WO2001094429A1 - Oligomeres et polymeres obtenus a partir de betaine crotonique ou de derives de betaine crotonique - Google Patents

Oligomeres et polymeres obtenus a partir de betaine crotonique ou de derives de betaine crotonique Download PDF

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Publication number
WO2001094429A1
WO2001094429A1 PCT/EP2001/005334 EP0105334W WO0194429A1 WO 2001094429 A1 WO2001094429 A1 WO 2001094429A1 EP 0105334 W EP0105334 W EP 0105334W WO 0194429 A1 WO0194429 A1 WO 0194429A1
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Prior art keywords
croton
formula
monomer
betaine
vinyl
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PCT/EP2001/005334
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German (de)
English (en)
Inventor
Jürgen Allwohn
Susanne Birkel
Thomas Krause
Birgit Kamm
Michael Kamm
Matthias Fischbach
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Wella Aktiengesellschaft
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Priority to AU79617/01A priority Critical patent/AU7961701A/en
Publication of WO2001094429A1 publication Critical patent/WO2001094429A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/30—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and unsaturated
    • 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
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to oligomers and polymers made from croton betaine or croton betaine derivatives, and to the production and use thereof.
  • Cationic substances such as cationic polymers and cationic surfactants have found widespread use, for example, in skin and hair cosmetics such as shampoos, styling agents or conditioners or in detergents and cleaning agents such as laundry detergents and dishwashing detergents and in textile treatment agents such as fabric softeners. They can either act on the substrate and clean it, keep it moist, give it shine, condition it, style it, give it protection and care, or act as a soil-release compound. However, you can also improve the consistency of the formulation or the properties of other ingredients by emulsifying, thickening, preserving or serving as a carrier or deposition polymer for other active ingredients.
  • cationic charge Due to their cationic charge, they are particularly suitable for attaching to surfaces with anionic groups, for example on damaged hair or on textiles, and thereby having a care effect. There is a continuing need for new and improved such cationic compounds. Of particular interest are compounds that can be produced from natural building blocks or their derivatives, ie from renewable raw materials.
  • the present application relates to oligomers or polymers which can be prepared by radical polymerization or oligomerization from at least one croton betaine or croton betaine derivative (A) of the formula (I)
  • X (_) is an anion, for example a halide, sulfate, phosphate, alkyl sulfate or alkyl phosphate or also an organic anion or an organic polyanion such as, for example, anionic polysaccharides, in particular carboxymethyl cellulose.
  • Croton betaine derivatives are understood in particular to be the salts, esters and amides of croton betaine.
  • the croton betaine esters can generally be obtained by reacting croton betaine or its salts with alcohols under acidic conditions
  • Preferred esters are those with methanol, ethanol, n- or isopropanol, n-, iso- or 2-butanol, hexanol, cyclohexanol, benzyl alcohol or allyl alcohol Esterification with ethylenically unsaturated alcohols such as allyl alcohol for leads to croton betaine esters with which it is possible to obtain cross-linked polymers.
  • Polymers and oligomers with a molecular weight of about 1000 to about 100000 are preferred it can be homooligomers or homopolymers or cooligomers or copolymers which have been copolymerized with at least one second, radically copolymerizable monomer (B) and are composed of structural units of the formula (III) - [CH (CH 2 N (+) R 1 R 2 R 3 ) -CH (COCT) -] n - [B] m - (III) or from structural units of the formula (IV)
  • N (+) R 1 R 2 R 3 represents a quaternary ammonium group
  • Z represents OR 4 or NR 5 R 6
  • R 4 , R 5 and R 6 represent hydrogen or an organic radical with preferably 1 to 30 C atoms
  • X ( -) means an anion, for example a halide, sulfate, phosphate, alkyl sulfate or alkyl phosphate or also an organic anion or an organic polyanion such as, for example, anionic polysaccharides, in particular carboxymethylcellulose
  • B stands for a radically copolymerized comonomer
  • n is a number larger 1
  • m is a number greater than or equal to zero.
