法国专利FR3025204A1 BLOCK COPOLYMERS FOR USE AS FLUIDIFYERS

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专利摘要:
The invention relates to a block copolymer comprising: - at least one block A not comprising a phosphonate group, and comprising at least one poly (alkylene oxide) group, and - at least one block B obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated monomer B1 comprising at least one phosphonate function, its controlled radical polymerization RAFT preparation method, and its uses.
公开号:FR3025204A1
申请号:FR1458083
申请日:2014-08-28
公开日:2016-03-04
发明作者:Lucia Ferrari；Frederic Leising
申请人:Chryso SAS；
IPC主号:

专利说明:

[0001] The present invention relates to polymers, to a process for their preparation and to their uses, in particular as a dispersant for mineral particles, as a fluidizing agent for inorganic particle suspensions, as an adhesion promoter, as an anti-corrosion agent, as flame retardant agent, as a stabilizing agent when grinding mineral particles, or as an anti-scale agent. The polymers are particularly useful as a fluidizing agent for compositions comprising a hydraulic binder such as cement.
[0002] Dispersants or fluidizers are usually added to the aqueous suspensions of mineral particles to lower their viscosity or to reduce the water content of these suspensions. Suspensions concerned include suspensions of calcium salts or calcium sulphate, or suspensions of inorganic oxides, such as titanium dioxide or iron oxide. It is only after being fluidized that these suspensions can be used for the preparation of various industrial products including paints, products for coating paper and formulations for rubbers and synthetic resins. Fluidifiers, also called plasticizers or superplasticizers, are usually added to hydraulic binders such as cements, plasters, calcium sulphates or lime to reduce the water content of the hydraulic binder paste. As a result, the hydraulic binder paste exhibits, after curing, a denser structure, which results in a higher mechanical strength. In this context, mention may be made of the use of polycarboxylate comb copolymers as a superplasticizer, which has made it possible to prepare fluid concretes, even with less water than is necessary to hydrate the constituents of the cement. These superplasticizers are branched polymers whose main chain comprises carboxylic groups and whose side chains are composed of long sequences of polyether type, in particular polyethylene oxide, such as poly [(meth) acrylic acid - grafted - polyethylene oxide]. Other polymeric superplasticizers for the fluidification of concrete mortars have been developed, such as the poly (ethylene oxide) bis-phosphonate mono- chains described in patent FR 2 696 736, and marketed by the company CHRYSO under the name of CHRYSO®Fluid Optima 100.
[0003] Other polymeric superplasticizers comprising phosphonated side groups are also described in applications FR 2 892 420 and FR 2 974 090. The polymers described therein are not block copolymers. Application FR 2 892 420 describes comb polymers whose phosphonic groups are attached to the main backbone by amino-bisalkylenephosphonic patches and obtained: either by radical copolymerization of an ethylenically unsaturated compound comprising a phosphonate group, a polyoxyalkylated ethylenically unsaturated compound and optionally a carboxylic acid or an ethylenically unsaturated ester in the presence of a catalyst, or by a so-called "post-grafting" process comprising the grafting of phosphonated and / or polyoxyalkylated side groups on a polymer comprising a hydrocarbon chain and carboxylic groups. The synthesis of the ethylenically unsaturated compound comprising an amino-bisalkylenephosphonic group is carried out by a reaction of MOEDRITZER-IRANI which requires the use of formaldehyde. Application FR 2 974 090 describes comb polymers whose side groups comprise gem-bisphosphonated groups, obtained either by radical copolymerization of a monomer comprising a gembisphosphonate group, a monomer comprising a polyoxyalkylated group and a monomer carrying a carboxylic group in the presence of a catalyst, or by a so-called "post-grafting" process comprising the grafting of gem-bisphosphonated side groups on a polymer comprising a hydrocarbon chain and carboxylic and polyoxyalkyl groups.
[0004] The preparation of polymers from ethylenically unsaturated monomers comprising a phosphonate function, especially monomer comprising a vinyl phosphonate function, is often difficult. In particular, the preparation of polymers from vinylphosphonic acid or dimethyl or diethyl vinylphosphonate is difficult because these monomers have low polymerizability due to the existence of undesirable side reactions in the presence of radicals. The synthesis of homopolymers or copolymers comprising monomers bearing phosphonate functions is generally carried out by conventional free radical means, that is to say by an uncontrolled mechanism.
[0005] Among the main "living" or controlled radical polymerization techniques, mention may be made of atom transfer radical polymerization (ATRP), radical polymerization controlled by stable nitroxyl radicals (NMP), transfer polymerization. degenerative iodine (ITP) and reversible addition-fragmentation transfer (RAFT) polymerization. Applications WO 2006/125892 and WO 2007/085623 describe a block copolymer comprising: at least one block A obtained by the polymerization of a mixture of ethylenically unsaturated monomers (AO) not comprising monomers with vinyl phosphonate functional groups, and at least one block B obtained by the polymerization of a mixture of ethylenically unsaturated monomers (B0) comprising at least one monomer B1 bearing at least one vinyl phosphonate function.
[0006] This block copolymer is free of polyoxyalkyl groups. In the application WO 2007/085623, this copolymer is obtained by an iodine transfer polymerization (ITP) process comprising the following steps: (a) a radical polymerization is carried out leading to obtaining a functionalized polymer in its form; end by an iodine atom useful as a transfer agent in a controlled radical polymerization reaction, said step being conducted by contacting: - ethylenically unsaturated monomeric molecules, - a source of free radicals, and - at less than an iodinated transfer agent, (b) following step (a), a radical polymerization step or several successive radical polymerization steps are carried out, said step (s) each consisting in carrying out a polymerization. radical leading to the production of a block copolymer functionalized at its end by an iodine atom useful as a transfer agent in a polymeric reaction radicalization, said one or more steps being carried out by bringing into contact: ethylenically unsaturated monomer molecules, at least one of which is different from those used in the preceding step, a source of free radicals, and the functionalized polymer resulting from the preceding step; It being understood that one of the polymerization steps (a) and (b) defined above leads to the formation of the block B, and that another of the polymerization stages of the steps (a) and (b) leads to in the formation of the block A. In the application WO 2006/125892, this copolymer is obtained by a controlled radical polymerization process of the RAFT type comprising the following steps: (a) a controlled radical polymerization is carried out leading to the obtaining of a functionalized polymer useful as a control agent in a controlled radical polymerization reaction, said step being conducted by contacting: - ethylenically unsaturated monomeric molecules, - a source of free radicals, and - at least one agent control chosen in particular from dithioesters, thioethersthiones, trithiocarbonates, dithiocarbamates including N, N-dialkyldithiocarbamates, dithiocarbazates and xanthates, preferably O-ethyl-S- (imethoxycarbonyl) ethyl) xanthate, (b) following step (a), a controlled radical polymerization step is carried out, or several successive controlled radical polymerization steps, said one or more step (s) each comprising performing a controlled radical polymerization leading to obtaining a functionalized block copolymer useful as a control agent in a controlled radical polymerization reaction, said step (s) being conducted contacting: - ethylenically unsaturated monomeric molecules different from those used in the preceding step, - a source of free radicals, and - the functionalized polymer resulting from the preceding step, it being understood that one of the polymerization steps (a) and (b) defined above leads to the formation of block B, and that another of the polymerization steps of steps (a) and (b) leads to to the formation of block A. In the examples, a diblock polybasic acrylic acid-b-polyvinylphosphonic acid copolymer P (AA) -b-P (AVP) was prepared.
