KR101290934B1 - Sequenced copolymer - Google Patents

Abstract

The present invention relates to a continuous unit copolymer, a composition containing the copolymer and a cosmetic treatment method. The present invention relates in particular to linear ethylenic continuous unit copolymers containing at least one ionic hydrophilic pattern in each of the continuous units. The pattern may differ from one continuous unit to the next, with each continuous unit containing from 2 to 100% by weight relative to the weight of the continuous unit. The present invention also relates to a cosmetic or pharmaceutical composition containing one of the copolymers, and to a cosmetic makeup method or care method for keratin materials using the composition.

Description

Continuous Unit Copolymer {SEQUENCED COPOLYMER}

The present invention relates to novel block copolymers, in particular their use in the field of cosmetics and compositions containing them.

In the field of cosmetics, polymers with conflicting properties are often required to obtain good fixation without stickiness, good water resistance products that can be removed well in shampooing, or makeup compositions combining comfort and fixation in use. Moreover, the polymer should preferably be delivered to water in dissolved or dispersed form.

For this reason, the formulator is more particularly directed towards copolymers having advantageous mechanical properties, in particular block polymers. They can yield conflicting properties because they are obtained from a combination of blocks having different properties in the same chain, for example one providing possibly rigidity and the other providing ductility.

Thus, it is possible to modify the styling properties of the styling product or lacquer. It can also optimize film adhesion to the nail and wear resistance in the case of nail polishes without the occurrence of stickiness on the film surface. To this end, blocks that provide adhesion and blocks that prevent sticking can be combined in the same chain.

In the field of cosmetics, more particularly, PEO-PPO (polyethylene oxide / polypropylene oxide) based copolymers are known as water-deliverable block copolymers. However, the polymer does not provide satisfactory mechanical properties. In particular, it does not provide hairstyle retention.

Among other water-transmissive block copolymers that may be mentioned are those described in patent application WO # 02/28358. In particular, block copolymers are described in which one block is a copolymer mainly containing nonionic hydrophilic units mixed with hydrophobic units. The copolymer is nonionic. To make it water soluble, the hydrophilic unit content is very high, but this limitation does not allow access to a wide range of structures. The document also describes block copolymers in which one block is a copolymer comprising acrylic acid units and the other block is a nonionic hydrophilic block. However, the block polymers exhibit very large fluctuations in their properties due to the action of moisture.

This applies similarly to the block copolymers described in WO # 02/28357, which are water soluble and all blocks are formed from nonionic monomers but whose properties are also very variable by moisture.

Patent application WO # 00/71591, which describes block copolymers comprising cationic homopolymer blocks in combination with nonionic hydrophilic blocks, and the use of such copolymers to improve foam quality in human cleansing products. Mention may also be made.

However, the polymers have the disadvantage of lacking compatibility with anionic compounds, in particular anionic surfactants, which are generally used in shampoos. Moreover, when used in styling products, for example lacquer types, the polymers have the disadvantage of being difficult to remove into shampoos.

Diblock or triblock copolymers which can provide gelled aqueous compositions are also known from patent application WO-01 / 16187, which copolymers are particularly poly (styrene / methacrylic acid) -b-poly (ethyl acrylate). / Methacrylic acid) type. However, the copolymer is a thickener, which in certain cases can be considered a disadvantage, especially due to formulation difficulties. The reason is that obtaining a gel is not always required, for example aerosols or nail polishes which require a fluid solution.

Thus, it has been found that many block copolymers intended to be delivered in water mainly contain hydrophobic units and tend to form gels, which is a disadvantage.

It is an object of the present invention to propose block copolymers which have advantageous mechanical properties and which can be used in large amounts without substantially affecting the viscosity or gelling of the compositions containing them and thus substantially without affecting viscosity. In particular, the copolymers according to the invention do not form viscoelastic gels in water, ie gels having a modulus of elasticity (G ′) greater than the viscosity coefficient (G ″).

Moreover, a copolymer is also sought that forms a film or deposit that can be completely removed by the shampoo.

Thus, one subject of the invention is a linear ethylenic block copolymer comprising at least one first block and at least one second block, each block being one or more ionic hydrophilic units, which blocks may be different from one another. ) And the ionic hydrophilic unit is present in the block at a rate of 2 to 100% by weight, based on the weight of each block.

Another subject is a cosmetic or pharmaceutical composition containing one or more copolymers as defined below in a physiologically acceptable medium, in particular in a cosmetically or dermatologically acceptable medium.

The copolymers according to the invention have satisfactory mechanical properties: they can be rigid while at the same time having a certain level of flexibility or elasticity, thus maintaining hair for a long time. They can also exhibit good adhesion without feeling sticky.

They find the most particular use in the field of cosmetics, especially in hair care or makeup.

When used in nail polishes, these polymers adhere to nails satisfactorily and form deposits that do not wear away easily.

The block polymers according to the invention are advantageously linear block ethylenic polymers which are film formable.

The term "ethylenic" polymer means a polymer obtained by the polymerization of ethylenically unsaturated monomers.

The term "block polymer" means a polymer containing at least two different consecutive blocks, ie blocks of different chemical properties.

The polymer according to the invention is a polymer of linear structure. In contrast, polymers of nonlinear structure are, for example, polymers such as branched, star or graft structures. In particular, all monomers used to prepare linear polymers are monofunctional, ie they contain only one polymerizable functional group. The polymerization initiator may itself be monofunctional or bifunctional.

The term "film forming polymer", alone or in the presence of a film forming aid, means a polymer capable of forming a continuous film attached to a substrate, in particular a keratin material.

Each block of the polymer according to the invention is derived from one type of monomer or several different types of monomers. This may mean that each block consists of a homopolymer or copolymer; The copolymers constituting the block may in turn be irregular or alternating or gradient copolymers; It is thus meant that the distribution of monomers in each block can be irregular or controlled depending on the nature and / or reactivity of the monomers and / or the production method used.

Thus, the block polymer according to the invention comprises at least two blocks, advantageously two blocks (two blocks) or three blocks (three blocks), each block at a rate of at least 2% by weight relative to the weight of the blocks. It contains one or more ionic hydrophilic monomers present in each block.

In each block, the ionic hydrophilic monomer may actually be a mixture of different ionic hydrophilic monomers.

In addition, the ionic hydrophilic monomer (s) may be the same or different blocks in whole or in part.

The ionic hydrophilic monomer is present in each block at a ratio of 2 to 100% by weight, in particular 3 to 70% by weight, more preferably 5 to 50% by weight and even 8 to 30% by weight, based on the weight of the block.

The monomer is called hydrophilic when the corresponding homopolymer is hydrophilic, ie water soluble or water dispersible.

Homopolymers are water soluble when dissolved in water at a rate of at least 5% by weight at 25 ° C.

Homopolymers are water dispersible when forming stable suspensions or dispersions of fine, generally spherical particles in water at a concentration of 5% by weight at 25 ° C. The average size of the particles constituting the dispersion is less than 1 µm, more generally in the range of 5 to 400 nm, preferably 10 to 250 nm. These particle sizes are measured by light scattering (using a Coulter Counter type device).

The hydrophilicity of the monomer can also be defined as the logarithm of the 1-octanol / water apparent partition coefficient (also known as log P); When the value is 2 or less, for example -8 to 2, preferably 1.5 or less, specifically 1 or less, in particular -7 to 1 and even -6 to 0, the monomer can be considered hydrophilic. .

Log P values are known and are determined according to standard tests to determine the concentration of monomers in octanol and water.

The value can in particular be calculated using Advanced Chemistry Development (ACD) software solaris V4.67; They can also be obtained from Exploring QSAR: hydrophobic, electronic and steric constants (ACS professional reference book, 1995).

There is also a website that provides estimates (http://esc.syrres.com/interkow/kowdemo.htm).

As mentioned above, the final polymer contains at least one hydrophilic monomer present in each block in a ratio of at least 2% by weight relative to the weight of the block.

To this end, it is possible to use ionic hydrophilic monomers as described below as starting monomers, which monomers are copolymerized according to the prior art to give the desired polymer.

However, it is also possible to modify the presynthetic polymer to obtain the hydrophilic monomers.

For example, when it contains units of the (meth) acrylic acid ester type that can be hydrolyzed to yield units containing carboxylic acid functional groups, it is possible to hydrolyze the polymer; This may be the case when the polymer contains units of the methyl, ethyl, hydroxyethyl, tert-butyl, benzyl, trimethoxysilyl or ethyltrimethoxysilyl (meth) acrylate type.

Thus, hydrolysis, once synthesized, results in acidic conditions (eg the presence of sulfuric acid, hydrochloric acid or trifluoroacetic acid) or basic conditions (eg alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide). , Alkali metal alkoxides such as potassium t-butoxide or amines such as aqueous ammonia). Hydrolysis generally takes place at 5 to 100 ° C, preferably 15 to 80 ° C. The hydrolyzed polymer can then be purified by repeated precipitation.

In addition, compounds of type HO-RX, NHR'-RX, HO-RY or NHR'-RY type (wherein X and Y have the meanings provided below) may be substituted for units of the glycidyl or azlactone type. It is conceivable to react with the preformed polymer to contain.

The ionic hydrophilic monomer present in the final polymer can be selected from anionic, cationic and / or amphoteric hydrophilic monomers.

Preferably, each block contains at least one anionic hydrophilic monomer and / or at least one cationic hydrophilic monomer.

In one particular embodiment, one or more blocks may contain both one or more cationic hydrophilic monomers and one or more anionic hydrophilic monomers.

Among the anionic hydrophilic monomers that may be mentioned in particular are ethylenically unsaturated monomers containing, for example, one or more carboxylic acid (COOH), phosphonic acid (PO ₃ H ₂ ) or sulfonic acid (SO ₃ H) functional groups, for example There are those of formula (I):

(Wherein:

R 1 is a hydrogen atom or a linear or branched hydrocarbon radical of the type C _p H _{2p +1} (p is an integer from 1 to 12).

R 1 may in particular represent a methyl, ethyl, propyl or butyl radical. R 1 preferably represents hydrogen or a methyl radical.

-Z is a divalent group selected from -COO-, -CONH-, -CONCH _3- , -OCO- or -O-; Preferably, Z is selected from -COO- and -CONH-;

-X is 0 or 1, preferably 1;

-M is 0 or 1;

— R 2 is a linear, branched or cyclic, optionally aromatic, saturated or unsaturated divalent carbon-based radical of 1 to 30 carbon atoms which may contain 1 to 30 heteroatoms selected from O, N, S and P .

In radical R2, the hetero atom (s), if present, may be inserted into the chain of said radical R2, or optionally said radical R2 may be hydroxyl or amino (NH2, NHR 'or NR'R "(wherein R is 'And R' may be the same or different and may be substituted with one or more groups including those such as linear or branched C1-C22 alkyl, especially methyl or ethyl).

R2 may in particular be:

-Methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene or n- Alkylene radicals such as docosanylene;

A phenylene radical optionally substituted with a C1-C12 alkyl radical optionally containing 1 to 8 heteroatoms selected from O, N, S and P -C ₆ H _4- (ortho, meta or para); Or a benzylene radical -C ₆ H ₄ -CH ₂ -optionally substituted with a C1-C12 alkyl radical optionally containing 1 to 8 heteroatoms selected from O, N, S and P;

-CH ₂ -CHOH-, -CH ₂ -CH ₂ -CHOH-, -CH ₂ -CH ₂ -CH (NH ₂ )-, -CH ₂ -CH (NH ₂ )-, -CH ₂ -CH ₂ -CH (NHR ')-, -CH ₂ -CH (NHR')-, -CH ₂ -CH ₂ -CH (NR'R ")-, -CH ₂ -CH (NR'R")-, -CH ₂ -CH = CH- (R 'and R "represent a linear or branched C1-C18 alkyl, in particular methyl or ethyl).

