EP2193159A1 - Copolymères séquencés de polysiloxane - Google Patents

Copolymères séquencés de polysiloxane

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Publication number
EP2193159A1
EP2193159A1 EP08787053A EP08787053A EP2193159A1 EP 2193159 A1 EP2193159 A1 EP 2193159A1 EP 08787053 A EP08787053 A EP 08787053A EP 08787053 A EP08787053 A EP 08787053A EP 2193159 A1 EP2193159 A1 EP 2193159A1
Authority
EP
European Patent Office
Prior art keywords
radical
polysiloxane block
block copolymer
polysiloxane
hair
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Withdrawn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
EP08787053A
Other languages
German (de)
English (en)
Inventor
Dirk Kuppert
Burghard Grüning
Brian Yang
Sven Balk
Gerd LÖHDEN
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.)
Evonik Operations GmbH
Original Assignee
Evonik Goldschmidt GmbH
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Filing date
Publication date
Application filed by Evonik Goldschmidt GmbH filed Critical Evonik Goldschmidt GmbH
Publication of EP2193159A1 publication Critical patent/EP2193159A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the invention relates to polysiloxane block copolymers, especially those suitable for use in cosmetic formulations and personal care formulations.
  • the invention further relates to the preparation of the polysiloxane block copolymers by atom transfer radical polymerization (hereinafter abbreviated to ATRP) and the preparation of the corresponding formulations containing the polysiloxane block copolymers, and their use in cosmetic and personal care applications.
  • ATRP atom transfer radical polymerization
  • a very particular aspect of the present invention is that polysiloxane-containing copolymers are prepared and used whose terminal halogen atoms have been removed by the addition of a reagent, optionally a functionalization of the polymer termini can be achieved. Simultaneously with the removal of the terminal halogen atoms, a removal of the transition metal compounds by precipitation takes place in a simultaneous process step, which allows easy removal of the transition metal compound from the reaction product.
  • Cosmetic and personal care formulations such as hair styling sprays, hair conditioners, foams, gels, and shampoos often contain resins, gums, and adhesives to provide a variety of beneficial effects, such as hair conditioning.
  • film-forming properties thickening properties
  • tactile properties such as improved grip and hair shaping properties to produce.
  • Polymers used in such formulations include, but are not limited to, organic or silicone-containing linear or graft copolymers can be constructed from a variety of different monomers.
  • the polymer blocks may be alternating, random, block-structured, branched or hyperbranched or homopolymer blocks.
  • Grafted polymers are known as film-forming polymers in cosmetic formulations for the treatment of hair or skin. These grafted polymers typically comprise a polymeric backbone and one or more macromonomers grafted onto the backbone, thereby increasing the physical and chemical properties, e.g. independently adjust the glass transition temperature and water solubility for the polymeric backbone and the grafted macromonomers to set the desired overall properties of the complete polymer.
  • WO95 / 01383 and WO95 / 01384 disclose the use of water and alcohol soluble or dispersible graft copolymers in hair and skin care compositions in which the copolymer has a backbone and one or more polymeric side chains prepared by the random copolymerization of monomer A and monomer B.
  • Monomer A is selected to have a hydrophobic character, and macromonomer B has a long hydrophilic part.
  • EP 0 412 704, EP 0 408 313 and EP 0 412 707 disclose the use of silicone-grafted acrylate copolymers in hair care applications.
  • US 4,988,506 describes the use of grafted polysiloxane copolymers in hair care applications.
  • Block copolymers have the advantage over grafted copolymers that the polymer construction can be better controlled. This is particularly important and important if you want to tailor polymers with areas that have special physical and chemical properties, eg provide alternating "hard” and “soft” segments in a polymer for hairspray applications for improved hold and feel.
  • No. 5,468,477 discloses cosmetic compositions comprising a vinyl-silicone grafted copolymer or a block copolymer characterized in that the copolymer contains a silicone segment and a vinyl polymer segment.
  • the block or grafted copolymer is prepared by free radical polymerization of a mercapto-functionalized SiIii- which works as a chain transfer agent, with a vinylic monomer.
  • Copolymers made by this method typically have low molecular weights and low silicone content due to the early chain termination reactions. Intramolecular crosslinking reactions additionally lead to an uncontrolled polymer structure. Thus, polydisperse systems are obtained with a mixture of chain lengths and different molecular architectures.
  • organopolysiloxane macroinitiators are organopolysiloxanes containing groups that can form radicals. Such compounds are described in US 5,523,365.
  • the use for the preparation of copolymers is disclosed in WO 98/48771 and US 6074628.
  • a disadvantage of this process is the handling of dangerous, prone to explosive decomposition, organosiloxane macroinitiators, which must be used in significant amounts, otherwise the final product contains too few silicone units.
  • organosiloxane macroinitiators which must be used in significant amounts, otherwise the final product contains too few silicone units.
  • the large-scale production of macroinitiators is extremely difficult and associated with a considerable amount of security.
  • the reaction is inefficient because large amounts of unreacted silicone oil must be removed by time-consuming extraction.
  • WO 00/71606 describes a process for the preparation of polysiloxane block copolymers in which an organopolysiloxane macroinitiator in an atom transfer radical polymerization (ATRP) with copper salts as a catalyst for the preparation of block copolymers with controlled architecture is used.
  • ATRP atom transfer radical polymerization
  • the document does not disclose anything about the copper content of the polymers produced.
  • the polymers produced are terminated with bromine atoms.
