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EP1989256A1 - Verfahren zur kontrollierten radikalpolymerisation oder -copolymerisation eines oder mehrerer monomere in gegenwart eines alkoxyamin-initiators - Google Patents

Verfahren zur kontrollierten radikalpolymerisation oder -copolymerisation eines oder mehrerer monomere in gegenwart eines alkoxyamin-initiators

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Publication number
EP1989256A1
EP1989256A1 EP07726608A EP07726608A EP1989256A1 EP 1989256 A1 EP1989256 A1 EP 1989256A1 EP 07726608 A EP07726608 A EP 07726608A EP 07726608 A EP07726608 A EP 07726608A EP 1989256 A1 EP1989256 A1 EP 1989256A1
Authority
EP
European Patent Office
Prior art keywords
group
polymerization
copolymer
monomers
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07726608A
Other languages
English (en)
French (fr)
Inventor
Jean-Luc Couturier
Manuel Hidalgo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP1989256A1 publication Critical patent/EP1989256A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/243—Phosphorus-containing polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/243—Phosphorus-containing polymers
    • C04B24/246—Phosphorus-containing polymers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
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    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/34—Flow improvers

Definitions

  • the present invention relates to a controlled radical polymerization or copolymerization process, in particular in an aqueous medium of one or more monomers in the presence of at least one particular alkoxyamine initiator.
  • the general field of the invention is that of controlled radical polymerization.
  • the controlled radical polymerization makes it possible to reduce the deactivation reactions of the growing radical species, in particular the termination stage, reactions which, in conventional radical polymerization, interrupt the growth of the polymer chain irreversibly and without control.
  • the alkoxyamines described in FR 2843394 should be used in a neutralized form with a strong base excess to be water soluble. To be usable for the polymerization or copolymerization of monomers in an aqueous medium and in particular for the polymerization of water-soluble monomers, it is therefore necessary to set up, before the polymerization or copolymerization, a step of preparing the alkoxyamine (for example, by neutralization by a strong base).
  • the invention relates to a process for the polymerization of one or more monomers, comprising a step of contacting, for example, in a medium comprising in particular water, said monomer or monomers. with at least one initiator of the following formula (I):
  • R 1 represents a hydrogen atom, a linear or branched alkyl group comprising from 1 to 8 carbon atoms, a phenyl group, a metal chosen from alkali metals, alkaline earth metals and transition metals, in particular, an alkali metal (Na, Li, K) or H 4 N + , Bu 4 N + , Bu 3 HN + , Bu representing an n-butyl group; - R.2 and R.3, identical or different, represent a linear or branched alkyl group comprising from 1 to 3 carbon atoms;
  • R 5 represents a hydrogen atom or an OCOR 8 group, Rs representing a linear or branched alkyl group comprising from 1 to 20 carbon atoms; R ⁇ and R ⁇ represent, independently, a linear or branched alkyl group comprising from 1 to 3 carbon atoms; R 4 represents: an aryl group carrying at least one acid group comprising at least one heteroatom selected from S and P, said acid group possibly existing in the form of a salt; or
  • heterocyclic group comprising one or more heteroatoms chosen from O, N and / or
  • said heterocyclic group optionally carrying at least one acid group comprising at least one heteroatom selected from S and P or bearing a hydrocarbon group optionally comprising one or more heteroatoms (for example N, S and / or O), said hydrocarbon group carrying at least one acid group as defined above, said heterocyclic group being able to exist in the form of a salt; or
  • a -CO-NR-Y or -CO-OY group with Y representing a hydrocarbon group optionally comprising one or more heteroatoms (for example, N, S and / or O) bearing at least one acidic group comprising a heteroatom chosen from S and P or representing a hydrocarbon group optionally comprising one or more heteroatoms (for example, N, S and / or O) containing at least one heterocyclic group comprising one or more heteroatoms chosen from N, O and S, said group - CO-NR-Y or -CO-OY which may optionally exist in the form of a salt and R representing a hydrogen atom or an alkyl group, preferably comprising from 1 to 24 carbon atoms.
  • R 4 may be an aryl group comprising, for example from 5 to 20 carbon atoms (for example, a phenyl group), said aryl group being carrier (that is to say substituted) of at least one acid group comprising at least one heteroatom selected from S and P, said acid group may exist in the form of a salt.
  • an acid group comprising at least one heteroatom selected from S and P there may be mentioned a sulfonic, phosphonic, phosphoric or phosphinic group and the salts thereof.
