EP0922061A2 - Polymerisats d'acides sacchariques insatures et leurs derives ainsi que leurs copolymerisats avec des composes ethyleniquement insatures, et leur procede de preparation - Google Patents

Polymerisats d'acides sacchariques insatures et leurs derives ainsi que leurs copolymerisats avec des composes ethyleniquement insatures, et leur procede de preparation

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Publication number
EP0922061A2
EP0922061A2 EP98940085A EP98940085A EP0922061A2 EP 0922061 A2 EP0922061 A2 EP 0922061A2 EP 98940085 A EP98940085 A EP 98940085A EP 98940085 A EP98940085 A EP 98940085A EP 0922061 A2 EP0922061 A2 EP 0922061A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
acetyl
benzoyl
benzyl
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98940085A
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German (de)
English (en)
Inventor
Klaus Buchholz
Bernhard Skeries
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev
Original Assignee
Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev
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Filing date
Publication date
Application filed by Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev filed Critical Institut fur Technologie Der Kohlenhydrate - Zuckerinstitut - Ev
Publication of EP0922061A2 publication Critical patent/EP0922061A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • 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
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined

Definitions

  • the invention relates to new polymers made from unsaturated saccharide acids (on acids, uronic acids, ars acids) and their salts or their derivatives, which contain a double bond in the ring or in the open chain form, and copolymers with ethylenically unsaturated compounds. These compounds can be produced and obtained by free-radically initiated (homo-, co-) polymerization of
  • N-vinylpyridines which are substituted on the heterocyclic ring by up to four Cl to C12 alkyl radicals and can be in N-quaternized form or salt form
  • vinyl ethers with a total of up to 18 C atoms in the alkyl radical , (1) allylamine, allyl acetate, allyl chloride, allyl acrylate,
  • Reactions following the polymerization are also included, such as the saponification of the abovementioned polymers.
  • the polymers according to the invention are used as material components, industrial aids such as as a thickener, dispersant, modified varnish, to increase viscosity or in the pharmaceutical, medical and cosmetic sectors.
  • the new polymers are also suitable as components for adhesives, composites and for reducing flow resistance.
  • Biocompatibility offers particular advantages in pastes, ointments, creams, joint linings, contact lenses, auxiliaries in biotechnology, e.g. chromatography and enzyme immobilization. Because of the given Reostructure of the saccharide component in the polymer is important as a separating material for antipode separation.
  • products of relatively low molecular weight less than about 20,000
  • medium molecular weight about 20,000 to 100,000
  • high molecular weight over 100,000
  • Desired swellability and chewing elasticity can also be achieved by crosslinking (also polymer-analog).
  • the invention relates to a process for the preparation of these polymers and their characterization.
  • Sugar acid derivatives with an ⁇ , ⁇ double bond to the carboxyl group in the ring or in open-chain form can be (co) polymerized.
  • the invention relates to new polymers of ⁇ , ⁇ -unsaturated saccharide acids or saccharide acid derivatives which contain a corresponding double bond in the ring or in the open-chain form, and copolymers with ethyl unsaturated compounds.
  • the polymers are obtained by polymerization initiated with free radical initiators in bulk, in solvents and / or aqueous or heterogeneous systems of (A) ethylenically unsaturated monosaccharide, disaccharide.
  • Oligosaccharide acids and acid derivatives such as esters, amides, nitriles, which contain a double bond in the ring (endocyclic) or in the open-chain form, chemically protected or unprotected, enzymatically or chemically modified unsaturated mono-, di- or oligosaccharide acids and derivatives or mixtures of the above Compounds (A) with a double bond in the ring (endocyclic in ⁇ , ⁇ position)
  • R 2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 4 is an alkyl group from 3 C atoms (also fatty alkyl) is, for a given stereo structure can represent R ⁇ and R 2, R 2 and R 3 groups also isopropylidene. of the following general formula II (stereoisomers)
  • Ri is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 2 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 3 is hydrogen or CH 2 OR 3 '(where R 3 ' is hydrogen, an acetyl, benzoyl, benzyl,
  • R 2 and R 3 ' represent a benzylidene group.
