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WO2019016336A1 - Polymère à base de monomères anioniques ou non ioniques présentant une distribution au moins bimodale des masses moléculaires - Google Patents

Polymère à base de monomères anioniques ou non ioniques présentant une distribution au moins bimodale des masses moléculaires Download PDF

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Publication number
WO2019016336A1
WO2019016336A1 PCT/EP2018/069685 EP2018069685W WO2019016336A1 WO 2019016336 A1 WO2019016336 A1 WO 2019016336A1 EP 2018069685 W EP2018069685 W EP 2018069685W WO 2019016336 A1 WO2019016336 A1 WO 2019016336A1
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polymer
monomer
polymerization
peak
monomer component
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PCT/EP2018/069685
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English (en)
Inventor
Thomas Weiss
Reinhold J. Leyrer
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Basf Se
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Publication of WO2019016336A1 publication Critical patent/WO2019016336A1/fr

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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
    • C08F2/32—Polymerisation in water-in-oil emulsions
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • 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
    • C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/08—N-Vinyl-pyrrolidine
    • 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

Definitions

  • the present invention relates to a polymer obtainable by polymerization of at least one anionic monomer and/or at least one nonionic monomer, at least one crosslinker and optionally chain transfer agents.
  • the polymer has an at least bimodal molecular weight distribution with at least one first peak (P1 ) and at least one second peak (P2), wherein the first peak has a rather low average sedimentation coefficient of ⁇ 15 Sved and the second peak has a rather high average sedimentation coefficient of ⁇ 10 000 Sved.
  • the present invention further relates to a process for obtaining such a polymer as well as to an inverse dispersion, a thickener or a deposition aid, comprising at least one of such polymers.
  • US 2008/0312343 discloses inverse latex compositions and on the use thereof as a thickeners and/or emulsifiers, for example for production of cosmetic or pharmaceutical formulations.
  • the inverse latex compositions comprise at least 50 to 80% by weight of at least one linear, branched or crosslinked organic polymer (P), at least 5 to 10% by weight of a water-in-oil-type emulsifier system, 5 to 45% by weight of at least one oil and up to 5% water.
  • the polymer P comprises uncharged monomers and optionally cationic or anionic monomers.
  • the inverse latex composition may optionally comprise up to 5% by weight of an oil-in-water-type emulsifier system.
  • the inverse latex compositions can be prepared by inverse emulsion polymerization.
  • WO 02/057400 relates to thickened fabric conditioners containing a particular polymeric thickener which is obtained by polymerizing from 5 to 100 mole percent of a cationic vinyl addition monomer, from 0 to 95 mole percent of acrylamide, and from 70 to 300 ppm of a difunctional vinyl addition monomer cross-linking agent.
  • a particular polymeric thickener which is obtained by polymerizing from 5 to 100 mole percent of a cationic vinyl addition monomer, from 0 to 95 mole percent of acrylamide, and from 70 to 300 ppm of a difunctional vinyl addition monomer cross-linking agent.
  • a particular polymeric thickener which is obtained by polymerizing from 5 to 100 mole percent of a cationic vinyl addition monomer, from 0 to 95 mole percent of acrylamide, and from 70 to 300 ppm of a difunctional vinyl addition monomer cross-linking agent.
  • WO 2009/019225 relates to an aqueous dispersion of an alkali-soluble copolymer which is suitable as an associative thickener.
  • the copolymer comprises polymerized-in units of a) at least one ethylenically unsaturated carboxylic acid, b) at least one nonionic ethylenically unsaturated surfactant monomer, c) at least one C 1 -C 2 -alkyl methacrylate and d) at least one C 2 -C 4 -alkyl acrylate, where the alkyl chain length averaged over the number of alkyl groups of the alkyl acrylate is 2.1 to 4.0.
  • the associative thickeners can be prepared by emulsion polymerization.
  • the associative thickeners are suitable for use in detergents and cleaners.
  • Liquid Dispersion Polymer (LDP) compositions are disclosed in WO 2005/097834. These LDP compositions comprise a hydrophilic, water-soluble or swellable polymer with a neutralization content of approximately 25 to approximately 100%, a nonaqueous carrier phase and an oil-in-water surfactant.
  • the hydrophilic, water-soluble or swellable polymer is preferably obtained by polymerization, for example of acrylic acid or methacrylic acid.
  • the LDP dispersions are suitable for producing microparticulate thickeners, as are used, for example, in aqueous or organic compositions, in particular in personal care or pharmaceutical formulations.
  • EP-A 172 025 relates to a dispersion in a continuous liquid phase of a polymer which is formed by polymerization of an ethylenically unsaturated monomer comprising a hydrophobic group of at least 8 carbon atoms and an ethylenically unsaturated monomer copolymerizable therewith.
  • the dispersion is stable, essentially anhydrous and comprises at least 40% by weight of polymer.
  • anionic monomers for example, can be used as copolymerizable, ethylenically unsaturated monomer.
  • the polymerization can be carried out as an inverse emulsion polymerization.
  • WO 2013/068394 relates to a thickener comprising at least one cationic polymer and at least one activator, wherein the ratio of activator to cationic polymer is > 10: 100 [% by weight/% by weight].
  • the cationic polymer is preparable by polymerization of at least one water-soluble, ethylenically unsaturated monomer and at least one ethylenically unsaturated associative monomer.
  • WO 2013/068394 further relates to a process for preparing the inventive thickener and to surfactant-containing formulations comprising at least one thickener.
  • WO 2013/068394 further provides for the use of the surfactant- containing formulations, for example as a softener or as a liquid washing composition, and to the use of the thickener, for example as a viscosity modifier.
  • WO 2013/174621 relates to an inverse dispersion comprising i) at least one anionic or nonionic polymer obtainable by the polymerization of a) at least one anionic monomer and optionally at least one nonionic monomer (compound A), b) optionally at least one crosslinker (compound B), c) optionally at least one chain transfer agent (compound C), ii) at least one stabilizing agent, wherein the stabilizing agent has one or more hydrophobic units with more than 30 carbon atoms per hydrophobic unit, iii) at least one oil phase.
  • WO 2013/068392 relates to a thickener comprising at least one polymer and at least one activator where the ratio of activator to polymer is > 10:100 [% by weight/% by weight].
  • the polymer is preparable by polymerizing at least one water-soluble, ethylenically unsaturated monomer comprising at least one anionic monomer and/or at least one nonionic monomer, and at least one ethylenically unsaturated associative monomer.
  • the thickener can be used as a viscosity modifier or in surfactant-containing formulations, for example as a softener or as a liquid detergent.
