EP1709026A1 - Dispersions polymeriques aqueuses contenant des anhydrides d'acide alcenylsuccinique, leur procede de production et leur utilisation - Google Patents

Dispersions polymeriques aqueuses contenant des anhydrides d'acide alcenylsuccinique, leur procede de production et leur utilisation

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Publication number
EP1709026A1
EP1709026A1 EP05700910A EP05700910A EP1709026A1 EP 1709026 A1 EP1709026 A1 EP 1709026A1 EP 05700910 A EP05700910 A EP 05700910A EP 05700910 A EP05700910 A EP 05700910A EP 1709026 A1 EP1709026 A1 EP 1709026A1
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EP
European Patent Office
Prior art keywords
miniemulsion
water
polymer dispersions
polymerization
dispersions containing
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EP05700910A
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German (de)
English (en)
Inventor
Rainer Dyllick-Brenzinger
Reinhold J. Leyrer
Andreas Brockmeyer
Markus Schmid
Roland Ettl
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BASF SE
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BASF SE
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Publication of EP1709026A1 publication Critical patent/EP1709026A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/13—Unsaturated aldehydes, e.g. acrolein; Unsaturated ketones; Ketenes ; Diketenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • the invention relates to aqueous polymer dispersions containing alkenyl succinic anhydrides, processes for their preparation by emulsifying alkenyl succinic anhydrides in water in the presence of stabilizers under the action of shear forces, and use of the aqueous dispersions containing alkenyl succinic anhydrides thus obtainable as sizing agents for paper, as hydrophobizing agents. natural and / or synthetic fibers and textiles.
  • aqueous alkenyl succinic anhydride emulsions which are stabilized with the aid of starch, as mass sizing agents for paper and paper products is known, cf. EP-A-0609 879, EP-A-0593 075 and US-A-3, 102,064.
  • emulsions are not stable in storage because the anhydride groups of the alkenylsuccinic anhydrides hydrolyze in the presence of water.
  • the stability of aqueous alkenyl succinic anhydride emulsions depends on several factors, e.g.
  • alkenyl succinic anhydride emulsions have to be used for mass sizing paper immediately after their production.
  • An overview of sizing with alkenyl succinic anhydrides is given, for example, by C.E. Farley and R.B. Wasser in The Sizing of Paper, Second Edition, (3), Sizing With Alkenyl Succinic Anhydride, TAPPI PRESS, 1989, ISBN 0-89852-051-7.
  • Aqueous polymer dispersions containing alkyldiketenes are known from DE-A 10248 879, which can be obtained by miniemulsion polymerization of hydrophobic monoethylenically unsaturated monomers such as styrene, acrylonitrile and / or (meth) acrylic acid esters in the presence of alkyldiketenes.
  • an organic phase which contains at least one alkyldiketene and at least one monoethylenically unsaturated hydrophobic monomer in solution is first emulsified in the presence of a surface-active agent in an aqueous phase with the aid of mechanical emulsifiers to form a miniemulsion with the particle size of the emulsified organic phase of at most 500 nm, at least one of the two phases additionally containing a radical-forming polymerization initiator or a polymerization initiator being added to the miniemulsion, and then polymerizing the monomers of the miniemulsion.
  • the particle size of the dispersed polymers and the dispersed alkyldiketenes in these dispersions is, for example, 50 to 500 nm, preferably 50 to 200 nm.
  • the aqueous polymer dispersions containing alkyldiketenes thus obtainable are used as sizing agents for paper, as water repellents for leather, natural and / or synthetic fibers. and textiles.
  • the storage stability of the dispersions is still in need of improvement.
  • mini emulsions are particularly fine-particle emulsions of hydrophobic monomers in water.
  • the particle size of the monomers emulsified in the aqueous phase is in the nanometer range, e.g. at 5 to 500 nm.
  • a surface-active agent such as sodium dodecyl sulfate and a hydrophobic component such as hexadecane or olive oil is subjected to ultrasound for homogenization.