[0007] According to a first object, the invention relates to a block copolymer (also called block copolymer) comprising: at least one block A not comprising a phosphonate group, and comprising at least one poly (alkylene oxide) group, and 3025204 At least one block B obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated monomer B1 comprising at least one phosphonate function.
[0008] Preferably, the block copolymer according to the invention is diblock or triblock. Diblock copolymers are particularly preferred. The block polymer may comprise a block consisting of a comb polymer, which comprises a main chain and pendant groups. Generally, at least one block of the block copolymer is not a comb copolymer.
[0009] Blocks of the block copolymer are covalently bonded. The blocks may be interconnected by a joining unit which does not correspond to a constituent unit of the blocks A or B. The block copolymer according to the invention comprises at least one block A comprising at least one poly (oxide) group. alkylene). The block copolymer according to the invention may comprise several blocks A of identical or different natures. Preferably, in each block A, each poly (alkylene oxide) group independently has the following formula (I): R3- (O-R4) n- (I) wherein R3 is a hydrogen atom or a monovalent hydrocarbon group having from 1 to 12 carbon atoms and optionally one or more heteroatoms, n represents an integer from 2 to 500, preferably from 3 to 200, each R 4 independently represents a linear or branched alkylene comprising from 2 to 6 carbon atoms. For the purpose of the present application: the preferred hetero atoms are oxygen or nitrogen, phenyl is the preferred aryl, unless otherwise stated, alkyl and alkenyl groups generally have 1 to 12 carbon atoms, typically 1 at 6 carbon atoms, the aryl groups generally comprise from 6 to 10 carbon atoms, the alkylaryl or arylalkyl groups generally comprises from 7 to 12 carbon atoms. The alkyl and alkenyl groups are linear or branched. By halogen atom is meant chlorine, fluorine, bromine, or iodine. Preferably, the halogen is a chlorine.
[0010] In the context of the invention, the expression (meth) acrylic, (meth) acrylate, (meth) acrylamide, respectively means acrylics and methacrylics, acrylates and methacrylates, acrylamides and methacrylamides.
[0011] Preferably, in the formula (I) above, R3 represents a hydrogen atom, an alkyl, an aryl, an alkylaryl or an arylalkyl having from 1 to 12 carbon atoms, wherein the alkyls are linear or branched. Typically, R3 is H or Me. Preferably, each R4 is independently -CH2-CH2-, -CHCH3-CH2-, -CH2-CHCH3- or -CH2-CH2-CH2-. The poly (alkylene oxide) groups are then poly (ethylene oxide), poly (propylene oxide) or their copolymers. Poly (ethylene oxide) and copolymers (ethylene oxide-propylene oxide) are particularly preferred poly (alkylene oxide) groups. Typically, the poly (ethylene oxide) is poly (ethylene oxide) (POE) 350, 750, 1000, 2000, 3000 or 5000. Block A of the block copolymer according to the invention comprises poly groups (Alkylene oxide), especially of formula (I) above. According to a first alternative, the block A typically comprises a main chain, generally a hydrocarbon chain, and side groups (also called pendent groups) at least a part of which comprises (or consists of) at least one poly (oxide) group. alkylene). These poly (alkylene oxide) groups can be linked to the main chain directly or via spacer groups, typically groups comprising ether, ester or amide functions. In this alternative, block A is in the form of a comb polymer. Typically, block A is then obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated monomer A1 and comprising at least one poly (alkylene oxide) group. The monomer A1 may, for example, have the following formula (II): R7 (R-R5) (R4-O) n-R3 (11)) in which: n, R3 and R4 are such that defined above, R5 represents -CH2-, -O- or -NR8- where R8 represents H or a linear or branched alkyl comprising 1 to 6 carbon atoms, preferably H or Me, - R6 is absent or represents - (0 = 0) - or - (CH2) q-, wherein q is 1, 2 or 3, - R7 is H or Me, and 5 - R17 and R15 are independently H or Me, typically R17 and R15 represent Me or R 17 and R 15 represent H, preferably R 17 and R 15 represent H. Among the monomers Al of formula (11), the monomers Al of formula (IIIa), (IIIb), (111c) and (111d) are particularly preferred R 7 O (R 4 -O) n -R 3 (111a), R 17 R 7 R 18 O- (R 4 -) n R 3 R 7 O (1 p. Illc), R7 0- (R4-O) n-R3 (111d) wherein n, R7, R3, R4, R17 and R15 are as defined above.
[0012] For example, block A may be obtained by polymerizing a mixture of ethylenically unsaturated monomers comprising (or consisting of) Al monomers of formula (IIIa), (IIIb), (111c), (111d) or a mixture of these. Preferably, each block A of the block copolymer is obtained by polymerizing a mixture of ethylenically unsaturated monomers comprising at least 60% by weight, typically at least 80% by weight, for example at least 95% by weight. weight of ethylenically unsaturated monomers A1 and comprising at least one poly (alkylene oxide) group. In one embodiment, each block A is obtained by the polymerization of a mixture of ethylenically unsaturated monomers A1 and comprising at least one poly (alkylene oxide) group, for example by polymerization of monomers of formulas (IIIa). , (111b), (111c) or (111d) as defined above or a mixture thereof. In another embodiment, at least one A block is obtained by polymerizing a mixture of ethylenically unsaturated monomers comprising: at least one ethylenically unsaturated Al monomer and comprising at least one polyalkylene oxide group , especially as defined above, and at least one other ethylenically unsaturated monomer (free of poly (alkylene oxide) group.) This (s) other ethylenically unsaturated monomer (s) can (independently) ) be: a functional monomer A2 capable of binding to the calcium ion or anionic ions present at the surface of a mineral particle, typically a monomer free of ionic group, or a monomer A3 comprising: at least one function capable of binding to the calcium ion (typically a monomer comprising an anionic group, for example a carboxylate function), and / or at least one function capable of binding to the anionic ions present on the surface of the a mineral particle (typically a monomer comprising a cationic group, for example a quaternary ammonium function). The monomer A3 is typically carrying an ionic group. Preferably, each block A of the block copolymer is obtained by polymerization of a monomer mixture comprising less than 10% by weight of monomers A3. Preferably, each block A of the block copolymer is obtained by polymerization of a monomer mixture comprising less than 10% by weight of monomers comprising an ionic group. In the sense of the application, a group is considered ionic if it is ionic in an aqueous solution of pH between 8 and 13. For example, a carboxylic acid function forms a carboxylate function at these pH and is considered ionic. Among the ionic groups, there may be mentioned the carboxylic acid, carboxylate, quaternary ammonium, sulphonic acid, sulphonate or boronic acid groups.