  • the ATRP provides a versatile process for the preparation of a variety of polymers and copolymers, e.g. Polyacrylates, polymethacrylates, polystyrenes or copolymers.
  • the ATRP method was decisively developed in the 1990s by Prof. Matyj aszewski and is described inter alia in J. Am. Chem. Soc, 1995, 117, p.5614 and WO 97/18247.
  • a particular advantage of ATRP is that both molecular weight and molecular weight distribution are controllable.
  • As a living polymerization it also allows the targeted construction of polymer architectures such as random copolymers or block copolymer structures.
  • initiators are e.g. additionally accessible unusual block copolymers and star polymers.
  • Theoretical fundamentals of the polymerization mechanism are described inter alia in Hans Georg Elias, Makromolekule, Volume 1, 6th edition, Weinheim 1999, p.344.
  • the ATRP process relies on a redox balance between the low concentration growing free radical polymer chain and a higher oxidation state transition metal compound (eg, copper II) and the dormant, preferably present, halogen or pseudohalogen terminated combination Polymer chain and the corresponding transition metal compound in a lower oxidation state (eg, copper I).
  • transition metal compound eg, copper II
  • the dormant, preferably present, halogen or pseudohalogen terminated combination Polymer chain and the corresponding transition metal compound in a lower oxidation state eg, copper I
  • the halogen atom always remains at the respective chain ends after termination of the reaction.
  • the fate of this organically bound halogen, in particular the organically bound bromine is disadvantageous for the use of polymers produced by the ATRP method in cosmetic and / or personal care formulations.
  • Halogenated compounds can lead to allergies.
  • organohalogen compounds are poorly metabolized by the body and tend to accumulate in adipose tissue.
  • transition metal compounds used in the ATRP and especially the Cu compounds used in the vast majority of polymer syntheses are also disadvantageous in cosmetic or personal care formulations, since copper leads to strongly colored products even at low concentrations. In addition, copper compounds can be irritating and sensitizing in contact with the skin.
  • US 2005/0900632 discloses a process for the substitution of the halogens by means of metal alcoholates with precipitation of the metal halide formed.
  • a disadvantage of this procedure is the limited availability of the metal alcoholates, their costs and that the process can be carried out only after a purification of the polymers.
  • Auke Snijder describes in his PhD thesis "Telechelic polymers for moisture-curable coatings by ATRP" (Technical University of Eindhoven, Eindhoven, 2002) the functionalization of polymer chain ends with OH groups through the use of mercaptoethanol. The removal of the terminal bromine atoms in this case is only to be regarded as a goal-oriented side effect. Thus, the reaction is described exclusively with mercaptoethanol as a reagent. A substitution with unfunctionalized or acid, amine or epoxy functionalized mercaptans is not mentioned. Another difference to the present invention is the polymer-analogous implementation. In the described document, the substitution reaction is carried out only after purification of the ATRP product in a second reaction stage.
  • low molecular weight compounds can be removed from solutions or even from solid polymers by means of extraction processes.
  • a method is e.g. in WO 02/28916.
  • the disclosure does not disclose the removal of transition metal compounds.
  • transition metal complexes almost completely - i. below a content of 2 ppm - to remove from a polymer solution, a pure extraction is unsuitable.
  • a special form of extraction is the aqueous liquid-liquid extraction from polymer solutions.
  • a copper catalyst is used, which is removed from the polymer solution by aqueous extraction after polymerization (see Ullmanns Encylopedia of Industrial Chemistry, 5 th revised edition 1992, Vol. A21, p. 606 f).
  • a disadvantage of this method is that many polar polymers can act as suspension or emulsion stabilizers and thereby prevent the two liquid phases can be separated. Thus, this method can not be used for the workup of polymethyl methacrylates.
  • Another disadvantage is the very complex transfer of such a method to large-scale production scales.
  • suitable precipitants are very polar solvents, such as methanol.
  • ligand sphere but also particularly non-polar precipitation media like hexane or pentane are used.
  • such a procedure is disadvantageous for various reasons. First of all, after the precipitation, the polymer is not in a uniform form, such as granules. For this reason, the separation and thus the further work-up is difficult.
  • precipitation processes are not transferable to large-scale production and can only be used sensibly on a laboratory scale.
  • CN 121011 discloses a method in which an adsorbent (in particular activated carbon or alumina) is added to the polymer solution after the ATRP process and then separated by filtration.
  • an adsorbent in particular activated carbon or alumina
  • the disadvantage here is that a complete separation is possible only by very large amounts of adsorbent.
  • the use of alumina is also claimed in JP 2002 363213.
  • JP 2005 015577 JP 2004 1449563 basic or acidic silica are used.
  • JP 2003 096130, JP 2003 327620, JP 2004 155846 acidic, basic or combinations of hydrotalcites are used as adsorbents in mostly multi-stage filtration processes. Also Here, large amounts of the inorganic material are used.
  • a disadvantage of the method is that such adsorbents are relatively expensive and are recycled very expensive.
  • this object can be achieved by adding a mercapto-functionalized compound to the polymerization mixture obtained in the polymerization.
  • a mercapto-functionalized compound By adding the mercapto-functional compound, polysiloxane block copolymers are obtained which have no or only a small amount of organically bonded, in particular terminal, halogen.
  • the transition metal used as a catalyst precipitates, and thus can be separated by a simple filtration.
