EP2049573A2 - Verfahren zur radikalischen polymerisation in wässriger dispersion zur herstellung von polymeren - Google Patents

Verfahren zur radikalischen polymerisation in wässriger dispersion zur herstellung von polymeren

Info

Publication number
EP2049573A2
EP2049573A2 EP07787075A EP07787075A EP2049573A2 EP 2049573 A2 EP2049573 A2 EP 2049573A2 EP 07787075 A EP07787075 A EP 07787075A EP 07787075 A EP07787075 A EP 07787075A EP 2049573 A2 EP2049573 A2 EP 2049573A2
Authority
EP
European Patent Office
Prior art keywords
water
soluble
derivatives
vinyl
reactor
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Withdrawn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
EP07787075A
Other languages
English (en)
French (fr)
Inventor
Patrick Lacroix-Desmazes
Jeff Tonnar
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.)
Macro M SA de CV
Original Assignee
Centro de Investigacion y Desarollo Technologico SA de CV CENIDET
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 Centro de Investigacion y Desarollo Technologico SA de CV CENIDET filed Critical Centro de Investigacion y Desarollo Technologico SA de CV CENIDET
Publication of EP2049573A2 publication Critical patent/EP2049573A2/de
Withdrawn legal-status Critical Current

Links

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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • 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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • 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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • 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
    • C08F4/40—Redox systems
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the present invention relates to a radical polymerization process in aqueous dispersion for the preparation of polymers and a radical polymerization process in aqueous dispersion for the preparation of block copolymers.
  • radical polymerization is the chain polymerization mechanism that accommodates the least demanding experimental conditions and the widest range of monomers, giving it the characteristics of a living polymerization has remained a major challenge for a very long time.
  • the main limitation of conventional free-radical polymerization stems from the crucial importance of irreversible termination reactions, by combination and / or disproportionation of the radicals responsible for chain growth.
  • the growing chains are primed, grow and then end randomly and irreversibly, along with the priming of new chains.
  • the polymerization ends when all the polymer chains are inactive, which are of variable length and unpredictable. This technique therefore offers little opportunity to act on the molar mass, the distribution of molar masses, the nature of the chain ends and, more generally, the molecular structure of the polymer.
  • nitroxide-controlled radical polymerization Nonroxide-Mediated Polymerization or NMP
  • Atom Transfer Radical Polymerization ATRP
  • addition-fragmentation chain transfer Reversible Addition- Fragmentation Chain Transfer Polymerization or RAFT / MADIX
  • ITP iodine Transfer Polymerization
  • Iodine Transfer Polymerization or RITP using iodine as a control agent has also been developed.
  • the application WO 03/097704 discloses such a controlled radical polymerization process according to which at least one ethylenically unsaturated monomer is polymerized in the presence of at least one radical-generating agent and molecular iodine.
  • the target average molar mass (M n ) of the polymer is controlled by the ratio between the mass of monomer and twice the number of initial moles of iodine (n 12; mit1 ai) according to equation 1 below, in which MA-I is the molar mass of the chain ends:
  • M n (mass of monomer) / (2x ni2, mitiai) + MA-I (equation 1) If the text of the application WO 03/097704 describes the polymerization of vinyl chloride in aqueous suspension, the process in question does not allow, however, not to obtain a polymer whose experimental average molar mass (20 000) is very close to the theoretical average molar mass (target molecular weight taking into account the conversion rate) (8700).
  • the present invention therefore relates to a radical polymerization process in aqueous dispersion for the preparation of polymers which allows a better control of the polymerization and therefore the average molar mass of the polymers obtained compared to the processes of the prior art while preserving their benefits.
  • the invention relates to a radical polymerization process in aqueous dispersion for the preparation of polymers using
  • At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • polymerization in aqueous dispersion is meant the polymerization processes taking place in water in the presence of at least one surfactant.
  • At least one surfactant it is meant that the polymerization process can take place in the presence of one or more surfactants.
  • surfactant any compound having in its structure one or more hydrophilic parts and one or more hydrophobic parts. This hydrophilic / hydrophobic balance allows the surfactant to have an interfacial activity which makes it possible to ensure dispersion and stabilization of the aqueous and organic phases in the presence.
  • Some polymerizations in aqueous dispersion can be carried out in the absence of surfactant but with the consequence of the formation of aqueous dispersions unstable and characterized by a very low solids content.
  • the present invention does not relate to such polymerizations but to polymerizations in aqueous dispersion carried out in the presence of at least one surfactant.
  • dispersing agents also called protective colloids or suspending agents (hereinafter referred to as dispersing agents), but also emulsifiers.
  • aqueous dispersion polymerization is intended to denote radical polymerization in aqueous suspension, radical polymerization in aqueous microsuspension, radical polymerization in aqueous emulsion and radical polymerization in aqueous miniemulsion.
  • radical polymerization in aqueous suspension is meant any radical polymerization process being carried out in an aqueous medium in the presence of dispersing agents as surfactants and oil-soluble radical generating agents.
  • aqueous microsuspension also called homogenized aqueous dispersion
  • any radical polymerization process in which is implemented oil-soluble radical generating agents and is carried out an emulsion of monomer droplets through a powerful mechanical agitation and which is characterized by the presence of emulsifying agents as surfactants.
  • radical polymerization in aqueous emulsion is meant any radical polymerization process being carried out in an aqueous medium in the presence of emulsifiers as surfactants and agents for generating water-soluble radicals.
  • the aqueous emulsion polymerization is sometimes also called ab initio emulsion polymerization.
  • aqueous mini-emulsion polymerization is intended to denote any radical polymerization process in which oil-soluble radical generating agents and / or water-soluble radical-generating agents and a hydrophobic agent are used and an emulsion of droplets is produced. of monomers thanks to a powerful mechanical agitation and which is characterized by the presence of emulsifiers and optionally dispersing agents as surfactants.
