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WO2005070971A1 - Procede pour preparer des derives de chitosane, derives obtenus, compositions contenant ces derniers et methode de traitement - Google Patents

Procede pour preparer des derives de chitosane, derives obtenus, compositions contenant ces derniers et methode de traitement Download PDF

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Publication number
WO2005070971A1
WO2005070971A1 PCT/EP2004/013021 EP2004013021W WO2005070971A1 WO 2005070971 A1 WO2005070971 A1 WO 2005070971A1 EP 2004013021 W EP2004013021 W EP 2004013021W WO 2005070971 A1 WO2005070971 A1 WO 2005070971A1
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Prior art keywords
chitosan
weight
inclusive
composition
derivatives
Prior art date
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Ceased
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PCT/EP2004/013021
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English (en)
Inventor
Michel Angel Lopez
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LOreal SA
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LOreal SA
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Filing date
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Priority claimed from FR0450099A external-priority patent/FR2865210B1/fr
Application filed by LOreal SA filed Critical LOreal SA
Publication of WO2005070971A1 publication Critical patent/WO2005070971A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • 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
    • A61K8/73—Polysaccharides
    • A61K8/736—Chitin; Chitosan; Derivatives thereof
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • the present invention relates to new chitosan derivatives, to their use, particularly in cosmetology or pharmacy, and to the compositions comprising them, particularly cosmetic or pharmaceutical compositions.
  • Chitosan derivatives are well-known compounds within the cosmetology field. Mention may be made for example of patent US 3,879,376, which relates to chitosan derivatives which can be employed particularly as a skin moisturizer or film former in cosmetic skincare or cleansing products. Mention may also be made of US 4,765,976, which relates to polymers derived from chitosan which can be used to treat the greasy appearance of hair.
  • n N-CMC N-carboxymethylchitosans
  • N-CMC N-CMC by reacting the free amino groups of shrimp-extract chitosan with glyoxylic acid to give a soluble imine, which is reduced using cyanoborohydride .
  • the N-CMC obtained contain free amino moieties, amino moieties which are acetylated, and N-carboxy ⁇ nethyl moieties, in proportions which are controlled, say the authors, as a function of the initial degree of acetylation and of the molecular weight of the chitosan, and of the amount of glyoxylic acid employed. Mention may also be made of the Muzzarelli et al . publication Carhohydr.
  • the Muzzarelli et al . document Int. J. Biol . Macromol . (1994) , 16(4), 177-180 describes, for its part, water-soluble N-CMC prepared from starting chitosan possessing a weight-average molecular mass (M w ) of 700,000.
  • the first reaction step (the formation of the imine) must be carried out, according to the literature, on a highly dilute aqueous chitosan solution, containing of the order of 6 g to 14 g of chitosan per litre of water, corresponding to a concentration of 0.6% to 1.4% by weight. It has been noted, in the prior art, that this dilution of the chitosan is necessary in order to prevent possible problems of gelling of the mixture during the formation of the N-CMC. However, the use of a highly dilute solution of chitosan is not desirable from an industrial standpoint, particularly since it implies, among other things, the use of large-sized reactors if the desire is to prepare industrial quantities of N-CMC.
  • the aim of the present invention is to provide new N-carboxymethylchitosan derivatives which are totally soluble in aqueous media within a wide pH range, thereby allowing them in particular to be employed advantageously in the cosmetic and pharmaceutical fields. Furthermore, another aim of the present invention is to provide a new process for synthesizing N-CMC which is simple to implement and can be transposed to the industrial scale with a substantial productivity.
  • the present invention accordingly first provides a process for preparing chitosan derivatives, comprising the following steps: in a first step, reacting a chitosan with a carboxymethylating agent to form an imine, - in a second step, reducing the imine formed, by using a reducing agent, characterized in that the weight-average molecular mass (M w ) of the starting chitosan is between 50 000 and 160 000, in particular between 60 000 and 150 000, and/or the level or degree of acetylation (DA) of the said chitosan is greater than or equal to 12%, in particular between 12% and 27%, or even 15%-25%, preferably 20%-24%.