  • WO 2013/068388 relates to a thickener preparable by a process in which a polymer is prepared by inverse emulsion polymerization at a constant temperature of at least 40°C.
  • the components used are at least one water-soluble, ethylenically unsaturated monomer comprising at least one anionic monomer and/or at least one nonionic monomer, and at least one ethylenically unsaturated associative monomer.
  • European application EP16152590.2 is drawn to a process for obtaining a cationic polymer by polymerization of at least one cationic monomer, at least one crosslinker and optionally further monomers, such as nonionic monomers, associative monomers and/or chain transfer agents.
  • the cationic polymer has an at least bimodal molecular weight distribution with at least one first peak (P1 ) and at least one second peak (P2), wherein the first peak has a lower average sedimentation coefficient of ⁇ 100 Sved and the second peak has a higher average sedimentation coefficient of ⁇ 1 000 Sved.
  • the polymerization is carried out in two subsequent steps I) and I I). In step I I), the crosslinker is either completely absent or present in a very limited amount. Step I I) is carried out after the polymerization of step I) is finished or vice versa.
  • European application EP16152583.7 discloses a cationic polymer obtainable by polymerization of at least one cationic monomer, at least one crosslinker and optionally further monomers, such as nonionic monomers, associative monomers and/or chain transfer agents.
  • the cationic polymer has an at least bimodal molecular weight distribution with at least one first peak (P1 ) and at least one second peak (P2), wherein the first peak has a rather low average sedimentation coefficient of ⁇ 10 Sved and the second peak has a rather high average sedimentation coefficient of ⁇ 10,000 Sved.
  • the water-soluble polymer components of the cationic polymer are ⁇ 25% by weight related to the total amount of cationic polymer.
  • the problem underlying the present invention consists in the provision of novel polymers and/or inverse dispersions, thickeners or deposition aids containing at least one of such polymers.
  • the object is achieved by a polymer obtainable by polymerization of a) at least one anionic monomer and/or at least one nonionic monomer (monomer component a), b) at least one crosslinker (monomer component b), c) optionally at least one chain transfer agent (monomer component c), wherein the polymer has an at least bimodal molecular weight distribution with at least one first peak (P1 ) with an average sedimentation coefficient of ⁇ 15 Sved and with at least one second peak (P2) with an average sedimentation coefficient of ⁇ 10 000 Sved and the amount of polymer components covered by the first peak (P1 ) is at least 25 % by weight related to the sum of polymer components covered by the first peak (P1 ) and the second peak (P2).
  • the polymers according to the present invention possess advantageous properties when they are employed, for example, within inverse dispersions, thickeners, deposition aids and/or (aqueous) home and personal care formulations.
  • the polymers contribute to an improved stability and effectiveness of the respective product, such as an aqueous formulation containing the respective polymer, the respective inverse dispersion or the respective deposition aids.
  • the polymers according to the present invention can be successfully employed as depositioning aids in liquid laundry formulations, especially in fabric softeners, i.e. to improve the depositioning of softening or freshness active ingredients such as quaternized compounds, silicone or fragrance on the textile fibres.
  • polymers according to the present invention contain both polymer components with a rather low molecular weight (having an average sedimentation coefficient of ⁇ 15 Sved) and polymer components with a rather high molecular weight (having an average sedimentation coefficient of ⁇ 10 000 Sved).
  • the polymers according to the present invention contain both types of said polymer components in a significant amount. Those polymer components having a rather low molecular weight are not cross-linked at all or only cross-linked to a very limited amount and are usually water-soluble. By contrast, the respective polymer components of the polymer according to the present invention having a rather high molecular weight exhibit a rather high degree of cross-linking. Said polymer components with a rather high molecular weight are nearly or completely insoluble in water and only more or less swellable in water. Furthermore, only a rather limited amount of crosslinker has to be employed for producing the polymers according to the present invention.
  • an inverse dispersion containing the polymers according to the present invention after being added to the aqueous formulation like a fabric softener, where the phase inversion from a water in oil to an oil in water system is taking place, in its basic state is viscous and thick whereas it is thin upon stirring.
  • the improved shear dilution has a positive effect on the life and properties of pumps during the production of the aqueous fabric softener, promotes convenient dosage for the consumer and promotes the residue-free use of the fabric softener, especially in the washing machines which have an automatic dosing device.
  • the inverse dispersions containing the polymers according to the invention improve the stability of the corresponding formulation.
  • aqueous formulation containing the inventive polymer after phase inversion the settling or creaming of additionally added particles like vesicles, different soap phases, microcapsules, silicon particles, aluminum flakes or other particles is effectively prevented, irrespective of whether they are within the order of magnitude of nanometers, micrometers or millimeters. Moreover, they have the advantages that any redispersion required as well as the thickening effect are achieved very quickly.
  • Embodiments of the present invention in which the polymers present in the inverse dispersion are prepared using little amount of crosslinker is likewise associated with advantages.
  • a further advantage of the inventive polymers or inverse dispersions, respectively, is manifested in surfactant-containing formulations because a high thickening performance and/or marked shear dilution are achieved in these formulations even at low thickener concentrations ( ⁇ 1% by weight of inverse dispersion related to the total weight of the formulation).
  • a further advantage of the inventive polymers or inverse dispersions, respectively, is manifested in fabric softeners having the above-mentioned advantages in the rheology. But the additional advantage is the high storage stability of aqueous fabric softeners formulations if they contain the inventive polymer.
  • the term "polymer” means the entirety of all polymer components of the respective polymer.
  • the polymer components may also be designated as individual polymer components, individual polymers, polymer molecules or individual polymer molecules.
  • the (individual) polymer components differ in respect of their (individual) molecular weight.
  • the molecular weight of an (individual) polymer component may be influenced, for example, by the amount of crosslinker employed within the respective polymerization process.
  • each polymer (known in the state of the art) has a molecular weight distribution since it contains a plurality of polymer components/individual polymer molecules.
  • the polymers according to the present invention have an at least bimodal molecular weight distribution (as further specified within the context of the present invention).
  • the term "at least bimodal molecular weight distribution” means that the molecular weight distribution within the polymer according to the present invention may be bimodal, trimodal, tetramodal or pentamodal, or it may contain an even higher modality.
  • the modality of the molecular weight distribution of the polymers according to the present invention is determined by the number of (main) peaks. Unless indicated otherwise, the peaks are determined/measured by an average sedimentation coefficient. Only those peaks are considered for determination of the respective modality, which contribute to an amount of more than 1 %, preferably of more than 5%, to the total amount of polymer (main peaks).
  • peaks in the baseline having a very low signal to noise ratio are not considered as a peak when determining the modality of the respective polymer.
