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WO2025024770A1 - Dispersions polymères de poids moléculaire élevé préparées dans un réacteur discontinu - Google Patents

Dispersions polymères de poids moléculaire élevé préparées dans un réacteur discontinu Download PDF

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Publication number
WO2025024770A1
WO2025024770A1 PCT/US2024/039757 US2024039757W WO2025024770A1 WO 2025024770 A1 WO2025024770 A1 WO 2025024770A1 US 2024039757 W US2024039757 W US 2024039757W WO 2025024770 A1 WO2025024770 A1 WO 2025024770A1
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batch reactor
monomer
ethylenically unsaturated
meth
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Nathalie Bruzzano
Markus BRÖCHER
Christian Boekelo
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Solenis Technologies Cayman LP
Solenis Technologies LP USA
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Solenis Technologies Cayman LP
Solenis Technologies LP USA
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    • 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • 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
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • 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
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide

Definitions

  • the present invention relates a batch reactor containing an aqueous reaction mixture for manufacturing a water-in-water polymer dispersion by radical polymerization, wherein the batch reactor comprises an agitator treated by an abrasive polishing technique, or wherein the batch reactor is free of baffles. Further, the present invention relates to a method of manufacturing a water-in-water polymer dispersion by radical polymerization in the batch reactor. Even further, the present invention relates to the use of the batch reactor in a method of manufacturing a water-in-water polymer dispersion.
  • the foremost objective is to unlock the potential of water and renewable resources to build a safer, healthier, more sustainable world.
  • Numberless industrial processes are water-based processes.
  • the replacement of environmental harmful substances or their volume reduction in water-based processes form the basis towards more sustainable solutions.
  • the invention aims at this foremost objective in the field of water-in-water polymer dispersions (w/w polymer dispersions).
  • w/w polymer dispersions directly correlate with the sustainability in downstream applications, as e.g. in the paper making process.
  • the better such w/w polymer dispersion work as additives in water-based processes, like in the paper making process, the less of such process additives are to be used.
  • substitution of hydrocarbons supports the foremost objective.
  • the water-in-water polymer dispersions are useful as flocculants, dewatering (drainage) aids and retention aids in papermaking besides applications in other technical fields.
  • Paper is manufactured by firstly making an aqueous slurry of cellulosic fibers which slurry has a water content of more than 95 wt-%.
  • the final paper sheet has a water content of less than 5 wt-%.
  • the dewatering (drainage) and retention represent crucial steps in papermaking and are important for an efficient paper making process.
  • High-performance w/w polymer dispersions represent a key factor in the paper making process.
  • a well-known flocculant is given by a w/w polymer dispersion, which is produced by copolymerizing ethylenically unsaturated monomers in an aqueous system comprising a polymeric dispersant resulting in a dispersion comprising the polymeric dispersant and the synthesized copolymer.
  • the US8476391B2 and US7323510B2 represent early publications of such w/w polymer dispersions. It is well-accepted knowledge in this technical field that the addition of separately synthesized copolymers on the one hand and polymer dispersants on the other hand results in a products having completely different properties compared to the w/w polymer dispersions as disclosed in the above patent documents.
  • the invention’s underlaying problem relates to overcoming the drawbacks of the state of the art.
  • the invention’s underlaying problem relates to the provision of means in the process of manufacturing a w/w polymer dispersion resulting in an improved product and resulting in ensuring an improved handling and an improved efficiency of the process of manufacturing w/w polymer dispersions.
  • the invention’s underlaying problems are solved by the subject-matter of claim 1.
  • the invention relates a batch reactor containing an aqueous reaction mixture for manufacturing a water-in-water polymer dispersion by radical polymerization, wherein the aqueous reaction mixture comprises a) a polymeric dispersant; b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more of a non-ionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; and c) an initiator, wherein the batch reactor comprises an agitator treated by an abrasive polishing technique, or wherein the batch reactor is free of baffles.
  • the first alternative refers to the batch reactor comprising an agitator treated by an abrasive polishing technique. That means, before the agitator is used in the batch reactor for applying the method of manufacturing the w/w polymer dispersion, the agitator has been treated accordingly. This action modifies the surface of the agitator.
  • agitators are sometimes covered with a layer of enamel. However, the enamel may chip from the metallic agitator surface. This causes artefacts being present in the product which is associated with major disadvantages.