  • R is a hydroxyl, acetamido, -O-acetyl, -O-benzoyl or a higher -O- acyl group with up to 17 C atoms and -O-alkyl group,
  • R 2 is a hydroxyl, -O-acetyl, -O-benzoyl or a higher -O- acyl group up to 17 carbon atoms and -O-alkyl group and
  • R 3 denotes hydrogen, acetyl, benzoyl or a higher acyl group up to 17 carbon atoms and alkyl group,
  • R 4 is hydrogen, acetyl, benzoyl or a higher acyl group up to 17 carbon atoms and alkyl group and is or R 3 and R 4 can represent an isopropylidene or benzylidene group.
  • R is an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 5 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 6 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group. given stereostructure, R 3 and R 4 , R 4 and R 5 can be an isopropylidene group, and R 5 and R 6 can be a benzylidene group.
  • R t is hydrogen, a methyl, ethyl, isopropyl, propyl group and R 2 is an acetyl, benzoyl, benzyl, alkyl, silyl group and R 3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group, R 5 is hydrogen or CH OR 5 '(where R 5 'is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group) and COOR 5 "(where R 5 " is hydrogen or alkyl group) or R 5 ' and R 4 are an isopropylidene or benzylidene group.
  • R is hydrogen, an alkyl group (also fatty alkyl group) and R 2 is an acetyl, benzoyl, benzyl, alkyl, silyl group and R 3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 5 is hydrogen or CH 2 OR 5 ' (where R 5 ' is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group ) means or R 5 ' and R 4 represent an isopropylidene, benzylidene group.
  • R hydrogen, an alkyl or fatty alkyl group
  • R 2 is an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 3 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, s lyl group
  • R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 5 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, s lyl group and
  • R represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 7 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 8 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 5 and R 6 , Rg and R 7 , R 4 and R 3 can be an isopropylidene and R 7 and R g can be a benzylidene group.
  • R hydrogen, an alkyl group or fatty alkyl group
  • R 2 is an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 3 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 5 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 6 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 7 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 8 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group, given a stereostructure
  • R 5 and R 6 , R 6 and R 7 , R 4 and R 3 can be an isopropyl and R 7 and R 8 represent a benzylidene group. of the following general formula IX (stereoisomers)
  • R 2 is an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 3 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 5 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 6 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 7 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 4 and R 5 , R 5 and R 6 , an isopropylidene and R 6 and R 7 can represent a benzylidene group.
  • R 1 is hydrogen, an alkyl or fatty alkyl group of up to 20 carbon atoms and R 2 is an acetyl, benzoyl, benzyl, alkyl, silyl group and R 3 is hydrogen an acetyl, benzoyl, benzyl, alkyl Represents silyl group
  • R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 5 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R ⁇ 5 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 7 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 4 and R 5 , R 5 and R 6 , an isopropylidene and R ⁇ and R 7 can represent a benzylidene group.
  • R is an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group or one
  • R 3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 4 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group or R 2 and R 3 , R 3 and R 4 can represent an isopropylidene, benzylidene group.
  • R ⁇ is an acetyl, benzoyl, benzyl, alkyl, silyl group and
  • R 2 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group or one
  • R 3 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group,
  • R 4 is hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group
  • R 5 represents hydrogen, an acetyl, benzoyl, benzyl, alkyl, silyl group or R 2 and R 3 , R 3 and R 4 , R and R 5 can represent an isopropylidene, benzylidene group.
  • Alkyl radicals can be substituted and can be in N-quaternized form or salt form, (k) vinyl ethers with a total of up to 18 carbon atoms in the alkyl radical, (1) allylamine, allyl acetate, allyl chloride, allyl acrylate, (m) unsaturated saccharides according to patent application P4408391 .2 and similar
  • alkyl means straight-chain or branched or ring-shaped, optionally unsaturated groups with 1 to 10 C atoms and "fatty alkyl” means alkyl residues with 10 to 20 C atoms derived from fatty acids Roger that.