  • the present invention therefore relates to polysiloxane block copolymers of the formula A [LB (S) Q] 1n , where A is a polysiloxane block, L is a bivalent organic radical which connects the units A and B, B is a polymer block composed of free-radically polymerized monomers M , S is a sulfur atom and Q is a monovalent organic radical and m is an integer from 1 to 50, their use, and compositions comprising these polysiloxane block copolymers.
  • polysiloxane block copolymers according to the invention a process for their preparation and their use are described below by way of example, without the invention being restricted to these exemplary embodiments.
  • ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their contents are intended to form part of the disclosure content of the present invention.
  • the polysiloxane block copolymers of the formula A [LB (S) Q] 1n according to the invention are characterized in that A is a polysiloxane block, L is a divalent organic radical (linker) which connects the units A and B, B is a polymer block radically polymerizable monomers, S is a sulfur atom and Q is a substituted or unsubstituted monovalent organic radical and m is an integer from 1 to 50, preferably 2 to 10 and preferably 2, 3 or 4.
  • the moiety A is preferably a branched or unbranched, substituted or unsubstituted polysiloxane radical which is described by formula (I) Rf
  • b is a number from 0 to 10, preferably ⁇ 5, particularly preferably 0, is a number from 1 to 500, preferably from 1 to 250 and special ⁇ DERS preferably 1 to 100,
  • R r is the same or different radicals R 1 or the linking radical L, with the proviso that at least one radical R f is a radical L and preferably at most 50 radicals R f are radicals L,
  • R 1 are alkyl radicals having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, particularly preferably methyl or an aryl radical, in ⁇ preferably phenyl, which radicals may be substituted or un- substituted 1 R.
  • the rest L can z.
  • an unbranched or branched substituted or unsubstituted organic radical in particular hydrocarbon radical having 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms and more preferably 3 to 10 carbon atoms.
  • the radical L may be interrupted by divalent radicals which are bonded to carbon atoms on both sides, for example -O-, -C (O) O-, CONR 4 , NR 4 C (O), or -C (O) - where at ⁇ R 4 is a monovalent substituted or unsubstituted, linear or branched 1 to 18 carbon atoms included- the rest is.
  • the radical L contains at least one -C (O) unit.
  • the polymer block B is composed of free-radically polymerizable monomers M.
  • the free-radically polymerizable monomers may be selected from the radically polymerizable monomers M described below (step A)).
  • the polymer block B is preferably composed of monomers selected from the group of (Meth ) acrylates or (meth) acrylic acids and their derivatives.
  • the monomers M are particularly preferably selected from the group consisting of substituted or unsubstituted (meth) acrylic acid or derivatives thereof.
  • Preferred monomers M include acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl ethacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate,
  • the unit B preferably has a number average molecular weight of from 1000 g / mol to 200000 g / mol, preferably a number average molecular weight of 4000 g / mol to 120000 g / mol and more preferably from 4000 g / mol to 75000 g / mol.
  • the unit B is particularly preferably a poly (meth) acrylate unit, preferably having a number average molecular weight of from 1000 g / mol to 200000 g / mol, preferably having a number average molecular weight of 4000 g / mol to 120000 g / mol and more preferably a number average molecular weight of 4000 g / mol to 75000 g / mol.
  • the radical Q in the polysiloxane block copolymer according to the invention is preferably an alkyl radical, an alcohol radical or an acid radical which preferably has 1 to 20, preferably 2 to 15, carbon atoms.
  • the radical SQ is a thioglycolacetic acid, mercaptopropionic acid, mercapto toethanol, mercaptopropanol, mercaptobutanol, mercaptohexyl, octylthioglycolate, methylmercaptan, ethylmercaptan, butylmercaptan, dodecylmercaptan, isooctylmercaptan or tert-dodecylmercaptan.
  • These radicals may carry further substituents.
  • the polysiloxane block copolymer according to the invention preferably has a number average molecular weight of from 5000 g / mol to 1,000,000 g / mol, preferably from 10,000 g / mol to 500,000 g / mol and very particularly preferably from 10,000 g / mol to 250,000 g / mol.
  • the polysiloxane block copolymer according to the invention preferably has less than 5 ppm by mass, preferably less than 2 ppm by mass, of organically bonded, in particular of terminal, halogen, in particular bromine. More preferably, the polysiloxane has no organically bound halogen or at least only undetectable amounts of organically bound halogen.
  • the polysiloxane block copolymers according to the invention can be prepared in various ways.
  • the polysiloxane block copolymers according to the invention are preferably obtainable by the process described below.
  • Polysiloxane macroinitiators of the formula A [LX] 1n can, for. B. be obtained by first providing a suitable free radical initiator with the / the reactive groups of a polysiloxane, eg. B. is reacted in a nucleophilic substitution reaction.
  • the polysiloxane used is preferably a polysiloxane which has at least one functional group which has a 0, N or S atom and is suitable for nucleophilic attack on these atoms.
  • polysiloxanes used for the preparation of polysiloxane macroinitiators of the formula A [LX] 1n can be linear, branched or hyperbranched, provided they are functionalized with at least one group as described above.
