EP1778708A1 - Nouveaux glycopolymeres, leurs utilisations, et monomeres utiles pour leur preparation - Google Patents
Nouveaux glycopolymeres, leurs utilisations, et monomeres utiles pour leur preparationInfo
- Publication number
- EP1778708A1 EP1778708A1 EP05790974A EP05790974A EP1778708A1 EP 1778708 A1 EP1778708 A1 EP 1778708A1 EP 05790974 A EP05790974 A EP 05790974A EP 05790974 A EP05790974 A EP 05790974A EP 1778708 A1 EP1778708 A1 EP 1778708A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- units
- glycoside
- monomer
- monomers
- 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- Withdrawn
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Classifications
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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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
-
- 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
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; 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
- A61K8/90—Block copolymers
-
- 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
-
- 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
- A61Q19/10—Washing or bathing preparations
-
- 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
- A61Q5/12—Preparations containing hair conditioners
-
- 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
- C07H15/12—Acyclic radicals, not substituted by cyclic structures attached to a nitrogen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/04—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen
- C07H5/06—Aminosugars
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- 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
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/606—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing other heteroatoms
Definitions
- Novel glycopolymers their uses, and monomers useful for their preparation
- the present invention relates to novel glycopolymers, their uses, as well as new monomers useful for their preparation.
- the invention also relates to processes for the preparation of novel monomers and glycopolymers.
- Glycopolymers are polymers comprising units comprising a glycoside unit. They can be obtained by polymerization of monomers comprising a glycoside, by copolymerization in the presence of other monomers, or by grafting on a polymer functionalized for this purpose.
- the present invention provides other glycopolymers, and other monomers comprising a glycoside. These novel glycopolymers and monomers may be useful in modulating the properties of the glycopolymers, and thus allow, in their use, to provide new products. It is thus possible to modulate the properties of polymers used for example in cosmetic compositions.
- glycopolymers are attracting increasing interest in the fields of industry and / or consumer products because they are products derived from natural products, benefiting from a positive image in terms of the protection of the environment and / or harmfulness and / or more simply marketing. There is a need for such products.
- the invention provides a polymer comprising units comprising a glycoside, characterized in that it comprises:
- cationic or potentially cationic units A 0 preferably derived from a cationic or potentially cationic mono-alpha-ethylenically unsaturated monomer
- X is a hydrogen atom or a methyl group
- L is a divalent linking group - Z is an oxygen or sulfur atom, or a group comprising a nitrogen atom and
- - G is a glycoside
- the invention also relates to uses of the polymer in compositions.
- the invention also relates to compositions comprising the polymer.
- the invention also relates to a monomer particularly suitable for preparing the polymer according to the invention.
- the invention also provides a monomer of formula (I 1 ) below
- X is a hydrogen atom or a methyl group
- - Z is an oxygen atom, or a group comprising a nitrogen atom and - G is a glycoside, characterized in that:
- L 1 is a divalent linking group, preferably a divalent hydrocarbon group, preferably a divalent C 1 -C 6 alkyl group,
- L 2 is a divalent linking group, preferably a divalent hydrocarbon group, preferably a divalent C 1 -C 6 alkyl group, and - G is linked to Z by an anomeric carbon of the glycoside.
- the monomer according to the invention can be used for the preparation of the polymers according to the invention. It can also be used for the preparation of other polymers, for example homopolymers of said monomer, or for the preparation of copolymers which do not comprise cationic or potentially cationic units, but which comprise other units. It may be, for example, copolymers comprising units derived from the monomer of formula (I 1 ) and; as other units, neutral, anionic, and / or potentially anionic, hydrophobic and / or hydrophilic units. Such units are described later.
- polymer any macromolecular compound comprising recurring units.
- the polymers include, in particular, homopolymers, copolymers, oligomers, co-oligomers, telomers, co-telomers.
- copolymer means any polymer comprising at least two different recurring units.
- the copolymers include, in particular, random copolymers, copolymers of controlled structure, co-oligomers (copolymers of relatively low molecular weight), co-telomers.
- Controlled structure (co) polymer is understood to mean any (co) polymer whose sequence of patterns is controlled (for example di-block, tri-block, but also concentration gradient polymer co-polymers) and / or the polydispersity is controlled (for example random (co) polymers with a polydispersity index of 1 to 1.5), as opposed to (co) polymers obtained by standard polymerization processes, which do not allow such a control of the polymer. unit patterns and polydispersity indices so small. It may be a copolymer comprising at least two parts A and B of distinct compositions in repeating units.
- the parts of a copolymer with a controlled structure may in particular be blocks, linear skeletons, side chains, grafts, "hair" or branches of microgels or stars, hearts of stars or microgels, or else further parts of polymer chains having different concentrations in different units.