  • Examples of formula I are (1 ', 3 ' , 4 ', 6'-tetra-ö-acetyl-ß-D-fructofuranosyl) - (2- l) - (methyl-2,3-di-O-acetyl- 4-deoxy- ⁇ -L- / ⁇ reo-hex-4-enopyranurate), (l ', 3', 4 ' , 6 ' -Tetra-0-acetyl-ß-D-fructofuranosyl) - (2- l) - (n-butyl-2,3-di-C-acetyl-4-deoxy- -Lt 2reo-hex-4-enopyranurate), octyl-l, 2,3-tri-O-acetyl-4-deoxy-ß-Lt / 2reo-hex-4-enopyranurate, dodecyl-l, 2,3-tri-0-acetyl-
  • Examples of formula II are 2,4,6-tri-0-acetyl-3-deoxy-D-er ⁇ t / zro-hex-2-enono-l, 5-lactone, 2,4,6-tri-O-acetyl -3-deoxy-Dt 7reo-hex-2-enono-l, 5-lactone and 2,4,6-tri-O-benzoyl-3-deoxy-D-eryt / zro-hex-2-enono- 1, 5-lactone.
  • Examples of formula III are 2-acetamido-5,6-di-0-acetyl-2,3-dideoxy-D-eryt / 2r ⁇ -hex-2-enono-l, 4-lactone, 2-0-acetyl-2 , 3-dideoxy-5,6-isopropylidene-D-er t / 7ro-hex-2-enono-l, 4-lac-ton.
  • Examples of formula IV are (2, '3', 4 ' , 6 ' -Tetra-O-acetyl-ß-D-galactopyranosyl) - (l ⁇ 4) - (2,6-di-O-acetyI-3- deoxy-D-eryt / 7ro-hex-2-enono-l, 5-lactone), (2, '3 ' , 4 ', 6 ' tetra-O-acetyl- ⁇ -D-glucopyranosyl) - (1 - 4) - (2,6-di-O-acetyl-3-deoxy-D-er t ⁇ ro-hex-2-enono- 1, 5-lactone) and (2, ' 3 ' , 4 ' , 6 ' tetra -0-acetyl- ⁇ -D-galactopyranosyl) - (l ⁇ 4) - (2,6-di-0-acetyl-3-
  • Examples of formula V are ethyl 2,4,5,6-tetra-0-acetyl-3-deoxy-Dr / 6o-hex-2-enonate, propyl-2,4,5,6-tetra -O-acetyl-3-deoxy-Dr ⁇ o-hex-2-en-onate, methyl-2,4,5,6-tetra-O-acetyl-3-deoxy-Dx / o-hex-2-en- onate and methyl 2,4,5,6-tetra-O-benzoyl-3-deoxy-Dr ⁇ o-hex-2-enonate.
  • Examples of formula VI are N-dodecanyl-2,4,5,6-tetra-O-acetyl-3-deoxy-Dr / ' ⁇ o-hex-2-enonamide, N- ⁇ ctadecanyl-2,4,5, 6-tetra-O-acetyl-3-deoxy-Dr / ' ⁇ o-hex-2-en-onamide, N-propyl-2,4,5,6-tetra-O-acetyl-3-deoxy-D- ⁇ / o-hex-2-en-onamide and 2,4,5,6-tetra-O-benzoyl-3-deoxy-D-rz ' ⁇ o-hex-2-en-onamide.
  • Examples of formula VII are (2, '3', 4 ', 6'-tetra-0-acetyl- ⁇ -D-galactopyranosyl) - (l-> 4) - (methyl-2,5,6-tri- ⁇ 9-acetyl-3-deoxy-D- ⁇ o-hex-2-enonate) and (2/3 ' , 4 ' , 6 ' tetra-O-acetyl- ⁇ -D-glucopyranosyl) - (l ⁇ 4 ) - (Methyl 2,5,6-tri-O-acetyl-3-deoxy-Dr ⁇ o-hex-2-enonate).
  • Examples of formula VIII are (2, ' 3 ' , 4 ' , 6 ' -Tetra-O-acetyl-ß-D-galactopyranosyl) - (1-4) - (N-propyl-2,5,6-tri- O-acetyl-3-deoxy-D-xy / o-hex-2-en-onamide) and (2, '3', 4 ', 6 ' -Tetra-O-acetyl- ⁇ -D-glucopyranosyl) - ( l ⁇ 4) - (N-propyl-2,5,6-tri-O-acetyl-3-deoxy-Dx / o-hex-2-en-onamide).
