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
  • 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
  • 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
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/20—Aqueous medium with the aid of macromolecular dispersing 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
  • 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
• • 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
• • 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
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C

Definitions

• the invention relates to a. process for the preparation in water of a polymer comprising the preparation of an emulsion comprising a HASE copolymer and a mixture of a monomer comprising at least one polymerizable olefinic monomer and a radical-generating compound, the polymerization of the emulsified monomer by heating at a temperature above the temperature required for the polymerization reaction.
• the invention also relates to the polymer prepared and its use.
• the processes of the state of the art for the preparation of emulsion polymers require the use of large amounts of surface-active compounds.
• the known processes do not always make it possible to control the size of the emulsified monomer particles or the size. monomer particles prepared.
• the processes for preparing polymers in aqueous medium of the state of the art do not always make it possible to achieve high solids levels.
• the process according to the invention makes it possible to provide a solution to all or part of the problems of the processes of the state of the art.
• the invention provides a method for preparing in water a polymer (PI) comprising:
• the process according to the invention can be carried out with reduced or very small amounts of surfactant compound (less than 5% by weight of monomer, preferably less than 3% by weight or less than 1% by weight monomer), or even in the absence of surfactant compound.
• droplets of monomer (b1) are dispersed by means of the copolymer (P2) of the HASE type.
• the polymer droplets (PI) are also dispersed by means of the copolymer (P2).
• the droplets formed during the implementation of the process according to the invention have a controlled size.
• the droplets of monomer (b1) or of polymer (P1) have a size ranging from 50 nm to 50 ⁇ m, more preferably from 50 nm to 500 nm or from 1 ⁇ m to 50 ⁇ m.
• the size of the monomer (b 1) or polymer (PI) droplets may also range from 50 nm to 1 ⁇ m, or from 500 nm to 50 ⁇ m,
• the monomer (bl) or polymer (PI) emulsion which is prepared using the HASE type (P2) copolymer has a dry extract which can vary rather widely.
• this solids content ranges from 10% by weight to 50% by weight, preferably from 5% by weight to 45% by weight or from 20% by weight to 40% by weight of emulsion.
• the copolymer (P2) used by the process according to the invention can generally be known as such.
• This copolymer (P2) is a HASE (Hydrophobically Modified Alkali-Soluble Emulsion) type polymer or hydrophobically modified polymeric emulsion which is rendered soluble by a basic treatment. It is a linear or crosslinked acrylic copolymer comprising acidic groups and hydrophobic groups.
• HASE copolymer results from the copolymerization of anionic monomers, such as acrylic or methacrylic acids, hydrophobic nonionic monomers and hydrophobic associative macromonomers.
• the HASE type acrylic copolymer is insoluble in water and is present in the form of a latex.
• the anionic groups are partially or completely neutralized and the copolymer solubilizes in water.
• the polymer (P2) of the HASE type is obtained by polymerization reaction: (ai) at least one anionic monomer comprising at least one polymerizable olefinic unsaturation, preferably an anionic monomer comprising at least one polynerizable olefinic unsaturation and at least one carhoxylic acid function, preferably the anionic monomer is chosen from acrylic acid and methacrylic acid, an acrylic acid salt, a methacrylic acid salt,
• (a2) at least one ester of a compound derived from an acid selected from acrylic acid, methacrylic acid, itaconic acid and maleic acid, preferably acrylic acid or methacrylic acid and
• n and n which may be identical or different, independently represent G or an integer or integer number at 150, m or n is other than G, - OE represents independently a CH 2 CH 2 O group;
• OP is independently a group chosen from CH (CH 3 ) CH 2 0 and CH 2 CH (Cr3 ⁇ 4) G,
• R 1 represents a linear or branched C 6 -C 40 -alkyl group, preferably a linear or branched C 8 -C 20 -alkyl group, and
• R 2 represents a group comprising at least one polymerizable olefinic unsaturation, preferably an acrylate group or a methacrylate group.
• the polymerization reaction of the process according to the invention can employ one or more other monomer (s) ,
• another monomer that can be used during the preparation of the polymer (P2) is a compound (a4) chosen from 2-aciylanudo-2-methylpropanesulphonic acid, ethoxymethacrylate sulfonic acid. sodium methallyl sulfonate, styrene sulfonate and their salts.
• the amount of monomer (a4) can vary quite widely.
• the polymer preparation reaction (P2) implements S 1 0% had weight to 7% by weight, preferably from 0.5% by weight to 5% by weight, more preferably 1% by weight at 3% by weight of monomer (a4) relative to the total amount by weight of monomer.
• another monomer used in the preparation of the polymer (P2) is a crosslinking compound (a5).
• the monomer (a5) is a compound comprising at least two reactive functional groups, in particular two polymerizable olefinic unsaturations.
• the monomer (a5) is preferably chosen from monomers comprising at least two olefinic unsaturations. More preferably, the monomer (a5) is a compound comprising at least two ethylenic unsaturations. Such monomers (a5) are known as such.