Y is a group selected from -COOH, -SO ₃ H, -OSO ₃ H, -PO (OH) ₂ and -OPO (OH) ₂ ).

More particularly preferred anionic hydrophilic monomers, in particular acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, diacrylic acid, dimethylfumaric acid, citraconic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2 Methylpropanesulfonic acid, styrenesulfonic acid, vinylbenzoic acid, vinyl phosphoric acid, vinylsulfonic acid, vinylbenzenesulfonic acid, acrylamidoglycolic acid of the formula CH ₂ = CH-CONHCH (OH) COOH, vinylphosphonic acid; 2-carboxyethyl (meth) acrylate, sulfopropyl methacrylate or acrylate (CH ₂ = C (CH ₃ ) CO ₂ (CH ₂ ) ₃ SO ₃ H), sulfoethyl methacrylate or acrylate and vinyl methyl Sulfone, 2- (methacryloyloxy) ethyl phosphate of the formula CH ₂ ═C (CH ₃ ) COOC ₂ H ₄ OP (O) (OH) ₂ ; Diallyl maleate of formula C ₃ H ₅ -CO ₂ -CH = CH-CO ₂ -C ₃ H ₅ ; Carboxylic acid anhydrides and also salts thereof having vinyl bonds such as maleic anhydride; And mixtures thereof.

Neutralization of the anionic groups can be carried out by inorganic bases such as LiOH, NaOH, KOH, Ca (OH) ₂ , NH ₄ OH or Zn (OH) ₂ ; Or organic bases such as primary, secondary or tertiary alkylamines, in particular triethylamine or butylamine. The primary, secondary or tertiary alkylamine may contain one or more nitrogen and / or oxygen atoms and thus may contain, for example, one or more alcohol functional groups; In particular, mention may be made of 2-amino-2-methylpropanol, triethanolamine and 2-dimethylaminopropanol. Mention may also be made of lysine or 3- (dimethylamino) propylamine.

Among the cationic hydrophilic monomers that may be mentioned are ethylenically unsaturated monomers containing at least one primary, secondary or tertiary amine functional group, in particular those of the formula (II):

[Wherein:

—R 1, Z, x, R 2 and m have the same meaning as in formula (I) above;

-X represents (a) a group of the formula -NR ₆ R _{7 wherein} R _{6 and} R ₇ independently of one another represent the following (i) to (iv):

(i) a hydrogen atom;

(ii) linear, branched or cyclic, saturated or unsaturated, optionally aromatic alkyl groups of 1 to 30 carbon atoms which may contain 1 to 10 heteroatoms selected from O, N, S and P; Especially methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, lauryl or stearyl groups;

(iii) Formula-(R8O) _y R9 wherein R8 represents linear or branched C2-C4 alkyl, R9 represents hydrogen or linear or branched C1-C30 alkyl radical, y is 1 to 250 Alkylene oxide groups;

(iv) R6 and R7 together with the nitrogen atom represent a total of 5, 6, 7 or 8 atoms, in particular 4, 5 or 6 carbon atoms and / or 2 to 4 hetero atoms selected from O, S and N To form saturated or unsaturated, optionally aromatic rings containing; The ring is also possibly one containing 5, 6 or 7 atoms each, in particular 4, 5, 6 or 7 carbon atoms and / or 2 to 4 hetero atoms selected from O, S and N Or other saturated or unsaturated, optionally fused with an aromatic ring);

Or optionally X is (b) a group of the group -R'6-N-R'7-, wherein R'6 and R'7 together with the nitrogen atom are a total of 5, 6, 7 or 8 atoms, In particular form a saturated or unsaturated, optionally aromatic ring containing 4, 5 or 6 carbon atoms and / or 2 to 4 heteroatoms selected from O, S and N; the rings are each preferably 5 , At least one other saturated or unsaturated, optionally aromatic ring containing 6 or 7 atoms, in particular 4, 5, 6, 7 or 8 carbon atoms and / or 2 to 4 heteroatoms selected from O, S and N Fused with).

For example, X can constitute an aromatic or non-aromatic ring containing a cationizable tertiary amine group, or can represent an aromatic or non-aromatic heterocycle containing a cationizable tertiary nitrogen.

Among the preferred radicals X which may be mentioned are pyridine, indolyl, isoindolinyl, imidazolyl, imidazolinyl, piperidinyl, pyrazolinyl, pyrazolyl, quinoline, pyrazolinyl, pyridinyl, pipera Radicals of the genyl, pyrrolidinyl, quinidinyl, thiazolinyl, morpholine, guanidino or amidino type and mixtures thereof.

Among the preferred cationic hydrophilic monomers, which may be mentioned alone or as a mixture, are the following:

2-vinylpyridine, 4-vinylpyridine, allylamine and allylpyridine;

-Aminoalkyl (meth) acrylates, for example [N, N-di- (C1-C4) alkylamino] (C1-C6) alkyl (meth) acrylate or [N- (C1-C4) alkylamino] (C1-C6) alkyl (meth) acrylates, in particular N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-aminoethyl (meth) acrylate and 2- (N-tert-butylamino) ethyl (meth) acrylate;

-Aminoalkyl (meth) acrylamides, for example [N, N-di- (C1-C4) alkylamino] (C1-C6) alkyl (meth) acrylamide or [N- (C1-C4) alkylamino] (C1-C6) alkyl (meth) acrylamides, in particular N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; 3-aminopropyl (meth) acrylamide;

-Vinylamine, vinylimidazole and 2- (diethylamino) ethylstyrene;

N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinylcarbazole;

And also salts thereof and / or quaternized forms thereof.

Among the chlorided forms which may be mentioned are salts of inorganic acids such as sulfuric acid, hydrochloric acid, bromic acid, iodic acid, phosphoric acid or boric acid.

Mention may also be made of salts of organic acids which may comprise one or more carboxylic acid groups, sulfonic acid groups or phosphonic acid groups. These may be linear, branched or cyclic aliphatic acids, or optionally aromatic acids. These acids may also contain one or more heteroatoms selected from O and N, for example in the form of hydroxyl groups. In particular, propionic acid, acetic acid, terephthalic acid, citric acid and tartaric acid may be mentioned.

Neutralization, similarly quaternization, of anionic or cationic units can be in whole or in part.

The tertiary amine groups may be quaternized with compounds containing unstable halogens, in particular alkyl halides such as C1-C12 alkyl chlorides or bromide (eg methyl bromide or ethyl chloride).

These groups are selected from compounds containing labile halogens, in particular sodium chloroacetate, including carboxylic acid or sulfonic acid functional groups; Or quaternized with cyclic sulfones, eg propane sulfone. Thus, amphoteric hydrophilic monomers (or betaines, containing at least one (+) charge and at least one (-) charge possessed by the same monomer) are obtained.

Quaternization can be carried out prior to polymerization on the presynthesized polymer or starting monomer.

Thus, the obtained polymer may possibly contain amphoteric monomers corresponding to formula (III):

[Wherein:

—R 1, Z, x, R 2 and m have the same meaning as in formula (I) above;

-X ' ⁺ is a divalent group of the formula -N ⁺ R' ₆ R ' ₇ wherein R'6 and R'7 independently of one another represent the following (i) to (iv):

(i) a hydrogen atom;

(ii) linear, branched or cyclic, optionally aromatic alkyl groups of 1 to 30 carbon atoms which may contain 1 to 8 heteroatoms selected from O, N, S and P; For example methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl or isobutyl groups;

(iii) of the formula-(R8O) _y R9, wherein R8 represents a linear or branched C2-C4 alkyl, R9 is hydrogen or a linear or branched C1-C30 alkyl radical, and y is from 1 to 250 Alkylene oxide groups;

(iv) R'6 and R'7 together with the nitrogen atom are a total of 5, 6, 7 or 8 atoms, in particular 4, 5, 6 or 7 carbon atoms and / or 2 selected from O, S and N Saturated or unsaturated, optionally containing an aromatic ring (NR′6R′7 or R′6NR′7) containing from 4 heteroatoms; Said ring possibly contains 5, 6, 7 or 8 atoms, in particular 4, 5, 6 or 7 carbon atoms and / or 2 to 4 hetero atoms selected from O, S and N One or more other saturated or unsaturated, optionally fused with an aromatic ring);

- Y 'is _{^{-COO -, -SO 3 -, -OSO}} 3 -, -PO 3 2 - and -PO ₄ ^{2 -} group is selected from and;

R 3 is a saturated or unsaturated, optionally aromatic, linear, branched or cyclic divalent carbon-based radical having 1 to 30 carbon atoms which may contain 1 to 18 heteroatoms selected from O, N, S and P.

In the radical R3, the hetero atom (s), if present, may be inserted into the chain of said radical R3, or optionally said radical R3 may be substituted with one or more groups, including those such as hydroxyl or amino; R3 may in particular be:

-Methylene, ethylene, propylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n- tetradecylene, n- Alkylene radicals such as docosanylene;

A phenylene radical optionally substituted with a C1-C12 alkyl radical optionally containing 1 to 5 heteroatoms selected from O, N, S, F, Si and P -C ₆ H _4- (ortho, meta or para) ; Or a benzylene radical -C ₆ H ₄ -CH ₂ -optionally substituted with a C1-C12 alkyl radical optionally containing 1 to 5 heteroatoms selected from O, N, S and P;

-N is 0 or 1].

In particular, N, N-dimethyl-N- (2-methacryloyloxyethyl) -N- (3-sulfopropyl) ammonium betaine, N, N-dimethyl-N- (3-methacrylamidopropyl) Mention may be made of -N- (3-sulfopropyl) ammonium betaine and 1- (3-sulfopropyl) -2-vinylpyridinium betaine, and mixtures thereof.

In one preferred embodiment, the copolymers according to the invention contain from 4 to 100% by weight, in particular from 8 to 80% by weight and even from 10 to 30% by weight, based on the total weight of the copolymer.

Advantageously, the copolymer according to the invention is dissolved or dispersed in water at a rate of 5% by weight at 25 ° C.

In addition to the ionic hydrophilic monomers, the blocks of the block copolymers according to the invention may contain one or more additional monomers selected from nonionic hydrophilic monomers and hydrophobic monomers, and mixtures thereof.

These additional monomers may be the same or different blocks from each other.

The additional monomer (s) are ethylenic monomers copolymerizable with the ionic hydrophilic monomer (s), regardless of their reactivity coefficient.

Preferably, the nonionic hydrophilic monomer is present in one or more blocks, moreover each block, in a proportion of 0 to 98% by weight, in particular 2 to 95% by weight, more preferably 3 to 92% by weight, relative to the weight of the block. Can be.

Preferably, the hydrophobic monomer may be present in one or more blocks, moreover in each block, in a proportion of 0 to 98% by weight, in particular 2 to 95% by weight, more preferably 3 to 92% by weight, relative to the weight of the block. .