[0013] Among the monomers A2 which have no function capable of binding to the calcium ion or to the anionic ions present on the surface of a mineral particle, mention may be made of: mono-alkyl esters of ethylenic unsaturated monocarboxylic acids and dialkyl esters ethylenically unsaturated dicarboxylic acids (such as acrylic, methacrylic acid, itaconic acid, maleic acid, or fumaric acid monoalkyl esters), preferably obtained by esterification with C3-C10 alcohols, such as hydroxypropyl (meth) acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, t-acrylate, butyl, n-butyl methacrylate, isobutyl methacrylate, or amides such as acrylamide or methacrylamide, or ethylenic monomers comprising a ureido group such as ethylene urea ethyl methacrylamide, or ethylene urea ethyl methacrylate, or cyclic amides vinyl amines, such as N-vinylpyrrolidone and vinylcaprolactam, or vinyl nitriles containing from 3 to 12 carbon atoms, and especially acrylonitrile or methacrylonitrile, or vinyl esters of carboxylic acids, such as vinyl acetate (VAc), vinyl versatate, or vinyl propionate, or vinyl or vinylidene halides, for example vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride, or styrenic-derived monomers such as styrene, alphamethylstyrene, paramethylstyrene or paratertiobutylstyrene, or aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides in which the amine function is primary, secondary or tertiary, such as dimethyl aminoethyl (meth) acrylate, dimethylamino propyl (meth) acrylate, ditertiobutylaminoethyl (meth) acrylate, dimethylamino methyl (meth) acrylamide, dimethylamino ropyl (meth) acrylamide, ethylene imine, vinylamine, 2-vinylpyridine, 4vinylpyridine. Preferably, the monomers A2 are chosen from among: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylamide (Am) or methacrylamide, N-vinylpyrrolidone, styrene, acetate vinyl (VAc), vinyl chloride, vinylidene choride, vinylidene fluoride or mixtures thereof. Among the monomers A3 comprising at least one function capable of binding to the calcium ion, and / or at least one function capable of binding to the anionic ions present on the surface of a mineral particle, mention may be made of: unsaturated ethylenic mono- and di-carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or fumaric acid, the ethylenic monomers containing a sulfonic acid group or a salt thereof alkali or ammonium, such as vinylsulfonic acid, vinylbenzene sulfonic acid, alpha-acrylamido-methylpropanesulfonic acid, or 2-sulfoethylene-methacrylate, or monomers carrying a boronic acid function such as p-vinylphenyl boronic acid, or the cationic monomers chosen from aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides in which the amine function is quaternary, ammonium salts of dialkyl, lyldialkyl (as well as in salt form, the salts being preferably chosen such that the counter-ion is a halide such as for example a chloride, or a sulphate, a hydrosulphate, an alkyl sulphate (for example comprising 1 to 6 carbon atoms). carbon), a phosphate, a citrate, a formate, an acetate), such as trimethylammonium chloride ethyl (meth) acrylate, trimethylammonium methyl sulfate ethyl acrylate, benzyl dimethylammonium chloride ethyl (meth) acrylate, chloride 4-benzoylbenzyl dimethyl ammonium ethyl acrylate, trimethyl ammonium chloride ethyl (meth) acrylamido, trimethylammonium chloride, vinylbenzyl chloride; diallyldimethylammonium chloride, or their salts, or the esters of acrylic acid or methacrylic acid with C1-C2 alcohols, such as, for example, methyl acrylate, acrylate and the like; ethyl, methyl methacrylate, ethyl methacrylate. These esters hydrolyze very rapidly in carboxylate function in a basic aqueous medium.
[0014] In this first alternative, block A of the block copolymer according to the invention generally has an average molar mass of between 350 and 50000 (Mw), preferably between 10000 and 20000 (Mw) as determined by SEC ("size exclusion"). chromatography ", molecular-blanket liquid chromatography) in standard poly (ethylene oxide) equivalents. Each block A according to this first alternative can independently be a homopolymer, a random copolymer, an alternating copolymer or a composition gradient copolymer.
[0015] According to a second alternative, block A of the block copolymer according to the invention consists of a poly (alkylene oxide), in particular a poly (alkylene oxide) of formula (I) as defined above. . In this second alternative, block A of the block copolymer according to the invention generally has an average molar mass of between 100 and 50000 (Mw), preferably between 100 and 20000 (Mw). When the block copolymer according to the invention comprises several blocks A, each block A may independently be according to the first or the second alternative 10 described above. Block A of the copolymer does not comprise a phosphonate group, while block B comprises thereof. Block A and block B of the copolymer according to the invention are therefore of different natures.
[0016] The block copolymer according to the invention comprises at least one block B obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated monomer B1 comprising at least one phosphonate function.
[0017] Block B of the block copolymer may be free of poly (alkylene oxide) groups. Amongst the ethylenically unsaturated monomers B1 comprising at least one phosphonate functional group, there may be mentioned compounds of the following formula (IV): ## STR2 ## in which: Y represents : linear or branched alkyl having 1 to 6 carbon atoms, -W- (CH 2), -P (= O) (1: 11) (OR 2), or (CH 2) x-R 25, wherein x is an integer from 0 to 4 and R25 is hydrogen, phenyl or -ON or -002R9, z is an integer from 0 to 4, single or a -000- or -CONH- group, it being understood that when z represents 0, W represents a single bond, R1, R2 and R9 independently represent H, a phenyl or a linear or branched alkyl having 1 to 6 carbon atoms. carbon and optionally substituted with one or more halogens, Preferably in the formula (IV), W is a single bond and z is 0. The B1 isomer then is a monomer carrying at least one vinylphosphonate function. Monomers B1 bearing at least one vinylphosphonate function of the following formula (IV '): R26 pR1P 0 // OR 2 (IV') in which: R26 represents a linear or branched alkyl having from 1 to 6 atoms carbon, P (= O) (01:11) (OR2), a hydrogen atom, a phenyl or a group -CN or 15 -OO2R9, and R1, R2 and R9 are as defined above, are particularly preferred. Among the monomers B 1 carrying at least one vinyl phosphonate function that are useful in the present invention, mention may be made in particular of vinyl phosphonic acid, the dimethyl ester of vinyl phosphonic acid and the bis (2-chloroethyl) ester of vinyl acid. phosphonic acid, vinylidene diphosphonic acid, tetraisopropyl ester of vinylidene diphosphonic acid, or alpha-styrene phosphonic acid, or mixtures thereof. The preferred monomer B1 according to the invention is vinylphosphonic acid.
[0018] The ethylenically unsaturated monomers B 1 comprising a mono- or di-phosphonic acid function can be used in free acid form, or in the form of their salts. They may be neutralized, partially or totally, optionally with an aminoalcohol or with an amine, for example dicyclohexylamine.
[0019] Block B may for example be obtained by the polymerization of monomers of formula (IV). Block B may be obtained by polymerizing a mixture of ethylenically unsaturated monomers comprising: at least one ethylenically unsaturated monomer B1 comprising at least one phosphonate functional group, in particular as defined above, and at least one other ethylenically unsaturated monomer (preferably free of poly (alkylene oxide) group).
[0020] Preferably, each block B of the block copolymer is obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least 50% by weight, typically at least 75% by weight, for example at least 90% by weight of ethylenically unsaturated monomer B1 comprising at least one phosphonate function.
