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WO2025168399A1 - Polymérisation en émulsion aqueuse avec des acrylates et des méthacrylates à chaîne alkyle longue - Google Patents

Polymérisation en émulsion aqueuse avec des acrylates et des méthacrylates à chaîne alkyle longue

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Publication number
WO2025168399A1
WO2025168399A1 PCT/EP2025/052175 EP2025052175W WO2025168399A1 WO 2025168399 A1 WO2025168399 A1 WO 2025168399A1 EP 2025052175 W EP2025052175 W EP 2025052175W WO 2025168399 A1 WO2025168399 A1 WO 2025168399A1
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Prior art keywords
aqueous
polymerization
meth
monomer composition
polymer dispersion
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English (en)
Inventor
Friederike Fleischhaker
Christoph Fleckenstein
Andrea Misske
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BASF SE
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BASF SE
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Publication of WO2025168399A1 publication Critical patent/WO2025168399A1/fr
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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
    • 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
    • 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
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—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
    • 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
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/38—Mixtures of peroxy-compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • Aqueous emulsion polymers with (meth)acrylates having long alkyl chains also referred to as fatty alcohol (meth)acrylates, as for example stearyl (meth)acrylate
  • fatty alcohol (meth)acrylates as for example stearyl (meth)acrylate
  • Polystearyl (meth)acrylate or polybehenyl (meth)acrylate for example are not regarded as substances of concern and are produced at least partially based on renewable raw materials, as stearyl, and behenyl alcohol are gained from bio-based natural sources.
  • Long alkyl chain poly(meth)acrylates have excellent water-repellent properties and are regarded as very promising sustainable materials in the ongoing substitution process of per- and polyfluoroalkyl substances (PFAS) in e.g. functional textiles.
  • PFAS per- and polyfluoroalkyl substances
  • aqueous emulsion polymers of long alkyl chain poly(meth)acrylates are of interest for example as PFAS-free, non-toxic, (partially) bio-based, sustainable, water-repellent impregnation or coating materials for functional textiles.
  • Further application fields of long alkyl chain poly(meth)acrylate emulsion polymers can be for example the use as flow improvers for diverse oils.
  • the aqueous emulsion polymerization of these monomers is challenging.
  • the monomers and oligomers transfer from a dispersed phase comprising the monomer through the aqueous phase into micelles where the polymerization occurs.
  • the hydrophobicity of long alkyl chain (meth)acrylate monomers like stearyl (meth)acrylate hinders the migration through the water phase.
  • homopolymerization of long chain alkyl (meth)acrylates leads to instable dispersions due to phase-separation and/or partial or complete coagulation by formation of undesired coarse polymer particles.
  • small amounts of long alkyl chain (meth)acrylates can be successfully polymerized with less hydrophobic comonomers as reaction partner in a conventional emulsion polymerization process.
  • WO 2021/191348 A1 is directed to polymer dispersions made from (meth)acrylates having long side chains, wherein the polymer dispersions contain copolymers derived from both (meth)acrylates and ethylenically unsaturated carboxylic acids.
  • a surfactant system comprising at least two different surfactants is applied to accomplish the emulsion polymerization.
  • the monomer composition comprises:
  • (Meth)acrylate is an abbreviation for acrylate and/or methacrylate.
  • (Meth)acrylic acid is an abbreviation for acrylic acid and/or methacrylic acid.
  • the C16- Ci8-alkyl (meth)acrylate is, in particular, octadecan-1 -yl (meth)acrylate and/or hexadecan- 1-y I (meth)acrylate, especially octadecan-1 -yl (meth)acrylate or a mixture of octadecan- 1-y I (meth)acrylate and hexadecan- 1-y I (meth)acry- late.
  • the Ci6-C22-alkyl (meth)acrylate can consist of octadecan- 1-y I (meth)acrylate.
  • Stearyl (meth)acrylate is an abbreviation for stearyl acrylate and/or stearyl methacrylate.