• monomers (a5) mention may be made of cross-linking unsaturated monomers, for example polyunsaturated aromatic monomers such as divinylbenzene, divinyl naphihalene and trivinylbenzene, polyunsaturated alicyclic monomers, for example 1,2,4-trivinylcyclohexane, difunctional phthalic acid esters such as diallyl phthalate, polyalkenyl ethers such as triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose and trimethylolpropane diallyl ether, polyunsaturated esters of polyalcohols or polyacids such as 1,6-hexanediol di (mem) acrylate, tetramethylene tri (meth) acrylate, allyl acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, tri
• R 3 is independently H or CH 3 - L ! independently represents a linear or branched C 1 -C 20 -alkylene group and
• p represents independently 0 or an integer ranging from 1 to 30, for example from 1 to 20, in particular from 1 to 15, in particular from 1 to 10,
• - R 5 independently represents H or CH 3
• L 2 independently represents an ethylene, propylene or butylene group
• q is independently 0 or an integer or decimal number ranging from 1 to 30.
• the amount of monomer (a5) can also vary quite widely.
• the preparation reaction of the polymer (P2) uses from 0.01% by weight to 5% by weight, preferably from 0.05% by weight to 3% by weight, more preferably 0.05% by weight. % by weight to 1% by weight of monomer (aS) relative to the total amount by weight of monomer.
• the HASE type copolymer (P2) is partially neutralized by means of a base, for example by means of an alkali metal derivative or an alkalimetal derivative derived from alkali metal. earth.
• the preferred bases are chosen from NaOH, KOH, NH 4 OH, Ca (OH) 2 , monoisopropylamine (AMP), triethylamine, diethylamine and monoethylamine.
• the method according to the invention also comprises the addition with stirring and at a temperature below 40 ° C of at least one monomer (M) comprising at least one polymerizable olefinic unsaturation and at least one compound (b2) generating radicals.
• the solubility in water of the monomer (M) makes it possible to obtain an emulsity during mixing with stirring in the copolymer (P2).
• a dispersion of nanometric droplets of monomer (b) is formed. 1) in water.
• the monomer (b 1) is a nonionic monomer, preferably a nonionic monomer comprising at least one polymerizable olefinic unsaturation, in particular a polymerizable ethylenic unsaturation and in particular a polymerizable vinyl function.
• the monomer (bl) is a nonionic monomer selected from esters of an acid comprising at least one monocarboxylic acid function, in particular an ester of an acid selected from acrylic acid, casetfaacryîique acid, acrylic acid salt, a methacrylic acid salt and mixtures thereof.
• monomer (b1) a compound chosen from styrene, vinylcaprolactaxn, alkyl acrylate, in particular C 1 -C 10 alkyl acrylate, preferentially C 1 -C 4 alkyl acrylate, more preferably acrylate, is preferred.
• Step (b) according to the invention implements at least one compound (b2) generating radicals. It can be soluble in water or soluble in the organic phase, especially in the monomer (bl).
• the radical-generating compound (b2) useful as an initiator or amoreor compound for the polymerization reaction, is an azo compound. More preferably, the radical-generating compound (b2) is a compound selected from azo-bis-isobutyronitrile (AZDN or AIBN), a peroxide compound, preferably benzoyl peroxide, benzoyl hydroperoxide and mixtures thereof. Mention may also be made of alkali metal persulfates, in particular sodium persulfate and potassium persulfate, amnionium persulfate, partially hydrosoluble peroxides, in particular succinic peracid, i-butyl hydroperoxide and hydroperoxide. cumyl, persulfates associated with a ferrous ion, a sulphite ion or a bisulphite ion and mixtures thereof,
• the radical generating compound (b2) can be associated with at least one controlled radical polymerization transfer agent, in particular a Raft transfer agent (reversibh adition-fmgmentation chain transfer or controlled radical polymerization by transfer of reversible chain by addition-fragmentation), for example a derivative of xanihate, preferably dipropyl trithiocarbonate (DPTTC or disodium 2,2 '- (thiocarbonylbisthio) dipropanoate - CAS No. 864970-33-2), n-dodéyl-mercaptan.
• a Raft transfer agent reversibh adition-fmgmentation chain transfer or controlled radical polymerization by transfer of reversible chain by addition-fragmentation
• xanihate preferably dipropyl trithiocarbonate (DPTTC or disodium 2,2 '- (thiocarbonylbisthio) dipropanoate - CAS No. 864970-33-2
• the radical generating compound (b2) preferably a hydrophobic radical generating compound (b2) and the monomer (b1) are added in the form of a mixed.
• the radical generating compound (b2) preferably a hydrophilic radical-generating compound (b2) and the monomer (b1) are added separately or successively, from preferably the radical generating compound (b2) is then added after the monomer (b1).
• the polymerization reaction of the process according to the invention can employ one or more other monomer (s).
