WO2004099273A1 - Water-soluble or water-dispersible polymers made from monoethylenically-unsaturated saccharide monomers - Google Patents

Water-soluble or water-dispersible polymers made from monoethylenically-unsaturated saccharide monomers Download PDF

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WO2004099273A1
WO2004099273A1 PCT/EP2004/004647 EP2004004647W WO2004099273A1 WO 2004099273 A1 WO2004099273 A1 WO 2004099273A1 EP 2004004647 W EP2004004647 W EP 2004004647W WO 2004099273 A1 WO2004099273 A1 WO 2004099273A1
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monomers
weight
water
polymers according
contain
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PCT/EP2004/004647
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German (de)
French (fr)
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Dieter Boeckh
Stefan Becker
Dietmar HÄRING
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Basf Aktiengesellschaft
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/10—Polymers provided for in subclass C08B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/02—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to water-soluble or water-dispersible polymers based on monoethylenically unsaturated saccharide monomers which
  • the invention relates to the production of these polymers and their use as an additive to detergents, laundry pretreatment and aftertreatment compositions, cleaning and care product formulations, cosmetic preparations, hair sprays and personal care products, as textile auxiliaries, paper auxiliaries, adhesive aids, concrete additive, film material, dispersants for inorganic and organic aqueous pigment preparations, scale inhibitors, protective colloid for the production of emulsions and for emulsion polymerization and as a coating aid for the protection of hard surfaces.
  • Polyhydroxy-functionalized polymers are important as functional additives for a variety of technical processes.
  • the technically available polyhydroxy-functionalized polymers do not always meet the expectations placed on them.
  • many natural and modified polysaccharides cannot be incorporated into liquid formulations, and polyvinyl alcohols can only be varied with comonomers to a limited extent due to the manufacturing processes.
  • the invention was therefore based on the object of providing broadly functionalizable polymers with a high content of hydroxy functionalities, which are also preferably water-soluble or at least water-dispersible. Accordingly, water-soluble or water-dispersible polymers based on monoethylenically unsaturated saccharide monomers have been found which
  • the polymers according to the invention can be homopolymers of the ethylenically unsaturated saccharide monomers (A) or copolymers of these monomers (A) with further monoethylenically unsaturated monomers (B).
  • the copolymers are usually preferred because, by the additional incorporation of the monomers (B), they enable the polymers to be functionalized further and thus to be adapted particularly flexibly to the respective application requirements.
  • the copolymers according to the invention generally contain 5 to 99% by weight of monomers (A) and 1 to 95% by weight of monomers (B).
  • the saccharide monomers (A) on which the polymers according to the invention are based are monoacrylic acid or monomethacrylic acid esters of saccharides and saccharide derivatives, the monoesters having a content of saccharides or saccharide derivatives esterified several times with acrylic acid or methacrylic acid of ⁇ 2.5% by weight, preferably ⁇ 1.25 % By weight, particularly preferably of 0.8% by weight and very particularly preferably of ⁇ 0.4% by weight.
  • the polymers according to the invention also show no or only negligible crosslinking and are therefore advantageously, if not even water-soluble, at least easily dispersible in water. It is particularly advantageous that the high molecular weight polymers according to the invention are soluble or dispersible in water in this way. If the polymers according to the invention are only water-dispersible, they are in at least one (preferably polar) organic solvent or in a solvent. mixed, especially a mixture of water and organic solvent, completely soluble.
  • Suitable polar solvents are C 1 -C 4 -alkanols, such as methanol, ethanol and isopropanol, cyclic and acyclic ethers, such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, acetone, dimethylformamide and N-methylpyrrolidone.
  • Mono-, di- and oligosaccharides are particularly suitable as saccharides as the basis for the ethylenically unsaturated saccharide monomers (A), aldoses and ketoses being suitable. Aldo and keto pentoses and hexoses are preferred.
  • the oligosaccharides can contain up to 20, preferably up to 5, saccharide units. Mono- and disaccharides are particularly suitable, monosaccharides being very particularly suitable.
  • Particularly suitable saccharide derivatives are the C 1 -C 30 -, especially the CrC 1 - alkyl glucosides and polyglucosides of these saccharides.
  • Suitable saccharides and saccharide derivatives are based primarily on glucose, fructose, lactose, sucrose, cellobiose, maltodextrins or inulins or their C-rC- 30 alkylglucosides or polyglucosides.
  • Glucose, fructose, sucrose, cellobiose, maltodextrins and their CC ⁇ -alkyl glucosides are preferred, and glucose and their CC 4 -alkyl glucosides are particularly preferred.
  • the esterification of the monomers (A) is preferably over 50% on a -CH 2 -OH group of the saccharide.
  • Such an alcohol group is particularly preferably selectively esterified to over 75% and very particularly preferably to over 90%.
  • the monoethylenically unsaturated saccharide monomers (A) can be obtained, as described, for example, in the unpublished DE-A-101 56 352, by the saccharide or saccharide derivative in the presence of an enzyme which transfers acrylate groups and in the presence of an organic solvent (less than 4.8 ml per mmol saccharide (derivative)) with (meth) acrylic acid or a C C ⁇ o-alkyl (meth) acrylic acid ester.
  • the molar ratio of (meth) acrylic acid (ester) to saccharide (derivative) is preferably 10: 1 to 3: 1.
  • the initial saccharide (derivative) concentration is in particular 0.1 to 20, preferably 0.15 to 10 mol / l reaction mixture.
  • Suitable enzymes that transfer acrylate groups are hydrolases, preferably esterases (EC 3.1. .-), in particular lipases (EC 3.1.1.3), and glycolases (EC 3.2.-.-) and proteases (EC 3.4.-.-) in free or immobilized form.
  • Novozym 435 lipase from Candida antartica B
  • lipase from Aspergillus sp., Burholderia sp., Candida sp., Pseudomonas sp. are particularly suitable. or pork pancreas.
  • the enzyme content in the reaction medium is usually in the range from 0.1 to 10% by weight, based on the saccharide (derivative).
  • Suitable organic solvents are, in particular, C 3 -C 6 -alkanols, such as tert-butanol and tert-amyl alcohol, pyridine, polyethylene glycol di-C 1 -C 4 -alkyl ethers, such as diethylene glycol dimethyl ether and polyethylene glycol dimethyl ether (M n 500), CC 4 alkylene carbonates, such as propylene carbonate, C 3 -C 6 alkyl acetate, such as tert-butyl acetate, acetone and aliphatic and cycloaliphatic ethers, such as dimethoxy methane, dimethoxyethane, 1,4-dioxane, 1, 3-dioxolane and tetrahydrofuran, as well as their mixtures.
  • the preferred amount of solvent used is 0.01 to 4, in particular 0.1 to 3 ml / mmol saccharide (derivative).
  • the organic solvent can also be used in combination with aqueous solvents, such as water itself or dilute aqueous buffers (usually 10 to 100 mM), for example buffers for the pH range 6 to 8, such as potassium phosphate or TRIS-HCl buffers Come into play.
  • aqueous solvents such as water itself or dilute aqueous buffers (usually 10 to 100 mM), for example buffers for the pH range 6 to 8, such as potassium phosphate or TRIS-HCl buffers Come into play.
  • the esterification of the saccharide (derivative) is generally carried out at 0 to 70 ° C., in particular at 20 to 60 ° C.
  • the polymers according to the invention can contain copolymerized nonionic water-insoluble monomers (B1), anionic monomers (B2), cationic monomers (B3) and / or nonionic water-soluble monomers (B4).
  • Suitable nonionic water-insoluble monomers (B1) are those monoethylenically unsaturated monomers whose solubility in water at room temperature is ⁇ 100 g / l. The incorporation of these monomers leads to partial hydrophobization of the polymers according to the invention. However, their solubility in water is not adversely affected by smaller proportions of these monomers. In the case of higher proportions of monomers (B1), the polymers according to the invention are no longer completely water-soluble, but are water-dispersible. Examples of suitable monomers (B1) are:
  • esters of monoethylenically unsaturated C 3 -C 6 carboxylic acids especially acrylic acid and methacrylic acid, and monohydric CrC ⁇ alcohols and hydroxyalkyl esters of monoethylenically unsaturated C 3 -C 6 carboxylic acids, especially acrylic acid and methacrylic acid, and dibasic C 2 -C 4 alcohols, such as methyl (meth) - acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert.-butyl (meth) acrylate, ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate and hydroxypropyl ( meth) acrylate,
  • Vinyl esters of saturated C 18 -carboxylic acids such as vinyl acetate and vinyl propionate
  • aliphatic and aromatic olefins such as ethylene, propylene, C -C 24 - ⁇ -olefins, for example butylene, isobutylene, diisobutene, styrene and ⁇ -methylstyrene, and also diolefins with an active double bond, for example butadiene,
  • unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • fluorine-containing monomers especially fluorine-containing olefins, such as fluorethylene, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride and hexafluoropropene, and
  • Preferred monomers (B1) are methyl (meth) acrylate, ethyl acrylate, n-butyl (meth) acrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, vinyl acetate, vinyl propionate, ethylene, propylene, butylene, diisobutene, Styrene and tetrafluoroethylene.
  • Methyl (meth) acrylate, ethyl acrylate, n- and tert-butyl acrylate and vinyl acetate are particularly preferred.
  • the polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 60% by weight of the monomers (B1) and 0 to 35% by weight of further monomers different from (B1).
  • Preferred polymers according to the invention have a content of 5 to 95% by weight, in particular 60 to 90% by weight, of the monomers (A) and 5 to 50% by weight, especially 10 to 40% by weight, of the monomers (B1).
  • Monoethylenically unsaturated monomers (B2) containing acidic groups are suitable, for example:
  • C 3 -C 6 monocarboxylic acids and their salts such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and vinyl acetic acid,
  • monoethylenically unsaturated C 4 -C 6 dicarboxylic acids especially maleic acid and itaconic acid, their anhydrides, salts and half-esters with C ⁇ C 6 alcohols, monoethylenically unsaturated sulfonic acids and phosphonic acids and their salts, such as acrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid, methallylsulfonic acid and vinyl phosphonic acid.
  • Preferred monomers (B2) are acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic acid semiesters, acrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid and vinyl phosphonic acid. Acrylic acid and methacrylic acid are particularly preferred.
  • the polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 95% by weight of the monomers (B2) and 0 to 35% by weight of other monomers different from (B2).
  • Preferred polymers according to the invention have a content of 40 to 95% by weight, in particular 40 to 90% by weight, of the monomers (A) and 5 to 80% by weight, especially 10 to 60% by weight, of the monomers (B2).
  • Monomers containing vinylimidazole and vinylimidazoline units and their alkyl derivatives, in particular CrC- 5 alkyl derivatives, and their quaternization products such as N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5- methylimidazole, N-vinyl-2-ethylimidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline,
  • esters of ethylenically unsaturated carboxylic acids especially the esters of ⁇ , ⁇ -unsaturated C 3 -C 6 monocarboxylic acids, especially acrylic acid and methacrylic acid, with amino alcohols, especially N, N-Di-CrC 4 -alkylamino-C 2 -C 6 - alcohols, and their quaternization products, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminoethyl acrylate, diethylaminopropyl acrylate, dimethylamino-nobutyl acrylate and diethylaminobutyl acrylate,
  • diallylalkylamines especially the diallyl-C 4 -alkylamines, and their quaternization products, such as diallylmethylamine and diallyldimethylammonium chloride, and
  • Vinyl pyridines and their quaternization products such as 4-vinyl pyridine, 2-vinyl pyridine, N-methyl-4-vinyl pyridine and N-methyl-2-vinyl pyridine.
