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EP2121781A1 - Dispersions polymères amylacées à fines particules - Google Patents

Dispersions polymères amylacées à fines particules

Info

Publication number
EP2121781A1
EP2121781A1 EP07857375A EP07857375A EP2121781A1 EP 2121781 A1 EP2121781 A1 EP 2121781A1 EP 07857375 A EP07857375 A EP 07857375A EP 07857375 A EP07857375 A EP 07857375A EP 2121781 A1 EP2121781 A1 EP 2121781A1
Authority
EP
European Patent Office
Prior art keywords
acid
starch
polymer dispersions
monomers
finely divided
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Withdrawn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
EP07857375A
Other languages
German (de)
English (en)
Inventor
Andreas Brockmeyer
Titus Leman
Roland Ettl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07857375A priority Critical patent/EP2121781A1/fr
Publication of EP2121781A1 publication Critical patent/EP2121781A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch

Definitions

  • the invention relates to finely divided starch-containing polymer dispersions which are obtainable by free-radically initiated emulsion copolymerization of ethylenically unsaturated monomers in the presence of a redox initiator and an enzymatically degraded starch.
  • EP-B 257 412 discloses sizing agents for paper based on finely divided, aqueous dispersions of copolymers which are degraded by copolymerizing acrylonitrile and / or methacrylonitrile, an acrylic acid ester and optionally other ethylenically unsaturated copolymerizable monomers in the manner of an emulsion polymerization in an aqueous solution
  • Starch with a viscosity ⁇ , from 0.12 to 0.5 dl / g are available using hydrogen peroxide or redox initiators.
  • the starch is degraded enzymatically. The enzymatic degradation of the starch is terminated by the addition of acetic acid.
  • Correspondingly structured emulsion polymers are known from EP-B 276 770. They differ only from the sizing agents known from EP-B 257 412 in that they are prepared in an aqueous solution of a degraded starch having a viscosity ⁇ of from 0.04 to less than 0.12 dl / g.
  • EP-A 307 816 discloses paper sizing agents which are obtainable by copolymerizing a monomer mixture of (i) acrylonitrile, methacrylonitrile and / or styrene, (ii) at least one acrylic or methacrylic acid ester, vinyl acetate, vinyl propionate and / or butadiene-1, 3, and optionally (iii) other ethylenically unsaturated, copolymerizable monomers in the manner of emulsion polymerization in an aqueous solution of a degraded cationic starch having a viscosity ⁇ of from 0.04 to 0.50 dl / g.
  • aqueous, finely divided polymer dispersions are known, which are used for surface sizing of paper, cardboard and cardboard.
  • the dispersions are obtainable by free-radically initiated emulsion polymerization of ethylenically unsaturated monomers in the presence of degraded starch having a number average molecular weight M n of from 500 to 10,000.
  • the monomer mixtures consist of (i) at least one optionally substituted styrene, (ii) at least one (meth) acrylic acid C 1 -C 4 -alkyl ester and (iii) optionally up to 10% by weight. % of other ethylenically unsaturated monomers.
  • the polymerization takes place in the presence of a graft-active, water-soluble redox system.
  • sizing and coating compositions for paper are prepared by free-radically initiated emulsion polymerization of a monomer mixture of (i) at least one (meth) acrylic acid ester of monohydric, saturated Cs-Cs alcohols and (ii) one or more a plurality of further ethylenically unsaturated monomers in the presence of degraded starch and / or a degraded starch derivative prepared, wherein monomers and initiator is continuously fed to an aqueous starch solution and the initiator is metered in two subsets under specially defined conditions.
  • the starch degradation is stopped by the addition of acetic acid before the emulsion polymerization is carried out in the aqueous solution of the degraded starch.
  • sizing agents are also known which are obtainable by free-radically initiated emulsion copolymerization of a monomer mixture (A) of, for example, (i) at least one optionally substituted styrene, (ii) optionally at least one C 4 -C 12 -alkyl (meth) acrylate and (iii) at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate and propyl acrylate in the presence of (B) starch having an average molecular weight of 1000 or greater, wherein the weight ratio of (A) :( B) is 0.6: 1 to 1.7 Is 1, the sizing agent is free of emulsifiers or surfactants having a molecular weight of less than 1000 and contains virtually no acid group-containing monomers in copolymerized form.
  • A monomer mixture
  • A of, for example, (i) at least one optionally substituted styrene, (ii) optionally at least
  • component (B) of the sizing agent is preferably cationic starch, in particular oxidized cationic corn starch into consideration, the component (A) preferably consists of a mixture of styrene, n-butyl acrylate and methyl acrylate.
  • the emulsion polymerization is usually carried out in the presence of redox catalysts. Due to the heavy metal content of these initiators, white dispersions are only obtained if they are mixed with a sufficient amount of a complexing agent for heavy metals.
  • sizing dispersions are carried out using aqueous solutions of enzymatically degraded starch, wherein the starch degradation is stopped by the addition of acetic acid, aqueous dispersions are obtained which, due to the use of acetic acid, have an undesirable content of volatile organic compounds.
