WO2007012763A1 - Block copolymer comprising a lcst block having a low critical solubility temperature, formulations comprising the copolymer and use thereof for vectorizing an active principle - Google Patents

Block copolymer comprising a lcst block having a low critical solubility temperature, formulations comprising the copolymer and use thereof for vectorizing an active principle Download PDF

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Publication number
WO2007012763A1
WO2007012763A1 PCT/FR2006/001835 FR2006001835W WO2007012763A1 WO 2007012763 A1 WO2007012763 A1 WO 2007012763A1 FR 2006001835 W FR2006001835 W FR 2006001835W WO 2007012763 A1 WO2007012763 A1 WO 2007012763A1
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WIPO (PCT)
Prior art keywords
block
copolymer
lcst
units
formulation
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PCT/FR2006/001835
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French (fr)
Inventor
Mathias Destarac
Bruno Bavouzet
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Rhodia Chimie
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Application filed by Rhodia Chimie filed Critical Rhodia Chimie
Priority to EP06794232A priority Critical patent/EP1913043A1/en
Publication of WO2007012763A1 publication Critical patent/WO2007012763A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • Block copolymer comprising an LCST block having a critical lower solubility temperature
  • formulations comprising the copolymer and use for targeting an active ingredient
  • the present invention relates to a novel copolymer comprising a block having a critical lower solubility temperature (LCST).
  • the present invention also provides formulations comprising the copolymer, and the use of the copolymer or formulations for targeting an active ingredient.
  • copolymer and the formulations of the invention may in particular be used in the field of cosmetics, pharmacy, in the fields of household care or in the fields of surface coatings.
  • formulations are made comprising active ingredients, intended to bring a property to a medium or a surface.
  • Formulations thus comprise a liquid vector, a vectorized product, and ingredients for formulation aid, for example protection, encapsulation, vectorization, stabilization, dispersion, rheology, and / or control of these functions. , if necessary under the influence of a parameter external to the formulation.
  • ingredients can of course also be active.
  • LCST critical lower solubility temperature
  • copolymers having an LCST are referred to as LCST copolymers.
  • WO 02/055607 discloses (grafted) comb copolymers having a hydrophilic backbone, for example deriving from polyacrylic acid, and LCST grafts of poly-N-isopropylacrylamide (pNIPAM) or LCST grafts comprising a polyether group.
  • pNIPAM poly-N-isopropylacrylamide
  • LCST grafts comprising a polyether group.
  • block copolymers used to improve the stability of formulations, especially cosmetic creams, when are subjected to different temperatures, by forming a gel during an increase in temperature.
  • WO 95/24430 discloses graft copolymers comprising a hydrophilic backbone and LCST grafts, for example a copolymer having a backbone derived from acrylic acid, and grafts derived from N-isopropylacrylamide
  • NIPAM NIPAM
  • the copolymer makes it possible to control the release of a dispersed active agent in a composition comprising the copolymer.
  • a controlled architecture copolymer preferably a linear block copolymer, comprising at least two different blocks A and B, at least one of which, block A for example, is a block having a critical lower temperature.
  • LCST solubility
  • the present invention provides a copolymer with controlled architecture, preferably linear block, comprising at least two different blocks A and B, chosen such that:
  • block A is a block having a critical lower solubility temperature (LCST) comprising LCST units,
  • block B is a block comprising organosiloxane units.
  • LCST unit means either a unit resulting from the polymerization of a monomer whose corresponding homopolymer has an LCST, or a unit resulting from the polymerization of a macromer having an LCST.
  • the present invention also provides a formulation comprising:
  • a vectorized product being a non-water-soluble active ingredient or a non-water-soluble composition comprising a water-soluble or non-water-soluble active ingredient, and the copolymer with controlled architecture according to the invention.
  • linear block copolymer a copolymer having at least two blocks of different compositions, interconnected, and forming a linear macromolecular chain. It is not excluded that the blocks have macromolecular side groups. These groups when they exist will not be considered blocks of the block copolymer.
  • 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 or vinylic 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) -.
  • Mbi oc [M] o * [Precursor] o * Conversion * (M) m o name .
  • [M] 0 is the initial monomer concentration
  • [Precursor] 0 is the initial precursor concentration (reversible transfer agent, initiator or first block) Conversion refers to the conversion to monomer (M) rn ⁇ nomere means the molar mass of the monomer.
  • the measured average molar mass of a copolymer, unless otherwise indicated, is a number-average molar mass, measured by steric exclusion chromatography (SEC), after formation of the copolymer.
  • the average measured molecular weight of a block is a number-average molar mass, measured by steric exclusion chromatography (SEC), after formation of the block, to which the measured molar mass of a previously formed block.
  • SEC steric exclusion chromatography
  • hydrophobic is used in its usual sense of "which has no affinity for water”; this means that the organic polymer of which it is made, taken alone (with the same composition and the same molar mass), would form a two-phase macroscopic solution in distilled water at 25 ° C., at a concentration greater than 1% by weight.
  • hydrophilic is also used in its usual sense of "having affinity for water", i.e., is not likely to form a macroscopic solution. diphasic in distilled water at 25 0 C at a concentration greater than 1% by weight.
  • the first object of the invention is therefore a preferably linear block-controlled architecture copolymer, comprising at least two different blocks A and B, characterized in that:
  • block A is a block having a critical lower solubility temperature
  • LCST comprising LCST units
  • - block B is a block comprising organosiloxane units.
  • the copolymer according to the invention can be a diblock copolymer (block A) - (block B), a triblock copolymer (block A) - (block B) - (block A) or a graft copolymer (block A) - g- ( block B) or alternatively (Block B) -g- (Block A), each block consisting of monomer units belonging to the same monomer or to different monomers.
  • the copolymer of the invention is water-soluble or water-dispersible.
  • Block A soluble or dispersible in water has an LCST of between 5 and 80 ° C. This LCST depends on the composition of the block A and the nature of the units composing it. Beyond this LCST, block A becomes insoluble in water.
  • Block A comprises LCST units, that is to say units derived from an LCST monomer, mixtures of LCST monomers or one or more LCST monomers mixed with monomers whose homopolymers do not exhibit of LCST.