[0021] This other ethylenically unsaturated monomer (s) may be a hydrophilic or ionic B2 monomer or a nonionic B3 monomer. Preferably, each block B of the block copolymer is obtained by polymerizing a monomer mixture comprising less than 10% by weight of nonionic B3 monomer. Each block B may be obtained by polymerization of a monomer mixture free of nonionic monomer B3. Among the hydrophilic or ionic monomers B2, mention may be made of: ethylenic unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or fumaric acid and their derivatives such as mono-alkyl esters preferably with C 1 -C 4 alcohols, and amides such as acrylamide, methacrylamide, and anhydrides such as maleic anhydride, or vinyl nitriles containing 3 carbon atoms, in particular acrylonitrile; Ethylenic monomers comprising a ureido group such as ethylene urea ethyl methacrylamide, or ethylene urea ethyl methacrylate, or ethylenic monomers having a sulfonic acid group or an alkali or ammonium salt thereof, such as, for example, vinylsulfonic acid, vinylbenzene sulphonic acid, alpha-acrylamido-methylpropanesulphonic acid, or 2-sulphoethylene-methacrylate, or monomers carrying a boronic acid function such as p-vinylphenyl boronic acid, or cationic monomers selected from aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom; diallyldialkyl ammonium salts; these monomers being taken alone or in mixtures, as well as in the form of salts, the salts being preferably chosen so that the counter-ion is a halide, for example a chloride, or a sulphate, a hydrosulphate or an alkyl sulphate; (For example comprising 1 to 6 carbon atoms), a phosphate, a citrate, a formate, an acetate, such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ditertiobutylaminoethyl (meth) acrylate dimethylamino methyl (meth) acrylamide, dimethylamino propyl (meth) acrylamide; ethylene imine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; trimethylammonium chloride ethyl (meth) acrylate, trimethylammonium methyl sulfate ethyl acrylate, benzyl dimethylammonium chloride ethyl (meth) acrylate, 4-benzoylbenzyl dimethyl ammonium chloride ethyl acrylate, trimethyl ammonium chloride ethyl (meth) acrylamido, trimethylammonium chloride of vinylbenzyl; diallyldimethyl ammonium chloride alone or in mixtures, or their corresponding salts, or the cyclic amides of vinylamine, such as N-vinylpyrrolidone and vinylcaprolactam, or of vinyl monomers carrying ester groups whose hydrolysis leads to alcohol functions, such as vinyl acetate for example, or more generally, monomers which can be rendered hydrophilic by chemical modification of a hydrophobic block, for example by hydrolysis of an alkyl acrylate to acrylic acid, or ethylenically unsaturated monomer comprising a phosphonic or phosphonate function, for example an aminomethylene bisphosphonic or gembisphosphonic function. For example, the following monomers of formulas (X), (XI), (XII) and (XIII) may be mentioned: ## STR2 ## 2 PO3H2 (xi), R20 O 30252040 (XII), R22 PO3H2OH PO3H2 (xm), wherein: R20, R21 and R22 are H or Me, R23 is O or NH, m and p are a whole number from 1 to 100. or their salts. As an example of a monomer of formula (XII), mention may be made of the monomers resulting from the reaction between (meth) acrylic acid and pamidronic acid or alendronic acid of the following formulas (Xlla) and (Xllb): R22 ## STR5 ## wherein R 22 is as defined above.
[0022] Preferably, the hydrophilic or ionic monomers B2 are chosen from acrylic acid (AA), methacrylic acid, acrylamide (Am), N-vinylpyrrolidone, vinyl acetate, an ethylenically unsaturated monomer comprising an aminomethylenebisphosphonic or gembisphosphonic function, especially those defined above, an ethylenically unsaturated monomer comprising a sulphonic or sulphonate functional group, such as 2-acrylamido-2-methyl-propanesulphonic acid (AMPS), the sulphonate of styrene (SS) or vinyl sulfonic acid (AVS), or mixtures thereof.
[0023] Even more preferably, the hydrophilic or ionic monomers B2 are chosen from acrylic acid (AA), methacrylic acid, 2-acrylamido-2-methyl-propanesulphonic acid (AMPS) and styrene sulphonate ( SS) or vinyl sulfonic acid (AVS) and an ethylenically unsaturated monomer comprising an aminomethylene bisphosphonic or gem-bisphosphonic function, especially those defined above. Nonionic B3 monomers include: styrenic derived monomers such as styrene, alphamethylstyrene, paramethylstyrene or paratertiobutylstyrene, or esters of acrylic acid or methacrylic acid with C3 alcohols - C12, preferably C1-C8, optionally fluorinated, such as, for example, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, vinyl nitriles containing from 4 to 12 carbon atoms, and especially methacrylonitrile, vinyl esters of carboxylic acids, such as vinyl (VAc), vinyl versatate, or vinyl propionate, and vinyl or vinylidene halides, for example, vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride. Preferably, the nonionic B3 monomers of the B block are esters of acrylic acid with linear or branched C 1 -C 8 and especially C 1 -C 4 alcohols, such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate (ABu) or 2-ethylhexyl acrylate (A2EH), fluorinated acrylates, or many styrenic derivatives such as styrene, or acetate of vinyl (VAc), or vinyl chloride, or vinylidene choride, or vinylidene fluoride. Preferably, the other monomer (s) with ethylenic unsaturation is (are) monomer (s) hydrophilic (s) or ionic (s) and comprises (s) at least one group COOH and / or a phosphonic or phosphonate function and / or a sulfonic function. These groups have indeed a good affinity for hydraulic binders, and their presence improves the effectiveness of the block copolymer according to the invention as a fluidizer for hydraulic binders. For example, the other monomers may be acrylic, methacrylic acid, an ethylenically unsaturated monomer comprising a sulfonic or sulfonate functional (such as 2-acrylamido-2-methyl-propanesulfonic acid (AMPS), styrene sulfonate (SS) or vinylsulfonic acid (AVS)), or an ethylenically unsaturated monomer 3025204 comprising an aminomethylenebisphosphonic or gem-bisphosphonic function (in particular the monomers of formulas (X), (XI), (XII) and ( XIII) defined above). According to a preferred embodiment of the invention, the block B is obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising: at least one ethylenically unsaturated monomer B1 comprising at least one phosphonate functional group, especially as defined herein above, at least one monomer B2 chosen from acrylic acid, methacrylic acid, an ethylenically unsaturated monomer comprising an aminomethylene bisphosphonic or gem-bisphosphonic function (in particular the monomers of formulas (X), (XI), ( XII) and (XIII) defined above) or an ethylenically unsaturated monomer comprising a sulfonic or sulfonate function (such as 2-acrylamido-2-methylpropanesulfonic acid (AMPS), styrene sulfonate (SS) or vinyl sulfonic acid (AVS)).
[0024] Each block B may independently be a homopolymer, a random copolymer, an alternating copolymer or a composition gradient copolymer. The polymer of the block B according to the invention generally has a degree of polymerization of 2 to 50, typically 3 to 15, preferably 3 to 10, for example 4 or 5 or 12. Polymerization levels of 3 to 10 for example 4 or 5 are particularly preferred because the block copolymers obtained are particularly effective dispersing and fluidizing agents. Block B of the block copolymer according to the invention generally has an average molar mass of between 350 and 50000 (Mw), preferably between 500 and 20000 (Mw). Block B of the block copolymer generally has a degree of polymerization (DP) of 1 to 15, preferably 2 to 6. In general, the block copolymers according to the invention have a weight average molar mass of from 450 to 100000, preferably from 2000 to 40000. The mass ratio between blocks A and B is such that B / (A + B) is preferably from 0.1 to 5, and still more preferably from 0.1 to 1. According to the invention the mass ratio of the blocks A and B typically varies between 1/99 and 99/1.
[0025] In one embodiment, the block copolymer has one of the following formulas (SM02), (HD2) or (HD3): (SM02), (HD2), 10 (HD3). The block copolymers according to the invention may also be the block copolymers obtained after hydrolysis of the terminal function of the block polymers described above (SMO 2, HD 2, HD 3), especially the block copolymers obtained after oxidation with H 2 O 2, the terminal function being then for example oxidized to sulfone or sulfonic group. According to a second subject, the invention relates to a process for the preparation of the block copolymer described above comprising the steps of: b) providing a compound of the following formula (V): block A R1 (V) in which: Block A is as defined above, L is absent or is a linking group covalently linking block A and the group -S- (CS) R10, R10 represents an alkyl, an arylalkyl aryl, alkylaryl, OR11, NR12R13 or SR14, R11, R12, R13 and R14 are independently alkyl or alkenyl, arylalkyl, aryl, alkylaryl, with the proviso that R12 and R13 may be linked between to form a ring with the nitrogen atom which carries them, c) controlled radical polymerization, or several successive controlled radical polymerizations, comprising contacting: the compound of formula (V) with a mixture of monomers with ethylenic unsaturation comprising at least one monomer B1 ethylenically unsaturated comprising at least one phosphonate function, and a source of free radicals (also called initiator). Preferred R10 groups are alkyl, arylalkyl, aryl, alkylaryl or SR14. R12 and R13 can be linked together to form a ring with the nitrogen atom that carries them. For example, the group NR12R13 may represent a pyrrolyl radical. Step b) of the process according to the invention consists in providing a compound of formula (V). The process may comprise, prior to step b), a step a) of preparing the compound of formula (V).