  • R 4 may be a heterocyclic group comprising one or more heteroatoms chosen from O, N and / or S, such as a pyrrole, pyridine, indole, thiophene, furan or pyrimidine group, optionally carrying at least an acid group comprising at least one heteroatom selected from S and P as defined above or said heterocyclic group carrying a hydrocarbon group, such as an alkyl group containing from 1 to 24 carbon atoms, optionally comprising one or more several heteroatoms, which hydrocarbon group is substituted one or more times with an acid group as defined above (i.e., an acidic group having at least one heteroatom selected from S and P).
  • a heterocyclic group comprising one or more heteroatoms chosen from O, N and / or S, such as a pyrrole, pyridine, indole, thiophene, furan or pyrimidine group, optionally carrying at least an acid group comprising at least one heteroatom selected from S and P as defined above or said hetero
  • R 4 may represent a group -CO-NR-Y or -CO-OY, with Y representing a hydrocarbon-based group, such as an alkyl group possibly comprising from 1 to 24 carbon atoms, optionally comprising one or several heteroatoms, and substituted by at least one acid group comprising at least one heteroatom selected from S and P, such as a sulfonic, phosphonic, phosphoric or phosphinic group.
  • Y may also be a hydrocarbon group, such as an alkyl group comprising from 1 to 24 carbon atoms.
  • the group Y can not be an unsubstituted alkyl group, since it is necessarily substituted by an acid group or a heterocyclic group as defined above.
  • R 4 is an aryl group carrying at least one acidic group comprising at least one heteroatom chosen from S and P, said acid group possibly being in the form of a salt.
  • R 4 may advantageously be a phenylene group carrying a group -SO3R9, R9 representing a hydrogen atom, a metal selected from alkali metals, alkaline earth metals, transition metals, and in particular an alkali metal (Na, Li, K) or H 4 N + , Bu 4 N + , Bu3HN + , Bu representing an n-butyl group.
  • a particular initiator according to the invention corresponds to the following formula (II):
  • the initiators described above can be obtained by radical addition of the type-1,2 of an olefin comprising a function Y on a starting alkoxyamine, according to the following reaction scheme: a) cleavage of the starting alkoxyamine in radicals l ibres:
  • the process is advantageously carried out in a medium comprising water.
  • This medium may be an aqueous or predominantly aqueous solution or a water / organic phase dispersed medium (dispersion, emulsion, miniemulsion, microemulsion, suspension, micellar, reverse suspension, inverse emulsion, inverse microemulsion).
  • the polymerization process of the invention consists of the polymerization of one or more monomers.
  • the monomer (s) will be, in particular, monomers whose patterns after polymerization will be different from the -CH 2 -CHR 4 - unit present in the polymerization initiator of formula (I).
  • At least one of the monomers can be a water-soluble or water-dispersible monomer.
  • water-soluble monomer is conventionally meant a monomer soluble in water, namely at a content of at least 1% by weight.
  • this monomer comprises functions which are capable of establishing hydrogen bonds with the water molecules, which ensures its solubility in water.
  • the water-soluble monomer or monomers capable of forming the polymers or copolymers prepared according to the process of the invention may be chosen from: water-soluble styrene derivatives such as sodium styrene sulphonate; water-soluble acrylic monomers such as acrylic acid and its salts, methyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, acrylates of methoxy-polyethylene glycol-polypropylene glycol and mixtures thereof, 2- (dimethylamino) ethyl acrylate (ADAME), [2- (acryloyloxy) ethyl] trimethylammonium chloride or sulfate, [2-
  • methacrylic monomers such as methacrylic acid and its salts, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, methoxypolyethylene glycol methacrylates, ethoxypolyethylene glycol methacrylates, methoxy-polyethylene glycol-polypropylene glycol methacrylates and mixtures thereof, 2- (dimethylamino) ethyl methacrylate (MADAME), [2- (methacryloyloxy) ethyl] trimethylammonium chloride or sulfate,
  • Acrylamide or substituted acrylamides N-methylolacrylamide, acrylamidopropyltrimethylammonium chloride (APTAC), acrylamidomethylpropanesulfonic acid (AMPS) and its salts; methacrylamide or substituted methacrylamides, 2-methyl-N- [2- (2-oxoimidazolidinyl) ethyl] acrylamide, N-methylolmethacrylamide, methacrylamidopropyltrimethylammonium chloride (MAPTAC); -Itaconic acid, maleic acid and its salts, maleic anhydride, maleates or hemimaleates alkyl or alkoxy or aryloxypolyalkylene glycol, vinylpyridine, vinylpyrrolidinone; and
  • the monomers capable of forming the polymers or copolymers prepared according to the process of the invention may be hydrophobic monomers chosen from:
  • vinylaromatic monomers such as styrene, ⁇ -methylstyrene; diene monomers, such as butadiene, isoprene;
  • hydrophobic acrylate monomers such as ethyl acrylate, n-butyl acrylate, ethylhexyl acrylate, phenyl acrylate, methoxypolypropylene glycol acrylates, fluorinated acrylates or silyl acrylates;
  • methacrylate monomers such as methyl methacrylate, lauryl, cyclohexyl, allyl, phenyl, methoxypolypropylene glycol methacrylates, 2- (tert-butylamino) ethyl methacrylate (MATBAE), fluorinated methacrylates, such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates such as 3-methacryloylpropyltrimethylsilane; Acrylonitrile; and mixtures thereof.