  • the LCST monomers are selected from the group comprising the following monomers: vinyl caprolactam, N-ethyl acrylamide, N, N'-methylethyl acrylamide, N 1 N'-diethyl acrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, 2-carboxy isopropyl acrylamide, N-methylisopropyl acrylamide, N-propyl acrylamide, N-acryloyl N-methylpiperazine, N-acryloyl N-ethylpiperazine, N-acryloyl N-propylpiperazine, N-propyl methacrylamide, N- (L) - (I - hydroxymethyl) propyl methacrylamide, N, N'-methylpropyl acrylamide and the monomers corresponding to the following formulas:
  • the units at LCST are selected from the following units:
  • units comprising at least one polyether group, such as poly (ethylene oxide and / or propylene oxide) in the form of macromolecular chains with a single type of units, or with several types of units, statistical or sequenced units comprising a polyvinyl methyl ether group (macromonomer),
  • polyether group such as poly (ethylene oxide and / or propylene oxide) in the form of macromolecular chains with a single type of units, or with several types of units, statistical or sequenced units comprising a polyvinyl methyl ether group (macromonomer)
  • macromonomers comprising units derived from substituted acrylamide or methacrylamide monomers (macromonomer).
  • the units with an LCST are preferably those derived from substituted acrylamide or methacrylamide monomers such as:
  • non-LCST monomers are hydrophilic monomers with ethylenic unsaturations such as acrylamide or hydrophobic ethylenically unsaturated such as N-butyl acrylamide.
  • the copolymer of the invention is defined so as to have an LCST adapted to the intended application.
  • Block A represents at least 30% by weight of the copolymer and preferably between 50 and 95% by weight of the copolymer. It has a number average mass of between 500 and 100000 and preferably between 2000 and 20000.
  • block B comprises:
  • alkyl a linear or branched hydrocarbon chain having 1 to 10 carbon atoms and preferably 1 to 4 carbon atoms.
  • Examples of preferred alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl.
  • cycloalkyl is meant a cyclic, monocyclic hydrocarbon group comprising 5 or 6 carbon atoms, preferably a cyclopentyl or cyclohexyl group.
  • aryl is meant an aromatic mono- or polycyclic group, preferably mono- or bicyclic comprising from 6 to 12 carbon atoms, preferably phenyl.
  • siloxane-type compounds which are used in the process of the invention correspond to the formula (I) in which R 1 and R 2 are identical and more particularly represent an alkyl group having from 1 to 4 carbon atoms.
  • R 1 and R 2 preferably represent a methyl group.
  • the average number-average mass of block B is between 500 and 100,000 and preferably between 1000 and 10,000.
  • One of the other objects of the invention is a formulation comprising:
  • a vectorized product being a non-water-soluble active ingredient or a non-water-soluble composition comprising a water-soluble or non-water-soluble active ingredient, and at least one copolymer according to the invention.
  • the vectorized product is dispersed in the liquid carrier, in the form of a dispersion of solid particles stabilized by the copolymer, or dispersion in the core of micelles of the copolymer, the formulation being at a temperature below the lower critical solubility temperature of the block. AT.
  • the formulations of the invention find their applications in various fields. Mention may be made, as indicative and non-limiting, of the formulations intended to be applied to the skin and / or the hair, to textile fibers, or to the hydraulic-bonded formulations, for example the cementitious formulations (the copolymer is a water-repellent). There may also be mentioned some applications in the field of coatings such as paints, varnishes, adhesives, etc.
  • the formulations of the invention are useful for vectorizing an active ingredient on a surface, by applying the formulation on said surface, and increasing the temperature, it is increased by any suitable means known to those skilled in the art such as for example rinsing after application with water at a temperature higher than that of the formulation before application.
  • Figure 1 Process for functionalization of a silicone oil with O-ethyl xanthate groups.
  • Step 1 Synthesis of functionalized poly (dimethyl siloxane) B bromopropionate at the ⁇ and ⁇ positions:
  • Step 2 Synthesis of Functionalized Poly (dimethyl siloxane) C O-ethyl xanthate at the ⁇ and Co Positions:
  • Step 3 Polymerization of N-isopropyl acrylamide (NIPAm) in the presence of poly (dimethyl siloxane) C functionalized O-ethyl xanthate at the ⁇ and ⁇ positions:
  • NIPAm N-isopropyl acrylamide
  • silicone oil C 1 g
  • dioxane 6 g
  • the reaction is stopped after 9 hours.
  • a 1 H NMR analysis confirmed that the NIPAM monomer is completely consumed.
  • DOSY NMR analysis has made it possible to demonstrate that the precursor PDMS population C is fully activated by transfer of the xanthate group during the polymerization of P (NIPAm).
  • the triblock copolymer P (NIPAm) -b-PDMS-bP (NIPAm) is thus obtained.

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Abstract

The invention concerns a novel block copolymer comprising a block having a low critical solubility temperature (LCST). The invention also concerns formulations comprising the copolymer, and the use of the copolymer or formulations for vectorizing an active principle. The copolymer and the formulations can in particular be used in the field of cosmetics, pharmacology, in the fields of household care or in the field of surface coatings.

Description

Copolymère à blocs comprenant un bloc LCST présentant une température inférieure critique de solubilité, formulations comprenant le copolymère et utilisation pour vectoriser un ingrédient actif Block copolymer comprising an LCST block having a critical lower solubility temperature, formulations comprising the copolymer and use for targeting an active ingredient
La présente invention se rapporte à un nouveau copolymère comprenant un bloc présentant une température inférieure critique de solubilité (LCST). La présente invention décrit également des formulations comprenant le copolymère, et l'utilisation du copolymère ou des formulations pour vectoriser un ingrédient actif.The present invention relates to a novel copolymer comprising a block having a critical lower solubility temperature (LCST). The present invention also provides formulations comprising the copolymer, and the use of the copolymer or formulations for targeting an active ingredient.
Le copolymère et les formulations de l'invention peuvent notamment être utilisés dans le domaine de la cosmétique, de la pharmacie, dans les domaines des soins ménagers ou encore dans les domaines des revêtements de surface.The copolymer and the formulations of the invention may in particular be used in the field of cosmetics, pharmacy, in the fields of household care or in the fields of surface coatings.
Dans de nombreux domaines, notamment dans les domaines de la cosmétique, de la pharmacie, et des soins ménagers, on réalise des formulations comprenant des ingrédients actifs, destinés à apporter une propriété à un milieu ou une surface. Des formulations comprennent ainsi un vecteur liquide, un produit vectorisé, et des ingrédients d'aide à la formulation par exemple de protection, d'encapsulation, de vectorisation, de stabilisation, de dispersion, de rhéologie, et/ou de contrôle de ces fonctions, le cas échéant sous l'influence d'un paramètre externe à la formulation. Ces ingrédients peuvent bien entendu, être également actifs.In many fields, particularly in the fields of cosmetics, pharmacy, and household care, formulations are made comprising active ingredients, intended to bring a property to a medium or a surface. Formulations thus comprise a liquid vector, a vectorized product, and ingredients for formulation aid, for example protection, encapsulation, vectorization, stabilization, dispersion, rheology, and / or control of these functions. , if necessary under the influence of a parameter external to the formulation. These ingredients can of course also be active.