  • the second alternative feature relates to the baffles being absent in the batch reactor. Baffles cause a mixing of reaction mixtures. However, there evolve spaces being free of a streaming or where the streaming has a very low velocity. Such spaces can be designated as no flow areas or no streaming areas. At surfaces closed to such areas, agglomerations may occur. Such agglomerations deteriorate the final product, or if deposited on the surface of the batch reactor, such depositions may require maintenance. Such maintenance again renders the process inefficient.
  • the two alternative features are characteristics of the batch reactor.
  • the benefits of these two features are associated with the kind of reaction taking place in the batch reactor.
  • the benefits are thus benefits of the batch reactor in which the reaction of manufacturing w/w polymer dispersions takes place.
  • Both alternative features i.e. the agitator treated by the abrasive polishing technique and the batch reactor being free of baffles, may be implemented in one batch reactor.
  • the batch reactor comprises an agitator treated by an abrasive polishing technique, and the batch reactor is free of baffles.
  • the method comprises the provision of a reaction mixture comprising the monomers to be copolymerized and a polymeric dispersant.
  • the monomers are polymerized in presence of the polymeric dispersant in an aqueous medium.
  • a polymer dispersion obtained by the method according to the invention cannot be obtained in that the monomer composition is subjected to a copolymerization, whereupon subsequently after the copolymerization, the polymeric dispersant is added.
  • Unique properties are conferred to the polymer dispersion by applying the method in the batch reactor with said two alternative features, which polymer dispersion represents the final product comprising the copolymer obtained from the radically polymerizable monomers together with the polymeric dispersant.
  • the batch reactor comprises an agitator treated by an abrasive polishing technique, wherein the abrasive polishing technique represents an electropolishing technique.
  • the electropolishing technique exhibits the beneficial effect due to the surface structure induced by the technique.
  • the combination of the kind of manufactured products together with a such treated agitator results in solving the above problems.
  • the electrochemical polishing technique is a known technique of an anodic polishing, or electrolytic polishing being an electrochemical process that removes material from a metallic workpiece, reducing the surface roughness by levelling micro-peaks and valleys, improving the surface finish. Electropolishing is often compared to, but distinctly different from, electrochemical machining.
  • the batch reactor comprises the agitator treated by the electropolishing technique and the inner walls of the batch reactor are covered at least partially by enamel.
  • the non-movable parts of the batch reactor may be covered with enamel because the risk of chipping parts of the enamel is very low.
  • the batch reactor contains an aqueous reaction mixture comprising a polymeric dispersant, a monomer composition, and an initiator.
  • the invention relates to a method of manufacturing a water-in-water polymer dispersion, wherein the method is performed in a batch reactor and the method comprises a step of subjection of an aqueous reaction mixture to a radical polymerization to synthesize a dispersed polymer and to form the water-in-water polymer dispersion, which aqueous reaction mixture comprises a) a polymeric dispersant; b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more of a non-ionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; and c) an initiator, wherein the batch reactor comprises an agitator treated by an abrasive polishing technique, or wherein the batch reactor is free of baffles.
  • the method of manufacturing the w/w polymer dispersion and also the w/w polymer dispersion obtained from the method according to the invention are improved by the characteristics of the batch reactor.
  • the abrasive polishing technique represents an electropolishing technique.
  • the batch reactor comprises the agitator treated by the electropolishing technique and the inner walls of the batch reactor are covered at least partially by enamel.
  • the aqueous reaction mixture comprises a monomer composition comprising radically polymerizable monomers.
  • the monomer composition comprises the radically polymerizable monomers which are selected from the group consisting of one or more of the following: i.
  • R 2 and R 3 are, independently of each other, hydrogen, C 1 -C 5 -alkyl or C 1 -C 5 - hydroxyalkyl, ii.
  • a cationic monomer of formula (II) where alkyl, preferably methyl, and Y is one of , where with one or more groups, or substituted with one hydroxy group; Y2, Y3, Y5, Y6, Y7 independently of each other, are each C1-C6-alkyl, preferably methyl; and Z- is a counterion, preferably a halogen, pseudo-halogen, acetate, or SO 4 CH 3 -; iii.
  • R1 means hydrogen or methyl
  • R 8 is a C 1 -C 6 alkylene group, preferably ethylene or propylene
  • R 5 and R 6 are, independently of each other, each C 1 -C 6 -alkyl, preferably methyl
  • R7 is a C8-C32 alkyl, optionally substituted with one or more hydroxy groups, preferably C12-C20 alkyl, optionally substituted with one hydroxy group
  • Z- is a counterion, preferably a halogen, pseudo-halogen, acetate, or SO 4 CH 3 -; or INTERNATIONAL PATENT APPLICATION 11300PC
  • Z 1 is O, NH, NR 4 , wherein R 4 means C 1 -C 4 -alkyl, preferably methyl, R 1 means hydrogen or methyl, R10 means hydrogen, C8-C32 alkyl, C8-
  • a cationic monomer is a monomer carrying permanently a positive charge.