  • Stearyl (meth)acrylate is understood to be a Ci8-alkyl (meth)acrylate with an alkyl chain having 18 carbon atoms or a mixture of Ci6-Ci8-alkyl (meth)acrylates with alkyl chains having 16 or 18 carbon atoms, respectively.
  • Stearyl (meth)acrylate can be produced for example by esterification as described in JP 2007/001886 A or by transesterification as described in DE 2317226 A1 , respectively.
  • the monomer composition consists to more than 95.0 wt.-%, more preferably to more than 99.0 wt.-%, more preferably to more than 99.5 wt.-% and even more preferably to more than 99.9 wt.-% of the at least one (meth)acry late, in particular of stearyl (meth)acry I ate, referring to the total monomer composition.
  • the aqueous composition comprises less than 1 .0 wt.-%, more preferably less than 0.5 wt.-%, even more preferably less than 0.1 wt.-% of (meth)acrylic acid, referring to the total aqueous composition.
  • the aqueous composition can be free of (meth)acrylic acid.
  • the monomer composition comprises less than 1.0 wt.-%, more preferably less than 0.5 wt.-%, even more preferably less than 0.1 wt.-% of (meth)acrylic acid, referring to the total monomer composition.
  • the monomer composition can be free of (meth)acrylic acid.
  • the emulsion polymerization is conducted in the presence of a surfactant.
  • the aqueous reaction medium comprises at least one surfactant.
  • the aqueous composition comprises
  • aqueous reaction medium 20.0 wt.-% to 80.0 wt.-%, more preferably 60.0 wt.-% to 80.0 wt.-%, of an aqueous reaction medium, referring to the total aqueous composition, wherein the aqueous reaction medium comprises:
  • the buffer salt comprises a citrate, carbonate, borate and/or phosphate salt. More preferably, the buffer salt comprises a phosphate salt selected from the group consisting of alkali dihydrogen phosphate, alkali hydrogen phosphate, alkali phosphate, alkali di-phosphate, alkali tri-phosphate, alkali poly-phosphate, alkali meta-phosphate and mixtures thereof.
  • the buffer salt is sodium di-phosphate and/or sodium hydrogen phosphate, such as sodium di-phosphate decahydrate and/or sodium hydrogen phosphate heptahydrate.
  • Sodium di-phosphate is also referred to as sodium pyrophosphate.
  • the polymerization initiator is preferably selected from the group consisting of peroxides such as organic hydroperoxides; peracids; azo compounds; redox initiator systems and persulfates, in particular persulfates.
  • the at least one surfactant may be anionic or non-ionic or a mixture of non-ionic and anionic surfactants.
  • the at least one surfactant is preferably an anionic surfactant.
  • the at least one surfactant is preferably selected from gemini surfactants, which are quasi-dimers of conventional surfactants, that are linked with a molecular spacer with each other. They additionally support the migration of the long alkyl chain (meth)acrylates through the aqueous reaction medium.
  • the at least one surfactant is more preferably selected from sulfosuccinates, in particular from bis(alkyl) sulfosuccinates, such as di-Ci-Ci8-alkyl sulfosuccinates.
  • the at least one surfactant is sodium dioctylsulfosuccinate and/or sodium ditridecylsulfosuccinate. With these surfactants the tendency of coagulate formation during emulsion polymerization of the monomer composition described above is reduced.
  • the emulsion polymerization is conducted in the presence of a chain transfer agent.
  • the chain transfer agent is preferably selected from the group consisting of aliphatic and/or araliphatic halogen compounds, for example n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide; organic thio compounds such as primary, secondary or tertiary aliphatic thiols, for example ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pen- tanethiol
  • the total amount of chain transfer agents does not exceed 1 wt.-%, based on the total amount of monomer composition.
  • the aqueous reaction medium comprises at least one chain transfer agent.
  • the at least one chain transfer agent is more preferably selected from alkylthiols. Even more preferably, the at least one chain transfer agent is dodecanethiol.
  • Anionic surfactants usually bear at least one anionic group, which is for example selected from phosphate, phospho- nate, sulfate and sulfonate groups.