  • the object is achieved according to the invention with finely divided, starch-containing polymer dispersions which are obtainable by free-radically initiated emulsion copolymerization of ethylenically unsaturated monomers in the presence of a redox initiator and an enzymatically degraded starch if the enzyme-degraded starch used is an aqueous reaction mixture which is stopped by stopping the enzymatic Starch degradation with at least one acid containing a phosphorus atom is available.
  • all phosphoric acids can be used, for example phosphoric acid (H 3 PO 4 ), phosphonic acid (H 3 PO 3 ), phosphinic acid (H 3 PO 2 ), peroxophosphoric acid (H 3 PO 5), hypodiphosphonic acid (H 4 PO 2 O 4),
  • Diphosphonic acid H4P2O5
  • hypodiphosphoric H4P2O6
  • diphosphoric acid H4P2O7
  • peroxodiphosphoric H4P2O8
  • at least a chain polyphosphoric acid of the formula H n + 2 P n ⁇ 3n + i as triphosphoric or Tetraphosphoklad at least one annular metaphosphoric of formula (HPO) 3n
  • phosphoric acids are derivatives derived, for example, from phosphoric acid or another acid containing a phosphorus atom by replacing one or two hydroxyl groups by a monovalent radical such as alkyl, aryl or amino, or with a d- to C ⁇ -alcohol such as methanol, ethanol, n-propanol, isopropanol, a butanol, n-hexanol or cyclohexanol esterified.
  • a monovalent radical such as alkyl, aryl or amino
  • a d- to C ⁇ -alcohol such as methanol, ethanol, n-propanol, isopropanol, a butanol, n-hexanol or cyclohexanol esterified.
  • phosphoric acid derivatives examples include nitrilotris (methylene triphosphonic acid), ethylenediaminetetrakis (methylenetetraphosphonic acid), diethylenetriaminepentakis (methylenephosphonic acid), 2-phosphonobutane-1, 2,4-tricarboxylic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1, 1-diphosphonic acid, phosphonoformic acid, phosphonoacetic acid, phenylphosphonic acid and also alkylphosphonic acids such as vinylphosphonic acid, methylphosphonic acid, ethylphosphonic acid,
  • Propylphosphonic acid isopropylphosphonic acid, n-butylphosphonic acid, isobutylphosphonic acid, n-hexylphosphonic acid and octylphosphonic acid.
  • polymers containing at least one vinylphosphone unit in copolymerized form preferably polyvinylphosphonic acid
  • the copolymers obtainable by free-radical copolymerization of vinylphosphonic acid with ethylenically unsaturated monomers are also suitable for stopping the enzymatic starch degradation.
  • suitable comonomers are acrylic acid esters and methacrylic acid esters of monohydric alcohols having 1 to 8 carbon atoms, acrylic acid, methacrylic acid, styrene and acrylonitrile.
  • the average molecular weight M w of the polymers is for example at most 100,000, usually less than 50,000 and is preferably in the range of 500 to 20,000.
  • the at least one phosphorus atom-containing acids to be used according to the invention can also be used in at least partially neutralized or in at least partially esterified form.
  • Suitable neutralizing agents are, for example, sodium hydroxide solution, potassium hydroxide solution or ammonia.
  • the at least partially neutralized or esterified, at least one phosphorus atom-containing acids for example, have a pK s value in the range of -3 to 9 or have such an acid strength that the pH of the enzyme-containing solution to a value below 5, preferably below 4, so that the enzymatic degradation is stopped.
  • the compounds in question must give a pH of less than 5.0, at least in aqueous solution.
  • Acids containing a phosphorus atom are described, for example, in Hoeleman-Wiberg, Lehrbuch der Anorganischen Chemie, 91.-100. Edition, Walter de Gruyter Verlag, Berlin, New York 1985, pp. 646-664 and Ullmann 's Encyclopedia of Industrial Chemistry, Sixth Completely Revised Edition, Wiley-VCH Verlag GmbH Co. KgaA, Weinheim 2003, Volume 26, pages 227- 229th
  • Phosphoric acid, phosphonic acid, diphosphoric acid, polyphosphonic acid and / or polyvinylphosphonic acid are preferably used to stop the starch degradation.
  • starch can be degraded enzymatically, z.
  • native starches or starch derivatives such as anionic or cationic modified, esterified, etherified or crosslinked starches.
  • the native starch can be obtained, for example, from potatoes, corn, wheat, rice, peas, tapioca or sorghum.
  • the proportion of the cationic or anionic groups in the respective starch is indicated by the degree of substitution (D.S.). It is usually 0.005 to 1.0, and is preferably in the range of 0.01 to 0.4.
  • an aqueous starch solution is needed for the stabilization of emulsion polymers.
  • the average molecular weight M w of the starch is at most 100 000. It is master- least in the range from 1000 to 65,000, especially from 2500 to 35 000.
  • the average molecular weights M w of the strength can be readily determined by art-known methods, for example by means of Gel permeation chromatography using a multi-angle light scattering detector.
  • the enzymatic starch degradation can be carried out separately, but is preferably carried out in the course of the preparation of aqueous polymer dispersions, by first applying the starch by known methods in an aqueous medium in the presence of least an enzyme degrades, for example, at a temperature in the range of 20 to 100 0 C, preferably 40 to 80 0 C.
  • the amount of enzyme is for example 50 mg to 5.0 g / kg of a 5% aqueous starch solution, preferably 200 mg to 2.5 g / kg of 5% aqueous starch solution.