- the controlled structure that a copolymer can present can be chosen from the following structures: - block copolymer, comprising at least two blocks, part A corresponding to one block, part B corresponding to another.
- Part A is usually composed of several different units, possibly having a composition gradient.
- Part A may also have a random copolymer structure. So the Part A may have a homopolymer structure (if it comprises A z units), a random copolymer or a composition gradient copolymer.
- It may for example be a block copolymer (block A) - (block B) - (block A), or (block B) - (block A) - (block B), or (block A) - (block B).
- - comb or graft copolymer comprising a backbone and side chains, with part A corresponding to the backbone and part B corresponding to side chains, or with part B corresponding to the backbone and part A corresponding to side chains.
- star or microgel copolymer comprising a polymer or non-polymer core, and peripheral polymer chains, one part corresponding to the core, the other corresponding to the peripheral chains.
- Part A may correspond to the core and part B may correspond to the peripheral chains.
- part B may correspond to the heart and part A may correspond to peripheral chains.
- Monomers are compounds which can be used for the preparation of polymers, homopolymers or copolymers (we can also speak of comonomers).
- the repeating units of the polymers derive from these monomers.
- the unit derived from a monomer denotes a unit that can be obtained directly from said monomer by polymerization.
- a unit derived from an acrylic or methacrylic acid ester does not cover a unit of the formula -CH 2 -CH (COOH) -, -CH 2 -C (CH 3 ) (COOH) -, - CH 2 - CH (OH) -, respectively, obtained for example by polymerizing an ester of acrylic or methacrylic acid, or vinyl acetate, respectively, and then hydrolyzing.
- a unit derived from acrylic or methacrylic acid for example covers a unit obtained by polymerizing a monomer (for example an acrylic or methacrylic acid ester), then reacting (for example by hydrolysis) the polymer obtained so as to obtain units of formula -CH 2 -CH (COOH) -, or - CH 2 -C (CH 3 ) (COOH) -.
- a unit derived from a vinyl alcohol for example covers a unit obtained by polymerizing a monomer (for example a vinyl ester), then reacting (for example by hydrolysis) the polymer obtained so as to obtain units of formula -CH 2 -CH (OH) -.
- the average molar masses are absolute weight average molar masses, which can be measured by exclusion chromatography in a suitable steric solvent (for example deionized Millipore water if appropriate), coupled to refractometer, to a conductivity meter and a multi-angle light scattering detector, with zero-angle extrapolation (GPC-MALS).
- a suitable steric solvent for example deionized Millipore water if appropriate
- glvcoside refers to any group comprising one or more glycoside units, and derivatives thereof.
- the glycoside comprises several glycoside units
- polyglycosides are also referred to.
- polyglycoside is meant a glycoside comprising at least two glycoside units.
- glycoside units the glycosides, the polyglycosides, their derivatives, their structures and formulas are known to those skilled in the art. It is specified for the glycoside units that it can in particular be aldoses, ketoses, or derivatives, in cycles with
- glycosides, polyglycosides, and derivatives thereof have an "anomeric carbon” reducing at one end, the right according to writing conventions. It is also known that the glycoside units, the glycosides, the polyglycosides, and their derivatives have hydroxyl groups (-OH), carboxylic acid, or amines, optionally protected.
- Glycosides include:
- O-, S-, N-, C-alkyl or aryl-glycosides optionally comprising at least one -COOH group
- Glucose for example D-glucose
- fructose for example D-glucose
- sorbose mannose
- galactose talose
- allose gulose
- idose glucosamine
- mannoamine galactosamine
- glucuronic acid rhamnose
- arabinose galacturonic acid
- fucose xylose
- lyxose ribose
- sucrose such as palatinose.
- glycosides examples include di- or oligosaccharide glycosides:
- maltose maltose, gentiobiose, lactose, cellobiose, isomaltose, melibiose, laminaribiose, chitobiose, xylobiose, maoriobiosis, sophorosis,
- maltodextrins in particular, maltotriose, isomaltotriose, maltotetraose, maltopentaose, maltoheptaose
- branched oligosaccharides such as xyloglucan
- xyloglucan branched oligosaccharides, such as xyloglucan
- mannotriose mannotriose
- mannotriose mannotriose
- the di- or oligosaccharides having ⁇ - or ⁇ -12, -3, -4, -5 or -6 bonds.
- glycosides are:
- starch derivatives in particular maltose, maltodextrins,
- pectins and their derivatives pectins and their derivatives, chitin, chitosan and their derivatives,
- derivatives of xyloglucans in particular derivatives obtained by hydrolysis, for example by enzymatic hydrolysis
- galactomannans and their derivatives for example guar polymers and their derivatives, obtained by hydrolysis of natural guar, and optionally chemical modification (derivatization).
- Natural guar is extracted from the albumen of certain plant seeds, for example Cyamopsis Tetragonalobus.