  • Examples of formula IX are (2 ' , 3 ' , 4 ' , 6'-tetra-O-acetyl- ⁇ -D-glucopyranosyl) - (l ⁇ 5) - (2,4-di-O-acetyl-3- deoxy-Dt / 7reo-pent-2-enonate), (2 ', 3 ' , 4 ' , 6 ' -Tetra-O-benzoyl- ⁇ -D-glucopyranosyl) - (l ⁇ 5) - (2,4- Di-O-benzoyl-3-deoxy-Dt / 2reo-pent-2-enonate).
  • Examples of formula X are (2 ' , 3 ' , 4 ', 6 ' - tetra-0-acetyl- ⁇ -D-glucopyranosyl) - (1-5) - (2,4-di-O-acetyl-3- deoxy-Dt zreo-pent-2-en-one-amide), (2 ', 3 ' , 4 ', 6' -Tetra-O-benzoyl- ⁇ -D-glucopyranosyl) - (l- »5) - (2,4-di-O-benzoyl-3-deoxy-Dt 2reo-pent-2-en-one-amide).
  • Examples of formula XI are 2,4,5,6-tetra-O-acetyl-3-deoxy-D- ⁇ & o-hex-2-enonitrile, 2,4,5,6-tetra-O-acetyl-3 -deoxy-D- ⁇ r ⁇ ? mo-hex-2-eno-nitrile, 2,4,5,6-tetra-O-benzoyl-3-deoxy-D-r / ⁇ o-hex-2-eno-nitrile.
  • Examples of formula XII are 2,4,5,6,7-penta-O-acetyl-3-deoxy-Dg / uco-hept-2-enonitrile, 2,4,5, 6,7-penta- 0-acetyl-3-deoxy-D-m ⁇ « « o-hept-2-eno-nitrile, 2,4,5,6,7-penta-O-benzoyl-3-deoxy-Dg / wcohept-2-eno -nitrile.
  • This group contains alkyl, hydroxyalkyl and vinyl esters such as methacrylate (MA), ethyl acrylate, n-propyl acrylate, n-butyl acrylate, methyl methacrylate (MMA), hydroxyethyl acrylate lat (HEA), hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA), hydroxyethyl methacrylate (HEMA) and vinyl formate, vinyl acetate (VA), vinyl propionate, vinyl laurate and mixtures thereof.
  • MA methacrylate
  • MMA methyl methacrylate
  • HPA hydroxyethyl acrylate lat
  • HPA hydroxypropyl acrylate
  • HBA hydroxybutyl acrylate
  • HEMA hydroxyethyl methacrylate
  • VA vinyl propionate
  • AM Acrylic acid amide
  • MAM methacrylic acid amide
  • N-dimethylacrylic acid amide N-dimethyl methacyl acid amide.
  • N-vinylimidazoles examples are e.g. 1-vinylimidazole, 2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 2,4-dimethyl-1-vinylimidazole or 2-ethyl-1-vinylimidazole.
  • Conventional quaternizing agents of organic chemistry can be used for the quaternized N-vinylimidazoles.
  • vinyl lactams examples include 1-vinylpyrrolidone, 1 -vinylcaprolactam, 1 -vinylpiperidone, 4-methyl-1-vinylpyrrolidone, 3,5-dimethyl-1-vinylcaprolactam.
  • maleic acid maleic anhydride, maleic acid dimethyl ester, maleic acid diethyl ester, maleimide, fumaric acid, di (ethyl) fumarate, di (isopropyl) fumarate, di (tert-butyl) fumarate, di (cyclohexyl) fumarate and fumarates and maleates with other alcohol components.
  • triethylamine (or other tertiary amines not integrated in the aromatic ring) can be obtained in a shorter reaction time by direct reaction of the aldonic acid derivatives (in particular esters such as lactones) with a defined amount of the base (DM Mackie, AS Perlin Carbohydr. Res., 24 (1972) 67; RM de Lederkremer, O. Varela Adv. Carbohydr. Chem. Biochem .. 50 (1994) 125; CR Nelson, JS Gratzl Carbohydr. Res., 60 (1978) 267; GM Cree, DM Mackie, AS Perlin Can. J.
  • the sugar monomers (A) with or without comonomers (B) are polymerized by free radical initiation.
  • the radical polymerization can be carried out in the presence or in the absence of inert or polar solvents, if appropriate in aqueous systems or as a dispersion in water.
  • the polymerization in the absence of solvents, substance for short, or in the melt polymerization, is carried out in vacuo or under nitrogen pressure.
  • Suitable inert solvents are, for example, benzene, toluene, o-, m-, p-xylene and their isomer mixtures, ethylbenzene, tert-butylbenzene, chlorobenzene, o-, m-, p-dichlorobenzene, aliphatic hydrocarbons such as hexane, heptane, octane, Nonane, dodecane, cyclohexane, and mixtures of the hydrocarbons mentioned.
  • Suitable polar solvents are dimethyl sulfoxide, tetrahydrofuran, dioxane, butanone and acetone, and mixtures of the solvents mentioned.
  • the polymerizations are preferably carried out in aqueous media.
  • the reactants can polymerize discontinuously by heating the reaction mixture to the polymerization temperature.
  • This temperature is generally in the range from 20 to 150 ° C. and particularly preferably between 40 and 130 ° C.
  • the polymerization is carried out under pressure.
  • the concentration of components (A) and (B) is 10 to 90, preferably 20 to 70 mol%.
  • the polymerization can be carried out continuously. Continuous polymerization at temperatures of 50 to 130 ° C is particularly suitable for this.
  • catalysts which form free radicals, for example inorganic and organic peroxides, persufates, azo compounds and so-called redox catalysts.
  • Suitable radical initiators are preferably all compounds which have a half-life of approximately 3 to 10 hours at the chosen polymerization temperature.
  • the polymerization is initially started at a low temperature and ends at a higher temperature, it is advisable to work with at least two initiators which decompose at different temperatures, namely to start with an initiator which decomposes at a low temperature and then to carry out the main polymerization with an initiator to finish, which disintegrates at a higher temperature.
  • Water-soluble and water-insoluble initiators or mixtures of water-soluble and water-insoluble initiators can be used.
  • the water-insoluble initiators are then soluble in the organic phase.
  • the initiators listed for this purpose can be used for the following temperature ranges:
  • salts or complexes of heavy metals e.g. Copper, cobalt, manganese, iron, vanadium, nickel or chromium salts, or organic compounds, e.g. Benzoin, dimethylaniline or ascorbic acid.
  • the reducing component of redox catalysts can be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate or hydrazine. 0.01 to 50 mol% of the reducing compounds are added as the redox component. Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often advantageous to use a combination of peroxide, reducing agent and heavy metal as a redox catalyst.
  • tert-butylhydroperoxide with the addition of 5 ppm copper III acetylacetonate or cobalt octanoate can already be activated in such a way that polymerisation can take place at 100 ° C.
  • the solution polymerization and the heterogeneous polymerizations are usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen.
  • the organic solvents and water are freshly distilled and degassed immediately before the polymerization batch.
  • the monomer compounds specified under (A) and (B) are very pure, free of water and stabilizers.
  • the monomers (A) and (B) are in dissolved or heterogeneous form with the solvent. During the polymerization, thorough mixing or defined dispersion of the reactants is ensured.
  • the polymers according to the invention can be prepared in conventional polymerization devices.
  • stirred kettles or flow-through kettles
  • double-wall reactors which are equipped with an anchor, blade, impeller or multi-stage impulse countercurrent stirrer.
  • Ethylenically unsaturated aldonic acid derivatives are obtained under the influence of defined bases and conditions.
  • the polymers according to the invention can be prepared by bulk polymerization, emulsion, suspension or solution polymerization of components (A) or (A) and (B) in nonpolar, polar solvents or in aqueous dispersion, the solution polymerization in water or water Alcohol mixture is particularly preferred.
  • solution polymerization in an aqueous medium the unprotected water-soluble sugar monomers and derivatives (A) and, if appropriate, the polar comonomers (B) and the water-soluble initiator are in dissolved form.
  • the polymerization reaction is carried out under the same conditions (temperature, initiator concentration, monomer ratio) as in the polymerization in solvent.
  • the polymers according to the invention can also be prepared in an alcoholic aqueous solution.
  • the alcohol content is from 1 to 50, preferably 5 to 20,% by weight.
  • Suitable alcohols are methanol, ethanol, isopropanol, n-propanol and mixtures of the inert solvents mentioned.