  • M w weight-average molecular mass
  • DA level or degree of acetylation
  • the invention secondly provides a process for preparing chitosan derivatives, comprising the following steps: - in a first step, reacting a chitosan with a carboxymethylating agent to form an imine, in a second step, reducing the imine formed, by using a reducing agent, characterized in that the average molecular mass M w and/or the degree of acetylation of the chitosan are selected such that the viscosity at 25°C of a solution of the said chitosan at 1% by weight in an aqueous solution containing 1% by weight of acetic acid is less than or equal to 4 mm 2 /s, in particular between 1 and 3.5 mm 2 /s, especially between 1.5 and 3.2 mm 2 /s, or even between 2.5 and 3.0 mm 2 /s.
  • the invention additionally provides the chitosan derivatives of the formula given below.
  • the invention further provides a composition, particularly a cosmetic or pharmaceutical composition, comprising the said chitosan derivatives. It has been found that, surprisingly, the process according to the invention, and especially the selection of the starting chitosan, makes it possible to obtain a chitosan derivative which no longer contains a free amine unit (-NH 2 ) and which is totally soluble in water. Moreover, the process according to the invention makes it possible to prepare N-CMC without having to carry out substantial dilution in water in order to employ the process, without, moreover, gelling of the mixture being observed.
  • the process according to the invention is characterized primarily in that the aqueous solution of chitosan is particularly concentrated especially in the first step, and possibly in the second step, of the process, thereby making it possible to reduce the size of the reactors employed, to generate less "waste" for recycling, to make energy savings, to improve the recovery of the end product , by having a more concentrated solution to filter, which also makes it possible to improve the yield.
  • the end product obtained exhibits excellent cosmetic characteristics which are entirely reproducible from one batch to the other; furthermore, the end product is totally water-soluble at 25°C.
  • the first step consists in reacting, in water, a chitosan with a carboxymethylating agent to form an imine.
  • the starting chitosan may be of any origin, especially from crab or from shrimp. Its weight-average molecular mass (M w ) is preferably between 50 000 and 160 000, in particular between 60 000 and 150 000. M w is determined by gel permeation liquid chromatography (solvent: aqueous solution containing 0.3 M acetic acid + 0.1 M ammonium acetate, in 1 litre of water; calibration curve constructed using dextran standards, refractometric detector) .
  • the chitosan employed preferably has a level or degree of acetylation (DA) of greater than or equal to 12%, in particular between 12% and 27%, or even 15%-25%, preferably 20%-24%.
  • the DA is determined by NMR or from the amine index.
  • the starting chitosan preferably has an amine index of less than or equal to 5.31 meq/g, in particular between 4.23 and 5.29 meq/g, especially between 4.37 and 5.08 meq/g, or even between 4.44 and 4.72 meq/g.
  • the amine index is determined by potentiometric assay (back-titration assay with NaOH of an acidic solution of chitosan) .
  • potentiometric assay back-titration assay with NaOH of an acidic solution of chitosan.
  • the reaction mixture remains continuously fluid, despite the fact that the concentration of chitosan is greater than in the prior-art processes.
  • M w of the chitosan is greater than approximately 150 000 the formation of a gel is generally observed during the reaction. Accordingly, commonly, the viscosity at 25°C of a solution of chitosan of M w 100 000 at 1% by weight in an aqueous solution containing 1% by weight of acetic acid is approximately 2.5 cSt (2.5 mm 2 /s) as measured in an Ubbelohde capillary tube viscometer, at 25°C and 1 atm.
  • the average molecular mass M w and/or the degree of acetylation of the chitosan are preferably selected such that the viscosity at 25 °C of a solution of the said chitosan at 1% by weight in an aqueous solution containing 1% by weight of acetic acid is less than or equal to 4 cSt (4 mm 2 /s) , in particular between 1 and 3.5 mm 2 /s, especially between 1.5 and 3.2 mm 2 /s, or even between 2.5 and 3.0 mm 2 /s.
  • the carboxymethylating agent used in the first reaction step may be an oxo acid, and especially oxalacetic acid, pyruvic acid or glyoxylic acid of formula CH(0)-COOH.
  • the carboxymethylating agent is very preferably present in excess relative to the chitosan, in particular in an amount of from 2 to 4 molar equivalents per equivalent of amine present in the starting chitosan.