- the guar macromolecule is constituted by a linear main chain constructed from monomeric ⁇ -D-mannose sugars linked together by (1-4) bonds, and ⁇ -D-galactose side units linked to ⁇ -D-mannoses. by links (1-6).
- Polyglycosides comprising several glycoside units, can be described as chains of glycosides (mono- and / or polyglycosides).
- a sequence of glycosides by the formula G a -G b -, wherein G a is a glycoside or a polyglycoside, and G b is a glycoside or a polyglycoside.
- G a or G b is a polyglycoside
- the latter may also be described by a formula G a ' -G b -, wherein G a' is a glycoside or a polyglycoside, and G b is a glycoside or a glycoside.
- the polymer comprises units derived from a monomer of formula (I) below:
- - L is a divalent linking group
- Z is an oxygen or sulfur atom, or a group comprising a nitrogen atom
- - G is a glycoside
- G can in particular be linked by:
- G has an acid or amine function on other positions, it can be grafted by this function.
- Z is an oxygen atom, a group -NH-, or -N [COCH 3 ] -, and
- G is linked to -Z- by an anomeric carbon of the glycoside.
- the group -LZG is a group of formula -O-CH 2 CH 2 -OG.
- Monomers having such a group are for example marketed by the company Nippon Seika, under the name Sucrograph.
- the group -L-Z-G may be a group of formula -CO-NH-G, or -CO-aryl-NH-G.
- the monomer of formula (I) is a monomer of formula (I 1 ) as described below.
- a monomer particularly suitable for the implementation of the invention has the following formula (I 1 )
- X is a hydrogen atom or a methyl group
- Z is an oxygen atom, or a group comprising a nitrogen atom and
- - G is a glycoside, characterized in that:
- Y is a divalent linking group or a linking atom
- L 1 is a divalent linking group, preferably a divalent hydrocarbon group, preferably a divalent Ci-C 6 alkyl group,
- L 2 is a divalent linking group, preferably a divalent hydrocarbon group, preferably a divalent C 1 -C 6 alkyl group, and
- - G is bound to Z by an anomeric carbon of the glycoside.
- Y is -O- or -NH-
- L 1 and L 2 are C 1 -C 4 alkyl groups.
- the monomer of formula (I) or (I 1 ) or (I ") has the following formula (III 1 ):
- the group -Z- of the formula (I) or (I 1 ) or (I ") is the group -N (COCH 3 ) -,
- the group -L- or -L'- of the formula (I) or (I 1 ) is the group -CONH- (CH 2 ) 2 -S- (CH 2 ) 3,
- the group L 1 of the formula (H ') is the group - (CH 2 V, and
- the L 2 group of the formula (II 1 ) is the group - (CH 2 ) 3 -.
- the monomer of formula (I), (I 1 ), (I ") or (III 1 ) may have one of the following formulas:
- m and n which are identical or different, are numbers from 0 to 10, preferably 0 or 1.
- the monomer of formula (I 1 ) can be prepared by a process comprising the following steps:
- the functionalizing reagent is preferably allylamine.
- reaction can be carried out in the absence of a solvent at room temperature, but other reaction modalities are not excluded.
- step a) may comprise the following steps: a1) reaction of the anomeric carbon of a glycoside of formula G-OH, comprising free -OH groups with excess allylamine, a2) elimination of allylamine in excess, a3) reaction with acetic anhydride, so as to protect the nitrogen atom, and optionally primary -OH groups of the glycoside.
- Step a3) of reaction with acetic anhydride can be carried out under conditions such that at least a portion of the -OH groups of the glycoside are acetylated, in addition to the nitrogen atom.
- This acetylation of -OH groups may be promoted, or retained, or removed in a subsequent step, for example by a slightly basic hydrolysing treatment of the O-acetates groups.
- the addition of the compound can be carried out by radical reaction, either in the presence of a radical initiator (initiator) or by photochemical reaction.
- the reaction preferably takes place in a minimum of solvent, for example water, if necessary by heating.
- solvent for example water
- This embodiment can make it possible in particular to implement lower amounts of solvent, to increase the kinetics of reaction, to improve the final yield obtained.
- Initiators that can be used are known to those skilled in the art.
- V50 alpha.alpha'-azodiisobutyramidine dihydrochloride dihydrochloride
- VA-041 (2,2'-Azobis [2- (5-methyl-2-imidazolin-2-yl) dihydrochloride). ) propane]
- VA-060 (2,2'-dihydrochloride) Azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ ).
- step c) is preferably a non-enzymatic chemical type reaction.
- the reaction can take place at room temperature and more preferably in the cold, in a solvent medium for example in water or a water / alcohol mixture.
- the solvent mixture is preferably adapted to have good solubility of the compounds in the presence.
- the alcohol may be, for example, methanol, isopropyl alcohol or tert-butyl alcohol.