  • methacrylate monomers such as methyl methacrylate, lauryl, cyclohexyl, allyl, phenyl, methoxypolypropylene glycol methacrylates, 2- (tert-butylamino) ethyl methacrylate (MATBAE), fluorinated methacrylates, such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates such
  • the initiator (s) of formula (I) may be present in a content ranging from 0.005% to 40% by weight relative to the total weight of the monomer (s) used and, preferably, at a content ranging from 0.01% at 10%.
  • the monomer (s) and / or the initiator of alkoxyamine type may optionally be introduced continuously into the polymerization medium.
  • the contacting step can be carried out, in addition to the initiator of formula (I), in the presence of an initiator chosen from hydroperoxides and dialkyl peroxides. , diacyl peroxides, peroxyesters, peroxydicarbonates, peroxyacetals or azo compounds.
  • an initiator chosen from hydroperoxides and dialkyl peroxides.
  • diacyl peroxides, peroxyesters, peroxydicarbonates, peroxyacetals or azo compounds as examples of hydroperoxides, mention may be made of tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane and the like. , diisopropylbenzene monohydroperoxide and paramenthane hydroperoxide.
  • dialkyl peroxides examples include 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne- (3), di-tert-butyl peroxide, di-tert-butyl peroxide and di-tert-butyl peroxide.
  • diacyl peroxide there may be mentioned benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, acetyl peroxide and cyclohexylsulphonyl peroxide.
  • peroxyesters there may be mentioned tert-butyl peroxybenzoate, tert-butyl peroxyacetate, peroxy-3,5,5 tert-butyl trimethylhexanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 00-tert-butyl-O-isopropyl-monoperoxycarbonate , 00-tert-butyl-O- (2-ethylhexyl) -monoperoxycarbonate, 00-tert-amyl-O- (2-ethylhexyl) -monoperoxycarbonate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate tert-amyl peroxy-2-ethylhexanoate, 2,5-
  • peroxydicarbonates there may be mentioned di (2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, di (n-propyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate.
  • peroxyacetals By way of examples of peroxyacetals, mention may be made of 1,1-di (tert-butylperoxy) cyclohexane, 1,1-di (tert-butylperoxy) 3, 3, 5-trimethylcyclohexane and 3,3-di ( tert-butylperoxy) ethyl butyrate, ethyl 3,3-di (tert-amylperoxy) butyrate, 4,4-di (tert-butylperoxy) n-butyl valerate, 2,2-di (tert butylperoxy) butane, 1,1-di (tert-amylperoxy) cyclohexane, 2,2-bis [4,4-di (tert-butylperoxy) cyclohexyl] propane.
  • the contacting step may also be carried out in the presence of inorganic oxidants such as sodium persulfates, potassium or ammonium, hydrogen peroxide, perchlorates, percarbonates, ferric salts.
  • inorganic oxidants such as sodium persulfates, potassium or ammonium, hydrogen peroxide, perchlorates, percarbonates, ferric salts.
  • oxidants may be used alone or in combination with inorganic or organic reducers such as sodium or potassium bisulfite and metabisulfite, vitamin C, sodium or potassium hypophosphites.
  • organic or inorganic reducers can also be used alone, that is to say, in the absence of inorganic oxidants.