  • the anionic surfactants such as sulfosuccinates, which bear at least one anionic group, are typically used in the form of their alkali metal salts, especially of their sodium salts or in the form of their ammonium salts.
  • the at least one surfactant can be selected from anionic surfactants, which bear in particular at least one sulfate or sulfonate group.
  • anionic surfactants which bear at least one phosphate or phosphonate group may be used, either as sole anionic surfactants or in combination with one or more anionic surfactants, which bear at least one sulfate or sulfonate group.
  • anionic surfactants which bear at least one sulfate or sulfonate group
  • the salts especially the alkali metal and ammonium salts, of sulfosuccinates, alkyl sulfates, especially of Cs-C22-al ky I sulfates
  • the salts especially the alkali metal and ammonium salts, of sulfuric monoesters of ethoxylated alkanols, especially of sulfuric monoesters of ethoxylated C8-C22- alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40
  • the salts especially the alkali metal and ammonium salts, of
  • the anionic surfactants can be selected from the following groups:
  • the salts especially the alkali metal salts, of di-Ci-Ci8-alkyl sulfosuccinates,
  • the salts especially the alkali metal and ammonium salts, of alkyl sulfates, especially of Cs-C22-al ky I sulfates,
  • sulfuric monoesters of ethoxylated alkylphenols especially of sulfuric monoesters of ethoxylated C4-Cis-al- kyl phenols (EO level preferably from 3 to 40), of alkylbenzenesulfonic acids, especially of C4-C22-al kyl benzenesulfonic acids, and
  • the salts, especially the alkali metal and ammonium salts, of phosphoric monoesters of C2-C3-alkoxylated alkanols preferably having an alkoxylation level in the range from 2 to 40, especially in the range from 3 to 30, for example phosphoric monoesters of ethoxylated C8-C22-alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric monoesters of propoxylated C8-C22-alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and phosphoric monoesters of ethoxylated-co- propoxylated C8-C22-alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20,
  • the salts especially the alkali metal and ammonium salts, of phosphoric monoesters of ethoxylated alkylphenols, especially phosphoric monoesters of ethoxylated C4-Cis-alky I phenols (EO level preferably from 3 to 40),
  • the salts especially the alkali metal and ammonium salts, of alkylphosphonic acids, espe-cially Cs-C22-al- kylphosphonic acids, and
  • the salts especially the alkali metal and ammonium salts, of alkylbenzenephosphonic acids, especially C4- C22-alkylbenzenephosphonic acids.
  • the surfactant may also comprise one or more nonionic surfactant.
  • Suitable nonionic surfactants are e.g. araliphatic or aliphatic nonionic surfactants, for example ethoxylated mono-, di- and trialkylphenols (EO level from 3 to 50, alkylchain: C4-C10), ethoxylates of long-chain alcohols (EO level: from 3 to 100, alkyl chain: Cs-C e), and polyethylene oxide/polypropylene oxide homo- and copolymers. These may comprise the alkylene oxide units copolymerized in random distribution or in the form of blocks. Very suitable examples are the EO/PO block copolymers.
  • ethoxylates of long-chain alkanols alkyl chain C1-C30, mean ethoxylation level from 5 to 100
  • preference is given to those having a C12-C20 alkyl chain and a mean ethoxylation level of 5 to 20, and also to ethoxylated mono-alkylphenols.
  • the at least one surfactant will be used in such an amount that the amounts of the at least one surfactant are in the range from 0.1 wt.-% to 25 wt.-%, especially in the range from 1.0 wt.-% to 15 wt.-%, based on the total monomer composition.
  • the aqueous reaction medium in the polymerization may in principle also comprise in addition to the glycol, which is in particular propane-1 ,2-diol, minor amounts, in particular of 5 wt.-% or less of water-soluble organic solvents, for example methanol, ethanol, isopropanol, butanols, pentanols, and/or acetone, referring to the total aqueous reaction medium.
  • the process of the invention is conducted in the absence of such additional organic solvents.
  • the polymerization according to the invention is preferably conducted under stirring.