A titre d'ingrédient de formulation, et éventuellement aussi d'actif, il est connu d'utiliser des copolymères présentant une température inférieure critique de solubilité, désignée par LCST.As a formulation ingredient, and possibly also an active ingredient, it is known to use copolymers having a critical lower solubility temperature, referred to as LCST.
Selon la présente invention les copolymères présentant une LCST sont désignés par copolymères LCST.According to the present invention, copolymers having an LCST are referred to as LCST copolymers.
Le document WO 02/055607 décrit des copolymères peigne (greffé) présentant un squelette hydrophile, par exemple dérivant d'acide polyacrylique, et des greffons LCST de poly-N-isopropylacrylamide (pNIPAM) ou des greffons LCST comprenant un groupe polyéther. Le document suggère également des copolymères à blocs, utilisés pour améliorer la stabilité de formulations, notamment des crèmes cosmétiques, lorsqu'elles sont soumises à différentes températures, par formation d'un gel lors d'une augmentation de la température.WO 02/055607 discloses (grafted) comb copolymers having a hydrophilic backbone, for example deriving from polyacrylic acid, and LCST grafts of poly-N-isopropylacrylamide (pNIPAM) or LCST grafts comprising a polyether group. The document also suggests block copolymers, used to improve the stability of formulations, especially cosmetic creams, when are subjected to different temperatures, by forming a gel during an increase in temperature.
Le document WO 95/24430 décrit des copolymères greffés comprenant un squelette hydrophile et des greffons LCST, par exemple un copolymère présentant un squelette dérivant d'acide acrylique, et des greffons dérivant de N-isopropylacrylamideWO 95/24430 discloses graft copolymers comprising a hydrophilic backbone and LCST grafts, for example a copolymer having a backbone derived from acrylic acid, and grafts derived from N-isopropylacrylamide
(NIPAM), obtenu par la réaction de couplage entre deux polymères, dont un est le poly(acide acrylique) et l'autre est par exemple le PNIPam terminé par NH2. Le copolymère permet de contrôler la libération d'un actif dispersé dans une composition comprenant le copolymère.(NIPAM), obtained by the coupling reaction between two polymers, one of which is poly (acrylic acid) and the other is for example the PNIPam terminated by NH 2 . The copolymer makes it possible to control the release of a dispersed active agent in a composition comprising the copolymer.
Il existe un besoin pour de nouveaux copolymères pouvant notamment conférer de nouvelles propriétés ou fonctions à de nouvelles formulations.There is a need for new copolymers which can in particular confer new properties or functions on new formulations.
La demanderesse a trouvé que ces besoins peuvent être comblés par un copolymère à architecture contrôlée, de préférence linéaire à blocs, comprenant au moins deux blocs différents A et B dont au moins un, le bloc A par exemple est un bloc présentant une température inférieure critique de solubilité (LCST) comprenant des unités LCST.The Applicant has found that these needs can be filled by a controlled architecture copolymer, preferably a linear block copolymer, comprising at least two different blocks A and B, at least one of which, block A for example, is a block having a critical lower temperature. of solubility (LCST) comprising LCST units.
Ainsi la présente invention propose un copolymère à architecture contrôlée, de préférence linéaire à blocs, comprenant au moins deux blocs différents A et B, choisis tels que :Thus, the present invention provides a copolymer with controlled architecture, preferably linear block, comprising at least two different blocks A and B, chosen such that:
- le bloc A est un bloc présentant une température inférieure critique de solubilité (LCST) comprenant des unités LCST,block A is a block having a critical lower solubility temperature (LCST) comprising LCST units,
- le bloc B est un bloc comprenant des unités organosiloxane.block B is a block comprising organosiloxane units.
Selon l'invention par unité LCST on entend soit une unité issue de la polymérisation d'un monomère dont l'homopolymère correspondant présente une LCST, soit une unité issue de la polymérisation d'un macromère présentant une LCST.According to the invention, LCST unit means either a unit resulting from the polymerization of a monomer whose corresponding homopolymer has an LCST, or a unit resulting from the polymerization of a macromer having an LCST.
La présente invention propose également une formulation comprenant:The present invention also provides a formulation comprising:
- un vecteur liquide aqueux,an aqueous liquid carrier,
- éventuellement un produit vectorisé, étant un ingrédient actif non hydrosoluble ou une composition non hydrosoluble comprenant un ingrédient actif hydrosoluble ou non hydrosoluble, et - le copolymère à architecture contrôlée selon l'invention.optionally a vectorized product, being a non-water-soluble active ingredient or a non-water-soluble composition comprising a water-soluble or non-water-soluble active ingredient, and the copolymer with controlled architecture according to the invention.
Dans la présente demande, on entend par copόlvmère linéaire à blocs un copolymère présentant au moins deux blocs de compositions différentes, reliés entre eux, et formant une chaîne macromoléculaire linéaire. Il n'est pas exclu que les blocs portent des groupes latéraux macromoléculaires. Ces groupes quand ils existent ne seront pas considérés comme des blocs du copolymère à blocs.In the present application, by linear block copolymer is meant a copolymer having at least two blocks of different compositions, interconnected, and forming a linear macromolecular chain. It is not excluded that the blocks have macromolecular side groups. These groups when they exist will not be considered blocks of the block copolymer.
Dans la présente demande, on désigne par unité dérivant d'un monomère une unité qui peut être obtenue directement à partir dudit monomère par polymérisation. Ainsi, par exemple, une unité dérivant d'un ester d'acide acrylique ou méthacrylique ou vinylique ne couvre pas une unité de formule -CH2-CH(COOH)-, -CH2-C(CH3)(COOH)-, -CH2-CH(OH)-, respectivement, obtenue par exemple en polymérisant un ester d'acide acrylique ou méthacrylique, ou de l'acétate de vinyle, respectivement, puis en hydrolysant. Une unité dérivant d'acide acrylique ou méthacrylique couvre par exemple une unité obtenue en polymérisant un monomère (par exemple un ester d'acide acrylique ou méthacrylique), puis en faisant réagir (par exemple par hydrolyse) le polymère obtenu de manière à obtenir des unités de formule -CH2-CH(COOH)-, ou - CH2-C(CH3)(COOH)-. Une unité dérivant d'un alcool vinylique couvre par exemple une unité obtenue en polymérisant un monomère (par exemple un ester vinylique), puis en faisant réagir (par exemple par hydrolyse) le polymère obtenu de manière à obtenir des unités de formule -CH2-CH(OH)-.In the present application, the unit derived from a monomer denotes a unit that can be obtained directly from said monomer by polymerization. Thus, for example, a unit derived from an acrylic or methacrylic or vinylic 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) -.