- a base sodium carbonate, sodium acetate, tertiary amine, etc.
- the reaction is generally rapid.
- One embodiment of this step can be represented by the following reaction scheme:
- the glycoside G is preferably a polyglycoside.
- Glycosides which may constitute G groups of monomers of formula (I), (! '), (I "), or (IH') have been described above in the" definitions "section.
- the polymer according to the invention comprises cationic or potentially cationic units A 0 , which can be derived from cationic or potentially cationic monomers.
- cationic or potentially cationic units it is meant units which comprise a cationic or potentially cationic group.
- Cationic units or groups are units or groups that have at least one positive charge (generally associated with one or more anions such as chloride ion, bromide ion, sulfate group, methyl sulfate group), regardless of pH of the medium where the copolymer is present.
- the potentially cationic units or groups are units or groups that can be neutral or have at least one positive charge depending on the pH of the medium where the copolymer is present. In this case, we will speak of potentially cationic units A 0 in neutral form or in cationic form. By extension we can speak of cationic or potentially cationic monomers.
- N dialkylaminoalkyl amides of ⁇ , ⁇ monoethylenically unsaturated carboxylic acids, such as 2 (N, N-dimethylamino) ethyl-acrylamide or -methacrylamide, 3 (N, N-dimethylamino) propyl-acrylamide or
- ⁇ - ⁇ mono-ethylenically unsaturated amino esters such as 2 (dimethyl amino) ethyl acrylate (ADAM), 2 (dimethyl amino) ethyl methacrylate (DMAM), 3 (dimethyl amino) propyl methacrylate, 2 (tert-butylamino) ethyl methacrylate, 2 (dipentylamino) ethyl methacrylate, 2 (diethylamino) ethyl methacrylate, ethylene urea ethyl methacrylate,
- Amine precursor monomers such as N-vinyl formamide, N-vinyl acetamide, which generate primary amine functions by simple acid or basic hydrolysis.
- Ammonium acryloyl or acryloyloxy monomers such as trimethylammoniumpropylmethacrylate chloride, trimethylammoniumethylacrylamide or methacrylamide chloride or bromide, methylsulfate trimethylammoniumbutylacrylamide or methacrylamide, trimethylammoniumpropylmethacrylamide methylsulfate (MES), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), (3-acrylamidopropyl) trimethylammonium chloride (APTAC), methacryloyloxyethyltrimethylammonium chloride or methylsulfate, acryloyloxyethyltrimethylammonium, acryloylethylbenzyl-dimethylammonium ethyl chloride (ADAMQUAT BZ);
- Polyquatemate monomers such as dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT) ...
- the polymer may also comprise other units, for example hydrophilic or hydrophobic neutral units A N and / or anionic units A A , anionic or potentially anionic.
- anionic or potentially anionic units A A are units which comprise an anionic or potentially anionic group.
- the units or anionic groups are units or groups which have at least one negative charge (generally associated with one or more cations such as cations of alkaline or alkaline-earth compounds, for example sodium, or cationic groups such as ammonium), whatever the pH of the medium where the copolymer is present.
- the potentially anionic units or groups are units or groups that can be neutral or have at least one negative charge depending on the pH of the medium where the copolymer is present. In this case, we will speak of potentially anionic units A A in neutral form or in anionic form. By extension, we can speak of anionic or potentially anionic monomers.
- Neutral AN units are understood to mean units which do not exhibit a charge, regardless of the pH of the medium in which the copolymer is present.
- anionic or potentially anionic monomers from which A A units may be derived mention may be made of: monomers possessing at least one carboxylic function, such as the ⁇ - ⁇ ethylenically unsaturated carboxylic acids or the corresponding anhydrides, such as acrylic, methacrylic, maleic, fumaric acid, itaconic acid, N-methacroyl alanine, N-acryloylglycine and their water-soluble salts
- Monomers having at least one sulphate or sulphonate function such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allyl sulphonic acid, 2-acrylamido-2-methylpropanesulphonic acid, sulphoethyl acrylate or methacrylate, acrylate or sulfopropyl methacrylate and their water-soluble salts
- Monomers having at least one phosphonate or phosphate function such as vinylphosphonic acid, esters of ethylenically unsaturated phosphates such as phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from RHODIA) and those derived from polyoxyalkylene methacrylates and their water-soluble salts
- hydropherically neutral nonionic monomers of which A N units may be suitable, mention may be made of:
- Vinylaromatic monomers such as styrene, alpha-methylstyrene, vinyltoluene, etc.