  • the polymerization as described herein is an emulsion polymerization and conducted in absence of ultrasonic waves and, more particularly, without ultrasonic pretreatment. It is an advantage of the present invention that the polymerization takes place within the micelles and reduction of the monomer droplet size of the dispersed monomer phase by means of ultrasonic treatment is not required. Therefore, the inventive process is readily scalable.
  • the monomer composition is typically present in form of a dispersed phase, preferably having a mean average droplet diameter D of more than 10 nm, more preferably more than 50 nm, even more preferably more than 100 nm, even more preferably more than 500 nm.
  • the mean average droplet diameter D of the monomer composition is preferably less than 100 pm, more preferably less than 50pm and even more preferably less than 10 pm, for example 1 pm.
  • the mean average droplet diameter D can be determined for example by dynamic light scattering (DLS) according to ISO 22412:2017.
  • the droplets of the monomer composition can also be referred to as reservoir for the monomers to be polymerized in the micelles. With progress of the polymerization the monomer composition is consumed and the monomers are converted into polymers within the micelles.
  • glycol in particular propane-1, 2-diol
  • the emulsion polymerization is initiated by means of the polymerization initiator.
  • the polymerization initiator in emulsion polymerization possesses typically hydrophilic properties.
  • the polymerization initiator is a hydrophilic polymerization initiator. Radical aqueous emulsion polymerization is triggered by means of a free-radical polymerization initiator.
  • polymerization initiators encompass peroxides such as persulfates, azo compounds and redox initiator systems.
  • the peroxides can be inorganic peroxides or organic peroxides.
  • the type and amount of the polymerization initiator, polymerization temperature and polymerization pressure are selected such that a sufficient amount of initiating radicals is always present to initiate or to maintain the polymerization reaction.
  • the polymerization initiator is a persulfate. More preferably, the polymerization initiator is sodium persulfate, potassium persulfate or ammonium persulfate, in particular potassium persulfate. Persulfates are inexpensive and commonly used in industrial processes.
  • only part or the entire amount of the aqueous composition is initially charged to a reaction vessel.
  • at least part of the entire amount of the aqueous reaction medium is initially charged to the reaction vessel before the monomer composition is added or fed.
  • at least part of the entire amount of glycol, in particular of propane-1, 2-diol is initially charged to the reaction vessel before the monomer composition is added.
  • at least part of the entire amount of glycol, in particular of propane-1 , 2-diol, at least part of the entire amount of the buffer salt and at least part of the entire amount of the surfactant are initially charged to the reaction vessel before the monomer composition is added.
  • none, part or the entire amount of the aqueous reaction medium is initially charged to the reaction vessel.
  • at least part of the entire amount of glycol, in particular of propane-1, 2-diol, at least part of the entire amount of the buffer salt and at least part of the entire amount of surfactant are initially charged to the reaction vessel before the monomer composition is added.
  • the total amount of the polymerization initiator for the emulsion polymerization is added to the reaction vessel in one portion.
  • the emulsion polymerization is carried out by adding a feed stream comprising at least part of the monomer composition to the reaction vessel during the emulsion polymerization, wherein the reaction vessel contains at least part of the aqueous reaction medium.
  • the emulsion polymerization of the invention is conducted at a reaction temperature in the range from 0°C to 170°C, more preferably in the range from 50°C to 95°C, most preferably in the range from 75°C to 95°C and in particularly the emulsion polymerization of the invention is conducted a temperature in the range from 80°C to 90°C.
  • the emulsion polymerization can be conducted at a pressure of less than, equal to or greater than 1 atm (101325 Pa).
  • the emulsion polymerization is conducted at a pressure of 0.20 MPa or less, more preferably of 0.15 MPa or less.
  • the emulsion polymerization is conducted at a pressure in a range from 0.05 MPa to 0.20 MPa, more particularly from 0.08 MPa to 0.13 MPa.
  • the reaction is post-polymerized for up to 3.0 hours, more preferably for a time range of 0.5 hours to 2.5 hours, in particular 2.0 hours.
  • the term post-polymerization denotes the continued reaction after all feeds, in particular the monomer composition, are added to the reaction mixture.