  • the monomers (B3) can be used in the form of the free bases or the salts with inorganic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, or organic acids, such as formic acid, acetic acid and propionic acid, or in quaternized form.
  • Suitable quaternizing agents are in particular alkylating agents, such as dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and benzyl chloride.
  • Particularly suitable monomers (B3) are dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylamide, dimethylaminopropylacrylamide, vinylimidazole and their derivatives quaternized with methyl chloride or dimethyl sulfate.
  • Dimethylaminoethyl acrylate, vinylimidazole and their derivatives quaternized with methyl chloride or dimethyl sulfate are particularly preferred.
  • the polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 95% by weight of the monomers (B3) and 0 to 35% by weight of further monomers different from (B3).
  • Preferred polymers according to the invention have a content of 40 to 98% by weight, in particular 50 to 95% by weight, of the monomers (A) and 2 to 60% by weight, especially 5 to 50% by weight, of the monomers (B3) on.
  • suitable nonionic water-soluble monomers (B4) are those monoethylenically unsaturated monomers whose solubility in water at room temperature is> 100 g / l. The incorporation of these monomers leads to largely hydrophilic water-soluble polymers according to the invention.
  • suitable monomers (B4) are: Esters of monoethylenically unsaturated C 3 -C 6 carboxylic acids, especially acrylic acid and methacrylic acid, and CC ⁇ alkyl polyalkylene glycols with 2 to 40 C 2 -C 4 alkylene glycol units,
  • Amides of monoethylenically unsaturated C 3 -C 6 carboxylic acids especially acrylic acid and methacrylic acid, with primary and secondary C 1 -C amines and end group-aminated C ⁇ C 4 alkyl polyalkylene glycols with 2 to 40 C 2 -C alkylene glycol units, such as (meth) acrylic amide, N-methyl (meth) acrylamide and N-butyl (meth) acrylamide and amides of (meth) acrylic acid with methyl polyalkylene glycols end-group-aminated with 2 to 40 C 2 -C 4 -alkylene glycol units, and
  • 8- carboxylic acids and N-vinyl lactams of lactams with 5- to 7-membered rings, such as N-vinyl formamide, N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl caprolactam and N-vinyl oxazolidone.
  • Preferred monomers (B4) are acrylamide, N-vinylformamide and N-vinylpyrrolidone.
  • the polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 95% by weight of the monomers (B4) and 0 to 35% by weight of other monomers different from (B4).
  • Preferred polymers according to the invention have a content of 20 to 95% by weight, in particular 40 to 90% by weight, of the monomers (A) and 5 to 80% by weight, especially 10 to 60% by weight, of the monomers (B4).
  • Particularly preferred polymers according to the invention are the copolymers of the monomers (A) with nonionic water-insoluble monomers (B1), anionic monomers (B2) or cationic monomers (B3), that is to say the hydrophobic, anionically or cationically modified polymers.
  • the polymers according to the invention have an average molecular weight M w of 5,000 to 2,500,000.
  • Their average molecular weight M w is preferably 10,000 to 1,000,000, particularly preferably 25,000 to 750,000 and very particularly preferably 50,000 to 500,000.
  • the molecular weights of the polymers according to the invention can be determined by known methods by dissolving them in a suitable solvent and then characterizing them by viscometry, light scattering or gel permeation chromatography.
  • the average molecular weights M w given in the examples were determined by gel permeation chromatography in water.
  • the polymers according to the invention can advantageously be obtained by the production process likewise according to the invention, which is characterized in that the monomers (A) and, if desired (B), a radical polymerization in a polar solvent, preferably in water or mixtures of water and polar organic solvents, in particular CC 4 alcohols and acetone.
  • the polymers according to the invention can also be prepared by precipitation polymerization, emulsion polymerization, polymerization in water-in-oil emulsions (W / O) or reverse suspension polymerization, but solution polymerization, in particular in water-containing solvents, especially in water itself, is preferred.
  • thermally activatable polymerization initiators with a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 90 ° C.
  • thermal initiators are organic peroxides, such as dibenzoyl peroxide and di-tert-butyl peroxide, peresters, perketals, hydroperoxides, inorganic peroxides, such as hydrogen peroxide, percarbonates, peroxosulfates, peroxodisulfates, azo compounds, boralkyl compounds and homolytically decomposing hydrocarbons.
  • photoinitiators examples include benzophenone, acetophenone, benzoin ether, benzyl dialkyl ketones and their derivatives.
  • the thermal initiators and / or photoinitiators are usually used in amounts of from 0.01 to 15% by weight, based on the monomers to be polymerized, and can be used individually or, to take advantage of advantageous synergistic effects Combination with each other.
  • customary regulators e.g. Mercapto compounds such as mercaptoethanol and thioglycolic acid can be added.
  • Suitable regulator amounts are generally 0.01 and 3% by weight, based on the monomers to be polymerized.
  • the polymerization temperature is generally 40 to 120 ° C, preferably 60 to 100 ° C.
  • the water-soluble or water-dispersible polymers according to the invention can be used advantageously in many industrial applications. They are particularly suitable as an additive to detergents, laundry pretreatment and aftertreatment agents, cleaning and care product formulations, cosmetic preparations, hair sprays and personal care products, as textile auxiliaries, paper aids, adhesive aids, concrete additive, film material, dispersants for inorganic and organic aqueous pigment preparations, coatings.
  • the hydrophobically modified polymers according to the invention which contain the monomers (B1) in copolymerized form, can be used particularly advantageously as an additive to detergents, laundry pretreatment and post-treatment agents, cleaning and care agent formulations, cosmetic preparations and hair sprays, as textile auxiliaries, adhesive aids, film material, protective colloid be used for the production of emulsions and for emulsion polymerization as well as a coating aid for the protection of hard surfaces.
  • the anionically modified polymers according to the invention which contain the monomers (B2) in copolymerized form, are particularly suitable as additives for detergents, laundry pretreatment agents, cleaning and care product formulations and cosmetic preparations, as textile auxiliaries, adhesive aids, concrete additives, dispersants for inorganic and organic aqueous pigment preparations, and coating inhibitors , Protective colloid for the production of emulsions and for emulsion polymerization as well as a coating aid for the protection of hard surfaces.
  • the cationically modified polymers according to the invention which contain the monomers (B3) in copolymerized form, can be used particularly advantageously as an additive to detergents, laundry pretreatment and aftertreatment agents, care product formulations, cosmetic preparations, hair sprays and personal care products, as textile auxiliaries, paper auxiliaries, adhesive auxiliaries, and protective colloid for the production of Emulsions and for emulsion polymerization as well as coating aids for the protection of hard surfaces.
  • nonionically hydrophilically modified, that is to say containing the monomers (B4) copolymerized, polymers according to the invention are particularly suitable as an additive to detergents, laundry pretreatment and aftertreatment agents, cleaning agents and Care formulations, cosmetic preparations and personal care products, as textile auxiliaries, adhesive aids, film material, protective colloid for the production of emulsions and for emulsion polymerization, and as coating aids for protecting hard surfaces.
  • formulation aids e.g. serve as binders for detergent granules and tablets and thickeners for liquid detergents, as fiber protection polymers, graying inhibitors, as deposit inhibitors and dispersants for dirt particles.
  • the polymers according to the invention can not only be added to the detergent or laundry aftertreatment agent, but can also be applied in a separate treatment step in dissolved form to the textile material by spraying or rinsing.
  • reaction mixture was polymerized for a further 1 h at the boiling point, cooled to 30 ° C. and neutralized with 50% strength by weight sodium hydroxide solution (pH 7.0).
  • the solids content of the polymer solution obtained was 19.6% by weight.
  • the molar mass M w of the polymer was 6500 D.
  • Feed 1 Mixture of 172.6 g of a 45% strength by weight aqueous solution of 6-O-acryloylmethylglucoside, 22.9 g of methacrylic acid and 4.6 g of water.
  • Feed 2 Solution of 1.5 g of sodium peroxodisulfate in 18.5 g of water
  • Feed 3 solution of 3.5 g of sodium hypophosphite monohydrate in 16.5 g of water
  • a pH of 6.5 was set by neutralization with 50% strength by weight sodium hydroxide solution.
  • the solids content of the polymer solution obtained was 17.4% by weight.
  • the molecular weight M w of the polymer was 11,000 D.
  • reaction mixture had been post-polymerized for one hour at 75 ° C. and a solution of 0.60 g of 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride in 9.4 g of water (5 min) had been added for a further 3 h stirred at 75 ° C.
  • the cooled polymer solution had a pH of 3.4. Their solids content was 15.2% by weight. The molar mass M w of the polymer was 48,000 D.
  • Feed 1 Mixture of 378.5 g of a 29.8% by weight aqueous solution of 6-O-acryloylmethyl glucoside and 27.5 g of an 80% by weight aqueous solution of [2- (acryloyloxy) ethyl] trimethylammonium chloride
  • Feed 2 solution of 0.13 g of 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride in 9.9 g of water
  • the cooled polymer solution had a pH of 3.3. Their solids content was 20.5% by weight. The molecular weight M w of the polymer was 560,000 D. II. Use of polymers according to the invention
  • Example 1 Use as an additive to liquid detergents
  • the formulations obtained were homogeneous and stable for 1 week at room temperature.
  • Example 2 Use as an additive to fabric softeners
  • aqueous solutions of the polymers 3 and 4 were of a commercial fabric softener emulsion (Lenor ®) in a weight ratio of 1: 9 (polymer solution: Fabric softener emulsion) was added. The mixtures obtained in each case were stirred for 15 minutes.
  • Linor ® fabric softener emulsion
  • the formulations obtained were homogeneous and stable for 1 week at room temperature.
  • Example 3 Use as a removable protective film on surfaces
  • aqueous solutions of polymers 1 to 4 were each applied as a thin liquid film to a glass plate.
  • the liquid films were dried at room temperature.

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Abstract

The invention relates to water-soluble or water-dispersible polymers made from monoethylenically-unsaturated saccharide monomers, comprising a polymer of (A) 5 to 100 wt. % of at least one ester, selected from the group of monoacrylate and monomethacrylate esters of saccharides and saccharide derivatives, whereby the monoester has a content of saccharides or saccharide derivatives multiply esterified with acrylic or methacrylic acid of = 2.5 wt. % and (B) 0 to 95 wt. % of at least one further monoethylenically-unsaturated monomer and which have a mean molecular mass Mw of 5,000 to 2,500,000.

Description

Wasserlösliche oder wasserdispergierbare Polymere auf Basis monoethylenisch ungesättigter SaccharidmonomereWater-soluble or water-dispersible polymers based on monoethylenically unsaturated saccharide monomers
Beschreibungdescription
Die vorliegende Erfindung betrifft wasserlösliche oder wasserdispergierbare Polymere auf Basis monoethylenisch ungesättigter Saccharidmonomere, dieThe present invention relates to water-soluble or water-dispersible polymers based on monoethylenically unsaturated saccharide monomers which
(A) 5 bis 100 Gew.-% mindestens eines Esters, ausgewählt aus der Gruppe der Mo- noacrylsäure- und Monomethacrylsäureester von Sacchariden und Saccharidderivaten, wobei die Monoester einen Gehalt an mehrfach mit Acrylsäure oder Methacrylsäure veresterten Sacchariden oder Saccharidderivaten von <2,5 Gew.-% aufweisen, und(A) 5 to 100% by weight of at least one ester selected from the group of the monoacrylic acid and monomethacrylic acid esters of saccharides and saccharide derivatives, the monoesters having a content of saccharides or saccharide derivatives which have been polyesterified with acrylic acid or methacrylic acid of <2.5 % By weight, and
(B) 0 bis 95 Gew.-% mindestens eines weiteren monoethylenisch ungesättigten Monomeren(B) 0 to 95% by weight of at least one further monoethylenically unsaturated monomer
einpolymerisiert enthalten und eine mittlere Molmasse Mw von 5000 bis 2 500 000 aufweisen.contain polymerized and have an average molecular weight M w of 5000 to 2 500 000.
Außerdem betrifft die Erfindung die Herstellung dieser Polymere und ihre Verwendung als Zusatz zu Waschmitteln, Wäschevor- und -nachbehandlungsmitteln, Reinigungsund Pflegemittelformulierungen, kosmetischen Präparationen, Haarsprays und Körperpflegemitteln, als Textilhilfsmittel, Papierhilfsmittel, Klebhilfsmittel, Betonadditiv, Folien- material, Dispergiermittel für anorganische und organische wäßrige Pigmentpräparationen, Belagsinhibitoren, Schutzkolloid für die Herstellung von Emulsionen und für die Emulsionspolymerisation sowie als Beschichtungshilfsmittel für den Schutz harter Oberflächen.In addition, the invention relates to the production of these polymers and their use as an additive to detergents, laundry pretreatment and aftertreatment compositions, cleaning and care product formulations, cosmetic preparations, hair sprays and personal care products, as textile auxiliaries, paper auxiliaries, adhesive aids, concrete additive, film material, dispersants for inorganic and organic aqueous pigment preparations, scale inhibitors, protective colloid for the production of emulsions and for emulsion polymerization and as a coating aid for the protection of hard surfaces.
Polyhydroxyfunktionalisierte Polymere sind als funktionale Additive für eine Vielzahl technischer Prozesse von Bedeutung. Nicht immer erfüllen die technisch verfügbaren polyhydroxyfunktionalisierten Polymere die an sie gestellten Erwartungen. Beispielsweise sind viele natürliche und modifizierte Polysaccharide nicht in flüssige Formulierungen einarbeitbar, und Polyvinylalkohole sind aufgrund der Herstellungsprozesse nur begrenzt mit Comonomeren variierbar.Polyhydroxy-functionalized polymers are important as functional additives for a variety of technical processes. The technically available polyhydroxy-functionalized polymers do not always meet the expectations placed on them. For example, many natural and modified polysaccharides cannot be incorporated into liquid formulations, and polyvinyl alcohols can only be varied with comonomers to a limited extent due to the manufacturing processes.
Der Erfindung lag daher die Aufgabe zugrunde, breit funktionalisierbare Polymere mit hohem Gehalt an Hydroxyfunktionalitäten, die zudem bevorzugt wasserlöslich oder doch zumindest wasserdispergierbar sind, bereitzustellen. Demgemäß wurden wasserlösliche oder wasserdispergierbare Polymere auf Basis monoethylenisch ungesättigter Saccharidmonomere gefunden, dieThe invention was therefore based on the object of providing broadly functionalizable polymers with a high content of hydroxy functionalities, which are also preferably water-soluble or at least water-dispersible. Accordingly, water-soluble or water-dispersible polymers based on monoethylenically unsaturated saccharide monomers have been found which
(A) 5 bis 100 Gew.-% mindestens eines Esters, ausgewählt aus der Gruppe der Mo- noacrylsäure- und Monomethacrylsäureester von Sacchariden und Saccharidderivaten, wobei die Monoester einen Gehalt an mehrfach mit Acrylsäure oder Methacrylsäure veresterten Sacchariden oder Saccharidderivaten von <2,5 Gew.-% aufweisen, und(A) 5 to 100% by weight of at least one ester selected from the group of the monoacrylic acid and monomethacrylic acid esters of saccharides and saccharide derivatives, the monoesters having a content of saccharides or saccharide derivatives which have been polyesterified with acrylic acid or methacrylic acid of <2.5 % By weight, and
(B) 0 bis 95 Gew.-% mindestens eines weiteren monoethylenisch ungesättigten Monomeren(B) 0 to 95% by weight of at least one further monoethylenically unsaturated monomer
einpolymerisiert enthalten und eine mittlere Molmasse Mw von 5000 bis 2500 000 aufweisen.contain polymerized and have an average molecular weight M w of 5000 to 2500 000.
Die erfindungsgemäßen Polymere können Homopolymere der ethylenisch ungesättigten Saccharidmonomere (A) oder Copolymere dieser Monomere (A) mit weiteren monoethylenisch ungesättigten Monomeren (B) sein.The polymers according to the invention can be homopolymers of the ethylenically unsaturated saccharide monomers (A) or copolymers of these monomers (A) with further monoethylenically unsaturated monomers (B).
Die Copolymere sind üblicherweise bevorzugt, da sie durch den zusätzlichen Einbau der Monomere (B) eine weitere Funktionalisierung der Polymere und damit eine besonders flexible Anpassung an die jeweiligen Anwendungserfordernisse ermöglichen. In der Regel enthalten die erfindungsgemäßen Copolymere 5 bis 99 Gew.-% Monomere (A) und 1 bis 95 Gew.-% Monomere (B).The copolymers are usually preferred because, by the additional incorporation of the monomers (B), they enable the polymers to be functionalized further and thus to be adapted particularly flexibly to the respective application requirements. The copolymers according to the invention generally contain 5 to 99% by weight of monomers (A) and 1 to 95% by weight of monomers (B).
Die den erfindungsgemäßen Polymeren zugrundeliegenden Saccharidmonomere (A) sind Monoacrylsäure- oder Monomethacrylsäureester von Sacchariden und Saccharidderivaten, wobei die Monoester einen Gehalt an mehrfach mit Acrylsäure oder Methacrylsäure veresterten Sacchariden oder Saccharidderivaten von <2,5 Gew.-%, bevorzugt von ≤1,25 Gew.-%, besonders bevorzugt von 0,8 Gew.-% und ganz besonders bevorzugt von <0,4 Gew.-% aufweisen.The saccharide monomers (A) on which the polymers according to the invention are based are monoacrylic acid or monomethacrylic acid esters of saccharides and saccharide derivatives, the monoesters having a content of saccharides or saccharide derivatives esterified several times with acrylic acid or methacrylic acid of <2.5% by weight, preferably ≤1.25 % By weight, particularly preferably of 0.8% by weight and very particularly preferably of <0.4% by weight.
Aufgrund dieser äußerst geringen bis überhaupt nicht auftretenden Mehrfachveresterung des Saccharids bzw. Saccharidderivats zeigen die erfindungsgemäßen Polymere auch keine bzw. nur vernachlässigbare Vernetzung und sind daher vorteilhafterweise, wenn nicht sogar wasserlöslich, so doch zumindest leicht in Wasser dispergierbar. Von besonderem Vorteil ist, daß auf diese Weise auch die hochmolekularen erfindungsgemäßen Polymere in Wasser löslich bzw. dispergierbar sind. Soweit die erfindungsgemäßen Polymere lediglich wasserdispergierbar sind, sind sie in mindestens einem (vorzugsweise polaren) organischen Lösungsmittel oder in einem Lösungsmitteige- misch, insbesondere einem Gemisch von Wasser und organischem Lösungsmittel, vollständig löslich. Als Beispiele für geeignete polare Lösungsmittel seien Cι-C4-Alka- nole, wie Methanol, Ethanol und Isopropanol, cyclische und acyclische Ether, wie Dioxan, Tetrahydrofuran und Ethylenglykoldimethylether, Aceton, Dimethylformamid und N-Methylpyrrolidon genannt.Because of this extremely low to nonexistent multiple esterification of the saccharide or saccharide derivative, the polymers according to the invention also show no or only negligible crosslinking and are therefore advantageously, if not even water-soluble, at least easily dispersible in water. It is particularly advantageous that the high molecular weight polymers according to the invention are soluble or dispersible in water in this way. If the polymers according to the invention are only water-dispersible, they are in at least one (preferably polar) organic solvent or in a solvent. mixed, especially a mixture of water and organic solvent, completely soluble. Examples of suitable polar solvents are C 1 -C 4 -alkanols, such as methanol, ethanol and isopropanol, cyclic and acyclic ethers, such as dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, acetone, dimethylformamide and N-methylpyrrolidone.
Als Basis für die ethylenisch ungesättigten Saccharidmonomere (A) eignen sich als Saccharide insbesondere Mono-, Di- und Oligosaccharide, wobei Aldosen und Ketosen geeignet sind. Bevorzugt sind Aldo- und Keto-Pentosen und -Hexosen. Die Oligo- saccharide können bis zu 20, vorzugsweise bis zu 5 Saccharideinheiten enthalten. Besonders geeignet sind Mono- und Disaccharide, wobei Monosaccharide ganz besonders geeignet sind.Mono-, di- and oligosaccharides are particularly suitable as saccharides as the basis for the ethylenically unsaturated saccharide monomers (A), aldoses and ketoses being suitable. Aldo and keto pentoses and hexoses are preferred. The oligosaccharides can contain up to 20, preferably up to 5, saccharide units. Mono- and disaccharides are particularly suitable, monosaccharides being very particularly suitable.
Als Saccharidderivate eignen sich insbesondere die Cι-C30-, vor allem die CrC1 - Alkylglucoside und -polyglucoside dieser Saccharide.Particularly suitable saccharide derivatives are the C 1 -C 30 -, especially the CrC 1 - alkyl glucosides and polyglucosides of these saccharides.
Geeignete Saccharide und Saccharidderivate basieren vor allem auf Glucose, Fructo- se, Lactose, Saccharose, Cellobiose, Maltodextrinen oder Inulinen oder deren C-rC-30- Alkylglucosiden oder -polyglucosiden. Bevorzugt sind dabei Glucose, Fructose, Saccharose, Cellobiose, Maltodextrine und deren C C^-Alkylglucoside, besonders bevorzugt sind Glucose und deren C C4-Alkylglucoside.Suitable saccharides and saccharide derivatives are based primarily on glucose, fructose, lactose, sucrose, cellobiose, maltodextrins or inulins or their C-rC- 30 alkylglucosides or polyglucosides. Glucose, fructose, sucrose, cellobiose, maltodextrins and their CC ^ -alkyl glucosides are preferred, and glucose and their CC 4 -alkyl glucosides are particularly preferred.
Bevorzugt ist die Veresterung bei den Monomeren (A) zu über 50% an einer -CH2-OH- Gruppe des Saccharids erfolgt. Besonders bevorzugt wird selektiv eine derartige Alko- holgruppe zu über 75% und ganz besonders bevorzugt zu über 90% verestert.The esterification of the monomers (A) is preferably over 50% on a -CH 2 -OH group of the saccharide. Such an alcohol group is particularly preferably selectively esterified to over 75% and very particularly preferably to over 90%.
Die monoethylenisch ungesättigten Saccharidmonomere (A) können, wie beispielsweise in der nicht vorveröffentlichten DE-A-101 56 352 beschrieben, erhalten werden, indem man das Saccharid bzw. Saccharidderivat in Anwesenheit eines Acrylat- gruppen übertragenden Enzyms sowie in Gegenwart eines organischen Lösungsmittels (weniger als 4,8 ml pro mmol Saccharid(derivat)) mit (Meth)Acrylsäure oder einem C Cιo-AIkyl(meth)acrylsäureester umsetzt.The monoethylenically unsaturated saccharide monomers (A) can be obtained, as described, for example, in the unpublished DE-A-101 56 352, by the saccharide or saccharide derivative in the presence of an enzyme which transfers acrylate groups and in the presence of an organic solvent (less than 4.8 ml per mmol saccharide (derivative)) with (meth) acrylic acid or a C Cιo-alkyl (meth) acrylic acid ester.
Das molare Verhältnis von (Meth)Acrylsäure(ester) zu Saccharid (derivat) beträgt dabei bevorzugt 10 : 1 bis 3 : 1. Die anfängliche Saccharid(derivat)konzentration liegt insbesondere bei 0,1 bis 20, vorzugsweise bei 0,15 bis 10 mol/l Reaktionsgemisch.The molar ratio of (meth) acrylic acid (ester) to saccharide (derivative) is preferably 10: 1 to 3: 1. The initial saccharide (derivative) concentration is in particular 0.1 to 20, preferably 0.15 to 10 mol / l reaction mixture.
Geeignete Acrylatgruppen übertragende Enzyme sind Hydrolasen, vorzugsweise Esterasen (E.C. 3.1.-.-), insbesondere Lipasen (E.C. 3.1.1.3), sowie Glykolasen (E.C. 3.2.-.-) und Proteasen (E.C. 3.4.-.-) in freier oder immobilisierter Form. Besonders geeignet sind Novozym 435 (Lipase aus Candida antartica B) oder Lipase aus Aspergillus sp., Burholderia sp., Candida sp., Pseudomonas sp. oder Schweinepan- kreas. Der Enzymgehalt im Reaktionsmedium liegt üblicherweise im Bereich von 0,1 bis 10 Gew.-%, bezogen auf das Saccharid(derivat).Suitable enzymes that transfer acrylate groups are hydrolases, preferably esterases (EC 3.1. .-), in particular lipases (EC 3.1.1.3), and glycolases (EC 3.2.-.-) and proteases (EC 3.4.-.-) in free or immobilized form. Novozym 435 (lipase from Candida antartica B) or lipase from Aspergillus sp., Burholderia sp., Candida sp., Pseudomonas sp. Are particularly suitable. or pork pancreas. The enzyme content in the reaction medium is usually in the range from 0.1 to 10% by weight, based on the saccharide (derivative).
Als organisches Lösungsmittel eignen sich insbesondere C3-C6-Alkanole, wie tert.-Bu- tanol und tert.-Amylalkohol, Pyridin, Polyethylenglykoldi-Cι-C4-alkylether, wie Diethy- lenglykoldimethylether und Polyethylenglykoldimethylether (Mn 500), C C4-AIkylen- carbonate, wie Propylencarbonat, Essigsäure-C3-C6-alkylester, wie Essigsäure-tert.- butylester, Aceton und aliphatische und cycloaliphatische Ether, wie Dimethoxyme- than, Dimethoxyethan, 1,4-Dioxan, 1,3-Dioxolan und Tetrahydrofuran, sowie auch deren Mischungen. Die bevorzugt eingesetzte Lösungsmittelmenge beträgt 0,01 bis 4, insbesondere 0,1 bis 3 ml/mmol Saccharid(derivat).Suitable organic solvents are, in particular, C 3 -C 6 -alkanols, such as tert-butanol and tert-amyl alcohol, pyridine, polyethylene glycol di-C 1 -C 4 -alkyl ethers, such as diethylene glycol dimethyl ether and polyethylene glycol dimethyl ether (M n 500), CC 4 alkylene carbonates, such as propylene carbonate, C 3 -C 6 alkyl acetate, such as tert-butyl acetate, acetone and aliphatic and cycloaliphatic ethers, such as dimethoxy methane, dimethoxyethane, 1,4-dioxane, 1, 3-dioxolane and tetrahydrofuran, as well as their mixtures. The preferred amount of solvent used is 0.01 to 4, in particular 0.1 to 3 ml / mmol saccharide (derivative).
Das organische Lösungsmittel kann auch in Kombination mit wäßrigen Lösungsmitteln, wie Wasser selbst oder verdünnten wäßrigen Puffern (in der Regel 10 bis 100 mM), beispielsweise Puffern für den pH-Bereich 6 bis 8, wie Kaliumphosphat- oder TRIS- HCI-Puffem, zum Einsatz kommen.The organic solvent can also be used in combination with aqueous solvents, such as water itself or dilute aqueous buffers (usually 10 to 100 mM), for example buffers for the pH range 6 to 8, such as potassium phosphate or TRIS-HCl buffers Come into play.
Die Veresterung des Saccharid (derivat)s wird im allgemeinen bei 0 bis 70°C, insbesondere bei 20 bis 60°C, durchgeführt.The esterification of the saccharide (derivative) is generally carried out at 0 to 70 ° C., in particular at 20 to 60 ° C.
Als monoethylenisch ungesättigte Comonomere (B) können die erfindungsgemäßen Polymere nichtionische wasserunlösliche Monomere (B1), anionische Monomere (B2), kationische Monomere (B3) und/oder nichtionische wasserlösliche Monomere (B4) einpolymerisiert enthalten.As monoethylenically unsaturated comonomers (B), the polymers according to the invention can contain copolymerized nonionic water-insoluble monomers (B1), anionic monomers (B2), cationic monomers (B3) and / or nonionic water-soluble monomers (B4).
Geeignete nichtionische wasserunlösliche Monomere (B1) sind solche monoethyle- nisch ungesättigten Monomere, deren Löslichkeit in Wasser bei Raumtemperatur < 100 g/l beträgt. Der Einbau dieser Monomere führt zu einer partiellen Hydrophobierung der erfindungsgemäßen Polymere. Ihre Wasserlöslichkeit wird durch kleinere Anteile dieser Monomere jedoch nicht nachteilig beeinflußt. Im Fall höherer Anteile an Monomeren (B1) sind die erfindungsgemäßen Polymere nicht mehr vollständig was- serlöslich, aber wasserdispergierbar. Als Monomere (B1 ) eignen sich beispielsweise:Suitable nonionic water-insoluble monomers (B1) are those monoethylenically unsaturated monomers whose solubility in water at room temperature is <100 g / l. The incorporation of these monomers leads to partial hydrophobization of the polymers according to the invention. However, their solubility in water is not adversely affected by smaller proportions of these monomers. In the case of higher proportions of monomers (B1), the polymers according to the invention are no longer completely water-soluble, but are water-dispersible. Examples of suitable monomers (B1) are:
Ester von monoethylenisch ungesättigten C3-C6-Carbonsäuren, vor allem Acrylsäure und Methacrylsäure, und einwertigen CrC^-Alkoholen sowie Hydroxyalkyl- ester von monoethylenisch ungesättigten C3-C6-Carbonsäuren, vor allem Acrylsäu- re und Methacrylsäure, und zweiwertigen C2-C4-Alkoholen, wie Methyl(meth)- acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat, sec.-Butyl(meth)acrylat, tert.- Butyl(meth)acrylat, Ethylhexyl(meth)acrylat, Hydroxyethyl(meth)acrylat und Hydro- xypropyl(meth)acrylat,Esters of monoethylenically unsaturated C 3 -C 6 carboxylic acids, especially acrylic acid and methacrylic acid, and monohydric CrC ^ alcohols and hydroxyalkyl esters of monoethylenically unsaturated C 3 -C 6 carboxylic acids, especially acrylic acid and methacrylic acid, and dibasic C 2 -C 4 alcohols, such as methyl (meth) - acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert.-butyl (meth) acrylate, ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate and hydroxypropyl ( meth) acrylate,
Vinylester von gesättigten Cι-C18-Carbonsäuren, wie Vinylacetat und Vinylpropio- nat,Vinyl esters of saturated C 18 -carboxylic acids, such as vinyl acetate and vinyl propionate,
- aliphatische und aromatische Olefine, wie Ethylen, Propylen, C -C24-α-Olefine, z.B. Butylen, Isobutylen, Diisobuten, Styrol und α-Methylstyrol, sowie auch Diolefine mit einer aktiven Doppelbindung, z.B. Butadien,aliphatic and aromatic olefins, such as ethylene, propylene, C -C 24 -α-olefins, for example butylene, isobutylene, diisobutene, styrene and α-methylstyrene, and also diolefins with an active double bond, for example butadiene,
ungesättigte Nitrile, wie Acrylnitril und Methacrylnitril, undunsaturated nitriles such as acrylonitrile and methacrylonitrile, and
fluorhaltige Monomere, vor allem fluorhaltige Olefine, wie Fluorethylen, Tetrafluorethylen, Chiortrifluorethylen, Vinylidenfluorid und Hexafluorpropen sowiefluorine-containing monomers, especially fluorine-containing olefins, such as fluorethylene, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride and hexafluoropropene, and
Mischungen dieser Monomere.Mixtures of these monomers.
Bevorzugte Monomere (B1) sind Methyl(meth)acrylat, Ethylacrylat, n-Butyl(meth)- acrylat, sec.-Butylacrylat, tert-Butylacrylat, Ethylhexylacrylat, Hydroxyethylacrylat, Hydroxypropylacrylat, Vinylacetat, Vinylproprionat, Ethylen, Propylen, Butylen, Diisobuten, Styrol und Tetrafluorethylen. Besonders bevorzugt sind dabei Methyl(meth)acrylat, Ethylacrylat, n- und tert.-Butylacrylat und Vinylacetat.Preferred monomers (B1) are methyl (meth) acrylate, ethyl acrylate, n-butyl (meth) acrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, vinyl acetate, vinyl propionate, ethylene, propylene, butylene, diisobutene, Styrene and tetrafluoroethylene. Methyl (meth) acrylate, ethyl acrylate, n- and tert-butyl acrylate and vinyl acetate are particularly preferred.
Die erfindungsgemäßen Polymere können 5 bis 99 Gew.-% der Monomere (A), 1 bis 60 Gew.-% der Monomere (B1 ) und 0 bis 35 Gew.-% weiterer, von (B1 ) verschiedener Monomere enthalten.The polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 60% by weight of the monomers (B1) and 0 to 35% by weight of further monomers different from (B1).
Bevorzugte erfindungsgemäße Polymere weisen einen Gehalt von 5 bis 95 Gew.-%, insbesondere 60 bis 90 Gew.-%, der Monomere (A) und 5 bis 50 Gew.-%, vor allem 10 bis 40 Gew.-%, der Monomere (B1 ) auf.Preferred polymers according to the invention have a content of 5 to 95% by weight, in particular 60 to 90% by weight, of the monomers (A) and 5 to 50% by weight, especially 10 to 40% by weight, of the monomers (B1).
Als anionische, d.h. saure Gruppen enthaltende, monoethylenisch ungesättigte Monomere (B2) eignen sich beispielsweise:As anionic, i.e. Monoethylenically unsaturated monomers (B2) containing acidic groups are suitable, for example:
- α, ?-ungesättigte C3-C6-Monocarbonsäuren und deren Salze, wie Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure und Vinylessigsäure,α,? -unsaturated C 3 -C 6 monocarboxylic acids and their salts, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid and vinyl acetic acid,
monoethylenisch ungesättigte C4-C6-Dicarbonsäuren, vor allem Maleinsäure und Itaconsäure, deren Anhydride, Salze und Halbester mit CτC-6-Alkoholen, monoethylenisch ungesättigte Sulfonsäuren und Phosphonsäuren sowie deren Salze, wie Acrylamido-2-methylpropansulfonsäure, Vinylsulfonsäure, Methallylsul- fonsäure und Vinylphosphonsäure.monoethylenically unsaturated C 4 -C 6 dicarboxylic acids, especially maleic acid and itaconic acid, their anhydrides, salts and half-esters with CτC 6 alcohols, monoethylenically unsaturated sulfonic acids and phosphonic acids and their salts, such as acrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid, methallylsulfonic acid and vinyl phosphonic acid.
Bevorzugte Monomere (B2) sind Acrylsäure, Methacrylsäure, Maleinsäure, Maleinsäureanhydrid, Maleinsäurehalbester, Acrylamido-2-methylpropansulfonsäure, Vinylsulfonsäure und Vinylphosphonsäure. Besonders bevorzugt sind Acrylsäure und Methacrylsäure.Preferred monomers (B2) are acrylic acid, methacrylic acid, maleic acid, maleic anhydride, maleic acid semiesters, acrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid and vinyl phosphonic acid. Acrylic acid and methacrylic acid are particularly preferred.
Die erfindungsgemäßen Polymere können 5 bis 99 Gew.-% der Monomere (A), 1 bis 95 Gew.-% der Monomere (B2) und 0 bis 35 Gew.-% weiterer, von (B2) verschiedener Monomere enthalten.The polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 95% by weight of the monomers (B2) and 0 to 35% by weight of other monomers different from (B2).
Bevorzugte erfindungsgemäße Polymere weisen einen Gehalt von 40 bis 95 Gew.-%, insbesondere 40 bis 90 Gew.-%, der Monomere (A) und 5 bis 80 Gew.-%, vor allem 10 bis 60 Gew.-%, der Monomere (B2) auf.Preferred polymers according to the invention have a content of 40 to 95% by weight, in particular 40 to 90% by weight, of the monomers (A) and 5 to 80% by weight, especially 10 to 60% by weight, of the monomers (B2).
Als kationische monoethylenisch ungesättigte Monomere (B3) sind insbesondere ge- eignet:The following are particularly suitable as cationic monoethylenically unsaturated monomers (B3):
Vinylimidazol- und Vinylimidazolineinheiten enthaltende Monomere und deren Alkylderivate, insbesondere CrC-5-Alkylderivate, sowie deren Quaternisierungs- produkte, wie N-Vinylimidazol, N-Vinyl-2-methylimidazol, N-Vinyl-4-methylimidazol, N-Vinyl-5-methylimidazoI, N-Vinyl-2-ethylimidazol, N-Vinylimidazolin, N-Vinyl-2- methylimidazolin und N-Vinyl-2-ethylimidazolin,Monomers containing vinylimidazole and vinylimidazoline units and their alkyl derivatives, in particular CrC- 5 alkyl derivatives, and their quaternization products, such as N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5- methylimidazole, N-vinyl-2-ethylimidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline,
basische Ester von ethylenisch ungesättigten Carbonsäuren, insbesondere die Ester von α,ß-ungesättigten C3-C6-Monocarbonsäuren, vor allem Acrylsäure und Methacrylsäure, mit Aminoaikoholen, vor allem N,N-Di-CrC4-alkylamino-C2-C6- alkoholen, und deren Quaternisierungsprodukte, wie Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Dimethylaminopropylacrylat, Dimethylaminopro- pylmethacrylat, Diethylaminoethylacrylat, Diethylaminopropylacrylat, Dimethylami- nobutylacrylat und Diethylaminobutylacrylat,basic esters of ethylenically unsaturated carboxylic acids, especially the esters of α, β-unsaturated C 3 -C 6 monocarboxylic acids, especially acrylic acid and methacrylic acid, with amino alcohols, especially N, N-Di-CrC 4 -alkylamino-C 2 -C 6 - alcohols, and their quaternization products, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminoethyl acrylate, diethylaminopropyl acrylate, dimethylamino-nobutyl acrylate and diethylaminobutyl acrylate,
basische Amide von ethylenisch ungesättigten Carbonsäuren, insbesondere die N.N-Di-Ci-C^alkylamino-Ca-Ce-alkylamide von α,ß-ungesättigten C3-C6-Mono- carbonsäuren, vor allem Acrylsäure und Methacrylsäure, und deren Quaternisierungsprodukte, wie Dimethylaminoethylacrylamid, Dimethylaminoethylmethacryl- amid, Diethylaminoethylacrylamid, Diethylaminoethylmethacrylamid, Dimethylami- nopropylacrylamid, Dimethylaminopropylmethacrylamid, Diethylaminopropylacryl- amid und Diethylaminopropylmethacrylamid, undbasic amides of ethylenically unsaturated carboxylic acids, in particular the NN-di-Ci-C ^ alkylamino-Ca-Ce-alkylamides of α, β-unsaturated C 3 -C 6 monocarboxylic acids, especially acrylic acid and methacrylic acid, and their quaternization products, such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylic amide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, dimethylaminopropyl methacrylamide, diethylaminopropylacrylamide and diethylaminopropyl methacrylamide, and
- basische Diallylalkylamine, insbesondere die Diallyl-C C4-alkylamine, und deren Quatemisierungsprodukte, wie Diallylmethylamin und Diallyldimethylammonium- chlorid, und- Basic diallylalkylamines, especially the diallyl-C 4 -alkylamines, and their quaternization products, such as diallylmethylamine and diallyldimethylammonium chloride, and
Vinylpyridine und deren Quatemisierungsprodukte, wie 4-Vinylpyridin, 2-Vinyl- pyridin, N-Methyl-4-vinyIpyridin und N-Methyl-2-vinylpyridin.Vinyl pyridines and their quaternization products, such as 4-vinyl pyridine, 2-vinyl pyridine, N-methyl-4-vinyl pyridine and N-methyl-2-vinyl pyridine.
Die Monomere (B3) können in Form der freien Basen oder der Salze mit anorganischen Säuren, wie Salzsäure, Schwefelsäure, Phosphorsäure und Salpetersäure, oder organischen Säuren, wie Ameisensäure, Essigsäure und Propionsäure, oder in qua- ternisierter Form eingesetzt werden. Geeignete Quatemisierungsmittel sind insbesondere Alkylierungsmittel, wie Dimethylsulfat, Diethylsulfat, Methylchlorid, Ethylchlorid und Benzylchlorid.The monomers (B3) can be used in the form of the free bases or the salts with inorganic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, or organic acids, such as formic acid, acetic acid and propionic acid, or in quaternized form. Suitable quaternizing agents are in particular alkylating agents, such as dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and benzyl chloride.
Besonders geeignete Monomere (B3) sind Dimethylaminoethylacrylat, Dimethylami- nopropylacrylat, Dimethylaminoethylmethacrylat, Dimethylaminopropylmethacrylat, Dimethylaminoethylacrylamid, Dimethylaminopropylacrylamid, Vinylimidazol und deren mit Methylchlorid oder Dimethylsulfat quaternisierte Derivate. Besonders bevorzugt sind Dimethylaminoethylacrylat, Vinylimidazol und deren mit Methylchlorid oder Dimethylsulfat quaternisierte Derivate.Particularly suitable monomers (B3) are dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylamide, dimethylaminopropylacrylamide, vinylimidazole and their derivatives quaternized with methyl chloride or dimethyl sulfate. Dimethylaminoethyl acrylate, vinylimidazole and their derivatives quaternized with methyl chloride or dimethyl sulfate are particularly preferred.
Die erfindungsgemäßen Polymere können 5 bis 99 Gew.-% der Monomere (A), 1 bis 95 Gew.-% der Monomere (B3) und 0 bis 35 Gew.-% weiterer, von (B3) verschiedener Monomere enthalten.The polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 95% by weight of the monomers (B3) and 0 to 35% by weight of further monomers different from (B3).
Bevorzugte erfindungsgemäße Polymere weisen einen Gehalt von 40 bis 98 Gew.-%, insbesondere 50 bis 95 Gew.-%, der Monomere (A) und 2 bis 60 Gew.-%, vor allem 5 bis 50 Gew.-%, der Monomere (B3) auf.Preferred polymers according to the invention have a content of 40 to 98% by weight, in particular 50 to 95% by weight, of the monomers (A) and 2 to 60% by weight, especially 5 to 50% by weight, of the monomers (B3) on.
Geeignete nichtionische wasserlösliche Monomere (B4) sind schließlich solche mono- ethylenisch ungesättigten Monomere, deren Löslichkeit in Wasser bei Raumtemperatur >100 g/l beträgt. Der Einbau dieser Monomere führt zu weitgehend hydrophilen wasserlöslichen erfindungsgemäßen Polymeren. Als Monomere (B4) eignen sich beispielsweise: Ester von monoethylenisch ungesättigten C3-C6-Carbonsäuren, vor allem Acrylsäure und Methacrylsäure, und C C^Alkylpolyalkylenglykolen mit 2 bis 40 C2-C4- Alkylenglykoleinheiten,Finally, suitable nonionic water-soluble monomers (B4) are those monoethylenically unsaturated monomers whose solubility in water at room temperature is> 100 g / l. The incorporation of these monomers leads to largely hydrophilic water-soluble polymers according to the invention. Examples of suitable monomers (B4) are: Esters of monoethylenically unsaturated C 3 -C 6 carboxylic acids, especially acrylic acid and methacrylic acid, and CC ^ alkyl polyalkylene glycols with 2 to 40 C 2 -C 4 alkylene glycol units,
- Amide von monoethylenisch ungesättigten C3-C6-Carbonsäuren, vor allem Acrylsäure und Methacrylsäure, mit primären und sekundären Cι-C- -Aminen und end- gruppenaminierten CτC4-Alkylpolyalkylenglykolen mit 2 bis 40 C2-C -Alkylengly- koleinheiten, wie (Meth)AcryΙamid, N-Methyl(meth)acrylamid und N-Butyl(meth)- acrylamid und Amide von (Meth)Acrylsäure mit endgruppenaminierten Methylpoly- alkylenglykolen mit 2 bis 40 C2-C4-Alkylenglykoleinheiten, undAmides of monoethylenically unsaturated C 3 -C 6 carboxylic acids, especially acrylic acid and methacrylic acid, with primary and secondary C 1 -C amines and end group-aminated CτC 4 alkyl polyalkylene glycols with 2 to 40 C 2 -C alkylene glycol units, such as (meth) acrylic amide, N-methyl (meth) acrylamide and N-butyl (meth) acrylamide and amides of (meth) acrylic acid with methyl polyalkylene glycols end-group-aminated with 2 to 40 C 2 -C 4 -alkylene glycol units, and
N-Vinylamide von gesättigten Cι-C-|8-Carbonsäuren und N-Vinyllactame von Lac- tamen mit 5- bis 7-gliedrigen Ringen, wie N-Vinylformamid, N-Vinylacetamid, N-Vinylpyrrolidon, N-Vinylcaprolactam und N-Vinyloxazolidon.N-vinylamides of saturated Cι-C- | 8- carboxylic acids and N-vinyl lactams of lactams with 5- to 7-membered rings, such as N-vinyl formamide, N-vinyl acetamide, N-vinyl pyrrolidone, N-vinyl caprolactam and N-vinyl oxazolidone.
Bevorzugte Monomere (B4) sind Acrylamid, N-Vinylformamid und N-Vinylpyrrolidon.Preferred monomers (B4) are acrylamide, N-vinylformamide and N-vinylpyrrolidone.
Die erfindungsgemäßen Polymere können 5 bis 99 Gew.-% der Monomere (A), 1 bis 95 Gew.-% der Monomere (B4) und 0 bis 35 Gew.-% weiterer, von (B4) verschiedener Monomere enthalten.The polymers according to the invention can contain 5 to 99% by weight of the monomers (A), 1 to 95% by weight of the monomers (B4) and 0 to 35% by weight of other monomers different from (B4).
Bevorzugte erfindungsgemäße Polymere weisen einen Gehalt von 20 bis 95 Gew.-%, insbesondere 40 bis 90 Gew.-%, der Monomere (A) und 5 bis 80 Gew.-%, vor allem 10 bis 60 Gew.-%, der Monomere (B4) auf.Preferred polymers according to the invention have a content of 20 to 95% by weight, in particular 40 to 90% by weight, of the monomers (A) and 5 to 80% by weight, especially 10 to 60% by weight, of the monomers (B4).
Besonders bevorzugte erfindungsgemäße Polymere stellen die Copolymere der Monomere (A) mit nichtionischen wasserunlöslichen Monomeren (B1), anionischen Monomeren (B2) oder kationischen Monomeren (B3) dar, also die hydrophob, anionisch oder kationisch modifizierten Polymere.Particularly preferred polymers according to the invention are the copolymers of the monomers (A) with nonionic water-insoluble monomers (B1), anionic monomers (B2) or cationic monomers (B3), that is to say the hydrophobic, anionically or cationically modified polymers.
Die erfindungsgemäßen Polymere haben eine mittlere Molmasse Mw von 5000 bis 2500 000. Bevorzugt beträgt ihre mittlere Molmasse Mw 10 000 bis 1 000000, besonders bevorzugt 25 000 bis 750000 und ganz besonders bevorzugt 50 000 bis 500 000.The polymers according to the invention have an average molecular weight M w of 5,000 to 2,500,000. Their average molecular weight M w is preferably 10,000 to 1,000,000, particularly preferably 25,000 to 750,000 and very particularly preferably 50,000 to 500,000.
Die Molmassen der erfindungsgemäßen Polymere können mittels bekannter Methoden durch Lösen in einem geeigneten Lösungsmittel und anschließende Charakterisierung durch Viskosimetrie, Lichtstreuung oder Gelpermeationschromatographie bestimmt werden. Die in den Beispielen angegebenen mittleren Molmassen Mw wurden durch Gelpermeationschromatographie in Wasser bestimmt. Die erfindungsgemäßen Polymere sind vorteilhaft nach dem ebenfalls erfindungsgemäßen Herstellungsverfahren zu erhalten, welches dadurch gekennzeichnet ist, daß man die Monomere (A) und gewünschtenfalls (B) einer radikalischen Polymerisation in einem polaren Lösungsmittel, vorzugsweise in Wasser oder Mischungen von Wasser und polaren organischen Lösungsmitteln, insbesondere C C4-Alkoholen und Aceton, unterwirft.The molecular weights of the polymers according to the invention can be determined by known methods by dissolving them in a suitable solvent and then characterizing them by viscometry, light scattering or gel permeation chromatography. The average molecular weights M w given in the examples were determined by gel permeation chromatography in water. The polymers according to the invention can advantageously be obtained by the production process likewise according to the invention, which is characterized in that the monomers (A) and, if desired (B), a radical polymerization in a polar solvent, preferably in water or mixtures of water and polar organic solvents, in particular CC 4 alcohols and acetone.
Grundsätzlich können die erfindungsgemäßen Polymere auch durch Fällungspolymerisation, Emulsionspolymerisation, Polymerisation in Wasser-in-ÖI-Emulsionen (W/O) oder umgekehrte Suspensionspolymerisation hergestellt werden, die Lösungspolymerisation, insbesondere in wasserhaltigen Lösungsmitteln, vor allem in Wasser selbst, ist jedoch bevorzugt.In principle, the polymers according to the invention can also be prepared by precipitation polymerization, emulsion polymerization, polymerization in water-in-oil emulsions (W / O) or reverse suspension polymerization, but solution polymerization, in particular in water-containing solvents, especially in water itself, is preferred.
Als Polymerisationsinitiatoren eignen sich sowohl thermisch als auch photochemisch (Photoinitiatoren) zerfallende und dabei Radikale bildende Verbindungen.Compounds which decompose thermally and photochemically (photoinitiators) and thereby form free radicals are suitable as polymerization initiators.
Unter den thermisch aktivierbaren Polymerisationsinitiatoren sind Initiatoren mit einer Zerfallstemperatur im Bereich von 20 bis 180°C, insbesondere von 50 bis 90°C, bevorzugt. Beispiele für besonders bevorzugte thermische Initiatoren sind organische Per- oxide, wie Dibenzoylperoxid und Di-tert.-butylperoxid, Perester, Perketale, Hydroperoxide, anorganische Peroxide, wie Wasserstoffperoxid, Percarbonate, Peroxosulfate, Peroxodisulfate, Azoverbindungen, Boralkylverbindungen und homolytisch zerfallende Kohlenwasserstoffe.Among the thermally activatable polymerization initiators, initiators with a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 90 ° C., are preferred. Examples of particularly preferred thermal initiators are organic peroxides, such as dibenzoyl peroxide and di-tert-butyl peroxide, peresters, perketals, hydroperoxides, inorganic peroxides, such as hydrogen peroxide, percarbonates, peroxosulfates, peroxodisulfates, azo compounds, boralkyl compounds and homolytically decomposing hydrocarbons.
Beispiele für geeignete Photoinitiatoren sind Benzophenon, Acetophenon, Benzoin- ether, Benzyldialkylketone und deren Derivate.Examples of suitable photoinitiators are benzophenone, acetophenone, benzoin ether, benzyl dialkyl ketones and their derivatives.
Die thermischen Initiatoren und/oder Photoinitiatoren werden je nach den Anforderungen des zu polymerisierenden Materials üblicherweise in Mengen von 0,01 bis 15 Gew.-%, bezogen auf die zu polymerisierenden Monomere, eingesetzt und können einzeln oder, zur Ausnutzung vorteilhafter synergistischer Effekte, in Kombination miteinander angewendet werden.Depending on the requirements of the material to be polymerized, the thermal initiators and / or photoinitiators are usually used in amounts of from 0.01 to 15% by weight, based on the monomers to be polymerized, and can be used individually or, to take advantage of advantageous synergistic effects Combination with each other.
Zur Begrenzung der Molmassen der erfindungsgemäßen Polymere können bei der Polymerisation übliche Regler, z.B. Mercaptoverbindungen, wie Mercaptoethanol und Thioglycolsäure, zugesetzt werden. Geeignete Reglermengen liegen im allgemeinen bei 0,01 und 3 Gew.-%, bezogen auf die zu polymerisierenden Monomere.To limit the molecular weights of the polymers according to the invention, customary regulators, e.g. Mercapto compounds such as mercaptoethanol and thioglycolic acid can be added. Suitable regulator amounts are generally 0.01 and 3% by weight, based on the monomers to be polymerized.
Die Polymerisationstemperatur beträgt in der Regel 40 bis 120°C, bevorzugt 60 bis 100°C. Die erfindungsgemäßen wasserlöslichen oder wasserdispergierbaren Polymere lassen sich in vielen technischen Anwendungen vorteilhaft einsetzen. Insbesondere eignen sie sich als Zusatz zu Waschmitteln, Wäschevor- und -nachbehandlungsmitteln, Rei- nigungs- und Pflegemittelformulierungen, kosmetischen Präparationen, Haarsprays und Körperpflegemitteln, als Textilhilfsmittel, Papierhilfsmittel, Klebhilfsmittel, Betonadditiv, Folienmaterial, Dispergiermittel für anorganische und organische wäßrige Pigmentpräparationen, Belagsinhibitoren, Schutzkolloid für die Herstellung von Emulsionen und für die Emulsionspolymerisation sowie als Beschichtungshilfsmittel für den Schutz harter Oberflächen.The polymerization temperature is generally 40 to 120 ° C, preferably 60 to 100 ° C. The water-soluble or water-dispersible polymers according to the invention can be used advantageously in many industrial applications. They are particularly suitable as an additive to detergents, laundry pretreatment and aftertreatment agents, cleaning and care product formulations, cosmetic preparations, hair sprays and personal care products, as textile auxiliaries, paper aids, adhesive aids, concrete additive, film material, dispersants for inorganic and organic aqueous pigment preparations, coatings. Protective colloid for the production of emulsions and for emulsion polymerization as well as a coating aid for the protection of hard surfaces.
Der Einbau der Comonomere (B) erlaubt dabei eine zusätzliche Anpassung der erfindungsgemäßen Polymere an die jeweiligen Anwendungserfordernisse.The incorporation of the comonomers (B) allows the polymers according to the invention to be additionally adapted to the respective application requirements.
So können die hydrophob modifizierten, also die Monomere (B1) einpolymerisiert ent- haltenden, erfindungsgemäßen Polymere besonders vorteilhaft als Zusatz zu Waschmitteln, Wäschevor- und -nachbehandlungsmitteln, Reinigungs- und Pflegemittelformulierungen, kosmetischen Präparationen und Haarsprays, als Textilhilfsmittel, Klebhilfsmittel, Folienmaterial, Schutzkolloid für die Herstellung von Emulsionen und für die Emulsionspolymerisation sowie als Beschichtungshilfsmittel für den Schutz harter Oberflächen verwendet werden.For example, the hydrophobically modified polymers according to the invention, which contain the monomers (B1) in copolymerized form, can be used particularly advantageously as an additive to detergents, laundry pretreatment and post-treatment agents, cleaning and care agent formulations, cosmetic preparations and hair sprays, as textile auxiliaries, adhesive aids, film material, protective colloid be used for the production of emulsions and for emulsion polymerization as well as a coating aid for the protection of hard surfaces.
Die anionisch modifizierten, also die Monomere (B2) einpolymerisiert enthaltenden, erfindungsgemäßen Polymere eignen sich ganz besonders als Zusatz zu Waschmitteln, Wäschevorbehandlungsmitteln, Reinigungs- und Pflegemittelformulierungen und kosmetischen Präparationen, als Textilhilfsmittel, Klebhilfsmittel, Betonadditiv, Dispergiermittel für anorganische und organische wäßrige Pigmentpräparationen, Belagsinhibitoren, Schutzkolloid für die Herstellung von Emulsionen und für die Emulsionspolymerisation sowie als Beschichtungshilfsmittel für den Schutz harter Oberflächen.The anionically modified polymers according to the invention, which contain the monomers (B2) in copolymerized form, are particularly suitable as additives for detergents, laundry pretreatment agents, cleaning and care product formulations and cosmetic preparations, as textile auxiliaries, adhesive aids, concrete additives, dispersants for inorganic and organic aqueous pigment preparations, and coating inhibitors , Protective colloid for the production of emulsions and for emulsion polymerization as well as a coating aid for the protection of hard surfaces.
Die kationisch modifizierten, also die Monomere (B3) einpolymerisiert enthaltenden, erfindungsgemäßen Polymere können besonders vorteilhaft als Zusatz zu Waschmitteln, Wäschevor- und -nachbehandlungsmitteln, Pflegemittelformulierungen, kosmetischen Präparationen, Haarsprays und Körperpflegemitteln, als Textilhilfsmittel, Papierhilfsmittel, Klebhilfsmittel, Schutzkolloid für die Herstellung von Emulsionen und für die Emulsionspolymerisation sowie als Beschichtungshilfsmittel für den Schutz harter Oberflächen eingesetzt werden.The cationically modified polymers according to the invention, which contain the monomers (B3) in copolymerized form, can be used particularly advantageously as an additive to detergents, laundry pretreatment and aftertreatment agents, care product formulations, cosmetic preparations, hair sprays and personal care products, as textile auxiliaries, paper auxiliaries, adhesive auxiliaries, and protective colloid for the production of Emulsions and for emulsion polymerization as well as coating aids for the protection of hard surfaces.
Die nichtionisch hydrophil modifizierten, also die Monomere (B4) einpolymerisiert enthaltenden, erfindungsgemäßen Polymere sind schließlich besonders geeignet als Zu- satz zu Waschmitteln, Wäschevor- und -nachbehandlungsmitteln, Reinigungs- und Pflegemittelformulierungen, kosmetischen Präparationen und Körperpflegemitteln, als Textilhilfsmittel, Klebhilfsmittel, Folienmaterial, Schutzkolloid für die Herstellung von Emulsionen und für die Emulsionspolymerisation sowie als Beschichtungshilfsmittel für den Schutz harter Oberflächen.Finally, the nonionically hydrophilically modified, that is to say containing the monomers (B4) copolymerized, polymers according to the invention are particularly suitable as an additive to detergents, laundry pretreatment and aftertreatment agents, cleaning agents and Care formulations, cosmetic preparations and personal care products, as textile auxiliaries, adhesive aids, film material, protective colloid for the production of emulsions and for emulsion polymerization, and as coating aids for protecting hard surfaces.
Von besonderem Interesse ist die Verwendung der erfindungsgemäßen Polymere als Zusatz zu Waschmitteln und Wäschenachbehandlungsmitteln. Ihre Wirkungsweise ist dabei sehr vielfältig.Of particular interest is the use of the polymers according to the invention as an additive to detergents and laundry treatment agents. Their mode of action is very diverse.
So können sie als Formulierungshilfsmittel, z.B. als Bindemittel für Waschmittelgranulate und -tabletten und Verdickungsmittel für flüssige Waschmittel, als Faserschutzpolymere, Vergrauungsinhibitoren, als Belagsinhibitoren und Dispergiermittel für Schmutzpartikel dienen.So they can be used as formulation aids, e.g. serve as binders for detergent granules and tablets and thickeners for liquid detergents, as fiber protection polymers, graying inhibitors, as deposit inhibitors and dispersants for dirt particles.
Besondere Bedeutung hat dabei ihre Wirkung als Faserschutzpolymere für Textilien. Die erfindungsgemäßen Polymere können zu diesem Zweck nicht nur dem Waschmittel oder Wäschenachbehandlungsmittel zugesetzt werden, sondern auch in einem separaten Behandlungsschritt in gelöster Form durch Aufsprühen oder Spülen auf das Textilmaterial aufgebracht werden.Their effect as fiber protection polymers for textiles is particularly important. For this purpose, the polymers according to the invention can not only be added to the detergent or laundry aftertreatment agent, but can also be applied in a separate treatment step in dissolved form to the textile material by spraying or rinsing.
BeispieleExamples
I. Herstellung von erfindungsgemäßen PolymerenI. Preparation of polymers according to the invention
a) Herstellung des Monomers (A)a) Preparation of the monomer (A)
Eine Mischung von 0,75 mol (145,6 g) Methyl-α-D-glucopyranosid, 7,5 mol (645,7 g) Methylacrylat, 750 ml Aceton, 60 g Molekularsieb (5 A), 161 mg Phenothiazin und 15,0 g Novozym 435 wurde bei 60°C gerührt. Nach 24 h wurde abfiltriert und das Fil- trat im Vakuum eingeengt.A mixture of 0.75 mol (145.6 g) methyl-α-D-glucopyranoside, 7.5 mol (645.7 g) methyl acrylate, 750 ml acetone, 60 g molecular sieve (5 A), 161 mg phenothiazine and 15 , 0 g of Novozym 435 was stirred at 60 ° C. After 24 h the mixture was filtered off and the filtrate was concentrated in vacuo.
Es wurden 59,9 g 6-O-Acryloylmethylglucosid mit einem Wertgehalt von 92% erhalten (GC-Analyse: 7,6 Gew.-% Methylglucosid, 0,4 Gew.-% eines Diacrylates von Me- thylglucosid). b) Herstellung der Polymere59.9 g of 6-O-acryloylmethylglucoside with a value of 92% were obtained (GC analysis: 7.6% by weight of methylglucoside, 0.4% by weight of a diacrylate of methylglucoside). b) Preparation of the polymers
Polymer IPolymer I
In einem 11-Glasreaktor mit Ölbadheizung, Ankerrührer, 3 automatischen Zulaufdosiereinrichtungen, Innenthermometer, Stickstoff-Einleitung und Rückflußkühler wurden 39,8 g Wasser auf 100°C erhitzt und unter Einleiten von Stickstoff inertisiert.In an 11-glass reactor with oil bath heating, anchor stirrer, 3 automatic feed metering devices, internal thermometer, nitrogen inlet and reflux condenser, 39.8 g of water were heated to 100 ° C. and rendered inert while introducing nitrogen.
Unter Rückfluß wurden dann als Zulauf 1 510,0 g einer 23,1 gew.-%igen wäßrigen Lösung von 6-O-Acryloylmethylglucosid gleichmäßig in 5 h zudosiert. Gleichzeitig beginnend, wurden als Zulauf 2 eine Lösung von 3,6 g Natriumperoxodisulfat in 8,5 g Wasser und als Zulauf 3 eine Lösung von 8,3 g Natriumhypophosphit-Monohydrat in 7,7 g Wasser, gleichmäßig in 5,25 h zudosiert.Then, under reflux, 1,510.0 g of a 23.1% strength by weight aqueous solution of 6-O-acryloylmethylglucoside were metered in uniformly as feed over the course of 5 hours. Starting simultaneously, a solution of 3.6 g of sodium peroxodisulfate in 8.5 g of water was fed in as feed 2 and a solution of 8.3 g of sodium hypophosphite monohydrate in 7.7 g of water was fed in as feed 3, uniformly in 5.25 h.
Nach Beendigung aller Zuläufe wurde die Reaktionsmischung noch 1 h bei Siedetemperatur nachpolymerisiert, auf 30°C abgekühlt und mit 50 gew.-%iger Natronlauge neutralisiert (pH-Wert 7,0).After all feeds had ended, the reaction mixture was polymerized for a further 1 h at the boiling point, cooled to 30 ° C. and neutralized with 50% strength by weight sodium hydroxide solution (pH 7.0).
Der Feststoffgehalt der erhaltenen Polymerlösung betrug 19,6 Gew.-%. Die Molmasse Mw des Polymers betrug 6500 D.The solids content of the polymer solution obtained was 19.6% by weight. The molar mass M w of the polymer was 6500 D.
Polymer 2Polymer 2
Es wurde analog wie bei der Herstellung von Polymer 1 vorgegangen. Es wurden je- doch 182,2 g Wasser vorgelegt, und als Zuläufe wurden folgende Lösungen eingesetzt:The procedure was analogous to that for the preparation of polymer 1. However, 182.2 g of water were initially introduced and the following solutions were used as feeds:
Zulauf 1 : Mischung aus 172,6 g einer 45 gew.-%igen wäßrigen Lösung von 6-O- Acryloylmethylglucosid, 22,9 g Methacrylsäure und 4,6 g Wasser Zulauf 2: Lösung von 1 ,5 g Natriumperoxodisulfat in 18,5 g WasserFeed 1: Mixture of 172.6 g of a 45% strength by weight aqueous solution of 6-O-acryloylmethylglucoside, 22.9 g of methacrylic acid and 4.6 g of water. Feed 2: Solution of 1.5 g of sodium peroxodisulfate in 18.5 g of water
Zulauf 3: Lösung von 3,5 g Natriumhypophosphit-Monohydrat in 16,5 g WasserFeed 3: solution of 3.5 g of sodium hypophosphite monohydrate in 16.5 g of water
Durch Neutralisation mit 50 gew.-%iger Natronlauge wurde ein pH-Wert von 6,5 eingestellt.A pH of 6.5 was set by neutralization with 50% strength by weight sodium hydroxide solution.
Der Feststoffgehalt der erhaltenen Polymerlösung betrug 17,4 Gew.-%. Die Molmasse Mw des Polymers betrug 11 000 D. Polymer 3The solids content of the polymer solution obtained was 17.4% by weight. The molecular weight M w of the polymer was 11,000 D. Polymer 3
In einem 11-Glasreaktor mit Ölbadheizung, Ankerrührer, 2 automatischen Zulaufdosiereinrichtungen, Innenthermometer, Stickstoff-Einleitung und Rückflußkühler wurden 169,6 g Wasser auf 75°C erhitzt und unter Einleiten von Stickstoff inertisiert.In an 11-glass reactor with oil bath heating, anchor stirrer, 2 automatic feed metering devices, internal thermometer, nitrogen inlet and reflux condenser, 169.6 g of water were heated to 75 ° C. and rendered inert while introducing nitrogen.
Unter Konstanthaltung der Temperatur auf 75°C wurden dann als Zulauf 1 eine Mischung aus 401,1 g einer 27,5 gew.-%igen wäßrigen Lösung von 6-O-AcryloyImethyl- glucosid und 8,9 g Ethylacrylat und als Zulauf 2 eine Lösung von 0,12 g 2,2'-Azobis(2- methylpropionsäureamidin)dihydrochlorid in 9,9 g Wasser gleichmäßig in 3h zudosiert.Maintaining the temperature constant at 75 ° C., a mixture of 401.1 g of a 27.5% strength by weight aqueous solution of 6-O-acryloyimethylglucoside and 8.9 g of ethyl acrylate was then added as feed 1 and one as feed 2 Solution of 0.12 g of 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride in 9.9 g of water was metered in uniformly in 3 hours.
Nach Beendigung der Zuläufe, einstündigem Nachpolymerisieren der Reaktionsmischung bei 75°C und Zugabe einer Lösung von 0,60 g 2,2'-Azobis(2-methylpropion- säureamidin)dihydrochlorid in 9,4 g Wasser (5 min) wurde weitere 3 h bei 75°C ge- rührt.After the feeds had ended, the reaction mixture had been post-polymerized for one hour at 75 ° C. and a solution of 0.60 g of 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride in 9.4 g of water (5 min) had been added for a further 3 h stirred at 75 ° C.
Die abgekühlte Polymerlösung hatte einen pH-Wert von 3,4. Ihr Feststoffgehalt betrug 15,2 Gew.-%. Die Molmasse Mw des Polymers betrug 48 000 D.The cooled polymer solution had a pH of 3.4. Their solids content was 15.2% by weight. The molar mass M w of the polymer was 48,000 D.