  • WO 04/037867 It is also known from WO 04/037867 to prepare aqueous dispersions containing alkyldiketenes by mini-emulsion polymerization of hydrophobic monoethylenically unsaturated monomers in the presence of alkyldiketenes and water-soluble or water-swellable polysaccharides. These dispersions are also used as sizing agents for paper and for waterproofing leather, natural and / or synthetic fibers and textiles.
  • the present invention has for its object to provide new formulations based on alkenylsuccinic anhydrides which have improved stability compared to the aqueous alkenylsuccinic anhydride emulsions known from the prior art.
  • aqueous polymer dispersions containing alkenylsuccinic anhydrides which can be obtained by miniemulsion polymerization of hydrophobic monoethylenically unsaturated monomers in the presence of alkenylsuccinic anhydrides.
  • Such polymer dispersions can be obtained, for example, by emulsifying an organic phase which comprises at least one alkenylsuccinic anhydride and at least one monoethylenically unsaturated hydrophobic monomer contains dissolved, in the presence of a surface-active agent in an aqueous phase using mechanical emulsification methods to form a miniemulsion with a particle size of the emulsified organic phase of at most 500 nm, at least one of the two phases additionally containing a radical-forming polymerization initiator or a polymerization initiator Mini emulsion is added, and polymerizing the monomers of the mini emulsion.
  • an organic phase which comprises at least one alkenylsuccinic anhydride and at least one monoethylenically unsaturated hydrophobic monomer contains dissolved, in the presence of a surface-active agent in an aqueous phase using mechanical emulsification methods to form a miniemulsion with a particle size of the emul
  • aqueous polymer dispersions containing alkenylsuccinic anhydrides can be obtained by polymerizing the miniemulsions described above, which are prepared, for example, by emulsifying the organic phase in the aqueous phase by the action of ultrasound or with the aid of high-pressure homogenizers.
  • the invention also relates to a process for the preparation of aqueous polymer dispersions containing alkenylsuccinic anhydrides, polymerizing hydrophobic monomers in the manner of a miniemulsion polymerization in the presence of at least one alkenylsuccinic anhydride.
  • the miniemulsion polymerization is preferably additionally carried out in the presence of at least one water-soluble and / or water-swellable polysaccharide.
  • the aqueous polymer dispersions containing alkenylsuccinic anhydrides according to the invention are prepared, for example, in such a way that an organic phase, the at least one alkenylsuccinic anhydride and at least one monoethylenically unsaturated hydrophobic monomer
  • a surface-active agent in an aqueous phase using mechanical emulsifiers to form a miniemulsion with a particle size of the emulsified organic phase of at most 500 nm and the monomers of the miniemulsion in the presence of at least one water-soluble and / or water-swellable polysaccharide and polymerized at least one polymerization initiator.
  • Alkenyl succinic anhydrides are known compounds. As can be seen from the references given in the prior art, TAPPI PRESS 1989, EP-A-0609879, EP-A-0 593 075 and US-A-3, 102.064, aqueous emulsions of alkynesuccinic anhydrides are used as sizing agents for paper. All alkenylsuccinic anhydrides which have been described for this application in the literature and have been used in practice for this purpose can be used in the process according to the invention for the preparation of polymer dispersions containing alkenylsuccinic anhydrides.
  • ASA alkenyl succinic anhydrides
  • substituted succinic anhydrides are decenyl succinic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride and n-hexadecenyl succinic anhydride.
  • the individual isomeric aikenylsuccinic anhydrides can have different sizing effects.
  • 2- and 3-hexadecenylsuccinic anhydrides are not as effective as bulk sizing agents as the isomeric 4-, 5-, 6-, 7- and 8-hexadecenylsuccinic anhydrides.
  • 7-Hexadecenylsuccinic anhydride is particularly effective as a sizing agent.
  • ASA from octadecenes and maleic anhydride show a similar activity profile as the isomeric hexadecenylsuccinic anhydrides.
  • 8-octadecenyl succinic anhydride is the most effective sizing agent, followed by 9- and 7-octadecenyl succinic anhydrides.
