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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/068—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
  • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes

Definitions

• the present invention relates to a new process of radical polymerization controlled by thermal means giving access to copolymers of silicone and organic natures as well as the products obtained by this process.
• copolymer products obtained consist of a silicone skeleton onto which organic groups are grafted in block or multiblock form.
• Block polymers are usually prepared by ionic polymerization.
• This type of polymerization has the disadvantage of only allowing the polymerization of certain types of apolar monomers, in particular styrene and butadiene, and of requiring a particularly pure reaction medium and temperatures often below ambient so as to minimize the parasitic reactions, hence severe implementation constraints.
• the radical polymerization has the advantage of being easily implemented without excessive conditions of purity being observed and at temperatures equal to or above ambient. However, until recently i! there was no radical polymerization process for obtaining block polymers. Recently, a new radical polymerization process has developed: it is called “controlled” or "living” radical polymerization (Matyjaszewski, K., Ed.
• Block copolymers are obtained when the ends of polymer chains are activated in the form of a radical by reversible homolytic cleavage of a bond (for example C-O, or C-Halogen).
• WO 98/58974 describes a living radical polymerization process allowing access to block copolymers by a process without UV irradiation, by using xanthatic compounds.
• this new process makes it possible to synthesize silicone and organic hybrid copolymers whose nature of the polymerized organic monomers is very varied.
• Another aim is to propose a controlled radical polymerization process for the synthesis of silicone and organic copolymers which do not contain metallic impurities harmful to their use.
• Another object is to obtain organic blocks of controlled lengths. Another object is to obtain organic blocks of narrow molecular distribution.
• Another object is the development of a process which can be implemented in solution, in bulk, in dispersion, in suspension or in emulsion, preferably in solution and in emulsion.
• the present invention relates to a process for the preparation, by radical polymerization under thermal activation, of silicone and organic hybrid copolymers consisting of a silicone skeleton and carrying organic groups and prepared from a silicone precursor, at least minus an ethylenically unsaturated organic monomer and a radical polymerization initiator.
• the invention also relates to the hybrid copolymers capable of being obtained by the above process.
• the invention relates to precursor silicones as well as their processes for obtaining, used for the preparation of hybrid copolymers.
• Other details and advantages of the invention will appear more clearly on reading the description and the examples.
• the invention therefore relates first of all to a process for the preparation by thermal activation of hybrid silicone and organic copolymers comprising units (I): R ⁇ U y SiO [4 . (x + y)] / 2 (I) in which:
• - x is equal to 0, 1, 2 or 3
• y is equal to 0, 1, 2 or 3 with 2 ⁇ (x + y) ⁇ 3 and y is different from 0 for at least one of the units of the hybrid copolymer
• R which are identical or different, represent: - a linear or branched alkyl radical containing 1 to 8 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl , octyl and 3,3,3-trifluoropropyl,
• an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms,
• - Z identical or different, represent a carbon, sulfur, oxygen, phosphorus, nitrogen atom and / or a free valence
• radicals (i), (ii) and (iii) which can be advantageously substituted by: substituted phenyl groups, substituted aromatic groups, or
• R identical or different, representing an alkyl or aryl group, and / or a polymer chain
• R 7 OR 9 in which: - R 6 , R 7 , identical or not, are chosen from a halogen group, -NO 2 , -SO3R 10 , -NCO, -CN, -OR 10 , -SR 10 , -N (R 10 ) 2 , -COOR 10 ,
• R 4 is chosen from alkyl, aryl, aralkyl, alkaryl, alkene or organosilyl groups, optionally perfluorinated and optionally substituted by one or more carboxyl, epoxy, hydroxyl
• radicals (i), (ii) and (iii) which can be advantageously substituted by: substituted phenyl groups, substituted aromatic groups, or
• R identical or different, representing an alkyl or aryl group, and / or a polymer chain
• - W identical or different, represent a divalent radical chosen from -O-,
• - hydrogen peroxides such as: tertiary butyl hydroperoxide, cumene hydroperoxide, t-butyl-peroxyacetate, t-butylperoxybenzoate, t-butylperoxyoctoate, t-butylperoxyneodecanoate, t-butylperoxyisobutarate, lauroyl peroxide, t-amylperoxypivalte, t-butylperoxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate,
• - azo compounds such as: 2-2'-azobis (isobutyronitrile), 2,2'-azobis (2-butanenitrile), 4,4'-azobis (4-pentanoic acid), 1, V- azobis (cyclohexane-carbonitrile), 2- (t-butylazo) -2-cyanopropane, 2,2'-azobis [2-methyl-N- (1, 1) - bis (hydroxymethyl) -2-hydroxyethyl] propionamide , 2,2'-azobis (2-methyl-N- hydroxyethylj-propionamide, 2,2'-azobis (N, N'-dimethylene isobutyramidine) dichloride, 2,2'-azobis (2-amidinopropane) dichloride, 2,2'-azobis (N, N'- dimethylene isobutyramide), 2,2'-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl propionamide), 2,2'-azobis (2
• the amount of initiator to be used is determined so that the amount of radicals generated is at most 20% by mole relative to the amount of silicone precursor compound (IV), preferably at most 5% by weight. mole.
• ethylenically unsaturated monomer the monomers chosen from styrene or its derivatives, butadiene, chloroprene, (meth) acrylic esters, vinyl esters, vinyl nitriles, vinyl esters and amides are used more specifically according to the invention.
• (meth) acrylic esters is meant the esters of acrylic acid and of methacrylic acid with hydrogenated or fluorinated OO 4 alcohols, preferably C r C 8 .
• Vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile.