  • dispersing agents By way of examples of dispersing agents, mention may be made of partially hydrolysed polyvinylacetates, gelatin, starch, polyvinylpyrrolidinone, copolymers of vinyl acetate and of maleic anhydride, cellulose-soluble ethers derivatives which are soluble in water. water such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose.
  • the dispersing agents are water-soluble cellulosic ether derivatives.
  • hydroxypropyl methylcellulose is particularly preferred.
  • the emulsifiers may be anionic emulsifiers, nonionic emulsifiers or cationic emulsifiers.
  • alkyl sulphates such as sodium lauryl sulphate, alkyl sulphonates such as sodium dodecylbenzene sulphonate and pure sodium 1-hexadecanesulphonate or in the form of a mixture of C 12 -C 20 alkyl sulphonates sometimes called paraffins sulfonates, alkylaryl mono or disulfonates and dialkyl sulfosuccinates such as sodium diethylhexylsulfosuccinate and sodium dihexylsulfosuccinate.
  • nonionic emulsifiers mention may be made in a nonlimiting manner, alkyl- or alkylarylethoxylated derivatives, alkyl- or alkylarylpropoxylated derivatives and sugar esters or ethers.
  • cationic emulsifiers mention may be made of ethoxylated alkylamines and propoxylated alkylamines.
  • the emulsifiers are preferably anionic emulsifiers, optionally in admixture with one or more nonionic emulsifiers.
  • Anionic emulsifiers are particularly preferred.
  • the hydrophobic agents may be alkanes such as hexadecane, silanes, siloxanes, perfluorinated alkanes or compounds usually used as pigments, comonomers, transfer agents, initiators or plasticizers as long as they are hydrophobic.
  • the process for the preparation of polymers according to the invention uses at least one ethylenically unsaturated monomer, one of which is used as the main monomer and is chosen from styrene and its derivatives, the acid acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N monomers -vinyliques.
  • ethylenically unsaturated monomer By at least one ethylenically unsaturated monomer, one of them being used as the main monomer, it is meant that the polymerization process may employ one or more ethylenically unsaturated monomers and that in the case where several monomers are, one of them is the main monomer.
  • main monomer is intended to denote the monomer present in a proportion of at least 100% by weight of the monomer mixture and which will generate at least 100% by weight of the monomeric units of the polymer obtained, where n is the number of monomers in the monomer unit. the monomeric mixture.
  • the ethylenically unsaturated monomer used as the main monomer is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, derivatives vinyls of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers.
  • styrene derivatives mention may be made of para-tert-butylstyrene, para-methylstyrene, meta-methylstyrene, alpha-methylstyrene, para-bromostyrene, para-chlorostyrene and meta- (1-chloroethyl) styrene, para-fluorostyrene, para-trifluoromethylstyrene, meta-trifluoromethylstyrene, pentafluorostyrene, para-acetoxystyrene, para-methoxystyrene, para-tertbutoxystyrene, para-epoxystyrene, para-aminostyrene, alkali metal salts styrene para-sulfonic acid, vinylbenzoic acid, alkali metal salts of vinylbenzoic acid, para-chloromethylstyrene, perfluorooctyleth
  • esters of acrylic acid is meant salts of acrylic acid such as alkali metal salts, acrylic acid protected with a trimethylsilyl group, tert-butyl, tetrahydropyranyl, 1-ethoxyethyl or benzyl, the acrylates alkyl, acrylonitrile, acrylamide and its derivatives.
  • alkyl acrylates mention may be made of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylate and the like.
  • s-butyl isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, stearyl acrylate, acrylate glycidyl, benzyl acrylate, isobornyl acrylate, lauryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-dimethylaminoethyl acrylate, acrylate chloride 2-trimethylaminoethyl, the potassium salt of 3-sulfopropyl acrylate, fluoroalkyl acrylates such as 1,1,2,2-tetrahydroperfluorodecyl acrylate, allyl acrylate, vinyl acrylate, sugars and nucleosides protected or not such as 2-beta-D-glucopyranosyloxyethyl acrylate, n-buty
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • salts of methacrylic acid such as alkali metal salts, methacrylic acid protected with a trimethylsilyl group, tert-butyl, tetrahydropyranyl, 1-ethoxyethyl or benzyl, methacrylates of alkyl, methacrylonitrile, methacrylamide and its derivatives.
  • alkyl methacrylates mention may be made of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, s-butyl methacrylate and methacrylate.
  • methacrylamide derivatives there may be mentioned N, N- (2-hydroxypropyl) methacrylamide, [3- (methacryloylamino) propyl] trimethyl ammonium chloride, methacryloylaminopropyldimethylammonium sulfobetaine.
  • diene monomers mention may be made of butadiene, isoprene, chloroprene and isobutene. Particularly preferred are butadiene and chloroprene.
  • vinyl esters mention may be made of vinyl acetate, vinyl trifluoroacetate, vinyl versatate, the ethylenic ester of tert-decanoic acid (VeoValO), the ethylenic ester of neononanoic acid (VeoVa9 ) and vinyl pivalate. Vinyl acetate is particularly preferred.
  • vinyl ethers there may be mentioned methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, 2-methoxyethyl vinyl ether, 2-chloroethyl vinyl ether, 2-chloroethyl propenyl ether, 3-bromo-n-propyl vinyl ether, 4-chloro-n-butyl vinyl ether, 2-hydroxy ethyl vinyl ether A-hydroxy butyl vinyl ether, 6-hydroxyhexyl vinyl ether, 4-hydroxymethyl cyclohexyl methyl vinyl ether, triethylene glycol monovinyl ether, diethylene glycol monovinyl ether, n-butyldiethoxy vinyl ether, n-hexyl ethoxy vinyl ether, methyl dipropylene glycol vinyl ether, cyclohe
  • vinyl derivatives of pyridine there may be mentioned 4-vinyl pyridine, 3-vinyl pyridine, 2-vinyl pyridine and 1 - (3-sulfopropyl) -2-vinylpyridinium betaine.
  • N-vinyl monomers include N-vinylcarbazole, N-vinylcarbamate, N-vinylcaprolactam, N-vinylpyrrolidinone and N-vinylimidazole.
  • the process according to the invention is therefore advantageously a radical polymerization process in aqueous dispersion for the preparation of polymers of styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives, N-vinyl monomers.
  • polymers is meant homopolymers and copolymers of these monomers as the main monomer.
  • copolymers is meant the copolymers of one of the aforementioned monomers, which is the main monomer, with one or more monomers copolymerizable therewith.
  • the copolymerizable monomers mention may be made, in a non-limiting manner, of the monomers listed above as main monomer but also the monomers of the maleimide, maleate, fumarate and allylic type as well as itaconic acid, cro tonic acid and maleic anhydride.
  • the process according to the invention is preferably a radical polymerization process in aqueous dispersion for the preparation of polymers of styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters and vinyl ethers.
