Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

• the subject of the present invention is a controlled architecture copolymer comprising at least one block A obtained by the polymerization of a mixture of ethylenically unsaturated monomers (A 0 ) not comprising monomers with vinyl phosphonate functions and at least one block B obtained. by polymerizing a mixture of ethylenically unsaturated monomers (B 0 ) comprising at least 50 mol% of at least one monomer B 1 bearing at least one vinyl phosphonate function.
• the present invention also relates to a process for synthesizing a controlled architecture copolymer comprising at least one block A obtained by polymerizing a mixture of ethylenically unsaturated monomers (A 0 ) not comprising monomers with vinyl phosphonate functions and at least one block B obtained by the polymerization of a mixture of ethylenically unsaturated monomers (B 0 ) comprising at least 50 mol% of at least one monomer B 1 bearing at least one vinyl phosphonate function.
• the subject of the present invention is also the use of the copolymer thus obtained as an anti-scale agent, as a dispersant, as an emulsifier or as a surface modifier.
• the controlled-architecture copolymers designate block copolymers, such as diblocks and triblocks, graft copolymers, star copolymers, microgels or branched block copolymers comprising a microgel core with variable and controlled crosslinking density ( as described in the application M. Destarac, B. Bavouzet, D. Taton, WO 2004014535, Rhodia Chimie).
• vinyl phosphonate functional monomer means a monomer which comprises at least one vinyl phosphonic acid function or an alkyl ester analog. Mention may be made in particular of vinyl phosphonate-functional monomers, the compounds of formula (I) below:
• Y represents a radical chosen from a hydrogen atom, an alkyl radical having from 1 to 6 carbon atoms, a cyano, a phenyl radical, an ester radical of formula -COOR, an acetate radical of formula -OCOR 1 , a phosphonic acid or a methyl, ethyl or isopropyl phosphonic acid ester;
• R, R ' identical or different represent an alkyl radical having 1 to 12 carbon atoms, and preferably an alkyl radical having 1 to 6 carbon atoms;
• R1, R2, identical or different represent a hydrogen atom, or an alkyl radical having 1 to 6 carbon atoms optionally substituted with a halogen atom;
• halogen atom means chlorine, fluorine, bromine or iodine.
• chlorine is used.
• the blocks according to the invention may be homopolymers, random copolymers, alternating copolymers or composition gradient copolymers.
• Controlled architectures copolymers are useful in various industries, such as dispersing, emulsifying, texturizing or surface modifying agents.
• the (co) polymers carrying phosphonic acid functions are industrially developed for their particular functions in various fields such as anti-scale agents, corrosion inhibitors, or pigment dispersants.
• the range of industrial monomers carrying phosphonate PO 3 R 1 R 2 function is very limited.
• the PO 3 H 2 phosphonic acid functions are often generated by the hydrolysis of the corresponding esters which can be provided by a monomer [Boutevin, B. et al. Polym. Bull. 1993, 30, 243] or a transfer agent [Boutevin, B. et al. Macromol. Chem. Phys. 2002, 203, 1049] suitable during the polymerization.
• polymers with phosphonate or phosphonic acid functions most commonly described are homopolymers, random copolymers or even telomeres functionalized phosphonic acid at their end, these polymers being obtained by conventional radical means, that is to say by a uncontrolled mechanism.
• ATRP atom transfer radical polymerization
• NMP stable radical polymerization controlled by nitroxyl-type stable radicals
• ITP degenerative transfer polymerization of iodine
• RAFT reversible addition-fragmentation transfer polymerization
• the phosphonic acid units and the ester analogs of the vinyl monomers and / or polymers formed tend to interact strongly with the ATRP (Cu, Ru, Fe, Ni) catalysts, which compromises the control of this polymerization.
• the low level of stabilization of the radicals derived from the vinyl phosphonic acid monomers or their ester analogs renders the polymerization of these monomers difficult to reconcile with the radical polymerization technique controlled by the stable "nitroxyl" type radicals.
• the AVP has been copolymerized statistically with acrylic acid.
• Dual hydrophilic P (Acrylamide) -bP (AA-stat-AVP) copolymers were synthesized as described in [M. Destarac, D. Taton, "Direct Access to Phosphonic Acid-Containing Block Copolymers via MADIX" 40th International Symposium on Macromolecules, MACRO 2004, Paris].
• P (ABu) -bP (AA-stat-AVP) amphiphilic copolymers were synthesized as described in WO2003076529 and WO2003076531.
• the vinyl phosphonate monomer is a monomer which is not very reactive, and is generally much more expensive than the comonomers which accompany it in the reaction mixture. Being able to locate it at will in a specific part of the polymer should allow to use less to achieve the property, and thus reduce costs.
• One of the aims of the present invention is to find a way to synthesize controlled architecture copolymers comprising at least one block based on monomers bearing vinyl phosphonate functions in a high vinyl phosphonate composition.
• the subject of the present invention is a controlled architecture copolymer comprising at least one block A obtained by the polymerization of a mixture of ethylenically unsaturated monomers (A 0 ) not comprising monomers with vinyl phosphonate functions and at least one block B obtained. by polymerizing a mixture of ethylenically unsaturated monomers (B 0 ) comprising at least 50 mol% of at least one monomer B 1 bearing at least one vinyl phosphonate function.
• the subject of the present invention is also a process for synthesizing a controlled architecture copolymer comprising at least one block A obtained by the polymerization of a mixture of ethylenically unsaturated monomers (A 0 ) not comprising vinyl-functional monomers.
• the subject of the present invention is also the use of the copolymer thus obtained as an anti-scale agent, as a dispersant, as an emulsifier or as a surface modifier.
• the controlled architecture copolymer of the invention may be a block copolymer (di or triblock), a graft copolymer, a star copolymer or a microgel, comprising at least one block A and at least one block B.
• the block A according to the invention is obtained by the polymerization of a mixture of ethylenically unsaturated monomers (A 0 ) not comprising vinyl phosphonate functional monomers.
• Block B is obtained by the polymerization of a mixture of ethylenically unsaturated monomers (B 0 ) comprising at least 50 mol% of at least one monomer B 1 carrying a vinyl phosphonate function.
• the blocks according to the invention may be homopolymers, random copolymers, alternating copolymers or composition gradient copolymers.
• the mass ratio of the blocks A and B varies between 1/99 and 99/1.
• Block A is obtained by the polymerization of a mixture of ethylenically unsaturated monomers (A 0 ) containing no vinyl phosphonate functional monomers.
• the group (A 0 ) comprises the hydrophilic (h) or hydrophobic (H) monomers chosen from the following monomers:
• hydrophilic monomers (h) mention may be made of: ethylenically 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, or ethylenic monomers comprising a ureido group such as ethylene-ethyl urea methacrylamide, or ethylene-urea ethyl methacrylate, or
• ethylenic monomers comprising a sulphonic acid group or an alkali metal or ammonium salt thereof, for example vinylsulfonic acid, vinylbenzene sulphonic acid, alpha-acrylamido-methylpropanesulphonic acid, or 2-sulphoethylene methacrylate; , or
• cationic monomers chosen from aminoalkyl (meth) acrylates and 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 such that the counterion is a halide such as, for example, a chloride, or a sulphate, a hydrosulphate, an alkyl sulphate (for example example comprising 1 to 6 carbon atoms), a phosphate, a citrate, a formate, an acetate, such as dimethyl amino ethyl (meth) acrylate, dimethyl amino propyl (meth) acrylate, ditertiobutyl aminoethyl (meth) acrylate, dimethyl amino methyl (meth)
• hydrophilic polymers from a chemical modification of a hydrophobic block, for example by hydrolysis of an alkyl polyacrylate polyacrylic acid.
• the hydrophilic monomeric units (h) are chosen from acrylic acid (AA), acrylamide (Am) and 2-acrylamido-2-methylpropanesulfonic acid.
• AMPS styrene sulfonate
• SS styrene sulfonate
• AVS vinyl sulfonic acid
• acrylic acid units (AA) or acrylamide (Am) are used.
• monomers having a hydrophobic character (H) mention may be made of:
• styrenic derived monomers such as styrene, alphamethylstyrene, paramethylstyrene or paratertiobutylstyrene, or
• esters of acrylic acid or methacrylic acid with C1-C12, preferably C1-C8, optionally fluorinated alcohols such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylate, n-butyl, isobutyl methacrylate, vinyl nitriles containing from 3 to 12 carbon atoms, and in particular acrylonitrile or methacrylonitrile,
• vinyl esters of carboxylic acids such as vinyl acetate (VAc), vinyl versatate, or vinyl propionate,
• vinyl or vinylidene halides for example vinyl chloride, vinylidene chloride and vinylidene fluoride, and diene monomers, for example butadiene or isoprene.
• the hydrophobic monomer units (H) of the architectures with controlled architectures of the invention are esters of acrylic acid with linear or branched C 1 -C 8 and especially C 1 -C 4 alcohols, for example, for example , methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate (Abu) or 2-ethylhexyl acrylate (A2EH), fluorinated acrylates, or styrenic derivatives such as as styrene or vinyl acetate (VAc).
• esters of acrylic acid with linear or branched C 1 -C 8 and especially C 1 -C 4 alcohols for example, for example , methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate (Abu) or 2-ethylhexyl acrylate (A2EH), fluorinated acrylates, or styrenic derivatives such as as sty
• block A is the acrylic polyacid or polyvinyl alcohol.
• the polyacrylic acid can be obtained either by polymerization of acrylic acid monomer, or by polymerization of an alkyl acrylate monomer such as for example methyl acrylate or butyl followed by hydrolysis.
• the polyvinyl alcohol can be obtained by polymerization of vinyl acetate followed by hydrolysis.
• the monomer comprising at least one vinyl phosphonate functional group B 1 may be a compound of formula (I):
• Y represents a radical chosen from a hydrogen atom, an alkyl radical having from 1 to 6 carbon atoms, a cyano, a phenyl radical, an ester radical of formula -COOR, an acetate radical of formula -OCOR ', a phosphonic acid or a methyl, ethyl or isopropyl phosphonic acid ester;
• R, R ' identical or different represent an alkyl radical having 1 to 12 carbon atoms, and preferably an alkyl radical having 1 to 6 carbon atoms;
• block B also comprises monomers B1 in which Y represents a hydrogen atom.
• halogen atom is meant chlorine, fluorine, bromine, or iodine.
• chlorine is used.
• vinyl phosphonic acid dimethyl ester of vinylphosphonic acid, bis (2-chloroethyl) ester of vinylphosphonic acid, vinylidene diphosphonic acid, tetraisopropyl ester of vinylidene diphosphonic acid, or alpha-styrene phosphonic acid, or mixtures thereof.
• Mono or di-vinyl phosphonic acid monomers B 1 can be used in free acid form, or in the form of their salts. They may be neutralized, partially or totally, optionally with an amine, for example dicyclohexylamine.
• the preferred monomer Bi according to the invention is vinylphosphonic acid.
• the monomer B 2 useful in the present invention may be chosen from the monomers A 0 defined above.
• the monomer B 2 is chosen from acrylic acid, acrylamide, vinyl sulphonic acid or mixtures thereof. Even more preferably, the monomer B 2 is acrylic acid.
• the copolymers with controlled architecture of the invention have a weight average mass of between 1000 and 100000. Most often between 4000 and 50000. They also have a polydispersity index of less than 2.5, preferably between 1, 3 and 2.5 and more preferably between 1.3 and 2.0.
• the mass ratio between blocks A and B is such that B / (A + B) is preferably between 0.01 and 0.5, and even more preferably between 0.02 and 0.2.
• the subject of the present invention is also a process for synthesizing a controlled architecture copolymer comprising at least one block A obtained by the polymerization of a mixture of ethylenically unsaturated monomers (A 0 ) not comprising monomers with vinyl phosphonate functions. and at least one block B obtained by the polymerization of a mixture of ethylenically unsaturated monomers
• (B 0 ) comprising at least 50 mol% of at least one monomer B 1 bearing at least one vinyl phosphonate functional group comprising the following steps: (a) controlled radical polymerization leading to the production of a functionalized polymer is carried out useful as a control agent in a controlled radical polymerization reaction, said step being conducted by contacting:
• step (b) following step (a), a controlled radical polymerization step is carried out, or several successive controlled radical polymerization steps, said step (s) each consisting in carrying out a controlled radical polymerization leading to obtaining a functionalized block copolymer useful as a control agent in a controlled radical polymerization reaction, said step or steps being carried out by bringing into contact:
• the concentration of monomer B 0 in the medium is such that the solids content must be greater than 50%, preferably greater than 60% and even more preferably greater than 70%, the solid content being defined in the manner next: mass B 0 / mass (B 0 + solvent) if B 0 is polymerized in the first block, mass (A 0 + B 0 ) / mass (A 0 + B 0 + solvent) if B 0 is polymerized in the second block; and
• the cumulative or total concentration of the initiator is between 0.5 and 20 mol% relative to the monomer mixture B 0 .
• step (s) b) ethylenically unsaturated monomeric molecules different from those used in the previous step.
• a mixture of monomers it is sufficient for this mixture to comprise at least one monomer other than the monomer (s) used during the mixing. previous step.
• all the monomers of (s) step (s) b) are different from those implemented in the previous step.
• the molecular masses of the block B are generally less than 10,000, preferably less than 5,000 and even more preferably less than 2,000.
• the initiator concentration and the initiation mode of the initiator are defined so as to obtain the right compromise between a high B 0 monomer conversion and a rate of uncontrolled chains as low as possible.
• the initiator is introduced batchwise at the start of the reaction, or in a spot, or continuously or semi-continuously, by putting the monomer B 1 preferably at the bottom of the tank so that the total or cumulative concentration of the initiator is between 0.5 and 20 mol% relative to the monomer mixture Bo.
• the level of monomer B 0 solid is high compared to the usual conditions in which the controlled radical polymerization processes are implemented.
• control agent that is useful for carrying out the process of the invention may be chosen from dithioesters, thioethers-thiones, trithiocarbonates and dithiocarbamates, including N, N-dialkyldithiocarbamates, dithiocarbazates and xanthates.
• control agent chosen from N, N-dialkyldithiocarbamates, dithiocarbazates and xanthates is used as control agent.
• control agent used is a compound chosen from xanthates.
• Xanthates are compounds of the following formula (II): S W
• a saturated or unsaturated carbon cycle optionally aromatic
• R2 a group (R2) O-, (R2) (R'2) N-, in which the radicals R2 and R'2, which are identical or different, each represent:
• alkyl, acyl, aryl, alkenyl or alkynyl group an alkyl, acyl, aryl, alkenyl or alkynyl group; a saturated or unsaturated carbon cycle, optionally aromatic; or
• R1 represents:
• alkyl, acyl, aryl, alkenyl or alkynyl group a saturated or unsaturated, optionally aromatic carbon ring;
• a particularly advantageous control agent is a compound of formula (II) in which R represents an ethyl radical, and R 1 represents a (methoxycarbonyl) ethyl radical.
• the polymerization may be carried out especially in bulk, in a solvent or in a dispersed medium.
• said solvent is ethyl acetate or an alcohol selected from ethanol, isopropanol, or their mixtures with water, if appropriate.
• the polymerization carried out in aqueous or aqueous-alcoholic solution constitutes a preferred embodiment of the invention.
• Water, an alcohol or an aqueous-alcoholic medium are more particularly recommended in the context of the implementation of hydrophilic monomers of the type of acrylic acid (AA), acrylamide (AM), acid 2- acrylamido-2-methyl-propanesulfonic acid (AMPS), and styrene sulfonate (SS) and / or in the context of the use of hydrophobic monomers such as n-butyl acrylate or acrylate of 2- ethylhexyl.
• the architectures with controlled architectures of the invention are useful in various industries. They can be used in particular as anti-scale agent, dispersant, inorganic surface modifier (glass, metal, ceramic), emulsifier or corrosion inhibitor.
• Part I Polymerization of vinyl phosphonic acid (PVA) by radical polymerization controlled by xanthates.
• PVA vinyl phosphonic acid
• the polymerization rates are 10 (Example 1) and 30 (Example 2), respectively.
• the solids content aimed at total conversion of the monomer is 70% in both cases.
• the DOSY 2D NMR analysis of the polymer of Example 1 makes it possible to observe the presence of high-mass species corresponding mainly to polyvinylphosphonic acid with a "living" character confirmed by the presence of the xanthate chain ends associated with it. (OCH 2 of the sulfur xanthate end).
• Vinyl phosphonic acid P (AVP) as first block A vinyl phosphonic acid oligomer (AVP) was synthesized in the presence of O-ethyl-S- (i-methoxycarbonyl) ethyl) xanthate X 1 .
• the initial concentrations of AVP and xanthate are chosen in such a way that the theoretical DP n is equal to 5.
• the reaction is carried out at 70 ° C. in a water / ethanol mixture (73/27 by weight) at a solids level of 70. %, and initiated by azobis cyanopentanoic acid. After 18 hours of reaction, the conversion rate to vinyl phosphonic acid (PVA) is 77% ( 31 P NMR).
• the amount of acrylic acid is chosen so that the acrylic polyacid block
• PAA polymerization
• the vinyl phosphonic acid oligomer terminated xanthate P (AVP) -X1 is a non-reactive transfer agent in the polymerization of acrylic acid (AA).
• the amount of vinyl phosphonic acid (AVP) is chosen so that the polyvinyl phosphonic acid block P (AVP) contains an average of 20 monomer units, with the hypothesis that the polymerization will be controlled.
• 3 g of polyacrylic acid solution (PAA) block 1 concentrated on a rotary evaporator to 85% solids is mixed with 7 g of vinylphosphonic acid (VPA), 4.6 g of water and 1 16 g of ethanol. 0.93 g of cyanopentanoic acid azobis (ACP) are added. The reaction is carried out at 70 ° C. After 6 hours of reaction, 0.93 g of cyanopentanoic acid azobis (ACP) are again added. The reaction is stopped after 18 hours. The product is then analyzed by GPC.
• FIG. 1 shows the superposition of the chromatograms R1 of the first acrylic polyacid block (PAA) as well as the final copolymer.
• Figure 2 is the analogue equipped with UV detection at 290 nm.
• AVP vinyl phosphonic acid

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