  • suitable ASAs are the reaction products of 7-tetradecene, eicosenes and docosenens with maleic anhydride.
  • the miniemulsion polymerization is, for example, in the Macromol reference mentioned at the beginning. Rapid Commun., Vol. 22, 896-936 (2001).
  • the essential feature of this polymerization process is that an organic phase is distributed particularly finely in an aqueous phase which contains a surface-active agent for stabilizing the emulsion.
  • the average particle diameter of the particles emulsified in the aqueous phase is, for example, in the range from 50 to 500 nm, preferably 50 to 200 nm and in particular 50 to 150 nm.
  • the particle size of the emulsified particles ideally changes during the polymerization not so that the average particle size of the polymers which are present in the aqueous polymer dispersions is also in the range given for the emulsified organic phase.
  • an emulsion polymerization is also observed in practice as a competitive reaction.
  • Such small particle sizes of at most 500 nm can be achieved if the organic phase used to prepare the emulsion is emulsified using mechanical emulsification processes.
  • mechanical emulsification processes Such methods are known. They are described in detail, for example, by H. Schubert et al., In Mixing and Stirring - Fundamentals and Modern Practical Practices, VDI Conference, 23J24.11.1988, Baden-Baden, under New Developments in the Field of Emulsification Technology.
  • the apparatus used is, for example, high-pressure homogenizers, ultrasound-generating devices, microfluidizers, rotor-stator apparatuses, Tay- lor reactors, Cuette cells, jet nozzles and equipment working with membrane technology.
  • the essential principle of these devices is based on the fact that high shear fields are built up in them at short notice.
  • the organic phase is preferably emulsified in the aqueous phase with the aid of ultrasound-producing devices or with the aid of high-pressure homogenizers.
  • Suitable hydrophobic monoethylenically unsaturated monomers which can be polymerized in the manner of a miniemulsion polymerization are, for example, monomers from the group consisting of styrene, methylstyrene, C 2 - to C 28 -olefins, esters of monoethylenically unsaturated carboxylic acids with 3 to 5 C atoms and monovalent Alcohols with 1 to 22 carbon atoms, vinyl esters of C to C 18 carboxylic acids, acrylonitrile and methacrylonitrile.
  • Monomers from this group which are preferably used are styrene, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate and acrylonitrile or mixtures of these monomers.
  • the hydrophobic monomers can optionally be used together with small amounts of hydrophilic monomers to modify the properties of the resulting minipolymer dispersions.
  • the hydrophilic monomers are used at most in such an amount that the resulting copolymers in water at a temperature of 20 ° C. and a pH of 2 have a solubility of at most 10 g / l, preferably 1 g / l.
  • Suitable hydrophilic compounds belong, for example, to the group of ethylenically unsaturated carboxylic acids having 3 to 5 carbon atoms, acrylamide, methacrylamide, N-vinylformamide, N-vinylpyrrolidone, N-vinylimidazole, vinyl ether, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, styrene sulfonic acid, Sulfopropyl acrylate, sulfopropyl methacrylate, fumaric acid, maleic acid, itaconic acid and / or maleic anhydride.
  • Preferred hydrophilic monomers are, for example, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid, maleic anhydride and / or maleic acid.
  • hydrophobic monomers can also optionally be used together with compounds which contain at least two ethylenically unsaturated double bonds, for example divinylbenzene, butadiene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, pentaerythritol tetraacrylate, pentaerythrylene tri-trimethylol ether, methane bis diuryl tri-dimethyl acrylate, methane tri-ethylenedi-ethyl-ether-diol-ethylenedi-acrylate-di-ethylenedi-methyl-di-acrylate-di-ethylenedi-acrylate-ethylenedi-methyl-di-acrylate-ethylenedi-methyl-di-acrylate-ethylenedi-methyl-di-acrylate-ethylenedi-ethylenedi-acrylate-ethylenedi-methyl-di-acrylate-ethylenedi-methyl-
  • crosslinkers These compounds are known to be used as crosslinkers in polymerization reactions. They also lead to crosslinking of the polymers formed from the above-mentioned hydrophobic monomers and any hydrophilic monomers used in the mini-emulsion polymerization. If crosslinking agents are also used, the amount of crosslinking agent is, for example, 0.001 to 10, preferably 0.01 to 1% by weight, based on the monomers used. Depending on the solubility, the crosslinkers can be added to the aqueous or organic phase all at once, in portions or metered in the feed mode. They can also be added to the miniemulsion before or during the polymerization.
