WO2023099310A1 - Préparation de latex sans tensioactif, à teneur élevée en solides, à l'aide d'un macro-agent raft à base d'eau amphiphile fonctionnel - Google Patents

Préparation de latex sans tensioactif, à teneur élevée en solides, à l'aide d'un macro-agent raft à base d'eau amphiphile fonctionnel Download PDF

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WO2023099310A1
WO2023099310A1 PCT/EP2022/082982 EP2022082982W WO2023099310A1 WO 2023099310 A1 WO2023099310 A1 WO 2023099310A1 EP 2022082982 W EP2022082982 W EP 2022082982W WO 2023099310 A1 WO2023099310 A1 WO 2023099310A1
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group
macro
waterborne
mol
raft agent
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PCT/EP2022/082982
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English (en)
Inventor
Bo Peng
Shi Cheng LI
Ke Xu
San Hoa Thang
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Basf Se
Basf (China) Company Limited
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Publication of WO2023099310A1 publication Critical patent/WO2023099310A1/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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the invention relates to a functional amphiphilic waterborne macro-RAFT agent and using this amphiphilic waterborne macro-RAFT agent for the surfactant-free RAFT-mediated emulsion polymerization.
  • the waterborne macro-RAFT agent is prepared by polymerization-induced self-assembly (PISA) strategy in aqueous phase. Then a series of surfactant-free RAFT latexes were obtained by using this type of waterborne macro-RAFT agent. All the targeting polymers have good stability, high solid content and a size range of 100 nm - 300 nm. After crosslinked with ADH, the enhanced and preferred mechanical properties were obtained.
  • the resulting dispersions can be applied in a wide range of applications, such as architectural coatings, adhesives, construction area, paper manufacture as well as furniture coatings.
  • Emulsion polymerization has been commercialized for several decades, the resulting product, is called latex.
  • Latexes have been applied in a wide range of industrial applications, such as architectural coatings, adhesives, construction area, paper manufacture as well as furniture coatings.
  • crosslinkers are induced for the desired mechanical properties.
  • Crosslinkers are commonly used in these fields.
  • the crosslinking efficiency is restricted in conversional emulsion polymerization and the preferred mechanical properties can only be obtained by high level of crosslinker amount.
  • RAFT Reversible addition-fragmentation chain transfer
  • RDRP reversible deactivation radical polymerization
  • CN 10469338613 discloses a process for the preparation of a cross-linkable composition
  • a cross-linkable composition comprising a block copolymer [A] x [B] y mediated by a xanthate small RAFT agent and a polymer P.
  • Polymer P is prepared in the presence of [A] x [B] y via emulsion polymerization.
  • [A] x [B] y block copolymer is prepared via RAFT solution polymerization.
  • the [A] x [B] y block copolymer does not contain carboxylic acid.
  • the low dispersity (£> ⁇ 1.50) from the [A] x [B] y block copolymer fails to show a good control of RAFT.
  • the disclosure also fails to show the ability to produce the waterborne surfactant-free polymers (P) with a high theoretical number average molecular weight (M n > 60,000), a high solid content (> 40 wt %) as well as the size range of 100 nm - 300 nm.
  • the functional amphiphilic macro-RAFT agent is prepared in aqueous phase with the low dispersity (£> ⁇ 1.30).
  • a series of high solid content > 40 wt %), good stability, carboxylic acid-free (or very low amount, i.e. less than 5 wt%), surfactant-free latexes are obtained with a size range of 100 nm to 300 nm.
  • One object of the present invention is to provide a functional amphiphilic waterborne macro- RAFT agent.
  • the amphiphilic waterborne macro-RAFT agent is prepared in aqueous phase.
  • the waterborne macro-RAFT agent is synthesized with (A) at least one water soluble monoethylenically unsaturated monomer, (B) at least one water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group, (C) at least one hydrophobic monoethylenically unsaturated monomer, and (D) at least one water soluble Chain Transfer Agent (“CTA”), wherein the at least one water-soluble Chain Transfer Agent has a general structure of Formula I: S
  • R 1 is selected from -CH2COOX, or -CH2COOR 3 , or -C(R 4 )(R 5 )COOX, or - C(R 4 )(R 5 )COOR 3 , or -C(R 4 )(CN)(CH 2 CH 2 COOX), or -C(R 4 )(CN)(CH 2 CH 2 COOR 3 ) wherein X is a hydrogen atom, an alkali metal, an alkaline earth metal, an organic ammonium salts, an ammonium; and R 3 , R 4 , R 5 are selected from an optionally substituted aryl, an optionally substituted alkyl, an optionally substituted (alkoxy)alkyl, an optionally substituted (alkoxycarbonyl)alkyl, an optionally substituted (carboxylate)alkyl, an optionally substituted carbamoyl (-C0N(
  • the wmacro-RAFT agent may have a structure of Formula II: Poly(A x -co-B y )-b-Poly(Cz) Formula II wherein it is synthesized with: i) 30 to 90 mol % (A) a water soluble monoethylenically unsaturated monomer which may contain at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid, or their salts thereof; ii) 1 to 60 mol % (B) a water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group selected from a diacetone group, an acetoacetoxyl group, a ureido group, an oxazoline group, and a carbodiimide group; iii) 1 to 50 mol % (C) unsaturated hydrophobic monomers, selecting from n
  • Another object of the present invention is to provide a polymer latex using the amphiphilic waterborne macro-RAFT agent.