Typiquement, la masse molaire moyenne théorique Mbioc d'un bloc, est calculée selon la formule suivante:Typically, the theoretical average molar mass M b i oc of a block is calculated according to the following formula:
Mbioc=[M]o*[Precurseur]o* Conversion*(M)monomère.Mbi oc = [M] o * [Precursor] o * Conversion * (M) m o name .
Dans laquelle,In which,
[M]0 désigne la concentration initiale en monomère [Precurseur]0 désigne la concentration initiale en précurseur (agent de transfert réversible, amorceur ou premier bloc) Conversion désigne la conversion en monomère (M)rnθnomère désigne la masse molaire du monomère. La Masse molaire moyenne mesurée d'un copolymère sauf indication contraire, est une masse molaire moyenne en nombre, mesurée par chromatographie d'exclusion stérique (SEC), après formation du copolymère.[M] 0 is the initial monomer concentration [Precursor] 0 is the initial precursor concentration (reversible transfer agent, initiator or first block) Conversion refers to the conversion to monomer (M) rnθ nomere means the molar mass of the monomer. The measured average molar mass of a copolymer, unless otherwise indicated, is a number-average molar mass, measured by steric exclusion chromatography (SEC), after formation of the copolymer.
La masse molaire moyenne mesurée d'un bloc, sauf indication contraire, est une masse molaire moyenne en nombre, mesurée par chromatographie d'exclusion stérique (SEC), après formation du bloc, à laquelle on soustrait éventuellement la masse molaire mesurée d'un bloc précédemment formé.The average measured molecular weight of a block, unless otherwise indicated, is a number-average molar mass, measured by steric exclusion chromatography (SEC), after formation of the block, to which the measured molar mass of a previously formed block.
Dans la présente demande, le terme «hydrophobe» est utilisé dans son sens usuel de «qui n'a pas d'affinité pour l'eau»; cela signifie que le polymère organique dont il est constitué, pris seul (de même composition et de même masse molaire), formerait une solution macroscopique diphasique dans de l'eau distillée à 25°C, à une concentration supérieure à 1% en poids. Dans la prés.ente demande, le terme «hydrophile» est également utilisé dans son sens usuel de «qui a de l'affinité pour l'eau», c'est-à-dire n'est pas susceptible de former une solution macroscopique diphasique dans de l'eau distillée à 250C à une concentration supérieure à 1% en poids.In the present application, the term "hydrophobic" is used in its usual sense of "which has no affinity for water"; this means that the organic polymer of which it is made, taken alone (with the same composition and the same molar mass), would form a two-phase macroscopic solution in distilled water at 25 ° C., at a concentration greater than 1% by weight. In the present application, the term "hydrophilic" is also used in its usual sense of "having affinity for water", i.e., is not likely to form a macroscopic solution. diphasic in distilled water at 25 0 C at a concentration greater than 1% by weight.
Le premier objet de l'invention est donc un copolymère à architecture contrôlée de préférence linéaire à blocs, comprenant au moins deux blocs différents A et B, caractérisé en ce que:The first object of the invention is therefore a preferably linear block-controlled architecture copolymer, comprising at least two different blocks A and B, characterized in that:
- le bloc A est un bloc présentant une température inférieure critique de solubilitéblock A is a block having a critical lower solubility temperature
(LCST) comprenant des unités LCST, - le bloc B est un bloc comprenant des unités organosiloxane.(LCST) comprising LCST units, - block B is a block comprising organosiloxane units.
Le copolymère selon l'invention peut être un copolymère dibloc (bloc A)-(bloc B), un copolymère tribloc (bloc A)-(bloc B)-(bloc A) ou un copolymère greffé (bloc A)-g-(bloc B) ou encore (Bloc B)-g-(Bloc A), chaque bloc étant constitué d'unités monomères appartenant au même monomère ou bien à des monomères différents.The copolymer according to the invention can be a diblock copolymer (block A) - (block B), a triblock copolymer (block A) - (block B) - (block A) or a graft copolymer (block A) - g- ( block B) or alternatively (Block B) -g- (Block A), each block consisting of monomer units belonging to the same monomer or to different monomers.
Le copolymère de l'invention est hydrosoluble ou hydrodispersable. Le bloc A soluble ou dispersable dans l'eau présente une LCST comprise entre 5 et 800C. Cette LCST dépend de la composition du bloc A et de la nature des unités le composant. Au delà de cette LCST le bloc A devient insoluble dans l'eau. Le bloc A comprend des unités LCST, c'est-à-dire des unités dérivées d'un monomère LCST, des mélanges de monomères LCST ou bien d'un ou de plusieurs monomères LCST en mélange avec des monomères dont les homopolymères ne présentent pas de LCST.The copolymer of the invention is water-soluble or water-dispersible. Block A soluble or dispersible in water has an LCST of between 5 and 80 ° C. This LCST depends on the composition of the block A and the nature of the units composing it. Beyond this LCST, block A becomes insoluble in water. Block A comprises LCST units, that is to say units derived from an LCST monomer, mixtures of LCST monomers or one or more LCST monomers mixed with monomers whose homopolymers do not exhibit of LCST.