  • polysiloxanes are used which are selected from polysiloxanes of the formula (Ia)
  • b is a number from 0 to 10, preferably ⁇ 5, preferably 0, a is a number from 1 to 500, preferably from 1 to 250 and before ⁇ Trains t 1 to 100,
  • R f is identical or different radicals R 1 or R 2 , with the measure that ⁇ at least one radical R f is a radical R 2 , R 1 is alkyl radicals having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, or an aryl radical, preferably phenyl, where the radicals R 1 may be substituted or unsubstituted,
  • R 1 is a radical of the general formula (II)
  • a divalent optionally branched substituted or unsubstituted hydrocarbon radical having 1 to 60 carbon atoms, preferably 1 to 20 carbon atoms and particularly preferably ⁇ 3 to 10 carbon atoms, and
  • Y is selected from the group consisting of -OH, -SH, -NH 2 and -NHR 3 , wherein R 3 is a monovalent substituted or unsubstituted, linear or branched radical containing 1 to 18 carbon atoms.
  • the divalent radical T may be interrupted by divalent radicals attached to carbon atoms on both sides, such as -O-, -C (O) O-, CONR 4 , NR 4 C (O), or -C (O ) -, wherein R 4 is a monovalent substituted or unsubstituted, linear or branched 1 to 18 carbon atoms containing radical.
  • radical initiator it is preferable to use a compound containing at least one C (O) X group in which X is a leaving group which can be substituted in a nucleophilic attack by the O, N or S atom of the functional group of the polysiloxane, and contains at least one organically bound halogen atom which is capable of forming radicals in the presence of transition metal catalysts.
  • Preferred free-radical initiators are compounds of the formula (III):
  • R 5 is an organic halogen group and X is the leaving group.
  • the leaving group is a halogen atom (F, Cl, Br, or I).
  • organic halogen group is generally understood as meaning a linear, branched or cyclic (aromatic or aliphatic), substituted or unsubstituted carbon-containing structural unit which likewise contains at least one halogen atom (F, Cl, Br, or I).
  • Particularly preferred free-radical initiators for the preparation of the polysiloxane macroinitiator of the formula A [LX] 1n are compounds of the formula (IV):
  • R 6 , R 7 are independently selected from the group consisting of hydrogen, monovalent branched or unbroken organic radicals, in particular alkyl radicals having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms or a Aryl radical, where the radicals R 6 and / or R 7 may be substituted or unsubstituted, r is 0 or 1, preferably 0,
  • R 8 is a divalent, optionally branched, substituted or unsubstituted organic radical, preferably an alkyl radical having 1 to 20 C atoms.
  • nucleophilic substitution reaction between functional polysiloxane and free-radical initiator can be carried out under the reaction conditions typical of such reactions, which are known to those skilled in the art.
  • the actual reaction in process step A) comprises the reaction (polymerization) of the polysiloxane macroinitiator with free-radically polymerizable monomers M in the presence of a transition metal catalyst, preferably a transition metal salt, to give a polysiloxane-containing copolymer.
  • a transition metal catalyst preferably a transition metal salt
  • Process step A) can be carried out as ATRP.
  • the organic halogen group of the polysiloxane macroinitiator acts as an initiator and the presence of free-radically polymerizable monomers M and the catalyst leads to the formation of a covalent linkage between at least one block B, formed from free-radically polymerized monomers, and the polysiloxane macroinitiator.
  • This block formed from radically polymerizable monomers forms block B of the polysiloxane copolymers according to formula A [LB (S) Q] 1n , where the polysiloxane macroinitiator forms block A.
  • transition ⁇ metal compounds suitable as z. In Chem. Rev. 2001, 101, p.2921ff, to which reference is expressly made, will be described in more detail.
  • all transition metal compounds can be used, which can form a redox cycle with the initiator or the polymer chain, which has a transferable atom group, for example a ⁇ Ha lie.
  • catalysts used are selected from copper, egg ⁇ transmitter, cobalt, chromium, manganese, molybdenum, silver, zinc, palladium, rhodium, platinum, ruthenium, iridium, ytterbium , Samarium, rhenium and / or nickel compounds, in particular those in which the transition metal is present in the oxidation state I.
  • Preference is given to using copper compounds.
  • copper compounds Preference is given to using copper compounds.
  • copper compounds Preference is given to using copper compounds.
  • ⁇ preferably be used as copper compounds, those selected from Cu 2 O, CuBr, CuCl, CuI, CuN 3, CuSCN, CuCN, CuNO 2, CuNO 3, CuBF 4, Cu (CH 3 COO) or Cu (CF 3 COO), and Mixtures used.
  • step A) for carrying out the process step A) as ATRP of step A) can also be used as so-called reverse ATRP Runaway ⁇ leads.
  • transition metal compounds in higher oxidation states such as
  • Reverse ATRP has S.7572 ff beschrie ⁇ ben, is expressly referred to among others, Wang and Matyjaszewski in Macromolecules, 1995, 28.
  • a variation of the reverse ATRP is the additional use of metals in the zero oxidation state. By ⁇ to be comproportionation with the transition metal compounds of higher oxidation state, an acceleration of the reaction rate is effected. This method is closer ⁇ be enrolled in WO 98/40415, to which reference is expressly made.
  • ligands can facilitate abstraction of the transferable atomic group by the transition metal compound.
  • a list of suitable ligands can be found, for example, in WO 97/18247, WO 97/47661 or WO 98/40415.
  • the ligand used as ⁇ th compounds usually have one or more nitrogen, oxygen, phosphorus and / or sulfur atoms as coordinative loading stand portion. Particularly preferred are nitrogen-containing compounds. Very particular preference is given to nitrogen-containing chelate ligands.