  • one or more of the above monomers given under items i. to iv. are used as monomers in the monomer composition to be polymerized. It is preferred that a copolymer is polymerized, i.e. that two of the above monomers given under items i. to iv. are provided for the monomer composition to be polymerized. It is preferred that one monomer of item i. and one monomer of item ii.
  • the radically polymerizable monomers comprise a radically polymerizable non- ionic monomer according to general formula (I); and a radically polymerizable cationic monomer according to general formula (II).
  • a radically polymerizable non- ionic monomer according to general formula (I) and a radically polymerizable cationic monomer according to general formula (II).
  • the method is characterized in that the monomer composition comprising the radically polymerizable monomers at least comprises the non-ionic monomer of formula (I) being selected from those in which R 1 means hydrogen or methyl, and R 2 and R 3 are both hydrogen, hydrogen and C1-C3 alkyl, hydrogen and hydroxyethyl, or both C 1 -C 3 alkyl, and/or the cationic monomer of formula (II) being selected from those in which R 1 means hydrogen or methyl, and Z 1 is O, NH or NR4, wherein R4 means methyl, Y1 is C2-C6 alkylene, preferably ethylene or propylene, Y5, Y6 and Y7 are all methyl, and Z- is a halogen.
  • R 1 means hydrogen or methyl
  • R 2 and R 3 are both hydrogen, hydrogen and C1-C3 alkyl, hydrogen and hydroxyethyl, or both C 1 -C 3 alkyl
  • the cationic monomer of formula (II) being
  • the radically polymerizable monomers comprise a radically polymerizable non-ionic monomer according to general formula (I) which is selected from the group consisting of (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N- ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl-N-ethyl(meth)-acrylamide, N- isopropyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide.
  • general formula (I) which is selected from the group consisting of (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N- ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl-N-ethyl(meth)-acrylamide, N- isopropyl(meth)acrylamide
  • the radically polymerizable monomers comprise a radically polymerizable cationic monomer according to general formula (II) which is selected from the group consisting of trimethylammonium-C2-C6-alkyl(meth)acrylate halides, and trimethylammonium-C2-C6- alkyl(meth)acrylamide halides.
  • general formula (II) which is selected from the group consisting of trimethylammonium-C2-C6-alkyl(meth)acrylate halides, and trimethylammonium-C2-C6- alkyl(meth)acrylamide halides.
  • the monomer composition comprises a radically polymerizable monomer being (meth)acrylamide together with a radically polymerizable monomer selected from trimethylammonium-C2-C6-alkyl(meth)acrylate halides, in particular being an acryloyl oxyethyl trimethylammonium halide.
  • the monomer composition comprising radically polymerizable monomers comprises a cross-linker. Cross—linkers are known to the skilled person.
  • the monomer composition preferably contains 0.0001 to 1.25 wt.-% of one or more preferably ethylenically unsaturated cross-linkers, based on the total weight of monomers.
  • ethylenically unsaturated cross-linkers contain 2, 3, 4 or 5 ethylenically unsaturated groups that are radically polymerizable.
  • cross-linkers with two radically polymerizable ethylenically unsaturated groups include: (1) Alkenyl di(meth)acrylates, such as 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, methylene di(meth)acrylate, 2,2’-bis(hydroxymethyl)-1,3-propanediol di(meth)acrylate, and preferably, ethylene glycol di(meth)acrylate, 1.3-propane-diol di(meth)acrylate
  • R 10 is hydrogen or methyl;
  • R 11 is selected from -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 - or -CH2CH2CH2CH2CH2CH2-; and
  • m is an integer in the range 2-50.
  • cross-linkers examples include polypropylene glycol di(meth)acrylates with m in the range 4-25; polybutylene glycol di(meth)acrylates with m in the range 5-40; and, preferably, polyethylene glycol di(meth)acrylates with m in the range 2-45, e.g.