- vinyl or vinylidene halides such as vinyl chloride, vinylidene chloride
- C 1 -C 12 alkyl esters of ⁇ - ⁇ monoethylenically unsaturated acids such as methyl, ethyl, butyl acrylates and methacrylates, 2-ethylhexyl acrylate, etc. • vinyl or allyl esters of carboxylic acids saturated such as acetates, propionates, versatates, stearates ... vinyl or allyl
- ⁇ -olefins such as ethylene ... conjugated dienes, such as butadiene, isoprene, chloroprene,
- part B may be a silicone, for example a polydimethylsiloxane chain or a copolymer comprising dimethylsiloxy units.
- neutral hydrophilic nonionic monomers from which A N units may be derived mention may be made of: Hydroxyalkyl esters of ⁇ - ⁇ ethylenically unsaturated acids such as hydroxyethyl acrylate, hydroxypropyl acrylate and methacrylate, glycerol monomethacrylate, etc.
- ⁇ - ⁇ ethylenically unsaturated amides such as acrylamide, N, N-dimethyl methacrylamide, N-methylolacrylamide, etc.
- ⁇ - ⁇ ethylenically unsaturated monomers bearing a water-soluble polyoxyalkylene segment of the polyethylene oxide type such as ⁇ -methacrylate ethylene oxide (BISOMER S20W, S10W, ... from LAPORTE) or ⁇ , ⁇ -dimethacrylates, the SIPOMER BEM from RHODIA (polyoxyethylene ⁇ -behenyl methacrylate), SIPOMER SEM-25 from RHODIA (methacrylate from polyoxyethylene ⁇ -tristyrylphenyl) ...
- ⁇ - ⁇ ethylenically unsaturated monomers precursors of hydrophilic units or segments such as vinyl acetate which, once polymerized, can be hydrolysed to generate vinyl alcohol units or polyvinyl alcohol segments.
- the polymer according to the invention may be a random copolymer, a block copolymer, a concentration gradient copolymer, a star copolymer, a co-oligomer or a co-telomer. It is preferably a random copolymer.
- the polymer is water-soluble or water-dispersible. This means that said polymer does not form in water, over at least a certain range of pH and concentration, a two-phase composition under the conditions of implementation.
- the polymer according to the invention may be presented in particular in the form of a powder, in the form of a dispersion in a liquid or in the form of a solution in a solvent (water or other).
- the shape generally depends on the requirements related to the use of the polymer. It can also be related to the process for preparing the polymer.
- the polymer may comprise from 0.1% to 99.9% by number (molar) of units derived from the monomer of formula (I) or (I '), based on the total number of units in the polymer. It preferably comprises from 0.1% to 15% by number (molar).
- the polymer may comprise from 0.1% to 99.9% by number (molar) of cationic or potentially cationic units, based on the total number of units in the polymer. It preferably comprises from 0.1% to 15% by number (molar).
- the weight average molar mass, absolute may preferably be between 1000 g / mol and 500,000 g / mol. It is preferably between 50,000 g / mol and 1,000,000 g / mol.
- the polymers according to the invention can be obtained by any known method, whether by radical polymerization, controlled or not, by ring-opening polymerization (in particular anionic or cationic, with appropriate monomers), by anionic or cationic polymerization, or again by chemical modification of a polymer.
- the radical polymerization is preferably carried out in an oxygen-free environment, for example in the presence of an inert gas (helium, argon, nitrogen, etc.).
- the reaction is carried out in an inert solvent, preferably methanol or ethanol, and more preferably in water.
- the polymerization is initiated by addition of a polymerization initiator.
- the initiators used are the free radical generators usually used in the art. Examples include organic peresters; organic compounds of the azo type, for example azobisamidinopropane hydrochloride, azobis-isobutyronitrile, azo-bis-2,4-dimethylvaleronitrile, etc.); inorganic and organic peroxides, for example ammonium peroxide, sodium peroxide, potassium peroxide, hydrogen peroxide, benzyl peroxide and butyl peroxide, etc .; redox initiator systems, for example those comprising oxidizing agents, such as persulfates (especially ammonium or alkali metal persulfates, etc.), chlorates and bramates (including inorganic chlorates and / or bramates) or organic), and reducing agents such as sulphites and bisulfites (including inorganic and / or organic sulphites or bisulfites), ox
- the polymerization can be initiated by irradiation with ultraviolet light.
- the amount of initiator used is generally an amount sufficient to effect the initiation of the polymerization.
- the initiators are present in an amount ranging from 0.001 to approximately 10% by weight relative to the total weight of the monomers, and preferably are included in an amount of less than 2% by weight relative to the total weight of the monomers. preferred amount being in the range of 0.05 to 1% by weight based on the total weight of the monomers.
- the initiator is added to the polymerization mixture, either continuously or discontinuously.
- the polymerization is carried out under effective reaction conditions to polymerize the monomers (c) and the monomers (a) in an oxygen-free atmosphere.
- the reaction is conducted at a temperature ranging from about 30 ° to about 100 ° and preferably between 60 ° and 90 ° C.