  • Oligomers are generally understood to mean compounds with a degree of polymerization of n or n + m of 2 to approximately 10, preferably from 4 to 10, and polymers are understood to mean compounds with a degree of polymerization of n or n + m of greater than 10.
  • the formulas (I) to (IV) can be both the E and the Z isomers.
  • the radicals R 1 to R 6 independently of one another represent identical or different organic groups which can also be cyclically linked to one another, preferably unsubstituted or with functional groups. nellen groups such as hydroxy, amino, alkoxy, etc. substituted, linear or branched Cl to C30 alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl groups, especially methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl , Hexyl, cyclohexyl and benzyl. Methyl is particularly preferred for R 1 , R 2 and R 3 .
  • croton betaine monomer (A) and comonomer (B) are preferably in a ratio of 2:98 to 98: 2, particularly preferably 20:80 to 80 : 20, most preferably from 30:70 to 70:30.
  • the comonomer (B) is preferably selected from the following groups, it also being possible to use mixtures of the monomers mentioned:
  • vinyl aromatics such as e.g. Styrene and styrene derivatives, which can be substituted on the aromatic ring by one to three Cl to C12 alkyl radicals
  • mono- or polyunsaturated hydrocarbons e.g. Ethylene, propylene or 1,3-butadiene
  • vinyl halides e.g. Vinyl chloride.
  • Suitable comonomers (B) are, for example: (a) acrylic acid, methacrylic acid, dimethylacrylic acid,
  • This group contains e.g. Alkyl, hydroxy, alkyl and vinyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert.
  • (c) in this group are, for example: dimethylaminoethyl acrylate, diethylaminoethyl acrylate, methyl ethylaminoethyl acrylate, di-tert. butylaminoethyl acrylate, dimethylamino methyl (or butyl, hexyl, octyl, stearyl) acrylate, dimethyl (or diethyl, methylethyl, di-tert.butyl) aminoethyl methacrylate, dimethylaminomethyl (or butyl, amyl) hexyl, octyl, stearyl) methacrylate.
  • N-vinyllactams examples include 1-vinylpyrrolidone, 1-vinylcaprolactam, 1-vinylpiperidone, 4-methyl-1-vinylpyrrolidone, 3, 5-dimethyl-1-vinylcapro-lactam.
  • alkyl and hydroxyalkyl vinyl ethers such as methyl, ethyl, propyl, isopropyl, butyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether.
  • Another object of the present invention is a process for the preparation of the oligomers or polymers defined above.
  • the monomers of the formulas (I) or (II) are radically polymerized, if appropriate in the presence of the comonomers (B).
  • the radical polymerization can in principle be carried out by any of the processes known for this. Based on the total monomer content used in the polymerization, preference is given to using 0.01 to 20, particularly preferably 0.1 to 10 mol% of a suitable radical polymerization initiator or a mixture of several polymerization initiators. In principle, all those who are capable of triggering a radical polymerization are suitable as initiators. It can be peroxides as well as persulfates, peroxodisulfates or azo compounds. The usual initiators can be used as polymerization initiators, for example peroxides such as dibenzoyl, dicumyl, dilauroyl, acetylcyclohexanesulfonyl, tert.
  • peroxides such as dibenzoyl, dicumyl, dilauroyl, acetylcyclohexanesulfonyl, tert.
  • -Butyl peroxide peroxodisulfuric acid or hydrogen peroxide
  • Hydroperoxides such as cumene, diisopropylbenzene or para-menthane hydroperoxide or methyl ethyl ketone dihydroperoxide
  • Peroxydicarbonates such as bis (4-t-butylcyclohexyl), dipropyl, diisopropyl, bis (2-ethylhexyl), dicyclohexyl or dimyristyl peroxydicarbonate
  • Azo compounds such as N, N-azobisisobutyronitrile or azobiscyanovaleric acid
  • Ethane derivatives such as benzpinacol or bis ((methyl) (ethyl) - (phenyl)) ethane or also vinylsilane triacetate, potassium persulfate or hydrogen peroxide in combination with polyvalent metal ions such as iron (II) ions.