  • the process according to the invention is particularly preferably a radical polymerization process in aqueous dispersion for the preparation of polymers of styrene and its derivatives, acrylic acid and its derivatives and methacrylic acid and its derivatives .
  • the mode of introduction of the ethylenically unsaturated monomer (s) (A) in the process according to the invention may be variable.
  • step (1) in the case where (A) consists of a single ethylenically unsaturated monomer, all the monomer can be introduced in step (1) or a fraction thereof can be introduced in step (1). and the balance in step (2).
  • the introduction to step (2) preferably takes place continuously.
  • step (1) In the case where (A) consists of at least two ethylenically unsaturated monomers, one part of the monomers can be introduced in step (1) and the other part in step (2), preferably in a continuous manner. . In the particular case where (A) consists of a mixture of at least two ethylenically unsaturated monomers, the entire mixture can be introduced in step (1) or a fraction of the mixture can be introduced in step ( 1) and the balance of the same mixture introduced in step (2), preferably in a continuous manner.
  • the process for the preparation of polymers according to the invention uses at least one agent generating radicals chosen from diazocompounds, peroxides and dialkyldiphenylalkanes.
  • At least one radical-generating agent chosen from diazocompounds, peroxides and dialkyldiphenylalkanes it is meant that the polymerization process may use one or more radical-generating agents chosen from diazocompounds, peroxides and dialkyldiphenylalkanes.
  • radical generating agent used in the singular or the plural must be understood as designating one or more radical-generating agents unless it is designated otherwise.
  • the process according to the invention preferably employs at least one agent generating radicals chosen from diazocompounds and peroxides.
  • the process according to the invention uses a single radical-generating agent.
  • the radical-generating agents may be oil-soluble or water-soluble.
  • oil-soluble radical generating agents is meant the soluble radical generating agents in the monomer or monomers, as used for the polymerization in aqueous suspension, microsuspension or aqueous mini-emulsion.
  • water-soluble radical-generating agents is intended to mean the water-soluble radical generating agents as used for the aqueous emulsion or mini-emulsion polymerization.
  • the agent that generates water-soluble radicals may be an oxidizer as defined below.
  • Diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide and didecanoyl peroxide,
  • Organic hydroperoxides such as cumyl hydroperoxide and tert-amyl hydroperoxide,
  • Dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate, dimyristyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di [2-ethylhexyl] peroxydicarbonate, di [4-tert-butyl] cyclohexyl peroxydicarbonate and dicetyl peroxydicarbonate,
  • Peresters such as t-amylperpivalate, t-butylperpivalate, t-amylperoxneodecanoate, t-butylperoxneodecanoate and cumylperoxineodecanoate.
  • water-soluble peroxides mention may be made of
  • Inorganic peroxides such as sodium, potassium and ammonium persulfates,
  • Persulfates of sodium, potassium and ammonium as well as hydrogen peroxide are preferred.
  • the mode of introduction of the radical generating agent (s) (B) in the process according to the invention may be variable.
  • step (1) all of the radical generating agent can be introduced in step (1) or a fraction thereof can be introduced to step (1) and the balance in step (2).
  • the introduction to step (2) preferably takes place continuously.
  • (B) consists of at least two radical generators
  • a part of the radical-generating agents can be introduced in step (1) and the other part in step (2), preferably continuously.
  • step (1) the entire mixture can be introduced in step (1) or a fraction of the mixture can be introduced in step ( 1) and the balance of the same mixture in step (2), preferably continuously.
  • the process according to the invention uses (C) molecular iodine.
  • Molecular iodine can be used as such or in the form of a precursor thereof.
  • precursor a compound capable of forming molecular iodine in the polymerization medium.
  • precursors include iodides of alkali metals, such as sodium iodide or potassium iodide.
  • the conversion of the precursor to molecular iodine can be obtained by adding an oxidant (D ') in the polymerization medium.
  • the oxidant (D ') that can be used for this purpose meets the definition of oxidant (D) as detailed below.
  • the number of moles of molecular iodine (C) relative to the number of moles of (A) is advantageously at least 2.5 ⁇ 10 -5 , preferably at least 5 ⁇ 10 -5 and particularly preferably at least 10 -4 .
  • the number of moles of molecular iodine (C) relative to the number of moles of (A) is advantageously at most 10 -1 and preferably at most 10 -2 .
  • At least 50 mol% of the molecular iodine (C) or its precursor and the oxidant (D ') are introduced into the reactor in step (1).
  • the 100% of the molecular iodine (C) or its precursor and the oxidant (D ') are introduced into the reactor in step (1). They may be introduced in step (1) at one time or in a continuous injection before step (2) begins.
  • the oxidant (D ') may be introduced into the reactor from the beginning of step (1) or delayed, all at once or in a continuous injection.
  • the method according to the invention implements (D) at least one oxidant whose solubility in water is at least 10 g / 1, at least one of which may be one of (B).
  • At least one oxidant (D) is meant that the polymerization process can implement one or more oxidants (D).
  • oxidant (D) is meant any compound which is able to oxidize iodide ions to molecular iodine; in other words, which is capable of generating an oxidation-reduction reaction with the iodide ions so that the iodide ions are oxidized to molecular iodine and the oxidant is reduced in its reduced form and therefore has a potential redox higher than that of the pair I 2 ZI " (0.53).
  • the oxidant (D) according to the invention has a solubility in water of at least
  • oxidants (D) having a solubility in water of at least 10 g / l there may be mentioned in particular sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, the compounds generating MnO 4 " , ClO “ , ClO 2 " , ClO 3 " ions, manganese (III) salts and iron (III) salts such as ferric citrate, ammonic / ferric citrate, ammonic / ferric sulfate, ferric acetylacetonate, ferric bromide, ferric phosphate and ferric pyrophosphate.
  • At least one oxidant at least one of which may be one of (B)
  • at least one of the oxidants (D) is one of the radical-generating agents (B), in particular the one of the water-soluble radical generating agents (B), or that none of the oxidants is one of the radical-generating agents (B), in particular one of the water-soluble radical generating agents (B).
  • the mode of introduction of the oxidant (s) (D) in the process according to the invention may be variable.