  • a peak such as the first peak (P1 ) is split into two or more peaks (P1 .1 , P1.2, ... P1.X)
  • said peaks (P1.1 , P1 .2, ... P1.X) may overlap.
  • the respective polymer is trimodal in respect of the peaks (P1 ) and (P2) and bimodal in respect of peak (P1 ).
  • polymers with an at least trimodal molecular weight distribution having at least one first peak (P1 ), at least one second peak (P2) and additionally at least one third peak with an average sedimentation coefficient outside the respective values of the peaks (P1 ) and (P2), for example with an average sedimentation coefficient in the range of 150 to 300 Sved.
  • the determination of the modality and the average sedimentation coefficient in the unit of Svedberg (Sved) is carried out according to P. Schuck, 'Size-distribution analysis of macromolecules by sedimentation velocity ultracentrifugation and Lamm equation modeling', Biophysical Journal 78, (3) (2000), 1606-1619.
  • the respective alkyl radical is derived from alkanes by removal of a hydrogen atom from any carbon atom according to the general formula -C n H 2 n + i , wherein n is any integer from 1 to 30 (in case of, for example, C-i-C 3 o-alkyl).
  • the alkyl radical may be either linear or branched and optionally cyclic.
  • the alkyl radical is linear or branched.
  • Alkyl radicals which have both a cyclic and a linear component are likewise covered by this definition.
  • the same also applies to other alkyl radicals, for example a C 1 -C 4 -alkyl radical or a C 16 -C 2 2-alkyl radical.
  • the alkyl radicals may optionally also be mono- or polysubstituted by functional groups such as amino, quaternary ammonium, hydroxyl, halogen, aryl or heteroaryl. Unless stated otherwise, the alkyl radicals preferably do not have any functional groups as substituents.
  • alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu/t-Bu), cyclohexyl, octyl, stearyl or behenyl.
  • the inventive polymer is obtainable by polymerization of the following monomer components a) and b) and optionally c).
  • the monomer component a) used is at least one anionic monomer and and/or at least one nonionic monomer.
  • Anionic monomers as such and nonionic monomers as such are known to persons skilled in the art.
  • At least one anionic monomer is present in component a), it is preferably selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid or a salt thereof, preferably selected from an alkali metal salt and/or a fluoro salt of said acids, more preferably selected from Na or Li acrylate, Na or Li methacrylate, Na or Li trifluorboroacrylate and/or Na or Li trifluorboromethacrylate, most preferably selected from Li acrylate or Li trifluorboroacrylate.
  • component a) comprises at least one anionic monomer
  • the at least one anionic monomer is preferably present in component a) in an amount of at least 50% by weight, more preferably at least 75% by weight and most preferably at least 90% by weight, in each case based on the total weight of component a).
  • monomer component a) comprises 100% by weight of at least one anionic monomer.
  • esters of the anionic monomers described above are also suitable as nonionic monomers.
  • Such nonionic monomers are preferably the methyl or ethyl esters of acrylic acid or methacrylic acid such as ethyl acrylate or methyl acrylate.
  • the nonionic monomer according to monomer component a) in the polymer is selected from N-vinylpyrrolidone, N-vinylimidazole, an associative monomer or a compound of the formula (I)
  • R 7 is H or d - C 4 - alkyl
  • R 8 is H or methyl
  • R 9 and R 10 are each independently H or C-i
  • Preferred compounds of the formula (I) include acrylamide, methacrylamide or dialkylaminoacrylamide, most preferably acrylamide.
  • the at least one nonionic monomer according to monomer component a) in the polymer preferably comprises at least one associative monomer.
  • Associative monomers as such are known to those skilled in the art. Suitable associative monomers are described, for example, in WO 2009/019225. Associative monomers are also described as surfactant monomers.
  • the associative monomer in the polymer is selected from a compound of the formula (II)
  • R is Ci - C 50 - alkyl, preferably Ci - C 30 - alkyl, especially Ci - C 2 2- alkyl,
  • R' is H or d - C 4 - alkyl, preferably H
  • R" is H or methyl
  • n is an integer from 0 to 500, preferably 3 to 100, especially 20 to 50.
  • the at least one associative monomer used is a compound of the formula (II) in which R is C 1 -C 22 -alkyl,
  • R' is H
  • R" is H or methyl
  • n 20 to 50.
  • Compounds of the formula (II) are commercially available in solution, for example under the Plex 6954 O name from Evonik Rohm GmbH. These are methacrylates of fatty alcohol ethoxylates.
  • a suitable fatty alcohol ethoxylate is, for example, the commercially available Lutensol ® AT 25 (BASF SE, Ludwigshafen, Germany).
  • the R radical in the compounds of the formula (II) may also be present as a mixture of radicals with different chain lengths, such as Ci 6 and Ci 8 .
  • Ci 6 and Ci 8 One example thereof is Ci 6 - C 18 -fatty alcohol-(ethylene glycol) 2 5-ether methacrylate, where both C 16 and C 18 fatty alcohol radicals (in non-negligible amounts) are present as a mixture.
  • the particular R radical is not present as a mixture but as a C22 or Ci 6 chain.
  • Other chain lengths occur only in the form of impurities.
  • the number "25" in these compounds of the formula (II) represents the size of the variables n.
  • the nonionic monomer according to monomer component a) in the polymer preferably contains at least two different associative monomers according to formula (I), wherein in the first monomer R is C-
  • component a) comprises at least one nonionic monomer
  • the at least one nonionic monomer is preferably present in component a) in an amount of at least 0.5% by weight, more preferably at least 10% by weight and most preferably at least 15% by weight, in each case based on the total weight of component a). It is also preferred that the at least one nonionic monomer is preferably present in component a) in an amount of not more than 50 % by weight, more preferably not more than 30 % by weight, most preferably not more than 25 % by weight, in each case based on the total weight of component a).
  • monomer component a) comprises 100% by weight of at least one nonionic monomer.
  • monomer component a) contains at least one anionic monomer and optionally at least one nonionic monomer in order to obtain an anionic polymer.
  • anionic polymer means that the respective monomer component a) (employed for obtaining said anionic polymer by polymerization) contains at least 10 % by weight, more preferably at least 50 % by weight, even more preferably at least 75 % by weight of at least one anionic monomer (in each cased based on the total weight of component a)).
  • an anionic polymer is also obtained in case monomer component a) contains further monomers, such as nonionic monomers, even in an amount up to 90 % by weight. It is also preferred that monomer component a) does not contain any further monomers besides anionic monomers and optionally nonionic monomers.
  • An anionic polymer is, of course, also obtained if monomer component a) comprises 100 % by weight of at least one anionic monomer.