Les monomères LCST sont choisis dans le groupe comprenant les monomères suivants : vinylcaprolactame, N-éthyl acrylamide, N,N'-méthyléthyl acrylamide, N1N'- diéthyl acrylamide, N-isopropyl acrylamide, N-isopropyl méthacrylamide, 2-carboxy isopropyl acrylamide, N-méthylisopropyl acrylamide, N-propyl acrylamide, N-acryloyl N'- méthylpipérazine, N-acryloyl N'-éthylpipérazine, N-acryloyl N'-propylpipérazine, N-propyl méthacrylamide, N-(L)-(I -hydroxyméthyl) propyl méthacrylamide, N,N'-méthylpropyl acrylamide et les monomères répondants aux formules suivantes :The LCST monomers are selected from the group comprising the following monomers: vinyl caprolactam, N-ethyl acrylamide, N, N'-methylethyl acrylamide, N 1 N'-diethyl acrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, 2-carboxy isopropyl acrylamide, N-methylisopropyl acrylamide, N-propyl acrylamide, N-acryloyl N-methylpiperazine, N-acryloyl N-ethylpiperazine, N-acryloyl N-propylpiperazine, N-propyl methacrylamide, N- (L) - (I - hydroxymethyl) propyl methacrylamide, N, N'-methylpropyl acrylamide and the monomers corresponding to the following formulas:
Figure imgf000006_0001
Figure imgf000006_0001
Les unités à LCST sont choisies parmi les unités suivantes:The units at LCST are selected from the following units:
- les unités comprenant au moins un groupe polyéther, tel que le poly(oxyde d'éthylène et/ou oxyde de propylène) sous forme de chaînes macromoléculaires à un seul type d'unités, ou à plusieurs types d'unités, statistiques ou séquencées, - les unités comprenant un groupe polyvinylméthyléther (macromonomère),units comprising at least one polyether group, such as poly (ethylene oxide and / or propylene oxide) in the form of macromolecular chains with a single type of units, or with several types of units, statistical or sequenced units comprising a polyvinyl methyl ether group (macromonomer),
- les unités à LCST dérivant de monomères d'acrylamide ou de méthacrylamide substitués,- LCST units derived from substituted acrylamide or methacrylamide monomers,
- vinyl caprolactame,- vinyl caprolactam,
- les macromonomères comprenant des unités dérivant de monomères d'acrylamide ou de méthacrylamide substitués (macromonomère).macromonomers comprising units derived from substituted acrylamide or methacrylamide monomers (macromonomer).
Les unités à LCST sont de préférence celles dérivant de monomères d'acrylamide ou de méthacrylamide substitués telles que :The units with an LCST are preferably those derived from substituted acrylamide or methacrylamide monomers such as:
- le N-isopropyl acrylamide, - le N-éthyl acrylamide,N-isopropyl acrylamide, N-ethyl acrylamide,
- le vinyl caprolactame,vinyl caprolactam,
- leurs mélanges. De manière générale les monomères non LCST sont des monomères hydrophiles à insaturations éthyléniques tels que Pacrylamide, ou hydrophobes à insaturations éthylèniques tels que le N-butyl acrylamide.- their mixtures. In general, non-LCST monomers are hydrophilic monomers with ethylenic unsaturations such as acrylamide or hydrophobic ethylenically unsaturated such as N-butyl acrylamide.
Le copolymère de l'invention est défini de manière à avoir une LCST adaptée à l'application visée.The copolymer of the invention is defined so as to have an LCST adapted to the intended application.
Le bloc A représente au moins 30 % en poids du copolymère et de préférence entre 50 et 95 % en poids du copolymère. Il présente une masse moyenne en nombre comprise entre 500 et 100000 et de préférence entre 2000 et 20000.Block A represents at least 30% by weight of the copolymer and preferably between 50 and 95% by weight of the copolymer. It has a number average mass of between 500 and 100000 and preferably between 2000 and 20000.
Selon l'invention le bloc B comprend :According to the invention block B comprises:
- des unités organosiloxanes de formule -SiR12O- dans laquelle R1 est un groupe hydrocarboné, de préférence un groupe méthyle,organosiloxane units of formula -SiR12O- in which R1 is a hydrocarbon group, preferably a methyl group,
- éventuellement des unités organosiloxanes de formule -SiR22O- ou -SiR1 R2O- dans laquelle R1 , R2, identiques ou différents, représentent un groupe alkyle, cycloalkyle, aryle,optionally organosiloxane units of formula -SiR22O- or -SiR1 R2O- in which R1, R2, which may be identical or different, represent an alkyl, cycloalkyl or aryl group,
Dans le cadre de l'invention, on entend par « alkyle », une chaîne hydrocarbonée linéaire ou ramifiée ayant de 1 à 10 atomes de carbone et de préférence de 1 à 4 atomes de carbone.In the context of the invention, the term "alkyl", a linear or branched hydrocarbon chain having 1 to 10 carbon atoms and preferably 1 to 4 carbon atoms.
Des exemples de groupes alkyle préférés sont notamment méthyle, éthyle, propyle, isopropyle, butyle, isobutyle, t-butyle.Examples of preferred alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl.
Par « cycloalkyle », on entend un groupe hydrocarboné cyclique, monocyclique comprenant de 5 ou 6 atomes de carbone, de préférence, un groupe cyclopentyle ou cyclohexyle.By "cycloalkyl" is meant a cyclic, monocyclic hydrocarbon group comprising 5 or 6 carbon atoms, preferably a cyclopentyl or cyclohexyl group.
Par « aryle », on entend un groupe mono- ou polycyclique aromatique, de préférence, mono- ou bicyclique comprenant de 6 à 12 atomes de carbone, de préférence, phényle.By "aryl" is meant an aromatic mono- or polycyclic group, preferably mono- or bicyclic comprising from 6 to 12 carbon atoms, preferably phenyl.
Les composés de type siloxane qui sont mis en oeuvre dans le procédé de l'invention répondent à la formule (I) dans laquelle R1 et R2 sont identiques et représentent plus particulièrement un groupe alkyle ayant de 1 à 4 atomes de carbone. R 1 et R2 représentent préférentiellement un groupe méthyle.The siloxane-type compounds which are used in the process of the invention correspond to the formula (I) in which R 1 and R 2 are identical and more particularly represent an alkyl group having from 1 to 4 carbon atoms. R 1 and R 2 preferably represent a methyl group.
La masse moyenne en nombre du bloc B est comprise entre 500 et 100000 et de préférence entre 1000 et 10000. Un des autres objets de l'invention est une formulation comprenant:The average number-average mass of block B is between 500 and 100,000 and preferably between 1000 and 10,000. One of the other objects of the invention is a formulation comprising:
- un vecteur liquide aqueux,an aqueous liquid carrier,
- éventuellement un produit vectorisé, étant un ingrédient actif non hydrosoluble ou une composition non hydrosoluble comprenant un ingrédient actif hydrosoluble ou non hydrosoluble, et - au moins un copolymère selon l'invention.optionally a vectorized product, being a non-water-soluble active ingredient or a non-water-soluble composition comprising a water-soluble or non-water-soluble active ingredient, and at least one copolymer according to the invention.