  • the whole of (D) can be introduced in step (1) or a fraction of it can be introduced in step (1) and the balance in step (2).
  • the introduction is preferably continuous.
  • the introduction to step (2) preferably takes place continuously.
  • all of (D) is introduced into the reactor between the beginning of step (1) and the moment of step (2) where the conversion rate reaches 70%.
  • the process according to the invention is either an aqueous suspension polymerization process or an aqueous suspension microsuspension polymerization process, preferably in aqueous suspension, for the preparation of polymers employing
  • At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • the process implements (D) at least one oxidant whose solubility in water is from minus 10 g / 1.
  • none of the oxidants is one of the radical-generating agents (B).
  • a single oil-soluble radical generating agent (B) is preferably used.
  • a single oxidant is preferably used as oxidant (D).
  • the preferred oxidant (D) is hydrogen peroxide.
  • the molecular iodine (C) in the form of a precursor and it is then necessary to add an oxidant (D ') in the medium.
  • the added oxidant (D ') is preferably hydrogen peroxide.
  • the total number of moles of oxidant (oxidizing agent (D) and optionally oxidizing agent (D ') relative to the number of moles of molecular iodine is preferably at least 0.5, particularly preferably at least 1.5, of very particularly preferably at least 2 and most preferably at least 3. A ratio of at least 4 is particularly advantageous.
  • the total number of moles of oxidant (oxidant (D) and optionally oxidizing agent (D ') relative to the number of moles of molecular iodine is preferably at most 10, particularly preferably at most 9.
  • the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers which implements
  • At least one of the oxidants (D) may be one of the water-soluble radical generating agents (B), preferably at least one of the oxidizing agents (D). ) is one of the water-soluble radical generating agents (B).
  • the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) and radical-generating agents (B) relative to the number of moles of molecular iodine is preferably at least 1.5, from particularly preferably at least 2, most preferably at least 2.5 and most preferably at least 3. A ratio of at least 4 is particularly preferred.
  • the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers employing (A) at least one ethylenically unsaturated monomer, one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers employing
  • At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • the radical-generating and oxidizing agent is chosen from sodium persulfate, ammonium persulfate and potassium persulfate.
  • the oxidant (D ') may be the radical generating agent (B) and oxidizing agent (D) or an oxidizing agent (D') different from (B), such as, for example, the peroxide of 'hydrogen.
  • the oxidant (D ') is the radical generating agent (B) and oxidizing agent (D).
  • the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers using
  • At least one ethylenically unsaturated monomer one of which is implemented as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, vinyl derivatives of the pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • one of the radical-generating agents is chosen from ammonium 4,4'-azobis (4-cyanovalerate), sodium 4,4'-azobis (4-cyanovalerate) and 4,4-azobis (4-cyanovalerate). potassium azobis (4-cyanovalerate) and the other which is also the oxidant (D) is hydrogen peroxide.
  • the oxidant (D ') is preferably the oxidant (D), thus particularly preferably hydrogen peroxide.
  • the first subvariant is preferred to the second subvariant.
  • the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers implementing
  • At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • the process uses a persulfate chosen from sodium persulfate, ammonium persulfate and potassium persulfate, and hydrogen peroxide.
  • the oxidant (D ') may be one of the two oxidants (D) or an oxidant different from the two oxidants (D).
  • the oxidant (D ') is one of the two oxidants (D), thus particularly preferably one of the above-mentioned persulfates or hydrogen peroxide.
  • the process according to the invention is an aqueous emulsion polymerization process for the preparation of polymers employing
  • At least one ethylenically unsaturated monomer one of which is used as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • the process according to the invention is an aqueous miniemulsion polymerization process for the preparation of polymers using (A) at least one ethylenically unsaturated monomer, one of which is implemented as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienes, vinyl esters, vinyl ethers, vinyl derivatives of the pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers, (B) at least one oil-soluble radical generating agent selected from oil-soluble diazocompounds and oil-soluble peroxides and / or at least one water-soluble radical generating agent selected from water-soluble diazocomposites and water-soluble peroxides, (C) molecular iodine, and
  • the process according to the invention is an aqueous miniemulsion polymerization process for the preparation of polymers using (A) at least one ethylenically unsaturated monomer, one of which between them is implemented as the main monomer and is selected from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, vinyl derivatives of pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers, (B) at least one oil-soluble radical generating agent chosen from oil-soluble diazocompounds and oil-soluble peroxides,
  • the process uses (D) at least one oxidant whose solubility in water is at least 10 g / l.
  • none of the oxidants is one of the radical-generating agents (B).
  • a single oil-soluble radical generating agent (B) is preferably used.
  • a single oxidant is also preferably used as oxidant (D).
  • the preferred oxidant (D) is hydrogen peroxide.
  • the molecular iodine (C) in the form of a precursor and it is then necessary to add an oxidizing agent (D ' ) in the polymerization medium to generate iodine, the added oxidant (D ') is preferably hydrogen peroxide.
  • the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) relative to the number of moles of molecular iodine is preferably at least 0.5, particularly preferably at least 1.5, of very particularly preferably at least 2 and most preferably at least 3. A ratio of at least 4 is particularly advantageous.
  • the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) relative to the number of moles of molecular iodine is preferably at most 10, particularly preferably at most 9.
  • the process according to the invention is an aqueous miniemulsion polymerization process for the preparation of polymers using (A) at least one ethylenically unsaturated monomer, one of which between them is implemented as the main monomer and is chosen from styrene and its derivatives, acrylic acid and its derivatives, methacrylic acid and its derivatives, dienics, vinyl esters, vinyl ethers, derivatives vinyl pyridine, vinylsulphonic acid and its derivatives, vinylphosphonic acid and its derivatives and N-vinyl monomers,