Polymer 4Polymer 4
Es wurde analog wie bei der Herstellung von Polymer 3 vorgegangen. Es wurden jedoch 252,0 g Wasser vorgelegt, und als Zuläufe wurden folgende Lösungen eingesetzt:The procedure was analogous to that for the preparation of polymer 3. However, 252.0 g of water were introduced and the following solutions were used as feeds:
Zulauf 1 : Mischung aus 378,5 g einer 29,8 gew.-%igen wäßrigen Lösung von 6-O- Acryloylmethylglucosid und 27,5 g einer 80 gew.-%igen wäßrigen Lösung von [2-(Acryloyloxy)ethyl]trimethylammoniumchlorid Zulauf 2: Lösung von 0,13 g 2,2'-Azobis(2-methylpropionsäureamidin)dihydrochlorid in 9,9 g WasserFeed 1: Mixture of 378.5 g of a 29.8% by weight aqueous solution of 6-O-acryloylmethyl glucoside and 27.5 g of an 80% by weight aqueous solution of [2- (acryloyloxy) ethyl] trimethylammonium chloride Feed 2: solution of 0.13 g of 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride in 9.9 g of water
Nachträglich wurde eine Lösung von 0,67 g 2,2'-Azobis(2-methylpropionsäureamidin)- dihydrochlorid in 9,3 g Wasser zugegeben.A solution of 0.67 g of 2,2'-azobis (2-methylpropionic acid amidine) dihydrochloride in 9.3 g of water was subsequently added.
Die abgekühlte Polymerlösung hatte einen pH-Wert von 3,3. Ihr Feststoffgehalt betrug 20,5 Gew.-%. Die Molmasse Mw des Polymers betrug 560 000 D. II. Anwendung von erfindungsgemäßen PolymerenThe cooled polymer solution had a pH of 3.3. Their solids content was 20.5% by weight. The molecular weight M w of the polymer was 560,000 D. II. Use of polymers according to the invention
Beispiel 1 : Verwendung als Zusatz zu flüssigen WaschmittelnExample 1: Use as an additive to liquid detergents
15 Gew.-%ige wäßrige Lösungen der Polymere 1 bis 4 wurden einem kommerziellen Flüssigwaschmittel (Ariel® Hydraktiv) im Gewichtsverhältnis 1 : 9 (Polymerlösung : Flüssigwaschmittel) zugesetzt. Die jeweils erhaltenen Mischungen wurden 15 min gerührt.15 wt .-% aqueous solutions of the polymers 1 to 4 were subjected to a commercial liquid detergent (Ariel ® Hydractive) in a weight ratio of 1: added: 9 (liquid detergent polymer solution). The mixtures obtained in each case were stirred for 15 minutes.
Die erhaltenen Formulierungen waren homogen und über 1 Woche bei Raumtemperatur stabil.The formulations obtained were homogeneous and stable for 1 week at room temperature.
Beispiel 2: Verwendung als Zusatz zu WäscheweichspülemExample 2: Use as an additive to fabric softeners
15 Gew.-%ige wäßrige Lösungen der Polymere 3 und 4 wurden einer kommerziellen Wäscheweichspüler-Emulsion (Lenor®) im Gewichtsverhältnis 1 : 9 (Polymerlösung : Weichspüler-Emulsion) zugesetzt. Die jeweils erhaltenen Mischungen wurden 15 min gerührt.15 wt .-% aqueous solutions of the polymers 3 and 4 were of a commercial fabric softener emulsion (Lenor ®) in a weight ratio of 1: 9 (polymer solution: Fabric softener emulsion) was added. The mixtures obtained in each case were stirred for 15 minutes.
Die erhaltenen Formulierungen waren homogen und über 1 Woche bei Raumtemperatur stabil.The formulations obtained were homogeneous and stable for 1 week at room temperature.
Beispiel 3: Verwendung als wiederablösbarer Schutzfilm auf OberflächenExample 3: Use as a removable protective film on surfaces
2 Gew.-%ige wäßrige Lösungen der Polymere 1 bis 4 wurden jeweils als dünner Flüssigkeitsfilm auf eine Glasplatte aufgebracht. Die Flüssigkeitsfilme wurden bei Raumtemperatur getrocknet.2% by weight aqueous solutions of polymers 1 to 4 were each applied as a thin liquid film to a glass plate. The liquid films were dried at room temperature.
Es wurden transparente, sehr fest haftende, harte Filme erhalten, die sich mit kaltem Wasser rasch und vollständig auflösen ließen. Transparent, very firmly adhering, hard films were obtained which could be quickly and completely dissolved with cold water.

Claims

Patentansprüche claims
1. Wasserlösliche oder wasserdispergierbare Polymere auf Basis monoethylenisch ungesättigter Saccharidmonomere, die1. Water-soluble or water-dispersible polymers based on monoethylenically unsaturated saccharide monomers which
(A) 5 bis 100 Gew.-% mindestens eines Esters, ausgewählt aus der Gruppe der Monoacrylsäure- und Monomethacrylsäureester von Sacchariden und Saccharidderivaten, wobei die Monoester einen Gehalt an mehrfach mit Acrylsäure oder Methacrylsäure veresterten Sacchariden oder Saccharid- derivaten von <2,5 Gew.-% aufweisen, und(A) 5 to 100% by weight of at least one ester, selected from the group of the monoacrylic acid and monomethacrylic acid esters of saccharides and saccharide derivatives, the monoesters having a content of saccharides or saccharide derivatives esterified several times with acrylic acid or methacrylic acid of <2.5 % By weight, and
(B) 0 bis 95 Gew.-% mindestens eines weiteren monoethylenisch ungesättigten Monomeren(B) 0 to 95% by weight of at least one further monoethylenically unsaturated monomer
einpolymerisiert enthalten und eine mittlere Molmasse Mw von 5000 bispolymerized contain and an average molecular weight M w of 5000 to
2 500 000 aufweisen.2,500,000.
2. Polymere nach Anspruch 1 , die einen Gehalt an Monomeren (A) von 5 bis2. Polymers according to claim 1, which have a content of monomers (A) of 5 to
99 Gew.-% und einen Gehalt an Monomeren (B) von 1 bis 95 Gew.-% aufwei- sen.99% by weight and a content of monomers (B) of 1 to 95% by weight.
3. Polymere nach Anspruch 1 oder 2, die als Monomere (A) Monoacrylsäure- oder Monomethacrylsäureester von Mono-, Di- oder Oligosacchariden oder deren C^Cso-Alkylglucosiden oder -polyglucosiden einpolymerisiert enthalten.3. Polymers according to claim 1 or 2, which contain as monomers (A) monoacrylic acid or monomethacrylic acid esters of mono-, di- or oligosaccharides or their C 1 -C 6 -alkylglucosides or -polyglucosides in copolymerized form.
4. Polymere nach den Ansprüchen 1 bis 3, die Monomere (A) einpolymerisiert enthalten, die zu über 50% an einer -CH2-OH-Gruppe des Saccharids mit Acryl- und/oder Methacrylsäure verestert sind.4. Polymers according to claims 1 to 3, which contain copolymerized monomers (A) which are esterified to over 50% on a -CH 2 -OH group of the saccharide with acrylic and / or methacrylic acid.
5. Polymere nach den Ansprüchen 1 bis 4, die als Monomere (B) nichtionische wasserunlösliche Monomere (B1), anionische Monomere (B2), kationische Monomere (B3) oder nichtionische wasserlösliche Monomere (B4) oder Gemische dieser Monomere einpolymerisiert enthalten.5. Polymers according to claims 1 to 4, which contain as monomers (B) nonionic water-insoluble monomers (B1), anionic monomers (B2), cationic monomers (B3) or nonionic water-soluble monomers (B4) or mixtures of these monomers.
6. Polymere nach den Ansprüchen 1 bis 5, die 50 bis 95 Gew.-% der Monomere (A) und 5 bis 50 Gew.-% nichtionische wasserunlösliche Monomere (B1) einpolymerisiert enthalten. 6. Polymers according to claims 1 to 5, which contain 50 to 95% by weight of the monomers (A) and 5 to 50% by weight of nonionic water-insoluble monomers (B1) in copolymerized form.
7. Polymere nach den Ansprüchen 1 bis 6, die 20 bis 95 Gew.-% der Monomere (A) und 5 bis 80 Gew.-% anionische Monomere (B2) einpolymerisiert enthalten.7. Polymers according to claims 1 to 6, which contain 20 to 95% by weight of the monomers (A) and 5 to 80% by weight of copolymerized anionic monomers (B2).
8. Polymere nach den Ansprüchen 1 bis 7, die 40 bis 98 Gew.-% der Monomere (A) und 2 bis 60 Gew.-% kationische Monomere (B3) einpolymerisiert enthalten.8. Polymers according to claims 1 to 7, which contain 40 to 98% by weight of the monomers (A) and 2 to 60% by weight of cationic monomers (B3) in copolymerized form.
9. Polymere nach den Ansprüchen 1 bis 8, die 20 bis 95 Gew.-% der Monomere (A) und 5 bis 80 Gew.-% nichtionische wasserlösliche Monomere (B4) einpolymerisiert enthalten.9. Polymers according to claims 1 to 8, which contain 20 to 95% by weight of the monomers (A) and 5 to 80% by weight of nonionic water-soluble monomers (B4) in copolymerized form.
10. Verfahren zur Herstellung von Polymeren gemäß den Ansprüchen 1 bis 9, dadurch gekennzeichnet, daß man die Monomere (A) und gewünschtenfalls (B) einer radikalischen Polymerisation in einem polaren Lösungsmittel unterwirft.10. A process for the preparation of polymers according to claims 1 to 9, characterized in that the monomers (A) and, if desired (B), are subjected to a radical polymerization in a polar solvent.
11. Verwendung von Polymeren gemäß den Ansprüchen 1 bis 10 als Zusatz zu11. Use of polymers according to claims 1 to 10 as an additive
Waschmitteln, Wäschevor- und -nachbehandlungsmitteln, Reinigungs- und Pflegemittelformulierungen, kosmetischen Präparationen, Haarsprays und Körperpflegemitteln, als Textilhilfsmittel, Papierhilfsmittel, Klebhilfsmittel, Betonadditiv, Folienmaterial, Dispergiermittel für anorganische und organische wäßrige Pig- mentpräparationen, Belagsinhibitoren, Schutzkolloid für die Herstellung vonDetergents, laundry pretreatment and aftertreatment agents, cleaning and care agent formulations, cosmetic preparations, hair sprays and body care agents, as textile auxiliaries, paper aids, adhesive aids, concrete additives, film material, dispersants for inorganic and organic aqueous pigment preparations, coating inhibitors for the production of protective colloids
Emulsionen und für die Emulsionspolymerisation sowie als Beschichtungshilfsmittel für den Schutz harter Oberflächen. Emulsions and for emulsion polymerization as well as coating aids for the protection of hard surfaces.
PCT/EP2004/004647 2003-05-05 2004-05-03 Water-soluble or water-dispersible polymers made from monoethylenically-unsaturated saccharide monomers WO2004099273A1 (en)

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EP2899213A1 (en) 2014-01-27 2015-07-29 Basf Se Modified polysaccharides, method for their production and their use

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WO2011157777A1 (en) * 2010-06-17 2011-12-22 Basf Se Polymers comprising saccharide side groups and use thereof
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EP2899214A1 (en) 2014-01-27 2015-07-29 Basf Se Ethylenically unsaturated polysaccharides, method for their production and their use
EP2899213A1 (en) 2014-01-27 2015-07-29 Basf Se Modified polysaccharides, method for their production and their use

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