  • monomer component a) contains at least one nonionic monomer and optionally at least one anionic monomer in order to obtain a nonionic polymer.
  • nonionic polymer means that the respective monomer component a) (employed for obtaining said nonionic polymer by polymerization) contains at least 90 % by weight, more preferably at least 95 % by weight, even more preferably at least 98 % by weight of at least one nonionic monomer (in each cased based on the total weight of component a)).
  • a nonionic polymer is also obtained in case monomer component a) contains further monomers, such as anionic monomers, even in an amount up to 10 % by weight. It is also preferred that monomer component a) does not contain any further monomers besides nonionic monomers and optionally anionic monomers.
  • a nonionic polymer is, of course, also obtained if monomer component a) comprises 100 % by weight of at least one nonionic monomer.
  • component a) does not comprise any further monomers besides at least one anionic monomer and/or at least one nonionic monomer.
  • component a) comprises from 20 to 100% by weight, preferably 30 to 100% by weight, more preferably 40 to 100% by weight of at least one anionic monomer and from 0 to 80% by weight, preferably 0 to 70% by weight, more preferably 0 to 60% by weight of at least one nonionic monomer, in each case based on the total weight of component a). If a nonionic monomer is present, it is preferably at least one associative monomer.
  • the monomer component a) contains at least one anionic monomer and at least one nonionic monomer.
  • the monomer component b) used is at least one crosslinker. Suitable crosslinkers are known to those skilled in the art.
  • the crosslinker in the polymer is selected from divinylbenzene; tetraallylammonium chloride; allyl acrylates; allyl methacrylates; diacrylates and dimethacrylates of glycols or polyglycols; butadiene; 1 ,7-octadiene; allylacrylamides or allylmethacrylamides; bisacrylamidoacetic acid; ⁇ , ⁇ '-methylenebisacrylamide; polyol polyallyl ethers such as polyallyl sucrose or pentaerythritol triallyl ether; pentaerythrityl triacrylate; pentaerythrityl tetraacrylate; 1 ,1 ,1 -trimethylolpropane tri(meth)acrylate; the ethoxylated compounds thereof or a mixture thereof.
  • divinylbenzene tetraallylammonium chloride
  • allyl acrylates allyl methacrylates
  • crosslinker is selected from N,N'-methylenebisacrylamide, pentaerythrityl triacrylate or pentaerythrityl tetraacrylate.
  • the crosslinker in the polymer is a trifunctional monomer, a tetrafunctional monomer or a mixture thereof.
  • the crosslinker of this embodiment is selected from tetraallylammonium chloride; allyl acrylates; allyl methacrylates; and tri- and tetramethacrylates of polyglycols; or polyol polyallyl ethers such as polyallyl sucrose or pentaerythritol triallyl ether, ditrimethylolpropane tetraacrylate, pentaerythrityl tetraacrylate, pentaerythrityl tetramethacrylate, pentaerythrityl triacrylate, pentaerythrityl triacrylate, ethoxylated, triethanolamine trimethacrylate, 1 ,1 ,1-trimethylolpropane triacrylate, 1 ,1 ,1 - trimethylolpropane
  • the crosslinker of this embodiment is selected alkyltrimethylammonium chloride, pentaerythrityl triacrylate, pentaerythrityl tetraacrylate, tetrallylammonium chloride, 1 ,1 ,1 -trimethylolpropane tri(meth)acrylate, or a mixture thereof.
  • these more preferred compounds can also be ethoxylated.
  • the crosslinker contains more than two reactive groups and/or is used in an amount of 10 to 500 ppm, preferably 30 to 490 ppm, more preferably 50 to 400 ppm, even more preferably less than 375 ppm, related to the total amount of polymer.
  • At least one chain transfer agent may optionally be present as monomer component c).
  • Suitable chain transfer agents are known to those skilled in the art.
  • the chain transfer agent in the polymer is selected from mercaptans, lactic acid, formic acid, isopropanol or hypophosphites. More preferably, the chain transfer agent is selected from mercaptans, isopropanol or sodium hypophosphite. Most preferably, the chain transfer agent is sodium hypophosphite. It is furthermore preferred that at least one chain transfer agent is employed within the polymerization for obtaining the polymer.
  • the inventive polymer is obtainable by polymerization of the monomer components a), b), and optionally c) as defined above.
  • the inventive polymer is obtainable by polymerization of the monomer components a), b), and c) as defined above.
  • the inventive polymer may be obtainable by additional polymerization of further monomer components which do not fall under the definition of the monomer components a), b) and c) as defined above.
  • the polymer has an at least bimodal molecular weight distribution with at least one first peak (P1 ) with an average sedimentation coefficient of ⁇ 15 Sved and with at least one second peak (P2) with an average sedimentation coefficient of ⁇ 10 000 Sved.
  • the second peak (P2) has an average sedimentation coefficient of ⁇ 14 000 Sved, more preferably in the range of 15 000 to 50 000 Sved, most preferably in the range of 16 000 to 22 000 Sved.
  • the range of 16 000 to to 22 000 Sved is most preferably obtained in case for polymers obtainable by a polymerization without employing any chain transfer agent (monomer component c)).
  • the second peak (P2) has most preferably an average sedimentation coefficient in the range of 16 000 to 42 000 Sved.
  • the first peak (P1 ) has a weight average peak maximum of ⁇ 400 000 g/mol, preferably in the range of 410 000 to 1 000 000 g/mol, most preferably in the range of 420 000 to 750 000 g/mol. This is preferably the case for polymers obtainable by a polymerization without employing any chain transfer agent (monomer component c)).
  • the first peak (P1 ) has a weight average peak maximum of ⁇ 50 000 g/mol, preferably in the range of 55 000 to 800 000 g/mol, most preferably in the range of 60 000 to 750 000 g/mol. This is preferably the case for polymers obtainable by a polymerization with employing a chain transfer agent (monomer component c)).
  • the first peak (P1 ) is split into at least two peaks (P1 .1 , P1 .2, ...
  • the second peak (P2) may also be split into at least two peaks (P2.1 , P2.2, ... P2.X).
  • the polymer has an at least trimodal molecular weight distribution, in particular a trimodal or tetramodal molecular weight distribution.
  • the amount of polymer components covered by the first peak (P1 ) is at least 25 % by weight related to the sum of polymer components covered by the first peak (P1 ) and the second peak (P2).
  • the polymer components covered by the first peak (P1 ) are, as already described above, water-soluble polymer components since the respective polymer components have a rather low molecular weight.