  • the process uses (D) at least one oxidant whose solubility in water is at least 10 g / l, of which at least one is one of (B).
  • a single water-soluble radical generating agent (B) is preferably used.
  • a single oxidant is also preferably used as oxidant (D).
  • the generating agent of water-soluble radicals and the oxidant (D) are particularly preferably the same compound.
  • the particularly preferred oxidant (D) and radical generating agent (B) is selected from sodium persulfate, potassium persulfate and ammonium persulfate.
  • the added oxidant (D ') is preferably the radical generating agent (B) and oxidizing agent (D).
  • the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) and radical-generating agents (B) relative to the number of moles of molecular iodine is preferably at least 1.5, from particularly preferably at least 2, most preferably at least 2.5 and most preferably at least 3. A ratio of at least 4 is particularly preferred.
  • the total number of moles of oxidants (oxidizing agent (D) and optionally oxidizing agent (D ')) and radical generating agents (B) relative to the number of moles of molecular iodine is preferably at most 11, from in a particularly preferred manner of at most 10.
  • means are used by which radicals are generated within it. For this purpose, it can especially heat it or expose it to intense light radiation.
  • the temperature at which the reactor contents is reacted is advantageously at least 30 ° C. and preferably at least 40 ° C. In addition, it is advantageously at most 200 ° C. and preferably at most 120 ° C.
  • step (2) is carried out until the ethylenically unsaturated monomer or monomers have reacted within certain limits.
  • the step (2) is carried out until the conversion rate of the ethylenically unsaturated monomer (s) is preferably at least 82%.
  • Step (2) will be carried out until the conversion rate of the ethylenically unsaturated monomer (s) is preferably at most 100%.
  • the radical polymerization process for the preparation of polymers according to the invention may optionally also comprise a step (3) during which the reaction is terminated by introducing a chemical agent capable of decomposing the excess radical generating agent. and / or extracting the fraction of (A) which has not reacted, these operations being performed simultaneously or successively, in the reactor or outside thereof.
  • the radical polymerization process for the preparation of polymers according to the invention may optionally further comprise a step, subsequent to the preceding steps, in which the polymer is isolated from the reactor contents (step (4)).
  • step (4) all the separation techniques known to those skilled in the art, in particular dewatering and drying in a fluidized bed, may be carried out in addition to the demonomerization treatment already discussed above (especially when the polymer has been produced by a slurry process) and spray drying or coagulation drying (particularly when the polymer has been produced by an emulsion or mini-emulsion process). These operations are advantageously carried out outside the reactor.
  • the present invention relates to a radical polymerization process in aqueous dispersion for the preparation of block copolymers.
  • the invention relates to a radical polymerization process in aqueous dispersion for the preparation of block copolymers using (A ') at least one ethylenically unsaturated monomer chosen from styrene and its derivatives, acrylic acid and its derivatives.
  • (1 ') is introduced into a reactor at least a fraction of (A') and at least a fraction of (E '), then
  • the process for the preparation of block copolymers according to the invention advantageously makes it possible to prepare copolymers comprising two blocks by polymerizing (A ') in the presence of a polymer prepared by the process according to the invention.
  • invention as described above but also copolymers of more than two blocks for example three blocks by polymerizing (A ') in the presence of a precursor block copolymer already comprising two blocks and so on.
  • the radical polymerization process for the preparation of block copolymers according to the invention has the same characteristics and preferences as those described above concerning the radical polymerization process for the preparation of polymers according to the invention, unless contraindicated or unless it is stated otherwise.
  • the number of ethylenically unsaturated monomers constituting (A ') can be any.
  • (E ') can be introduced into the reactor in any form whatsoever, especially in the form of an aqueous powder or dispersion, and after being isolated or not from the reactor contents in which it was previously prepared .
  • (E ') is introduced into the reactor preferably in the form of an aqueous dispersion containing the polymer prepared by the process according to the invention; this being then used as it is for the process of synthesis of block copolymers according to the invention without having undergone prior treatment.
  • the number of polymers constituting (E ') may be any but preferably 1.
  • all of (E ') is introduced into the reactor in step (1').
  • the weight of (E ') with respect to the weight of (A') is advantageously at least 0.05, preferably at least 0.1 and particularly preferably at least 0.5. In addition, it is advantageously at most 19, preferably at most 10 and particularly preferably at most 4.
  • (B ' ) at least one radical generating agent selected from peroxides, diazocompounds and dialkyldiphenylalkanes.
  • (B ') has the same characteristics and preferences as (B), and to whatever degree of preference it is.
  • (B ') may be introduced entirely in step (1'), partly in step (1 ') and partly in step (2') or completely in step (2 ').
  • step (3 ') it is possible, for example, to cool the contents of the reactor and / or introduce therein a chemical agent capable of decomposing the excess radical generating agent and / or extracting the fraction thereof.
  • (A ') which has not reacted (demonomerization) these operations can be performed simultaneously or successively, in the reactor or outside thereof.
  • the demonomerization operation can be carried out as described above for step (3).
  • the radical polymerization process for the preparation of block copolymers according to the invention may optionally further comprise a step (4 '), subsequent to the preceding steps, wherein the copolymer is isolated from the reactor contents.
  • Step (4 ') can be performed as previously described for step (4).
  • the radical polymerization method in aqueous dispersion for the preparation of polymers according to the invention has multiple advantages.
  • the process according to the invention makes it possible to improve the control of the number-average molecular weight (or weight) of the polymers prepared in dispersion. aqueous as well as their polydispersity.
  • the difference between the theoretical molecular mass and the experimental molecular mass is significantly smaller than in the case of the previous process.