- the oxygen-free atmosphere is maintained throughout the duration of the reaction, for example by maintaining a nitrogen sweep throughout the reaction.
- the direct grafting consists in polymerizing the monomer (s) chosen (s) by a radical route, in the presence of the polymer selected to form the skeleton of the final product. If the monomer / backbone pair and the operating conditions are judiciously chosen, then there may be transfer reaction between the growing macroradical and the backbone. This reaction generates a radical on the skeleton and it is from this radical that the graft grows.
- the primary radical derived from the initiator can also contribute to the transfer reactions.
- the copolymerization implements in a first step the grafting at the end of the future segment during a radical polymerizable function.
- This grafting can be carried out by usual methods of organic chemistry.
- the macromonomer thus obtained is polymerized with the monomer chosen to form the skeleton and a so-called "comb" polymer is obtained.
- the grafting can advantageously be carried out in the presence of a polymerization control agent as cited in the references above.
- the processes for preparing star-shaped polymers can be essentially classified into two groups.
- the first corresponds to the formation of the polymer arms from a multifunctional compound constituting the center ("core-first” technique) (Kennedy, JP et al., Macromolecules, 29, 8631 (1996), Deffieux, A. and al Ibid, 25, 6744, (1992), Gnanou, Y. et al., Ibid, 31, 6748 (1998)) and the second corresponds to a method where the molecules of polymers that will constitute the arms are first synthesized and then bonded together on a heart to form a star-shaped polymer ("arm-first" technique).
- arm-first As an example of synthesis of this type of polymer, reference may be made to patent WO 00/02939. Mention may also be made of polymerization processes starting from core comprising a plurality of transfer groups, and micelle cross-linking methods.
- the polymer according to the invention may in particular be used as an emulsifier or co-emulsifier for preparing or stabilizing emulsions. It can for example be used in emulsions of which one phase is a silicone oil. It can also be used to compatibilize several compounds within a formulation. It can also be used as a deposit aid for another compound, or as a trigger for the deposit of another compound. It can find a utility for vectorizing a compound, for example silicone, on a surface.
- the polymer may especially be used in cosmetic compositions, in detergent compositions for household care, in laundry care compositions, or as a molecular recognition agent, or as a transmembrane passage agent, or as an additive for paper pulp, coating composition for paper, paint, eg wood paint.
- cosmetic compositions include shampoos, conditioners, gel-shower or creams for the care of the skin.
- These compositions may further comprise at least one anionic and / or amphoteric surfactant, and optionally agents such as silicone oils, non-silicone oils and optionally modified polysaccharides.
- the polymer can provide conditioning, conditioning aid, sensory or "cosmetic" effects, touch effects, softness, suppleness, detangling aid, shine, hair styling ability on dry or wet hair.
- Step 1 Synthesis of ⁇ -acetyl- ⁇ -allyl- ⁇ -D-glucopyranosyl- (1-> 4) - ⁇ -D-glucopyranosylamine (Product 2) (Product 2)
- Cellobiose (Fluka) (5g, 14.6 mmol) is dissolved in allylamine (Aldrich) (150 ml).
- the reaction mixture is kept under magnetic stirring for 72 h at room temperature.
- Thin layer chromatography (“TLC", ethyl acetate / 1: 1 petroleum ether) is carried out on an acetylated aliquot according to a conventional method (pyridine / acetic anhydride 1/1). After evaporation to dryness, the product obtained is a white powder.
- the reaction crude is seleneacetylated in a methanol / acetic anhydride solution (100 mL, 5/1, v / v).
- the conversion is followed by thin layer chromatography (acetonitrile / water 7/3).
- the solution is stirred for 4 h and then evaporated to dryness after addition of methanol (3 times).
- TLC shows the formation of a second probably O-acetylated compound.
- To eliminate the crude is taken up in methanol (10OmL), and a 1M MeONa solution is added dropwise until a pH of 10 is obtained. This pH is determined by deposition of a drop of reaction mixture on a strip of moistened pH paper. TLC control shows the disappearance of the O-acetylated compound.
- the solution is then neutralized on Resin Amberite IR 120 H + , filtered, evaporated to dryness, and lyophilized.
- the product 2 is obtained in quantitative yield (6.18 g).
- Step 3 synthesis of ⁇ / -acetyl-W - [( ⁇ / -2-thioethyl) -2-propenamide] propyl] - ⁇ -D-glucopyranosyl- (1-4) - ⁇ -D-glucopyranosylamine (Product 4 )
- the product 3 (5 g, 10 mmol) is solubilized in a water / methanol mixture (75 mL, 1/1, v / v) in the presence of sodium carbonate (7.7 g).
- the medium is maintained at 0 ° C. with magnetic stirring while a solution of acryloyl chloride (4.6 ml, 56.9 mmol, Fluka) and THF (35 ml) is gradually added for 5 minutes.