  • a further variation in the properties of the polymers can be achieved by carrying out the miniemulsion polymerization in the presence of regulators.
  • regulators preferably at least one regulator at a time, in portions or in the feed mode, is added to the organic phase before the emulsification or to the miniemulsion at the start of the polymerization or during the polymerization.
  • the amounts are, for example, 0.01 to 10, preferably 0.1 to 2,% by weight, based on the monomers used.
  • a non-polymerizable hydrophobic compound e.g. a hydrocarbon, an alcohol with 10 to 24 carbon atoms, hydrophobic polymers with molecular weights Mw ⁇ 10000, tetraalkylsilanes and / or mixtures of the above
  • Such stabilizers are hexadecane, olive oil, polystyrene with a molecular weight Mw of 500 to 5000, siloxanes with a molecular weight Mw of 500 to 5000, cetyl alcohol, stearyl alcohol, palmityl alcohol and / or behenyl alcohol and water-insoluble acrylates and methacrylates such as lauryl acrylate, lauryl methacrylate, palladium mityl acrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate and / or behenyl methacrylate.
  • the organic phase which is emulsified in the aqueous phase for the production of the mini-emulsions contains, for example, 45 to 95, preferably 60 to 80% by weight of at least one hydrophobic monomer and optionally other monomers and 5 to 50% by weight, preferably 10 to 30 wt .-% of at least one alkenyl succinic anhydride. If necessary, the organic phase can contain 1 to 10% by weight, preferably 2 to 5% by weight, of a non-polymerizable hydrophobic compound.
  • the aqueous phase which is used to prepare the mini-emulsions consists of water and optionally contains a surface-active agent which stabilizes the finely divided monomer droplets formed in the emulsion of the organic phase in the aqueous phase and, if appropriate, a water-soluble and / or water-swellable one Pplysaccharid.
  • the surface-active agent is present, for example, in amounts of 0.05 to 5% by weight, preferably 0.1 to 1% by weight, in the aqueous phase, the organic phase or in both phases. It is preferably added to the aqueous phase before emulsification. In principle, all surfactants can be used. Anionic compounds are preferred surface-active agents.
  • the organic phase consists of a solution, a binary or polynary mixture and / or a dispersion
  • At least one d - to C- 22 alkenyl succinic anhydride at least one monomer from the group styrene, methyl styrene, C 2 - to C 28 olefins, esters from monoethylenically unsaturated carboxylic acids with 3 to 5 C atoms and monohydric alcohols with 1 to 22 C atoms, vinyl esters of d- to C 18 -carboxylic acids, acrylonitrile and methacrylonitrile, and - at least one hydrocarbon, an alcohol with 10 to 24 C atoms, hydrophobic polymers with molecular weights Mw ⁇ 10000, tetraalkylsilanes and / or mixtures of the compounds mentioned
  • the monomers are not completely miscible with one another in the presence of ASA, binary, ternary or polynary mixtures or dispersions are formed, which are then emulsified in the aqueous phase.
  • the organic phase contains hydrophilic monomers in addition to hydrophobic.
  • a procedure in which the organic phase consists of a solution which contains at least one C 16 / C 8 alkenyl succinic anhydride and styrene, n-butyl acrylate, tert-butyl acrylate and / or acrylonitrile is particularly preferred
  • the polymerization can also be carried out in the presence of at least one polysaccharide.
  • the polysaccharides in question are water-soluble or water-swellable. They are described, for example, in Römpp, Chemistry Lexicon 9th Edition, Volume 5, page 3569 or in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/2 Chapter IV Conversion of Cellulose and Starch by E. Husemann and R Werner, pages 862-915 and in Ulimann's Encyclopedia for Industrial Chemistry, 6th edition, volume 28, pages 533 ff under Polysaccharides.
