon atoms comprise, based on the weight of the outermost shell.
  • Polymer preferably in the range of 2 to 250 g of iodine per 100 g of polymer, more preferably 5 to 100 g of iodine per 100 g
  • Polymer and most preferably 10 to 50 g of iodine per 100 g of polymer, measured in accordance with DIN 53241-1.
  • the (meth) acrylic polymer may have an acid number in the range of 0 to 40 mg KOH / g, preferably 1 to 20 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g.
  • the acid number can also be determined by dispersion according to DIN EN ISO 2114.
  • the hydroxyl number of the (meth) acrylic polymer may preferably be in the range from 0 to 200 mg KOH / g, more preferably 1 to 100 mg KOH / g and most preferably in the range from 3 to 50 mg KOH / g.
  • the hydroxyl number can be determined according to DIN EN ISO 4629.
  • the molecular weight of the polymers is initially uncritical within wide limits.
  • Coating agent with good mechanical properties desired, as high a molecular weight may be helpful.
  • Proportion of polymers which are insoluble in THF can be obtained in the manner set forth above.
  • Coating compositions which are particularly easy and easy to process may also have lower molecular weight polymers, the
  • Coatings reached a relatively high level.
  • these polymers having a particularly good processability, a molecular weight below 1 000 000 g / mol, preferably below 500 000 g / mol and more preferably below 250 000 g / mol.
  • the molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.
  • Polymers in particular low molecular weight emulsion polymers, can be prepared by the addition of
  • Molecular weight regulators are obtained in the reaction mixture before or during the polymerization. Sulfur-free molecular weight regulators and / or
  • sulfur-containing molecular weight regulators are used.
  • the sulfur-free molecular weight regulators include, for example, but without limitation, dimeric methylstyrene (2,4 diphenyl-4-methyl-1-pentene), enol ethers aliphatic and / or cycloaliphatic aldehydes, terpenes, ⁇ -terpinene, terpinolene, 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1,4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6 Dihydro-2H-pyran, preferred is dimeric methylstyrene.
  • Dialkyl disulfides and / or diaryl sulfides are used.
  • the following polymerization regulators are given by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide,
  • Diethanol sulfide, di-t-butyl trisulfide and dimethyl sulfoxide Preferably used as molecular weight regulators
  • Dialkyl disulfides and / or diaryl sulfides are ethyl thioglycolate, 2-
  • Thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.
  • Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids.
  • the molecular weight regulators are preferably used in amounts of 0.05 to 10, more preferably 0.1 to 5 wt .-%, based on the monomers used in the polymerization. Of course, mixtures of polymerization regulators can also be used in the polymerization.
  • the proportion of molecular weight regulators may be such that the (meth) acrylic polymers or the coating compositions of the invention have a minimum film-forming temperature (MFT) of at most 60 ° C, more preferably at most 50 ° C and most preferably
  • MFT minimum film-forming temperature
  • the adjustment of the particle radii can be influenced inter alia by the proportion of emulsifiers. The higher this proportion, especially at the beginning of the polymerization, the smaller the particles are obtained.
  • Emulsion polymer in particular the (meth) acrylic polymer uncrosslinked or crosslinked so low that the in
  • Tetrahydrofuran (THF) at 20 ° C soluble fraction is above 60 wt .-% based on the weight of the emulsion polymer.
  • THF Tetrahydrofuran
  • Emulsion polymer has a content of 0 to 60 wt .-%, particularly preferably 5 to 50 wt .-% and most preferably 10 to 40 wt .-%, based on the weight of
  • Emulsion polymer which is soluble in THF at 20 ° C. To determine the soluble fraction is an under
  • a 0.5 g sample of a vacuum-dried emulsion polymer can be stored in 150 ml of THF for 4 hours.
  • Polymers of the invention may preferably have a relatively low minimum film-forming temperature, although they have a high molecular weight.
  • these polymers can have a relatively high proportion of constituents which are dissolved in tetrahydrofuran (THF) at 20.degree
  • the particle radius of the emulsion polymers can be in a wide range.
  • emulsion polymers having a particle radius in the range of 10 to 500 nm, preferably 10 to 100 nm, particularly preferably 20 to 60 nm can be used.
  • particle radii below 50 nm can be advantageous for the film formation and the
  • the radius of the particles can be determined by PCS (Photon Correlation Spectroscopy), the data given refer to the r50 value
  • Emulsion polymers in particular (meth) acrylic polymers, exhibit a swelling factor of at least 1, in particular
  • Swelling factor is first the particle radius of the
  • volume ratio of THF / water 90:10 set. The measurement is carried out at 20 ° C, the dispersion is swollen after addition of the solvent (THF) for 5 minutes. The quotient of the particle volumes calculated from the obtained particle radii (r Lsgm . And ⁇ asser) is defined as swelling factor (QF):
  • High swelling factors in particular show emulsion polymers which have low crosslinking. Accordingly, in particular, emulsion polymers obtained from a monomer mixture having a low content of compounds having two or more (meth) acrylate groups show a high swelling factor.
  • Low swelling factors may in particular also be due to the fact that there is a high residual monomer content and / or a high content of low molecular weight oligomers which each transferred to the THF / water phase. As a result, swelling factors smaller than 1 can be measured.
  • Such coating compositions are also the subject of the present invention.
  • Coating agent preferably 40 to 80 wt .-%, particularly preferably 50 to 75 wt .-% of at least one
  • (Meth) acrylic polymer having units derived from (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl radical.
  • compositions of the invention do not require siccatives, but these may be included as an optional ingredient in the compositions.
  • organometallic compounds such as metal soaps of transition metals, such as
  • Alkaline earth metals such as lithium, potassium and calcium.
  • the siccatives can be used individually or as a mixture, with particular preference being given to mixtures containing cobalt, zirconium and lithium salts.
  • the proportion of siccatives in preferred coating compositions may preferably be in the range of 0.5 to 5 wt .-%, especially preferably in the range of 1 to 3 wt .-% based on the
  • the coating agents may comprise solvents. These coating compositions can over a particularly wide
  • the term of the solvent is to be understood here broadly.
  • the preferred solvents include in particular
  • aromatic hydrocarbons such as toluene, xylene
  • Esters in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate
  • Ketones preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone
  • Alcohols especially isopropanol, n-butanol, isobutanol
  • Ether in particular
  • glycol monomethyl ether glycol monoethyl ether
  • Glycol monobutyl ether Aliphatic, preferably pentane, hexane, cycloalkane and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gasoline, biodiesel; but also