- Me Me Me (V50) Product 4 (0.376 g) and MAPTAC (6 g, Aldrich) are diluted in a minimum of water (3 g) at 80 ° C. under a stream of nitrogen. The V50 is injected every hour for three hours.
- Step 1 Hydrolysis of xyloglucans Obtaining oligomers XXXG, XXLG (or XLXG) and XLLG (products 5,6,7) by cellulase 3042A
- the mixture 5, 6 and 7 (5g) is dissolved in allylamine (100 ml, Aldrich).
- the reaction mixture is kept under magnetic stirring for 4 days at room temperature. After evaporation to dryness (co-evaporation with toluene), the mixture obtained is a white solid which is selectively acetylated overnight in 1 L of a MeOH / Ac 2 O solution (20/1, v / v). The conversion is followed by thin layer chromatography (CH 3 CN / H 2 O: 6/4).
- Step 3 Synthesis of N-acetyl-N - [(N-2-thioaminoethyl) propyl] - ⁇ -D-glucosylamine (products 11, 12, 13)
- Step 4 Synthesis of 3- (2-N - [(N-2-thioethyl) -2-propenamide] propyl] - ⁇ -D-glucosylamine macromonomers (products 14, 15, 16)
- the products 11, 12 and 13 (7.8 g, 5.43 mmol) are solubilized in a water / methanol mixture (40 mL, 1-1) in the presence of sodium carbonate (4 g).
- the medium is maintained at 0 ° C. with magnetic stirring while a solution of acryloyl chloride (2.4 mL, 29.6 ⁇ 10 -3 mol, Fluka) and THF (20 mL) is gradually added for 5 minutes.
- Thin layer chromatography (CH 3 CN / H 2 O: 6/4) The mixture is taken up in 120 ml of water and then reconcentrated and taken up again in 80 ml of water in the presence of radical inhibitor (2).
- the products 14, 15 and 16 (0.976 g) and MAPTAC (6 g, Aldrich) are diluted in a minimum of water (7 g) at 80 ° C. under a stream of nitrogen.
- the V50 is injected every hour for three hours.
- the polymerization follows the protocol: t °: injection of initiator at 0.4 mol% relative to the sum of the monomers (13.8 mg in 250 ⁇ l H 2 O) t 1 : injection of initiator at 0.4 mol% relative to the sum of the monomers (13.8 mg in 250 ⁇ L H 2 O) t 2 : initiator injection at 0.2 mol% relative to the sum of the monomers
- t 3 injection of initiator at 0.2 mol% relative to the sum of the monomers (6.9 mg in 250 ⁇ L H 2 O) cooking for one hour at 85 ° C.
- t 4 the solution is allowed to return to room temperature
- Step 1 Synthesis of ⁇ -acetyl- ⁇ -allyl- ⁇ -D-glucopyranosyl- (1 ⁇ 4) - ⁇ -D-glucopyranosylamine (Product 2bis)
- the reaction mixture is kept under magnetic stirring for 72 h at room temperature.
- Thin layer chromatography (“TLC", ethyl acetate / petroleum ether 1/1) is carried out on an acetylated aliquot according to a method classical (pyridine / acetic anhydride 1/1). After evaporation to dryness, the product obtained is a white powder.
- the reaction crude is seleneacetylated in a methanol / acetic anhydride solution (100 mL, 5/1, v / v).
- the conversion is followed by thin layer chromatography (acetonitrile / water 7/3).
- the solution is stirred for 4 h and then evaporated to dryness after addition of methanol (3 times).
- TLC shows the formation of a second probably O-acetylated compound.
- To eliminate the crude is taken up in methanol (10OmL), and a 1M MeONa solution is added dropwise until a pH of 10 is obtained. This pH is determined by deposition of a drop of reaction mixture on a strip of moistened pH paper. TLC control shows the disappearance of the O-acetylated compound.
- the solution is then neutralized on Amberlite Resin IR 120 H + , filtered, evaporated to dryness, and lyophilized.
- the product 2bis is obtained with a quantitative yield (6.18 g).
- Step 2 synthesis of ⁇ -acetyl- ⁇ / - [( ⁇ / -2-thioaminoethyl) propyl] - ( ⁇ -D-glucopyranosyl) - (1 ⁇ 4) - ⁇ -D-glucopyranosylamine (product 3bis) - to using water-soluble initiators
- the solution is then purified on ion exchange resin column (DOWEX X 50 WX4) H + ion form and eluted successively with H 2 O and 0.05M NH 4 OH then 0.1 M.
- the product 3bis is then lyophilized and is obtained in a yield of 95% (28 g, 56 mol).