  • solubility of the polymer is determined by methods known to those skilled in the art, for example, by admixing the polymer present in the inventive inverse dispersion with a defined amount of water (see, for example, EP-A 343 840 or preferably the above mentioned determination method of the sedimentation coefficient in the unit of svedberg (Sved) according to P. Schuck).
  • the amount of polymer components covered by the first peak (P1 ) of the polymer is between 25 to 90% by weight, preferably between 35 and 75% by weight, more preferably between 50 and 60% by weight, related to the sum of polymer components covered by the first peak (P1 ) and the second peak (P2).
  • the water-soluble polymer components of the polymer are ⁇ 25% by weight related to the total amount of polymer.
  • the water-soluble polymer components of the polymer are between 25 to 90% by weight, preferably between 35 and 75% by weight, more preferably between 50 and 60% by weight, related to the total amount of polymer.
  • the anionic monomer according to monomer component a) in the polymer is selected from Li acrylate or Li trifluorboroacrylate, and/or ii) the nonionic monomer according to monomer component a) in the polymer contains at least two different associative monomers according to formula (I), wherein in the first monomer R is C-
  • Suitable polymerization processes for the preparation of the polymer or the inventive inverse dispersion comprising at least one polymer, and any additives, further compounds or assistants used in the polymerization or the inverse dispersion preparation process, are defined in detail in the text below.
  • the inventive polymer is preparable by polymerization of a) 97 to 100% by weight, preferably 95 to 99.95% by weight, related to the total amount of polymer, of at least one anionic monomer and/or at least one nonionic monomer, b) 10 to 500 ppm, preferably 30 to 490 ppm, more preferably 50 to 400 ppm, even more preferably less than 375 ppm, related to the total amount of the polymer, of at least one crosslinker, c) 0 to 3% by weight, preferably 0.05 to 0.5% by weight, related to the total amount of the polymer, of optionally at least one chain transfer agent, It is preferred that the polymerization of the polymer according to the present invention is carried out in two subsequent steps I) and II) with:
  • step II) polymerization of monomer component a) and monomer component b), polymerization of monomer component a), optionally monomer component c) and in the complete absence or in the presence of ⁇ 10 ppm (related to the total amount of polymer) of monomer component b), wherein step II) is carried out after the polymerization of step I) is finished or step I) is carried out after the polymerization of step II) is finished.
  • step II ⁇ 25% by weight of the polymer components covered by the first peak (P1 ) of the polymer are produced related to the sum of polymer components covered by the first peak (P1 ) and the second peak (P2).
  • the polymerization for obtaining the polymer according to the present invention is carried out under consideration of at least one of the following options i) to v), wherein step II) is carried out after the polymerization of step I) is finished, and/or step II) is carried out by polymerization of monomer component a) and monomer component c), preferably monomer component a) contains at least one anionic monomer and optionally at least one associative monomer, and/or monomer component b) is completely absent during the polymerization according to step II), and/or step I) is carried out by polymerization of monomer component a), 10 to 500 ppm, preferably 30 to 490 ppm, more preferably 50 to 400 ppm, (related to the total amount of the polymer) of monomer component b) and optionally monomer component c), and/or in step II), 25 to 90% by weight, preferably between 35 and 75% by weight, more preferably between 50 and 60% by weight of the polymer components covered by the first peak (P
  • step II The polymerization as such is known to the person skilled in the art.
  • the above- described steps I) and II) can be carried out by any method known to the person skilled in the art.
  • the order of carrying out the steps I) and II) can be freely chosen. It is even possible to carry out step I) and II) for several times as independent batches. However, it is preferred to first carry out step I) and, after the polymerization is finished, step II) follows.
  • step I) is initiated at a lower temperature than the temperature of step II
  • step I) is carried out at a temperature in the range of -5°C to 40°C, preferably in the range of 20°C to 30°C, more preferably the temperature is kept constant during step I
  • step II) is carried out at a temperature in the range of 70°C to 120°C, preferably in the range of 80°C to 100°C, more preferably the temperature is kept constant during step II)
  • step I) is started at a temperature in the range of -5°C to 40°C, preferably in the range of 15°C to 25°C, and heated-up by the exothermal polymerization under adiabatical conditions.
  • steps I) and II) is carried out by an emulsion polymerization, preferably by an inverse emulsion polymerization. It is also preferred that steps I) and II) as described above are carried out in the same polymerization vessel. Any vessel suitable for polymerization and known to the skilled person can be used, such as a glass vessel or a reactor.
  • LDP technology Liquid Dispersion Polymer Technology
  • the persulfates (peroxodisulfates), especially sodium persulfate, are most preferred.
  • the initiator is used in a sufficient amount to initiate the polymerization reaction.
  • the initiator is typically used in an amount of about 0.01 to 3% by weight, based on the total weight of the monomers used.
  • the amount of initiator is preferably about 0.05 to 2% by weight and especially 0.1 to 1 % by weight, based on the total weight of the monomers used.
  • the emulsion polymerization is effected typically at 0°C to 100°C. It can be performed either as a batch process or in the form of a feed process.
  • the feed method at least a portion of the polymerization initiator and optionally a portion of the monomers are initially charged and heated to polymerization temperature, and then the rest of the polymerization mixture is supplied, typically over several separate feeds, one or more of which comprise the monomers in pure or emulsified form, continuously or stepwise while maintaining the polymerization. Preference is given to supplying the monomer in the form of a monomer emulsion. In parallel to the monomer supply, further polymerization initiator can be metered in.
  • the entire amount of initiator is initially charged, i.e. there is no further metering of initiator parallel to the monomer feed.
  • the thermally activatable free-radical polymerization initiator is therefore initially charged completely and the monomer mixture, preferably in the form of a monomer emulsion, is fed in.
  • the initial charge is brought to the activation temperature of the thermally activatable free-radical polymerization initiator or a higher temperature.
  • the activation temperature is considered to be the temperature at which at least half of the initiator has decomposed after one hour.
  • Suitable oxidizing agent components are, for example, peroxides and/or hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide, dicyclohexyl percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide. Hydrogen peroxide and tert-butyl hydroperoxide are preferred.
  • peroxides and/or hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide, dicyclohexyl percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide. Hydrogen peroxide and tert-butyl hydroperoxide are preferred.
  • Suitable reducing agent components or catalysts are also iron(ll) salts, for example iron(l l) sulfate, tin(l l) salts, for example tin(ll) chloride, titanium(l l l) salts such as titanium(l l l) sulfate.