• (b1) is a monomer chosen from:
• (b3) at least one hydrophilic nonionic monomer, for example vinyl lactams such as N-vinylpyrrolidone, hydroxypropyl acrylates, hydroxy-C1-C5-alkyl-acrylate, hydroxy-C1-C5-alkyl-methacrylate, acrylamides. methacrylamides, diacetoneacrylamide N-isopropylacrylamide,
• vinyl lactams such as N-vinylpyrrolidone
• hydroxypropyl acrylates hydroxy-C1-C5-alkyl-acrylate
• hydroxy-C1-C5-alkyl-methacrylate hydroxy-C1-C5-alkyl-methacrylate
• acrylamides methacrylamides, diacetoneacrylamide N-isopropylacrylamide
• (b4) at least one anionic monomer, preferably an anionic monomer comprising at least one polymerizable olefinic unsaturation, in particular polymerizable emyelenic unsaturation and in particular a vinyl function polymerizingWe, and at least one carboxylic acid function, preferably a monomer selected from acrylic acid, methacrylic acid, masonic acid, itaconic acid, crotonic acid, an acrylic acid salt, a salt, methacrylic acid, a salt of masic acid, a salt of itaconic acid, a salt of crotonic acid,
• (b5) at least one compound selected from 2-acrylamido-2-methylpropane sulfonyl acid, ethoxymethacrylate sulfonic acid, sodium methallyl sulfonate, styrene sulfonate and their salts and
• the monomer (b6) at least one monomer comprising at least two olefinic maturations. More preferably according to the invention, the monomer (b3) is chosen from hydroxyethylacrylate, hydroxyethylmethacrylate hydroxypropylacrylate hydroxypropylmethacrylate, N-isopropylacrylamide.
• the monomer (b4) is methacrylic acid.
• the amount by weight of monomer (M) used is less than the amount by weight of monomer (b 1).
• the amount of monomer (b5) can vary quite widely.
• the polymerization reaction of the monomer (b1) can carry out from 0.1% by weight to 7% by weight, preferably 0.5% by weight. weight at 5% by weight, more preferably from 1% by weight to 3% by weight of monomer (b5) relative to the total amount by weight of monomer,
• another monomer that can be used during the polymerization of the monomer (b1) is generally a rericulaate compound (b6).
• the monomer (b6) is a compound comprising at least two reactive functional groups, in particular two polymerizable olefinic unsaturations.
• the monomer (b6) is preferably selected from monomers comprising at least two olefinic unsaturations. More preferably, the monomer (b6) is a compound comprising at least two ethylenic unsaturations. Such monomers (b6) are known as such.
• monomer (b6) there may be mentioned the monomers defined as particular monomers (a5) according to the invention.
• the amount of monomer (b6) can also vary quite widely.
• the polymerization reaction of the monomer (b1) can carry out from 0.01% by weight to 5% by weight, preferably from 0.05% by weight to 3% by weight, more preferably from 0.05% by weight to 1% by weight of monomer (b6) relative to the total amount by weight of monomer.
• the temperature of steps (a) and (b) is less than 40 ° C in order to avoid the polymerization of the monomer (b1).
• the temperature of steps (a) and (b), which may be identical or different, may be less than 35 ° C. or less than 25 ° C.
• the heating of step (c) makes it possible to carry out the polymerization of the monomer (b 1).
• the temperature of the stage (e) is greater than 60 ° C, preferably greater than 70 ° C.
• the invention also relates to the polymer (PI) that can be prepared according to the invention.
• the process according to the invention can make it possible to prepare an emulsion in which the monomer (b1) is surrounded by the HASE type copolymer (P2).
• the droplets of monomer (bl) then constitute as many nanoreactors or polymerization microreactors.
• the polymer (P1) formed can then also be in the form of droplets surrounded by copolymer (P2).
• a core-bark composite can therefore be prepared during the implementation of the method according to the invention.
• the invention therefore also relates to a composite comprising at least one polymer (PI) prepared according to the invention surrounded by HASE type copolymer (P2) implemented according to the invention.
• PI polymer
• P2 HASE type copolymer
• a mixture of monomer (b1) and radical generating compound (b1) is added to prepare a monomer emulsion (b1) by means of the copolymer (P2). Then, with stirring and at a temperature of 25 ° C, an aqueous solution of gluconolactonic acid is added.
• the mixture is heated at a temperature of 70 ° C. for 2 hours. Then, the medium is cooled and the polymer (PI) according to the invention is obtained.
• the mixture is heated at a temperature of 70 ° C. for 2 hours. Then, the medium is cooled and the copolymer (PI) according to the invention is obtained.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polymerisation Methods In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Graft Or Block Polymers (AREA)

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• 2016
  • 2016-10-25 FR FR1660345A patent/FR3057867B1/fr not_active Expired - Fee Related
• 2017
  • 2017-10-20 BR BR112019006297A patent/BR112019006297A2/pt not_active Application Discontinuation
  • 2017-10-20 WO PCT/FR2017/052883 patent/WO2018078247A1/fr unknown
  • 2017-10-20 MX MX2019004719A patent/MX2019004719A/es unknown
  • 2017-10-20 KR KR1020197015012A patent/KR20190076002A/ko unknown
  • 2017-10-20 CN CN201780065824.9A patent/CN109863177A/zh active Pending
  • 2017-10-20 US US16/340,849 patent/US20190264019A1/en not_active Abandoned
  • 2017-10-20 EP EP17794391.7A patent/EP3532508A1/fr not_active Withdrawn

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