  • radical polymerization process for the preparation of polymers and the radical polymerization process for the preparation of block copolymers according to the invention is that the growth of the polymer chains prepared in aqueous dispersion can be restarted by reacting the polymers with ethylenically unsaturated monomers, identical or different from those which had been polymerized beforehand. In this way, block copolymers can be prepared.
  • radical polymerization process it is not usually possible to synthesize such copolymers.
  • radical polymerization processes according to the invention do not require the use of usually expensive raw materials such as iodinated organic transfer agents.
  • a last specific advantage to the first sub-variant of the first particularly preferred variant of the second embodiment is that it is entirely appropriate for industrial operation in terms of saving industrial hygiene costs.
  • the degree of conversion to monomers was determined by gravimetric analysis in an aluminum cup. For this, a known amount of aqueous dispersion was weighed. A grain of inhibitor was then added to stop the polymerization and the water and residual monomer were evaporated. The dry polymer extract was recovered after drying under vacuum at 40 ° C. and the degree of conversion calculated according to the equation: (Esf-Eso) / (Esth-Eso) in which Esf is the final dry extract, Eso is the initial extract and Esth is the theoretical final dry extract at 100% conversion. Determination of molecular weights
  • the target molecular weight (M njVls e e ), for a 100% conversion, was determined by applying the formula according to equation (1) namely M njVls ee (monomer mass) / (2x ni2, mitiai) + MA-I (equation 1) according to which nomai is the number of initial moles of molecular iodine and M A - I is the molar mass of the chain ends (A being the end of chain from the radical generating agent and I being the iodine atom).
  • the experimental molecular weight (M njexp ) was determined by steric exclusion chromatography on dry samples dissolved in tetrahydrofuran using a Spectra Physics Instruments SP8810 pump equipped with a Shodex RIse-61 refractometric detector, a spectrometric detector Milton Roy Ultra-Violet and two columns thermostated at 30 ° C.
  • Tetrahydrofuran was used as eluent at a flow rate of 1 ml.min -1 . Calibration was performed using polystyrene standards from Polymer Laboratories.
  • the polydispersity index PDI M w / M n is the ratio of the weight-average molecular weight to the number-average molecular mass determined by steric exclusion chromatography. Determination of the average diameter
  • the average particle diameter of the aqueous dispersion (d p ) was determined using a Nanotrac Particle Size Analyzer 250 particle analyzer (Microtrac Inc.) based on the retro-scattering of light and the Doppler effect.
  • a polyBuA-b- [poly (BuA-co-styrene)] block copolymer was prepared by seeded polymerization of styrene.
  • 40.45 g (0.64 mmol) of the aqueous dispersion obtained in Example 1 (80% conversion) was introduced into a 100 ml glass reactor and purged by bubbling argon for 20 minutes.
  • the reaction medium was stirred for 1 hour and the polymerization continued under argon in the absence of light and for 14 hours at 75 ° C.
  • the intended molecular weight (M njVls é e), the polymerization time, the conversion rate, the theoretical molecular weight (M n> th), the experimental molecular weight (M njeX p), the polydispersity index (PDI ) measured on the obtained block copolymer are shown in Table 2 as well as the average particle diameter of the aqueous dispersion (d p ).
  • Example 8 was reproduced in the absence of iodine, hydrochloric acid and hydrogen peroxide, all other conditions being equal.
  • the pH measured at the end of the experiment after recovery of the aqueous dispersion was 4.74.
  • the polymerization time, the conversion rate, the experimental molecular mass (M n> exp ), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are shown in Table 3.
  • Example 10 comparativative
  • Example 8 was repeated in the absence of hydrochloric acid and hydrogen peroxide and with a Perkadox / iodine ratio of 2 instead of 2.5, all other conditions being equal.
  • the pH of the aqueous phase measured at the end of the experiment after recovery of the aqueous dispersion was 2.36.
  • the polymerization time, the conversion rate, the experimental molecular weight (M n> exp ), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are given in Table 3.
  • the target molecular weight (M njVls e e ), the polymerization time, the conversion rate, the experimental molecular weight (M njexp ), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are shown in Table 3.
  • Example 11 (according to the invention)
  • Example 8 was reproduced in the absence of hydrochloric acid, all other conditions being equal.
  • the pH of the aqueous phase measured at the end of the experiment after recovery of the aqueous dispersion was 6.75 and the polymerization time was 18 hours.
  • the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 3.
  • Example 9 In the absence of iodine (Example 9), the PDI is much higher and the polymer obtained does not allow to restart the chains to make a block copolymer.
  • Example 13 (according to the invention)
  • the target molecular weight (M njVls e e ), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular weight (M njexp ) and the polydispersity index (PDI) measured on the block copolymer obtained are shown in Table 4 as well as the average particle diameter of the aqueous dispersion (d p ).
  • the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 5.
  • the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 6.
  • the intended molecular weight (M njVls é e), the polymerization time, conversion rate, the theoretical molecular weight (M n> th), the experimental molecular weight (M njeX p) and the polydispersity index (PDI ) measured on the block copolymer obtained are shown in Table 7 as well as the average particle diameter of the aqueous dispersion (d p ).
  • the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the mean particle diameter of the aqueous dispersion (d p ) are given in Table 8.
  • the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (Mn, target), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M nyX p), the polydispersity index (PDI) and the average particle diameter of the aqueous dispersion (d p ) are given in Table 9.
  • the molar ratio [hydrogen peroxide] / [I2], the target molecular weight (M njVls ee), the polymerization time, the conversion rate, the theoretical molecular weight (M n> t h), the experimental molecular mass (M njeX p), the polydispersity index (PDI) are shown in Table 10.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)
EP07787075A 2006-07-04 2007-07-04 Verfahren zur radikalischen polymerisation in wässriger dispersion zur herstellung von polymeren Withdrawn EP2049573A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0606079A FR2903409A1 (fr) 2006-07-04 2006-07-04 Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres
US81827606P 2006-07-05 2006-07-05
PCT/EP2007/056779 WO2008003729A2 (fr) 2006-07-04 2007-07-04 Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres

Publications (1)

Publication Number Publication Date
EP2049573A2 true EP2049573A2 (de) 2009-04-22

Family

ID=37719193

Family Applications (2)

Application Number Title Priority Date Filing Date
EP07787074.9A Active EP2041185B1 (de) 2006-07-04 2007-07-04 Polymerisierungsverfahren mit freien radikalen in wässriger dispersion zur herstellung eines blockcopolymers mit mindestens einem halogenierten polymerblock
EP07787075A Withdrawn EP2049573A2 (de) 2006-07-04 2007-07-04 Verfahren zur radikalischen polymerisation in wässriger dispersion zur herstellung von polymeren

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP07787074.9A Active EP2041185B1 (de) 2006-07-04 2007-07-04 Polymerisierungsverfahren mit freien radikalen in wässriger dispersion zur herstellung eines blockcopolymers mit mindestens einem halogenierten polymerblock

Country Status (6)

Country Link
US (2) US8541524B2 (de)
EP (2) EP2041185B1 (de)
JP (1) JP5201419B2 (de)
FR (1) FR2903409A1 (de)
MX (1) MX2008016485A (de)
WO (2) WO2008003728A1 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7741524B2 (en) 2003-04-22 2010-06-22 Solvay (Societe Anonyme) Iodinated organic substances of low molecular mass and process for preparing them
FR2903409A1 (fr) * 2006-07-04 2008-01-11 Solvay Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres
DE102008054482A1 (de) * 2008-12-10 2010-06-17 Wacker Chemie Ag Pfropfcopolymere und deren Verwendung als Low-Profile-Additive
JP2013018953A (ja) * 2011-06-15 2013-01-31 Canon Inc 高分子粒子の製造方法
KR101507999B1 (ko) 2011-08-03 2015-04-07 인하대학교 산학협력단 Ｒｉｔｐ 중합법과 용액 재결정법을 이용한 안정화된 단분산 구형 고분자 입자의 제조 방법
JP6312599B2 (ja) * 2011-12-21 2018-04-18 ソルヴェイ（ソシエテ アノニム） 塩化ビニリデン重合体の製造方法
US9394394B2 (en) * 2013-09-30 2016-07-19 Honeywell International Inc. Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization
FR3053970A1 (fr) 2016-07-13 2018-01-19 Centre National De La Recherche Scientifique (Cnrs) Procede de synthese d'une polyolefine par romp en presence d'un catalyseur a base de ruthenium
EP4107229A4 (de) 2020-02-21 2024-03-06 Swimc LLC Fleckenblockierende polymere, primer, kits und verfahren
CN117715885A (zh) 2021-07-30 2024-03-15 巴斯夫欧洲公司 组合物及其在受控活性水基乳液聚合中的应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003097704A1 (fr) * 2002-05-17 2003-11-27 Solvay (Société Anonyme) Procedes de polymerisation radicalaire et polymeres halogenes