  • a particularly preferred redox initiator system is the sodium peroxodisulfate/sodium hydrogensulfite system, for example 0.001 to 5.0% by weight of sodium peroxodisulfate and 0.001 to 2.0% by weight of sodium hydrogensulfite, especially 0.005 to 1 .0% by weight of sodium peroxodisulfate and 0.005 to 1 .0% by weight of sodium hydrogensulfite, more preferably 0.01 to 0.5% by weight of sodium peroxodisulfate and 0.01 to 0.5% by weight of sodium hydrogensulfite.
  • a further particularly preferred redox initiator system is the t-butyl hydroperoxide/hydrogen peroxide/ascorbic acid system, for example 0.001 to 5.0% by weight of t-butyl hydroperoxide, 0.001 to 5.0% by weight of hydrogen peroxide and 0.001 to 2.0% by weight of ascorbic acid, especially 0.005 to 1 .0% by weight of t-butyl hydroperoxide, 0.005 to 1 .0% by weight of hydrogen peroxide and 0.005 to 1 .0% by weight of ascorbic acid, more preferably 0.01 to 0.5% by weight of t-butyl hydroperoxide, 0.01 to 0.5% by weight of hydrogen peroxide and 0.01 to 0.5% by weight of ascorbic acid.
  • the polymer is preferably prepared by inverse emulsion polymerization, by first separately preparing an aqueous phase of the water-soluble components and an oil phase. Thereafter, the two phases are mixed with one another to obtain a water-in-oil dispersion. The mixture is polymerized by adding a redox initiator system; optionally, another, thermal initiator can subsequently be added or, if already present, thermally activated.
  • the aqueous phase comprises, for example, a chain transfer agent, a crosslinker, an anionic monomer and/or a nonionic monomer, and optionally further components.
  • Suitable further components are, for example, complexing agents for salts such as pentasodium diethylenetriaminepentaacetic acid, or compounds which can be used to adjust the pH and/or stabilizing agents, such as citric acid.
  • the oil phase comprises, for example, an emulsifier, a stabilizer, a high-boiling oil, a low-boiling oil and/or optionally a nonionic monomer, preferably an associative monomer.
  • an associative monomer according to monomer component a) is added to the oil phase in the inverse emulsion polymerization.
  • the temperature can be kept constant or else it can rise.
  • the rise in the temperature can be performed continuously or in stages.
  • the temperature can rise by 0.2 to 10°C per minute during the polymerization, preferably from 1 to 3°C per minute.
  • the temperature rise is controlled by the rate of initiator addition.
  • the starting temperature value may be 0 to 30°C, preferably 10 to
  • the temperature in the inverse emulsion polymerization is kept constant (cold method); the temperature is 0 to 30°C, preferably 10 to 20°C.
  • the temperature is kept constant within a higher temperature range (hot method).
  • the temperature in the polymerization is 40 to 150°C, preferably 70 to 120°C.
  • the temperature is kept constant during the inverse emulsion polymerization, the temperature being at least 40°C, preferably 50 to 90°C.
  • the temperature is kept constant in a polymerization, especially in an inverse emulsion polymerization, this means that the temperature is kept at a constant value from the start of the polymerization.
  • Variations of +/- 5°C, preferably +/- 2°C and especially +/- 1 °C during the polymerization process are considered to be a constant temperature (based on the desired constant temperature value).
  • the temperature is kept constant until the polymerization has ended, which is preferably the case after a conversion of more than 90% of the monomers used, more preferably more than 95% by weight and especially preferably at full conversion (100% by weight).
  • the temperature can be kept constant by removing the heat of reaction which arises by cooling.
  • the start of the polymerization is normally the addition of the polymerization initiator, preferably the addition of a redox initiator system. Normally, the system is first heated to the desired temperature and a constant temperature is awaited while stirring. Subsequently, the polymerization initiator is added, as a result of which the polymerization process commences. In one embodiment of the present invention, the temperature is kept constant at a value above the melting point of the associative monomer used.
  • an aqueous phase and an oil phase are employed, and/or ii) the aqueous phase in step I) contains at least one anionic monomer, at least one crosslinker and optionally at least one nonionic monomer, and/or iii) the oil phase in step I) and/or step II) contains at least one stabilizing agent, at least one low-boiling oil, at least one high-boiling oil and optionally at least one associative monomer, and/or iv) the aqueous phase in step II) contains at least one anionic monomer, optionally at least one nonionic monomer, and optionally at least one chain transfer agent, and/or v) in step II), the mixture of the aqueous phase and the oil phase is completely added to the polymerization vessel (batch reaction) and afterwards the initiators are added continuously, and/or vi) in step II), the mixture of the aqueous phase and the oil phase is continuously added to
  • step II) polymerization of monomer component a), optionally monomer component c) and in the complete absence or in the presence of ⁇ 10 ppm (related to the total amount of polymer) of monomer component b), wherein step II) is carried out after the polymerization of step I) is finished.
  • monomer component a) comprises at least one anionic monomer and at least one nonionic monomer
  • ii) monomer component b) is employed during the polymerization according to step I) in an amount of 30 to 490 ppm, more preferably 50 to 400 ppm, (related to the total amount of the polymer) and monomer component b) is completely absent during the polymerization according to step II), and/or iii) monomer component c) is present, and/or iv) the first peak (P1 ) has an average sedimentation coefficient in the range of 5.5 to 8.5 Sved and the second peak (P2) has an average sedimentation coefficient in the range of 16 000 to 22 000 Sved.
  • the anionic monomer is Na or Li acrylate, Na or Li methacrylate
  • the at least one nonionic monomer is acrylamide or at least one associative monomer selected from a compound of the formula (II)
  • monomer component b) is selected from N,N'-methylenebisacrylamide, pentaerythrityl triacrylate or pentaerythrityl tetraacrylate
  • iii) monomer component c) is selected from mercaptans, isopropanol or sodium hypophosphite.
  • the present invention further provides an inverse dispersion comprising at least one polymer as defined above.
  • Methods for producing such an inventive inverse dispersion are also described in context with the (inverse) emulsion polymerization.
  • the inverse dispersion may further comprise at least one oil (phase), at least one activator, at least one stabilizing agent, optionally at least one complexing agent and optionally additional additives.
  • the inverse dispersion is a water-in-oil emulsion.
  • stabilizing agents such as emulsifiers, oils such as low-boiling oils and high-boiling oils and/or any further components as such, which may be present within the inventive inverse dispersion, are known to those skilled in the art. These compounds can be used individually or in the form of mixtures.
  • Activators as such are known in principle to those skilled in the art. Suitable activators are preferably surfactants, for example anionic, nonionic, cationic and/or amphoteric surfactants, which are disclosed, for example, in WO 2009/019225. Preference is given to using anionic and/or nonionic surfactants.