  • 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.
  • 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.
  • Dibenzoyl peroxide tert. -Butylper-2-ethylhexanoate, tert. - Butyl permaleinate, diethyl 2, 2 '-azobis-isobutyrate.
  • suitable salts are also used as redox catalysts, i.e. combined systems which are composed of at least one reducing agent and at least one oxidizing agent.
  • Suitable oxidizing agents are, for example, peroxides or
  • Hydroperoxides such as benzoyl peroxide or hydrogen peroxide or potassium, sodium or ammonium persulfate.
  • the reducing agents activate the formation of free radicals and thus enable the polymerization to be carried out at lower temperatures, for example at 20 to 55 ° C.
  • the reducing agent used is based on the redox initiator from 0.01 to 50 mol% of the reducing compounds.
  • the reducing component of redox catalysts can be formed, for example, by compounds such as sodium sulfite, sodium bisulfite, alkali thiosulfate, sodium formaldehyde sulfoxylate, mercaptans or hydrazine.
  • Suitable reducing agents are ascorbic acid, acetone bisulfite, the sodium salt of hydroxymethanesulfinic acid or sodium dithionite.
  • suitable reducing agents are ascorbic acid, acetone bisulfite, the sodium salt of hydroxymethanesulfinic acid or sodium dithionite.
  • iron (II) salts such as iron (I-) sulfate.
  • a water-soluble iron (II) salt a combination of Fe / V salts is often used. The advantage of these systems is that they enable the polymerization to be carried out at even lower temperatures.
  • Examples of such systems are ascorbic acid / iron (II) sulfate / hydrogen peroxide or sodium dithionite / sodium formaldehyde sulfoxylate / iron (II) sulfate / para-menthane hydroperoxide or diisopropylbenzene hydroperoxide.
  • a chelating agent is often added to such systems to ensure that the metallic component is in solution and is not removed from the reaction system by precipitation.
  • Such a chelating agent is, for example, the sodium salt of ethylenediaminetetraacetic acid.
  • the metallic component is frequently added directly as a chelate complex.
  • crosslinking compounds or grafting agents can be added.
  • Suitable crosslinkers are, for example, divinylbenzene, diacrylates of polyethylene glycol such as, for example, ethylene glycol dimethacrylates, diacrylates of polypropylene glycol, N, N ⁇ -bis-methylene acrylamide, divinyl ethers of the aliphatic diols, diallyl ether, 1, 7-octadiene, 1, 9-decadiene, triallyl amine , Diallyl phthalate or tetraallyl ethylenediamine.
  • Suitable grafting agents are, for example, acrylic or methacrylic acid allyl esters, acrylic or methacrylic acid methyl allyl esters, fumaric acid, maleic or itaconic acid mono- or diallyl esters or fumaric acid, maleic or itaconic acid mono- or dimethyl halides.
  • a particularly suitable, double ethylenically unsaturated monomer according to the invention is croton betaine allyl ester.
  • mol% regulators so-called molecular weight regulators (chain transfer agents) can be added to the mixture to be polymerized, based on the monomer content.
  • Suitable regulators are mercaptans, in particular C3 to C15 alkanethiols, and aldehydes and chlorinated hydrocarbons. Tert are preferred.
  • -Dodecyl mercaptan and n-dodecyl mercaptan are preferred.
  • the polymerization is usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen and in a purified and degassed solvent or in bulk.
  • the monomers used are preferably pure and free of stabilizers.
  • the reactants are thoroughly mixed during the polymerization.
  • the manufacture of the invented Oligomers and polymers according to the invention can be carried out in conventional polymerization devices. If the croton betain derivatives to be polymerized are esters or amides, the pH should be kept in the neutral range (6-8, preferably 6.5 to 7.5) to avoid saponification. This can be done, for example, by adding sodium hydrogen carbonate or other suitable buffers.