  • the enzymatic degradation of the starch is carried out, for example, to such an extent that the viscosity of a 2.5% strength by weight aqueous solution of the enzymatically degraded starch is 10 to 1500 mPas, preferably 100 to 800 mPas (Brookfield viscometer, spindle 4, 20 rpm, 20 ° C).
  • Enzymatic degradation of starches is state of the art. Enzymes are defined in EC classes by the International Union of Biochemistry and Molecular Biology, see Enzyme Nomenclature 1992 [Academic Press, San Diego, Calif., ISBN 0-12-227164-5 (hardback), 0-12-227165]. 3 (paperback)] with Supplement 1 (1993), Supplement 2 (1994), Supplement 3 (1995), Supplement 4 (1997) and Supplement 5 (in Eur. J. Biochem., 1994, 223, 1-5; Eur. J. Biochem., 1995, 232, 1-6; Eur. J. Biochem., 1996, 237, 1-5; Eur. J. Biochem. 1997, 250; 1-6, and Eur. J. Biochem., 1999 , 264, 610-650.) A constantly updated list of enzyme classes can be found on the Internet at http://www.chem.qmul.ac.uk/iubmb/enzyme/.
  • Preferably eligible enzymes are from the upper class of "hydrolases EC 3.-.-.-", the class of “glycosylases EC 3.2.-.-” or the subclass “glycosidases, which can hydrolyze O- and S-glycosidic compounds EC 3.2.1.- ".
  • Suitable examples are ⁇ -amylase EC 3.2.1.1., ⁇ -amylase EC 3.2.1.2., ⁇ -amylase EC 3.2.1.3 and pullulanase EC 3.2.1.41.
  • an acid containing a phosphorus atom is added to the aqueous solution of the degraded starch to destroy the enzyme and thereby prevent the further degradation of starch.
  • the amount of acid which has at least one phosphorus atom is, for example, 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the starch used.
  • the invention therefore also provides the use of an acid containing at least one phosphorus atom to stop the enzymatic degradation of starch.
  • an emulsion polymerization is preferably carried out directly by polymerizing ethylenically unsaturated monomers therein in the presence of at least one surface-active compound and at least one radical-forming polymerization initiator.
  • Emulsion polymers obtained by polymerizing ethylenically unsaturated Monomers obtainable in the presence of a degraded starch belong to the state of the art. They are used, for example, as a sizing agent for paper, cf.
  • Suitable emulsion polymers are polymers containing at least 40% by weight of so-called main monomers selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of saturated carboxylic acids containing up to 20 C atoms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers are constructed.
  • main monomers selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of saturated carboxylic acids containing up to 20 C atoms, vinylaromatics having up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2
  • the emulsion polymers are preferably a polymer which consists of at least 70% by weight, particularly preferably at least 95% by weight, of so-called main monomers which are emulsifiable in water.
  • Hexyl acrylate, 2-ethylhexyl acrylate and 3-propylheptyl acrylate and the esters of methacrylic acid with C 1 to C 10 alkanols such as ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate and the like.
  • Suitable monomers of this type are also vinyl and allyl esters of saturated aliphatic carboxylic acids having 1 to 18 carbon atoms, for example vinyl acetate, vinyl propionate and the vinyl esters of Versatic® acids (vinyl versatates), vinyl halides such as vinyl chloride and vinylidene chloride and C2-C4o Olefins such as ethylene, propene, 1-butene, 1-hexene, decene, dodecene and octadecene.
  • Preferred monomers are vinylaromatic monomers, C 2 -C 6 -alkyl acrylates, in particular C 2 -C 8 -alkyl acrylates, especially tert-butyl acrylate and C 2 -C 18 -alkyl methacrylates and in particular C 2 -C 4 -alkyl methacrylates.
  • At least 60% by weight of the main monomers used in the emulsion polymerization are selected from vinyl aromatic monomers, in particular styrene, esters of methacrylic acid with C 2 -C 4 -alkanols and tert-butyl acrylate.
  • Particularly preferred monomers of this type are vinylaromatic monomers, especially styrene, and mixtures of vinylaromatic monomers with the abovementioned C 2 -C 8 -alkyl acrylates and / or C 2 -C 4 -alkyl methacrylates.
  • the monomer composition may also optionally contain up to 20% by weight, based on the total weight of the monomers, of one or more monoethylenically unsaturated monomers (ii) other than the main monomers (i).
  • the proportion of the monomers (ii) in the total amount of the monomers makes up 15% by weight, in particular up to 5% by weight.
  • the monomers (ii) are used only in amounts such that the resulting polymers are insoluble in water, so that dispersions are always obtained.
  • the monomers (ii) include in particular monoethylenically unsaturated monomers which have at least one acid group such as a sulfonic acid, a phosphonic acid or one or two carboxyl groups and the salts of these monomers, in particular the alkali metal salts, for. As the sodium or potassium salts and ammonium salts.
  • This group of monomers (ii) includes ethylenically unsaturated sulfonic acids, in particular vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid,
  • the proportion of acid group-containing monomers is often not more than 20 wt .-%, preferably not more than 15 wt .-%, z. B. 0.1 to 15 wt .-% and in particular 0.5 to 10 wt .-%, based on the total amount of the monomers constitute.