[0026] When block A is obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated monomer A1 and comprising at least one poly (alkylene oxide) group (for example an Al monomer of formula ( II) or (III)), the compound of formula (V) may be prepared: either by a process comprising a controlled radical polymerization conducted by contacting: a mixture of ethylenically unsaturated monomers comprising at least one unsaturated Al monomer ethylene group and comprising at least one poly (alkylene oxide) group a source of free radicals, a control agent of the following formula (VI): ## STR5 ## wherein R 10 is as defined above and R 15 represents a arylalkyl, aryl, alkylaryl or alkyl optionally substituted with CN or COOR16 where R16 is alkyl, or by a process comprising the steps of: a1) providing a a polymer whose main chain comprises at its end a terminal functional group and obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated monomer A1 and comprising at least one poly (alkylene oxide) group, A2) grafting at the end of the main chain of said polymer a group of formula - S (C = S) R10 where R10 is as defined above. The terminal group of the polymer that is functional and used in step a1) is functional, which makes it possible to graft a group of formula -S (C = S) Rio, either directly or via a spacer group ("Linker" in English).
[0027] When block A of the block copolymer according to the invention consists of a poly (alkylene oxide), in particular poly (alkylene oxide) of formula (I), step a) of preparing the compound of formula (V) comprises the steps of: a3) providing a poly (alkylene oxide), in particular a poly (alkylene oxide) of formula (I), a4) grafting at one end of said poly (oxide of alkylene) a group of formula - S (C = S) R10 where R10 is as defined above. Step c) of the process makes it possible to prepare block B of the block copolymer. The compound of formula (V) serves as a transfer agent in RAFT-controlled radical polymerization of step c). When the block copolymer is diblocked, step c) comprises a single controlled radical polymerization. When the block copolymer comprises more than two blocks, step c) several successive controlled radical polymerizations.
[0028] Typically, at the end of step c), a block copolymer is obtained whose end is functionalized with a group -S- (C = S) -R10 where R10 is as defined above. This block copolymer may be used as it is, or the process may comprise, after step c), a step d) of oxidation (for example with oxygenated water). ) to obtain a block copolymer whose end is functionalized with a SO 3 group. The invention also relates to the block copolymer obtainable by the process according to the invention. According to a third subject, the invention relates to the use of the block copolymer as defined above (or obtainable by the process defined above), as dispersing agent for mineral particles, as a fluidifying agent for the particles. suspensions of inorganic particles, as an adhesion promoter (especially on metals), as anti-corrosion agent, as flame retardant, as a stabilizing agent during the grinding of mineral particles, or as an anti-scale agent. These copolymers are used from 0.01 to 10%, preferably from 0.1% to 5% by weight relative to the weight of mineral particles.
[0029] The mineral particles may in particular be mineral fillers or inorganic pigments (for example mineral oxides such as titanium dioxide or an iron oxide), calcium salts, in particular calcium sulphate. These particles are usually suspended in an aqueous medium. Suspensions of such mineral particles are used, for example, as inks, paints, paper coating products, or formulations for rubbers or for synthetic resins or compositions comprising a hydraulic binder. The block copolymers according to the invention are particularly useful as a fluidizing agent (also known as a plasticizer or superplasticizer) for compositions comprising a hydraulic binder such as cement. Compositions comprising a hydraulic binder are used to prepare hydraulic compositions, such as mortars, concretes and screeds. Generally, the block copolymer is used in proportions of 0.2 to 2% by solids content of the composition comprising a hydraulic binder. The term "hydraulic binder" is intended to mean any compound having the property of hydrating in the presence of water and whose hydration makes it possible to obtain a solid having mechanical characteristics, in particular a cement such as a Portland cement, cement aluminous, pozzolanic cement or an anhydrous or semi-hydrated calcium sulfate. The hydraulic binder can be a cement according to the standard EN197-1 (2001) and 3025204 22 in particular a Portland cement, mineral additions, especially dairy, or a cement comprising mineral additions. "Cement" is understood to mean a cement according to the EN 197-1 (2001) standard and in particular a CEM I, CEM II, CEM III, CEM IV or CEM V type cement according to the standard 5 Cement NF EN 197-1 (2012). ). The cement may include mineral additions. The term "mineral additions" refers to slags (as defined in NF Cement Standard EN 197-1 (2012) section 5.2.2), steelmaking slags, pozzolanic materials (as defined in NF Cement Standard). EN 197-1 (2012) paragraph 5.2.3), fly ash (as defined in standard Cement NF EN 197-1 (2012) 10 section 5.2.4), calcined shales (as defined in the standard Cement NF EN 197-1 (2012) section 5.2.5), limescale (as defined in standard Cement NF EN 197-1 (2012) section 5.2.6) or even fumed silica (as defined in the standard Cement NF EN 197-1 (2012) section 5.2.7) or their mixtures. Other additions, not currently recognized by the standard Cement NF EN 197-1 (2012), can also be used. These include metakaolins, such as type A metakaolins conforming to standard NF P 18-513 (August 2012), and siliceous additions, such as the siliceous additions of mineralogy Qz conforming to standard NF P 18- 509 (September 2012).
[0030] Without wishing to be bound by any particular theory, the fluidifying properties of the block copolymers according to the invention could be explained by the fact that the block A acts as a stabilizing block and that the block B acts as an anchoring block in adsorbing on the grains of cement. Block A has little or no affinity for mineral particles. The poly (alkylene oxide) groups of block (es) A are hydrophilic and would avoid flocculation of the cement grains by steric stabilization. The phosphonate functions and the possible carboxylate functions of the block B interact with the calcium ions present on the surface of the mineral particles, in particular cement, which would cause the anchoring of the B block (es) on the particles of particles. mineral. According to a fourth subject, the invention relates to an adjuvant comprising a block copolymer as defined above (or obtainable by the process defined above) and a solvent, preferably an aqueous solvent, alcoholic or alcoholic.
[0031] The concentration of the adjuvant in polymer depends mainly on the intended application. Generally, the adjuvant comprises from 1 to 50, preferably 10 to 30% by weight of polymer relative to the total weight. Alternatively, the adjuvant may also be presented in dry form, especially in powder form. The adjuvant formulation may further include other conventional additives, such as defoamers, accelerators, retarders, water repellents, deaerants, viscosity modifiers, other dispersants, air entrainers or anti-foam stabilizers.