  • the process of the invention is particularly suitable for the preparation of water-soluble (co) polymers by polymerization of one or more water-soluble monomers chosen from:
  • amine salt (meth) acrylates such as [2- (methacryloyloxy) ethyl] trimethylammonium chloride or sulfate, [2- (methacryloyloxy) ethyl] dimethylbenzylammonium chloride or sulfate;
  • hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl methacrylate
  • polyethylene glycol, alkoxy- or aryloxypolyalkyleneglycol (meth) acrylates such as methoxypolyethylene glycol (meth) acrylates, ethoxypolyethylene glycol (meth) acrylates; and - mixtures thereof.
  • the water-soluble monomers used are methacrylic acid, acrylic acid, methoxypolyethylene glycol methacrylates.
  • These copolymers may also comprise a minor fraction of hydrophobic monomer, preferably methyl methacrylate or styrene.
  • the process is also particularly suitable for the preparation of amphiphilic copolymers, namely copolymers having both hydrophilic and hydrophobic parts.
  • the hydrophilic monomers used are methacrylic acid and / or methacrylates of
  • alkyloxy polyethylene glycol and / or the water-soluble cationic monomers such as [2- (methacryloyloxy) ethyl] trimethylammonium chloride and, preferably, the hydrophobic monomers used are methyl methacrylate and / or styrene and / or methacrylate.
  • aqueous or organic dispersions of particles according to polymerization techniques well known to those skilled in the art, such as dispersion or precipitating polymerization, suspension polymerization, and mini-emulsion polymerization.
  • conventional emulsion polymerization, microemulsion polymerization, inverse suspension polymerization, inverse emulsion polymerization, inverse microemulsion polymerization or micellar polymerization and is more particularly suitable for the preparation of dispersions.
  • aqueous particles predominantly hydrophobic by well known suspension polymerization and emulsion polymerization techniques. In the latter case, the aqueous dispersions of hydrophobic particles obtained are of colloidal size, they diffuse the light and are known to those skilled in the art under the generic name "synthetic" latex.
  • the process of the invention is particularly advantageous for preparing fluid latices, especially for incorporation into cement, plaster, paint or cosmetic compositions.
  • the process of the invention may also comprise a step of isolating the polymer or copolymer, for example by precipitation followed by filtration.
  • the isolated polymer or copolymer may be used directly for a given application, or may be subsequently reintroduced into a polymerization medium.
  • the process of the invention may comprise a step of in situ preparation of the initiator of formula (I), preferably before the contacting step.
  • initiators of formula (I) in the context of the process has many advantages: they allow the preparation of polymers in aqueous medium, and whatever the pH of the medium and in the presence of acidic monomers such as than methacrylic acid and including in media aqueous acids such as those often used in emulsion polymerization;
  • the method of the invention makes it possible to obtain polymers or copolymers having at least one reactive end having the following formula:
  • R 1, R 2 , R 3 and R 4 being as defined above.
  • the polymers or copolymers will in particular have a unit of formula -CH 2 -CHR 4 - derived from the alkoxyamine present at the end of chains, the other units resulting from the polymerization of the monomers, which units will be different from said -CH 2 -CHR unit 4 -.
  • This polymer or copolymer having such a reactive end can be made to undergo a chemical transformation of this end by reaction thereof with appropriate reagents.
  • the invention relates, according to a first object, to polymers or copolymers that can be obtained by a process as defined above.
  • copolymers according to the invention are copolymers comprising repeating units resulting from the polymerization of methacrylic acid, a methoxypolyethylene glycol methacrylate and methyl methacrylate.
  • Another particular copolymer may be a copolymer comprising repeating units resulting from the polymerization of methyl methacrylate and 2- (tert-butylamino) ethyl methacrylate.
  • a particular polymer may be a polymer comprising repeating units resulting from the polymerization of methyl methacrylate.
  • Particular polymers or copolymers according to the invention are amphiphilic polymers or copolymers comprising: hydrophilic repeating units resulting from the polymerization of methacrylic acid and / or of (alkyloxy) polyethylene glycol methacrylate and / or of a hydrophilic cationic monomer; and hydrophobic repeating units resulting from the polymerization of methyl methacrylate and / or styrene and / or 2- (tert-butylamino) ethyl methacrylate.
  • the polymers or copolymers of the invention in particular when they mainly comprise water-soluble monomers, can in particular be used as dispersing agents, in particular of pigments or mineral fillers in an aqueous medium. They make it possible in particular to give good fluidity to aqueous dispersions of mineral particles, and more particularly to compositions based on hydraulic binders such as cement and plaster. They also ensure a good compromise between the properties of water reduction and maintenance of rheology over time.