  • the monomers of group (ii) also include monoethylenically unsaturated, neutral monomers such as the amides of the abovementioned ethylenically unsaturated carboxylic acids, in particular acrylamide and methacrylamide, hydroxyalkyl esters of the abovementioned ⁇ , ⁇ -ethylenically unsaturated Cs-Cs monocarboxylic acids and the C 4 -Cs Dicarboxylic acids, in particular 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, 2- and 3-hydroxypropyl methacrylate, esters of the abovementioned monoethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 4 - polyalkylene glycols, in particular the esters of these carboxylic acids Polyethylene glycol or alkyl polyethylene glycols, wherein the (alkyl) polyethylene glycol radical usually has a mole
  • the monomers (ii) also include N-vinylamides such as N-vinylformamide, N-vinylpyrrolidone, N-vinylimidazole and N-vinylcaprolactam.
  • the proportion of these monomers is also chosen so that the resulting polymers are insoluble in water. It is preferably not more than 20 wt .-%, and in particular not more than 10 wt .-%, z. B. 0.1 to 10 and in particular 0.5 to 5 wt .-%, based on the total amount of the monomers.
  • the monomers of group (ii) furthermore include monoethylenically unsaturated monomers which have at least one cationic group and / or at least one amino group which can be protonated in the aqueous medium, a quaternary ammonium group, a protonatable imino group or a quaternized imino group.
  • monomers having a protonatable imino group are N-vinylimidazole and N-vinylpyridines.
  • Examples of monomers having a quaternized imino group are N-alkylvinylpyridinium salts and N-alkyl-N'-vinylimidazolinium salts such as N-methyl-N'-vinylimidazolinium chloride or methosulfate.
  • these monomers in particular the monomers of general formula I are preferred
  • R 1 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
  • R 2 , R 3 are independently C 1 -C 4 -alkyl, in particular methyl, and
  • R 4 is hydrogen or C 1 -C 4 -alkyl, in particular hydrogen or methyl
  • A is C 2 -C 8 alkylene, e.g. B. 1, 2-ethanediyl, 1, 2- or 1, 3-propanediyl, 1, 4-butanediyl or 2-methyl-1, 2-propanediyl, which is optionally interrupted by 1, 2 or 3 non-adjacent oxygen atoms is and
  • X- for an anion equivalent e.g. B. for Ch, HSO 4 -, V 2 SO 4 2 " or CH 3 OSO 3 - etc.
  • Examples of such monomers are 2- (N, N-dimethylamino) ethyl acrylate,
  • the proportion of cationic monomers in the emulsion polymer is advantageously 0.1 to 20% by weight, in particular 0.5 to 10% by weight, and particularly preferably 1 to 7% by weight, based on the total amount of the monomers.
  • the polymers may optionally contain a further group of monomers (iii) in copolymerized form, which can usually be used as crosslinking agent in an emulsion polymerization.
  • a further group of monomers (iii) in copolymerized form which can usually be used as crosslinking agent in an emulsion polymerization.
  • the proportion of monomers (iii) which have two or more ethylenically unsaturated double bonds usually does not exceed 10% by weight, in most cases not more than 5% by weight, in particular not more than 2% by weight.
  • z. B 0.01 to 2 wt .-% and in particular 0.05 to 1, 5 wt .-%, based on the total amount of the monomers.
  • crosslinkers are butanediol diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, glycol dicarylate, glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diacrylates and dimethacrylates of alkoxylated dihydric alcohols, divinylurea and / or conjugated diolefins such as butadiene or isoprene.
  • the monomers of group (iii) may also include so-called functional monomers, i.
  • Monomers which, in addition to a polymerizable C C double bond, also have a reactive functional group, for example an oxirane group, a reactive carbonyl group, eg. An acetoacetyl group, an isocyanate group, an N-hydroxymethyl group, an N-alkoxymethyl group, a trialkylsilyl group, a trialkoxysilyl group or any other nucleophile-reactive group.
  • emulsion polymers whose monomer composition is selected such that the resulting polymer has a glass transition temperature of at least 0, preferably at least 10 ° C., in particular in the range from 20 to 130 ° C.
  • the monomers (i) in the monomer mixture are chosen such that they correspond to a polymer 1 having a theoretical glass transition temperature according to Fox Tg (Fox) of at least 50.degree. According to Fox (TG Fox, Bull. Am. Phys Soc. (Ser. II) 1, 123 [1956] and Ullmann's Encyclopedia of Industrial Chemistry, Weinheim (1980), pp 17-18) applies to the glass transition temperature of not or weakly cross-linked copolymers at high molecular weights in a good approximation 1 X 1 X 2 X "
  • X 1 , X 2 , ..., X n is the mass fractions of the monomers 1, 2, ..., n and T 9 1 , T 9 2 , ..., T 9 "the glass transition temperatures of each of only one of Monomers 1, 2,..., N, which are, for example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p J. Brandrup, EH Immergut, Polymer Handbook 3rd ed., J. Wiley, New York 1989.
  • the polymerization of the monomers is carried out by the method of emulsion polymerization, i. the monomers to be polymerized are present in the polymerization mixture as an aqueous emulsion.
  • the monomers to be polymerized are present in the polymerization mixture as an aqueous emulsion.