Among the nonionic hydrophilic or hydrophobic monomers that can be copolymerized with the ionic hydrophilic monomers for forming the polymers according to the invention, the following may be mentioned alone or as a mixture:

(i) ethylenic hydrocarbons having 2 to 10 carbon atoms, such as ethylene, isoprene or butadiene;

(ii) (meth) acrylate or the following formula:

[Wherein, R ₂ is hydrogen or methyl (CH ₃ ),

R ₃ represents the following:

A linear or branched alkyl group having 1 to 30 carbon atoms optionally inserted with one or more heteroatoms selected from O, N, S and P (the alkyl group is also OH, halogen atoms (Cl, Br, I and F), and- _May be optionally substituted with one or more substituents selected from Si (R ₄ R ₅ R ₆ ) and —Si (R ₄ R ₅ ) O groups, wherein R ₄ , R ₅ and R ₆ , which may be the same or different, are hydrogen An atom, a C ₁ to C ₆ alkyl group or a phenyl group; R ₃ in particular methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, especially 2-ethylhexyl, octyl, lauryl, Isooctyl, isodecyl, dodecyl, cyclohexyl, t-butylcyclohexyl or stearyl group; 2-ethylperfluorohexyl or 2-ethylperfluorooctyl; or C1-C4 hydroxyalkyl group, such as 2-hydroxy hydroxyethyl, 2-hydroxybutyl and 2-hydroxypropyl; or (C _{1 -4)} alkoxy (C _{1 -4)} alkyl group, such as methoxy ethyl, Ethoxyethyl and methoxy may be a propyl),

C ₃ to C ₁₂ cycloalkyl groups, such as isobornyl groups,

C ₃ to C ₂₀ aryl groups, such as phenyl groups,

C4-C30 aralkyl groups (C ₁ to C ₈ alkyl groups), such as 2-phenylethyl, t-butylbenzyl or benzyl,

4- to 12-membered heterocyclic group containing at least one hetero atom selected from O, N and S, wherein the ring is aromatic or non-aromatic;

-Heterocycloalkyl (alkyl of 1 to 4 C) such as furfurylmethyl or tetrahydrofurfurylmethyl,

(The cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl group is a linear or branched C 1-4 optionally substituted with a hydroxyl group, a halogen atom and one or more hetero atoms selected from O, N, S and P. May be substituted with one or more substituents selected from alkyl groups, said alkyl groups also being —OH, halogen atoms (Cl, Br, I and F), and —Si (R ₄ R ₅ R ₆ ) and —Si (R ₄ R ₅ ) optionally substituted with one or more substituents selected from O groups, wherein R ₄ , R ₅ and R ₆ , which may be the same or different, represent a hydrogen atom, a C ₁ to C ₆ alkyl group or a phenyl group),

-(OC ₂ H ₄ ) _m -OR "groups where m = 5 to 300 and R" = H or C ₁ to C ₃₀ alkyl, for example-(OC ₂ H ₄ ) _m -OH,-(OC ₂ H ₄ ) _m - O -methyl or-(OC ₂ H ₄ ) _m - O -behenyl; a-(OC ₃ H ₆ ) _m -OR "group, such as-(OC ₃ H ₆ ) _m -OH, wherein m = 5 to 300 and R" = H or C ₁ to C ₃₀ alkyl; Or optionally an irregular or block mixture of (OC ₂ H ₄ ) _m and (OC ₃ H ₆ ) _m groups.

(Iii) acrylamide of formula

[Wherein R ₈ represents H or methyl;

R ₇ and R _6, which may be the same or different, represent the following:

- a hydrogen atom; or

A linear or branched alkyl group of 1 to 30 carbon atoms optionally inserted with one or more heteroatoms selected from O, N, S and P (the alkyl group is also -OH, halogen atoms (Cl, Br, I and F), and Optionally substituted with one or more substituents selected from -Si (R ₄ R ₅ R ₆ ) and -Si (R ₄ R ₅ ) O groups, wherein R ₄ , R ₅ and R ₆ are hydrogen atoms, C ₁ to C ₆ alkyl group or phenyl group; R ₆ or R ₇ in particular methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, octyl, lauryl, isooctyl, isodecyl, dodecyl , cyclohexyl, t- butylcyclohexyl or stearyl group; 2-ethyl-perfluoro-hexyl, 2-ethyl perfluorooctyl; or C _{1 -4} hydroxyalkyl group, e.g., 2-hydroxyethyl, 2-hydroxyethyl butyl or 2-hydroxypropyl; or (C _{1 -4)} alkoxy (C _{1 -4)} alkyl group such as methoxyethyl, ethoxyethyl or to be methoxypropyl C),

C ₃ to C ₁₂ cycloalkyl groups, such as isobornyl groups,

C ₃ to C ₂₀ aryl groups, such as phenyl groups,

C ₄ to C ₃₀ aralkyl groups (C ₁ to C ₈ alkyl groups), such as 2-phenylethyl, t-butylbenzyl or benzyl,

4- to 12-membered heterocyclic groups containing at least one hetero atom selected from O, N and S, wherein the ring is aromatic or non-aromatic;

Heterocycloalkyl groups (C1-C4 alkyl) such as furfurylmethyl or tetrahydrofurfurylmethyl,

(The cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl group is a linear or branched C 1 -C 4 optionally substituted with a hydroxyl group, a halogen atom, and one or more hetero atoms selected from O, N, S and P. Optionally substituted with one or more substituents selected from alkyl groups, said alkyl groups also being —OH, halogen atoms (Cl, Br, I and F), and —Si (R ₄ R ₅ R ₆ ) and —Si (R ₄ Optionally substituted with one or more substituents selected from R ₅ ) O groups, wherein R ₄ , R ₅ and R ₆ , which may be the same or different, represent a hydrogen atom, a C ₁ to C ₆ alkyl group or a phenyl group);

-(OC ₂ H ₄ ) _m -OR "groups where m = 5 to 300 and R" = H or C ₁ to C ₃₀ alkyl, for example-(OC ₂ H ₄ ) _m -OH,-(OC ₂ H ₄ ) _m -O-methyl or-(OC ₂ H ₄ ) _m -O-behenyl; a-(OC ₃ H ₆ ) _m -OR "group, such as-(OC ₃ H ₆ ) _m -OH, wherein m = 5 to 300 and R" = H or C ₁ to C ₃₀ alkyl; Or optionally an irregular or block mixture of (OC ₂ H ₄ ) _m and (OC ₃ H ₆ ) _m groups.

Examples of such additional monomers include (meth) acrylamide, N-ethyl (meth) acrylamide, N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethyl (meth) acrylamide , N, N-dibutylacrylamide, N-octylacrylamide, N-dodecylacrylamide, N-undecylacrylamide and N- (2-hydroxypropylmethacrylamide).

-(Iv) 'vinyl compound of formula:

CH ₂ = CH-R ₉

[Wherein R ₉ is a hydroxyl group; Halogen (Cl or F); NH ₂ group; An OR ₁₀ group in which R ₁₀ represents a phenyl group or a C ₁ to C ₁₂ alkyl group (the monomer is a vinyl or allyl ether); Acetamide group (NHCOCH ₃ ); R ₁₁ represents an OCOR ₁₁ group which represents a linear or branched alkyl group having 2 to 12 carbon atoms (the monomer is a vinyl or allyl ester), C 3 -C 12 cycloalkyl, C 3 -C 20 aryl or C 4 -C 30 arallyl; Or optionally R ₉ is selected from:

A linear or branched alkyl group of 1 to 30 carbon atoms optionally inserted with one or more heteroatoms selected from O, N, S and P (the alkyl group is also -OH, halogen atoms (Cl, Br, I and F), and _May be optionally substituted with one or more substituents selected from -Si (R ₄ R ₅ R ₆ ) and -Si (R ₄ R ₅ ) O groups, wherein R ₄ , R ₅ and R ₆ , which may be the same or different, are Hydrogen atom, C ₁ to C ₆ alkyl group or phenyl group);

C ₃ to C ₁₂ cycloalkyl groups, such as isobornyl or cyclohexane,

C ₃ to C ₂₀ aryl groups, such as phenyl,

C ₄ to C ₃₀ arylalkyl or alkylaryl groups (C ₁ to C ₈ alkyl groups), such as 2-phenylethyl or benzyl,

4- to 12-membered heterocyclic groups containing at least one hetero atom selected from O, N and S, wherein the ring is aromatic or non-aromatic, such as N-vinylpyrrolidone and N-vinylcapro Lactams;

Heterocycloalkyl groups (alkyl of 1 to 4 C), such as furfurylmethyl or tetrahydrofurfurylmethyl

(The cycloalkyl, aryl, aralkyl, heterocyclic or heterocycloalkyl group is a linear group of 1 to 4 C optionally substituted with a hydroxyl group, a halogen atom and one or more hetero atoms selected from O, N, S and P or Optionally substituted with one or more substituents selected from branched alkyl groups, said alkyl groups also being -OH, halogen atoms (Cl, Br, I and F), and -Si (R ₄ R ₅ R ₆ ) and -Si ( _May be optionally substituted with one or more substituents selected from R ₄ R ₅ ) O groups, where R ₄ , R ₅ and R ₆ , which may be the same or different, represent a hydrogen atom, a C ₁ to C ₆ alkyl group or a phenyl group) ].

Examples of such additional monomers include vinylcyclohexane and styrene (hydrophobic); N-vinylpyrrolidone and N-vinylcaprolactam (nonionic hydrophilic); Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ethylhexanoate, vinyl neononanoate and vinyl neododecanoate (hydrophobic); Methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether.

(Iii) allyl compounds of the formula:

CH ₂ = CH-CH ₂ -R ₉ or CH ₂ = C (CH ₃ ) -CH ₂ -R ₉

[Wherein R9 has the same meaning as above].

Especially allyl methyl ether, 3-allyloxy-1,2-propanediol (CH ₂ = CHCH ₂ OCH ₂ CH (OH) CH ₂ OH) and 2-allyloxyethanol (CH ₂ = CHCH ₂ OC ₂ H ₄ OH) May be mentioned.

-(Vi) silicone-based (meth) acrylic, (meth) acrylamide or vinyl monomers such as methacryloxypropyltris (trimethylsiloxy) silane or acryloxypropylpolydimethylsiloxane, or silicone-based (meth) acrylamide .

Among the more preferred addition monomers (particularly nonionic hydrophilic monomers), the following monomers, to which Tg is given in parentheses as a guide, may be mentioned alone or as a mixture:

Hydroxyalkyl (meth) acrylates and (meth) acrylamides having 2 to 4 carbon atoms of the-alkyl group, in particular 2-hydroxyethyl acrylate (Tg = 15 ° C), 2-hydroxyethyl methacrylate (55 ° C) ), 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and N- (2-hydroxypropyl) (meth) acrylamide;

- (C _{1 -4)} alkoxy (C _{1 -4)} alkyl (meth) acrylate and (meth) acrylamides, such as methoxyethyl, 2-ethoxyethyl, methoxypropyl, and bis (2-ethoxyethyl) (Meth) acrylates and (meth) acrylamides; More particularly 2-ethoxyethyl methacrylate;

-(Meth) acrylamide and N, N-dimethylacrylamide;

(meth) acrylates and (meth) acrylamides containing the group-(OC ₂ H ₄ ) _m -OR "where m = 5 to 300 and R" = H or C ₁ to C ₄ alkyl, for example polyethylene glycol (Meth) acrylates and (meth) acrylamides (containing methoxy or hydroxyl end groups); More particularly polyethylene glycol methacrylate containing hydroxyl end groups (n = 8, 10, 12, 45, 90 or 200) and polyethylene glycol methacrylate containing methoxy end groups (n = 8, 10, 12, 45, 90 or 200) (Tg = -55 ° C);

-Vinyllactams such as vinylpyrrolidone and vinylcaprolactam;

—Vinyl ethers such as methyl vinyl ether (Tg = −34 ° C.) and ethyl vinyl ether;

-Vinylacetamide, N-vinylpyrrolidone and N-vinyl-caprolactam;

Polysaccharide (meth) acrylates such as sucrose acrylate and ethylglucoside (meth) acrylate.