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467636A (en) 1967-02-24 1969-09-16 Du Pont Redox catalyst system for preparing vinylidene fluoride interpolymers
LU73211A1 (de) 1975-08-18 1977-04-15
JPS5386787A (en) * 1977-09-30 1978-07-31 Daikin Ind Ltd Polymer having fluorine-containing segment and its production
JPS63260914A (ja) * 1987-04-17 1988-10-27 Nippon Mektron Ltd ブロツク共重合体の製造方法
BE1007648A3 (fr) 1993-10-21 1995-09-05 Solvay Procede pour la polymerisation radicalaire du chlorure de vinyle a ph acide en dispersion aqueuse.
EP1026152B1 (de) * 1997-03-31 2006-07-26 Daikin Industries, Limited Verfahren zur herstellung von perfluorvinylethersulfonsäure-derivaten
EP0947527A1 (de) 1998-04-03 1999-10-06 The B.F. Goodrich Company Wässrige Blockcopolymere und ein Verfahren zu deren Herstellung
US6911515B2 (en) 2001-03-23 2005-06-28 University Of Pennsylvania Aqueous room temperature living radical polymerization of vinyl halides
FR2826658B1 (fr) * 2001-06-29 2003-09-05 Rhodia Chimie Sa Synthese de polymeres par voie radicalaire controlee en miniemulsion
FR2839725A1 (fr) * 2002-05-17 2003-11-21 Solvay Polymeres alpha-fluoroacryliques a faible indice de polydispersite, procede pour les synthetiser et procede de fabrication d'articles les mettant en oeuvre
US7034085B2 (en) 2002-07-23 2006-04-25 Nuplex Resins, B.V. Method for polymerizing ethylenically unsaturated monomers by degenerative iodine transfer
WO2004094356A1 (en) 2003-04-22 2004-11-04 Solvay (Societe Anonyme) Iodinated organic substances of low molecular mass and process for preparing them
FR2858319B1 (fr) 2003-08-01 2005-09-23 Solvay Procede de preparation de substances organiques iodees de faible masse moleculaire et substances organiques iodees de faible masse moleculaire
US7741524B2 (en) 2003-04-22 2010-06-22 Solvay (Societe Anonyme) Iodinated organic substances of low molecular mass and process for preparing them
FR2896505B1 (fr) 2006-01-26 2008-03-07 Rhodia Recherches & Tech Procede de preparation par polymerisation par transfert d'iode d'un copolymere a architecture controlee de type telomere ou de copolymere a bloc issu de monomeres vinyl phosphonate
FR2903409A1 (fr) * 2006-07-04 2008-01-11 Solvay Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres
EP2158237B1 (de) * 2007-06-21 2012-10-24 DSM IP Assets B.V. Verfahren zum erhalt von niedrigen niveaus freier monomere in einer mittels (inverser) iodtransferpolymerisation hergestellten blockcopolymeremulsion

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003097704A1 (fr) * 2002-05-17 2003-11-27 Solvay (Société Anonyme) Procedes de polymerisation radicalaire et polymeres halogenes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. TONNAR, P. LACROIX-DESMAZES, B. BOUTEVIN: "Controlled radical polymerization of styrene by reverse iodine transfer polymerization (RITP) in miniemulsion: Use of hydrogen peroxide as oxidant", MACROMOLECULES, vol. 40, 22 December 2006 (2006-12-22), pages 186 - 190 *
See also references of WO2008003729A2 *

Also Published As

Publication number Publication date
US8541524B2 (en) 2013-09-24
US20090292071A1 (en) 2009-11-26
US20090306302A1 (en) 2009-12-10
JP5201419B2 (ja) 2013-06-05
JP2009541567A (ja) 2009-11-26
FR2903409A1 (fr) 2008-01-11
WO2008003729A3 (fr) 2008-05-08
WO2008003728A1 (en) 2008-01-10
EP2041185A1 (de) 2009-04-01
MX2008016485A (es) 2009-02-25
EP2041185B1 (de) 2019-01-09
WO2008003729A2 (fr) 2008-01-10

Similar Documents

Publication Publication Date Title
WO2008003729A2 (fr) Procede de polymerisation radicalaire en dispersion aqueuse pour la preparation de polymeres
EP1711536B1 (de) Verfahren zur radikalischen emulsionspolymerisation unter verwendung von wasserlöslichen alkoxyaminen
EP0991683B1 (de) Verfahren zur herstellung von blockcopolymeren durch kontrollierte radikalische polymerisation
EP1044231B1 (de) Verfahren zur herstellung von blockcopolymeren durch eine kontrollierte radikalpolymerisation mit dithioester
EP2780383B1 (de) Herstellung von amphiphilen blockpolymeren durch kontrollierte radikalische mizellare polymerisation
CA2343339C (fr) Polymeres multimodaux par polymerisation radicalaire controlee en presence d'alcoxyamines
FR2781487A1 (fr) Polymerisation en emulsion en presence d'un radical libre stable
EP1319043B1 (de) Latex mit modifizierten eigenschaften durch zugabe eines wasserlöslichen amphiphilen polymers
EP1976888A1 (de) Verfahren zur herstellung eines copolymers mit kontrollierter architektur vom telomer- oder blockcopolymer-typ, erhalten aus vinylphosphonatmonomeren durch iodtransferpolymerisation
EP2621959A1 (de) Herstellung von hydrophilen polymeren mit hoher masse durch kontrollierte radikalische polymerisation
EP1263796B1 (de) Herstellungsverfahren von einem latex mit hohem feststoffgehalt, mit einer niedrigen viskosität und eine einer bimodalen verteilung
Wang et al. Xanthates in RAFT polymerization
FR2826658A1 (fr) Synthese de polymeres par voie radicalaire controlee en miniemulsion
FR2861400A1 (fr) Procede pour preparer un latex a chimie de surface modifiee, le latex susceptible d'etre obtenu par ce procede et ses utilisations dans le domaine de la construction
EP1527105B1 (de) Synthese von statistischen mikrogelen durch kontrollierte radikalpolymerisation
FR2799471A1 (fr) Procede de preparation de polymeres greffes
FR2720751A1 (fr) Copolymère polyoléfinique greffe.
CN117715885A (zh) 组合物及其在受控活性水基乳液聚合中的应用
WO2012080646A1 (fr) Procede de preparation en emulsion d'un pvc greffe sur elastomere vinyl aromatique
FR2937037A1 (fr) Compositions moulables a base de polymere d'halogenure de vinyle.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090129

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20100420

R17D Deferred search report published (corrected)

Effective date: 20080508

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MACRO-M S.A. DE C.V.

RIC1 Information provided on ipc code assigned before grant

Ipc: C08F 293/00 20060101ALI20130123BHEP

Ipc: C08F 2/22 20060101ALI20130123BHEP

Ipc: C08F 2/16 20060101AFI20130123BHEP

Ipc: C08F 4/04 20060101ALI20130123BHEP

Ipc: C08F 2/38 20060101ALI20130123BHEP

Ipc: C08F 4/40 20060101ALI20130123BHEP

Ipc: C08F 2/18 20060101ALI20130123BHEP

Ipc: C08F 214/06 20060101ALI20130123BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130723