  • a dispersion stabilizer for the preparation of the aqueous dispersions of reactive sizes, e.g.
  • surfactants especially anionic surfactants, water-soluble starch, preferably anionic starch and protective colloids.
  • the monomers may be initially charged in the reactor prior to the start of the polymerization or added under polymerization conditions in one or more portions or continuously to the polymerizing reaction mixture. For example, you can submit the majority of the monomers, in particular at least 80% and particularly preferably the total amount in the polymerization vessel and then immediately start the polymerization by adding a polymerization initiator.
  • a further process variant consists in initially introducing a part (for example 5 to 25%) of the monomers or the monomer emulsion in the polymerization reactor, starting the polymerization by adding an initiator and then continuously adding the remaining amount of monomer or monomer emulsion to the reactor in portions and the polymerization of the monomers leads to the end.
  • the polymerization initiator may in this process variant, for example, be introduced partially or completely into the reactor or metered separately from the remaining monomers into the reactor.
  • the starters which are suitable for emulsion polymerization are, in principle, all polymerization initiators which are suitable and usually used for emulsion polymerization and which initiate free-radical polymerization of ethylenically unsaturated monomers.
  • polymerization initiators which are suitable and usually used for emulsion polymerization and which initiate free-radical polymerization of ethylenically unsaturated monomers.
  • azo compounds such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide, 1, 1 '.
  • Azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) dihydrochloride, and 2,2'-azobis (2-amidinopropane) dihydrochloride, organic or inorganic peroxides such as diacetylperoxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroperoxide, dibenzoyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert.
  • organic or inorganic peroxides such as diacetylperoxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl per
  • the polymerization is preferably carried out using a redox initiator system, in particular a redox initiator system which contains as oxidizing agent a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide.
  • a redox initiator system which contains as oxidizing agent a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide.
  • the redox initiator systems preferably contain a sulfur compound, which is selected in particular from sodium hydrogen sulfite, sodium hydroxymethanesulfinate and the bisulfite adduct to acetone.
  • sulfur compound which is selected in particular from sodium hydrogen sulfite, sodium hydroxymethanesulfinate and the bisulfite adduct to acetone.
  • phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates
  • redox initiator systems may contain an addition of small amounts of redox metal salts, such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.
  • redox metal salts such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.
  • Particularly preferred redox initiator systems are acetone bisulfite adduct / organic hydroperoxide such as tert-butyl hydroperoxide; Sodium disulfite (Na2S2 ⁇ s) / organic hydroperoxide such as tert-butyl hydroperoxide; Sodium hydroxymethanesulfinate / organic hydroperoxide such as tert-butyl hydroperoxide; and ascorbic acid / hydrogen peroxide.
  • the initiator is usually employed in an amount of 0.02 to 2% by weight and in particular 0.05 to 1.5% by weight, based on the amount of the monomers.
  • the optimum amount of initiator naturally depends on the initiator system used and can be determined by the person skilled in the art in routine experiments.
  • the initiator may be partially or completely charged in the reaction vessel. In most cases, a portion of the amount of initiator is taken together with a portion of the monomer emulsion and the remaining initiator is added continuously or batchwise together with the monomers, but separately therefrom.
  • the temperature naturally depends on the initiator system used.
  • the optimum polymerization temperature can be determined by a person skilled in the art with the aid of routine experiments.
  • the polymerization is onstemperatur in the range from 0 to 110 0 C, often in the range of 30 to 95 0 C.
  • the polymerization is usually carried out at atmospheric pressure or ambient pressure. But it can also at elevated pressure, z. B. to 10 bar or at reduced pressure z. B. at 20 to 900 mbar, but usually be carried out at> 800 mbar.
  • the polymerization time is preferably 1 to 120 minutes, in particular 2 to 90 minutes and more preferably 3 to 60 minutes, with longer or shorter polymerization times being possible.
  • the polymerization is preferably carried out under the so-called “starved conditions", ie conditions which allow only little or no formation of empty micelles and thus the formation of active ingredient-free polymer particles
  • starved conditions ie conditions which allow only little or no formation of empty micelles and thus the formation of active ingredient-free polymer particles
  • the surface-active substances contained in the polymerization mixture serve in the Essentially for the purpose of wetting the surface and transporting the monomers (i) through the continuous aqueous phase.
  • a dispersion stabilizer is added to stabilize the resulting emulsion polymers, it is preferable to add at least one further surface-active substance in an amount of, for example, up to 5% by weight, e.g. B. 0.1 to 5 wt .-%, based on the monomers to be polymerized.
  • a further surface-active substances in addition to the nonionic surface-active substances in particular anionic emulsifiers, eg.
  • alkyl sulfates As alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alkyl ether sulfates, alkylaryl ether sulfates, anionic starch, sulfosuccinates such as sulfosuccinic monoesters and sulfosuccinic diesters and alkyl ether and further cationic emulsifiers into consideration.
  • the emulsion polymerization of the monomers is carried out in the presence of, for example, up to 20% by weight, usually up to 10% by weight, based on the total dispersion, of a cationically or anionically modified starch.
  • reaction mixture can be polymerized, other additives that are common in emulsion polymerization, for example, glycols, polyethylene glycols, buffer / pH regulators, molecular weight regulators and chain transfer inhibitors.