[0032] According to a fifth embodiment, the invention also relates to a mineral particle composition comprising at least one copolymer according to the invention. The mineral particles may in particular be mineral fillers or inorganic pigments (for example mineral oxides such as titanium dioxide or an iron oxide), calcium salts, in particular calcium sulphate. The mineral particle compositions can in particular be hydraulic binder compositions. The figures and examples below illustrate the invention. FIG. 1 represents the evolution of the amount of polymer adsorbed on the cement particles (in mg / g) as a function of the free polymer concentration in mg / L for a CHRYSO®Fluid Optima100 polymer (comparative - diamonds), HD2 (triangles), HD3 (squares) and SM02 (rounds). The arrow shows the increase in the number of P032- functions. EXAMPLE 1 Synthesis of a POE-b-PVPA Copolymer (polyvinylphosphonic acid) In this example, the copolymer is diblocked with: a block A of formula A block B obtained by homopolymerization of vinylphosphonic acid, the blocks A and B being linked by a joining unit of formula - (C = O) -CHMe-. 1.1. Preparation of the transfer agent of formula corresponding to formula (V) (steps a3) and a4) of the process according to the invention). (Compound The w-hydroxy end of the poly (ethylene oxide) was modified with a xanthate group (2-bromopropionate bromide) The synthesis was made from a commercial molar mass methoxypolyethylene glycol homopolymer 2012 gmol-1 (DP = 45) in dichloromethane at room temperature (20 ° C.) for 12 h in the presence of triethylamine, which was first reacted with the following BryBr dibromized compound in order to to obtain a polymer terminated with halogen functionality in place of the hydroxyl function, as illustrated in Scheme 1 below: E NH m = 2147 gmol-OH 45 m = 2012 g.mo1-1 Et3N (excess) Figure 1: Introduction of halogen functionality at one end of the poly (ethylene oxide).
[0033] In a second step, the xanthate functionality was introduced following the reaction of Scheme 2. C - KBr rn = 2147 g.mo1-1 Excess m = 2188 g.mot1 Scheme 2: Introduction of xanthate functionality on one of the ends poly (ethylene oxide). NMR spectroscopic analysis 1H 400 MHz confirmed the disappearance of the terminal hydroxyl group of the poly (ethylene oxide) and the appearance of a xanthate group.
[0034] The product was after purification in the form of a beige powder. The total yield of the synthesis was close to 80%. 1 H NMR analysis confirmed that all polyethylene glycol polymers were terminated by RAFT functionality. This polymer was then used as a macro-RAFT agent to polymerize vinylphosphonic acid 1.2. Polymerization of vinylphosphonic acid (step c)) The polymerization of vinylphosphonic acid (VPA) was initiated by AIBA [V50 10 = 2,2'-azo bis (2-amidinopropane) dihydrochloride of the following formula: at 65 ° C in water in the presence of POE-xanthae block (Figure 12). Analysis of the reaction crude by 31 P showed that residual VPA remained in significant amount. The operating conditions were optimized to minimize the residual vinylphosphonic acid level. Three attempts were made using the transfer agent prepared in 1.1. as a macro-agent RAFT. Polymerization of VPA was carried out at 65 ° C in water. The conversion reached the limit of 58% at 24h. The product was purified by ultrafiltration to yield a copolymer having less than 2% residual vinylphosphonic acid monomer. 1H and 31P NMR spectroscopic analyzes confirmed the production of a polyvinylphosphonic acid block of DP polymerization degrees respectively of 4 (SMO 2 - block copolymer 1), of 5 (HD 2 - block copolymer 2) and of 12 (HD3 - block copolymer 5).
[0035] SMO2 block copolymer 1 HD2 block copolymer 2 HD3 block copolymer 3 The diblock copolymers obtained were then formulated by adding 0.5% by weight of oleic amine to 2 moles of ethylene oxide (commercially available). under the name NORAMOX 02 by CECA) and 1.2% by weight of tributyl phosphate (antifoaming agent).
[0036] Finally, the products were diluted with water to obtain a solids content of 20% and then neutralized with sodium hydroxide at pH 7. The dispersants thus prepared are ready for use.
[0037] EXAMPLE 2 Determination of adsorption isotherms of the diblock copolymers of Example 1 on the surface of the cement particles The diblock polymers of Example 1 were tested with an approach which combines a rheology study for 2 hours with adsorption measurements of the molecules on the cement particles. The Kinexus rheometer (Malvern Instruments, UK) was programmed to perform stress-shear stress measurements (flow curves) after 5 ', 60', and 120 'debructure of the cement paste. Between two flow curve measurements, the apparatus performs a creep curve, i.e. records the evolution of the viscosity, hence the structuring tendency given by the hydration of the cement, under a constant stress of 4 Pa. In synchronization with the flow curves, about 5 ml of cement juice was extracted by centrifugation of the paste (2 min at 5000 rpm) and filtered (0.2 μm nylon) in order to obtain a clean solution. The solutions were diluted and analyzed by measuring Total Organic Carbon (TOC) to detect the amount of polymer remaining in the interstitial fluid. The difference in TOC values before and after contact with the cement gives the amount of polymer adsorbed. The cement paste was prepared with a Krups mixer according to the proportions reported in Table 1.
[0038] Table 1: Dough Composition (g ± 0.02) CEM I 52.2N Le Havre Filler Erbray Sand Water 0 / 0.160 Sand 0 / 0.315 mm mm 254.55 145.45 167.35 36.15 163.85 The diblock molecules were dosed between 0.8% and 2% on the mass of total binder (cement + filler). These different assays made it possible to plot the adsorbed polymer values as a function of the free polymer concentration, thus to obtain an adsorption isotherm. The curves obtained in FIG. 1 correspond to the adsorption isotherms of the polymers on the cement particles. They show very clearly that HD3, with 12 units of vinylphosphonic acid, has a higher affinity for cement grains than HD2 and SM02 which respectively have only 5 and 4 phosphonic acid units. CHRYSO®Fluid Optima 100 is the least adsorbed polymer. Example 3 Use of the Diblock Copolymers of Example 1 in a Cement Paste Formulation Composition of the Evaluation Formulation The diblock copolymers of Example 1 were evaluated according to the following formulation: CEM I 52.5 N Le Havre 624.9 g ERBRAY calcareous filler 412.1 g 30 FULCHIRON (sandy) 587.7 g AFNOR standardized sand 1350 g Total water 375.1 g 3025204 28 The copolymer content is expressed in% relative to the total binder (filler + cement = 1037 g). Procedure for the preparation of the mortar The mortar was prepared according to the following procedure: the two sand, standardized and FULCHIRON, were introduced into the bowl of a PERRIER kneader. After mixing the sands for 30 seconds at a rate of about 140 rpm, prewetting water, which was 1/3 of the total water to be introduced, was added over 15 seconds. The mixture was continued for 15 seconds before allowing the mass to stand for 4 minutes. Then the cement and the calcareous filler (origin ERBRAY supplied by the company MEAC) were introduced and then the mixture was continued for 1 minute before adding the rest of the mixing water and the totality of the adjuvant in the water. space of 30 seconds. The kneader was then stopped for a few moments to scrape the edges of the kneading bowl for a homogeneous mass and then the mixture was continued for a further 1 minute at a rapid rate of 280 rpm. Evaluation Criterion The evaluation of the application properties of block copolymers was carried out using rheological measurements. Thus, the workability of the hydraulic compositions formulated in the presence of these diblock copolymers was estimated by measuring the spreading diameter (slump flow-diameter of the puddle formed after flow). The spreading was measured at 5, 30, 60, 90 and 120 minutes in 2 diameters at 90 °. The tests were carried out at 20 ° C. Results The spreading measurements of the cementitious pastes are presented in Table 2. Adjuvant Optima 100 (reference) HD2 Dosage (%) 1.10 1.10 Spread at 5min 290 410 Table 2: Spreading of the mortar according to the adjuvant. On examining Table 2, it can be seen that the diblock copolymer poly (ethylene oxide-b-polyvinylphosphonic acid) HD 2 has, at equal dosage, a fluidification capacity which is much greater than that of the Optima 100 control.