  • ligands are, for. 2,2'-bipyridine, N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA), tris (2-aminoethyl) amine (TREN), N, N, N', N '-Tetrra methylethylendiamin or 1, 1, 4, 7, 10, 10-hexamethyltriethylenetetramine. It will be apparent to those skilled in the art that a variety of other ligands can also be used.
  • ligands can form coordination compounds in situ with the metal compounds, or they can first be prepared as coordination compounds and then added to the reaction mixture.
  • the ratio of ligand to transition metal is dependent on the denticity of the ligand and the coordination number of the transition metal.
  • enough ligand is used that the molar ratio of ligand to transition metal is from 100: 1 to 0.1: 1, preferably 6: 1 to 0.1: 1 and more preferably 3: 1 to 1: 1 is.
  • the polymerization in step A) can be carried out in bulk or in solution.
  • the polymerization in step A) can be carried out as emulsion polymerization, miniemulsion or microemulsion polymerization or suspension polymerization.
  • step A) is carried out in the presence of a solvent
  • halogen-free solvents preferably toluene, xylene, acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone; ether; Aliphatic, preferably pentane, hexane; or alcohols, preferably cyclohexanol, butanol, hexanol.
  • water or mixtures of water and water-miscible solvents are suitable as solvents.
  • the polymerization in step A) can be carried out at atmospheric pressure, underpressure or overpressure, preferably at atmospheric pressure.
  • the polymerization can preferably be carried out from 0 0 C to 130 0 C, particularly preferably from 30 ° C to 120 ° C within a temperature range of -20 0 C to 200 0 C.
  • ethylenically unsaturated monomers are preferably used in step A).
  • polymerizable is meant monomers which, as described in the present invention, are polymerizable using the ATRP ATRP the polymer chain length and the polymer architecture are controlled in a known manner and can be obtained with respect to the polydispersity of the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) closely distributed polymers.
  • ethylenically unsaturated monomers monomers having at least one polymerizable carbon-carbon double bond, which double bond may be mono-, di-, tri-, or tetra-substituted., Either individual monomers or mixtures of monomers may be used are preferably selected to correspond to the desired physical and chemical properties of the polysiloxane block copolymer.
  • Suitable ethylenically unsaturated monomers M which can be used for the polymerization can be described by the general formula (V):
  • radicals R 9 and R 10 can be selected independently of one another from the group comprising hydrogen, C 1 -C 10 straight or branched alkyl radicals, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl or 2-ethoxyethyl.
  • the group G may be selected from the group consisting of -hydroxy, -O (M) i / v, -OR 11 , -NH 2 , -NHR 11 and -N (R 11 ) (R 12 ); wherein M is a counterion of valence v selected from the group of metal ions such as alkali metal ions, alkaline earth metal ions, ammonium ions, substituted ammonium ions such as mono-, di-, tri- or tetraalkylammonium ions, and each R 11 and R 12 are independently selected may be selected from the group consisting of hydrogen, C 1 -C 40 straight-chain or branched alkyl chains, polyether radicals, polyetheramine radicals optionally substituted with one or more substituents from the group consisting of hydroxy, amino, Ci - C 3 alkoxy, Ci - C 3 alkylamino and di (Ci - C 3 alkyl) amino, z.
  • M is a counterion
  • N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl Representative non-limiting examples of monomers also include protected or unprotected acrylic acid and methacrylic acid, as well as salts and esters and amides of these acids.
  • the salts can be derived from any non-toxic metal, ammonium or substituted ammonium counterion.
  • the esters can be derived from Ci - C 40 overall radkettigen, C 3 - C 40 branched alkyl chains, or C 3 - C 40 carbocyclic alcohols, from polyfunctional alcohols containing from 2 to 8 carbon atoms and from 2 to 8 hydroxy groups, amino alcohols and polyethylene glycols or polypropylene glycols or other polyether radicals and hydroxyl functionalized polyethers.
  • Non-limiting examples include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, and 1,2,6-hexanetriol) of amino alcohols (nonlimiting examples include aminoethanol, dimethylaminoethanol, diethylaminoethanol, and their quaternized products); or from ether alcohols (non-limiting examples include methoxyethanol and ethoxyethanol).
  • the amides may be unsubstituted, N-alkyl or N-alkylamino monosubstituted or N, N-dialkyl, or N, N-dialkyamino di-substituted, wherein the alkyl or alkylamino groups are derived from Ci - C 40 straight-chain or C 3 -C 40 branched, or C 3 - C 40 cyclic units.
  • the alkylamino group may be quaternized.
  • Also usable monomers are protected or unprotected acrylic and / or methacrylic acids, their salts, esters and amides, wherein the second or third carbon position of the acrylic acids and / or methacrylic acids may be substituted independently of one another.
  • the substituents can be be selected from the group containing C 1 -C 4 -alkyl radicals, hydroxyl, -CN, and -COOH, for example methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid.
  • the salts, esters and amides of these substituted aryl and methacrylic acids as described above can also be used.
  • Other useful monomers M include: vinyl and allyl esters of straight chain, 3 to 40 carbon atom containing, branched or 3 to 40 carbon atoms containing carbocyclic carboxylic acids, pyridines substituted with at least one vinyl or allyl group (eg vinylpyridine or allylpyridine), hydrocarbons having at least one unsaturated carbon-carbon double bond (eg styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutene , para-methylstyrene) and mixtures thereof.