  • the first reaction step is carried out at a pH of between 2 and 3.2, in particular at a pH of between 2.3 and 3.0, and hence without addition of base such as NaOH, and at ambient temperature (20-25°C) .
  • the second step of the process consists in reducing the imine formed, using a reducing agent, such as sodium borohydride or sodium cyanoborohydride .
  • the second reaction step is preferably carried out at a temperature of between 5 and 20°C, preferably between 10 and 15°C.
  • the N-CMC thus obtained may then be precipitated, in methanol or ethanol for example, and then filtered and dried according to the usual methods.
  • the reaction scheme may be illustrated as follows :
  • this novel process for preparing chitosan derivatives is particularly advantageous: it allows these derivatives to be prepared on the industrial scale in so far as it can be conducted in standard light equipment under pH, pressure and temperature conditions which can be employed without danger on the industrial scale. Furthermore, it does not require large amounts of water for its implementation, particularly in the first step of the process. This is because of the specific choice of the initial chitosan, which makes it possible to operate at a higher concentration of product in water than in the prior art, without any increase in viscosity being noted.
  • water-soluble By water-soluble is meant that the N-CMC of formula (I) form a homogeneous aqueous solution, without visually apparent deposition, at a concentration of 10% by weight in water at 25°C. It has even been noted that the chitosan derivatives of formula (I) according to the invention could advantageously still be soluble in water at 25°C at a concentration which may range up to 20% by weight, or even 25% by weight.
  • the chitosan derivatives preparable according to the process of the present invention are new products per se.
  • x is between 15 and 25 inclusive or even 20-24 inclusive.
  • z is between 3 and 10 inclusive, in particular between 4 and 6 inclusive.
  • y is between 65 and 77 inclusive, in particular between 70 and 74 inclusive.
  • the values x, y and z are statistical values and represent the relative molar proportion (molar %) of each of the units; x corresponds to the initial degree of acetylation of the chitosan and can be determined by NMR or from the amine index of the initial chitosan. The values of y or z can be determined by 13 C NMR.
  • the chitosan derivatives according to the invention have a viscosity at 25°C and 1 atm in solution at 20% by weight in an aqueous solution of less than or equal to 22 000 mPa.s, in particular between 2000 and 21 600 mPa.s, preferably between 2500 and 18 000 mPa.s, or even between 3000 and 15 500 mPa.s.
  • the viscosity of the chitosan derivatives is measured at 25°C by means of a Rheomat rheometer at a shear rate (imposed stress) of 200 s "1 .
  • the chitosan derivatives have a weight-average molecular mass (M w ) of between 200 000 and 600 000, preferably between 400 000 and 550 000; the average molecular mass is measured by gel permeation liquid chromatography, with an aqueous solution containing 0.1 M NaHC0 3 and 0.1 M Na 2 C0 3 per litre of water, as solvent; the calibration curve is drawn up with dextran standards, and the detector is refractometric .
  • M w weight-average molecular mass
  • M w weight-average molecular mass
  • the said derivative may be present in a proportion of from 1% to 20% by weight in the composition, in particular from 2% to 12.5% by weight or even from 5% to 10% by weight.
  • the cosmetically or pharmaceutically acceptable medium may comprise the customary adjuvants which are incorporated into cosmetic or pharmaceutical compositions.
  • fatty substances and particularly hydrocarbon and/or silicone waxes, oils, gums and/or pasty fats, and pulverulent compounds such as pigments, fillers and/or nacres.
  • waxes that may be present in the composition according to the invention mention may be made, alone or in a mixture, of hydrocarbon waxes such as beeswax; carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fibre wax or sugarcane wax; paraffin wax and lignite wax; microcrystalline waxes; lanolin wax; montan wax; ozokerites; polyethylene waxes; waxes obtained by Fischer-Tropsch synthesis; hydrogenated oils, fatty esters and glycerides which are solid at 25°C. It is also possible to use silicone waxes, among which mention may be made of the alkyls, alkoxys, and/or polymethylsiloxane esters .
  • hydrocarbon waxes such as beeswax; carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fibre wax or sugarcane wax; paraffin wax and lignite wax; microcrystalline waxes; lanolin wax; montan