  • Suitable for the preparation of the aqueous polymer dispersions containing ASA according to the invention are, for example, all types of starches, for example both amylose and amylopectin, native starches, hydrophobically or hydrophilically modified starches, anionic starches, cationically modified starches, degraded starches, the starch degradation being, for example, oxidative, thermal , hydrolytically or enzymatically and can be used both as native and for starch degradation as starch modified starches can also be used, dextrins, crosslinked, water-soluble starches which are water-swellable are described, for example, in Ulimanns Encyclopedia of Industrial Chemistry, 6th edition, volume 33, cf. Starch, pages 735 - 737.
  • Typical crosslinkers for the production of such starches are, for example, POCI 3 , epichlorohydrin and mixed anhydrides.
  • polysaccharides are glycogens, inulins, chitins, chitosans, pectins, water-soluble cellulose derivatives such as carboxyalkyl celluloses, cellulose sulfate, cellulose phosphoric acid esters, cellulose formate and hydroxiethyl celluloses, hemicelluloses such as xylans, mannans, galactans and glyopolysaccharides, glycoprotein.
  • native starches which can be converted into a water-soluble form, for example with the aid of starch digestion, cationic starch, preferably cationically modified potato starch, and anionically modified starches such as oxidized potato starch.
  • Anionically modified starches which have been subjected to a reduction in molecular weight are particularly preferred.
  • the molecular weight reduction of the starches is preferably carried out enzymatically.
  • the average molar mass of the degraded starches is, for example, 500 to 100,000, preferably 1000 to 30,000.
  • the degraded starches have, for example, an intrinsic viscosity r) of 0.04 to 0.5 dl / g.
  • starches are described for example in EP-B-0257412 and in EP-B-0276770. If a starch is used as a protective colloid, for example 1 to 9, preferably 3 to 5 parts by weight of at least one starch are used per part by weight of ASA.
  • the polymer dispersions containing ASA according to the invention are preferably prepared in the presence of a water-soluble and / or water-swellable polysaccharide.
  • a water-soluble and / or water-swellable polysaccharide For example, it can be placed in an aqueous solution - optionally together with at least one polymerization initiator - and heated to a temperature at which the polymerization of the monomers takes place, for example at a temperature up to 40 ° C., for example in the temperature range from -20 to +40 ° C, preferably 0 to 20 ° C.
  • the miniemulsion is then added to this solution so that the monomers contained in the miniemulsion polymerize.
  • the miniemulsion is prepared in the presence of at least one water-soluble polysaccharide and the miniemulsion is then subjected to the polymerization by heating it to a temperature at which the polymerization initiators contained or subsequently added form free radicals.
  • the organic phase contains at least one alkenyl succinic anhydride and - at least one monoethylenically unsaturated hydrophobic monomer in solution.
  • a surface-active agent to emulsify in an aqueous phase which contains at least one water-soluble and / or water-swellable polysaccharide with the aid of mechanical emulsifiers to form a miniemulsion with a particle size of the emulsified organic phase of at most 500 nm.
  • the monomers of the miniemulsion are then polymerized in the presence of at least one polymerization initiator.
  • the miniemulsion is preferably mixed with an aqueous solution which contains a degraded starch and polymerizes therein.
  • a mode of operation is particularly preferred in which the miniemulsion is mixed continuously or in portions with the aqueous solution of a polysaccharide and polymerized therein.
  • the polymerization can be carried out e.g. Carry out at temperatures up to 40 ° C. Since the rate of hydrolysis of ASA is relatively high at temperatures above 40 ° C. in the presence of water, it is advisable to carry out the polymerization of the monomers of the miniemulsion at temperatures below 40 ° C., preferably below 30 ° C.
  • polymerisation takes place in the temperature range from 0 to 20 ° C.
  • the polymerization can also be carried out at temperatures below 0 ° C, provided that the water contained in the system does not freeze, the other components do not crystallize and the mini-emulsion is stable.