权利要求:
Claims (19)
[0001]
CLAIMS A block copolymer comprising: at least one block A not comprising a phosphonate group, and comprising at least one poly (alkylene oxide) group, and at least one block B obtained by the polymerization of a mixture of unsaturated monomers ethylenic composition comprising at least one ethylenically unsaturated monomer B1 comprising at least one phosphonate function.
[0002]
2. Block copolymer according to claim 1, wherein in each block A, each poly (alkylene oxide) group independently has the following formula (I): R3- (0-1: 14) n (I) in which: R 3 is a hydrogen atom or a monovalent hydrocarbon group having from 1 to 12 carbon atoms and optionally one or more heteroatoms, n represents an integer from 2 to 500, preferably from 3 to 200, each R 4 represents independently a linear or branched alkylene comprising from 2 to 6 carbon atoms.
[0003]
3. Block copolymer according to claim 2, wherein in each block A, each R4 independently represents a group -CH2-CH2-, -CHCH3-CH2-, -CH2-CHCH3- or -CH2-CH2-CH2- preferably a -CH2-CH2- group.
[0004]
4. Block copolymer according to any one of claims 1 to 3, wherein the block A is obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one monomer Al ethylenically unsaturated and comprising at least one poly (alkylene oxide) group.
[0005]
5. Block copolymer according to claim 4, wherein the monomer A1 has the following formula (II): R17 R7> - <118 R R-R5 6 (R4-O) n-R3 (II) 3025204 in which: n, R3 and R4 are as defined above, R5 represents -CH2-, -O- or -NR8- where R8 represents H or a linear or branched alkyl comprising from 1 to 6 carbon atoms, preferably H or Me, R6 is absent or is - (0 = O) - or - (CH2) q-, where q is 1, 2 or 3, R7 is H or Me, and R17 and R15 are independently H or Me.
[0006]
The block copolymer according to any of claims 1 to 5, wherein each block copolymer block A is obtained by polymerizing a monomer mixture comprising less than 10% by weight of monomers comprising an ionic group. .
[0007]
7. Block copolymer according to any one of claims 1 to 3, wherein the block A block copolymer according to the invention consists of a poly (alkylene oxide), in particular a poly (oxide of alkylene) of formula (I) as defined in claim 2.
[0008]
8. A block copolymer according to any one of claims 1 to 7, wherein in the B block, the B1 monomer has the following formula (IV): Y / OR1 W- (CH2) z-O p II Wherein: Y is: linear or branched alkyl having 1 to 6 carbon atoms, -W- (CH 2), -P (= O) (OR 1) (OR 2), or a group (CH2) x-R25, where x represents an integer between 0 and 4 and R25 represents a hydrogen atom, a phenyl or a -CN or -002R9 group, z represents an integer between 0 and 4; W represents a single bond or a group -000- or -CONH-, it being understood that when z represents 0, W represents a single bond, (R1, R2 and R9 independently represent H, phenyl or linear alkyl). or branched having from 1 to 6 carbon atoms and optionally substituted with one or more halogens.
[0009]
9. Block copolymer according to claim 8, wherein W represents a single bond and z represents 0.
[0010]
10. Block copolymer according to claim 9, wherein the monomer B1 is vinyl phosphonic acid. 10
[0011]
11. Block copolymer according to any one of claims 1 to 10, wherein the block B is obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising: at least one monomer B1 ethylenically unsaturated comprising at least one Phosphonate function, especially a monomer B1 of formula (IV) as defined in claim 8 or 9, and at least one monomer B2 chosen from acrylic acid, methacrylic acid, an ethylenically unsaturated monomer comprising an aminomethylene function; bisphosphonic or gem-bisphosphonic or an ethylenically unsaturated monomer comprising a sulfonic or sulfonate function.
[0012]
12. Block copolymer according to any one of claims 1 to 11, wherein the block B has a degree of polymerization of 1 to 15, preferably 2 to 6. 25
[0013]
13. Block copolymer according to any one of claims 1 to 12 having a weight average molecular weight of 450 to 100000, preferably from 2000 to 40000.
[0014]
A process for the preparation of a block copolymer according to any one of claims 1 to 13 comprising the steps of: b) providing a compound of the following formula (V): block A R10 (V) 3025204 32 in which: block A is as defined in any one of claims 1 to 7, L is absent or is a linking group covalently connecting block A and the group -S- (CS) R10, R10 represents alkyl, arylalkyl, aryl, alkylaryl or a group OR11, NR12R13 or SR14, R11, R12, R13 and R14 are independently alkyl or alkenyl, arylalkyl, aryl, alkylaryl, with the proviso that R12 and R13 may be linked together to form a ring with the nitrogen atom carrying them, c) controlled radical polymerization, or several successive controlled radical polymerizations, comprising contacting: the compound of formula (V), a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated monomer B1 comprising at least one phosphonate function, and - a source of free radicals.
[0015]
15. Process. Preparation compound according to claim 14, a block copolymer comprising a block A as defined in any one of claims 4 to 6, comprising, prior to step b), a step a) of preparing the compound of formula (V): either by a process comprising controlled radical polymerization conducted by contacting: a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated Al monomer and comprising at least one poly (alkylene oxide) group , in particular a monomer Al of formula (II) as defined in claim 5, a source of free radicals, a control agent of formula (VI) below: RISS Rio S (VI) in which R10 is as defined at claim 14 and R15 represents an arylalkyl, an aryl, an alkylaryl or an alkyl optionally substituted by CN or by COOR.16 where R16 represents an alkyl, or by a process comprising the steps of: 3 025204 33 a1) providing a polymer whose main chain comprises at its end a terminal functional group obtained by the polymerization of a mixture of ethylenically unsaturated monomers comprising at least one ethylenically unsaturated Al monomer and comprising at least one poly group (Alkylene oxide), in particular a monomer A1 of formula (II) as defined in claim 5, a2) grafting at the end of the main chain of said polymer a group of formula -S (C = S) R10 where Rloest as defined in claim 14.
[0016]
16. Preparation process according to claim 14 of a block copolymer comprising a block A as defined in claim 7, comprising, prior to step b), a step a) of preparing the compound of formula (V) ) comprising the steps of a3) supplying a poly (alkylene oxide), in particular a poly (alkylene oxide) of formula (I) as defined in claim 2, 15 a4) graft to an end of said poly (alkylene oxide) a group of formula -S (C = S) Rwoù Rloest as defined in claim 14.
[0017]
17. Use of the block copolymer according to any one of claims 1 to 13, as a dispersing agent for mineral particles, as a fluidizing agent for mineral particle suspensions, as an adhesion promoter, as an anti-corrosion agent, as flame retardant, as a stabilizing agent when grinding mineral particles, or as an anti-scale agent.
[0018]
18. Use according to claim 17 of the block copolymer according to any one of claims 1 to 13 as a fluidizing agent for compositions comprising a hydraulic binder.
[0019]
19. A mineral particle composition comprising a copolymer according to any one of claims 1 to 13.