  • vinyl and allyl esters of straight chain 3 to 40 carbon atom containing, branched or 3 to 40 carbon atoms containing carbocyclic carboxylic acids
  • pyridines substituted with at least one vinyl or allyl group eg vinylpyridine or allylpyr
  • Preferably used monomers M include acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso Butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl meth
  • monomers selected from the group comprising methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate , 2-ethylhexyl methacrylate, decyl methacrylate, octyl methacrylate, N-octylacrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, and mixtures
  • monomers selected from the group comprising methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate and mixtures thereof.
  • the termination of the polymerization in the ATRP can, for. B. as known to those skilled by oxidation of the transition metal. This can be z. B. happen that in the polymerization oxygen, z. B. by passing air, is passed.
  • the addition of the sulfur compound Q-SH to the polymerization of step A) may, for. B. after or during the termination of the polymerization reaction.
  • the addition of the compound Q-SH can be done directly or it can be added to a suitable compound from which a compound Q-SH is obtained or released.
  • the addition of the sulfur compound Q-SH can be carried out directly into the polymerization mixture obtained in polymerization step A) or else into a worked-up polymerization mixture.
  • the addition is preferably carried out directly in the polymerization mixture obtained in process step A) without prior workup.
  • the sulfur compound Q-SH is used, based on the chain ends (organically bound halogen), only in a minimal excess of 1.6 equivalents, preferably 1.2 equivalents and particularly preferably from 1 to 1.1 equivalents.
  • the addition of the mercapto-functionalized sulfur compound is believed to remove the terminal halogen atoms, presumably by substitution thereof.
  • the transition metal compound is precipitated so that it is in a simple Separate filtration from the polymer solution. This minimal excess leads to only a very low residual sulfur content in the polymer solution, which can be easily removed by modification of the following filtration step, for example by As adsorbents such as activated carbon are added to the mixture or filter material as an activated carbon filter is used.
  • the polysiloxane block copolymers according to the invention can be obtained which are halogen-free or virtually halogen-free.
  • This step also makes it possible to obtain polysiloxane block copolymers having terminal thioether groups with a copper content ⁇ 5 ppm by mass, particularly preferably ⁇ 2 ppm by mass.
  • the sulfur compounds Q-SH may have one or more SH groups.
  • the sulfur compounds used in the process according to the invention are preferably Q-SH thioglycolic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol, octylthioglycolate, methylmercaptan, ethylmercaptan, butylmercaptan, dodecylmercaptan, isooctylmercaptan or tert-dodecylmercaptan.
  • compositions according to the invention are characterized in that they have at least one polysiloxane block copolymer according to the invention.
  • the compositions of the invention may, for. For example, cosmetic compositions or body care compositions.
  • compositions of the invention may, for.
  • a conditioner for hair treatment agents as a hair aftertreatment agent and to improve the hair structure
  • the compositions according to the invention can be used for the treatment of hair, in particular for use as a hair conditioner.
  • the polysiloxane block copolymers according to the invention can also be used in a wide range of different types of products, such as. Hair spray compositions, hair styling compositions, mousses, gels, lotions, sprays, shampoos, conditioners, hand and body lotions, facial moisturizers, sunscreen, anti-acne formulations, anti-aging formulations, topical analgesics, mascara and the like, the enumeration is exemplary and not exhaustive.
  • the vehicles and additional components needed to formulate such products vary with the type of product and can be readily selected by one skilled in the art. In the following, some possible carrier substances and additional components which may be contained in compositions according to the invention are described.
  • compositions of the invention may, for. As a carrier or a mixture of different carriers, which are suitable for use on hair.
  • the content of carrier in the formulation is from 0.5% by weight to 99.5% by weight, preferably from 5.0% by weight to 99.5% by weight, particularly preferably 10.0 Wt .-% to 98 wt .-%.
  • suitable for use on hair means that the wearer does not damage the hair, does not adversely affect the aesthetic appearance of the hair, or produce any irritation on the underlying skin.
  • Suitable carriers for the use of hair care agents in the present invention include e.g. For example, those that are used in hair sprays, mousses, tonics, gels, shampoos, conditioners or rinses.
  • Suitable carrier depends on the block copolymer used and whether the formulated product is to remain on the surface to which it has been applied (eg, hair spray, mousse, tonic or gel) or rinsed off after application (e.g. B. shampoo, conditioner, rinses).
  • the carriers used may comprise a wide range of compounds commonly used in hair care compositions.
  • the carriers may comprise a solvent to dissolve or disperse the copolymer used, with water, C 1 -C 6 alcohols, alkyl acetates having alkyl groups comprising one to ten carbon atoms, and mixtures thereof being preferred.
  • the carriers may contain a wide range of additional materials such as acetone, hydrocarbons (eg, iso-butane, pentane, hexane, decene), halogenated hydrocarbons (such as freons), and volatile silicone derivatives such as cyclomethicone.
  • the preferred solvents include water, ethanol, volatile silicone derivatives and mixtures thereof.
  • the solvents used in such mixtures may be miscible or immiscible with each other.
  • Mousses and aerosol hair sprays may also contain any conventional propellant to apply the material as a foam (in the case of mousse) or as a fine, uniform spray (in the case of the aerosol hair spray).
  • suitable blowing agents include materials from the group comprising trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethyl ether, propane, n-butane or isobutane or mixtures thereof.
  • a tonic or hair spray product with a low viscosity may also contain an emulsifier.
  • suitable emulsifiers include nonionic, cationic, anionic surfactants or mixtures thereof.
  • the composition contains the emulsifier in a concentration of 0.01% to 7.5%.