  • additives that are common in emulsion polymerization, for example, glycols, polyethylene glycols, buffer / pH regulators, molecular weight regulators and chain transfer inhibitors.
  • the emulsion polymerization can optionally be carried out in the presence of at least one polymerization regulator.
  • polymerization regulators are organic compounds which contain sulfur in bound form, such as dodecyl mercaptan, thiodiglycol, ethylthioethanol, di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropan.
  • a regulator is used in the polymerization, the quantity used in each case is for example 0.01 to 5, preferably 0.1 to 1 wt .-%, based on the monomers used in the polymerization.
  • Polymerization regulators and crosslinkers can be used together in the polymerization. This can be used, for example, to control the rheology of the resulting polymer dispersions.
  • the polymerization is generally carried out at pH values of 2 to 9, preferably in the weakly acidic range at pH values of 3 to 5.5.
  • the pH can be adjusted to the desired value before or during the polymerization with customary acids such as hydrochloric acid, sulfuric acid or acetic acid or else with bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia, ammonium carbonate, etc.
  • the dispersion is preferably adjusted to a pH of between 5 and 7 using sodium hydroxide solution, potassium hydroxide solution or ammonia.
  • a postpolymerization is expediently carried out after completion of the actual polymerization.
  • the polymer dispersion after completion of the main polymerization for example, an initiator from the group of hydrogen peroxide, peroxides, hydroperoxides and / or azo starters.
  • suitable reducing agents such as ascorbic acid or sodium bisulfite
  • oil-soluble, sparingly soluble in water initiators are used, for.
  • organic peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide or bis-cyclohexylperoxidicarbonat used.
  • the reaction mixture is heated, for example, to a temperature corresponding to the temperature at which the main polymerization was carried out or which is up to 20 0 C, preferably up to 10 0 C higher.
  • the main polymerization is complete when the polymerization initiator is consumed or the monomer conversion is, for example, at least 98%, preferably at least 99.5%.
  • tert-butyl hydroperoxide is preferably used.
  • the polymerization is carried out, for example, in a temperature range from 40 to 100.degree. C., usually 50 to 95.degree.
  • the starch-containing polymer dispersions contain dispersed particles having an average particle size of, for example, 20 to 500 nm, preferably 50 to 250 nm.
  • the mean particle size can be determined by methods known to the person skilled in the art, such as, for example, laser correlation spectroscopy, ultracentrifugation or CHDF (capillary hydrofunctioning fractionation) .
  • Another measure of the particle size of the dispersed polymer particles is the LD (translucency) value.
  • the particular polymer dispersion to be examined is measured in 0.1% strength by weight aqueous dilution in a cuvette with an edge length of 2.5 cm with light of wavelength 600 nm and with the corresponding permeability of water under the same measurement conditions compared.
  • the permeability of water is given as 100%.
  • the average particle size can be calculated from the measured values, cf. B. Verner, M. Bärta, B. Sedläcek, Tables of Scattering Functions for Spherical Particles, Prague, 1976, Edice Marco, Rada D-DATA, SVAZEK D-1.
  • the solids content of the starch-containing polymer dispersion is, for example, 5 to 50% by weight, and is preferably in the range of 15 to 40% by weight.
  • the finely divided, starch-containing polymer dispersions according to the invention contain, for example, an emulsion polymer
  • Atoms having saturated carboxylic acids vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitrile, vinyl halide, vinyl ethers of alcohols having 1 to 10 carbon atoms, aliphatic hydrocarbon having 2 to 40
  • the emulsion polymer contains copolymerized units
  • the basic compounds can be used in the form of the free bases, in acids neutralized form or in quaternized form, while the acids can also be polymerized as salts or partially neutralized with bases such as sodium hydroxide, potassium hydroxide or ammonia neutralized form.
  • bases such as sodium hydroxide, potassium hydroxide or ammonia neutralized form.
  • emulsion polymers obtained by free-radical emulsion polymerization of
  • ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, hexyl acrylate and / or ethylhexyl acrylate and optionally (iii) other monomers are obtainable in an aqueous solution of an enzymatically degraded starch, wherein the enzymatic starch degradation is stopped by addition of an acid having at least one phosphorus atom.
  • the polymer dispersions may contain, for example, up to 20% by weight of at least one enzymatically degraded starch. In most cases, the content of enzymatically degraded starch in the emulsion polymers is 5 to 15% by weight.
  • starch-containing polymer dispersions are finely divided polymer dispersions which are obtainable by free-radically initiated emulsion copolymerization of ethylenically unsaturated monomers in the presence of at least one redox initiator and starch, if the ethylenically unsaturated monomers are used
  • polymer dispersions obtainable by free-radically initiated emulsion copolymerization of ethylenically unsaturated monomers in the presence of at least one redox initiator and enzymatically degraded starch, when used as ethylenically unsaturated monomers
  • Another example is emulsion polymers obtainable by radical polymerization of
  • Isobutene, diisobutene, octene-1, decene-1, dodecene-1 and mixtures of such olefins are preferably used as olefins for the preparation of these polymer dispersions.