• the vinyl esters of carboxylic acid more particularly include vinyl acetate, vinyl versatate, vinyl propionate.
• the amides of the unsaturated carboxylic acids more particularly include acrylamide, methacrylamide, N-methylolacrylamide or methacrylamide, N-alkylacrylamides.
• styrene can be replaced in whole or in part by derivatives such as palphamethylstyrene or vinyltoluene.
• the other ethylenically unsaturated monomers which can be used alone or in mixtures or which can be copolymerized with the above monomers are in particular: - vinyl halides,
• - amides of vinylamine in particular vinylformamide or vinylacetamide, - unsaturated ethylenic monomers containing a secondary, tertiary or quaternary amino group, or a heterocyclic group containing nitrogen such as for example vinylpyridines, vinylimidazole, ( aminoaikyl meth) acrylates and aminoaikyl (meth) acrylamides such as dimethylaminoethyl- (meth) acrylate, ditertiobutylaminoethyl acrylate or -methacrylate, dimethylamino methyl-acrylamide or -methacrylamide. It is likewise possible to use zwitterionic monomers such as, for example, sulfopropyl (dimethyl) aminopropyl acrylate.
• the amides of vinylamine for example vinylformamide or vinylacetamide, are preferably used as ethylenically unsaturated monomers. Then the copolymer obtained is hydrolyzed at acidic or basic pH.
• the hybrid silicone and organic copolymer consists of a linear silicone skeleton comprising from 1 to 300 units of formula (I), preferably 1 to 200, and bearing from 1 to 50 radicals U , preferably 1 to 10.
• At least one of the monovalent radicals U ′ is preferably of formula (VI):
• R and R identical or different, represent a hydrogen atom, a cyano, allkoxycarbonyl, alkyl, acyl, aryl, alkene or alkyne group optionally substituted; and W is of definition identical to that given previously, and preferably is equal to an oxygen atom.
• silicone precursors in which U 'corresponds to:
• At least part of the monovalent radicals U 'of (s) silicone precursor (s) (IV) and therefore at least part of the groups U of the hybrid copolymer obtained are such that Z either an oxygen atom and / or a sulfur atom.
• the hybrid silicone and organic copolymer according to the invention can comprise units
• - And F is a group carrying at least one function such as hydroxy, aikoxy, thiol, amine, epoxy and or polyether.
• These groups F can optionally provide complementary and / or additional properties to the hybrid copolymers prepared according to the process of the invention. They can in particular be contained initially within the silicone precursor of formula (IV).
• the process according to the invention makes it possible to prepare hybrid polymers carrying organic block groups (ie multiblock). For this, the process consists in repeating the implementation of the preparation process described above using:
• this process for preparing multiblock copolymers when it is desired to obtain copolymers with homogeneous blocks and not with a composition gradient, and if all the successive polymerizations are carried out in the same reactor, it is essential that all the monomers used during one step has been consumed before the polymerization of the next step begins, therefore before the new monomers are introduced.
• this method of polymerization of block copolymers has the advantage of leading to block copolymers having a low polydispersite index. It also makes it possible to control the molecular mass of block polymers.
• the precursor silicone compound of general formula (IV) used within the process for the preparation of hybrid copolymers according to the invention can be obtained by reaction:
• - W and Sp are definitions identical to those given above, - L is an electrofuge group, for example: Br “ , CI “ , I “ , OTs “ , OMs ⁇ ,
• 2+ represents an alkaline earth metal such as Ca 2+ , Ba 2+ and Sr 2 ++ ,
• - M ' represents Zn, Cd, m is equal to 1 or 2, n is equal to 1, 2, 3 or 4 and preferably m is equal to 1 and n is equal to 2.
• This silicone of formula (VII) can in particular be obtained from (i) of a silicone comprising units of formula (XII): R x U "'ySiOr _ ( X + y)] / 2 where the monovalent radical U'" is of formula (XIII): -Sp-WH and (ii) of a compound of formula:
• the hybrid copolymers prepared according to the process of the invention has the advantage of leading to a low polydispersite index. This process also makes it possible to control the molecular mass of these polymers.
• the invention therefore also relates to these hybrid polymers.
• the preferred hybrid copolymers are those having at least one block chosen from polystyrene, poly (methyl acrylate), poly (ethyl acrylate), tert-butyl polyacrylate, poly (vinyl acetate, butyl polyacrylate, polyacrylamide, 2- polyacrylate). dimethyl-aminoethyl and / or 2-hydroxyethyl polyacrylate. These polymers generally have a polydipersity index of at most 2, and preferably at most 1.5.
• the polymerization can be carried out in bulk, in solution or in emulsion. Preferably, it is used as an emulsion. Preferably, the method is implemented semi-continuously.
• the temperature can vary between room temperature and 150 ° C depending on the nature of the monomers used.
• the instantaneous content of copolymer relative to the instantaneous amount of monomer and copolymer is between 50 and 99% by weight, preferably between 75 and 99%, even more preferably between
• This content is maintained, in known manner, by controlling the temperature, the rate of addition of the reagents and the polymerization initiator.
• the process is generally carried out in the absence of a UV source.
• Example 3 Preparation of a triblock copolymer of ethyl polyacrylate-b-polydimethylsiloxane-b-ethyl polyacrylate.
• precursor A from Example 1, 1.39 g of ethyl acrylate, 2 g of toluene and 2.28 mg of AIBN are placed in a Carius tube. Three cycles of 'freeze-vacuum-return to l 'ambient' are carried out on the contents of the tube. The tube is then sealed under vacuum with a flame, then the tube is placed in a thermostated bath at 80 ° C. for 8 hours The tube is then cooled and then opened.
• Example 4 Preparation of a polyvinyl acetate-b- polydimethylsiloxane-b- polyvinyl acetate triblock copolymer.

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