  • the polymers or copolymers of the invention may also be used as dispersants or co-stabilizers of emulsions of organic products, such as bitumen. They allow, in combination with conventional surfactants to make these emulsions more stable over time.
  • dispersants or co-stabilizers are copolymers comprising repeating units resulting from the polymerization of methacrylic acid, a methoxypolyethylene glycol methacrylate and methyl methacrylate or a copolymer comprising repeating units resulting from the polymerization of methyl methacrylate and 2- (tert-butylamino) ethyl methacrylate.
  • the polymers or copolymers of the invention in particular can also be used as thickeners, for example in drilling muds, as adhesives, as absorbents or as binders.
  • these polymers or copolymers can enter, in particular, into the constitution of numerous compositions such as: cosmetic compositions comprising, besides said polymers or copolymers, a cosmetically acceptable medium; adhesive compositions comprising, besides said polymers or copolymers, additives such as tackifying resins, plasticizers, etc .;
  • One of these compositions is the cement mortar obtained by mixing cement, standardized sand, water and the aqueous solution or dispersion containing the dispersing copolymers of the invention optionally comprising antifoaming agents.
  • the mortar is prepared in the presence of a dispersing or fluidizing copolymer according to the invention, according to standardized methods and a hollow truncated cone, of well-defined dimensions, known as the "mini-cone of Abrams", is filled with the mortar.
  • the cone has a top fill opening and a lower drain opening.
  • the mortar is inside, because the cone is placed on a flat plate that obstructs the lower opening.
  • the cone is lifted off its support, which has the effect of causing the mortar to flow on the flat plate by spreading therefrom in the form of a round cake.
  • the more the mortar preparation is fluid the more the mortar will spread and the larger the diameter of the slab.
  • the maximum spread diameter of the wafer known to those skilled in the art as "slump value” or “spread value" is a fairly reliable measure of the fluidity of the preparation.
  • This fluidity can vary essentially by playing on two parameters, which are the ratio Water / Cement
  • E / C ratio of the mortar and the content of the fluidizing copolymer expressed in% of dry matter of dispersing copolymer relative to the cement (% SP).
  • the protocol described in paragraph a) allows to know the initial spread value, that is to say immediately after filling the cone with the mortar for the first time.
  • the spread mortar may, however, be recovered and remixed according to a standardized procedure and the spreading measure may be repeated at different times counted from the first initial spreading or spreading.
  • the fluidity of the mortar can be followed over a period, usually, up to two or three hours. This measurement makes it possible to know the behavior of the mortar added in terms of evolution of the fluidity over time. It is often desirable that the fluidity remains as high as possible for the longest possible times up to the limit of 2 or 3 hours.
  • EXAMPLE 2 In a 1-liter glass reactor equipped with a variable-speed stirring motor, entries for the introduction of reagents, taps for the introduction of inert gases for the removal of oxygen, such as nitrogen, and measurement probes (eg temperature), a vapor-reflux condensing system, a jacket for heating / cooling the contents of the reactor through the circulation therein, d. 195.6 g of deionized water are introduced, the stirring is started at a moderate speed, the system is heated to reach 70 ° C. in the reactor and is degassed by bubbling nitrogen into the reactor. the liquid for at least 15 minutes.
  • Norsocryl N402 consisting of a 58% aqueous solution of dry extract of methoxypolyethylene glycol methacrylate monomer (side chain of polyethylene glycol with a number average molecular weight of 2080 g / mol), of methacrylic acid (at a rate of 2.77%) and methoxypolyethylene glycol (5.32%);
  • (II) (2) are then added in parallel in the reactor, using metering pumps, over a period of 2 hours. If necessary, to maintain the homogeneity of the mixture (1), the container containing it is kept stirring for two hours of the addition. The solution (2) is homogeneous and does not need to be agitated during the two hours of the addition. During this time, the temperature of the reactor is maintained at least 70 ° C. At the end of the addition, the temperature is maintained at least 70 ° C for at least 3 additional hours, then the solution is cooled to room temperature. The solids content of the aqueous dispersant copolymer solution thus obtained was measured by gravimetry at 37.1%. The final viscosity of the solution, which has a Newtonian (non-shear rate dependent) behavior, measured by a Brookfield viscometer, was 414 mPa.s.