  • hydrocarbon oils such as liquid paraffin or vaseline; perhydrosqualene; acara oil; sweet almond oil, calophyllum oil, palm oil, castor oil, avocado oil, jojoba oil, olive oil or cereal germ oil; esters of lanolic acid, of oleic acid, of lauric a'cid,
  • silicone oils such as PDMS, optionally in phenylated form such as the phenyltrimethicones .
  • volatile oils such as cyclotetradimethyl- siloxane, cyclopentadimethylsiloxane, cyclohexadi- methylsiloxane, methylhexyldimethylsiloxane, hexa- methyldisiloxane or isoparaffins .
  • the pigments may be white or coloured, mineral and/or organic.
  • mineral pigments mention may be made of titanium dioxide, zirconium dioxide or cerium dioxide, and also zinc oxide, iron oxide or chromium oxide, and ferric blue.
  • organic pigments mention may be made of carbon black and lakes of barium, strontium, calcium or aluminium.
  • the nacres may be selected from mica covered with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride, and also coloured titanium mica .
  • the fillers may be mineral or synthetic, lamellar or non-lamellar. Mention may be made of talc, mica, silica, kaolin, nylon powder and polyethylene powder, Teflon, starch, mica-titanium, natural nacre, boron nitride, hollow microspheres such as Expancel (Nobel Industrie) , polytrap (Dow Corning) and silicone resin microbeads (Tospearls from Toshiba, for example) .
  • the medium may further comprise water and/or an organic solvent such as a C1-C8 alcohol or a polyol, for example glycerol .
  • the composition may further comprise any additive which is commonly used in the cosmetic field, such as antioxidants, perfumes, essential oils, preservatives, cosmetic actives, moisturizers, vitamins, essential fatty acids, sphingolipids, sunscreens, surfactants, fat-soluble polymers such as polyalkylenes, especially polybutene, polyacrylates and silicone polymers which are compatible with the fatty substances.
  • any additive which is commonly used in the cosmetic field such as antioxidants, perfumes, essential oils, preservatives, cosmetic actives, moisturizers, vitamins, essential fatty acids, sphingolipids, sunscreens, surfactants, fat-soluble polymers such as polyalkylenes, especially polybutene, polyacrylates and silicone polymers which are compatible with the fatty substances.
  • compositions according to the invention may be present in any form which is acceptable and customary for a cosmetic or pharmaceutical composition, and particularly in the form of a hair composition, especially a hair washing, hair care or hair shape retention composition; a face or body skin care composition; or a composition for making up the face, body, nails or hair.
  • the present invention likewise provides a cosmetic treatment process for the care, cleansing and/or making-up of keratin materials such as the skin of the body or face, the scalp, eyebrows, eyelashes, lips and nails, which consists in applying to the said keratin materials a composition as defined above.
  • the invention is illustrated in greater detail in the examples below.
  • Example 1 A reactor is charged with 1 kg of shrimp chitosan, with a weight-average molecular mass (M w ) of 148 900 and a degree of acetylation of 23%, 1.14 litres of 50% aqueous glyoxylic acid solution and 9.86 litres of water.
  • M w weight-average molecular mass
  • This initial charge is mixed at 20°C for 1 hour until the chitosan has completely dissolved; stirring of the solution is continued at 20°C for 6 hours.
  • the solution has a pH of 3.
  • a solution is prepared containing 283 g of NaBH / 910 ml of water and 20 g of 35% sodium hydroxide.
  • the reaction mixture is cooled to 10°C and then the solution of NaBH is run in over 1 hour, during which the temperature is held below 15°C. Stirring is continued for 1 hour after the end of the addition of NaBH 4 (the pH is 7.4) .
  • 35 litres of methanol are cooled to 10 °C and then the reaction mixture containing the product is poured on top.
  • a white precipitate forms which is isolated by filtration, washed with isopropanol and dried under vacuum at 40 °C.
  • Turbidity zone (range of insolubility of an aqueous solution containing 2% by weight of the derivative) : between a pH of 2.4 and 5.3
  • Solubility greater than 20% by weight in water at 25°C It is therefore found that, with the process according to the invention, a derivative of chitosan is obtained for which all of the free amine functions are substituted.
  • Example 2 New derivatives of chitosan according to the invention are prepared in accordance with Example 1, varying the weight-average molecular mass (M w ) and/or the degree of acetylation (DA) of the starting chitosan.
  • M w weight-average molecular mass
  • DA degree of acetylation
  • Example 3 A mascara is prepared comprising the following ingredients (in % by weight) :