  • the functional waterborne macro-RAFT agent demonstrates the ability to produce a series of surfactant-free stable latex with high solid content and a size range of 100 nm to 300 nm.
  • a third object of the present invention is to provide a polymer composition with the abovementioned polymer latex and a post-added chemical for crosslinking.
  • polymer or “polymers”, as used herein, includes both homopolymer(s), that is, polymers prepared from a single reactive compound, and copolymer(s), that is, polymers prepared by reaction of at least two polymer forming reactive, monomeric compounds.
  • derivative means compound that is derived from a similar compound with one or more hydrogen atoms been substituted with a function group, such as a halogen, a carboxylate group, an alkoxyl group, etc.
  • water soluble means a chemical that has a water solubility of at least 1.0 g/L at 20 °C under 1 atm. If a chemical is reactive with sodium hydroxide, to form a salt, the water solubility refers to solubility of the salt form, otherwise, the water solubility refers to the solubility of itself.
  • hydrophobic monomers means a monomer that has a water solubility less than 1.0 g/L at 20 °C under 1 atm. If a monomer is reactive with sodium hydroxide to form a salt, the water solubility refers to solubility of the salt form, otherwise, the water solubility refers to the solubility of itself.
  • particle size means the size of a particle measured with Dynamic Light Scattering (DLS), unless otherwise specified.
  • One object of the present invention is to provide a waterborne macro-RAFT agent is synthesized with (A) at least one water soluble monoethylenically unsaturated monomer, (B) at least one water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group, (C) at least one hydrophobic monoethylenically unsaturated monomer, and (D) at least one water soluble Chain Transfer Agent (“CTA”), wherein the at least one water-soluble Chain Transfer Agent has a general structure of Formula I:
  • R 1 is selected from -CH2COOX, or -CH2COOR 3 , or -C(R 4 )(R 5 )COOX, or - C(R 4 )(R 5 )COOR 3 , or -C(R 4 )(CN)(CH 2 CH 2 COOX), or -C(R 4 )(CN)(CH 2 CH 2 COOR 3 ) wherein X is a hydrogen atom, an alkali metal, an alkaline earth metal, an organic ammonium salts, an ammonium; and R 3 , R 4 , R 5 are selected from an optionally substituted aryl, an optionally substituted alkyl, an optionally substituted (alkoxy)alkyl, an optionally substituted (alkoxycarbonyl)alkyl, an optionally substituted (carboxylate)alkyl, an optionally substituted carbamoyl (-CON(
  • the at least one water soluble monoethylenically unsaturated monomer (A) may be monoethylenically unsaturated monomers containing at least one group selected from the group consisting of carboxyl, carboxylic anhydride and sulfonic acid, phosphoric acid and their salts thereof.
  • the at least one water soluble monoethylenically unsaturated monomer (A) includes, but is not limited to, monoethylenically unsaturated carboxylic acids, such as 2- acrylamido-2-methylpropane-sulfonic acid (AMPS), (meth)acrylic acid, itaconic acid, fumaric acid, citraconic acid, sorbic acid, cinnamic acid, glutaconic acid and maleic acid; monoethylenically unsaturated carboxylic anhydride, such as itaconic acid anhydride, fumaric acid anhydride, citraconic acid anhydride, sorbic acid anhydride, cinnamic acid anhydride, glutaconic acid anhydride and maleic acid anhydride ⁇ sodium-styrenesulfonate (SSS) or styrene sulfonic acid.
  • monoethylenically unsaturated carboxylic acids such as 2- acrylamido-2-methylpropane
  • 2-acrylamido-2-methylpropane- sulfonic acid or its salt, acrylic acid, methacrylic acid, itaconic acid, sodium- styrenesulfonate (SSS) or a mixture thereof is preferred as the at least one water soluble monoethylenically unsaturated monomer.
  • AMPS 2-acrylamido-2- methylpropane-sulfonic acid
  • SSS sodium-styrenesulfonate
  • the at least one water soluble monoethylenically unsaturated monomer (A) may account for, based on the total moles of monomers for the synthesis of the waterborne macro-RAFT agent, 30 to 90 mol %, preferably 35 to 85 mol %, more preferably 40 to 85 mol %, and most preferably 40 to 80 mol %.
  • the at least one water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group (B) may contain a functional group selected from a diacetone group, an acetoacetoxyl group, a ureido group, an oxazoline group, a carbodiimide group or any mixture thereof.
  • the at least one water soluble monoethylenically unsaturated monomer with at least one hydroxy group includes, but not limited to, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 3-phenoxy-2-hydroxy-propyl methacrylate, glycerol monomethacrylate, N-(2- hydroxypropyl)methacrylamide and N-hydroxyethyl acrylamide.
  • the at least one water soluble monoethylenically unsaturated monomer with at least one diacetone group includes, but not limited to, diacetone acrylamide (DAAM), hydroxymethyl diacetone acrylamide.
  • DAAM diacetone acrylamide
  • the at least one water soluble monoethylenically unsaturated monomer with at least one acetoacetoxyl group includes, but not limited to, acetoacetoxyethyl methacrylate (AAEM), acetoacetoxyethyl acrylate (AAEA), 2-[(E)-but-2-enoyl]oxyethyl 3-oxobutanoate, 2- methylprop-2-enyl 3-oxobutanoate, (E)-but-2-en-1-yl 3-oxobutanoate, prenyl 3-oxobutanoate and 2,3-dimethyl-but-2-enyl acetoacetate.
  • AAEM acetoacetoxyethyl methacrylate
  • AAAA acetoacetoxyethyl acrylate
  • the at least one water soluble monoethylenically unsaturated monomer with at least one ureido group includes, but not limited to, ureido methylacrylate, ureido acrylate, chemicals with the following structure:
  • the at least one water soluble monoethylenically unsaturated monomer with at least one oxazoline group includes, but not limited to, 2-vinyl-2-oxazoline, 2-ethylene-4-methyl-2- oxazoline, 2-ethylene-5-methyl-2-oxo, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2- oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline.
  • the at least one water soluble monoethylenically unsaturated monomer with at least one carbodiimide group includes, but not limited to, 1-vinylcarbodiimide, N-ethyl-N'-[(E)-1-methyl- 2-(methoxycarbonyl)vinyl]carbodiimide, N-propyl-N'-[(E)-1-methyl-2- (methoxycarbonyl)vinyl]carbodiimide, 1-cyclohexyl-3-(1-phenylvinyl)carbodiimide, 1-phenyl-3- (l-phenylvinyl)carbodiimide, N-phenyl-N'-(4-vinylphenyl)carbodiimide, and N-phenyl-N'- ethenylcarbodiimide.
  • the functional group is selected from a diacetone group, an acetoacetoxyl group, an oxazoline group or any mixture thereof.
  • the at least one water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group (B) is selected from diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate (AAEM), ureidomethacrylate (UMA) or any mixture thereof.
  • DAAM diacetone acrylamide
  • AAEM acetoacetoxyethyl methacrylate
  • UMA ureidomethacrylate
  • the at least one water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group (B) may account for, based on the total moles of monomers for the synthesis of the waterborne macro-RAFT agent, 1 to 60 mol %, preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and most preferably 3 to 40 mol %.
  • the at least one hydrophobic monoethylenically unsaturated monomer (C) may be selected from the group consisting of (meth)acrylate monomers, (meth)acrylonitrile monomers, styrene monomers, vinyl alkanoate monomers and monoethylenically unsaturated di-and tricarboxylic ester monomers.
  • the (meth)acrylate monomers may be Ci-Ci9-alkyl (meth)acrylates, for example, but not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate (i.e.
  • the styrene monomers may be unsubstituted styrene or Ci-Ce-alkyl substituted styrenes, for example, but not limited to, styrene, a-methylstyrene, ortho-, meta- and paramethylstyrene, ortho-, meta- and para-ethylstyrene, o,p-dimethylstyrene, o,p-diethylstyrene, ispropylstyrene, o-methyl-p-isopropylstyrene or any mixture thereof.
  • the vinyl alkanoate monomers may be vinyl esters of C2-Cn-alkanoic acids, for example, but not limited to, vinyl acetate, vinyl propionate, vinyl butanoate, vinyl valerate, vinyl hexanoate, vinyl versatate or a mixture thereof.
  • the monoethylenically unsaturated di-and tricarboxylic ester monomers may be full esters of monoethylenically unsaturated di-and tricarboxylic acids, for example, but not limited to, diethyl maleate, dimethyl fumarate, ethyl methyl itaconate, or any mixture thereof.
  • one or more Ci-Ci2-alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, styrene or a mixture thereof is chosen as the at least one hydrophobic monoethylenically unsaturated monomer (C).