  • additional di(meth)acrylates which may be used include benzylidene di-(meth)- acrylate, bisphenol-A di(meth)acrylate, 1,3-di(meth)acryloyloxy-Z-propanol, hydro-quinone di(meth)acrylate, ethanedithiol di(meth)acrylate, propanedithiol di(meth)acrylate, polyethylene dithiol di(meth)acrylate, and polypropylene dithiol di(meth)acrylate; (5) Divinyl compounds, for example, 1,4-butanediol divinyl ether, divinylbenzene
  • cross-linkers having 3 or more ethylenically unsaturated radically polymerizable groups include glycerin tri(meth)acrylate, 2,2-dihydroxymethyl-1-butanol tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, trimethacrylamide, (meth)allylidene di(meth)-acrylate, 3-allyloxy-1,2- propanediol di(meth)acrylate, triallyl amine, triallyl cyanurate or triallyl isocyanurate; and also (as representative compounds with more than 3 ethylenically unsaturated radically polymerizable groups) pentaerythritol tetra(meth)acrylate and N,N,N'N'-tetra(meth)acryloyl-1 ,5-pentanediamine.
  • cross-linker having 5 ethylenically unsaturated radically polymerizable groups is dipentaerithritol-pentaacrylate.
  • Particularly preferred cross-linkers are selected from the group constsiting of methylene bisacrylamide, polyethylene glycol diacrylate and triallylamine.
  • Further preferred cross-linkers include asymmetrically cross-linkable monomers, i.e. cross-linkable monomers which rely on different functional groups with respect to the incorporation reaction into the polymer backbone and the cross-linking reaction. Examples of such asymmetrically cross-linkable monomers include N'-methylol acrylamide, N'-methylol methacrylamide and glycidyl(meth)acrylate.
  • cross-linkers of this type have the advantage that cross-linking may be initiated subsequently.
  • cross-linking may be performed under different conditions than the radical polymerization of the main- backbone.
  • cross-linking is initiated after changing the reaction conditions, 6.9. the pH value (addition of acid or base), the temperature, and the like.
  • the monomer composition further comprises a hydrophobic monomer, preferably a hydrophobic (meth)acrylic acid C4-18-alkyl ester; and/or an ethylenically unsaturated monomer.
  • the method is characterized in that the radically polymerizable monomers are selected from the non-ionic monomer of formula (I) and/or the cationic monomer of formula (II), wherein the amount of the radically polymerizable monomers being selected from the non-ionic 8 INTERNATIONAL PATENT APPLICATION 11300PC monomer of formula (I) and/or the cationic monomer of formula (II) is between 80 and less than 100 wt-%, preferred 85 and 99 wt-%, most preferred 90 and 95 wt-% based on the total amount of radically polymerizable monomers, wherein the remainder is selected from the group consisting of any other ethylenically polymerizable monomer, a monomer of formula (III), a monomer of formula (IV), and the ethylenically unsaturated cross-linker containing 2, 3, 4 or 5 ethylenically unsaturated groups.
  • the sum of the values in wt-% needs not to amount to 100 wt-%, since further ethylenically unsaturated monomers besides the monomers of formulae (I) and/or (II) may be contained in the monomer composition, i.e. in the reaction mixture, which have to be taken into account when determining the total amount of monomers.
  • the monomer composition consists of monomers (a) and (b) so that the sum of the two values in wt-% amounts to 100 wt-%, i.e. no further monomers are present.
  • the monomer composition comprises - at least 5 wt.-%, preferably at least 20 wt.-% of the non-ionic monomer of formula (I) C1-C5-alkyl or C1-C5-hydroxyalkyl; - at least 5 wt.-%, preferably at least 20 wt.-%, more preferred 25 to 47 wt.-%, most preferred 50.5 to 80 wt.-%, of the cationic monomer of formula (II) Z1 is O, NH or NR4, wherein R4 means C1-C4-alkyl, preferably methyl, and Y is one of where Y0 with one or more hydroxy groups, preferably ethylene or propylene, optionally substituted with one hydroxy group; Y2, Y3, Y5, Y6, Y7 independently of each other, are each C 1 -C 6 -alkyl, preferably methyl; and Z- is a counterion, preferably a halogen,
  • the sum of the values in wt-% needs not to amount to 100 wt-%, since further ethylenically unsaturated monomers besides the monomers of formulae (I) and/or (II) may be contained in the monomer composition, i.e. in the reaction mixture, which have to be taken into account when determining the total amount of monomers.
  • the monomer composition consists of monomers (a) and (b) so that the sum of the two values in wt-% amounts to 100 wt-%, i.e. no further monomers are present. In the present application, all percentages with regard to the monomer composition is based on the total amount of monomers.
  • the aqueous reaction mixture comprises a polymeric dispersant.
  • alternative aqueous polymeric systems are stabilized by low molecular weight salts.
  • a high salt content ensures the stability of the polymeric system.
  • the stabilization of the w/w polymer dispersion according to the invention is basically ensured by the polymeric dispersant. This system renders moot a high salt concentration as in state of the art aqueous polymeric systems.
  • the polymer dispersion has a salt content of less than 15 wt.%, more preferred a salt content of 0.1 to 10 wt.-%, most preferred 1 to 5 wt.-% based on the polymer dispersion.
  • salt content low molecular weight salts are meant.
  • the polymeric electrolytes do not count for the calculation of the salt content.
  • the cationic polymeric dispersant is substantially linear, i.e. is not derived from monomer mixtures containing cross-linkers.
  • the polymeric dispersant is derived from one or more radically polymerizable, ethylenically unsaturated monomers.
  • the polymeric dispersant is derived from one type of a radically polymerizable, ethylenically unsaturated monomer, i.e. the polymeric dispersant is essentially a homopolymer.
  • the term “essentially” means in this regard, that no second type of a monomer is purposely added when synthesizing the polymeric dispersant.
  • the polymeric dispersant is derived from one or more cationic monomers, more preferably from a single cationic monomer.
  • the method is characterized in that the polymeric dispersant is a homopolymer made of the cationic monomer of formula (II) 10 INTERNATIONAL PATENT APPLICATION 11300PC , where preferably methyl, and Y is one of one or more hydroxy with one hydroxy group; Y2, Y3, Y5, Y6, Y7 independently of each other, are each C 1 -C 6 -alkyl, preferably methyl; and Z- is a counterion, preferably a halogen, pseudo-halogen, acetate, or SO4CH3-.
  • Y1, Y2 and Y3 are identical, preferably methyl.
  • Z1 is O or NH
  • Y0 is ethylene or propylene
  • R 1 is hydrogen or methyl
  • Y 1 , Y 2 and Y 3 are methyl.
  • Preferred radically polymerizable cationic monomers according to general formula (II) include quaternized dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl(meth)acrylamides with 1 to 3 C atoms in the alkyl or alkylene groups, more preferably the methyl chloride-quaternized ammonium salt of dimethylamino methyl(meth)acrylate, dimethylamino ethyl(meth)acrylate, dimethylamino propyl(meth)acrylate, diethylamino methyl(meth)acrylate, diethylamino ethyl-(meth)acrylate, diethylamino propyl(meth)acrylate, dimethylamino methyl(meth)acrylamide, dimethylamino ethyl(meth)acrylamide, dimethylamino propyl(meth)acrylamide, diethylamino methyl(meth)acrylamide, diethylamin
  • Quaternized dimethylaminoethyl acrylate and dimethylaminopropylacrylamide are particularly preferred. Quaternization may be affected using dimethyl sulfate, diethyl sulfate, methyl chloride or ethyl chloride. In a preferred embodiment, monomers are quaternized with methyl chloride. In a preferred embodiment, the polymeric dispersant is a homopolymer of trimethylammonium-propyl acrylamide chloride (DIMAPA quat) designated by IUPAC as (3-acrylamidopropyl)trimethylammonium chloride (APTAC).
  • DIMAPA quat trimethylammonium-propyl acrylamide chloride
  • APITAC (3-acrylamidopropyl)trimethylammonium chloride
  • the polymeric dispersant is derived from a monomer composition comprising a cationic monomer selected from the group consisting of (alk)acrylamidoalkyltrialkyl ammonium halides (e.g., trimethylammonium-alkyl(meth)acrylamide halides), (alk)acryloyloxyalkyl trialkyl ammonium halides (e.g., trimethylammoniumalkyl(meth)acrylate halides), alkenyl trialkyl ammonium halides and dialkenyl dialkyl ammonium halides (e.g., diallyldialkylammonium halides).
  • a cationic monomer selected from the group consisting of (alk)acrylamidoalkyltrialkyl ammonium halides (e.g., trimethylammonium-alkyl(meth)acrylamide halides), (alk)acryloyloxyalkyl trialkyl ammonium halides (e.
  • the polymeric dispersant is a cationic polymer derived from a monomer composition comprising a cationic monomer selected from the group consisting of trimethylammonium-alkyl(meth)acrylate halides, trimethylammoniumalkyl(meth)acrylamide halides and diallyldialkylammonium halides.
  • a cationic monomer selected from the group consisting of trimethylammonium-alkyl(meth)acrylate halides, trimethylammoniumalkyl(meth)acrylamide halides and diallyldialkylammonium halides.
  • the aforementioned cationic monomers comprise 6 to 25 carbon atoms, more preferably 7 to 20 carbon atoms, most preferably 7 to 15 carbon atoms and in particular 8 to 12 carbon atoms.
  • the polymeric dispersant is derived from a dialkenyl dialkyl ammonium halide, preferably a diallyl dimethyl ammonium halide (DADMAC).
  • the method is characterized in that the polymeric dispersant is a homopolymer made of a (meth)acryloyl amidopropyl trimethylammonium salt or a (meth)acryloyl oxyethyl trimethylammonium salt.
  • a homopolymer of a (meth)acrylate means, that either the homopolymer is a methacrylate or an acrylate.
  • the halide may be any acceptable halide as e.g. chloride, bromide or iodide;
  • the counter ions of the salts may be any acceptable counter ions as e.g. halides, methosulfate, sulfate or others.
  • the method is characterized in that the polymeric dispersant has a weight average molecular weight Mw as determined by size exclusion chromatography of 40.000 to less than 150.000 g/mol, preferred 50.000 to 140.000 g/mol, more preferred 60.000 to 130.000, most preferred 85.000 to 120.000 g/mol.
  • the method is characterized in that the viscosity of the polymer dispersion amounts to 1.800 mPas to less than 6.700 mPas , preferably 2.000 mPas to 6.000 mPas, more preferred 2.200 mPas to 5.500 mPas, most preferred 2.500 mPas to 5.000 mPas, as measured with a Brookfield viscometer with spindle 4 at 20°C and an angle speed of 10 rpm.
  • the viscosity is preferably the bulk viscosity which refers to the viscosity right after having obtained the cooled down product.
  • the ratio of the polymeric dispersant to the dispersed polymer in the polymer dispersion is in the range of 0.45 : 1 to 1 : 0.9, preferred in the range of 0.5 : 1 to 1 : 1, more preferred in the range of 0.55 : 1 to less than 1 : 1, even more preferred in the range of 0.6 : 1 to 0.99 : 1, in particular in the range of 0.65 : 1 to 0.9 : 1.
  • the invention is in particular efficient if the method is characterized in that the total weight of the polymeric dispersant based on the total weight of the polymer dispersion is in the range of 10 to 28 wt.-%, preferred 12 to 26 wt.%, more preferred 14 to 24 wt.-%, even more preferred 16 to 22 wt.-%. According to a further embodiment, the method is characterized in that the total weight of the polymeric dispersant based on the total weight of the polymer dispersion is between 18 and 26 wt.-%, preferred 19 to 25 wt.-%. Further, the aqueous reaction mixture comprises an initiator.
  • the initiator is a redox initiator system comprising an oxidizing agent and a reducing agent.
  • the method is characterized in that the step of subjection of an aqueous reaction mixture to a radical polymerization is performed by sequentially or simultaneously adding the redox initiator system comprising the oxidizing agent and the reducing agent.
  • the first time phase starts per definition with the injection of the first part of the initiator.
  • the second time phase does not start before all of the initiator used for the initiation of the polymerization has been injected into the batch reactor, whereupon however those parts of the initiator injected for destroying residual monomers do not count for the start of the second time phase.
  • the method is characterized in that the oxidizing agent has a redox potential of from 0.6 to 2.0 V.
  • Preferred oxidizing agents being used in the redox initiator system for controlling the adiabatic conditions are peroxydiphosphates; hydrogen peroxide (1.14 V); alkyl hydroperoxides, more preferred t-butyl hydroperoxide; or aryl hydroperoxides, more preferred cumene hydroperoxide.
  • the method is characterized in that the oxidizing agent is selected from alkyl hydroperoxides, in particular t-butyl hydroperoxide, or aryl hydroperoxides, in particular cumene hydroperoxide.
  • Persulfates as agents in an initiator system may also be used. However, it has been found that persulfates with a redox potential of 2.01 V does not have such an impact on the method of manufacturing that it is able to fulfill the feature according to which the method is conducted under controlled adiabatic conditions. If persulfates are used as initiators in the present method, there is used a further oxidizing agent in the redox initiator system having a potential of 2 V or less and 0.6 V or more. However, in a preferred embodiment, the redox initiator system is devoid of a persulfate salt. In a preferred embodiment, the method is characterized in that the reducing agent has a redox potential of from -2 to 0.3 V.
  • Preferred reducing agents are selected from sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite (-1.12 V), potassium sulfite, ammonium sulfite, a hydrogen sulfite (-0.08 V); a thiosulfate (-.017 V); an amine; an acid, more preferred ascorbic acid (0.127 V) or erythorbic acid (0.127 V). More preferred reducing agents are bisulfites, in particular sodium bisulfite, potassium bisulfite, or ammonium bisulfite. 13 INTERNATIONAL PATENT APPLICATION 11300PC The redox potential is determined according to standard methods known by a skilled person.
  • the redox initiator system comprises an alkyl/aryl hydroperoxide together with a bisulfite.
  • more oxidizing agent is used than reducing agent in terms of mass.
  • the method is characterized in that the weight ratio between the reducing agent and the oxidizing agent is below 35 :1 and above 2 :1, preferably below 15 :1 and above 3 : 1, more preferred below 9 : 1 and above 4 : 1.
  • the method is characterized in that the step of polymerizing is performed by agitating while measuring torque of a motor-driven agitator.
  • the method is characterized in that the step B of polymerizing is performed by agitating and torque of a motor-driven agitator is kept below 65 N/cm.
  • the method comprises the step of reducing the residual monomer content by adding to the reaction mixture an initiator at about the time of reaching the maximum temperature (T max ).
  • T max maximum temperature
  • the step is conducted isothermally, even more preferred, the step is performed by holding the temperature during this step on a level above 55°C and below 80°C, most preferred above 60°C and below 70°C.
  • the initiator used for reducing the residual monomer content could be any of the above additional initiators.
  • the initiator is selected from a peroxide or an azo-compound, even more preferred selected from the group consisting of a hydroperoxide, a dialkylperoxide, a diacylperoxide and an azo-compound being substituted by tertiary carbon atoms, preferably carrying alkyl groups, nitrile groups and/or ester groups.
  • the initiator used in step C is 2,2'- azobis(2-amidinopropane) dihydrochloride (V-50).
  • the invention relates to the use of a batch reactor in a method of manufacturing a water-in-water polymer dispersion, wherein the method comprises a step of subjection of an aqueous reaction mixture to a radical polymerization to synthesize a dispersed polymer and to form the water-in-water polymer dispersion, which aqueous reaction mixture comprises a) a polymeric dispersant; b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more of a non-ionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; and c) an initiator, wherein the batch reactor comprises an agitator treated by an abrasive polishing technique, or wherein the batch reactor is free of baffles.
  • a further aspect of the invention as disclosed herewith relates to the use of the polymer dispersion according to the invention a. as a flocculant in the sedimentation, flotation or filtration of solids, b. as a thickener, c. as a contaminant control, d. as a dry strength aid, retention agent or drainage aid in papermaking.
  • Preferred embodiments of this aspect are characterized by features being disclosed in combination with any one of the first to third aspect of the invention.
  • An even further aspect of the invention as disclosed herewith relates to a w/w polymer dispersion obtained by a method according to the second aspect of the invention.
  • Preferred embodiments of this aspect are characterized by features being disclosed in combination with any one of the first to third aspect of the invention.
  • Features relating to preferred embodiments of the first aspect of the present invention, which are solely disclosed relating to the first aspect of the invention represent preferred embodiments of the second and third embodiment as well.
  • exemplary embodiments (A) to (H) are disclosed which represent particularly preferred embodiments.
  • (E) Method of manufacturing a water-in-water polymer dispersion wherein the method is performed in a batch reactor and the method comprises a step of subjection of an aqueous reaction mixture to a radical polymerization to synthesize a dispersed polymer and to form the water-in-water polymer dispersion, which aqueous reaction mixture comprises a) a polymeric dispersant; b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more of a non-ionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; and c) an initiator, wherein the batch reactor comprises an agitator treated by an electropolishing polishing technique, or wherein the batch reactor comprises an agitator treated by an electropolishing polishing technique and the batch reactor is free of baffles
  • (F) Method of manufacturing a water-in-water polymer dispersion wherein the method is performed in a batch reactor and the method comprises a step of subjection of an aqueous reaction mixture to a radical polymerization to synthesize a dispersed polymer and to form the water-in-water polymer dispersion, which aqueous reaction mixture comprises a) a polymeric dispersant; b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more of a non-ionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; and c) an initiator, wherein the batch reactor comprises an agitator treated by an electropolishing polishing technique, or 18 INTERNATIONAL PATENT APPLICATION 11300PC wherein the batch reactor is free of baffles; wherein
  • (G) Method of manufacturing a water-in-water polymer dispersion wherein the method is performed in a batch reactor and the method comprises a step of subjection of an aqueous reaction mixture to a radical polymerization to synthesize a dispersed polymer and to form the water-in-water polymer dispersion, which aqueous reaction mixture comprises a) a polymeric dispersant; b) a monomer composition comprising radically polymerizable monomers, wherein the radically polymerizable monomers are selected from the group consisting of one or more of a non-ionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an amphiphilic ethylenically unsaturated monomer; and c) an initiator, wherein the batch reactor comprises an agitator treated by an electropolishing polishing technique, or wherein the batch reactor is free of baffles; wherein the polymeric dispersant is a homopolymer made of
  • the molecular weights are characterized via aqueous SEC using Pullulan standards for the calibration.
  • Sample Preparation The samples are diluted with the eluent (polymer make-down in a measuring flask) and filtered through a 1 ⁇ m filter (M&N) (via syringe) before they are injected. If the machine is equipped with an autosampler filter the solution through a 1 ⁇ m filter into a vial.
  • M&N 1 ⁇ m filter
  • Example 1 Synthesis of the polymeric dispersant: At first, 294.06 g water, 666.7 g acryloyl amidopropyl trimethylammonium chloride (DIMAPA quat.) (60wt%) and sulfuric acid (50wt%) to adjust the pH to 5.0 ⁇ 0.2 were weighed in a 2 L vessel. Then the monomer solution was sparged with nitrogen for 30 min by stirring. Subsequently, the aqueous solution was heated up to 65 °C and 2-mercaptoethanol and V-50 (2,2'-Azobis(2-amidinopropane) dihydrochloride) were added to the solution. After reaching Tmax, the vessel is cooled down to ⁇ 80°C.
  • DIMAPA quat. 666.7 g acryloyl amidopropyl trimethylammonium chloride
  • sulfuric acid 50wt%)
  • the water-phase was prepared at 200 rpm. Firstly, 206.90 kg soft water, 261.80 kg Bio-acryl amide (49 wt.-%), 77.20 kg acryloyl oxyethyl trimethylammonium chloride (ADAME quat) (80 wt%), 412.50 kg polymeric dispersant of Example 1, 10.00 kg ammonium sulphate and 0.20 kg Trilon C were loaded into the reaction vessel. The pH value was adjusted to pH 5.0 ⁇ 0.2 with approximately 0.10 kg of sulphuric acid (50 %). The vessel was evacuated five times before being aerated with nitrogen.
  • the initiator composition was added at a 23 INTERNATIONAL PATENT APPLICATION 11300PC negative pressure of 0.5 bar and maximum agitator speed. Initiating started at 22 ⁇ 1°C with the addition of 0.34 kg V-50 in 3.05 kg soft water, 0.025 kg sodium persulfate in 0.47 kg soft water, 0.014 kg sodium bisulfite in 0.27 kg soft water, and 0.003 kg t-butylhydroperoxide (70 %) in 1 kg soft water. Afterwards the vessel was aerated again with nitrogen. After reaching the maximum temperature, a solution of 0.17 kg V-50 in 1.53 kg soft water was added to reduce the monomer content. After a one-hour post reaction time, the product was cooled down to a temperature below 40°C. Then, 8.30 kg citric acid and 0.82 kg of the biocide Acticide SPX were added and the product was cooled down to a temperature below 30°C. 24

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Abstract

La présente invention concerne un réacteur discontinu contenant un mélange réactionnel aqueux pour la fabrication d'une dispersion de polymère eau-dans-eau par polymérisation radicalaire, le réacteur discontinu comprenant un agitateur traité par une technique de polissage abrasif, ou le réacteur discontinu étant exempt de déflecteurs. De plus, la présente invention concerne un procédé de fabrication d'une dispersion de polymère eau-dans-eau par polymérisation radicalaire dans le réacteur discontinu. En outre, la présente invention concerne l'utilisation du réacteur discontinu dans un procédé de fabrication d'une dispersion de polymère eau-dans-eau.
PCT/US2024/039757 2023-07-26 2024-07-26 Dispersions polymères de poids moléculaire élevé préparées dans un réacteur discontinu Pending WO2025024770A1 (fr)

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US6428199B1 (en) * 1997-03-17 2002-08-06 Basf Aktiengesellschaft Chemical reactor with stirrer and incoming and outgoing lines on the reactor floor
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US6428199B1 (en) * 1997-03-17 2002-08-06 Basf Aktiengesellschaft Chemical reactor with stirrer and incoming and outgoing lines on the reactor floor
US7323510B2 (en) 2000-12-08 2008-01-29 Ashland Licensing And Intellectual Property Llc Method for the production of water-in-water polymer dispersions
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EP2945970B1 (fr) * 2013-01-16 2019-04-10 Solenis Technologies Cayman, L.P. Dispersions polymériques de poids moléculaire élevées

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