  • the free-radical polymerization for producing the oligomers and polymers according to the invention is advantageously carried out in such a way that the total amount of the polymerization batch (including, if appropriate, the molecular weight regulator) minus the free-radical generator is placed in the polymerization vessel, warmed to the polymerization temperature and then (as a rule all at once) Introduces free radical generator into the polymerization vessel and polymerizes to the desired final conversion, for example 90% or 98%.
  • the polymerization can then be stopped by adding polymerization inhibitors such as diethylhydroxylamine and unreacted monomer can be removed in a known manner by deodorization (preferably stripping and / or steam distillation) or by means of membrane technology (preferably ultrafiltration membrane or dialysis membrane). During the polymerization, further radical formers can also be added to achieve the desired final conversion.
  • polymerization inhibitors such as diethylhydroxylamine and unreacted monomer can be removed in a known manner by deodorization (preferably stripping and / or steam distillation) or by means of membrane technology (preferably ultrafiltration membrane or dialysis membrane).
  • further radical formers can also be added to achieve the desired final conversion.
  • the oligomers and polymers according to the invention have a number of advantages.
  • the monomers croton betaine or croton betaine derivatives are building blocks natural basis or from the natural product and biotech product carnitine easily accessible by dehydration and, if necessary, esterification.
  • the monomers are readily water-soluble, readily biodegradable and physiologically harmless. This means that residual monomers which have not been reacted in the polymerization and the polymerization solutions (when using non-toxic catalysts) are largely harmless and the oligomers or polymers obtained are particularly suitable for pharmaceutical or cosmetic applications.
  • the oligomers and polymers are readily biodegradable and the degradation products are not toxic.
  • the oligomers or polymers have a high density of hydrophilic groups.
  • oligomers and polymers according to the invention are particularly capable of attaching to surfaces with anionic groups, for example on hair, in particular damaged hair, or on textiles, and thereby exerting a high care effect.
  • anions organic and inorganic
  • properties of the oligomers and polymers according to the invention can be varied in a simple manner without manipulating or changing the oligomer or polymer structure.
  • polyelectrolyte complexes can be produced.
  • the oligomers and polymers according to the invention can be used for the production of lacquers, paints, adhesives, polymer-modified building materials, sealants in the construction and living areas, pharmaceutical or cosmetic products, hair treatment agents, textile treatment agents, detergents and cleaning agents as well as thickeners for water or aqueous systems, as emulsifiers, protective colloids, film formers or as oil field chemicals.
  • Anionic polymers can be: polycarboxylic acids, polyphosphoric acids, but particularly preferred are anionic polymers on a natural basis, in particular anionic polysaccharides or cellulose derivatives, for example gum arabic, carrageenan, alginic acid, heparin, nucleic acids, lignin sulfonates or carboxymethyl cellulose.
  • the polyelectrolyte complexes are suitable, for example, for the production of release and support materials such as Separation membranes, microcapsules and flocculants.
  • Tailor-made separation membranes can be made from the polyelectrolyte complexes, e.g. for the separation of solvent mixtures such as water / alcohol as well as for ion separations (e.g. separation of divalent and monovalent ions).
  • Microcapsules can also be produced from the polyelectrolyte complexes for the encapsulation of drugs, cosmetic active ingredients or also living cells for a targeted local
  • a mixture of 250 ml of acetic acid (glacial acetic acid) and 250 ml of acetic anhydride are placed in a stirrer (stirrer, reflux condenser) and 100 g (0.556 mol) of L-carnitine hydrochloride are added with thorough stirring.
  • the mixture is stirred under reflux for 30 min and the solvent mixture is removed on a rotary evaporator in vacuo.
  • the residue is stirred with isopropanol and collected. It is filtered off, washed with cold isopropanol and dried in vacuo over CaCl 2 .
  • 83.61 g (92%) of a white crystalline croton betaine hydrochloride are obtained. It can be recrystallized from n-propanol or isopropanol.