  • the aqueous composition is preferably stirred at an elevated temperature, in particular at a post-polymerizing temperature in the range from 0°C to 170°C, more preferably in the range from 50°C to 95°C, most preferably in the range from 75°C to 95°C.
  • the polymerization and optionally the post-polymerization are carried out at a polymerization temperature in a range from 50°C to 95°C, the resulting aqueous polymer dispersion is cooled to a storage temperature of 45°C or less and then the pH value, in particular of the aqueous polymer dispersion, is adjusted to a range from 7 to 8, in particular from 7.0 to 7.5.
  • the at least part of the monomer composition being fed to the aqueous composition during polymerization, and optionally the part of the aqueous reaction medium are preheated to a preheating temperature of 25°C or more before being fed to the aqueous composition. More preferably, the preheating temperature is in a range from 30°C to 40°C.
  • the emulsion polymerization can be conducted in presence of protective colloids.
  • the protective colloids are understood to mean polymeric compounds having molecular weights above 2000 Daltons.
  • the emulsion polymerization can be performed in the presence of a seed latex.
  • a seed latex is a polymer latex which is present in the aqueous reaction medium before the metering of the monomer composition is started. The seed latex may help to better adjust the particle size of the final aqueous polymer dispersion obtained in the emulsion polymerization of the invention.
  • Every polymer latex may serve as a seed latex. Preference is given to seed latices, where the particle size of the polymer particles is comparatively small.
  • the Z average particle diameter of the polymer particles of the seed latex, as determined by dynamic light scattering at 20°C is preferably in the range from 10 nm to 80 nm, in particular from 10 nm to 50 nm.
  • the polymer particles of the seed latex are made of ethylenically unsaturated monomers, which comprise at least 95% by weight, based on the total weight of the monomers forming the seed latex, of one or more monomers selected from C2-Cio-alkyl esters of acrylic acid, in particular ethyl acrylate, n-butyl acrylate, 2-ethyl-hexyl acrylate, Ci-C4-alkyl esters of methacrylic acid, in particular methyl methacrylate, and vinylaromatic monomers, in particular styrene.
  • ethylenically unsaturated monomers which comprise at least 95% by weight, based on the total weight of the monomers forming the seed latex, of one or more monomers selected from C2-Cio-alkyl esters of acrylic acid, in particular ethyl acrylate, n-butyl acrylate, 2-ethyl-hexyl acrylate, Ci-C4
  • the seed latex is usually charged into the reaction vessel before the metering of the monomer composition is started.
  • the seed latex is charged into the reaction vessel followed by establishing the polymerization conditions and charging at least a portion of the polymerization initiator into the reaction vessel before the metering of the monomer composition is started.
  • the resulting aqueous polymer dispersion is neutralized to an essentially neutral pH value in the range from 7 to 8, in particular after the polymerization reaction, preferably after the polymerization reaction is accomplished to a conversion of at least 99 % by weight, by adding a basic compound.
  • the basic compound is selected from water-soluble hydroxides, oxides, carbonates, hydrogen carbonates (bicarbonates), acetates, citrates, borates, phosphates, hydrogen phosphates of alkali or alkaline earth metals or ammonium.
  • Other basic compounds are also possible, like ammonia or water-soluble organic amines such as lower aliphatic amines.
  • Preferred basic compounds are the hydroxides of sodium, potassium and ammonium, the carbonates of sodium and potassium and hydrogen carbonates (bicarbonates) of sodium and potassium.
  • the basic compound is more preferably ammonium, in particular aqueous ammonium.
  • the basic compound is preferably dissolved in water.
  • the pH value of the aqueous polymer dispersion is adjusted by addition of an aqueous ammonia solution and/or alkali hydroxides.
  • the present invention also concerns the aqueous polymer dispersions obtainable or obtained by the process of the invention as well as their use.
  • the aqueous polymer dispersion preferably has a pH value in a range from 7 to 8, more preferably from 7.0 to 7.5.
  • the glycol, in particular propane-1 , 2-diol, as additive can remain in the aqueous polymer dispersion.