Le produit vectorisé est dispersé dans le vecteur liquide, sous forme d'une dispersion de particules solides stabilisée par le copolymère, ou de dispersion au cœur de micelles du copolymère, la formulation étant à une température inférieure à la température inférieure critique de solubilité du bloc A.The vectorized product is dispersed in the liquid carrier, in the form of a dispersion of solid particles stabilized by the copolymer, or dispersion in the core of micelles of the copolymer, the formulation being at a temperature below the lower critical solubility temperature of the block. AT.
Les formulations de l'invention trouvent leurs applications dans divers domaines. On peut citer à titres indicatifs et non limitatifs les formulations destinées à être appliquées sur la peau et/ou les cheveux, sur des fibres textiles, ou les formulations à liant hydraulique, par exemple les formulations cimentaires (le copolymère est un hydrofugeant). On peut citer aussi certaines applications dans le domaine des revêtements telles que les peintures, vernis, adhésifs etc..The formulations of the invention find their applications in various fields. Mention may be made, as indicative and non-limiting, of the formulations intended to be applied to the skin and / or the hair, to textile fibers, or to the hydraulic-bonded formulations, for example the cementitious formulations (the copolymer is a water-repellent). There may also be mentioned some applications in the field of coatings such as paints, varnishes, adhesives, etc.
Les formulations de l'invention sont utiles pour vectoriser un ingrédient actif sur une surface, par application de la formulation sur ladite surface, et augmentation de la température, celle-ci est augmentée par tout moyen approprié connu de l'homme du métier tel que par exemple le rinçage après application à l'aide d'eau à température supérieure à celle de la formulation avant application .The formulations of the invention are useful for vectorizing an active ingredient on a surface, by applying the formulation on said surface, and increasing the temperature, it is increased by any suitable means known to those skilled in the art such as for example rinsing after application with water at a temperature higher than that of the formulation before application.
D'autres détails ou avantages de l'invention pourront apparaître au vu de(s) exemple(s) ci-dessous uniquement à titre indicatif. Exemples :Other details or advantages of the invention may appear in view of (s) example (s) below only for information. Examples:
Exemple 1. Synthèse d'un copolymère tribloc Poly(N-isopropyl acrylamide)-b-Poly(dimethyl siloxane)-b-Poly(N-isopropyl acrylamide)EXAMPLE 1 Synthesis of a triblock copolymer Poly (N-isopropyl acrylamide) -b-Poly (dimethyl siloxane) -b-Poly (N-isopropyl acrylamide)
Les deux étapes 1 et 2 pour accéder à l'huile silicone fonctionnalisée xanthate C sont décrites sur la figure 1 ci-dessous.
Figure imgf000009_0001
The two steps 1 and 2 to access the functionalized silicone oil xanthate C are described in Figure 1 below.
Figure imgf000009_0001
Figure 1. Procédé de fonctionnalisation d'une huile silicone par des groupements O-ethyl xanthate.Figure 1. Process for functionalization of a silicone oil with O-ethyl xanthate groups.
Etape 1 : Synthèse de poly(dimethyl siloxane) B fonctionnalisé bromopropionate aux positions α et ω :Step 1: Synthesis of functionalized poly (dimethyl siloxane) B bromopropionate at the α and ω positions:
0,88 ml (2,4 équivalents) de bromure de 2-bromopropionyle sont additionnés goutte à goutte à température ambiante à une solution contenant 10 g d'une huile poly(dimethylsiloxane) A de Mn~2700 g/mol (1 équivalent) et 1 ,2 g (4 équivalents) de pyridine dans 200 ml d'éther éthylique. Après une nuit à température ambiante, 50 ml d'eau sont introduits. Deux extractions par 100 ml d'acétate d'éthyle sont ensuite effectuées. Les phases organiques sont mélangées, puis lavées successivement par une solution aqueuse de NaOH 1 M, une solution aqueuse d'HCI à 10%, de la saumure, puis déshydratées par du MgSO4. Les solvants sont ensuite évaporés et le brut réactionnel est purifié par chromatograpie sur colonne sur gel de silice (heptane 9/ether 1) pour donner 11g de l'huile silicone fonctionnelle B. 1H NMR (CDCI3) δ 0 (m, Si-CH3), 0.55 (m, 4H)1 1.7 (m,4H), 1.83 (d, 6H), 4.12 (m,4H), 4.37 (q,2H).0.88 ml (2.4 equivalents) of 2-bromopropionyl bromide are added dropwise at room temperature to a solution containing 10 g of a poly (dimethylsiloxane) A oil of Mn ~ 2700 g / mol (1 equivalent) and 1.2 g (4 equivalents) of pyridine in 200 ml of ethyl ether. After one night at room temperature, 50 ml of water are introduced. Two extractions per 100 ml of ethyl acetate are then carried out. The organic phases are mixed and then washed successively with a 1M aqueous NaOH solution, a 10% aqueous solution of HCl, brine and then dried with MgSO 4 . The solvents are then evaporated and the crude reaction product is purified by column chromatography on silica gel (heptane 9 / ether 1) to give 11 g of the functional silicone oil B. 1 H NMR (CDCl 3) δ 0 (m, Si-CH3), 0.55 (m, 4H) 1 1.7 (m, 4H), 1.83 (d, 6H), 4.12 (m, 4H), 4.37 (q, 2H ).
Etape 2 : Synthèse de poly(dimethyl siloxane) C fonctionnalisé O-ethyl xanthate aux positions α et co :Step 2: Synthesis of Functionalized Poly (dimethyl siloxane) C O-ethyl xanthate at the α and Co Positions:
5 g d'huile silicone fonctionnalisée bromopropionate B est additionnée à une solution de 1 ,07 g de potassium O-éthyl xanthate (4 équivalents) dans 150 ml d'acetonitrile. La réaction est maintenue pendant 4 heures à température ambiante. Le solvent est ensuite évaporé, puis le polymère est dissout dans l'éther éthylique ; le mélange est alors filtré. Après evaporation du solvant, 5.2 g de silicone C sont récupérés.5 g of functionalized silicone oil bromopropionate B is added to a solution of 1.07 g of potassium O-ethyl xanthate (4 equivalents) in 150 ml of acetonitrile. The reaction is maintained for 4 hours at room temperature. The solvent is then evaporated and the polymer is dissolved in ethyl ether; the mixture is then filtered. After evaporation of the solvent, 5.2 g of silicone C are recovered.
La RMN1 H du produit final montre les signaux caractéristiques de l'extrémité de chaîne O-ethyl xanthate, avec des déplacements chimiques à 4.40 et 4.60 ppm correspondant respectivement à l'hydrogène méthine (RO(C=O)CH(Me)S(C=S)OCH2-CH3) et aux deux hydrogènes méthylèniques (RO(C=O)CH(Me)S(C=S)OCH2-CH3).The 1 H NMR of the final product shows the characteristic signals of the O-ethyl xanthate chain end, with chemical shifts at 4.40 and 4.60 ppm respectively corresponding to hydrogen methine (RO (C = O) CH (Me) S ( C = S) OCH 2 -CH 3 ) and to the two methylenic hydrogens (RO (C = O) CH (Me) S (C = S) OCH 2 -CH 3 ).
Etape 3 : Polymérisation du N-isopropyl acrylamïde (NIPAm) en présence de poly(dimethyl siloxane) C fonctionnalisé O-ethyl xanthate aux positions α et ω :Step 3: Polymerization of N-isopropyl acrylamide (NIPAm) in the presence of poly (dimethyl siloxane) C functionalized O-ethyl xanthate at the α and ω positions:
Dans un ballon bicol de 50 ml muni d'une agitation magnétique et d'un réfrigérant, 5,19 g de N-isopropyl acrylamide (NIPAm), 1 g d'huile silicone C et 6,19g de dioxane sont introduits. Le mélange est porté à 700C, température à laquelle 0,056 mg d'azobisisobutyronitrile sont introduits. La réaction est stoppée après 9 heures. Une analyse RMN 1H a permis de confirmer que le monomère NIPAm est totalement consommé. Une analyse RMN DOSY a permis de mettre en évidence que la population de PDMS précurseur C est intégralement activée par transfert du groupe xanthate durant la polymérisation du P(NIPAm). Le copolymère tribloc P(NIPAm)-b-PDMS-b-P(NIPAm) est ainsi obtenu. In a 50 ml two-neck flask equipped with a magnetic stirrer and a condenser, 5.19 g of N-isopropyl acrylamide (NIPAm), 1 g of silicone oil C and 6.19 g of dioxane are introduced. The mixture is heated to 70 ° C., at which temperature 0.056 mg of azobisisobutyronitrile are introduced. The reaction is stopped after 9 hours. A 1 H NMR analysis confirmed that the NIPAM monomer is completely consumed. DOSY NMR analysis has made it possible to demonstrate that the precursor PDMS population C is fully activated by transfer of the xanthate group during the polymerization of P (NIPAm). The triblock copolymer P (NIPAm) -b-PDMS-bP (NIPAm) is thus obtained.

Claims

REVENDICATIONS
1. Copolymère à architecture contrôlée, de préférence linéaire à blocs, comprenant au moins deux blocs différents A et B, caractérisé en ce que:A copolymer with controlled architecture, preferably linear block, comprising at least two different blocks A and B, characterized in that:
- le bloc A est un bloc présentant une température inférieure critique de solubilité (LCST) comprenant des unités LCST,block A is a block having a critical lower solubility temperature (LCST) comprising LCST units,
- le bloc B est un bloc comprenant des unités organosiloxane.block B is a block comprising organosiloxane units.
2. Copolymère selon la revendication 1 caractérisé en ce que la LCST du bloc A est comprise entre 5 et 80 ° C.2. Copolymer according to claim 1 characterized in that the LCST of the block A is between 5 and 80 ° C.
3. Copolymère selon l'une des revendications précédentes caractérisé en ce qu'il est hydrosoluble ou hydrodispersable.3. Copolymer according to one of the preceding claims characterized in that it is water-soluble or water-dispersible.
4. Copolymère selon l'une des revendications précédentes, caractérisé en ce que le copolymère est4. Copolymer according to one of the preceding claims, characterized in that the copolymer is
- un copolymère dibloc (bloc A)-(bloc B),a diblock copolymer (block A) - (block B),
- un copolymère tribloc (bloc A)-(bloc B)-(bloc A),a triblock copolymer (block A) - (block B) - (block A),
- un copolymère greffé (blocA)-g-(bloc B) ou bien (bloc B)-g-(bloc A).a graft copolymer (blockA) -g- (block B) or (block B) -g- (block A).
5. copolymère selon l'une des revendications précédentes caractérisé en ce que le bloc A comprend des unités LCST et des unités issues de monomères non LCST hydrophiles à insaturations éthyléniques tels que l'acrylamide ou hydrophobes à insaturations éthyléniques tels que le N-butyl acrylamide.5. Copolymer according to one of the preceding claims, characterized in that the block A comprises LCST units and units derived from hydrophilic non-LCST monomers with ethylenic unsaturations such as acrylamide or hydrophobic ethylenically unsaturated such as N-butyl acrylamide. .
6. Copolymère selon la revendication 5 caractérisé en ce que les unités LCST sont choisies parmi les unités suivantes:6. Copolymer according to claim 5, characterized in that the LCST units are chosen from the following units:
- les unités comprenant au moins un groupe polyéther, tel que le poly(oxyde d'éthylène et/ou oxyde de propylène) sous forme de chaînes macromoléculaires à un seul type d'unités, ou à plusieurs types d'unités, statistiques ou séquencées, - les unités comprenant un groupe polyvinylméthyléther (macromonomère), - les unités à LCST dérivant de monomères d'acrylamide ou de méthacrylamide substitués,units comprising at least one polyether group, such as poly (ethylene oxide and / or propylene oxide) in the form of macromolecular chains with a single type of units, or with several types of units, statistical or sequenced units comprising a polyvinyl methyl ether group (macromonomer), - LCST units derived from substituted acrylamide or methacrylamide monomers,
- vinyl caprolactame- vinyl caprolactam
- les macromonomères comprenant des unités dérivant de monomères d'acrylamide ou de méthacrylamide substitués (macromonomère).macromonomers comprising units derived from substituted acrylamide or methacrylamide monomers (macromonomer).
7. Copolymère selon la revendication 6, caractérisé en ce que les unités à LCST dérivant de monomères d'acrylamide ou de méthacrylamide substitués, sont choisies parmi:7. Copolymer according to claim 6, characterized in that the LCST units derived from substituted acrylamide or methacrylamide monomers are chosen from:
- le N-isopropyl acrylamide, - le N-éthyl acrylamide,N-isopropyl acrylamide, N-ethyl acrylamide,
- le vinyl caprolactame- vinyl caprolactam
- leurs mélanges.- their mixtures.