  • UV-Vis UV (CH 3 OH), ⁇ ⁇ x [ran], (lg ⁇ ): 204.0 (3.87); UV (H a O), ⁇ max [nm], (lg ⁇ ): 195.0 (4.19);
  • croton betaine hydrochloride 8.0 g (44.5 mol) of croton betaine hydrochloride are suspended in 250 ml of 25 ° C. warm cyclohexyl alcohol while stirring well. HCl gas is passed in without heating until the batch is completely clear, with an increase in temperature being observed. The solution is then stirred at 100 ° C. for 5 hours. It is concentrated in vacuo on a rotary evaporator, the residue is washed twice with 50 ml of cyclohexanol to remove acid residues and concentrated to dryness. The residue is stirred with 80 ml of acetonitrile and left to stand at + 4 ° C. for 10 h.
  • UV-Vis UV (CH 3 OH), ⁇ max [nm], (lg ⁇ ): 205.6 (3.98);
  • UV-Vis UV (CH 3 OH), ⁇ max [nm], (Ig ⁇ ): 206.0 (4.14); UV (H 2 0), ⁇ max [nm], (lg ⁇ ): 190.0 (4.65), 205.6 (S);
  • the mixture is stirred for 4 hours at this temperature, after about 20 minutes a yellowish-brown color and turbidity of the reaction solution can be observed.
  • the solvent mixture is then removed on a vacuum rotary evaporator and the inorganic salts are separated off by adding 15 ml of methanol.
  • the polymeric fraction is then separated from the residual monomer by fractional crystallization from acetonitrile or acetone or by means of an ultrafiltration membrane.
  • the conversions of poly (crotonbetaincyclohexyl ester chloride) after drying in vacuo at 40 ° C are 52-59% based on the monomer used.
  • TLC TLC, silica gel 60: eluent CHCl 3 / CH 3 OH / (CH 3 ) 2 CH-0H / H 2 0 / Hac [42: 28: 7: 10: 10], I 2 detection: 0, 13 to 0.25.
  • the starting monomer has an Rf value of 0.4.
  • TLC TLC, silica gel 60
  • methanol acetone: HC1, 37% [2: 18: 1]
  • R F start (J 2 detection).
  • the starting monomer has an Rf value of 0.21.
  • Example 7 Copolymerization of crotonbetain-cyclohexyl ester hydrochloride and vinyl acetate
  • the polymer solution is poured into petri dishes; the polymerization was interrupted by adding 20 ⁇ l crotonaldehyde. It is concentrated in vacuo on a rotary evaporator at 60 ° C. Unreacted monomer is removed by fractional precipitation with diethyl ether or by separation using a dialysis membrane or ultrafiltration membrane. The polymer is dried in vacuo at 40 ° C.
  • the fractionated polymer was dissolved in the flux and separated at 0.8 ml / min over a period of 30 minutes.
  • the evaluation was carried out against a calibration curve (polystyrene standard in the flux) by detection using a refractive index (Rl).
  • Croton betaine cyclohexyl ester unit 3.98 (s, br. IH), 3.32 (m br., IH), 3.30 (s, br. 9H), 3.2 (m, 2H), 2.3 ( s br. IH), 1.53 (m, 4H), 1.29 (m, 6H).
  • Vinyl acetate unit 3.90 (m, br. IH), 2.01 (s, 3H), 1.88 (m, 2H)
  • Elemental analysis poly (crotonbetaincyclohexylester- chloride-co-vinyl acetate), based on the ratios of the signal intensities of the Crotonbetaincyclohexylester- unit and the vinyl acetate unit of the ⁇ ⁇ -NMR spectrum ((C 13 H 24 ClNO 2) 0, 04 ( C 4 H 6 ⁇ 2)) o.96 n (254, 76) n
  • reaction solution showed a dark yellow color after the completion of the reaction.
  • solvent mixture is then removed in vacuo.
  • rotary evaporator and separates the inorganic salts by adding 15 ml of methanol.
  • the polymeric fraction is then separated from the residual monomer by fractional crystallization from acetonitrile or acetone or by means of an ultrafiltration membrane.