  • the content of propellant can be adjusted as needed, but is usually between 3% and 30% for mousse compositions and from 15% to 50% in aerosol hairsprays.
  • Suitable containers for spraying are well known to those skilled in the art and include conventional non-aerosol pump sprays, i. H. "Atomisers", aerosol cans or cans with propellant as described above, and also pump aerosol cans that used compressed air as the propellant.
  • the carrier may contain a wide variety of conditioning compounds. If the hair care compositions are shampoos, the carrier may contain surfactants, suspending aids and thickeners.
  • the wearer may include various appearances.
  • the carrier may be an emulsion comprising e.g. As oil-in-water emulsions, water-in-oil emulsions, water-in-oil-in-water and oil-in-water-in-silicone emulsions.
  • the viscosity of the emulsions can range from 100 cps to 200,000 cps.
  • These emulsions can also be sprayed using either mechanical pump containers or pressurized aerosol containers with the usual propellants.
  • the carriers can also be applied in the form of mousse.
  • suitable topical carriers include non-aqueous liquid solvents such as oils, alcohols and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicones, cyclomethicones, and the like), water-based liquid monophase solvents (eg, water / alcohol solvents). gel systems) and thickened variants of these non-aqueous and water-based liquid monophasic solvents (eg those in which the viscosity of the solvent has been increased to a solid or a semi-solid by the addition of suitable gums, waxes, resins, polymers, salts and similar substances).
  • non-aqueous liquid solvents such as oils, alcohols and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicones, cyclomethicones, and the like), water-based liquid monophase solvents (eg, water / alcohol solvents). gel systems) and thickened variants of these non-aqueous and water-based liquid monophasic solvents
  • compositions of the present invention can be used in the compositions of the present invention, particularly in the cosmetic and personal care compositions of the present invention.
  • additional components include but not limited to:
  • Methylbenzylidene camphor, titanium dioxide, zinc oxide, silica, iron oxide and mixtures thereof.
  • Antidandruff agents such as bis (2-pyridylthio) zinc 1, 1 'dioxide, piroctone, selenium disulphide, sulfur, coal tar and the like.
  • Conditioners for hair care compositions such as hydrocarbons, liquid silicones, and cationic materials.
  • the hydrocarbons may be unbranched or branched and contain between 10 and 16 carbon atoms, preferably between 12 and 16 carbon atoms.
  • suitable hydrocarbons are decane, dodecane, tetradecane, tridecane and mixtures thereof.
  • conditioners containing silicones include, among others, cyclic or linear polydimethylsiloxanes, phenyl and alkylphenyl silicones, and silicone polyols.
  • Cationic conditioning agents Useful in the compositions include quaternary ammonium salts or the salts of fatty acid amines. Surfactants for hair shampoos and conditioning compositions.
  • the content of surfactants is preferably from 10% to 30% and more preferably from 12% to 25% of the composition.
  • the preferred content of surfactants is from about 0.2% to 3%.
  • the surfactants useful in the compositions include anionic, nonionic, zwitterionic, cationic and amphoteric surfactants.
  • Polymeric thickeners with carboxylic acid groups contain one or more derivatives of acrylic acid, substituted acrylic acid, salts and esters of these acrylic acids and substituted acrylic acids, in the case of crosslinked polymers, the crosslinking agent containing two or more carbon-carbon double bonds.
  • the poly- mers thickeners are those selected from the group consisting of carbomers, acrylates / C O -C 3O alkyl acrylates networked copolymers and mixtures thereof.
  • Compositions of the present invention may contain from 0.025% to 1%, preferably from 0.05% to 0.75%, and more preferably from 0.10% to 0.50% of the polymeric thickeners having carboxylic acid groups.
  • Emulsifiers for the emulsification of various carrier substances described in compositions in this invention include polyethylene glycol 20 sorbitan monolaurate (polysorbate 20), polyethylene glycol 5 soybean sterol, steareth-20, ceteareth-20, PPG-2 methyl glucose ether distearate, ceteth-10, polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate and mixtures thereof.
  • the emulsifiers may be used singly or as a mixture of two or more emulsifiers.
  • the cosmetic or personal care composition Composition may comprise an emulsifier content of 0.15 to 10%, preferably from 1% to 7% and particularly preferably from 1% to 5%.
  • Vitamins and derivatives thereof e.g., ascorbic acid, vitamin E, tocopherol acetate, retinoic acid, retinol,
  • Cationic polymers e.g., cationic guar derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chlorides, available under the tradename Jaguar C from Rhone
  • cationic guar derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chlorides, available under the tradename Jaguar C from Rhone
  • quaternary ammonium salts of hydroxyethyl cellulose such as Polyquaternium-10, available from Amerchol Corp. Under the trade names Ucare ® Polymer JR / LR / SC / KG. Preservatives, antioxidants, chelating agents and complexing agents, pearlescing agents, aesthetic components such as perfume, perfumes, dyes, pigments, hair nutrients, and essential oils. Additives that are obvious to the person skilled in the art, but are not listed here.