Furthermore, among the more preferred addition monomers (particularly hydrophobic monomers), the following monomers, to which Tg is given in parentheses as a guide, may be mentioned alone or as a mixture:

T-butylbenzyl acrylate, t-butylcyclohexyl acrylate, isobornyl acrylate (94 ° C.), furfuryl acrylate, n-hexyl acrylate (45 ° C.), t-butyl acrylate (50 ° C.) , Cyclohexyl acrylate (19 ° C), hydroxyethyl acrylate (15 ° C), methyl acrylate (10 ° C), ethyl acrylate (-24 ° C), isobutyl acrylate (-24 ° C), methoxyethyl Acrylate (-33 ° C), n-butyl acrylate (-54 ° C), ethylhexyl acrylate (-50 ° C), hexyl acrylate, octyl acrylate, lauryl acrylate, isooctyl acrylate, isodecyl acryl Rate;

T-butylbenzyl methacrylate, t-butylcyclohexyl methacrylate, isobornyl methacrylate (111 ° C), methyl methacrylate (100 ° C), cyclohexyl methacrylate (83 ° C), ethyl meth Acrylate (65 ° C), benzyl methacrylate (54 ° C), isobutyl methacrylate (53 ° C), butyl methacrylate (20 ° C), n-hexyl methacrylate (-5 ° C), ethylhexyl meta Methacrylate, octyl methacrylate, lauryl methacrylate, isooctyl methacrylate, isodecyl methacrylate;

-Xylene (100 ° C.), vinylcyclohexane, vinyl acetate (23 ° C.), methyl vinyl ether (-34 ° C.), vinyl neononanoate, vinyl neododecanoate;

—N-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dibutylacrylamide, N-t-butylacrylamide, N-octylacrylamide.

Preferably, the copolymer according to the invention is isobornyl acrylate, cyclohexyl acrylate (19 ° C.), ethyl acrylate (10 ° C.), methyl methacrylate (100 ° C.), cyclohexyl methacrylate (83 And at least one block containing monomers selected from ethyl methacrylate (65 ° C.), butyl methacrylate (20 ° C.) and styrene (100 ° C.).

Preferably, the copolymers according to the invention are n-hexyl methacrylate (-5 ° C), ethyl acrylate (-24 ° C), isobutyl acrylate (-24 ° C), n-butyl acrylate (-54 ° C), ethylhexyl acrylate (-50 ° C); Methoxy poly (ethylene glycol) monomethacrylate, wherein the number m of ethylene glycol units is 8, 12, 90, 180 or 200; methoxy poly (ethylene glycol) monomethacrylamide with m '= 8, 12, 90, 180 or 200; poly (ethylene glycol) OH (meth) acrylate with m '= 8, 12, 90, 180 or 200; poly (ethylene glycol) OH (meth) acrylamide with m '= 8, 12, 90, 180 or 200; Vinylpyrrolidone, vinyl caprolactam; One or more blocks containing monomers selected from methyl vinyl ether and ethyl vinyl ether may be included.

Preferably, the copolymer according to the invention comprises two blocks (two blocks) Copolymers, such as:

-Poly (acrylic acid-co-butyl acrylate) -b-poly (methyl methacrylate-co-acrylic acid), and

-Poly (methacrylic acid-co-butyl acrylate) -b-poly (methyl methacrylate-co-methacrylic acid).

Preferably, the copolymer according to the invention comprises three blocks (three blocks) Copolymers, such as:

-Poly (methyl methacrylate-co-acrylic acid) -b-poly (acrylic acid -co-butyl acrylate) -b-poly (methyl methacrylate -co-acrylic acid),

-Poly (methyl methacrylate-co- (meth) acrylic acid) -b-poly (methacrylic acid-co-butyl acrylate) -b-poly (methyl methacrylate-co-methacrylic acid),

-Poly (methyl acrylate-co-acrylic acid) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (methyl acrylate-co-acrylic acid),

-Poly (acrylic acid-co-butyl acrylate) -b-poly (methyl methacrylate-co-acrylic acid) -b-poly (acrylic acid-co-butyl acrylate);

-Poly (acrylic acid) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid);

-Poly (methacrylic acid) -b-poly (methacrylic acid-co-butyl acrylate) -b-poly (methacrylic acid);

-Poly (acrylic acid-co-cyclohexyl acrylate) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-cyclohexyl acrylate);

-Poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-cyclohexyl acrylate) -b-poly (acrylic acid-co-butyl acrylate);

-Poly (acrylic acid-co-cyclohexyl methacrylate) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-cyclohexyl methacrylate);

-Poly (acrylic acid-co-isobornyl acrylate) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-isobornyl acrylate);

-Poly (methyl methacrylate-co-acrylic acid) -b-poly (acrylic acid-co-methoxypoly (ethylene glycol) monomethacrylate with m '= 12) -b-poly (methyl methacrylate-co-acrylic acid );

-Poly (m- = acrylic acid-co-methoxypoly (ethylene glycol) monomethacrylate) -b-poly (methyl methacrylate-co-acrylic acid) -b-poly (m- = acrylic acid with cov12) Methoxypoly (ethylene glycol) monomethacrylate).

In general, the monomers that make up each block are preferably selected to promote phase separation between the blocks, as this will determine the properties of the final polymer.

Preferably, at least one of the blocks of the copolymer according to the invention has a glass transition temperature (Tg) of 20 ° C. or less.

Also preferably, at least one of the blocks of the copolymer according to the invention has a glass transition temperature (Tg) of at least 20 ° C.

The measuring method of Tg value is demonstrated before an Example.

In one particular embodiment, the copolymer according to the invention may comprise both blocks having a Tg of at least 20 ° C. and blocks having a Tg of less than 20 ° C. The copolymer obtained has "elastomer" properties.

This may be a diblock copolymer or triblock copolymer comprising only these two blocks, or three different blocks, eg, a central block with a Tg of less than 20 ° C. and two blocks of terminals with a Tg of at least 20 ° C .; Or optionally a copolymer comprising a central block having a Tg of 20 ° C. or more and two blocks of a terminal having a Tg of 20 ° C. or less.

In another embodiment of the invention, the copolymer may comprise two or more different blocks, all having a Tg of at least 20 ° C. The block copolymer then has "hard" properties.

Blocks having a Tg of more than 20 ° C. are homopolymerized with monomers having a homopolymer of Tg> 20 ° C. or copolymerization of monomers having a Tg>, 20 ° C., as well as monomers with a Tg 있는> 20 ° C. to which a monomer having Tg <20 ° C. can be added. It can be obtained by copolymerization of.

Similarly, a block having a Tg of less than 20 ° C. may be used for homopolymerization of a monomer having a Tg <20 ° C. or a copolymer of a monomer having a Tg <20 ° C., as well as for a monomer having a Tg <20 ° C. to which a monomer having a Tg <20 ° C. may be added. It can be obtained by.

In another embodiment, the total content in the copolymer of the monomers whose homopolymer has a Tg greater than 20 ° C. is preferably at least 50% by weight, in particular from about 70% to 100% by weight, relative to the total weight of the block copolymer % to be. In that case, the block copolymer also has "hard" properties.

In another embodiment of the invention, the copolymer may comprise two or more different blocks, all having a Tg of 20 ° C. or less. In that case, the block copolymer has "adhesive" properties.

In another embodiment, the total content in the copolymer of the monomers whose homopolymer has a Tg of less than 20 ° C. is preferably at least 60% by weight, in particular about 70% to 100% by weight relative to the total weight of the block copolymer % to be. The block copolymer then has "sticky" properties.

Furthermore, in one particular embodiment, the copolymers according to the invention comprise at least one hydrophilic block having a Tg of at least 0 ° C, for example 0 to 250 ° C, in particular 50 ° C to 200 ° C.

The weight-average molecular mass Mw of the block copolymers according to the invention is preferably from 4000 to 1 000 000 000, preferably from 10 000 000 to 800 000 000, more preferably from 20 000 000 to 500 000 000, especially from 60 000 000 to 350 000 000. .

Advantageously, the weight-average molecular mass Mw of each block is from 2000 to 500 000 000, preferably from 5000 to 400 000 000, more preferably from 10 000 000 to 300 000 000.

Polymers according to the invention include diblock polymers of the AB type; Or ABA, BAB or a triblock polymer of type ABC with C different from A and B; Or optionally, more than three blocks of type (AB) n, (ABA) n, (BAB) n, (ABC) n or ABCD, for example with different chemical properties A, B, C and D Containing multiblock polymers.

Preferably, the polymer according to the invention comprises at least three continuous blocks, which differ in two consecutive blocks, for example of the ABA or ABC type.

The polymer may be prepared according to methods known to those skilled in the art. Among these methods, anionic polymerization, controlled free-radical polymerization (eg by xanthan, dithiocarbamate or dithioester); Polymerization with nitroxide type precursors; Atom-shifted radical polymerization (ATRP); Mention may be made of group-shift polymerization.

For example, the block copolymers according to the invention are also known as controlled free-radical polymerization, in particular described in "New Method of Polymer Synthesis", Blackie Academic & Professional, London, 1995, volume 2, page 1. It can be obtained by either living or pseudo-living polymerization.

Controlled free-radical polymerization usually refers to polymerization in which secondary reactions (termination or transfer reactions) that lead to the disappearance of proliferating species are less likely to occur than proliferation reactions by free-radical modulators. The drawback of the polymerization scheme is that when the concentration of free radicals is higher than the monomer concentration, the secondary reaction tends to enlarge the mass distribution by becoming a determining factor.

Recall that living or pseudo-living polymerization is a polymerization in which growth of polymer chains is stopped only by the disappearance of monomers. The number-average mass (Mn) increases as the conversion proceeds. Such polymerization leads to copolymers having low mass dispersibility, ie, polymers having a mass polydispersity (Ip) of generally less than 2.

Anionic polymerization is a typical example of living polymerization.

Pseudo-living polymerization itself serves as a controlled free-radical polymerization. Among the main types of controlled free-radical polymerization that may be mentioned are:

Free-radical polymerization controlled with nitroxides (in particular, patent applications WO 96/24620 and WO 00/71501 describing tools for their polymerization and their use, and also papers published by Fischer [Chemical Reviews, 2001, 101]). , 3581], published by Tordo and Gnanou [J. Am. Chem. Soc. 2000, 122 , 5929] and published by Hawker [J. Am. Chem. Soc. 1999, 121 , 3904]. Reference);

-Atom-shifted radical polymerization, in particular described in patent application WO # 96/30421, which proceeds to the bonding of carbon-halogen type via reversible insertion into an organometallic complex;

As described in patent applications FR 2821620, WO 98/01478, WO 99/35177, WO 98/58974, WO 99/31144, WO 97/01478 and Rizzardo et al. [Macromolecules, 1998, 31 , 5559] Free-radical polymerization controlled by sulfur derivatives of the xanthan, dithioester, trithiocarbonate or carbamate type.