  • Plasticizers such as low molecular weight polypropylene glycols or phthalates.
  • Coating agents may in particular be in the range from 0 to 50% by weight, more preferably in the range from 1 to 20% by weight.
  • a surprisingly good processability show coating compositions whose solids content is preferably at least 50% by weight, more preferably at least 60% by weight. This information applies in particular to
  • Coating compositions comprising organic solvents.
  • coating compositions according to the invention a relatively high Proportion of water, with aqueous dispersions being particularly preferred coating agents.
  • the aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight.
  • These coating compositions often comprise only a very small, preferably no fraction of organic
  • aqueous dispersions comprise at most 5% by weight, more preferably at most 2% by weight, of volatile organic constituents (VOC), such as residual monomers or organic solvents. These coating compositions are therefore characterized by a particularly high
  • coating compositions according to the invention may contain conventional additives, in particular UV stabilizers,
  • Flushing aids and biocides are included.
  • the dynamic viscosity of the coating agent is dependent on the solids content and may include a wide range. So this can be more than at high polymer content
  • Coating agents preferably have a minimum film-forming temperature (MFT) of at most 60 ° C, more preferably at most 50 ° C, and most preferably
  • Coating compositions of the invention exhibit a minimum film-forming temperature (MFT) in the range of -30 ° C to 15 ° C. Those available according to the present invention
  • the present invention provides a method for producing a coating in which a coating composition of the invention is applied to a substrate and cured.
  • the coating composition of the invention can be applied by conventional application methods, in particular by roller application or spraying. Continue to be
  • the curing of the coating agent is carried out by drying and by oxidative crosslinking means
  • the present coating composition can be used in particular as a varnish, varnish, sealant, adhesive and printing ink
  • coating composition according to the invention can be provided include in particular wood, metals, especially iron and steel, and plastics.
  • the present invention provides coated articles obtainable by a method according to the invention.
  • the weight loss after treatment with MIBK is preferably at most 50% by weight, preferably at most 35% by weight.
  • the uptake of MIBK is preferably at most 1000 wt .-%, more preferably at most 600 wt .-%, based on the weight of the coating used. These values are measured at a temperature of about 25 ° C and an exposure time of at least 4 hours, whereby a completely dried coating is measured, which was crosslinked.
  • Coating agents are obtained show a high
  • the pendulum hardness is preferably at least 15 s, preferably at least 25 s, measured in accordance with DIN ISO 1522.
  • Inventive coatings show surprisingly good mechanical properties. Of particular interest are, in particular, coatings which have a nominal elongation at break of preferably at least 100%, particularly preferably at least 200%, measured in accordance with DIN EN ISO 527 Part 3.
  • coatings are furthermore preferred which have a tensile strength, measured in accordance with DIN EN ISO 527 Part 3, of at least 0.5 MPa, more preferably at least 2 MPa.
  • Coatings are available, which have a tensile strength of at least 1 MPa, more preferably at least 2 MPa, an elongation at break of at least 100%, more preferably at least 200%.
  • preferred coatings which are obtainable from the coating compositions of the invention have a surprisingly high adhesive strength, which can be determined in particular according to the cross-cut test.
  • the reaction mixture was heated to boiling.
  • Methyl methacrylate / methanol azeotrope was separated, with the head temperature gradually increasing to 100 ° C.
  • Dosing of the emulsion from a feed vessel, a Lewa piston metering pump, type HK with 5 mm piston was set to a capacity of 1.66 g / min used.
  • the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 7.3, a viscosity of 10 mPas and an r N5 value of 110 nm.
  • the swelling factor of the emulsion was determined.
  • Emulsion polymers in water (r water ) by PCS Photon
  • THF tetrahydrofuran
  • the measurement was carried out at 20 ° C, the dispersion was swollen after addition of the solvent (THF) for 5 minutes.
  • the quotient of the calculated particle radii (r Lsgm and r water )
  • Particle volumes are defined as swelling factor (QF):
  • the emulsion polymers showed a swelling factor of 1.15
  • Dosing of the emulsion from a feed vessel, a Lewa piston metering pump, type HK with 5 mm piston was set to a capacity of 1.66 g / min used. After the end of the feed was stirred at 80 ° C for 1 hr. It was then cooled to room temperature and the dispersion was filtered through VA mesh with 0.09 mm mesh size.
  • the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 7.2, a viscosity of 12 mPas and an rN5 value of 105 nm.
  • Lewa piston metering pump type HK with 5 mm piston set to a capacity of 1.66 g / min. Used.
  • the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 7.3, a viscosity of 12 mPas and an r N5 value of 79 nm.
  • Methacrylic acid 7.5 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 6 g of Disponil FES 32 (30%), 9 g of Triton X305, 0.3 g of NaHCO 3 in 10 g water, 0.63 g Na 2 C0 3 in 10 g water, 0.2 g regulator (2-
  • Dosing of the emulsion from a feed vessel was a Lewa piston metering pump, type HK with 5 mm piston set to a capacity of 1.58 g / min used.
  • the produced emulsion had a solids content of 40 ⁇ 1%, a pH of 7.6, a viscosity of 11 mPas and an r N5 value of 104 nm.
  • Dosing of the emulsion from a feed vessel was a Lewa piston metering pump, type HK with 5 mm piston set to a capacity of 1.59 g / min used.
  • the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 7.3, a viscosity of 16 mPas and an rN5 value of 92 nm.
  • Solvent resistance was determined using methyl isobutyl ketone (MIBK), with a sample (A) swollen with MIBK at room temperature for 4 hours. The sample was then removed from the solvent, excess solvent removed and the weight determined. Subsequently, the sample was dried for 1 hour at about 140 ° C (B). From the difference in weight between A and B, the fraction of the sample removed by the solvent is calculated. The swelling was calculated based on the weight of sample B freed from soluble fractions and will be referred to herein as "true swelling".
  • MIBK methyl isobutyl ketone
  • the resulting coating composition had a minimum film-forming temperature (MFT) of 9.5 ° C and a
  • Dihydrogen phosphate and hydrogen phosphate was used.
  • a 4: 1 mixture (molar) was used, wherein the molar concentration of dihydrogen phosphate was 0.02 mol / 1 and the molar concentration of hydrogen phosphate 0.005 mol / 1.
  • the pH of the emulsion was 6.5.
  • the resulting coating composition had a minimum film-forming temperature (MFT) of less than 0 ° C and a swelling factor of 1.00.
  • MFT film-forming temperature
  • the true swelling in MIBK after 4 hours was 258% and the weight loss related to the sample released from soluble portions was 37.1%.
  • the coating composition obtained had a minimum
  • MFT Film Forming Temperature