  • a model mortar is prepared from 518.5 g of dry cement of the LUMBRES type (CEM I 42.5 R) and 1350 g of standardized sand (CEN EN 196-1), 279 99 g of demineralised water and 2.44 g of the aqueous dispersant copolymer solution, previously added with 1% by weight relative to the solids content of an anti-foaming agent (CLEROL).
  • CLEROL anti-foaming agent
  • the mortar is prepared by mixing, first the water and the dispersant solution. This mixture constitutes the mixing water which is then introduced into a mortar mixer. After adding the cement, the mixer is started at 65 rpm for 30 seconds. After adding the sand, the mixer is once again, started at 65 rpm for 30 seconds. The mixture is kneaded at 125 rpm for 60 seconds.
  • the mortar thus obtained makes it possible to fill the mini-cone of Abrams whose weight and dimensions are as follows:
  • the cone Before filling, the cone is placed on a 50 * 50cm PVC sheet for 1 cm thick, moistened with a sponge.
  • the filling of the cone is carried out according to a well-defined procedure of filling in three times with one third of the height of the filled cone each time all over a total duration of 2 minutes.
  • the contents of the cone are tamped by tapping it with a metal rod 30 cm long and 5 mm in diameter.
  • the filled cone is raised, which causes the spreading of its contents on the support plate.
  • the spreading measurement is taken 30 seconds after lifting the cone by measuring the length of two perpendicular diameters of the slab.
  • the average between these two diameters is the initial spreading measurement of the mortar.
  • the spread mortar is recovered, returned to the mixer and left to rest well covered to prevent the evaporation of water.
  • a mixing at 125 rpm for 60 seconds is performed.
  • the cone is filled according to the mentioned procedure, and the spreading is again measured as indicated above for initial spreading.
  • Table I shows the evolution of the spread as a function of time for the mortar prepared with the dispersant of this example. For comparison, this table also shows the performance of a mortar prepared under the same conditions and with the same values of E / C and% SP from a conventional dispersant (ECOCRYL 5930 from Cray Valley). Table 1
  • a 1-liter glass reactor equipped with a variable speed stirring motor, entries for the introduction of reagents, taps for the introduction of inert gases for the removal of oxygen, such as nitrogen, and measuring probes (for example, temperature), a vapor-reflux condensing system, a jacket for heating / cooling the contents of the reactor through the circulation therein, a 195.6 g of deionized water is introduced, the stirring is started at a moderate speed, the system is heated to reach 60 ° C. in the reactor and degassed by bubbling nitrogen into the liquid. for at least 15 minutes.
  • the following containers are prepared: 1) a mixture comprising: 259.4 g of Norsocryl N402 consisting of a 58% aqueous solution of dry extract of methoxypolyethylene glycol methacrylate monomer (side chain of polyethylene glycol with a number average molecular weight of 2080 g / mol), of methacrylic acid (at a rate of 2.77%) and methoxypolyethylene glycol (5.32%);
  • (II) (2) are then added in parallel in the reactor, using metering pumps, over a period of 2 hours. If necessary, to maintain the homogeneity of the mixture (1), the container containing it is kept stirring for two hours of the addition. The solution (2) is homogeneous and does not need to be agitated during the two hours of the addition. During this time, the temperature of the reactor is maintained at at least 60 ° C. At the end of the addition, the temperature is maintained at at least 60 ° C. for at least another 3 hours, then the solution is cooled to ambient temperature. The solids content of the aqueous dispersant copolymer solution thus obtained was measured gravimetrically at 35.8%. The final viscosity of the solution, which has a Newtonian behavior (no depending on the shear rate), measured by a Brookfield viscometer, was 520 mPa.s.
  • Example 2 In order to measure the fluidizing power of the copolymer, the same procedure described in Example 2 is followed, and the same experimental conditions are used.
  • the mortar is prepared starting from 518.5 g of LUMBERS dry cement (CEM I 42.5 R) and 1350 g of standardized sand (CEN EN 196-1), 279.99 g of deionized water and 2, 53 g of the aqueous dispersant copolymer solution, previously added with 1% by weight relative to the solids content of an anti-foaming agent (CLEROL).
  • Table II shows the evolution of the spread as a function of time for the mortar prepared with the dispersant of this example. For comparison, this table also shows the performance of a mortar prepared under the same conditions and with the same values of E / C and% SP from a conventional dispersant (ECOCRYL 5930 from Cray Valley).