  • the minimum temperature for the polymerization is essentially determined by the freezing point depression of the water, which is caused by the components of the aqueous phase and the miniemulsion dissolved therein.
  • salts such as sodium chloride, potassium chloride, magnesium sulfate, magnesium chloride, ammonium sulfate and / or ammonium chloride or organic solvents or organic solvents to the lowering of the freezing point to the freezing point of the water, e.g. Ethylene glycol, propylene glycol, polyethylene glycol with molecular weights up to 2000, trimethyolpropane and / or glycerin.
  • salts such as sodium chloride, potassium chloride, magnesium sulfate, magnesium chloride, ammonium sulfate and / or ammonium chloride or organic solvents or organic solvents
  • the procedure is, for example, that an aqueous solution which optionally contains an emulsifier and a water-soluble and / or water-swellable polysaccharide and optionally at least one polymerization initiator and which has a temperature in the range from, for example, 0 to 20 ° C, the miniemulsion is metered in continuously or in portions at a rate such that the temperature of the reaction mixture can be controlled by removing the heat of polymerization by cooling. In the case of smaller batches, the miniemulsion can also be added all at once to the above-mentioned aqueous solution.
  • the temperature of the miniemulsion is expediently adapted to the temperature at which the polymerization is also to be carried out.
  • the miniemulsion is preferably added in accordance with the progress of the polymerization.
  • a water-soluble poly Saccharide is preferably a degraded starch, especially a degraded cationic or degraded anionic potato starch.
  • the polymerization can also be initiated by adding an initiator to one of the two phases or else to both phases in the preparation of the miniemulsion before emulsifying the organic phase in the aqueous phase.
  • an initiator it is preferred to use those initiators which dissolve in the organic phase, e.g. Lauroyl peroxide or tert-butyl hydroperoxide.
  • the choice of initiators depends on the optimal polymerization temperature.
  • the addition of initiators to the aqueous phase is preferred. As a rule, water-soluble starters are used for this, e.g.
  • Hydrogen peroxide or redox systems preferably of hydrogen peroxide and a reducing agent such as ascorbic acid, isoascorbic acid, acetone bisulfite adducts or sodium sulfite.
  • the amount of initiators which is used in each of the two or in both phases is, for example, 0.05 to 10% by weight, preferably 0.1 to 0.5% by weight, based on the monomers to be polymerized. Since the polymerization is preferably carried out at relatively low temperatures, redox initiators are preferably used. However, the polymerization can also be initiated with the help of high-energy rays such as UV rays.
  • the mini-emulsion polymerization can optionally also be carried out in the presence of at least one alkyl diketene.
  • This process variant is based on an organic phase which comprises at least one alkenyl succinic anhydride and at least one alkyl diketene and at least one monoethylenically unsaturated hydrophobic monomer
  • aqueous phase which preferably contains at least one water-soluble polysaccharide, with the aid of mechanical emulsifiers to form a miniemulsion with a particle size of the emulsified organic phase of at most 500 nm and polymerizes the monomers of the miniemulsion in Presence of at least one polymerization initiator.
  • Finely divided alkenylsuccinic anhydrides and alkyl ketene dimers (AKD) are then obtained in the form of a polymer matrix dispersed in water.
  • ASA / AKD hybrids Such aqueous polymer dispersions.
  • alkyl ketene dimers in the ASA / AKD hybrids is in the range of the particle size of the ASA particles, namely 50 to 500 nm, preferably 50 to 200 nm.
  • Alkyldiketenes (AKD) are known compounds that are used in the form of aqueous dispersions as bulk sizes for paper. For example, they are produced from carboxylic acid chlorides by splitting off hydrogen chloride with tertiary amines.
  • C 14 to C 1-4 alkyldiketenes are particularly suitable for the sizing of paper.
  • Such compounds are described, for example, in WO-A-96/31650, page 3, lines 31 to 46.
  • Of particular technical interest are, for example, stearydiketes, oleyl dikets, palmityldiketes and behenyl dikets.