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Abstract

La présente invention concerne un procédé pour préparer des dérivés de N-carboxyméthylchitosane ainsi que les dérivés de chitosane obtenus, des compositions cosmétiques et pharmaceutiques contenant lesdits dérivés et une méthode de traitement cosmétique utilisant ces derniers.
PCT/EP2004/013021 2004-01-20 2004-11-17 Procede pour preparer des derives de chitosane, derives obtenus, compositions contenant ces derniers et methode de traitement Ceased WO2005070971A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR0450099A FR2865210B1 (fr) 2004-01-20 2004-01-20 Procede de preparation de derives de chitosane, derives obtenus, compositions les comprenant et procede de traitement
FR0450099 2004-01-20
US56097304P 2004-04-12 2004-04-12
US60/560,973 2004-04-12

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WO2005070971A1 true WO2005070971A1 (fr) 2005-08-04

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2105459A4 (fr) * 2007-01-16 2013-05-22 Dainichiseika Color Chem Composition à solution aqueuse
EP2697264A4 (fr) * 2011-04-13 2014-11-05 Teknologian Tutkimuskeskus Vtt Oy Procédé de dissolution de polymères naturels
CN112852023A (zh) * 2021-01-13 2021-05-28 武汉理工大学 一种生物质高介电纳米复合膜的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0212688A2 (fr) * 1985-06-21 1987-03-04 Consiglio Nazionale Delle Ricerche Glycanes substitués et réticulés, procédé et pour leur préparation et leur utilisation
US4765976A (en) * 1986-04-18 1988-08-23 L'oreal Method for combating the greasy appearance of hair
WO1988008698A1 (fr) * 1987-05-09 1988-11-17 Wella Aktiengesellschaft Nouveaux derives macromoleculaires tensio-actifs quaternaires de chitosan n-substitues et cosmetique a base de ces nouveaux derives de chitosan
DE19857546A1 (de) * 1998-12-14 2000-06-15 Cognis Deutschland Gmbh N-substituierte Biopolymere
DE19857545A1 (de) * 1998-12-14 2000-06-15 Cognis Deutschland Gmbh Verfahren zur Herstellung N-substituierter Biopolymere

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0212688A2 (fr) * 1985-06-21 1987-03-04 Consiglio Nazionale Delle Ricerche Glycanes substitués et réticulés, procédé et pour leur préparation et leur utilisation
US4765976A (en) * 1986-04-18 1988-08-23 L'oreal Method for combating the greasy appearance of hair
WO1988008698A1 (fr) * 1987-05-09 1988-11-17 Wella Aktiengesellschaft Nouveaux derives macromoleculaires tensio-actifs quaternaires de chitosan n-substitues et cosmetique a base de ces nouveaux derives de chitosan
DE19857546A1 (de) * 1998-12-14 2000-06-15 Cognis Deutschland Gmbh N-substituierte Biopolymere
DE19857545A1 (de) * 1998-12-14 2000-06-15 Cognis Deutschland Gmbh Verfahren zur Herstellung N-substituierter Biopolymere

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Title
MUZZARELLI R A A: "CARBOXYMETHYLATED CHITINS AND CHITOSANS", CARBOHYDRATE POLYMERS, APPLIED SCIENCE PUBLISHERS, LTD. BARKING, GB, vol. 8, 1988, pages 1 - 21, XP000940578, ISSN: 0144-8617 *
RICCARDO A. A. MUZZARELLI ET AL.: "n-(carboxymethylidene)chitosansand n-(carboxymethyl)-chitosans: novel chelating polyampholytes obtained from chitosan glyoxylate", CARBOHYDRATE RESEARCH, vol. 107, no. 2, September 1982 (1982-09-01), NL, pages 199 - 214, XP002292524 *
RINAUDO M ET AL: "SUBSTITUENT DISTRIBUTION ON O,N-CARBOXYMETHYLCHITOSANS BY 1H AND 13C N.M.R", INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES, vol. 14, no. 6, June 1992 (1992-06-01), pages 122 - 128, XP008034084 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2105459A4 (fr) * 2007-01-16 2013-05-22 Dainichiseika Color Chem Composition à solution aqueuse
EP2697264A4 (fr) * 2011-04-13 2014-11-05 Teknologian Tutkimuskeskus Vtt Oy Procédé de dissolution de polymères naturels
CN112852023A (zh) * 2021-01-13 2021-05-28 武汉理工大学 一种生物质高介电纳米复合膜的制备方法

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