  • the nonionic surfactants used are preferably fatty alcohol alkoxylates. Fatty alcohol alkoxylates are also referred to as polyalkylene glycol ethers.
  • alcohol ethoxylates with linear radicals formed from alcohols of native or technical origin with 12 to 18 carton atoms for example formed from coconut alcohol, palm alcohol, tallow fat alcohol or oleyl alcohol - or mixtures as derivable, for example, from castor oil - and an average of 2 to 8 EO per mole of alcohol.
  • alkyl glycosides or alkyl polyglycosides may also be alkyl glycosides or alkyl polyglycosides.
  • Alkyl glycosides or alkyl polyglycosides are generally understood by the person skilled in the art to mean compounds composed of at least one alkyl fragment and at least one sugar or polysugar fragment.
  • the alkyl fragments preferably derive from fatty alcohols having a carbon atom number of 12 to 22, and the sugar fractions preferably from glucose, sucrose or sorbitan.
  • a further class of nonionic surfactants used with preference which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, is that of alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598, or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances, which can be obtained typically by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine, and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of the polyhydroxy fatty acid amides also includes compounds of the formula
  • R 4 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 5 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms
  • R 6 is a linear, branched or cyclic alkyl radical or an aryl radical, or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C 4 -alkyl or phenyl radicals
  • [Z] 1 is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical.
  • [Z] 1 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted to the desired polyhydroxy fatty acid amides, for example, according to WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • the anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Useful surfactants of the sulfonate type include alkylbenzenesulfonat.es, preferably C 9 - C -alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonat.es, and disulfonates as obtained, for example, from C 12 -C 18 - monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates preferably secondary alkanesulfonates, which are obtained, for example, from C 12 -C 18 -alkanes by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of a- sulfone fatty acids esters of a- sulfone fatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut fatty acids, palm kernel fatty acids or tallow fatty acids.
  • Suitable anionic surfactants are sulfonated fatty acid glyceryl esters.
  • Fatty acid glyceryl esters are understood to mean the mono-, di- and triesters, and mixtures thereof as obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • Preferred sulfonated fatty acid glyceryl esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • sulfuric monoesters of the straight-chain or branched C 7 -C 21 - alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -fatty alcohols with 1 to 4 EO.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters, and which are monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates comprise C 8 -C 18 - fatty alcohol radicals or mixtures thereof.
  • Especially preferred sulfosuccinates comprise a fatty alcohol radical which derives from ethoxylated fatty alcohols.
  • sulfosuccinates whose fatty alcohol radicals derive from ethoxylated fatty alcohols with narrow homolog distribution. It is likewise also possible to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
  • the activator is preferably selected from fatty alcohol alkoxylates, alkyl glycosides, alkyl carboxylates, alkylbenzenesulfonat.es, secondary alkanesulfonates and fatty alcohol sulfates, more preferably selected from fatty alcohol alkoxylates.
  • fatty alcohol alkoxylates is C 6 -C 17 (secondary)-poly(3-6)ethoxylate.
  • Activators with a high HLB value are preferably i) fatty alcohol alkoxylates formed from secondary alcohols or mixtures of alcohols having 12 to 18 carbon atoms and ethylene oxide or propylene oxide, and ii) alkyl glycosides formed from sucrose and C 8 to C 22 fatty alcohols.
  • Examples of such activators are the commercially available Synperonic 87 K from Croda GmbH, Berlinpfad-Sud 33, 41334 Nettetal, Germany; Croduret 40 or other ethoxylated hydrogenated castor oils (ricinus oils) such as Etocas 40 or Crodesta F1 10, all from Croda.
  • the activators used with a low HLB value are preferably alkyl glycosides formed from sucrose or sorbitan and C 8 to C 2 2 fatty alcohols or fatty acids, such as sorbitan laurate or sorbitan stearate.
  • Examples of such activators are the commercially available Crill 1 , Crill 3 or Crodesta F10 from Croda.
  • the ratio of activator to the polymer is preferably > 10 : 100 [% by weight/% by weight], preferably 10.5 to 50 : 100 [% by weight/% by weight], more preferably 1 1 .5 to 20 : 100 [% by weight/% by weight].
  • Suitable stabilizing agents are preferably emulsifiers such as polymeric emulsifiers.
  • Typical emulsifiers are anionic emulsifiers, for example sodium laurylsulfate, sodium tridecyl ether sulfates, dioctylsulfosuccinate sodium salt and sodium salts of alkylaryl polyether sulfonates; and nonionic emulsifiers, for example alkylaryl polyether alcohols and ethylene oxide-propylene oxide copolymers. Sorbitan trioleate is likewise suitable as an emulsifier.
  • Preferred emulsifiers have the following general formula (4):
  • n is an integer from 2 to 100.
  • Preferred stabilizers are copolymers of stearyl methacrylate and methacrylic acid.
  • emulsifiers having more than 30 carbon atoms, preferably more than 50 carbon atoms containing hydrophobic chains.
  • the employment of such emulsifier as stabilizing agent is resulting in a dramatic increase of the stabilizing effect for the hydrophilic polymer particles dispersed in the hydrophobic continuous phase.
  • all emulsifiers or polymeric stabilizers containing more than 30 carbon atoms, preferably more than 50 carbon atoms in their hydrophobic chains can be used.
  • this hydrophobic chain can be interrupted after every 6, preferred 10 or more carbon atoms by other atoms like oxygen, nitrogen, sulfur, phosphorus or by groups like carbonate, isocyanate, carbamide, esters or others in an amount that they do not essentially disturb the hydrophobic character of the chain in order to get the low HLB-values as described below.
  • Block-, graft- or comb- structure preferably are based on polyhydroxystearic acid.
  • the AB- or especially ABA-blocks are preferred.
  • the A block is preferably based on polyhydroxystearic acid and the B block on polyalkylene oxide.
  • R-i is hydrogen or a monovalent C-i to C 24 hydrocarbon group
  • p is an integer from 0 to 200.
  • emulsifiers used in the invention are e.g. PEG 30 Dipolyhydroxystearate.
  • Other similar emulsifiers for use with the invention are block copolymers (A-B-A) of polyethylene glycol and polyhydroxystearic acid with a molecular weight of approximately 5 000 g/mol.
  • the surfactant-containing acidic or alkaline formulations according to the invention can comprise further ingredients known to the person skilled in the art.
  • suitable ingredients comprise one or more substances from the group of builders, bleachers, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH modifiers, fragrances, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, antishrink agents, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, antistats, ironing aids, phobicization and impregnation agents, swelling and antislip agents, and UV absorbers.