  • the temperature is maintained at at least 70 ° C. and 31 g of a 12% by weight solution of sodium metabisulfite (Aldrich) in demineralized water are introduced into the reactor at 20 ° C. minutes using a dosing pump.
  • the temperature of the reactor is maintained at least 70 ° C. for at least another 3 hours, then the solution is cooled to ambient temperature.
  • the dry extract of the aqueous dispersant copolymer solution thus obtained was measured by gravimetry at 37.8%.
  • the final viscosity of the solution measured by a Brookfield viscometer, was 425 mPa.s.
  • the solution keeps a non-colored appearance as a function of time.
  • a model mortar is prepared from 518.5 g of dry cement of the LUMBRES type (CEM I 42.5 R) and 1350 g of standardized sand (CEN EN 196-1), 279 , 99 g of demineralized water and 2.40 g of the aqueous solution of dispersant copolymer, previously added with 1% by weight relative to the solids content of an anti-foaming agent (CLEROL).
  • Table III shows the evolution of the spread as a function of time for the mortar prepared with the dispersant of this example. For comparison, this table also shows the performance of a mortar prepared under the same conditions and with the same values of E / C and% SP from a conventional dispersant (ECOCRYL 5930 from Cray Valley).
  • Norsocryl N402 consisting of a 58% aqueous solution of dry extract of methoxypolyethylene glycol methacrylate monomer (side chain of polyethylene glycol with a number average molecular weight of 2080 g / mol), of methacrylic acid (at a rate of 2.77%) and methoxypolyethylene glycol (5.32%); 19.2 g of methacrylic acid; and
  • (II) (2) are then added in parallel in the reactor, using metering pumps, over a period of 2 hours. If necessary, to maintain the homogeneity of the mixture (1), the container containing it is maintained under stirring for two hours of addition. The solution (2) is homogeneous and does not need to be agitated during the two hours of the addition. During this time, the temperature of the reactor is maintained at at least 60 ° C. At the end of the addition, the temperature is maintained at at least 60 ° C. and 31 g of a 12% by weight solution of sodium metabisulphite (Aldrich) in demineralized water are introduced into the reactor at 20 ° C. minutes using a dosing pump. The temperature of the reactor is maintained at at least 60 ° C.
  • the solution is cooled to ambient temperature.
  • the dry extract of the aqueous dispersant copolymer solution thus obtained was measured by gravimetry at 37.4%.
  • the solution keeps a non-colored appearance as a function of time.
  • a model mortar is prepared from 518.5 g of dry cement of the LUMBRES type (CEM I 42.5 R) and 1350 g of standardized sand (CEN EN 196-1), 279 , 99 g of demineralized water and 2.42 g of the aqueous dispersant copolymer solution, previously added with 1% by weight relative to the solids content of an anti-foaming agent (CLEROL).
  • Table IV shows the evolution of the spread as a function of time for the mortar prepared with the dispersant of this example.
  • this table also presents the performance of a mortar prepared in the same conditions and with the same values of E / C and% SP from a conventional dispersant (ECOCRYL 5930 from Cray Valley).
  • the following example illustrates the synthesis of a cationic dispersing polymer comprising repeating units resulting from the polymerization of methyl methacrylate and 2- (tert-butylamino) ethyl methacrylate.
  • (II) (2) are then added in parallel in the reactor, using metering pumps, over a period of 60 minutes. During this time, the temperature of the reactor is maintained at at least 50 ° C. At the end of the addition, the temperature is maintained at least 50 ° C. for at least 2 additional hours.
  • a "baking" treatment intended to minimize the residual monomer can then be applied by raising the temperature of the reactor to at least 60 ° C. for at least an additional hour, then the The suspension is cooled to room temperature. The product obtained is in the form of macroscopic particles (grains or beads) in aqueous suspension. The suspension is removed from the reactor and filtered to separate the hydrophobic polymer
  • the grains freed of the excess of aqueous phase are then dried in an oven with vacuum application or not and taking care not to exceed 55 ° C during drying to avoid agglomeration.
  • the dried grains can be crushed and sieved to obtain a final product in the form of a homogeneous white powder.
  • This powder naturally insoluble in water (hydrophobic polymer) can be suspended in water and protonated by the addition of a strong acid, which has the effect of passing it in aqueous solution.
  • a strong acid which has the effect of passing it in aqueous solution.