By polymerization of these modes, the polymer chains of the copolymer grow simultaneously, thus incorporating the same proportion of comonomer at each instant. Therefore, all the chains have the same structure or similar structure, so that the composition dispersibility is low. These chains also have low mass polydispersities.

Accordingly, the polymerization is atom transfer in accordance with the description of (atom transfer radical polymerization (Atom Transfer Radical Polymerization), or "ATRP"), or cut rock by the reaction of the seed and, or alternatively, "reversible addition-fragmentation chain transfer (reversible addition -fragmentation chain transfer ) " According to the description of ("RAFT") or, finally, by the description of "inverse ATRP".

The technique of atomic transfer radical polymerization consists of blocking free-radical species growing in the form of bonds of the C-halide type (in the presence of metal / ligand complexes). This type of polymerization is reflected by the mass control and low mass dispersion of the polymer formed. In general, atomic transfer radical polymerization is carried out by the polymerization of one or more monomers which can be free-radically polymerized in the presence of:

An initiator containing at least one mobile halogen atom;

Halogenated compounds comprising transition metals and "dormant" polymer chains which may be involved in the reduction step by the initiator, which will be known as "chain-transfer agents"; And

Ligands that can be selected from compounds containing nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) atoms, which can be coordinated with the compound containing a transition metal via a-σ bond Formation of direct bonds between the compound and the polymer, including the transition metal, is avoided).

The halogen atom is preferably a chlorine or bromine atom.

This method is described in particular in patent application WO 97/18247 and in the paper by Matyjasezwski et al. (JACS publication, 117, page 5614 (1995)).

The free-radical polymerization technique by reaction with nitroxide is CO-NR _a R (Wherein Ra and Rb are independently of each other a ring comprising 2 to 30 carbon atoms or each comprising 4 to 20 carbon atoms together with a nitrogen atom, for example 2,2,6, Blocking the growing free-radical species, which are in the form of a bond of the type), which may be an alkyl radical forming a 6-tetramethyl-piperidyl ring. This polymerization technique is described in particular in the paper ["Living free radical polymerization: a unique technique for preparation of controlled macromolecular architectures" CJ Hawker; Chem. Res. 1997,30,373-82, and ["Mcromolecular engineering via living free radical polymerizations" published in Macromol. Chem. Phys. 1998, vol. 199, pages 923-935, or optionally in patent application WO-A-99 / 03894.

The RAFT polymerization (reversible addition-fragmentation chain transfer) technique is to block the growing free-radical species, which are C-S type binding forms. Dithio compounds such as dithioester (-C (S) S-) such as dithiobenzoate, dithiocarbamate (-NC (S) S-) or dithiocarbonate (-OC ( This is done using S) S-) (xanthate). These compounds control the chain growth of a wide range of monomers. However, dithioesters inhibit the polymerization of vinyl esters, while dithiocarbamates are very weak with respect to methacrylates, which limits the application of such compounds to a range. This technique is described in particular in Rhodia's patent application WO-A-98 / 58974 and in a paper ["a more versatile route to block copolymers and other polymers of complex architecture by living radical polymerization: the RAFT process", published in Macromolecules, 1999, volume # 32 , pages 2071-2074. The patent application WO-A-98 / 58974 and the patent application WO-A-99 / 31144 of CSIRO, already cited, relate to the use of dithiocarbamates as "RAFT" reagents.

By varying the ratio of monomer concentration to chain-transfer concentration, the molecular mass of the polymer can be modified.

The polymerization generally proceeds in several stages according to the following general reaction scheme:

a) in a first step, polymerizing the first monomer or monomer mixture to form a polymer initiator or precursor;

b) the precipitate can be dried in vacuo to purify the polymer;

c) in the second step, carrying out the polymerization of a second block of monomers or monomer mixtures at the ends of the polymer initiator.

Steps b and c are repeated as many times as necessary depending on the number of blocks, which means that a two-block, AB-type, triblock or multiblock polymer of type AB (AB) n or (ABC) n (A, B and C Different chemical properties).

Difunctional initiators are generally used to make symmetric triblock polymers of type ABA or BAB.

The chain-transfer agent and the solvent may be the same or different in steps a) and b).

Block polymers according to the invention can also be obtained using standard free-radical polymerization techniques by sequentially adding monomers. In this case, only the property control of the block is possible (no mass control).

In a first step, for example, kinetically, after monitoring the consumption over time, when M1 is consumed about 95%, introducing new monomer M2 into the polymerization reactor results in monomer M1 polymerization in the polymerization reactor. Is a problem. Thus, polymers of the block structure of the M1-M2 type are easily obtained.

The copolymers according to the invention are 0.1% to 60% by weight, preferably 0.5% to 50% by weight, in particular 1% to 30% by weight and even 2 to the total weight of the composition according to the invention It may be present in an amount of 20% by weight.

They may be present in the composition, for example in dissolved form in water or an organic solvent, or optionally in the form of an aqueous or organic dispersion. Preferably they are in the form of a dispersion of polymer particles in water, which particles are from 5 to 400 nm, in particular from 10 to 250 nm, if the size as determined by light scattering (using a Coulter counter) is possible.

One of the features of the copolymers according to the invention is that they do not form viscoelastic gels in water at 25 ° C., at concentrations of 5% by weight, in particular 10% by weight and even 20% by weight.

In particular, the copolymers according to the invention have an aqueous solution of such a copolymer at a concentration of 20% by weight of from 1 to 10 000 centipoises (or mPa.s), in particular from 2 to 5000 mPa.s, in particular from 5 to 25 ° C. It has a viscosity of 3000 mPa.s.

Viscosity is measured using a Brookfield viscometer with a needle (spindle) module.

One skilled in the art can, based on his general knowledge, know how to select needle spindles from "velocity / time" pairs and needles in the 00 to 07 number range, to make measurements of less viscous liquid compounds. 35% with No. 02 pairs of needles are preferably used.

The rheological aspects of the copolymers according to the invention can also be explained using their elastic modulus (G ') and viscosity modulus (G ") values.

Thus, aqueous solutions comprising 5% by weight of copolymers preferably have an elastic modulus less than the viscosity coefficient (G '<G "); in particular, the elastic modulus is from 0.1 to 20 kPa and the viscosity coefficient is from 0.1 to 20 kPa. These coefficient values are at 25 ° C., 1 Hz, a stress-controlled flow meter (Haake RS 150) equipped with an anti-evaporation device and a sand-jet titanium body with a cone-plate measuring body of 6 cm in diameter and 2 ° in angle. The shear rate or stress frequency is 1 Hz (s ^-1 ).

Cosmetic or pharmaceutical compositions according to the invention, in addition to the above polymers, include physiologically acceptable media, in particular cosmetically or dermatologically acceptable media, ie facial skin or body skin, hair, eyelashes, eyebrows and nails. And media compatible with the same keratin materials.

The composition thus comprises water or water and a hydrophilic organic solvent (s), for example an alcohol, in particular a linear or branched lower monoalcohol comprising 2 to 5 carbon atoms, for example ethanol, isopropanol or n-propanol, And hydrophilic media comprising polyols such as glycerol, diglycerol, propylene glycol, sorbitol or pentylene glycol, and polyethylene glycol, or optionally a mixture of hydrophilic C2 ether and C2-C4 aldehyde.

Water or a mixture of water and hydrophilic organic solvent may be present in the composition according to the invention in an amount in the range of from 0.1% to 99% by weight, preferably from 10% to 80% by weight relative to the total weight of the composition.

The composition may also comprise a fatty phase, especially consisting of fatty substances which are liquid at room temperature (generally 25 ° C.) and / or fatty substances which are solid at room temperature, such as fatty substances such as waxes, pastes and gums, and mixtures thereof. Such fatty substances may be of animal, vegetable, mineral or synthetic origin. This fatty phase may also include lipophilic organic solvents.

Fatty substances that are liquid at room temperature, often referred to as oils, which may be used in the present invention, include hydrocarbon-based oils of animal origin such as perhydrosqualene; Hydrocarbon-based vegetable oils such as liquid triglycerides of fatty acids having 4 to 10 carbon atoms, for example heptanoic or octanoic triglycerides, or optionally sunflower oil, corn oil, soybean oil, grape seed oil, sesame oil, apricot oil, macadamia oil , Castor oil, avocado oil, capryl / caproic triglycerides, jojoba oil, shea butter oil; Linear or branched hydrocarbons of mineral or synthetic origin such as liquid paraffins and derivatives thereof, petroleum jelly, polydekenes, hydrogenated polyisobutenes such as parleam; Especially synthetic esters and ethers of fatty acids, for example perceline oil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate ; Hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, and fatty alcohol heptanoate, octa Noate and decanoate; Polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; And pentaerythritol esters; Fatty alcohols containing 12 to 26 carbon atoms, for example octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol and oleyl alcohol; Partially hydrocarbon-based fluoro oils and / or partially silicone-based fluoro oils; Silicone oils such as volatile or nonvolatile linear or cyclic polymethylsiloxanes (PDMS) (liquid or glue at room temperature) such as cyclomethicone, dimethicone (optionally containing phenyl groups), for example phenyl trimeth Ticone, phenyltrimethylsiloxydiphenylsiloxane, diphenylmethyldimethyltrisiloxane, diphenyldimethicone, phenyl dimethicone and polymethylphenylsiloxane; Mention may be made of mixtures thereof.

Such oils may be present in amounts ranging from 0.01% to 90%, more preferably from 0.1% to 85% by weight relative to the total weight of the composition.

The composition according to the invention may also comprise one or more physiologically acceptable organic solvents.

Such solvents are generally from 0.1% to 90% by weight, preferably from 0.5% to 85% by weight, more preferably from 10% to 80% by weight and more preferably from 30% by weight to the total weight of the composition. It may be present in an amount in the range of 50% by weight.

In addition to the hydrophilic organic solvents mentioned above, ketones which are liquid, especially at room temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone and acetone; Propylene glycol ethers that are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol mono-n-butyl ether; Short-chain esters (comprising 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and isopentyl acetate; Ethers which are liquid at 25 ° C., such as diethyl ether, dimethyl ether or dichlorodiethyl ether; Alkanes that are liquid at 25 ° C., such as decane, heptane, dodecane, isododecane and cyclohexane; Aromatic cyclic compounds which are liquid at 25 ° C., such as toluene and xylene; Mention may be made of aldehydes such as benzaldehyde and acetaldehyde, and mixtures thereof, which are liquid at 25 ° C.

For the purposes of the present invention, the term “wax” means a lipophilic compound that is solid at room temperature (25 ° C.), which undergoes a reversible solid / liquid state change and may have a melting point of at least 25 ° C. and up to 120 ° C. . The wax can be brought into a liquid state (melt), making it miscible with oils that may be present and forming a micro homogeneous mixture, but when the temperature of the mixture returns to room temperature, recrystallization of the wax in the oil of the mixture Painter is done. The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example a calorimeter sold under the name DSC 30 by Mettler.