  • Water-insoluble protected sugar acid monomer derivatives (A) and mixtures of water-insoluble monomers (A) and (B) can be polymerized as an aqueous dispersion using oil-soluble initiators and in the presence of suspending agents or protective colloids.
  • the polymers according to the invention can also be prepared by emulsion polymerization.
  • Water-insoluble saccharide acid derivatives (A) or (A) and (B) are converted into an aqueous emulsion with the aid of emulsifiers and started with water-soluble initiators and redox initiators.
  • Isolation and characterization of the polymers according to the invention The chain reactions were stopped after the addition of inhibitors such as hydroquinone, N-phenyl- ⁇ -naphthalene, pyrocatechol or by vigorous cooling. The polymers formed in substance and solution are precipitated (in ten times the volume of the Precipitant) and filtration isolated. In general, methanol, ether, diethyl ether, hexane or mixtures thereof were used as precipitants. Polymers from the emulsion and suspension polymerization were filtered off or centrifuged, washed with water and dried under reduced pressure at 20-80 ° C.
  • inhibitors such as hydroquinone, N-phenyl- ⁇ -naphthalene, pyrocatechol or by vigorous cooling.
  • the polymers formed in substance and solution are precipitated (in ten times the volume of the Precipitant) and filtration isolated. In general, methanol, ether, diethyl ether, hexane or mixtures thereof were used
  • the molecular weights and distributions of the polymers were determined by gel permeation chromatography coupled to a multi-angle light scattering detector and refractive index detector (GPC-MALLS system).
  • composition of the polymers was calculated by elemental analysis, partial NMR spectroscopy or wet analysis. In various examples, the FT-IR spectra / NMR spectra were also determined.
  • the water-insoluble liquid monomers (A) or monomer mixtures (A) / (B) or mixtures of several components are dispersed in degassed water, the volume ratio of monomer (monomers) to degassed water being from 1: 1 to 1: 3 becomes.
  • protective colloids which are water-soluble organic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylates, methyl cellulose, are used as suspending agents or mixtures. Hydroxyethyl cellulose (or other cellulose ethers), pectins, gelatin and alginates.
  • suspending aids such as calcium carbonate, barium sulfate, hydroxylapatite, aluminum hydroxides, kaolin, magnesium silicates, magnesium phosphate and calcium phosphate, used to about • 0.1% (based on the monomer).
  • Radical starters form oil-soluble water-insoluble initiators, as are also used for solution polymerization for certain temperature ranges. After dispersion, the polymerizations are carried out at temperatures between 40 to 90 ° C. under a defined stirring speed and in a protective gas atmosphere (nitrogen).
  • a water-insoluble monomer (A) or monomer mixture (A) and (B) or multi-component mixtures is dispersed with the aid of an emulsifier or emulsifier mixture.
  • a ionic, cationic or neutral emulsions are gators used between 0.5 to 5 percent by weight based on the monomer.
  • Anionic emulsifiers form alkali salts of fatty acids, aliphatic sulfonic acids or resin acids. Examples are sodium dodecyl sulfate, sodium diisopropyl naphthalene sulfonate, abietic acid.
  • Cationic emulsifiers form salts of quaternizing fatty amines.
  • Neutral emulsifiers form ethoxylated fatty alcohols, fatty acids or phenols as well as fatty acid esters of polyhydric alcohols (pentaerythritol or sorbitol). Examples are nonyl phenol oxyethylate.
  • emulsifiers are usually mixtures of several homologues and are used as such.
  • water-soluble per compounds such as potassium peroxodisulfate (40 to 70 ° C.) or conventional redox systems are used as initiators, as have already been mentioned for aqueous solution polymerization. They are used at temperatures at which the half-life of the decay is between 10 and 100 hours.
  • the emulsion polymerization is carried out at 40 to 90 ° C under a defined stirring speed and protective gas atmosphere. It can be carried out batchwise, semi-continuously or continuously in a conventional manner.
  • a buffer mixture to stabilize the pH value may be necessary for pH-sensitive monomers or monomer mixtures.
  • Common phosphate, acetate or borate buffers are suitable for this. Examples with saccharidic acid derivatives with double bond in the ring
  • Feed 2 was prepared from 0.12 g of azo-bis-isobutyronitrile and 10 ml of benzene.