  • the aqueous polymer dispersion preferably comprises the glycol, in particular propane-1 , 2-diol.
  • the aqueous polymer dispersion preferably comprises 0.5 wt.-% to 20.0 wt.-%, more preferably 1 .0 wt.-% to 15.0 wt.-%, of the glycol, in particular propane-1 , 2-diol, referring to the total aqueous polymer dispersion.
  • the aqueous polymer dispersion obtained has a polymer solid content in the range from 10 wt.-% to 60 wt.-%, preferably 20 wt.-% to 55 wt.-%, more preferably 25 wt.-% to 50 wt.-%, and most preferably 30 wt.-% to 40 wt.-%, based in each case on the total weight of the aqueous polymer dispersion.
  • the aqueous polymer dispersion obtained comprises polymer particles with a mean average particle diameter D P of less than 10 m, preferably less than 1 pm, more preferably less than 800 nm, even more preferably less than 500 nm.
  • the aqueous polymer dispersion obtained comprises polymer particles with a mean average particle diameter DP of at least 10 nm, preferably at least 50 nm, more preferably at least 100 nm.
  • the mean average particle diameter DP of the polymer particles comprised in the obtained aqueous polymer dispersion is for example in a range from 100 nm to 400 nm.
  • the mean average particle diameter DP can be determined by dynamic light scattering (DLS) according to ISO 22412:2017.
  • aqueous polymer dispersions are the use for hydrophobic coatings, textile functionalization such as for water repellency of textiles; and/or as flow aids for oils.
  • the obtained aqueous polymer dispersions in particular, can serve as sustainable substitution for PFAS containing impregnations.
  • a glass reactor with a volume of 2 L and equipped with a stirrer moving at 220 rpm, temperature control, nitrogen inlet and reflux condenser was charged with 100.0 g deionized water, 20.0 g propane-1 , 2-diol, 0.9 g sodium di-phos- phate decahydrate, 4.0 g Aerosol® TR-70, purchased from Solvay (sodium ditridecylsulfosuccinate) and 3.7 g Aerosol® OT-75, purchased from Solvay (sodium dioctylsulfosuccinate). This first part of the aqueous reaction medium was purged with nitrogen and heated to 80°C.
  • the temperature was maintained at 80°C and 1.0 g potassium persulfate dissolved in 20 g deionized water was added in one portion.
  • SA 18 stearyl acrylate
  • aqueous composition was stirred for 2 hours at 80°C, then cooled to 20°C, neutralized by addition of aqueous ammonia solution, comprising 5 wt.-% of ammonia, to a pH value of 7.0 and filtered over filter with a pore size of 125 pm.
  • the aqueous polymer dispersion was stored at 20°C for 2 months. No optical changes, coagulation or remarkable changes in particle size were observed.
  • a glass reactor with a volume of 2 L and equipped with a stirrer moving at 220 rpm, temperature control, nitrogen inlet and reflux condenser was charged with 100.0 g deionized water, 20.0 g propane-1 , 2-diol, 0.9 g sodium di-phos- phate decahydrate, 4.0 g Aerosol® TR-70, purchased from Solvay (sodium ditridecylsulfosuccinate) and 3.7 g Aerosol® OT-75, purchased from Solvay (sodium dioctylsulfosuccinate). This first part of the aqueous reaction medium was purged with nitrogen and heated to 80°C.
  • a stable, not coagulated aqueous polymer dispersion was obtained having a solid content of 35.5 wt.-%, referring to the total aqueous polymer dispersion, and an average particle diameter of 336 nm.
  • the temperature was maintained at 80°C and 1.0 g potassium persulfate dissolved in 20 g deionized water was added in one portion.
  • aqueous composition was stirred for 2 hours at 80°C, then cooled to 20°C, neutralized by addition of aqueous ammonia solution, comprising 5 wt.-% of ammonia, to a pH value of 7.5 and filtered over filter with a pore size of 125 pm.