The wax may be a hydrocarbon-based wax, a fluoro wax and / or a silicone wax, and may be of vegetable, mineral, animal and / or synthetic origin. In particular, the melting point of the wax is above 30 ° C, more preferably above 45 ° C. As waxes that can be used in the compositions of the present invention, beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline wax, ceresin or ozokerite, synthetic waxes such as polyethylene wax or Fischer-Tropsch wax, and Mention may be made of silicone waxes, for example alkyl or alkoxy dimethicones comprising from 16 to 45 carbon atoms.

The gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides, and grass-like materials are generally hydrocarbon-based compounds such as lanolin and derivatives thereof, or PDMS.

The nature and amount of the solid material depends on the desired mechanical properties and texture. For reference, the composition may comprise 0.1 wt% to 50 wt%, more preferably 1 wt% to 30 wt% of the wax, based on the total weight of the composition.

The composition according to the invention may also comprise, in particulate form, pigments and / or nacres and / or fillers conventionally used in cosmetic compositions.

The composition may also include other pigments selected from water soluble dyes and / or fat soluble dyes well known to those skilled in the art.

The term "pigment" is understood to mean white or colored mineral or organic particles of any shape which are insoluble in the physiological medium and are intended to color the composition.

The term "filler" should be understood to mean colorless or white, mineral or synthetic, platy or critical particles intended to give the composition a density or strength, and / or a softness, matte effect and uniformity to the makeup result. do.

The term "pearl layer" should be understood to mean any form of pearlescent particles, especially made in its shell by a particular mollusk or otherwise synthesized.

The pigment may be present in the composition in a proportion of 0.01% to 25% by weight, preferably 3% to 10% by weight of the final composition. They can be white or colored and can be mineral or organic. Titanium oxide, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide or chromium oxide, ferric blue, chromium hydrate, carbon black, ultramarine (aluminosilicate polysulfide), manganese pyrophosphate and certain metallic powders such as Mention may be made of silver or aluminum powder. Mention may also be made of D & C pigments and lakes commonly used to provide makeup effects to the lips and skin, which are calcium, barium, aluminum, strontium or zirconium salts.

The nacres may be present in the composition in a proportion of 0.01% to 20% by weight, preferably from about 3% to 10% by weight. Among the conceivable nacres, mention may be made of mica coated with natural mother-of-pearl, titanium oxide, iron oxide, natural pigments or bismuth oxychloride, and also colored titanium mica.

Fat-soluble, which may be present in the composition, alone or in a mixture, in a ratio of 0.001% to 15% by weight, preferably 0.01% to 5% by weight, especially 0.1% to 2% by weight, relative to the total weight of the composition, or Among the water-soluble dyes, vermilion disodium salt, alizarin green disodium salt, quinoline yellow, purplish trisodium salt, tarrazine disodium salt, rhodamine monosodium salt, fuchsin disodium salt, xanthophyll, methylene blue, coach Nyl carmine, halo-acid dyes, azo dyes, anthraquinone dyes, copper sulfate, iron sulfate, Sudan Brown, Sudan Red and Anato, and also beetroot juice and carotene.

The composition according to the invention may also comprise one or more fillers, in particular in the content in the range from 0.01% to 50% by weight, preferably in the range from 0.02% to 30% by weight relative to the total weight of the composition. The filler may be mineral or organic in any form, small plate shape, spherical or elliptical. Talc, mica, silica, kaolin, polyamide (Nylon®) powder, poly-β-alanine powder and polyethylene powder, tetrafluoroethylene polymer (Teflon®) powder, laurolysine, starch, boron nitride, hollow polymer Microspheres such as those of polyvinylidene chloride / acrylonitrile, for example Expancel® (Nobel Industrie) or acrylic acid copolymers (Polytrap® from Dow Corning) and silicone resin microbeads (for example Toshibas from Toshiba), elastomers Particulate polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, and 8 to 22 carbon atoms, preferably Metal soaps derived from organic carboxylic acids containing 12 to 18 carbon atoms, for example zinc, magnesium or lithium Oh rate, mention may be made of zinc laurate or magnesium myristate.

The composition may also comprise additional polymers such as film-forming polymers. According to the invention, the term "film-forming polymer" means a polymer capable of forming a continuous film attached to a support, in particular a keratin material, by itself or in the presence of an auxiliary film-forming agent. Among the film-forming polymers that can be used in the compositions of the invention, synthetic polymers, free-radical types or polycondensate types, polymers of natural origin and mixtures thereof, in particular acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and Mention may be made of cellulosic polymers such as nitrocellulose.

The compositions according to the invention also contain ingredients commonly used in cosmetics such as vitamins, thickeners, gelling agents, trace elements, emollients, sequestrants, flavorings, acidifying or basicizing agents, preservatives, sunscreens, surfactants, antioxidants, hair Anti-loss agents, anti-dandruff agents, propellants and ceramides or mixtures thereof. Of course, those skilled in the art will carefully select these or these optional additional compound (s), and / or their amounts so that the imaginary addition does not adversely or substantially adversely affect the advantageous properties of the composition according to the invention. will be.

The compositions according to the invention can be prepared using a carrier, in particular suspensions of water in oil, dispersions; Optionally thickened further gelled oil solution; Water-in-oil, oil-in-water or complex emulsions; Gel or mousse; Oil or emulsion gels; Dispersions of carriers, in particular lipid carriers; Two-phase or multiphase lotions; spray; Glass, compacted or cast powder; It may be in the form of anhydrous paste. The composition may have the appearance of lotions, creams, plasters, soft pastes, ointments, cast or molded solids (especially in the form of sticks or dishes), or compressed solids.

Those skilled in the art, based on their general knowledge, will be able to select the appropriate herbal form, and also the method of preparation thereof, in view of the nature of the components used first, in particular the solubility in their supports, and secondly the intended use of the composition. will be.

The cosmetic composition according to the invention may be in the form of care and / or makeup products, anti-sun products, self-tanning products, moreover hair care products for body or facial skin, lips and hair.

In particular it may find particularly advantageous use in the field of makeup of the skin, mucous membranes, mucous membranes and / or foreskin (nails, eyelashes, eyebrows, hair and hair).

It may also be used in care and / or makeup compositions, especially in color products such as foundations, makeup loose or eyeshadows; Lip products such as lipsticks or lip care products; Concealer products; Blusher, mascara or eyeliner; Eyebrow makeup products, lip pencils or eye pencils; Nail products such as nail polishes or nail care products; Body makeup products; It may be in the form of a hair makeup product (hair mascara or hair lacquer).

Compositions according to the present invention may be used for the skin, protective or care compositions of the face, neck, hands or body, in particular anti-wrinkle compositions, anti-fatigue compositions for making skin radiance, moisturizing or treating compositions; Sunscreen compositions or artificial tanning compositions.

The composition according to the invention may also be a hair care product, in particular for maintaining the hairstyle or for shaping the hair. Hair care compositions are preferably shampoos, hair fixative lotions or gels, blow-drying lotions, and fixative and styling compositions such as lacquers or sprays. The lotion may be packaged in various forms, in particular in an emanator, pump-dispensing bottle or aerosol container, allowing the composition to be applied in the form of divergence or mousse.

The subject matter of the present invention is also a method of making up a keratin material, in particular body or facial skin, nails, hair and / or eyelash make-up or care cosmetics, comprising applying a cosmetic composition to said material as defined above.

The invention also relates to an adhesive composition comprising the copolymer according to the invention. In this case, the copolymer is advantageously present in an amount of at least 5% by weight relative to the total weight of the composition.

The adhesive composition may comprise additives such as plasticizers such as bonding resins, oils, in which case it will constitute a hot-melt pressure-sensitive adhesive composition (known as abbreviation HMPSA).

The copolymers of the present invention contribute to improving the mechanical properties of the adhesive composition, especially when they are exposed to high temperatures (eg, post-it type strips placed in sunlight-winding windows).

In general, the oil used as a plasticizer in the HMPSA composition is an oil of trimellitate type, such as trioctyl trimellitate, or optionally primarily naphthenic oil such as Catenex N956 of Shell. Oils of paraffin type (typically Primol 352 oil of Exxon-Mobil) or liquid polybutene type (typically Mapvis 10) are not recommended because under certain conditions, they are incompatible with the copolymer and are exuded from the mixture.

According to the invention, the bonding resin is generally a colophony-based resin such as Foral AX, a polophony ester resin such as Foral F85, a resin known under the pure monomer name such as Krystallex F85, a polyterpene such as Dercolyte A 115 of DRT, Hydroxylated polyester (typically Reagen 5110 from DRT), styrene terpene (typically Dercolyte TS 105 from DRT), pentaerythritol terpene (typically Dertoline P2L), and phenol-terpene-based resins (typically Dertophene T105 of DRT).

The compositions of the present invention can be used in various fields, such as hygiene, wood, bonding and packaging, for example as adhesives that make up adhesive tapes, labels and strips.

The invention also relates to the use of the copolymer as defined as a component of the adhesive composition as defined above.

Finally, the present invention relates to a thermoplastic composition. In this case, the copolymer is advantageously present in an amount of at least 1% by weight relative to the total weight of the composition.

As an additive, such compositions may also comprise one or more thermoplastic polymers, such as polymethyl methacrylate, polystyrene and polyvinyl chloride.

By using the copolymer of the present invention, it will be possible to increase the hardness of the thermoplastic polymer present in the composition.

Finally, the present invention relates to the use of the copolymer as defined in the thermoplastic composition as a component.

The invention is explained in more detail in the following examples.

Tg  How to measure

The glass transition temperature of a block can be a theoretical Tg value determined from the theoretical Tg value of the constituent monomers of each block according to the following relationship known as Fox's law, which is a reference manual, such as Polymer Handbook, 3rd edition, 1989, John Wiley. You can find it at:

[wi is the mass fraction of monomer i in the block under consideration and Tgi is the glass transition temperature of the homopolymer of monomer i].

Unless otherwise indicated, the Tg values shown for a block are theoretical Tg values.

Molecular mass

Weight-average molar masses (Mw) and number-average molar masses are measured by liquid gel permeation chromatography, or GPC (THF solvent, establishing calibration curve with linear polystyrene standard, refraction detector).

Dispersion index is calculated in the following manner: Ip = Mw / Mn.

GPC is performed on a Styragel HR4 / 7.8 × 300 mm column sold by Waters WAT044225.

Detection is performed with a Waters 410 refractometer.

Eluent is THF at flow rate 1 ml / min.

The injection volume is 50 microliters at 25 ° C.

The formed first block is characterized by GPC to measure the mass of the first block.

The entire block copolymer is characterized by GPC to determine the mass of the total copolymer.

The theoretical weight-average mass of the block is given as the ratio (weight (g) of the monomer constituting the block / weight (g) of the initiator).

The relative molar ratios of the various monomers in the first block are determined by NMR:

% Monomer M1 = (% moles of M1) / (total moles of monomers in block).

The relative proportions of the various monomers between the first block and the second block are measured by NMR.

Typical synthesis methods

The polymers of the examples are synthesized via the ATRP method:

Copper in the form of copper halide (Cu1), for example CuBr (purity 99%) sold by Aldrich, or CuCl (99% purity) sold by Acros,

Use of initiators of the RBr type,

And ligands of the amine type.

Fluka PMDETA or N, N, N ', N ", N" -pentamethyldiethylenetriamine is used as ligand.