  • the starch used in enzymatic degradation may already have been subjected to oxidative and / or hydrolytic degradation. It is likewise possible to additionally supply an enzymatically degraded starch to another starch degradation, such as oxidative degradation. It is only essential that the enzymatic degradation is stopped by the addition of an acid containing a phosphorus atom and that the molecular weight of the degraded starch is in the range indicated above.
  • the finely divided, starch-containing polymer dispersions according to the invention have a lighter color than the starch-containing polymer dispersions known from the prior art.
  • no complexing agents for heavy metal ions are required.
  • the finely divided, starch-containing polymer dispersions described above are used as sizing agents for paper and paper products, such as cardboard and board. They can be used both as surface sizing agents and as engine size agents in the customary amounts.
  • the application is preferred as a surface sizing agent.
  • the starch-containing polymer dispersions according to the invention can be processed with all process methods suitable for surface sizing.
  • the dispersion is usually the size presses liquor in an amount of 0.05 to 5 wt .-%, based on solid substance added.
  • the amount of polymer dispersion depends on the desired degree of sizing of the papers or paper products to be finished.
  • the size press fleet may contain other substances, such as.
  • the sizing agent dispersion can be applied to paper, cardboard or cardboard by means of a size press or other application units such as film press, speed sizer or gate-roll.
  • the amount of polymer thus applied to the surface of paper products is, for example, 0.005 to 1.0 g / m 2 , preferably 0.01 to 0.5 g / m 2 .
  • the starch-containing polymer dispersion according to the invention can be used for the production of all types of paper, for.
  • As of writing and printing papers and packaging papers in particular of papers for the packaging of liquids.
  • Paper products sized with the finely divided, starch-containing polymer dispersions of the present invention have improved sizing levels, good instant size, improved ink-jet printability, good toner adhesion, and higher whiteness over papers sized with known sizing agents.
  • the percentages in the examples always weight percent, the parts are parts by weight.
  • the particle sizes were determined by means of a High Performance Particle Sizer (HPPS) from Messrs. MaIvern using a He-Ne laser (633 nm) at a scattering angle of 173 °.
  • the LD values of the aqueous polymer dispersions were determined in 0.1% aqueous dilutions using a device from Hach DR / 2010 at a wavelength of 600 nm.
  • a monomer feed consisting of 49.3 g of water, 122.5 g of styrene, 61, 25 g of n-butyl acrylate and 61, 25 g of t-butyl acrylate was started and metered in over 120 min.
  • a feed of 56.2 g of 18% strength hydrogen peroxide solution was started over a period of 150 minutes.
  • the mixture was post-polymerized for 30 minutes and then cooled to 50 0 C.
  • For postpolymerization was added within 60 minutes 17.6 g of t-butyl hydroperoxide 10% strength, the temperature was maintained at 50 0 C and the reaction mixture was then cooled to 30 0 C.
  • a finely divided polymer dispersion having a solids content of 35.7% and an LD value (0.1%) of 51% was obtained.
  • the mean particle size of the dispersed particles was 106 nm.
  • a monomer feed consisting of 300 g of demineralized water, 0.48 g of a mixture of the sodium salt of alkanesulfonates having an average chain length of cis-alkyl (40% strength), 5.05 g of tert-dodecylmercaptan, 204 was started , 04 g of styrene, 102.02 g of ethylhexyl acrylate and 102.02 g of tert-butyl acrylate.
  • the feed time was 90 min.
  • a feed of 107.4 g of 18% strength hydrogen peroxide solution was started over a period of 120 minutes.
  • the mixture was after-polymerized for 30 minutes and then cooled to 50.degree. Then 4.9 g of tert-butyl hydroperoxide 10% strength, stirred for a further 30 min and then cooled to 30 ° C from. Then, 20.94 g of NaOH 25% and 100 ml of water were added, whereby the dispersion was made neutral.
  • a monomer feed consisting of 300 g of demineralized water, 0.48 g of a mixture of the Na salt of alkanesulfonates with a mean chain length of cis-alkyl (40%), 204.04 g of styrene, 102.02 g n-butyl acrylate and 102.02 g of tert-butyl acrylate.
  • the feed time was 90 min.
  • a feed of 107.4 g of 18% strength hydrogen peroxide solution was started over a period of 120 minutes.
  • the mixture was post-polymerized for 30 min and then cooled to 50 0 C.
  • a monomer feed consisting of 49.3 g of water, 332.8 g of acrylonitrile and 270.6 g of n-butyl acrylate was started and metered in over 120 minutes.
  • the mixture was post-polymerized for 30 minutes and then cooled to 50 0 C. 17.6 g of t-butyl hydroperoxide 10% were added to the postpolymerization within 60 minutes, the temperature was kept at 50 ° C. and the reaction mixture was subsequently cooled to 30 ° C.
  • a finely divided polymer dispersion having a solids content of 35% and an LD value (0.1%) of 51% was obtained.
  • the mean particle size of the dispersed particles was 103 nm.
  • a monomer feed consisting of 300 g of demineralized water, 0.48 g of a mixture of the sodium salt of alkanesulfonates having a mean chain length of cis-alkyl (40% strength), 576.4 g of acrylonitrile, 274.6 g n-butyl acrylate.
  • the feed time was 90 min.