  • the polymer is dried in vacuo at 40 ° C.
  • the starting monomer has an Rf value of 0.4.
  • the evaluation was carried out against a calibration curve PEG / PEO in the flux by detection using a refractive index

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Abstract

L'invention concerne des oligomères et des polymères que l'on peut obtenir par polymérisation radicalaire ou oligomérisation, à partir d'au moins une bétaïne crotonique ou un dérivé de bétaïne crotonique de formule (I): R?1R2R3N(+)-CH¿2-CH=CH-COO(-) ou de formule (II): R?1R2R3N(+)-CH¿2-CH=CH-C(=O)Z X?(-), où R1R2R3N(+)¿ représente un groupe ammonium quaternaire, Z représente OR?4 ou NR5R6, R4, R5 et R6¿ représentent hydrogène ou un reste organique possédant de préférence 1 à 30 atomes de carbone, et X(-) représente un anion. Les oligomères et les polymères présentés peuvent être utilisés dans des vernis, des peintures, des adhésifs, des matériaux de construction modifiés par polymères, des produits d'étanchéité utilisés dans le domaine du bâtiment et de l'habitation, des produits pharmaceutiques ou cosmétiques, des produits de traitement pour textiles, des produits de lavage et de nettoyage, ou pour la production de complexes polyélectrolytiques.
PCT/EP2001/005334 2000-06-02 2001-05-10 Oligomeres et polymeres obtenus a partir de betaine crotonique ou de derives de betaine crotonique WO2001094429A1 (fr)

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AU79617/01A AU7961701A (en) 2000-06-02 2001-05-10 Oligomers and polymers from crotonic betaine or crotonic betaine derivatives

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DE10027391A DE10027391B4 (de) 2000-06-02 2000-06-02 Oligomere und Polymere aus Crotonbetain oder Crotonbetainderivaten
DE10027391.2 2000-06-02

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5164424A (en) * 1986-12-19 1992-11-17 Deutsche Carbone Ag Polymer having a betaine structure, solution diffusion membrane, process for producing same and use thereof
FR2687398A1 (fr) * 1992-02-17 1993-08-20 Oreal Monomeres betauiniques, polymeres correspondants ainsi que leur utilisation, et procedes de preparation y relatifs.
JPH11222470A (ja) * 1998-02-02 1999-08-17 Osaka Organic Chem Ind Ltd グリシンベタインモノマーの製法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2592107A (en) * 1948-11-19 1952-04-08 Hercules Powder Co Ltd Synthetic amphoteric polymers containing free amino groups and free acid groups
US3744969A (en) * 1970-06-09 1973-07-10 Rohm & Haas Break resistant leather
DE3201226A1 (de) * 1982-01-16 1983-07-28 Basf Ag, 6700 Ludwigshafen Verfahren zum nachgerben
DE4227974C2 (de) * 1992-08-26 1996-04-18 Stockhausen Chem Fab Gmbh Alkoxygruppenhaltige Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung zum Nachgerben von Leder
IT1261230B (it) * 1993-04-08 1996-05-09 Sigma Tau Ind Farmaceuti Procedimento migliorato per la preparazione di l-(-)-carnitina a partire da suoi precursori aventi opposta configurazione.
DE4316242A1 (de) * 1993-05-14 1994-11-17 Henkel Kgaa Haarbehandlungsmittel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5164424A (en) * 1986-12-19 1992-11-17 Deutsche Carbone Ag Polymer having a betaine structure, solution diffusion membrane, process for producing same and use thereof
FR2687398A1 (fr) * 1992-02-17 1993-08-20 Oreal Monomeres betauiniques, polymeres correspondants ainsi que leur utilisation, et procedes de preparation y relatifs.
JPH11222470A (ja) * 1998-02-02 1999-08-17 Osaka Organic Chem Ind Ltd グリシンベタインモノマーの製法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199943, Derwent World Patents Index; Class A41, AN 1999-512438, XP002178136 *

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