  • the polymer dispersions according to the invention optionally contain, for example, from 0.01 to 100, preferably from 0.1 to 1.0, part by weight of at least one alkyldiketene per 1 part by weight of ASA.
  • the water-soluble and / or water-swellable polysaccharides are contained in the aqueous polymer dispersions containing ASA according to the invention in amounts of, for example, 10 to 50, preferably 15 to 35,% by weight.
  • the dispersions according to the invention have a polymer content of preferably 20 to 60, in particular 20 to 40% by weight and contain 5 to 50% by weight of at least one alkenylsuccinic anhydride.
  • the particle size of the dispersed polymers and the emulsified alkenylsuccinic anhydrides in the dispersions according to the invention is, for example, 50 to 500 nm, preferably 50 to 200 nm and is usually in the range from 50 to 100 nm.
  • the dispersions containing ASA according to the invention are used as sizing agents for paper, as water repellents for leather, natural and / or synthetic fibers and textiles. They can be used both for the mass sizing of paper and for the surface sizing of paper.
  • the process chemicals customary in paper production such as strengthening agents, retention aids, drainage agents, bactericides and / or dyes, can be used in the usual amounts. You can glue all types of paper and paper products such as cardboard and cardboard with the dispersions according to the invention.
  • the dispersions containing ASA are used, for example, in amounts of 0.03 to 3.0, preferably 0.2 to 1.0,% by weight, based on the solids content of the dispersion and dry paper stock.
  • a typical application for the dispersions according to the invention is the surface sizing of paper and paper products.
  • the amounts of the polymer dispersions containing ASA are, for example, 0.03 to 3, preferably 0.2 to 1.0,% by weight, based on the solids content of the dispersion and dry paper.
  • the papers glued with this have the advantage over the papers glued with conventional alkyldiketene dispersions alone that they have an excellent adhesion for toners on papers used for making copies in copiers. Since toners adhere well to these papers, they can also be used with advantage in laser printers.
  • the percentages in the examples mean percent by weight.
  • the particle sizes were measured with a Coulter N4 Plus laser diffraction device or alternatively with a Coulter 230 LS.
  • This two-phase mixture was then emulsified twice at 300 bar using an APV-Gaulin high-pressure homogenizer at a maximum of 25 ° C., the pH being about 3.5.
  • the mean drop diameter of the miniemulsion was 138 nm (measured with a Coulter N4 Plus device).
  • the polydispersity index was 0.11. This emulsion was then immediately used to prepare the dispersion.
  • the miniemulsion described above feed 1 and 69.5 g of a 5% strength aqueous solution of Rongalit C (feed 2) were metered in, with the proviso that feed 1 after 15.5 h and feed 2 after 16 h were added, the first 2.7 g of the mini-emulsion being metered in 10 minutes, the next 5.4 g of the mini-emulsion in a further 10 minutes and 8.1 g of the mini-emulsion also being metered in 10 minutes. The rest of the mini emulsion (520.3 g) was then metered in over 15 hours. During the polymerization, the temperature of the reaction mixture was kept in the range of 11-12 ° C.
  • a sample from the batch showed that the non-volatile components were 19.7%, which corresponded to a conversion of> 85%.
  • the average particle size of the polymer dispersion was 127 nm.
  • 4 g of 10% strength aqueous tert-butyl hydroperoxide were then added at 11-12 ° C. The temperature rose by about 1 ° C. The peroxide test was negative after a short time.
  • the dispersion was tested as a bulk sizing agent and as a surface sizing agent for paper. Sized papers with a good degree of sizing were obtained, which allowed perfect writing on with ink and printing.
  • the dispersions according to the invention have compared to the conventional C-ie / Cis
  • Alkenylsuccinic anhydride sizing agents have a greatly improved storage stability.
  • the dispersions according to the invention still had a gluing effect even after storage at 40 ° C. for 12 hours.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymerisation Methods In General (AREA)
  • Paper (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne des dispersions polymériques aqueuses contenant des anhydrides d'acide alcénylsuccinique et obtenues par polymérisation en miniémulsion de monomères monoéthyléniquement insaturés hydrophobes en présence d'anhydrides d'acide alcénylsuccinique. L'invention concerne également le procédé de production de ces dispersions polymériques par polymérisation de monomères hydrophobes à la manière d'une polymérisation en miniémulsion en présence d'au moins un anhydride d'acide alcénylsuccinique et éventuellement d'un alkyldicétène. L'invention concerne enfin l'utilisation des dispersions polymériques aqueuses contenant des anhydrides d'acide alcénylsuccinique ainsi obtenues comme produit de collage dans la masse et en surface pour le papier et pour l'imperméabilisation du cuir, de fibres naturelles et/ou synthétiques et de textiles.
EP05700910A 2004-01-21 2005-01-14 Dispersions polymeriques aqueuses contenant des anhydrides d'acide alcenylsuccinique, leur procede de production et leur utilisation Withdrawn EP1709026A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004003261A DE102004003261A1 (de) 2004-01-21 2004-01-21 Alkenylbernsteinsäureanhydride enthaltende wässrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2005/000308 WO2005070912A1 (fr) 2004-01-21 2005-01-14 Dispersions polymeriques aqueuses contenant des anhydrides d'acide alcenylsuccinique, leur procede de production et leur utilisation

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EP1709026A1 true EP1709026A1 (fr) 2006-10-11

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US (1) US20090188054A1 (fr)
EP (1) EP1709026A1 (fr)
CN (1) CN1910170A (fr)
BR (1) BRPI0506950A (fr)
CA (1) CA2551769A1 (fr)
DE (1) DE102004003261A1 (fr)
WO (1) WO2005070912A1 (fr)

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WO2007147726A1 (fr) * 2006-06-20 2007-12-27 Basf Se Procédé de production de dispersions polymères aqueuses renfermant au moins une substance active lipophile, et leur utilisation
CN101568687B (zh) * 2006-12-20 2012-06-27 巴斯夫欧洲公司 纸施胶剂混合物
JP5803225B2 (ja) * 2011-04-06 2015-11-04 Dic株式会社 水性顔料分散体用樹脂、水性顔料分散液、インクジェット記録用インク、及び水性顔料分散液の製造方法
AT512143B1 (de) * 2011-11-08 2013-12-15 Chemiefaser Lenzing Ag Cellulosefasern mit hydrophoben Eigenschaften und hoher Weichheit und der dazugehörige Herstellungsprozess
FI126316B (en) * 2014-02-06 2016-09-30 Kemira Oyj Stabilized adhesive formulation
FI126960B (en) * 2014-02-06 2017-08-31 Kemira Oyj Stabilized adhesive formulation
CN106638122B (zh) * 2016-12-20 2018-11-30 宁波益富乐生物科技有限公司 一种包装纸箱用高分子抑菌原纸材料及其制备方法

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JPH086008B2 (ja) * 1985-11-18 1996-01-24 星光化学工業株式会社 置換コハク酸無水物の水性分散液
JPS63294557A (ja) * 1987-05-27 1988-12-01 Fuji Photo Film Co Ltd 写真印画紙用支持体
US5190616A (en) * 1988-12-27 1993-03-02 Akimoto Shin Ichi Self-emulsifying sizing agents
JPH06128896A (ja) * 1992-10-16 1994-05-10 Mitsubishi Oil Co Ltd アルケニルコハク酸系エマルションサイズ剤
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US6162328A (en) * 1997-09-30 2000-12-19 Hercules Incorporated Method for surface sizing paper with cellulose reactive and cellulose non-reactive sizes, and paper prepared thereby
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DE10248879A1 (de) * 2002-10-18 2004-04-29 Basf Ag Alkyldiketene enthaltende wässrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung

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US20090188054A1 (en) 2009-07-30
BRPI0506950A (pt) 2007-06-26
CN1910170A (zh) 2007-02-07
DE102004003261A1 (de) 2005-08-18
WO2005070912A1 (fr) 2005-08-04
CA2551769A1 (fr) 2005-08-04

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