  • a feed of 107.4 g of 18% strength hydrogen peroxide solution was started over a period of 120 minutes. The mixture was allowed to stand for 30 minutes postpolymerized and then cooled to 50 0 C. Then 4.9 g of tert-butyl hydroperoxide 10% strength, stirred for a further 30 min and then cooled to 30 0 C from.
  • Comparative Example 1 (Example 2 from EP-A 307 816)
  • 31.1 g of an oxidatively degraded potato starch (Amylofax® 15 from Avebe) were stirred under nitrogen atmosphere and with stirring. presented in 199.5 g of demineralized water.
  • the starch was dissolved with stirring by heating to 85 ° C. 5.6 g of glacial acetic acid, 0.05 g of iron (II) sulfate (FeSO 4 .7H 2 O) and 1.2 g of one were added successively at this temperature 30 wt .-% hydrogen peroxide solution.
  • the degree of sizing was determined according to Cobb ⁇ O in accordance with DIN EN 20 535.
  • the HST value was determined according to the Hercules Sizing Test in accordance with Tappi Standard T 530.
  • the whiteness of paper was determined as CIE white according to ISO 1 1475.
  • An anionically modified potato starch was dissolved by heating at 95 ° C for 30 minutes. Subsequently, the starch solution was mixed with the polymer dispersion to be tested and diluted with enough water to have a starch concentration of 8% in the finished mixture. The mixture of starch solution and polymer dispersion was then applied by means of a size press to a paper with a gram maturity of 80g / m 2 , which was not pre-sized in the mass, applied at a temperature of 55 ° C. The application rates of polymer dispersion on the paper were 1 g / l, 2 g / l and 3 g / l (based on solids of the polymer dispersion). The preparation uptake was in the range of 50-56%. Subsequently, the papers thus treated were dried by means of contact drying at 90 ° C., air-conditioned at 50% atmospheric humidity for 24 hours and then subjected to the tests. The respective results of the tests are given in the table.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Polymerisation Methods In General (AREA)
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Abstract

Dispersions polymères amylacées à fines particules, qui peuvent être obtenues par copolymérisation en émulsion radicalairement initiée de monomères éthyléniquement insaturés en présence d'un initiateur redox et d'un amidon enzymatiquement dégradé, sachant que la dégradation enzymatique de l'amidon est stoppée en ajoutant au mélange réactionnel un acide contenant au moins un atome de phosphore. L'invention concerne aussi l'utilisation d'un acide contenant au moins un atome de phosphore pour stopper la dégradation enzymatique d'amidon. L'invention concerne enfin l'utilisation des dispersions polymères amylacées à fines particules de polymères en émulsion comme agent d'encollage pour du papier et des produits à base de papier, notamment comme agent d'encollage en surface.
EP07857375A 2006-12-14 2007-12-11 Dispersions polymères amylacées à fines particules Withdrawn EP2121781A1 (fr)

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WO2012080145A1 (fr) * 2010-12-15 2012-06-21 Akzo Nobel Chemicals International B.V. Dispersion aqueuse d'un polymère contenant de l'amidon pour applications en papeterie
BR112018003138A2 (pt) * 2015-08-25 2018-09-18 Basf Se processo para preparação de uma dispersão aquosa de polímero, dispersão aquosa de polímero, aglutinante, adesivo, cola apropriada, e, uso de uma dispersão aquosa de polímero.
AU2017225237B2 (en) 2016-03-01 2020-08-20 Kemira Oyj Polymer composition, its use and a surface size
CN106868940B (zh) * 2017-02-15 2018-03-02 四川新华扬山野生物有限公司 一种纸页表面施胶用淀粉胶及其加工方法
CN107558297B (zh) * 2017-09-08 2018-09-04 湖北金庄科技再生资源有限公司 一种防水防潮增强型的施胶剂及其制备方法
CN108677605A (zh) * 2018-06-11 2018-10-19 华东理工大学 一种表面施胶剂及其制备方法
CN108824077A (zh) * 2018-06-11 2018-11-16 华东理工大学 一种瓦楞纸用施胶剂的制备方法
CN108914695A (zh) * 2018-06-11 2018-11-30 华东理工大学 一种瓦楞纸施胶剂的制备方法
CN108755247A (zh) * 2018-06-11 2018-11-06 华东理工大学 一种板纸表面施胶剂的制备方法
CN108716159A (zh) * 2018-06-11 2018-10-30 华东理工大学 瓦楞纸表面施胶剂及其制备方法
CN108642960A (zh) * 2018-06-11 2018-10-12 华东理工大学 一种阳离子细粒径乳液施胶剂的制备方法
CN108797201A (zh) * 2018-06-11 2018-11-13 华东理工大学 一种瓦楞纸施胶剂及其制备方法
CN108951283A (zh) * 2018-06-11 2018-12-07 华东理工大学 一种瓦楞纸表面施胶剂的制备方法
CN109399595B (zh) * 2018-11-08 2022-05-17 深圳大学 介孔膦酸钼材料及其制备方法和应用
EP3983462B1 (fr) * 2019-06-14 2025-01-08 Basf Se Dispersions de polymères aqueuses appropriées utilisées en tant qu'opacifiants dans des formulations liquides

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DE3730887A1 (de) * 1987-09-15 1989-03-23 Basf Ag Verfahren zur verbesserung der bedruckbarkeit von papier
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