The monomer is passed through an aluminum column beforehand to remove any stabilizer.

Synthesis of the diblock is carried out using a monofunctional initiator such as Aldrich sold by ethyl 2-bromoisobutyrate with 98% purity.

Synthesis of triblock was performed with 3-[(2-bromo-2-methylpropinoyl) oxy] propyl 2-bromo-2-methylpropanoate: (CH ₃ ) ₂ BrC-C (= 0) -O Proceeds through polymerization starting with a bifunctional initiator of the type-(CH ₂ ) ₄ -OC (= 0) -C (CH ₃ ) ₂ Br.

The polymerization proceeds in several stages:

First step : formation of a first block by polymerization of monomers (or monomer mixtures) constituting the first block according to the following general reaction scheme:

Monomers of the right amount and nature are introduced into the round bottom flask. Argon was flowed and bubbled with stirring for 5 minutes, followed by introduction of ligand followed by copper and finally initiator under argon flow with continued stirring. Three vacuum / argon degassing cycles are performed.

The mixture is stirred and, if homogeneous, placed in an oil bath at 90 ° C. (bath temperature). The polymerization is carried out at 90 ° C. for a given time.

The polymer is passed through an alumina column to separate the copper based catalyst.

The polymer is then precipitated in water / methanol mixture (20/80) under low temperature cardice.

Thus a first block is obtained, which acts as a precursor (or polymer initiator) for the polymerization of the second block: it has a functional group capable of reinitiating the polymerization of the second monomer (or monomer mixture) constituting the second block. It is a "functional" polymer comprising at the end. This precursor can be represented schematically as Polymer-Br.

Second Step : Formation of the Second Block by Polymerization (or Monomer Mixture) at the Termination of the Polymer Initiator (Polymer-Br) or (Br-Polymer-Br)

Ligand, solvent and copper are then added to the polymer initiator under argon flow, followed by the monomer or monomer mixture. The mixture is cooled with liquid nitrogen. Once the mixture has cured, three vacuum-argon degassing cycles are performed. After returning the mixture to the liquid state, the reactor is placed in an oil bath at a temperature of 90 ° C.

The polymer is passed through an alumina column to separate and purify the copper catalyst.

The final polymer is then precipitated from the water / methanol mixture (20/80) under low temperature cardice.

Example  One

Preparation of Poly (butyl acrylate-co-acrylic acid) -b-poly (methyl methacrylate-co-acrylic acid) diblock polymer

The polymer was prepared by hydrolyzing a poly (butyl acrylate-co-tert-butyl acrylate) -b-poly (methyl methacrylate-co-tert-butyl acrylate) diblock copolymer.

One/ Poly (Butyl Acrylate -nose- tert - Butyl Acrylate ) -b-poly ( methyl Methacrylate -nose- tert - Butyl Acrylate ):

Step 1: Poly (Butyl Acrylate -nose- tert - Butyl Acrylate ) - Br  Synthesis of Polymer Initiator

In accordance with the general procedure described above, the mixture of monomers was polymerized in the following proportions:

Reactant Monomer 1 Monomer 2 Ligand catalyst Initiator Butyl
Acrylate tert-butyl
Acrylate PMDETA: (N, N, N ', N ", N" -pentamethyldiethylenetriamine) CuBr Ethyl 2-bromo-isobutyrate confiscation 1.56 0.251 2.4 × 10 ^-3 2.4 × 10 ^-3 2.4 × 10 ^-3 Mass (g) 200 32.2 0.416 0.344 0.468

Theoretical conversion rate: 33

Reaction time: 3 hours 35 minutes

characteristic :

Theoretical Mw (g / mol): 31

Mn measured by GPC (g / mol): 54 900

Mw measured by GPC (g / mol): 59 500

-Mp (mean mass at the peak measured by GPC) (g / mol): 58 600

-Ip = 1.1

Poly (butyl acrylate-co-tert-butyl acrylate) -Br Theoretical Acrylate / Total Acrylate (by weight) % Mol measured by NMR % By weight derived from NMR measurement [Butyl acrylate] / [butyl acrylate + tert-butyl acrylate] 86.1 81.0 81.0 [tert-butyl acrylate] / [butyl acrylate + tert-butyl acrylate] 13.9 19.0 19.0

2nd step: Polymer initiator Poly (butyl Acrylate -nose- tert - Butyl Acrylate ) - Br  At the end methyl Methacrylate Of tert - Butyl Acrylate  Polymerization of the mixture

The polymer initiator obtained from the first step was placed in a vessel equipped with an egg-shaped magnetic rod and evaporated under reduced pressure for 12 hours to remove the maximum amount of possible residual monomer.

GPC was performed immediately before the synthesis of the second block; The polymer initiator and the final block were measured under the same conditions.

Reactant Ligand Polymer initiator catalyst Monomer 1 Monomer 2 menstruum PMDETA
(N, N, N ', N ", N" -pentamethyldiethylenetriamine) Poly (butyl acrylate-co-tert-butyl acrylate) -Br CuBr Methyl methacrylate tert-butyl
Acrylate Diphenyl ether confiscation 2.77 × 10 ^-4 2.77 × 10 ^-4 2.77 × 10 ^-4 0.296 2.17 × 10 ^-2 0.572 Mass (g) 4.79 × 10 ^-2 16.6 2.74 × 10 ^-2 30 2.78 97.4

Theoretical conversion rate: 50%

Reaction time: 10 hours

Formed Eblock  Copolymer characteristic :

Theoretical MW (g / mol): 118 117

Mn measured by GPC (g / mol): 97 985

Mw measured by GPC (g / mol): 114 579

-Mp (mean mass at the peak measured by GPC) (g / mol): 115 080

-Ip = 1.17

Poly (butyl acrylate-co-tert-butyl acrylate) -b-poly (methyl methacrylate-co-tert-butyl acrylate) weight% mole% Butyl acrylate 40.0 35.2 tert-butyl acrylate 11.1 9.8 Methyl methacrylate 48.9 55.0 % Of total amount of monomer

2/ Poly (Butyl Acrylate -Co-acrylic acid) -b- Poly ( methyl Methacrylate Co-acrylic acid) Of this block  synthesis

tert-butyl acrylate units were hydrolyzed with trifluoroacetic acid. A six-fold excess of acid was used for tert-butyl units.

Amount of polymer (g) 16.14 amount of tert-butyl acrylate (g) 1.792 moles of tert-butyl acrylate 1.398 × 10 ^-2 Number of moles of trifluoroacetic acid 8.389 × 10 ^-2 Amount of trifluoroacetic acid (g) 9.56 Amount of dichloromethane (g) 43.3

Hydrolyzed Eblock  Properties of Copolymers:

Poly (Butyl Acrylate -Co-acrylic acid) -b-poly ( methyl Methacrylate Co-acrylic acid) NMR  Measured mole% NMR  Measured weight% Butyl acrylate 35.2 42.0 Acrylic acid 9.8 6.6 Methyl methacrylate 55.0 51.4

Finally a diblock copolymer with the following distribution was obtained:

-% Mol:

Poly (methyl methacrylate 97.1% -co-acrylic acid 2.9%)-b-poly (butyl acrylate 81.0% -co-acrylic acid 19.0%)

- weight%:

Poly (methyl methacrylate 97.9% -co-acrylic acid 2.1%)-b-poly (butyl acrylate 88.4% -co-acrylic acid 11.6%)

Aqueous Dissolution / Dispersion of 3 / Prepolymer

2-amino-2-methylpropanol (AMP) was added to neutralize the acid units.

After dissolving the polymer in THF, AMP and water were added with vigorous stirring using an Ultra-Turrax blender.

A poor viscous white milk with a bluish stray was obtained.

Particle size by Coulter device: 390nm

Dry extract of the solution: 18.1 wt%

Example  2

Preparation of poly (methyl methacrylate-co-methacrylic acid) -b-poly (butyl acrylate-co-methacrylic acid) -b-poly (methyl methacrylate-co-methacrylic acid) triblock.

The polymer is poly (methyl methacrylate-co-tert-butyl methacrylate) -b-poly (butyl acrylate-co-tert-butyl methacrylate) -b-poly (methyl methacrylate-co-tert -Butyl methacrylate) triblock copolymer was prepared by hydrolysis.

One/ Poly ( methyl Methacrylate -nose- tert - Butyl Methacrylate ) -b-poly (butyl acrylate-co- tert - Butyl Methacrylate ) -b-poly ( methyl Methacrylate -Co-tert-butyl Methacrylate ) Synthesis of

Step 1: Two-handedness Polymer initiator Br -Poly( tert - Butyl Acrylate -Co-tert-butyl Methacrylate ) - Br  synthesis

Bifunctional initiator: polymerizing the monomer mixture using (CH ₃ ) ₂ BrC-C (= O) -O- (CH ₂ ) ₄ -OC (= O) -C (CH ₃ ) ₂ Br to prepare the polymer initiator. Synthesized.

Two-handedness  Preparation of Polymerization Initiator

Difunctional initiators were prepared according to the following schemes:

HO- (CH ₂ ) ₄ -OH + 2 (CH ₃ ) ₂ (Br) CC (= O) Br → (CH ₃ ) ₂ BrC-C (= O) -O- (CH ₂ ) ₄ -OC (= O) -C (CH ₃ ) ₂ Br

18 μg (0.2 μmol) of 1,4-butanediol was mixed with 100 μg of tetrahydrofuran and the mixture was allowed to equilibrate at room temperature for 10 μg. Subsequently, 40.4 g (0.4 mol) of triethylamine was slowly added over 30 min so that the temperature of the solution did not rise suddenly. Next, 92 kg (0.4 mmol) of 2-bromoisobutyryl bromide was added very slowly while cooling to 5 ° C. over 3 kPa. During the addition, gradual yellowing of the reaction solution was observed. After stirring was continued at 25 ° C. overnight, the temperature was gradually raised to room temperature.

THF was evaporated off to concentrate the reaction solution and the residue precipitated from water. The aqueous phase was then extracted three times with ethyl ether, and then the ether phase was dried over magnesium sulfate.

After the ether was evaporated off, this gave 63 g of bis (n-butyl 1,4-bromoisobutyrate), corresponding to 80% yield.

According to the general procedure described above, the mixture of the following monomers was polymerized in the following proportions:

Reactant Monomer 1 Monomer 2 Ligand catalyst Initiator Butyl acrylate tert-butyl methacrylate PMDETA: (N, N, N ', N ", N" -pentamethyldiethylenetriamine) CuBr The bifunctional polymerization initiator confiscation 2.34 0.268 3.69 × 10 ^-3 3.69 × 10 ^-3 1.85 × 10 ^-3 Mass (g) 300 38.1 0.64 0.53 0.716

Polymerization conversion: 40% by weight

Reaction time: 9 hours 15 minutes

characteristic:

Theoretical MW (g / mol): 73 259

Mn measured by GPC (g / mol): 68 400

Mw measured by GPC (g / mol): 77 294

-Mp (mean mass at the peak measured by GPC) (g / mol): 75 292

-Ip = 1.13

Br-Poly (butyl acrylate-co-tert-butyl methacrylate) -Br % Acrylate / total theoretical% acrylate (by weight) % Mol measured by NMR Weight percent derived from NMR measurements Butyl acrylate 88.7 80.2 78.5 tert-butyl methacrylate 11.3 19.8 21.5

2nd step: Two-handedness  Precursor Br Poly (butyl Acrylate -nose- tert - Butyl Methacrylate ) - Br  At the end methyl Methacrylate - tert - Butyl Methacrylate  Polymerization of the mixture

The precursor was injected into a vessel equipped with an egg-shaped magnetic rod and evaporated under reduced pressure for 12 hours to remove the maximum amount of possible residual monomer.