- Step 3 A / -acetyl- ⁇ / - [( ⁇ / -2-thioethyl) -2-propenamide] propyl] - ⁇ -D-glucopyranosyl- (1 ⁇ 4) - ⁇ -D-glucopyranosylamine synthesis (Product 4a)
- the product 3bis (5 g, 10 mmol) is solubilized in a water / methanol mixture (75 mL, 1/1, v / v) in the presence of sodium carbonate (7.7 g).
- the medium is maintained at 0 ° C. with magnetic stirring while a solution of acryloyl chloride (4.6 ml, 56.9 mmol, Fluka) and THF (35 ml) is gradually added for 5 minutes.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0407818A FR2873123B1 (fr) | 2004-07-13 | 2004-07-13 | Nouveaux glycopolymeres, leurs utilisations, et monomeres utiles pour leur preparation |
PCT/FR2005/001799 WO2006016063A1 (fr) | 2004-07-13 | 2005-07-12 | Nouveaux glycopolymeres, leurs utilisations, et monomeres utiles pour leur preparation |
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EP05790974A Withdrawn EP1778708A1 (fr) | 2004-07-13 | 2005-07-12 | Nouveaux glycopolymeres, leurs utilisations, et monomeres utiles pour leur preparation |
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US (1) | US20080281064A1 (fr) |
EP (1) | EP1778708A1 (fr) |
FR (1) | FR2873123B1 (fr) |
WO (1) | WO2006016063A1 (fr) |
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FR2944957B1 (fr) * | 2009-04-30 | 2011-06-10 | Ahlstrom Coroporation | Support cellulosique contenant des derives de mannose aptes a fixer les bacteries dotees de pilis de type 1, application aux lingettes desinfectantes notamment |
FR2952642B1 (fr) * | 2009-11-16 | 2012-01-06 | Centre Nat Rech Scient | Polymeres comprenant une majorite de monomeres amphiphiles destines au piegeage et a la manipulation de proteines membranaires |
MX2014002231A (es) | 2011-08-31 | 2014-04-25 | Akzo Nobel Chemicals Int Bv | Composiciones de detergente de lavanderia que comprenden el agente de desprendimiento de suciedad. |
US9174871B2 (en) | 2012-11-02 | 2015-11-03 | Empire Technology Development Llc | Cement slurries having pyranose polymers |
US9238774B2 (en) | 2012-11-02 | 2016-01-19 | Empire Technology Development Llc | Soil fixation, dust suppression and water retention |
US9468595B2 (en) | 2012-11-02 | 2016-10-18 | Empire Technology Development Llc | Acrylamide derivatives |
US9212245B2 (en) | 2012-12-04 | 2015-12-15 | Empire Technology Development Llc | High performance acrylamide adhesives |
US20140178344A1 (en) * | 2012-12-04 | 2014-06-26 | Empire Technology Development Llc | Acrylamide hydrogels for tissue engineering |
JP2015168653A (ja) * | 2014-03-07 | 2015-09-28 | 学校法人東京理科大学 | 細胞内送達用高分子担体 |
DE102017003004A1 (de) | 2017-03-23 | 2018-09-27 | Friedrich-Schiller-Universität Jena | Kationische Polymere mit D-Fructose-Substituenten |
CN114989344B (zh) * | 2022-06-14 | 2023-09-19 | 万华化学集团股份有限公司 | 一种偏氟乙烯共聚物及其制备方法和在锂离子电池中的应用 |
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DE10260100A1 (de) * | 2002-12-19 | 2004-07-01 | Basf Ag | Kationische Makromonomere enthaltende Polymere und ihre Verwendung in kosmetischen Zubereitungen |
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US4079025A (en) * | 1976-04-27 | 1978-03-14 | A. E. Staley Manufacturing Company | Copolymerized starch composition |
US4719272A (en) * | 1984-06-27 | 1988-01-12 | National Starch And Chemical Corporation | Monomeric cationic glycoside derivatives |
SE463314B (sv) * | 1989-03-01 | 1990-11-05 | Biocarb Ab | Sampolymerer av en n-acylerad glykosylamin och en amid, n-akryloyl-eller metakryloylglykosylaminer samt foerfarande foer framstaellning av dessa |
BR0108014B1 (pt) * | 2000-02-02 | 2011-04-05 | composição para a lavagem e/ou enxágüe em lavagem de roupa e processo de liberação de sujeira de um artigo para lavagem de roupa. |
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- 2004-07-13 FR FR0407818A patent/FR2873123B1/fr not_active Expired - Fee Related
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- 2005-07-12 WO PCT/FR2005/001799 patent/WO2006016063A1/fr active Application Filing
- 2005-07-12 US US11/632,623 patent/US20080281064A1/en not_active Abandoned
- 2005-07-12 EP EP05790974A patent/EP1778708A1/fr not_active Withdrawn
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US20080281064A1 (en) | 2008-11-13 |
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FR2873123A1 (fr) | 2006-01-20 |
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