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  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition pour la préparation de polymères, contenant au moins un monomère et au moins un initiateur de radicaux. L'initiateur de radicaux est un composé azo, au moins un monomère est un monomère amide ou amine, et au moins un monomère est un (méth)acryl-monomère présentant dans le reste alkyle au moins une double liaison C-C et 8 à 40 atomes de carbone. L'invention concerne par ailleurs un (méth)acryl-polymère pouvant être obtenu à partir de la composition selon l'invention, un agent de revêtement et un revêtement.
PCT/EP2011/060831 2010-07-06 2011-06-28 Composition pour la préparation de polymères, (méth)acryl-polymère, agent de revêtement et revêtement WO2012004160A1 (fr)

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DE102010030970A DE102010030970A1 (de) 2010-07-06 2010-07-06 Zusammensetzung zur Herstellung von Polymeren, (Meth)acryl-Polymer, Beschichtungsmittel und Beschichtung
DE102010030970.2 2010-07-06

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WO2012004160A1 true WO2012004160A1 (fr) 2012-01-12

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WO2006013061A1 (fr) 2004-08-03 2006-02-09 Imperial Chemical Industries Plc Revetements et peintures a faible teneur en composes organiques volatils
WO2008094503A2 (fr) 2007-01-30 2008-08-07 University Of South Mississippi Dérivés d'huile végétale fonctionnalisés dépourvus d'ester de glycérol et leurs compositions de latex
WO2010026119A1 (fr) * 2008-09-08 2010-03-11 Evonik Röhm Gmbh Monomère de (méth)acrylate, polymère et produit de revêtement

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TW201217407A (en) 2012-05-01

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