WO2007057365A2 - Procede de production d'une dispersion de polymere aqueuse - Google Patents

Procede de production d'une dispersion de polymere aqueuse Download PDF

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WO2007057365A2
WO2007057365A2 PCT/EP2006/068371 EP2006068371W WO2007057365A2 WO 2007057365 A2 WO2007057365 A2 WO 2007057365A2 EP 2006068371 W EP2006068371 W EP 2006068371W WO 2007057365 A2 WO2007057365 A2 WO 2007057365A2
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monomer
weight
monomers
aqueous polymer
atoms
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PCT/EP2006/068371
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WO2007057365A3 (fr
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Rajan Venkatesh
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Basf Se
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    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide

Definitions

  • the present invention is a process for the preparation of an aqueous polymer dispersion by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one dispersant and at least one free-radical initiator, which is characterized in that for the emulsion
  • DE-OS 1720277 discloses a process for the preparation of film-forming aqueous polymer dispersions using vinyl esters and 1-octene.
  • the weight ratio of vinyl ester to 1-octene can be from 99: 1 to 70:30.
  • the vinyl esters may be minor in admixture with other copolymerizable ethylenically unsaturated compounds are used for emulsion polymerization.
  • Suitable monomers A are all alkenes having 4 C atoms and having an ethylenically unsaturated double bond which can be free-radically copolymerized and which, in addition to carbon and hydrogen, have no further elements. These include in particular the alkenes n-butene-1, n-butene-2 (cis- and trans-form) and 2-methylpropene (isobutene). Preference is given to using n-butene-1 and / or 2-methylpropene. Of course, it is also possible to use mixtures of the abovementioned monomers A or gas mixtures containing them.
  • C4 sections of a naphtha cracker in particular the raffinate II section (consisting of 30 to 50 wt .-% n-butene-1, 30 to 50 wt .-% n-butene-2, 10 bis 30% by weight of n-butane and ⁇ 10% by weight of other compounds).
  • monomers B are esters based on a 3 to 6 C-atoms, in particular a 3, or 4 C-containing ⁇ , ß-monoethylenically unsaturated mono- or dicarboxylic acid, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid and a 1 to 12 carbon atoms alkanols, preferably an alkanol having 1 to 8 carbon atoms and in particular a 1 to 4 C
  • Atoms containing alkanol in particular methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methylpropanol-1, tert-butanol, n-pentanol, 3-methylbutanol-1, n-hexanol, 4-methylpentanol -1, n-heptanol, 5-methylhexanol-1, n-octanol, 6-methylheptanol-1, n-nonanol, 7-methyloctanol-1, n-decanol, 8-methylnonanol-1, n-dodecanol, 9-methyldecanol -1 or 2-ethylhexanol-1 use.
  • acrylic and methacrylic acid methyl, ethyl, n-butyl, iso-butyl, pentyl, hexyl, heptyl, toetyl, nonyl, decyl, ethylhexyl or dodecyl ester, fumaric and maleic acid dimethyl ester or di-n-butyl ester used.
  • esters can be used.
  • monomers C are optionally 3 to 6 carbon atoms having ⁇ , ß-monoethylenically unsaturated mono- or dicarboxylic acids and / or their amides, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid or acrylamide or methacrylamide used.
  • monomers C can also be used.
  • Examples of monomers D which differ from the monomers A to C are .alpha.,. Beta.-ethylenically unsaturated compounds, such as, for example, vinylaromatic monomers, such as styrene, .alpha.-methylstyrene, o-chlorostyrene or vinyltoluenes, vinyl halides, such as vinyl chloride or vinylidene chloride, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 C atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, nitriles ⁇ , ⁇ -mono- or diethylenically unsaturated Carboxylic acids, such as acrylonitrile, methacrylonitrile, fumaronitrile, malononitrile and 4 to 8 carbon atoms having conjugated dienes, such as 1, 3-butadiene and isoprene, moreover vinylsulfonic acid, 2-
  • Examples include two vinyl radicals containing monomers, two vinylidene radicals having monomers and two alkenyl radicals having monomers. Particularly advantageous are the diesters of dihydric alcohols with .alpha.,. Beta.-monoethylenically unsaturated monocarboxylic acids, of which the acrylic and methacrylic acids are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and ethylene glycol dimethacrylate, 1, 2.
  • methacrylic acid and acrylic acid C 1 -C 8 -hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate, and also compounds such as glycidyl acrylate or methacrylate, diacetone acrylamide and acetylacetoxyethyl acrylate or methacrylate.
  • monomers D can be used.
  • the monomers A to D add up to 100% by weight.
  • monomers A are in particular n-butene-1 and / or 2-methylpropene
  • monomers B in particular n-butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate and / or tert-butyl acrylate
  • monomers C in particular acrylic acid, methacrylic acid and / or Itaconic acid and used as monomers D divinylbenzene, allyl methacrylate and / or diacetoneacrylamide.
  • Particular preference is given to free-radically initiated aqueous emulsion polymerization
  • the monomers A to D also add up to 100 wt .-%.
  • At least a partial amount or the total amount of the monomers A to D in the aqueous reaction medium can be initially charged and the residual amount remaining in the aqueous reaction medium, after initiation of the free-radical polymerization reaction, batchwise in one portion, discontinuously in several portions and continuously with constant or changing Volumes are added.
  • the monomers B to D are added to the aqueous reaction medium in the form of a mixture.
  • the addition of monomers B to D takes place in the form of an aqueous monomer emulsion, while monomer A is added via a separate feed.
  • dispersants are used in the context of the present process which keep both the monomer droplets and the polymer particles formed dispersed in the aqueous medium and thus ensure the stability of the aqueous polymer dispersion produced.
  • Suitable dispersants are both the protective colloids commonly used for carrying out free-radical aqueous emulsion polymerizations and emulsifiers.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N-
  • Vinylcarbazole 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, pages 41 1 to 420.
  • mixtures of protective colloids and / or emulsifiers can be used.
  • dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature.
  • anionic emulsifiers are compatible with each other and with nonionic emulsifiers.
  • anionic and cationic emulsifiers are usually incompatible with each other.
  • emulsifiers are used in particular as dispersants.
  • Nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and also ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: Cs to C36).
  • Lutensol ® A grades C 2 Ci4-fatty alcohol ethoxylates, EO units: 3 to 8
  • Lutensol ® AO-marks C13C15- oxo alcohol ethoxylates, EO units: 3 to 30
  • Lutensol ® AT-marks Ci Ci 6 8 - fatty alcohol ethoxylates, EO units: 1 1 to 80
  • Lutensol ® ON brands C10 oxo alcohol ethoxylates, EO units: 3 to 11
  • Lutensol ® tO brands C13 oxo alcohol ethoxylates, EO : 3 to 20
  • Typical anionic emulsifiers include alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical: C12 to C 8) and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C 4 to C 12), of alkylsulfonic acids (alkyl radical: C 12 to Cis) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis).
  • Further anionic emulsifiers further compounds of the general formula (I)
  • R 1 and R 2 are H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms, and M 1 and M 2 may be alkali metal ions and / or ammonium ions, has been found to be suitable.
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R 1 and R 2 are not both simultaneously H and Atoms are.
  • M 1 and M 2 are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • Suitable cationic emulsifiers are usually a ce to cis-alkyl
  • Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N 1 N 1 N-trimethylammonium) ethylparaffinklar, N-cetylpyridinium, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium sulfate, N- dodecyl N, N, N-trimethylammoniumsulfat, N-octyl-N, N, N-trimethylammoniumsulfat, N 1 N- distearyl-N, N-dimethylammonium sulfate, and also the gemini surfactant N 1 N'-(lauryl) ethylendiamindisulfat, ethoxylated tallow -N-methyl ammonium sulfate and ethoxylated oleylamine (for example Uniperol.RTM ®
  • nucleophilic such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and konju- g.
  • organosulfonic acids for example methylsulfonate, trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate ,
  • the emulsifiers preferably used as dispersants are advantageously used in a total amount of> _ 0.005 and ⁇ 10 wt .-%, preferably> _ 0.01 and ⁇ 5 wt .-%, in particular> _ 0.1 and ⁇ 3 wt .-%, in each case based on the total amount of monomers used.
  • the total amount of the protective colloids used as dispersing agents in addition to or instead of the emulsifiers is often _ 0.1 and ⁇ 10% by weight and frequently _ 0.2 and ⁇ 7% by weight, in each case based on the total amount of monomer.
  • free-radical polymerization initiator can be both peroxides and azo compounds.
  • redox initiator systems come into consideration.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides
  • alkyl hydroperoxides For example, tert-butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or Diarylperoxide, such as di-tert-butyl or di-cumyl peroxide are used.
  • Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
  • Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulphites, for example potassium and / or sodium sulphite, alkali hydrogen sulphites, for example potassium and / or sodium hydrogen sulphite, alkali metal bisulphites, for example potassium and / or sodium metabisulphite, formaldehyde sulphoxylates, for example potassium and / or
  • alkali metal salts especially potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, iron (II ) phosphate, endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing saccharides, such as sorbose,
  • Glucose, fructose and / or dihydroxyacetone are used.
  • the amount of the radical initiator used based on the total amount of monomers, 0.01 to 5 wt .-%, preferably 0.1 to 3 wt .-% and particularly preferably 0.2 to 1, 5 wt .-%.
  • the total amount of the radical initiator can be initially charged in the aqueous reaction medium.
  • the reaction temperature for the free-radical aqueous emulsion polymerization according to the invention is the entire range from 0 to 170 ° C into consideration. In this case, temperatures of 50 to 120 ° C, often 60 to 1 10 ° C and often 70 to 100 ° C are usually applied.
  • the inventive radical aqueous emulsion polymerization can in principle be carried out at a pressure of less than, equal to or greater than 1 bar (absolute), so that the polymerization temperature can exceed 100 ° C. and can be up to 170 ° C.
  • the pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar or even higher values.
  • polymerisation takes place under such a pressure, under which monomer A is in the liquid phase.
  • novel free-radical aqueous emulsion polymerization is carried out in the absence of atmospheric oxygen, for example under an inert gas atmosphere, in particular nitrogen or argon, or after repeated rinsing of the reaction vessel with monomer A.
  • the aqueous reaction medium may in principle also comprise water-soluble organic solvents, such as, for example, methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc. in amounts of ⁇ 10% by weight, based on the total dispersion.
  • water-soluble organic solvents such as, for example, methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • the process according to the invention is preferably carried out in the absence of such solvents.
  • free radical-transferring compounds in the process according to the invention in order to reduce or control the molecular weight of the polymers obtainable by the polymerization.
  • free radical-transferring compounds such as, for example, n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide , organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethi
  • n-nonanethiol and its isomeric compounds n-decanethiol and its isomeric compounds
  • n-undecanethiol and its isomeric compounds n-dodecanethiol and its isomeric compounds
  • n-tridecanethiol and its isomeric compounds substituted thiols such as 2-hydroxyethanethiol aromatic thiols, such as benzenethiol, ortho-, meta- or para-methylbenzenethiol, as well as all others in Polymerhandbook 3 rd edtition, 1989, J.
  • the total amount of radical-chain-transferring compounds optionally used in the process according to the invention is generally ⁇ 5% by weight, often ⁇ 3% by weight and frequently ⁇ 1% by weight.
  • a partial or total amount of the optionally used radical chain-transmitting compound is fed to the reaction medium before the initiation of the free-radical polymerization.
  • a partial or total amount of the radical chain-transferring compound can advantageously also be fed to the aqueous reaction medium together with the monomers A to D during the polymerization.
  • the polymers obtainable by the process according to the invention can in principle have glass transition temperatures in the range from -70 to +150 ° C, often -30 to +100 ° C and often -20 to +50 ° C.
  • the monomers A to D are chosen such that the resulting polymer has a glass transition temperature T 9 ⁇ + 20 ° C.
  • the monomers A to D are chosen such that polymers having a T g value ⁇ +10 ° C, ⁇ 0 ° C, ⁇ -10 ° C, ⁇ -20 ° C, ⁇ -30 ° C, ⁇ -40 ° C or ⁇ -50 ° C are formed.
  • glass transition temperature is meant here the midpoint temperature according to ASTM D 3418-82, determined by differential thermal analysis (DSC) [cf. also Ullmann 's Encyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992 and Zosel in paint and varnish, 82, pages 125 to 134, 1976].
  • DSC differential thermal analysis
  • Glass transition temperatures of each of only one of the monomers 1, 2 n constructed polymers in degrees Kelvin The glass transition temperatures of these homopolymers of most ethylenically unsaturated monomers are known (or can be determined experimentally in a simple manner known per se) and, for example, in J. Brandrup, EH Immergut, Polymer Handbook 1 st Ed. J. Wiley, New York, 1966, 2 nd Ed. J. Wiley, New York, 1975 and 3 rd Ed. J. Wiley, New York, 1989, and in Ullmann 's Cncyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992.
  • the free-radically initiated aqueous emulsion polymerization in the presence of a polymer seed for example in the presence of 0.01 to 3 wt .-%, often from 0.02 to 2 wt .-% and often from 0.04 to 1, 5 wt. % of a polymer seed, in each case based on the total amount of monomers.
  • a polymer seed is used in particular when the particle size of the polymer particles to be prepared by free-radical aqueous emulsion polymerization is to be specifically adjusted (see, for example, US Pat. No. 2,520,959 and US Pat. No. 3,397,165).
  • a polymer seed is used whose polymer seed particles have a narrow particle size distribution and weight-average diameters D w ⁇ 100 nm, often> 5 nm to ⁇ 50 nm and often 15 nm to ⁇ _ 35 nm.
  • the determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, by the method of the analytical ultracentrifuge.
  • weight-average particle diameter of the weight-average D determined by the method of the analytical ultracentrifuge W 5o value is in this document understood (see. This SE Har- ding et al.
  • narrow particle size distribution is to be understood as meaning the ratio of the weight-average particle diameter D w determined by the method of the analytical ultracentrifuge and the number-average particle diameter DN 50 [D W 5O / DN 50] ⁇ 2.0, preferably ⁇ 1.5 and particularly preferably ⁇ 1, 2 or ⁇ 1, 1.
  • the polymer seed is used in the form of an aqueous polymer dispersion.
  • the aforementioned amounts are based on the polymer solids content of the aqueous Polymersaatdispersion; they are therefore given as parts by weight of polymer seed solids, based on the total amount of monomers.
  • a foreign polymer seed is understood to mean a polymer seed which in one Separate reaction step was prepared and their monomeric composition is different from the radical prepared by the free radical aqueous emulsion polymerization, but this means nothing else than that different monomers or monomer mixtures used with different composition for producing the Fremdpolymersaat and for preparing the aqueous polymer become.
  • the preparation of a foreign polymer seed is familiar to the person skilled in the art and is usually carried out by initially charging a relatively small amount of monomers and a relatively large amount of emulsifiers in a reaction vessel and adding a sufficient amount of polymerization initiator at reaction temperature.
  • polymer foreign seed having a glass transition temperature> 50 ° C., frequently> 60 ° C. or> 70 ° C. and often> 80 ° C. or> 90 ° C.
  • polystyrene or polymethyl methacrylate polymer seed Particularly preferred is a polystyrene or polymethyl methacrylate polymer seed.
  • the total amount of Fremdpolymersaat can be submitted before the beginning of the addition of the monomers A to D in the reaction vessel. But it is also possible to submit only a subset of the Fremdpolymersaat before the beginning of the addition of the monomers A to D in the reaction vessel and to add the remaining amount during the polymerization. If necessary, however, it is also possible to add the total amount of polymer seed in the course of the polymerization. Preferably, the total amount of Fremdpolymersaat before the beginning of the addition of the monomers A to D is placed in the reaction vessel.
  • the aqueous polymer dispersion obtained according to the invention usually has a polymer solids content of> 10 and ⁇ 80% by weight, frequently> 20 and ⁇ 70% by weight and often> 25 and ⁇ 60% by weight, based in each case on aqueous polymer dispersion, on.
  • the quasi-elastic light scattering (ISO standard 13 321) determined number average particle diameter (cumulant z average) is usually between 10 and 2000 nm, often between 20 and 1000 nm and often between 100 and 700 nm and 100 to 400 nm.
  • aqueous polymer dispersions obtainable by the process according to the invention can be used in particular for the production of adhesives, sealants, plastic plasters, paper coating slips, fiber webs, paints and coating compositions for organic substrates, such as leather or textile materials, and for the modification of mineral binders.
  • the aqueous polymer dispersions obtainable by the process according to the invention are preferably tackified, i. a tackifying resin is added.
  • Tackifiers are, for example, from Adäsive Age, July 1987, pages 19 to 23 or Polym. Mater. Be. Closely. 61 (1989), pages 588 to 592 known.
  • Tackifiers are e.g. Natural resins, such as rosin resins and their derivates resulting from disproportionation or isomerization, polymerization, dimerization or hydrogenation. These may be in their salt form (with, for example, monovalent or polyvalent counterions [cations]) or preferably in their esterified form. Alcohols used for esterification may be monovalent or polyvalent. Examples are methanol, ethanediol, diethylene glycol, triethylene glycol, 1, 2,3-propanetriol (glycerol) or pentaerythritol.
  • Natural resins such as rosin resins and their derivates resulting from disproportionation or isomerization, polymerization, dimerization or hydrogenation. These may be in their salt form (with, for example, monovalent or polyvalent counterions [cations]) or preferably in their esterified form. Alcohols used for esterification may be monovalent or polyvalent. Examples are methanol, ethanedio
  • hydrocarbon resins e.g. Coumarone-indene resins, polyester terpene resins, hydrocarbon resins based on unsaturated C-H compounds, such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene or vinyltoluenes Use.
  • unsaturated C-H compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene or vinyltoluenes
  • unsaturated C-H compounds such as butadiene, pentene, methylbutene, is
  • tackifiers are increasingly also polyacrylates, which have a low molecular weight used.
  • these polyacrylates have a weight average molecular weight below 30,000 g / mol.
  • the polyacrylates are preferably at least 60, in particular at least 80 wt .-% of d-Cs-alkyl acrylates or methacrylates.
  • Preferred tackifiers are natural or chemically modified rosin resins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
  • the tackifiers can be added in a simple manner to the aqueous polymer dispersions obtainable according to the invention.
  • the tackifiers are preferably themselves in the form of an aqueous dispersion.
  • the amount of tackifier is preferably 5 to 100 wt .-%, particularly 10 to 50 wt .-%, each based on the total amount of the polymer (solid / solid).
  • tackifiers In addition to tackifiers, it is of course also possible to use other customary additives, for example thickeners, defoamers, plasticizers, pigments, wetting agents or fillers in the formulation of pressure-sensitive adhesives.
  • the aqueous polymer dispersions may by conventional methods, for example by rolling, knife coating, brushing, etc. on substrates, such as paper or polymer tapes and films, preferably consisting of polyethylene, polypropylene, which may be stretched biaxially or monoaxially, polyethylene terephthalate, polyvinyl chloride, polystyrene, Polyamide or metal surfaces are applied.
  • substrates such as paper or polymer tapes and films, preferably consisting of polyethylene, polypropylene, which may be stretched biaxially or monoaxially, polyethylene terephthalate, polyvinyl chloride, polystyrene, Polyamide or metal surfaces are applied.
  • the water can be easily removed by drying at 50 to 150 ° C.
  • the pressure-sensitive adhesive-coated side of the substrates for example the labels or tapes, can be covered with a release paper, for example with a siliconized paper.
  • aqueous polymer dispersions obtainable by the process according to the invention are advantageously suitable as components in adhesives, in particular pressure-sensitive adhesives.
  • these adhesives according to the invention advantageously have improved adhesion to plastic surfaces, in particular polyethylene surfaces.
  • the nitrogen is then added by pressing in isobutene three times to a pressure of 3 bar and then releasing it to atmospheric pressure. removed. Subsequently, 200 g of isobutene were added to the reactor at room temperature, whereby a pressure of about 4 bar was established. Subsequently, the reactor contents were heated to 85 ° C. with stirring.
  • the monomer feed consisting of 215 g of deionized water, 1 1, 2 g of a 15 wt% aqueous solution of dodecylbenzenesulfonic acid sodium salt, 8.4 g of acrylic acid, 41 1, 6 g of n-butyl acrylate and 4 , 2 g of allyl methacrylate and the initiator feed, consisting of 150 g of deionized water and 4.2 g of sodium persulfate, started simultaneously and the monomer feed continuously over 3 hours, and the initiator feed continuously over 3.5 hours dosed. Then allowed to the obtained aqueous polymerisation satdispersion further 2 h at 85 0 C to react further.
  • the aqueous polymer dispersion had a solids content of 32% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature of the polymer was -30 ° C.
  • the solids content was determined by drying a defined amount of the aqueous polymer dispersion (about 5 g) at 140 ° C. in a drying oven to constant weight. Two separate measurements were made. The value given in the example represents the mean value of the two measurement results.
  • the determination of the glass transition temperature was carried out according to DIN 53765 by means of a DSC 820 device, TA 8000 series from Mettler-Toledo.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de production d'une dispersion de polymère aqueuse, avec utilisation d'alcènes présentant 4 atomes de C, et utilisation des dispersions de polymères aqueuses obtenues comme composants dans des substances adhésives.
PCT/EP2006/068371 2005-11-18 2006-11-13 Procede de production d'une dispersion de polymere aqueuse WO2007057365A2 (fr)

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DE102005055537A DE102005055537A1 (de) 2005-11-18 2005-11-18 Verfahren zur Herstellung einer wässrigen Polymerisatdispersion
DE102005055537.3 2005-11-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020002070A1 (fr) * 2018-06-25 2020-01-02 Basf Se Système bicomposant pour réaliser des composites à liaison de matière ou pour réaliser des ancrages chimiques

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2222718B1 (fr) * 2007-12-21 2016-09-07 Lubrizol Advanced Materials, Inc. Copolymérisation en émulsion d'acrylate d'oléfine
WO2009135812A1 (fr) * 2008-05-08 2009-11-12 Basf Se Procédé de production d'une dispersion aqueuse de polymères

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1116990A (en) * 1964-09-29 1968-06-12 Grace W R & Co Improvements in the production of olefin copolymers
WO2003070833A2 (fr) * 2002-02-15 2003-08-28 Ppg Industries Ohio, Inc. Compositions durcissables par rayonnement contenant des copolymeres alternes de monomeres du type isobutylene
WO2003070783A1 (fr) * 2002-02-15 2003-08-28 Ppg Industries Ohio, Inc. Compositions filmogenes a base d'eau contenant des copolymeres alternes de monomeres de type isobutylene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1116990A (en) * 1964-09-29 1968-06-12 Grace W R & Co Improvements in the production of olefin copolymers
WO2003070833A2 (fr) * 2002-02-15 2003-08-28 Ppg Industries Ohio, Inc. Compositions durcissables par rayonnement contenant des copolymeres alternes de monomeres du type isobutylene
WO2003070783A1 (fr) * 2002-02-15 2003-08-28 Ppg Industries Ohio, Inc. Compositions filmogenes a base d'eau contenant des copolymeres alternes de monomeres de type isobutylene

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020002070A1 (fr) * 2018-06-25 2020-01-02 Basf Se Système bicomposant pour réaliser des composites à liaison de matière ou pour réaliser des ancrages chimiques
US11584689B2 (en) 2018-06-25 2023-02-21 Basf Se Two-component system for formation of cohesive bonds or for chemical anchoring

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DE102005055537A1 (de) 2007-05-24
WO2007057365A3 (fr) 2007-11-01

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