  • a stable, not coagulated aqueous polymer dispersion was obtained having a solid content of 36.2 wt.-%, referring to the total aqueous polymer dispersion, and an average particle diameter of 194 nm.
  • the aqueous polymer dispersion was stored at 20°C for 2 months. No optical changes, coagulation or remarkable changes in particle size were observed.
  • a glass reactor with a volume of 2 L and equipped with a stirrer moving at 220 rpm, temperature control, nitrogen inlet and reflux condenser was charged with 100.0 g deionized water, 20.0 g propane-1, 2-diol, 0.8 g sodium hydrogen phosphate heptahydrate, 4.0 g Aerosol® TR-70, purchased from Solvay (sodium ditridecylsulfosuccinate) and 3.7 g Aerosol® OT-75, purchased from Solvay (sodium dioctylsulfosuccinate). This first part of the aqueous reaction medium was purged with nitrogen and heated to 80°C.
  • the temperature was maintained at 80°C and 1.0 g potassium persulfate dissolved in 20 g deionized water was added in one portion.
  • SA 18 stearyl acrylate
  • aqueous composition was stirred for 2 hours at 80°C, then cooled to 20°C, neutralized by addition of aqueous ammonia solution, comprising 5 wt.-% of ammonia, to a pH value of 7.5 and filtered over filter with a pore size of 125 pm.
  • a stable, not coagulated aqueous polymer dispersion was obtained having a solid content of 34.5 wt.-%, referring to the total aqueous polymer dispersion, and an average particle diameter of 243 nm.
  • the aqueous polymer dispersion was stored at 20°C for 2 months. No optical changes, coagulation or remarkable changes in particle size were observed.
  • a glass reactor with a volume of 2 L and equipped with a stirrer moving at 220 rpm, temperature control, nitrogen inlet and reflux condenser was charged with 100.0 g deionized water, 20.0 g propane-1, 2-diol, 0.8 g sodium hydrogen phosphate heptahydrate, 4.0 g Aerosol® TR-70, purchased from Solvay (sodium ditridecylsulfosuccinate) and 3.7 g Aerosol® OT-75, purchased from Solvay (sodium dioctylsulfosuccinate). This first part of the aqueous reaction medium was purged with nitrogen and heated to 80°C.
  • aqueous composition was stirred for 2 hours at 80°C, then cooled to 20°C, neutralized by addition of aqueous ammonia solution, comprising 5 wt.-% of ammonia, to a pH value of 7.5 and filtered over filter with a pore size of 125 pm.
  • the aqueous polymer dispersion was stored at 20°C for 2 months. No optical changes, coagulation or remarkable changes in particle size were observed.
  • aqueous composition was stirred for 2 hours at 80°C, then cooled to 20°C, neutralized by addition of aqueous ammonia solution, comprising 5 wt.-% of ammonia, to a pH value of 7.5 and filtered over filter with a pore size of 125 pm.
  • a stable, not coagulated aqueous polymer dispersion was obtained having a solid content of 36.7 wt.-%, referring to the total aqueous polymer dispersion, and an average particle diameter of 209 nm.
  • the aqueous polymer dispersion was stored at 20°C for 2 months. No optical changes, coagulation or remarkable changes in particle size were observed.
  • Example 8 Emulsion copolymerization of stearyl methacrylate and methacrylic acid
  • a glass reactor with a volume of 2 L and equipped with a stirrer moving at 220 rpm, temperature control, nitrogen inlet and reflux condenser was charged with 100.0 g deionized water, 20.0 g propane-1, 2-diol, 0.8 g sodium hydrogen phosphate heptahydrate, 4.0 g Aerosol® TR-70, purchased from Solvay (sodium ditridecylsulfosuccinate) and 3.7 g Aerosol® OT-75, purchased from Solvay (sodium dioctylsulfosuccinate). This first part of the aqueous reaction medium was purged with nitrogen and heated to 80°C.
  • the temperature was maintained at 80°C and 1.0 g potassium persulfate dissolved in 20 g deionized water was added in one portion.