  • inlet 1 and inlet 2 are heated to 60 ° C. with stirring. After the intended temperature had been reached, stirring was continued at this temperature for a further 24 or 48 hours. After the reaction was completed, a white solid was obtained with a yield of 25.0% by weight.
  • GPC -MALLS analysis gave a weight average molecular weight of 10,000 Daltons.
  • Example 2 Example 1 was repeated with the modification that instead of styrene, 3.883 g of N-vinyl-2-pyrrolidone (VPy) was used. A white solid was obtained with a yield of 25% by weight and had a weight average molecular weight of 50,000 daltons.
  • VPy N-vinyl-2-pyrrolidone
  • Example 1 was repeated with the modification that 3.008 g of vinyl acetate (VAc) was used instead of styrene.
  • VAc vinyl acetate
  • a white solid was obtained in 20% by weight yield, which had a weight average molecular weight of 10,000 daltons.
  • Example 1 was repeated with the modification that 3.50 g of butyl vinyl ether (PVb) was used instead of styrene.
  • PVb butyl vinyl ether
  • a white solid was obtained with a yield of 20% by weight and which had a weight-average molecular weight of 12,000 daltons.

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Abstract

L'invention concerne de nouveaux polymérisats d'acides sacchariques insaturés (acides aldoniques, acides uroniques, acides arsénieux) ainsi que leurs sels ou leurs dérivés, qui contiennent une liaison double dans le noyau ou dans la forme à chaîne ouverte, ainsi que des copolymérisats avec des composés éthyléniquement insaturés. Ces composés se préparent et s'obtiennent par (homo-, co-) polymérisation à initiation radicalaire (A) d'acides monosacchariques, disacchariques ou oligosacchariques éthyléniquement insaturés et de dérivés acides, tels qu'esters, amides, nitriles, qui renferment une liaison double dans le noyau (endocyclique) ou dans la forme à chaîne ouverte, d'acides mono-, di- ou oligosacchariques insaturés protégés ou non protégés chimiquement, modifiés par voie enzymatique ou chimique, et de dérivés ou de mélanges des composés (A) précités, ou bien copolymérisation des constituants selon (A) avec (B) des monomères ou des mélanges de monomères de composés éthyléniquement insaturés.
EP98940085A 1997-06-27 1998-06-25 Polymerisats d'acides sacchariques insatures et leurs derives ainsi que leurs copolymerisats avec des composes ethyleniquement insatures, et leur procede de preparation Withdrawn EP0922061A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1997127362 DE19727362A1 (de) 1997-06-27 1997-06-27 Polymerisate aus ungesättigten Saccharidsäuren und deren Derivaten sowie deren Copolymerisate mit ethylenisch ungesättigten Verbindungen und Verfahren zu ihrer Herstellung
DE19727362 1997-06-27
PCT/EP1998/003901 WO1999000436A2 (fr) 1997-06-27 1998-06-25 Polymerisats d'acides sacchariques insatures et leurs derives ainsi que leurs copolymerisats avec des composes ethyleniquement insatures, et leur procede de preparation

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DE19919785A1 (de) * 1999-04-30 2000-12-07 Wella Ag Haarbehandlungsmittel mit Polymeren aus ungesättigten Sacchariden, ungesättigten Saccharidsäuren oder deren Derivaten
DE19945235B4 (de) * 1999-09-21 2004-10-07 Wella Ag Kosmetische Mittel mit einem Gehalt an Saccharidpolymeren, insbesondere mit einem Gehalt an Saccharidpolymerlatices
KR20020046274A (ko) * 1999-11-04 2002-06-20 부쳐-랄슨 에이. 무수과당 유도체를 포함하는 코폴리머의 합성
BR112012032218A2 (pt) * 2010-06-17 2016-11-22 Basf Se "copolímero, uso de um copolímero, e, composição de detergente têxtil"

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DE4408391A1 (de) * 1994-03-12 1995-09-14 Buchholz Klaus Prof Dr Polymerisate aus ungesättigten Sacchariden und deren Derivaten sowie deren Copolymerisate mit ethylenisch ungesättigten Verbindungen und Verfahren zu ihrer Herstellung

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