Reactant Ligand Precursor catalyst Monomer 1 Monomer 2 menstruum PMDETA Br-Poly (butyl acrylate-co-tert-butyl methacrylate) -Br CuCl Methyl methacrylate tert-butyl
Methacrylate Diphenyl ether confiscation 2.23 × 10 ^-4 1.11 × 10 ^-4 2.23 × 10 ^-4 8.25 × 10 ^-2 3.87 × 10 ^-2 0.191 Mass (g) 2.23 × 10 ^-4 8.60 2.23 × 10 ^-4 8.26 5.51 32.5

Polymerization conversion: 30% by weight

Reaction time: 70 minutes

Three blocks  Properties of Copolymers:

Theoretical Mw (g / mol): 114 222

Mn measured by GPC (g / mol): 103 ° 727

Mw measured by GPC (g / mol): 133 295

-Mp (mean mass at the peak measured by GPC) (g / mol): 114 983

-Ip = 1.29

Poly (methyl methacrylate-co-tert-butyl methacrylate) -b-poly (butyl acrylate-co-tert-butyl methacrylate) -b-poly (methyl methacrylate-co-tert-butyl meta Methacrylate) % Mol measured by NMR Weight percent derived from NMR measurements Butyl acrylate 47.3 48.7 tert-butyl methacrylate 25.5 21.9 Methyl methacrylate 27.2 29.2

2/ Poly ( methyl Methacrylate -Co-methacrylic acid) -b- Poly (Butyl Acrylate -Co-methacrylic acid) -b-poly ( Methyl methacrylate Preparation of co-methacrylic acid)

To this end, the prepared poly (methyl methacrylate-co-tert-butyl methacrylate) -b-poly (butyl acrylate-co-tert-butyl methacrylate) -b-poly (methyl methacrylate- Co-tert-butyl methacrylate) was hydrolyzed.

tert-butyl acrylate units were hydrolyzed with trifluoroacetic acid. A 5-fold excess of acid was used for tert-butyl units. The polymer was dissolved 30% in dichloromethane. The reaction was carried out at room temperature for 16 ms.

Amount of polymer (g) 14 Amount of tert-butyl methacrylate in the polymer (g) 4.09 moles of tert-butyl methacrylate 2.87 × 10 ^-2 Number of moles of trifluoroacetic acid 0.144 Trifluoroacetic acid (g) 16.4 Solvent: Dichloromethane (g) 32.7

Hydrolyzed Three blocks  Properties of Copolymers:

Poly (methyl methacrylate-co-methacrylic acid) -b-poly (butyl acrylate-co-methacrylic acid) -b-poly (methyl methacrylate-co-methacrylic acid) % Mol measured by NMR Weight percent derived from NMR measurements Butyl acrylate 47.3 55.2 Methacrylic acid 25.5 20 Methyl methacrylate 27.2 24.8

Finally a triblock polymer having the following distribution (% by weight in triblock) was obtained:

Poly (methyl methacrylate 34.9-co-methacrylic acid 15.1) 15% -b-poly (butyl acrylate 86-co-methacrylic acid 14) 70% -b-poly (methyl methacrylate 34.9-co-metha Krylic acid 15.1) 15%

3 / aqueous solution / dispersion of polymer

AMP was added to the water to neutralize the acid units. The polymer thus obtained is water soluble.

Dry extract of the solution: 5.1 wt%

pH = 8.5

Viscosity in water: 47.6 mPa.s at a concentration of 25 ° C. and 20% by weight (measured with a pair of 38.1% and No. 02 needles).

Example  3

The polymer of Example 1 was dissolved in water at a rate of 15 μg (15 wt.% Solution) of the polymer in 100 mL of water.

To obtain a haircare composition that can be packaged in a pump-dispenser container, applied to the hair; The composition imparts styling to the head of the hair.

Example  4

The polymer of Example 2 was dissolved in water at a rate of 15 μg (15 wt.% Solution) of the polymer in 100 mL of water.

To obtain a haircare composition that can be packaged in a pump-dispenser container, applied to the hair; The composition imparts styling to the head of the hair.

Example  5

The polymer of Example 1 was dissolved in ethyl acetate in a proportion of 25 μg (25 wt% solution) of the polymer in 100 mL of ethyl acetate.

After the addition of the appropriate dyes, a nail varnish was applied to the nail.

Claims (48)

A linear ethylenic block copolymer comprising two or three blocks, each block comprising one or more ionic hydrophilic units, the blocks may be different from each other, and the ionic hydrophilic units of each block Present in the block in a ratio of 2 to 100% by weight, the ionic hydrophilic unit is an anionic hydrophilic monomer selected from acrylic acid and methacrylic acid, The copolymer comprising two blocks is selected from: -Poly (acrylic acid-co-butyl acrylate) -b-poly (methyl methacrylate-co-acrylic acid), or -Poly (methacrylate-co-butyl acrylate) -b-poly (methyl methacrylate-co-methacrylic acid) The copolymer comprising three blocks is a block copolymer selected from: -Poly (methyl methacrylate-co-acrylic acid) -b-poly (acrylic acid -co-butyl acrylate) -b-poly (methyl methacrylate -co-acrylic acid), -Poly (methyl methacrylate-co- (meth) acrylic acid) -b-poly (methacrylic acid-co-butyl acrylate) -b-poly (methyl methacrylate-co-methacrylic acid), -Poly (methyl acrylate-co-acrylic acid) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (methyl acrylate-co-acrylic acid), -Poly (acrylic acid-co-butyl acrylate) -b-poly (methyl methacrylate-co-acrylic acid) -b-poly (acrylic acid-co-butyl acrylate); -Poly (acrylic acid) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid); -Poly (methacrylic acid) -b-poly (methacrylic acid-co-butyl acrylate) -b-poly (methacrylic acid); -Poly (acrylic acid-co-cyclohexyl acrylate) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-cyclohexyl acrylate); -Poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-cyclohexyl acrylate) -b-poly (acrylic acid-co-butyl acrylate); -Poly (acrylic acid-co-cyclohexyl methacrylate) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-cyclohexyl methacrylate); -Poly (acrylic acid-co-isobornyl acrylate) -b-poly (acrylic acid-co-butyl acrylate) -b-poly (acrylic acid-co-isobornyl acrylate); -Poly (methyl methacrylate-co-acrylic acid) -b-poly (acrylic acid-co-methoxypoly (ethylene glycol) monomethacrylate with m = 12 corresponding to the number of ethylene glycol units) -b-poly ( Methyl methacrylate-co-acrylic acid); or -Poly (acrylic acid-co-methoxypoly (ethylene glycol) monomethacrylate with m '=' 12 corresponding to the number of ethylene glycol units) -b-poly (methyl methacrylate-co-acrylic acid) -b-poly ( Acrylic acid-co-methoxypoly (ethylene glycol) monomethacrylate), wherein m = 12 corresponding to the number of ethylene glycol units). The copolymer of claim 1, wherein the ionic hydrophilic monomer or monomers are present in each block in a ratio of 3 to 70 weight percent, based on the weight of the block. The copolymer according to claim 1 or 2, wherein at least one of the blocks of the copolymer has a glass transition temperature (Tg) of 20 ° C or less. The copolymer according to claim 1 or 2, wherein at least one of the blocks of the copolymer has a glass transition temperature (Tg) of at least 20 ° C. The copolymer according to claim 1 or 2, wherein the aqueous solution at a concentration of 20% by weight has a viscosity of 1 to 10 000 centipoise (or mPa.s) at 25 ° C. The copolymer according to claim 1 or 2, which is dissolved or dispersed in water at a rate of 5% by weight at 25 ° C. Cosmetic composition comprising, in a physiologically acceptable medium, at least one copolymer according to claim 1. 8. A cosmetic composition according to claim 7, wherein the copolymer or copolymers are present in an amount of 0.1% to 60% by weight relative to the total weight of the composition. 8. A cosmetic composition according to claim 7, wherein the copolymer is present in the composition in dissolved form or, optionally, in the form of an aqueous or organic dispersion. 8. The method of claim 7, further comprising: water, a hydrophilic organic solvent; Fatty phase; One or more physiologically acceptable organic solvents; Particulate form which may comprise one or more selected from pigments, nacres or fillers; Water-soluble or fat-soluble dyes; Film forming polymers; Choose from vitamins, thickeners, gelling agents, trace elements, emollients, sequestrants, flavorings, acidifying or basicizing agents, preservatives, sunscreens, surfactants, antioxidants, hair loss inhibitors, antidandruff agents, propellants and ceramides, or mixtures thereof Cosmetic composition containing one or more constituents. 8. A cosmetic composition according to claim 7, in the form of care, makeup, or care and makeup products, sun protection products, self-tanning products or hair care products for body or facial skin, lips and hair. 8. The composition of claim 7, in the form of a hair care product. A pharmaceutical composition comprising, in a physiologically acceptable medium, at least one copolymer according to claim 1. The pharmaceutical composition of claim 13, wherein the copolymer or copolymers are present in an amount from 0.1% to 60% by weight relative to the total weight of the composition. The pharmaceutical composition of claim 13, wherein the copolymer is present in the composition in dissolved form or, optionally, in the form of an aqueous or organic dispersion. The composition of claim 13, further comprising: water, a hydrophilic organic solvent; Fatty phase; One or more physiologically acceptable organic solvents; Particulate form which may comprise one or more selected from pigments, nacres or fillers; Water-soluble or fat-soluble dyes; Film forming polymers; Choose from vitamins, thickeners, gelling agents, trace elements, emollients, sequestrants, flavorings, acidifying or basicizing agents, preservatives, sunscreens, surfactants, antioxidants, hair loss inhibitors, antidandruff agents, propellants and ceramides, or mixtures thereof A pharmaceutical composition containing one or more constituents. An adhesive composition containing the copolymer according to claim 1. 18. The adhesive composition of claim 17, wherein the copolymer is present in an amount of at least 5% by weight relative to the total weight of the composition. 18. The adhesive composition of claim 17, further comprising an additive selected from bonding resins and plasticizers. 20. The adhesive composition of claim 19 wherein the plasticizer is selected from oils of trimellitate type and naphthenic oils. 20. The method of claim 19, wherein the bonding resin is from a colophony-based resin, a colophony ester resin, a polyterpene resin, a hydroxylated polyester resin, a styrene terpene resin, a pentaerythritol terpene resin or a phenol-terpene resin. Adhesive composition selected. Adhesive tape containing the composition according to claim 17. Adhesive label containing the composition according to claim 17. Adhesive strip containing the composition according to claim 17. delete A thermoplastic composition containing the copolymer according to claim 1. 27. The thermoplastic composition of claim 26, which also contains one or more thermoplastic polymers. 28. The thermoplastic composition of claim 27, wherein the thermoplastic polymer is selected from polymethyl methacrylate, polystyrene, and polyvinyl chloride. delete A cosmetic method for the care makeup of keratin materials, comprising applying the cosmetic composition according to claim 7 to said materials. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete