EP2609121A1 - Dispersion aqueuse de polymère pouvant être obtenue par polymérisation en émulsion à amorçage radicalaire en présence d'une composition régulant le poids moléculaire - Google Patents

Dispersion aqueuse de polymère pouvant être obtenue par polymérisation en émulsion à amorçage radicalaire en présence d'une composition régulant le poids moléculaire

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Publication number
EP2609121A1
EP2609121A1 EP11746574.0A EP11746574A EP2609121A1 EP 2609121 A1 EP2609121 A1 EP 2609121A1 EP 11746574 A EP11746574 A EP 11746574A EP 2609121 A1 EP2609121 A1 EP 2609121A1
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EP
European Patent Office
Prior art keywords
acid
weight
parts
monomers
ethylenically unsaturated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11746574.0A
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German (de)
English (en)
Inventor
Elitsa Evstatieva
Dirk Lawrenz
Johannes Jan-Bessel Minderhoud
Florian Garlichs
Peter Bassler
Jens Baldamus
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11746574.0A priority Critical patent/EP2609121A1/fr
Publication of EP2609121A1 publication Critical patent/EP2609121A1/fr
Withdrawn legal-status Critical Current

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46—Non-macromolecular organic compounds
    • D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid

Definitions

  • Aqueous polymer dispersion obtainable by free-radically initiated emulsion polymerization in the presence of a molecular weight regulator composition
  • the invention relates to aqueous polymer dispersions containing a polymer which can be prepared by free-radically initiated emulsion polymerization of ethylenically unsaturated, radically polymerizable monomers, wherein the polymerization of the monomers takes place in the presence of a specific molecular weight regulator composition.
  • the invention also relates to a process for the preparation of the aqueous polymer dispersions and to the use of the polymer dispersions as binders, adhesives, sizing agents for fibers, for the production of coatings or for the production of paper coating slips.
  • Aqueous polymer dispersions which can be prepared by free-radically initiated emulsion polymerization of ethylenically unsaturated, free-radically polymerizable monomers have a wide range of uses.
  • binders for paper coating slips are known based on copolymers of vinylaromatic compounds such as styrene, aliphatic dienes such as 1, 3-butadiene and ethylenically unsaturated acid such as acrylic acid or methacrylic acid or based on styrene / acrylate copolymers.
  • molecular weight regulators or chain transfer agents are used to set a molecular weight suitable for the respective field of application.
  • the most effective and commonly used molecular weight regulators include alkyl mercaptan, that is, thiol substituted alkanes such as tertiary dodecyl mercaptan (TDMC). These substances have the advantage that, in addition to the properties regulating the molecular weight of the polymers, they additionally lead to good performance properties of paper coating compositions.
  • polymeric binders having a high binding force and paper-containing coating compositions containing polymeric binders having good surface resistance, for example good dry picking strength and good wet pick resistance are desired.
  • TDMC meets these requirements, but has the disadvantage of an unpleasant odor. This can be annoying in the production as well as in the final product. In addition, for product safety reasons, TDMC is undesirable in some applications.
  • the preparation is carried out by polymerization of conjugated diene monomer, another ethylenically unsaturated monomer and an ethylenically unsaturated carboxylic acid monomer in the presence of a combination of a hydrophilic chain transfer agent and a hydrophobic chain transfer agent.
  • a hydrophilic chain transfer agent e.g., alkyl mercaptans and mercaptoalkyl esters of alkylcarboxylic acids are mentioned as hydrophobic chain transfer agents.
  • PCT / EP2010 / 051833 discloses aqueous polymer dispersions prepared from vinyl aromatic compound, conjugated aliphatic diene and ethylenically unsaturated acid, wherein the polymerization in the presence a mercaptoalkylcarboxylic ester of a C 2 -C 4 -carboxylic acid, in particular mercaptoethylpropionate, as a molecular weight regulator.
  • Molecular weight regulators are usually used in the highest possible purity with respect to sulfur-containing compounds in order to minimize the unforeseeable and undesired effects of the sulfur-containing compounds on the course of the emulsion polymerization and on the quality and product properties of the polymer formed.
  • Molecular weight regulators based on Mercaptoalkylcarbonklaestern such. Mercaptoethyl propionate have the disadvantage that the cleaning is very complex and expensive. The reason is that, due to the nature of the synthesis, both low-boiling components (for example ethylene sulfide), middle-boiling components (for example mercaptoethanol) and high-boiling components (for example oligomeric and polymeric polyethylene sulfides and their esters) are obtained side by side.
  • low-boiling components for example ethylene sulfide
  • middle-boiling components for example mercaptoethanol
  • high-boiling components for example oligomeric and polymeric polyethylene sulfides and their
  • Mercaptoethyl propionate can be prepared, for example, by acid-catalyzed transesterification of propionic acid esters with mercaptoethanol or by acid-catalyzed azeotropic esterification of propionic acid with mercaptoethanol in the presence of organic solvents as entrainer to remove the water of reaction.
  • the problem is that both the mercaptoethanol used as alcohol component and the product mercaptoalkylcarboxylic ester are both temperature-labile and acid-labile. This usually results in the synthesis of oligomeric polyethylene sulfides.
  • the energy input into the distillation bottoms must be carried out so gently that decomposition of the high-boiling oligomeric polyethylene sulfides does not lead to the formation of light and medium-boiling components which contaminate the desired mercaptoalkyl carboxylic ester product again.
  • a multiple distillation at a very reduced pressure using a distillation unit with a high number of separation stages to obtain a pure product of value (purity> 99.8%) is required.
  • the object of the invention is to make available aqueous polymer dispersions having a molecular weight set by use of a molecular weight regulator, which are produced as simply and inexpensively as possible, in comparison with alkylmercyl captans produced dispersions have the most neutral odor and should have the best possible application properties as binders in paper coating, in particular the best possibleimiffestmaschine and a very good Nassrupffesttechnik.
  • an aqueous polymer dispersion comprising a polymer which can be prepared by free-radically initiated emulsion polymerization of one or more ethylenically unsaturated, radically polymerizable monomers, wherein the polymerization of the monomers takes place in the presence of a molecular weight regulator composition, and wherein the molecular weight regulator composition
  • X and Y independently of one another may be identical or different and denote an oxygen atom or a sulfur atom
  • A is a divalent to Ci8 alkylene group
  • n is a number from 1 to 8 and m is a number from 0 to 2.
  • the emulsion polymerization is carried out in the presence of at least one polymerization regulator.
  • at least one polymerization regulator Essentially, no alkylmercaptan is used, i. E. Alkylmercaptans are not used at all or at least not in the odor properties of the polymer dispersion affecting amounts.
  • the molecular weight regulator used is at least one molecular weight regulator composition which contains as main constituent (a) at least one mercaptoalkylcarboxylic acid ester of a C 2 - to C 4 -carboxylic acid.
  • the underlying carboxylic acids are acetic acid, propionic acid, isobutyric acid or n-butanoic acid, preferably propionic acid.
  • the mercaptoalkyl groups may be linear, branched or cyclic hydrocarbon radicals having at least one SH group and, for example, up to 18 carbon atoms. Preference is given to compounds of the formula
  • R1 -C ( 0) -O-R2-SH
  • R 1 is an alkyl group having 1 to 3 C atoms
  • R 2 is a divalent alkylene group having 1 to 18 C atoms.
  • 2-Mercaptoethyl propionate is particularly preferably used as the main component of the molecular weight regulator composition.
  • the mercaptoalkyl carboxylates (a) are preferably contained in the molecular weight controlling composition in an amount of 60 to 95% by weight or 65 to 90% by weight or 70 to 85% by weight.
  • the molecular weight regulator composition contains as further constituent (b) at least one oligomeric compound of the formula
  • X and Y independently of one another may be identical or different and denote an oxygen atom or a sulfur atom
  • A is a divalent to Ci8 alkylene group
  • n is a number from 1 to 8 and m is a number from 0 to 2.
  • R 1 is -X- (CH 2 -CH 2 -S-) n -CH 2 -CH 2 -YR 2
  • X and Y independently of one another may be the same or different and represent an oxygen atom or a sulfur atom, and n is a number from 1 to 8.
  • the oligomeric compounds (b) are contained in the molecular weight controlling composition preferably in an amount of 1 to 20% by weight or from 1.5 to 10% by weight or from 2 to 5% by weight.
  • the molecular weight regulator composition preferably also contains, as further constituents, small amounts of mercaptoethanol (in particular 2-mercaptoethanol) and / or ethylene sulfide.
  • Mercaptoethanol can be used in the molecular weight regulator composition e.g. be contained in an amount of 0.1 to 10 wt .-% or from 0.2 to 5 wt.%, or from 0.3 to 1 wt.%.
  • Ethylene sulfide may be included in the molecular weight regulator composition e.g. be contained in an amount of 0.05 to 5 wt .-% or from 0.1 to 2 wt.% or from 0.15 to 1 wt.%.
  • the molecular weight regulator composition may also contain non-sulfur containing ingredients, for example, propionic acid in an amount of, for example, 0.1 to 10 wt.% Or from 0.2 to 5 wt.% Or from 0.3 to 1 wt.%; organic solvents, in particular aliphatic or aromatic hydrocarbons having 6 to 8 carbon atoms and a boiling point of 80 to 140 ° C at atmospheric pressure, for example in an amount of 1 to 20 wt.% or 1, 5 to 10 wt.% or 2 to 5% by weight.
  • An embodiment of the invention is, for example, an aqueous polymer dispersion wherein the molecular weight regulator composition
  • An embodiment of the invention is e.g. also an aqueous polymer dispersion wherein the molecular weight regulator composition
  • polymerization regulators may be used but are not essential.
  • further polymerization regulators which may optionally be used are organic compounds which contain sulfur in bound form, such as thiodiglycol, ethylthioethanol, di-n-butylsulfide, di-n-octylsulfide, diphenylsulfide, diisopropyldisulfide, 1,3-mercaptopropanol , 3-mercaptopropan-1, 2-diol, 1, 4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioacetic acid and thiourea.
  • polymerization regulators are aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, organic acids such as formic acid, sodium formate or ammonium formate, alcohols such as in particular isopropanol and phosphorus compounds such as sodium hypophosphite.
  • the amount of all molecular weight regulators is for example 0.01 to 5, preferably 0.1 to 1 wt .-%, based on the monomers used in the polymerization.
  • the regulators are preferably added together with the monomers. However, they may also be present partially or completely in the template. You can also be gradually added to the monomers added.
  • ethylenically unsaturated, free-radically polymerizable monomers are polymerized.
  • Suitable monomers are, for example, vinylaromatic compounds, conjugated aliphatic dienes, ethylenically unsaturated acids, ethylenically unsaturated carboxylic acid amides, ethylenically unsaturated carboxylic acid nitriles, vinyl esters of saturated C 1 - to C 20 -carboxylic acids, esters of acrylic acid or of methacrylic acid with monohydric C 1 - to C 20 -alcohols, Allyl esters of saturated carboxylic acids, vinyl ethers, vinyl ketones, dialkyl esters of ethylenically unsaturated dicarboxylic acids, N-vinylpyrrolidone, N-vinylpyrrolidine, N-vinylformamide, N, N-dialkylaminoalkylacrylamides, ⁇ , ⁇ -dialkylaminoalkylmethacrylamides, N, N-dialkylaminoalkylacrylates, ⁇ , ⁇ -dial
  • the emulsion polymer is preferably at least 40 wt .-%, preferably at least 60 wt .-%, more preferably at least 80 wt .-% of so-called main monomers.
  • the main monomers are selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of from 1 to 10 carbon atoms. Atoms containing alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers. To name a few are z. B.
  • (Meth) acrylic acid alkyl esters having a C 1 -C 10 -alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, alpha- and p-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers z.
  • Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds may be mentioned ethylene, propylene, butadiene, isoprene and chloroprene.
  • Preferred main monomers are C 1 -C 10 -alkyl (meth) acrylates and mixtures of the alkyl (meth) acrylates with vinylaromatics, in particular styrene (also referred to as polyacrylate binder) or hydrocarbons having 2 double bonds, in particular butadiene, or mixtures of such hydrocarbons with vinyl aromatics, especially styrene (collectively referred to as polybutadiene binder).
  • styrene also referred to as polyacrylate binder
  • hydrocarbons having 2 double bonds in particular butadiene, or mixtures of such hydrocarbons with vinyl aromatics, especially styrene (collectively referred to as polybutadiene binder).
  • Binders can the weight ratio of butadiene to vinyl aromatic (in particular styrene) z. B. 10:90 to 90:10, preferably 20:80 to 80:20. Particularly preferred are polybutadiene binders.
  • the polymer may contain other monomers, for. As monomers with carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Called z. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid and aconitic acid. The content of ethylenically unsaturated acids in the emulsion polymer is generally less than 5 wt .-%. Other monomers are z. As well as hydroxyl-containing monomers, in particular C1-C10-hydroxyalkyl (meth) acrylates, or amides such as (meth) acrylamide.
  • the polymer is at least 60% by weight of butadiene or mixtures of butadiene and styrene or at least 60% by weight of C1 to C20 alkyl (meth) acrylates or mixtures of C1 to C20 alkyl (meth) acrylates and Built up styrene.
  • the polymer is at least 60% by weight of butadiene or mixtures of butadiene and styrene or at least 60% by weight of C1 to C20 alkyl (meth) acrylates or mixtures of C1 to C20 alkyl (meth) acrylates and Built up styrene.
  • the polymer is at least 60% by weight of butadiene or mixtures of butadiene and styrene or at least 60% by weight of C1 to C20 alkyl (meth) acrylates or mixtures of C1 to C20 alkyl (meth) acrylates and Built up styrene.
  • the polymer is at least 60% by
  • (D1) 0 to 20 parts by weight, preferably 0.1 to 15 parts by weight, of at least one other monoethylenically unsaturated monomer other than the monomers (A1) to (C1)
  • (B2) 19.8 to 80 parts by weight, preferably 25 to 70 parts by weight, of at least one monomer selected from C1 to C18 alkyl esters of acrylic acid and C1 to C18 alkyl esters of methacrylic acid,
  • (D2) 0 to 20 parts by weight, preferably 0.1 to 15 parts by weight, of at least one other monoethylenically unsaturated monomer other than the monomers (A2) to (C2)
  • Suitable monomers of group (A1) or (A2) are vinylaromatic compounds, e.g. Styrene, ⁇ -methylstyrene and / or vinyltoluene. From this group of monomers, styrene is preferably used. 100 parts by weight of the total monomer mixtures used in the polymerization contain, for example, 19.8 to 80 parts by weight and preferably 25 to 70 parts by weight of at least one monomer of the group (A1) or (A2).
  • Monomers of group (B1) are, for example, butadiene-1,3-isoprene, pentadiene-1,3-dimethyl-diadiene-1,3-and cyclopentadiene.
  • the monomer mixtures used in the emulsion polymerization in total contain, for example, 19.8 to 80 parts by weight, preferably 25 to 70 parts by weight, and more preferably 25 to 60 parts by weight, of at least one monomer of the group (B1).
  • Monomers of the group (C1) or (C2) are, for example, ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids and vinylphosphonic acid.
  • the ethylenically unsaturated carboxylic acids used are preferably .alpha.,. Beta.-monoethylenically unsaturated mono- and dicarboxylic acids having from 3 to 6 carbon atoms in the molecule. Examples of these are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid and vinyllactic acid.
  • Suitable ethylenically unsaturated sulfonic acids are, for example, nylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate. Particularly preferred are acrylic acid and methacrylic acid, especially acrylic acid.
  • the acid group-containing monomers of group (C1) or (C2) can be used in the form of the free acids as well as partially or completely neutralized with suitable bases in the polymerization. Sodium hydroxide solution, potassium hydroxide solution or ammonia are preferably used as neutralizing agent.
  • 100 parts by weight of the monomer mixtures used in the emulsion polymerization contain, for example, 0.1 to 15 parts by weight, preferably 0.1 to 10 parts by weight or 1 to 8 parts by weight of at least one monomer of the group (C1) or (C2).
  • Suitable monomers of group (B2) are esters of acrylic acid and of methacrylic acid with monohydric C to C 18 -alcohols, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-propyl methacrylate.
  • 100 parts by weight of the total monomer mixtures used in the polymerization contain, for example, 19.8 to 80 parts by weight and preferably 25 to 70 parts by weight of at least one monomer of the group (B2).
  • Suitable monomers of group (D2) are other monoethylenically unsaturated compounds.
  • these are ethylenically unsaturated carboxylic acid amides such as, in particular, acrylamide and methacrylamide, ethylenically unsaturated carbonitriles, in particular acrylonitrile and methacrylonitrile, vinyl esters of saturated C 1 - to C 18 -carboxylic acids, preferably vinyl acetate, allyl esters of saturated carboxylic acids, vinyl ethers, vinyl ketones, dialkyl esters of ethylenically unsaturated dicarboxylic acids, N-vinylpyrrolidone , N-vinylpyrrolidine, N-vinylformamide, N, N-dialkylaminoalkylacrylamides, ⁇ , ⁇ -dialkylaminoalkylmethacrylamides, N, N-dialkylaminoalkylacrylates, ⁇ , ⁇ -dialkylaminoalkyl
  • monomers of group (D1) are the monomers of group (D2) and also esters of acrylic acid and methacrylic acid with monohydric C6-C4 alcohols such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, Isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate.
  • the group of monomers is optionally used to modify the polymers.
  • 100 parts by weight of the monomer mixtures used in the emulsion polymerization contain, for example, 0 to 20 parts by weight, or 0.1 to 15 parts by weight and in particular 0.5 to 10 parts by weight of at least one monomer of group (D1) or (D2).
  • the further monomers (D1) and (D2) are used in amounts of 0.1 to 15 parts by weight;
  • the vinylaromatic compound is selects from styrene, methylstyrene and their mixture;
  • the conjugated aliphatic diene is selected from 1,3-butadiene, isoprene and their mixture;
  • the ethylenically unsaturated acid is selected from one or more compounds of the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid, vinylmicacid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, vinylphosphonic acid and Salts of these acids.
  • initiators which form radicals under the reaction conditions.
  • the initiators are used, for example, in amounts of up to 2% by weight, preferably at least 0.9% by weight, for example from 1.0 to 1.5% by weight, based on the monomers to be polymerized.
  • Suitable polymerization initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, sodium or potassium persulfate, redox catalysts and azo compounds such as 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile) and 2,2-azobis (2-amidinopropane) dihydrochloride.
  • Examples of other suitable initiators are dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, diauroyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide , tert-Butalperacetat, tert-Butylpermaleinat, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl hydroperoxide, azo-bis-isobutyronitrile, 2,2 'azo-bis- (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile
  • initiators selected from the group of peroxodisulfates, peroxosulfates, azo initiators, organic peroxides, organic hydroperoxides and hydrogen peroxide.
  • Particular preference is given to using water-soluble initiators, eg. For example, sodium persulfate, potassium persulfate, ammonium persulfate, sodium peroxodisulfate, potassium peroxodisulfate and / or ammonium peroxodisulfate.
  • the emulsion polymerization takes place in at least two stages, the beginning of the addition of the monomeric vinylaromatic compound (A) offset in time from the beginning of the addition of the monomeric conjugated aliphatic diene he follows.
  • at least a portion of the monomeric vinyl aromatic compounds e.g. At least 3.5 wt .-% of the total amount of all monomeric vinyl aromatic compounds under polymerization in the aqueous medium or the polymerization onsmischung added before the addition of monomeric conjugated aliphatic dienes is started.
  • the invention also provides a process for preparing aqueous polymer dispersions, wherein one or more of the abovementioned ethylenically unsaturated, free-radically polymerizable monomers are polymerized by free-radically initiated emulsion polymerization in the presence of the molecular weight regulator composition described above.
  • the protective colloids and / or emulsifiers customarily used as dispersants.
  • 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.
  • number-average molecular weight is usually below 2000 g / mol or preferably below 1500 g / mol, while the number average molecular weight of the protective colloids is above 2000 g / mol, for example from 2000 to 100000 g / mol, in particular from 5000 to 50 000 g / mol
  • Suitable emulsifiers are, for example, ethoxylated Ce- to C36-fatty alcohols having a degree of ethoxylation of 3 to 50, ethoxylated mono-, di- and tri-C 4 - to C 12 -alkylphenols having a degree of ethoxylation of 3 to 50, alkali metal salts of dialkyl esters of sulfosuccinic acid, alkali metal and ammonium salts of C 1 -C 12 -alkyl sulfates, alkali metal and ammonium salts of C 12 -C 10 -alky
  • Cation-active emulsifiers are, for example, compounds having at least one amino or ammonium group and at least one C 8 -C 22 -alkyl group. If emulsifiers and / or protective colloids are used as auxiliaries for dispersing the monomers, the amounts used thereof are, for example, from 0.1 to 5% by weight, based on the monomers.
  • Suitable protective colloids are, for example, degraded starch, in particular maltodextrin. Suitable starches for the production of degraded starches are all native starches such as starches from corn, wheat, oats, barley, rice, millet, potatoes, peas, tapioca, sorghum or sago.
  • amylopectin content of these starches is above 90%, usually 95 to 100%.
  • chemically modified by etherification or esterification starches can be used to prepare the polymer dispersions of the invention.
  • Such products are known and commercially available. They are prepared, for example, by esterification of native starch or degraded native starch with inorganic or organic acids, their anhydrides or chlorides.
  • phosphated and acetylated degraded starches are particularly useful.
  • the most common method of etherifying starches is to treat starch with organic halogen compounds, epoxies or sulfates in aqueous alkaline solution.
  • Known starch ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allyl ethers.
  • the reaction products of starches with 2,3-Epoxipropyltrimethylammoniumchlorid are.
  • degraded native starches in particular native starches degraded to maltodextrin.
  • Further suitable starches are cationically modified starches, ie starch compounds which have amino groups or ammonium groups.
  • the degraded starches have, for example, an intrinsic viscosity n, i of less than 0.07 dl / g or less than 0.05 dl / g.
  • the intrinsic viscosity ⁇ of the degraded starches is preferably in the range of 0.02 to 0.06 dl / g.
  • the intrinsic viscosity ⁇ is determined according to DIN EN 1628 at a temperature of 23 ° C.
  • the emulsion polymerization takes place in the presence of seed particles.
  • the template then contains polymer seed, in particular a polystyrene seed, ie an aqueous dispersion of finely divided polymer, preferably polystyrene, having a particle diameter of 20 to 40 nm.
  • the emulsion polymerization takes place in an aqueous medium. This may be e.g. to act completely desalinated water or mixtures of water and a miscible solvent such as methanol, ethanol or tetrahydrofuran ran.
  • a miscible solvent such as methanol, ethanol or tetrahydrofuran ran.
  • the metering of the monomers begins. For example, they may be continuously pumped into the reactor within, for example, 60 minutes to 10 hours, most often within 2 to 4 hours.
  • the reaction mixture is heated in the template to the required temperature at which the polymerization proceeds. These temperatures are for example 80 to 130 ° C, preferably 85 to 120 ° C.
  • the polymerization may also be carried out under pressure, e.g. at pressures up to 15 bar, e.g. at 2 to 10 bar.
  • the monomer feed can be carried out as a batch process, continuously or stepwise.
  • the pH may be, for example, 1 to 5 in the polymerization. After the polymerization, the pH is adjusted to a value between 6 and 7, for example. An aqueous polymer dispersion is obtained whose dispersed particles have an average particle diameter of preferably 80 to 200 nm.
  • the average particle diameter of the polymer particles can be determined by dynamic light scattering on a 0.005 to 0.01% strength by weight aqueous polymer dispersion at 23.degree. C. with the aid of an Autosizers NC from Malvern Instruments, England.
  • the data relate in each case to the mean diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function according to IOS Standard 13321.
  • the solids content of the aqueous polymer dispersion according to the invention is 40 to 60% by weight.
  • the solids content may e.g. by adjusting the amount of water used in the emulsion polymerization and / or the amounts of monomers.
  • the aqueous polymer dispersions according to the invention are used as binders, adhesives, sizing agents for fibers, for the production of coatings or for the production of paper coating slips.
  • the aqueous polymer dispersions according to the invention are suitable both for sizing textile fibers and also for sizing mineral fibers, in particular dere glass fibers. Due to their good adhesion, in particular when using comonomers, which lead to a low glass transition temperature of the copolymer (eg less than 20 ° C.), they can also be used as an adhesive and for the production of coatings.
  • the novel aqueous polymer dispersions are preferably used as binders in paper coating slips and as binders for fibers, in particular for textile fibers.
  • An object of the invention is therefore also a paper coating slip containing
  • paper coating slips In addition to water, paper coating slips generally contain pigments, binders and auxiliaries for adjusting the required rheological properties, eg. B. thickener.
  • the pigments are usually dispersed in water.
  • the paper coating composition contains pigments in an amount of preferably at least 80% by weight, e.g. 80 to 95 wt.% Or 80 to 90 wt.%, Based on the total solids content.
  • white pigments come into consideration.
  • Suitable pigments are, for example, metal salt pigments, such as e.g. Calcium sulfate, calcium aluminate sulfate, barium sulfate, magnesium carbonate and calcium carbonate, of which carbonate pigments, in particular calcium carbonate, are preferred.
  • the calcium carbonate may be ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), lime or chalk.
  • Suitable calcium carbonate pigments are e.g. available as Covercarb® 60, Hydrocarb® 60 or Hydrocarb® 90 ME.
  • Other suitable pigments are e.g. Silicas, aluminum oxides, aluminum hydrate, silicates, titanium dioxide, zinc oxide, kaolin, clay, talc or silica.
  • Suitable further pigments are e.g. available as Capim® MP 50 (Clay), Hydragloss® 90 (Clay) or Talcum C10.
  • the paper coating contains at least one binder.
  • the polymer dispersion prepared according to the invention can be used in the paper coating slip as the sole binder or in combination with further binders.
  • the most important tasks of binders in paper coating slips are to join the pigments to the paper and the pigments and to partially fill voids between pigment particles. For example, from 1 to 50 parts by weight, preferably from 1 to 25 parts by weight, or from 5 to 20 parts by weight of an organic binder (solid, ie without water or otherwise at 21 ° C.) are used per 100 parts by weight of pigments. 1 bar of liquid solvent).
  • binders are natural-based binders, in particular starch-based binders, and synthetic binders which are different from the polymers prepared according to the invention, in particular emulsion polymers preparable by emulsion polymerization.
  • polymers prepared according to the invention are included as the only synthetic binder.
  • starch-based binders is used in this Any native, modified or degraded starch should be understood. Native starches may consist of amylose, amylopectin or mixtures thereof. Modified starches may be oxidized starch, starch esters or starch ethers. Hydrolysis can reduce the molecular weight of the starch (degraded starch). The degradation products are oligosaccharides or dextrins into consideration.
  • Preferred starches are corn, corn and potato starch. Particularly preferred are corn and corn starch, most preferably cereal starch.
  • Paper coating slips according to the invention may additionally contain further additives and auxiliaries, e.g. Fillers, co-binders and thickeners for further optimization of viscosity and water retention, optical brighteners, dispersants, surfactants, lubricants (eg calcium stearate and waxes), neutralizing agents (eg NaOH or ammonium hydroxide) for pH adjustment, defoamers, deaerating agents, preservatives ( For example, biocides), flow control agents, dyes (especially soluble dyes), etc.
  • As thickeners next synthetic polymers (eg cross-linked polyacrylate), in particular celluloses, preferably carboxymethylcellulose into consideration.
  • Optical brighteners are e.g. Fluorescence or phosphorescent dyes, in particular stilbenes.
  • aqueous paper coating slip it is preferably an aqueous paper coating slip; in particular, it already contains water through the formulation of the constituents (aqueous polymer dispersions, aqueous pigment slurries); the desired viscosity can be adjusted by adding more water.
  • Typical solids contents of the paper coating slips are in the range of 30 to 70 wt .-%.
  • the pH of the paper coating slip is preferably adjusted to values of 6 to 10, in particular 7 to 9.5.
  • One embodiment of the invention relates to a paper coating slip, wherein the polymers of the aqueous polymer dispersion prepared according to the invention are used in an amount of 1 to 50 parts by weight, based on the total amount of pigments, and wherein the pigments are present in an amount of 80 to 95 parts by weight, based on the total solids content, and are selected from the group consisting of calcium sulfate, calcium aluminum sulfate, barium sulfate, magnesium carbonate, calcium carbonate, silicas, aluminum oxides, aluminum hydrate, silicates, titanium dioxide, zinc oxide, kaolin, clay, talc and silica and the paper coating slip additionally contains at least one excipient selected from the group consisting of thickeners, other polymeric binders, co-binders, optical brighteners, fillers, flow control agents, dispersants, surfactants, lubricants, neutralizing agents, defoamers, deaerators, preservatives agents and dyes.
  • the invention also provides a paper or board coated with a paper coating slip according to the invention and a method for painting paper or board, wherein - an aqueous polymer dispersion is prepared or made available according to the invention; and - With this polymer dispersion, at least one pigment and optional further excipients, a paper coating slip is prepared; and the paper coating is applied to at least one surface of paper or board.
  • the paper coating slip is preferably applied to uncoated base papers or uncoated cardboard.
  • the amount is generally 1 to 50 g, preferably 5 to 30 g (solid, ie without water or other at 21 ° C, 1 bar liquid solvent) per square meter.
  • the coating can be carried out by customary application methods, for example by means of a size press, film press, blade coater, air brush, doctor blade, curtain coating method or spray coater.
  • aqueous dispersions of the water-soluble copolymers can be used in paper coating slips for the base coat and / or for the top coat.
  • Paper coating slips according to the invention also have good performance properties. They have a good running behavior in paper coating processes and a high binding power. The coated papers and cartons have a good surface strength, in particular a very high wet and dry pick resistance. They are well printable in the usual printing processes, such as letterpress, gravure, offset, digital, inkjet, flexo, newspaper, letterpress, sublimation, laser, electrophotographic, or a combination of these.
  • the indication of a content refers to the content in aqueous solution or dispersion.
  • the solids contents are determined by drying a defined amount of the respective aqueous polymer dispersion (about 5 g) at 140 ° C. in a drying oven to constant weight. In each case, two separate measurements are carried out and the mean value is formed.
  • the determination of the glass transition temperature is carried out according to DIN 53765 by means of a
  • DSC820 instrument TA8000 series from Mettler-Toledo Int. Inc.
  • the average particle diameter of the polymer particles are determined by dynamic light scattering on a 0.005 to 0.01 wt .-% aqueous polymer dispersion at 23 ° C by means of a Autosizer NC from Malvern Instruments, England. The middle one is given
  • tert-Dodecyl mercaptan as molecular weight regulator
  • 29 kg of deionized water, 2.2 kg of polystyrene latex (30 nm) and in each case 5% by weight are added at room temperature and under nitrogen atmosphere.
  • the feeds 1 A and 1 B submitted.
  • the reactor contents are heated with stirring (180 rpm) to 90 ° C, and when reaching 85 ° C, 1 kg of a 7 wt .-% aqueous sodium persulfate solution is added.
  • the remaining amount (in each case 95%) of feed 1 A and feed 1 B is metered in continuously within 360 minutes and feed 2 within 390 minutes with constant flow rates. Over the entire metering time, the mass flows of feed 1 A and feed 1 B are homogenized just before they enter the reactor. Subsequently, the reactor contents are allowed to react for a further 2 hours at 90.degree. Thereafter, the reactor contents are cooled to room temperature, adjusted with a 15 wt .-% aqueous NaOH solution to a pH of 6.5 and relaxes the pressure vessel to atmospheric pressure.
  • the resulting aqueous dispersion (D1) had a solids content of 49% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature was determined to 17 ° C and the particle size to 160 nm.
  • Example 2 High purity mercaptoethyl propionate as a molecular weight regulator
  • the resulting aqueous dispersion (D2) had a solids content of 49.5% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature was determined to 16 ° C and the particle size to 158 nm.
  • Gel content 75% Example 3
  • the resulting aqueous dispersion (D3) had a solids content of 49.4% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature was determined to 18 ° C and the particle size to 157 nm.
  • aqueous polymer dispersions D1 to D7 prepared according to the examples are used as binders for paper coating slips.
  • the coating composition is prepared in a stirring unit into which the individual components are fed in succession.
  • the pigments are added in predispersed form (slurry).
  • the other components are added after the pigments, the order of the order in the specified coating color recipe corresponds.
  • the final solids content is adjusted by the addition of water.
  • the coating color is applied by means of a technique coater on one side to a base paper and dried by IR emitters.
  • the weight of the applied coating layer is about 10 g / m 2 .
  • the coated paper was tested for surface strength using test methods known to those skilled in the art. The following test methods were used:
  • Strips were cut from the papers to be tested and printed with the IGT test printing device.
  • the printing inks used are special test inks from Lorillieux, which transfer different tensile forces.
  • the test strips are fed through the printing unit at a continuously increasing speed (maximum speed 200 cm / s).
  • maximum speed 200 cm / s the location on the sample print strip is determined at which 10 out breaks from the paper surface (picking points) have taken place after the start of printing.
  • the speed in cm / sec which was present at this location during printing and the test color used are indicated. The higher the speed of printing on the tenth picking point, the better the quality of a paper surface.
  • Strips were cut from the papers to be tested and printed with the IGT test printing device.
  • the printing device has been set up so that the test strips are moistened with water before printing.
  • the printing inks used are special test paints from the company Lorilleux (No. 3807), which transfer different tensile forces.
  • the pressure is carried out at a constant speed of 0.6 cm / s. Tears from the paper surface are visible as unprinted areas.
  • To determine the wet pick resistance the color density is determined with a color densitometer in comparison to the full hue in%. The higher the specified color density, the better the wet pick resistance.
  • the coated papers were evaluated by a trained group of persons for odor.
  • the procedure for such odor tests is known to the person skilled in the art.
  • Example 3 has significantly better wet pick resistance on both the top and bottom of the coated paper, as well as significantly better dry pick resistance on the underside of the coated paper.
  • the coated paper has an acceptable odor which is better than that of a paper coated with Example 1.
  • the mass flows of feed 1 A and feed 1 B are homogenized just before they enter the reactor. Subsequently, the reactor contents are allowed to react for a further 2 hours at 90.degree. Thereafter, the reactor contents are cooled to room temperature, adjusted with a 15 wt .-% aqueous NaOH solution to a pH of 6.5 and relaxes the pressure vessel to atmospheric pressure.
  • the resulting aqueous dispersion (D4) had a solids content of 48% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature was determined to 8 ° C and the particle size to 160 nm.
  • the resulting aqueous dispersion (D5) had a solids content of 49.4% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature was determined to 9 ° C and the particle size to 157 nm.
  • feed 1 A and feed 1 B is metered in continuously within 360 minutes and feed 2 within 390 minutes with constant flow rates. Over the entire metering time, the mass flows of feed 1 A and feed 1 B are homogenized just before they enter the reactor. Subsequently, the reactor contents are allowed to react for a further 2 hours at 90.degree. Thereafter, the reactor contents are cooled to room temperature, adjusted with a 15 wt .-% aqueous NaOH solution to a pH of 6.5 and relaxes the pressure vessel to atmospheric pressure. Feed 1 A, homogeneous mixture of
  • the resulting aqueous dispersion (D6) had a solids content of 50% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature was determined to be 18 ° C and the particle size to 165 nm.
  • the resulting aqueous dispersion (D7) had a solids content of 50.4% by weight, based on the total weight of the aqueous dispersion.
  • the glass transition temperature was determined to be 19 ° C. and the particle size to be 168 nm.
  • the examples of contaminated (74%) mercaptoethyl propionate generally have better wet pick resistance on both the top and bottom of the coated paper and better dry pick resistance.
  • the papers coated with contaminated (74%) mercaptoethyl propionate-containing dispersions generally have a better odor than coated dispersions containing tert-dodecylmercaptan.

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Abstract

L'invention concerne une dispersion aqueuse de polymère contenant un produit de polymérisation qui peut être obtenu par polymérisation en émulsion à amorçage radicalaire à partir de monomères éthyléniquement insaturés polymérisables par amorçage radicalaire, la polymérisation des monomères se faisant en présence d'une certaine composition régulant le poids moléculaire. Cette composition régulant le poids moléculaire contient au moins un carboxylate de mercaptoalkyle issu d'un acide carboxylique en C2 à C4 et au moins un composé oligomère de formule R1-X-(A-S-)n-A-Y-R2, où R1 et R2 représentent un atome d'hydrogène ou un groupe CH3-(CH2)0-2-C(=O)-, X et Y représentent un atome d'oxygène ou de soufre, A représente un groupe alkylène divalent en C1 à C18, et n est un nombre valant de 1 à 8. L'invention concerne également un procédé de préparation de la dispersion aqueuse de polymère. Cette dispersion de polymère peut être utilisée comme liant, comme adhésif, comme agent d'encollage de fibres, pour produire des revêtements ou pour préparer des produits de couchage du papier.
EP11746574.0A 2010-08-27 2011-08-24 Dispersion aqueuse de polymère pouvant être obtenue par polymérisation en émulsion à amorçage radicalaire en présence d'une composition régulant le poids moléculaire Withdrawn EP2609121A1 (fr)

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EP11746574.0A EP2609121A1 (fr) 2010-08-27 2011-08-24 Dispersion aqueuse de polymère pouvant être obtenue par polymérisation en émulsion à amorçage radicalaire en présence d'une composition régulant le poids moléculaire
PCT/EP2011/064497 WO2012025545A1 (fr) 2010-08-27 2011-08-24 Dispersion aqueuse de polymère pouvant être obtenue par polymérisation en émulsion à amorçage radicalaire en présence d'une composition régulant le poids moléculaire

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US5191008A (en) * 1991-10-21 1993-03-02 The Goodyear Tire & Rubber Company Process for the production of latexes by the selective monomer addition
DE4236316A1 (en) 1991-10-31 1993-05-06 Takeda Chemical Industries Ltd Copolymer lattices, useful as binders in paper coating compsns. - by two=stage emulsion polymerisation of monomer mixt., with hydrophilic chain transfer agent and hydrophobic agent in second stage
CN1048504C (zh) * 1991-10-31 2000-01-19 武田药品工业株式会社 共聚物胶乳的制备
EP0575625B1 (fr) * 1992-01-10 1998-07-08 Sumitomo Dow Limited Procede pour la production de latex copolymere et utilisation de ce latex
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EP2398831B1 (fr) * 2009-02-19 2013-05-29 Basf Se Dispersion aqueuse de polymère à base d'un composé vinylaromatique, d'un diène conjugué aliphatique et d'un acide à insaturation éthylénique

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CN103189395A (zh) 2013-07-03
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