  • Example 2 In a three-necked flask equipped with stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel, under N 2 atmosphere, 74.4 g of n-lauryl methacrylate, 4.6 g of dimethylaminoethyl methacrylate, 150.0 g Butyl acetate, 3.1 g of copper (I) oxide and 7.9 g of PMDETA
  • Example 5 In a three-necked flask equipped with stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel, under N 2 atmosphere, 81.1 g of n-butyl acrylate, 5.0 g of dimethylaminoethyl methacrylate, 140.0 g of butyl acetate, 1.8 g of copper ( I) oxide and 4.4 g of PMDETA (N, N, N ', N ", N" -pentamethyldiethylenetriamine). The solution was stirred at 80 ° C. for 15 min. Subsequently, 53.2 g of the macroinitiator of the formula (VII) with n
  • hair tresses are used for sensory tests are represented by a permanent ⁇ wave treatment and a bleaching treatment superiors standardized damaged.
  • hairdressing customary products are used. The test procedure, the base materials used and the details of the evaluation criteria are described in DE 103 27 871.
  • Test formulation The polysiloxane copolymers were tested in a simple Haarspü ⁇ lung with the given in Table 1.
  • conditioner refers to the polysiloxanes block copolymers described in Examples 1 to 5.
  • the hair tresses previously damaged as described above were treated with the conditioning rinse described above as follows: The hair strands were wetted under running, warm water. The excess water was easily be manually ⁇ suppressed, then the rinse was applied and gently worked into the hair (1 ml / tress of hair (2 g)). After a residence time of 1 min, the hair was rinsed for 1 min.
  • the hair was dried in air at 50% humidity and 25 ° C. for at least 12 hours.
  • composition of the test formulation is to avoid influencing the test results by (usually EXISTING ⁇ dene) formulation ingredients deliberately chosen to be simple.
  • OF INVENTION ⁇ dung modern formulations may contain, in addition to the ingredients mentioned and / or instead of the above ingredients still WEI tere ingredients.
  • the combination with other ingredients can lead to a synergistic improvement of the conditioning effect.
  • Such ingredients are described above.
  • Test criteria were scored on scores ranging from 1 to 5, with 1 being the worst and 5 being the best scores.
  • the individual test criteria each receive their own rating.
  • the test criteria are: De- tangling, wet combing, wet grip, dry comb, Tro ⁇ ckengriff, shine, volume.
  • the polysiloxane block copolymers have hair-conditioning properties. They are significantly better than the control without conditioner control. Table 2: Conditioning properties of the polysiloxane block copolymers
  • the polysiloxane block copolymer of Example 6 was incorporated into a formulation for a non-aerosol hair spray with 80% by mass of volatile organic compounds (so-called 80% VOC non-aerosol hairspray) according to the composition listed in Table 3.
  • ABIL B 8843 (INCI name: PEG-14 dimethicone) is a product of Evonik Goldschmidt GmbH. SD Alcohol 40: Ethanol.
  • the polysiloxane block copolymer of Example 6 was incorporated into a formulation for a hair styling gel according to the composition listed in Table 4.
  • AMP-95 (INCI name: Aminomethyl Propanol) is a product of Angus.
  • Carbopol ETD 2020 (INCI name: Acrylates / C10-30 Alkyl Acrylic Crosspolymer) is a product of Noveon.
  • the formulation from Table 4 forms a gel with a pudding-like consistency which, when applied as a styling gel, leads to sufficient stability in the hair, while at the same time providing flexibility and a pleasant grip.

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Abstract

L'invention se rapporte à des copolymères séquencés de polysiloxane de formule A[LB(S)Q]m dans laquelle A est un bloc polysiloxane, L est une séquence de liaison organique divalente, B est un bloc polymère constitué par des monomères polymérisables par voie radicalaire, S est un atome de soufre et Q est un radical organique monovalent et m est un nombre entier allant de 1 à 50. L'invention se rapporte également à un procédé pour leur préparation ainsi que pour leur utilisation dans les domaines des cosmétiques et des soins du corps.
EP08787053A 2007-09-27 2008-08-08 Copolymères séquencés de polysiloxane Withdrawn EP2193159A1 (fr)

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BRPI0921894A2 (pt) * 2008-11-13 2015-12-29 Novartis Ag copolímeros de polissiloxano com cadeias de polímero hidrofílicas terminais
DE102009003274A1 (de) * 2009-05-20 2010-11-25 Evonik Goldschmidt Gmbh Zusammensetzungen enthaltend Polyether-Polysiloxan-Copolymere
DE102010002180A1 (de) * 2010-02-22 2011-08-25 Evonik Goldschmidt GmbH, 45127 Stickstoffhaltige silizium-organische Pfropfmischpolymere
BR112012029218A2 (pt) 2010-05-19 2016-11-29 Evonik Goldschmidt Gmbh copolímeros de polissiloxano em blocos e seu uso em formulações cosméticas
US20130035452A1 (en) 2010-05-19 2013-02-07 Evonik Goldschmidt Gmbh Polysiloxane block copolymers and use thereof in cosmetic formulations
DE102010062156A1 (de) 2010-10-25 2012-04-26 Evonik Goldschmidt Gmbh Polysiloxane mit stickstoffhaltigen Gruppen
DE102011078382A1 (de) 2011-06-30 2013-01-03 Evonik Goldschmidt Gmbh Mikroemulsion von quaternären Ammoniumgruppen enthaltenden Polysiloxanen, derenHerstellung und Verwendung
DE102011110100A1 (de) 2011-08-12 2013-02-14 Evonik Goldschmidt Gmbh Verfahren zu Herstellungen von Polysiloxanen mit stickstoffhaltigen Gruppen
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CN101784585B (zh) 2013-05-29
JP2010540704A (ja) 2010-12-24
US20090087399A1 (en) 2009-04-02

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