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KR102255617B1|2020-01-13|2021-05-25|한국화학연구원|Flame Retardant Particle and Additives Containing Phosphorus using Surfactant-free RAFT Emulsion Polymerization, and Producing Method thereof|

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优先权:

申请号 | 申请日 | 专利标题

FR1458083A|FR3025204B1|2014-08-28|2014-08-28|BLOCK COPOLYMERS FOR USE AS FLUIDIFYERS|

FR1458083|2014-08-28|FR1458083A| FR3025204B1|2014-08-28|2014-08-28|BLOCK COPOLYMERS FOR USE AS FLUIDIFYERS|

ES15756164T| ES2715021T3|2014-08-28|2015-08-27|Block copolymers useful as fluidizers|

EP15756164.8A| EP3194473B1|2014-08-28|2015-08-27|Block copolymers for use as fluidizing agent|

TR2019/01387T| TR201901387T4|2014-08-28|2015-08-27|Block copolymers for use as plasticizer.|

PCT/EP2015/069688| WO2016030482A1|2014-08-28|2015-08-27|Block copolymers that can be used as plasticisers|

US15/506,428| US10533066B2|2014-08-28|2015-08-27|Block copolymers that can be used as plasticisers|

ZA201701489A| ZA201701489B|2014-08-28|2017-02-28|Block copolymers which can be used as plasticisers|

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