  • Such a solution can be used as a dispersing or costabilizing additive, inter alia, for the formation of emulsions of organic phases in water (so-called H / E or oil-in-water emulsions), such as bitumen emulsions.
  • the remainder of the preemulsion of monomers (1) and the remainder of the solution of the initiator (II) ( 2) are then added in parallel in the reactor, using dosing pumps, over a period of 120 minutes.
  • the temperature of the reactor is maintained at least 70 ° C.
  • the temperature is maintained at least 70 ° C for at least 2 additional hours.
  • a "baking" treatment intended to minimize the residual monomer may then be applied by raising the temperature of the reactor to at least 80 ° C. for at least another hour.
  • the product of this emulsion polymerization reaction is a bluish white latex. The latex is cooled to room temperature.
  • the resulting latex contains a significant amount of residual methyl methacrylate monomer, which can be converted by the addition of free radical initiators. classic like those described above.
  • the residual monomer can also be removed by evaporation with or without recycling.
  • the final polymethyl methacrylate, essentially free of the residual monomer can be used in the form of a latex or after recovery in the form of a powder, in applications specific to polymeric materials or as a preparation additive, such as adhesives, cosmetics, plastic or mineral materials, paints or coatings.

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EP07726608A 2006-03-02 2007-03-02 Verfahren zur kontrollierten radikalpolymerisation oder -copolymerisation eines oder mehrerer monomere in gegenwart eines alkoxyamin-initiators Withdrawn EP1989256A1 (de)

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PCT/EP2007/052014 WO2007099167A1 (fr) 2006-03-02 2007-03-02 Procede de polymerisation ou copolymerisation radicalaire controlee d'un ou plusieurs monomeres en presence d'un amorceur de type alcoxyamine

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CN102351972B (zh) * 2011-07-28 2014-04-23 中山大学 一种含烷氧胺基团的热可逆自修复交联聚合物
CN104334589B (zh) * 2012-04-04 2018-02-06 罗地亚经营管理公司 由丙烯酸、其盐之一或它们的混合物合成聚合物的方法
KR101684649B1 (ko) * 2014-06-13 2016-12-08 주식회사 엘지화학 고흡수성 수지의 제조 방법 및 이를 통해 제조된 고흡수성 수지
FR3030526B1 (fr) * 2014-12-18 2018-06-15 Arkema France Polymerisation radicalaire d'alcoxyamines a basse temperature
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DE19909028A1 (de) * 1999-03-02 2000-09-07 Aventis Res & Tech Gmbh & Co Sulfonierte aromatische Polymere, Membran enthaltend diese Polymeren, Verfahren zu deren Herstellung und deren Verwendung
WO2000053640A1 (en) * 1999-03-09 2000-09-14 Symyx Technologies, Inc. Controlled free radical emulsion and water-based polymerizations and seeded methodologies
FR2807439B1 (fr) * 2000-04-07 2003-06-13 Atofina Polymeres multimodaux par polymerisation radicalaire controlee en presence d'alcoxyamines
WO2003062293A1 (fr) * 2002-01-22 2003-07-31 Atofina Procede de fabrication et utilisation de materiaux renforces au choc contenant des copolymeres blocs obtenus par polymerisation radicalaire controlee en presence de nitroxydes
US6762263B2 (en) * 2002-02-01 2004-07-13 Atofina Chemicals, Inc. High-solids coatings resins via controlled radical polymerization
FR2843394B1 (fr) * 2002-08-07 2005-12-30 Atofina Alcoxyamines issues de nitroxydes b-phosphore, leur utilisation en polymerisation radicalaire
FR2848557B1 (fr) * 2002-12-13 2006-07-07 Atofina Copolymeres a gradient solubles ou du moins dispersibles dans l'eau comme dans les solvants organiques
FR2864455B1 (fr) * 2003-12-24 2006-03-17 Coatex Sas Utilisation de polymeres hydrosolubles structures obtenus par polymerisation radicalaire controlee comme dispersant et agent d'aide au broyage de matieres minerales
FR2866026B1 (fr) * 2004-02-06 2008-05-23 Arkema Procede de polymerisation radicalaire en emulsion mettant en oeuvre des alcoxyamines hydrosolubles

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FR2898127A1 (fr) 2007-09-07
CN101405337A (zh) 2009-04-08
FR2898127B1 (fr) 2008-07-11
BRPI0708472A2 (pt) 2011-05-31

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