  • the present invention further relates to the use of a surfactant-containing acidic formulation, a polymer, an inverse dispersion and/or a thickener according to the invention in hair cosmetics, in hairstyling, as a shampoo, as a softener, as a care composition, as a conditioner, as a skin cream, as a shower gel, as a fabric softener for laundry, or as an acidic cleaner, preferably for the toilet or the bath.
  • Brookfield viscosity is measured using a Brookfield DV-E viscometer fitted with a LV2 spindle at 60 RPM. The test is conducted in accordance with the instrument's instructions. Initial viscosity is defined as the Brookfield viscosity measured within 24 hours of making the sample. Samples are stored in glass jars with a screw cap lid and aged undisturbed in a constant temperature room maintained at 35 °C. Physical stability is assessed by visual observation of the product in the undisturbed glass jar. Products are deemed stable when no clear layer is observed at the bottom of the jar. Products are deemed unstable when a clear layer is observed at the bottom of the jar. Brookfield viscosity of the aged sample is measured after tipping the jar by hand to homogenize the sample.
  • Fabrics are assessed under NA Top Load wash conditions using Kenmore FS 600 and/or 80 series washer machines. Wash Machines are set at: 32°C/15°C wash/rinse temperature, 6 gpg hardness, normal cycle, and medium load (64 liters). Fabric bundles consist of 2.5 kilograms of clean fabric consisting of 100% cotton. Test swatches are included with this bundle and comprise of 100% cotton Euro Touch terrycloth towels (purchased from Standard Textile, Inc. Cincinnati, OH). Bundles are stripped according to the Fabric Preparation-Stripping and Desizing procedure before running the test. Tide Free liquid detergent (1 x recommended dose) is added under the surface of the water after the machine is at least half full.
  • the clean fabric bundle is added.
  • the fabric care testing composition is slowly added (1 x dose), ensuring that none of the fabric care testing composition comes in direct contact with the test swatches or fabric bundle.
  • each wet fabric bundle is transferred to a corresponding dryer.
  • the dryer used is a Maytag commercial series (or equivalent) dryer, with the timer set for 55 minutes on the cotton/high heat/timed dry setting. This process is repeated for a total of three (3) complete wash-dry cycles. After the third drying cycle and once the dryer stops, 12 Terry towels from each fabric bundle are removed for actives deposition analysis.
  • the fabrics are then placed in a constant Temperature/Relative Humidity (21 °C, 50% relative humidity) controlled grading room for 12-24 hours and then graded for softness and/or actives deposition.
  • the Fabric Preparation-Stripping and Desizing procedure includes washing the clean fabric bundle (2.5 Kg of fabric comprising 100% cotton) including the test swatches of 100% cotton EuroTouch terrycloth towels for 5 consecutive wash cycles followed by a drying cycle.
  • AATCC American Association of Textile Chemists and Colorists
  • HE High Efficiency
  • Stabilizing agent B is a nonionic ABA-block copolymer with molecular weight of about 5000g/mol, and a hydrophobic lipophilic balance value (HLB) of 5 to 6, wherein the A block is based on polyhydroxystearic acid and and the B block on polyalkylene oxide.
  • HLB hydrophobic lipophilic balance value
  • Stabilizing agent D nonionic block copolymer: Alcyd Polyethylenglycol Poly-isobutene stabilizing surfactant with HLB 5-7 Oil soluble group : poly-iso-butylene
  • An aqueous phase of water soluble components is prepared by admixing together the following components:
  • the two phases are mixed together in a ratio of 40 parts oil phase to 60 parts aqueous phase under high shear to form a water-in-oil emulsion.
  • the resulting water-in-oil emulsion is transferred to a reactor equipped with nitrogen sparge tube, stirrer and thermometer. The emulsion is purged with nitrogen to remove oxygen.
  • Polymerisation is effected by addition of a redox couple of sodium metabisulphite and tertiary butyl hydroperoxide stepwise such that is a temperature increase of 2°C/min. After polymerisation are fed simultaneously 10.15g (0,25pphm) of tertiary butyl hydroperoxide (6.16% solution in solvent) and 1 1 .98g (0,25pphm) of sodium metabisulphite (5.26% emulsion) for 120 min. ( chem. deso.).
  • An aqueous phase (2) of water soluble components is prepared by admixing together the following components:
  • the two phases (2) are mixed together in a ratio of 40 parts oil phase to 60 parts aqueous phase under high shear to form a water-in-oil emulsion.
  • the resulting water- in-oil emulsion is transferred to a reactor equipped with nitrogen sparge tube, stirrer and thermometer. The emulsion is purged with nitrogen to remove oxygen.
  • Examples 4 to 8 are carried out as outlined above for example 1 under consideration of the variations as depicted in tables 1 and 2 (below).
  • the following tables 1 and 2 depict the synthetic variations and the corresponding analytical data in respect of the working examples 1 to 8 as well as comparative example 1 .
  • Table 1 Overview of all Examples

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Abstract

La présente invention concerne un polymère pouvant être obtenu par polymérisation d'au moins un monomère anionique et/ou d'au moins un monomère non ionique, en présence d'au moins un agent de réticulation et éventuellement d'agents de transfert réversible de chaîne. Le polymère présente une distribution au moins bimodale des masses moléculaires, avec au moins un premier pic (P1) et au moins un second pic (P2), le premier pic présentant un coefficient de sédimentation moyen plutôt faible (≤ 15 Sved) et le second pic présentant un coefficient de sédimentation moyen plutôt élevé (≥ 10 000 Sved). L'invention concerne également un procédé d'obtention d'un tel polymère, ainsi qu'une dispersion inverse, un agent épaississant ou un adjuvant de dépôt, comprenant au moins l'un desdits polymères.
PCT/EP2018/069685 2017-07-21 2018-07-19 Polymère à base de monomères anioniques ou non ioniques présentant une distribution au moins bimodale des masses moléculaires WO2019016336A1 (fr)

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CN110074100A (zh) * 2019-04-29 2019-08-02 河南牧业经济学院 一种热带狼尾草在温带地区冬季鲜藏方法
CN114560967A (zh) * 2021-12-28 2022-05-31 爱森（中国）絮凝剂有限公司 一种压裂用低温抗冻性乳液聚合物稠化剂制备方法

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Publication number Priority date Publication date Assignee Title
CN110074100A (zh) * 2019-04-29 2019-08-02 河南牧业经济学院 一种热带狼尾草在温带地区冬季鲜藏方法
CN114560967A (zh) * 2021-12-28 2022-05-31 爱森（中国）絮凝剂有限公司 一种压裂用低温抗冻性乳液聚合物稠化剂制备方法

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