  • aqueous composition was stirred for 2 hours at 80°C, then cooled to 20°C, neutralized by addition of aqueous ammonia solution, comprising 5 wt.-% of ammonia, to a pH value of 7.5 and filtered over filter with a pore size of 125 pm.
  • a stable, not coagulated aqueous polymer dispersion was obtained having a solid content of 34.9 wt.-%, referring to the total aqueous polymer dispersion, and an average particle diameter of 174 nm.
  • the aqueous polymer dispersion was stored at 20°C for 2 months. No optical changes, coagulation or remarkable changes in particle size were observed.
  • the emulsion polymerization was carried out according to example 2 with the difference that no aqueous ammonia solution was added and thus the pH was not adjusted to pH 7.0.

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Abstract

L'invention concerne un procédé de préparation d'une dispersion aqueuse de polymère par polymérisation, en particulier par polymérisation en émulsion radicalaire, d'une composition de monomère dans une composition aqueuse et en présence d'un initiateur de polymérisation, la composition aqueuse comprenant 10,0 % en poids à 60,0 % en poids de la composition de monomère, par rapport à la composition aqueuse totale, la composition de monomère comprenant : 90,0 % en poids à 100,0 % en poids d'au moins un (méth)acrylate d'alkyle en C16-C22, 0 % en poids à 10,0 % en poids d'acide (méth)acrylique, en référence à la composition de monomère totale ; 40,0 % en poids à 90,0 % en poids d'un milieu réactionnel aqueux, par rapport à la composition aqueuse totale, le milieu réactionnel aqueux comprenant : 70,0 % en poids à 98,9 % en poids d'eau, 1,0 % en poids à 25,0 % en poids d'un glycol, en particulier du propane-1,2-diol, 0,1 % en poids à 5,0 % en poids d'un sel tampon, par rapport au milieu réactionnel aqueux total, la valeur de pH étant ajustée à une plage de 7 à 8, de préférence de 7 à 7,5. L'invention concerne en outre une dispersion aqueuse de polymère pouvant être obtenue, ou étant obtenue, par le procédé et son utilisation.
PCT/EP2025/052175 2024-02-09 2025-01-29 Polymérisation en émulsion aqueuse avec des acrylates et des méthacrylates à chaîne alkyle longue Pending WO2025168399A1 (fr)

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DE2317226A1 (de) 1973-04-06 1974-10-24 Texaco Ag Verfahren zur herstellung von hoeheren alkylacrylaten bzw. -methacrylaten
US4269749A (en) 1979-04-30 1981-05-26 The Dow Chemical Company Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions
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JP2007001886A (ja) 2005-06-21 2007-01-11 Osaka Organic Chem Ind Ltd （メタ）アクリル酸エステルの製造法
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WO2021191348A1 (fr) 2020-03-26 2021-09-30 Evonik Operations Gmbh Dispersion polymère à base de (méth)acrylates ayant de longues chaînes latérales

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2317226A1 (de) 1973-04-06 1974-10-24 Texaco Ag Verfahren zur herstellung von hoeheren alkylacrylaten bzw. -methacrylaten
US4269749A (en) 1979-04-30 1981-05-26 The Dow Chemical Company Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions
DE4003422A1 (de) 1990-02-06 1991-08-08 Basf Ag Waessrige polyurethanzubereitungen
JPH06192341A (ja) * 1992-12-24 1994-07-12 Kao Corp 長鎖（メタ）アクリレート系ラテックスおよびその製造法
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EP1690909A1 (fr) * 2003-11-13 2006-08-16 Daikin Industries, Ltd. Dispersion liquide aqueuse d'agent hydrofuge et oleofuge
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WO2015111668A1 (fr) * 2014-01-24 2015-07-30 日華化学株式会社 Composition d'agent hydrofuge, et produit textile hydrofuge ainsi que procédé de fabrication de celui-ci
JP2019108641A (ja) * 2017-12-20 2019-07-04 日華化学株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法
WO2021191348A1 (fr) 2020-03-26 2021-09-30 Evonik Operations Gmbh Dispersion polymère à base de (méth)acrylates ayant de longues chaînes latérales

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