8. Copolymère selon l'une des revendications précédentes, caractérisé en ce que le bloc B comprend :8. Copolymer according to one of the preceding claims, characterized in that the block B comprises:
- des unités organosiloxanes de formule -SiR1 2O- dans laquelle R1, identique ou différent est un groupe hydrocarboné, de préférence un groupe méthyle,organosiloxane units of formula -SiR 1 2 O- in which R 1 , identical or different, is a hydrocarbon group, preferably a methyl group,
- éventuellement des unités organosiloxanes de formule -SiR2 2O- ou -SiR1R2O- dans laquelle R1, R2, identiques ou différents, représentent un groupe alkyle notamment méthyle, éthyle, propyle, isopropyle, butyle, isobutyle, t-butyle., cycloalkyle tel que cyclopentyle ou cyclohexyle., aryle mono- ou bicyclique comprenant de 6 à 12 atomes de carbone, de préférence, phényle.,optionally organosiloxane units of formula -SiR 2 2 O- or -SiR 1 R 2 O- in which R 1 , R 2 , which may be identical or different, represent an alkyl group, especially methyl, ethyl, propyl, isopropyl, butyl or isobutyl, t-butyl, cycloalkyl such as cyclopentyl or cyclohexyl., mono- or bicyclic aryl comprising from 6 to 12 carbon atoms, preferably phenyl.
9. Copolymère selon l'une des revendications précédentes caractérisé en ce que le bloc A représente au moins 30 % en poids du copolymère et de préférence entre 50 et 95 % en poids du copolymère.9. Copolymer according to one of the preceding claims characterized in that the block A represents at least 30% by weight of the copolymer and preferably between 50 and 95% by weight of the copolymer.
10. Copolymère selon l'une des revendications précédentes caractérisé en ce que la masse moyenne en nombre du bloc A est comprise entre 500 et 100000 et de préférence entre 2000 et 20000.10. Copolymer according to one of the preceding claims characterized in that the average mass number of the block A is between 500 and 100000 and preferably between 2000 and 20000.
11. Copolymère selon l'une des revendications précédentes caractérisé en ce que la masse moyenne en nombre du bloc B est comprise entre 500 et 100000 et de préférence entre 1000 et 10000.11. Copolymer according to one of the preceding claims characterized in that the average mass number of the block B is between 500 and 100000 and preferably between 1000 and 10000.
12. Formulation comprenant: - un vecteur liquide aqueux,12. Formulation comprising: an aqueous liquid carrier,
- éventuellement un produit vectorisé, étant un ingrédient actif non hydrosoluble ou une composition non hydrosoluble comprenant un ingrédient actif hydrosoluble ou non hydrosoluble, et - le copolymère selon l'une des revendications précédentes.optionally a vectorized product, being a non-water-soluble active ingredient or a non-water-soluble composition comprising a water-soluble or non-water-soluble active ingredient, and the copolymer according to one of the preceding claims.
13. Formulation selon la revendication 12, caractérisée en ce que le produit vectorisé est dispersé dans le vecteur liquide, sous forme d'une dispersion de particules solides stabilisée par le copolymère, de dispersion de gouttelettes liquides stabilisée par le copolymère, ou de dispersion au coeur de micelles du copolymère, la formulation étant à une température inférieure à la température inférieure critique de solubilité du bloc A.13. Formulation according to claim 12, characterized in that the vectorized product is dispersed in the liquid carrier, in the form of a dispersion of solid particles stabilized by the copolymer, dispersion of liquid droplets stabilized by the copolymer, or dispersion at micelle core of the copolymer, the formulation being at a temperature below the critical lower solubility temperature of the A block.
14. Formulation selon l'une des revendications 12 à 13, caractérisée en ce qu'il s'agit:14. Formulation according to one of claims 12 to 13, characterized in that it is:
- d'une formulation destinée à être appliquée sur la peau et/ou les cheveux, sur des fibres textiles, ou - d'une formulation à liant hydraulique, par exemple une formulation cimentaire (le copolymère est un hydrofugeant), oua formulation intended to be applied to the skin and / or the hair, to textile fibers, or to a formulation with a hydraulic binder, for example a cementitious formulation (the copolymer is a water-repellent), or
- d'une formulation destinée aux applications dans le domaine des revêtements telles que peintures, vernis ou adhésifs.a formulation intended for applications in the field of coatings such as paints, varnishes or adhesives.
15. Utilisation de la formulation selon l'une des revendications 12 à 13 pour vectoriser un ingrédient actif sur une surface par application de la formulation sur ladite surface à une température inférieure à la LCST et augmentation de la température à une température supérieure à la LCST. 15. Use of the formulation according to one of claims 12 to 13 for vectorizing an active ingredient on a surface by applying the formulation on said surface at a temperature below the LCST and increasing the temperature to a temperature above the LCST .
PCT/FR2006/001835 2005-07-27 2006-07-27 Block copolymer comprising a lcst block having a low critical solubility temperature, formulations comprising the copolymer and use thereof for vectorizing an active principle WO2007012763A1 (en)

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FR0508026A FR2889194A1 (en) 2005-07-27 2005-07-27 BLOCK COPOLYMER COMPRISING LCST BLOCK HAVING LOW SOLUBILITE CRITICAL TEMPERATURE, FORMULATIONS COMPRISING THE COPOLYMER, AND USE FOR VECTORIZING AN ACTIVE INGREDIENT

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WO2010010124A1 (en) * 2008-07-23 2010-01-28 Rhodia Operations Heat-sensitive emulsions
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US10392531B2 (en) 2009-11-30 2019-08-27 Basf Se Process for removing a bulk material layer from a substrate and a chemical mechanical polishing agent suitable for this process
EP2428541A1 (en) 2010-09-08 2012-03-14 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrates containing silicon oxide dielectric and polysilicon films
WO2012032469A1 (en) 2010-09-08 2012-03-15 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices
WO2012032466A1 (en) 2010-09-08 2012-03-15 Basf Se Aqueous polishing compositions containing n-substituted diazenium dioxides and/or n'-hydroxy-diazenium oxide salts
US9070632B2 (en) 2010-10-07 2015-06-30 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrates having patterned or unpatterned low-k dielectric layers
US9524874B2 (en) 2010-12-10 2016-12-20 Basf Se Aqueous polishing composition and process for chemically mechanically polishing substrates containing silicon oxide dielectric and polysilicon films
US9496146B2 (en) 2011-03-11 2016-11-15 Basf Se Method for forming through-base wafer vias
US11837119B2 (en) 2019-11-20 2023-12-05 Lg Display Co., Ltd Display device
CN114133583A (en) * 2021-12-13 2022-03-04 青岛科技大学 Triblock polymer grafted reduced graphene oxide composite material and preparation method and application thereof

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