  • the at least one hydrophobic monoethylenically unsaturated monomer (C) may account for, based on the total moles of monomers for the synthesis of the waterborne macro-RAFT agent, 1 to 50 mol %, preferably 5 to 45 mol %, more preferably 10 to 40 mol % and most preferably 15 to 35 mol %.
  • the at least one water-soluble Chain Transfer Agent has a general structure of Formula I: Formu
  • an "alkyl” refers to a monovalent group which is generated after a chain or cyclic aliphatic hydrocarbon (alkane) loses a hydrogen atom.
  • the alkyl group is generally represented by CkH2k+i- (wherein, k is a positive integer).
  • a chain alkyl group may be a straight chain or branched chain.
  • a cyclic alkyl group may be consisted of a cyclic structure.
  • a cyclic alkyl group may have a structure in which a chain alkyl group is linked to the cyclic structure.
  • An alkyl group may have an arbitrary natural number of carbon atoms. Preferably, an alkyl group has 1 to 30 carbon atoms.
  • a "lower alkyl” refers to an alkyl group having a relatively small number of carbon atoms.
  • a lower alkyl is a C1-10 alkyl group. More preferably, a lower alkyl is a C1-5 alkyl group. Further preferably, a lower alkyl is a C1-3 alkyl group. For instance, specific examples include methyl, ethyl, propyl and isopropyl.
  • an "alkoxy” refers to a group in which an oxygen atom is bound to the aforementioned alkyl group. That is, when the alkyl group is represented by R-, the alkoxy refers to a group represented by RO-.
  • a chain alkoxy group may be a straight chain or branched chain. Cyclic alkoxy may be composed only of a cyclic structure, or may have a structure formed from a cyclic structure further linked with chain alkyl.
  • the number of carbon atoms in the alkoxy may be any natural number. The number of carbon atoms is preferably from 1 to 30.
  • a “hydroxyalkyl” refers to a group in which a hydroxyl group is bonded to the aforementioned alkyl group. That is, when the alkyl group is represented by -R, the alkoxy refers to a group represented by -ROH.
  • a chain hydroxyalkyl group may be a straight chain or branched chain. Cyclic hydroxyalkyl may be composed only of a cyclic structure, or may have a structure formed from a cyclic structure further linked with chain alkyl.
  • the number of carbon atoms in the alkoxy may be any natural number. The number of carbon atoms is preferably from 1 to 30.
  • an "aryl” refers to a group which is generated after a hydrogen atom, which is bound to a ring of an aromatic hydrocarbon, is removed.
  • an aryl includes a phenyl group, naphthyl group, or anthracenyl group.
  • a "substituted aryl” is preferred, which refers to a group which is generated after a substituent bind to an aryl group.
  • a “carboxylate” refers to a “alkylcarboxyl”.
  • An "alkylcarboxyl” refers to a group in which a carboxyl group is bound to the aforementioned alkyl group. That is, when the alkyl group is represented by R-, the alkylcarboxyl refers to a group represented by RCOO-.
  • a chain alkylcarboxyl group may be a straight chain or branched chain.
  • a cyclic alkylcarboxyl group may be composed only of a cyclic structure, or may have a structure formed from a cyclic structure further linked with chain alkyl. The number of carbon atoms in the alkylcarboxyl may be any natural number.
  • the number of carbon atoms is preferably from 1 to 30.
  • a “carbonyl” refers to a “alkylcarbonyl”.
  • An "alkylcarbonyl” refers to a group in which a carbonyl group is bound to the aforementioned alkyl group. That is, when the alkyl group is represented by R-, the alkylcarbonyl refers to a group represented by RCO-.
  • a chain alkylcarbonyl group may be a straight chain or branched chain. Cyclic alkylcarbonyl may be composed only of a cyclic structure, or may have a structure formed from a cyclic structure further linked with chain alkyl.
  • the number of carbon atoms in the alkylcarbonyl may be any natural number.
  • the number of carbon atoms is preferably from 1 to 30.
  • a “lower alkylcarboxyl” and/or a “lower alkylcarbonyl” is preferred as the R 2 and/or R 3 .
  • a “lower alkylcarboxyl” refers to an alkylcarboxyl group having relatively fewer carbon atoms.
  • the lower alkylcarboxyl is preferably C1-10 alkylcarboxyl.
  • a “lower alkylcarbonyl” refers to an alkylcarbonyl group having relatively fewer carbon atoms.
  • the lower alkylcarbonyl is preferably C1-10 alkylcarbonyl.
  • an “acetoacetyl” group means a group with the following structure: wherein R a is a Ci to C22 alkylene group and R b is a Ci to C22 alkyl group.
  • R a is a Ci to C4 alkylene group and R b is a Ci to C4 alkyl group, and more preferably, R a is methylene (-CH2-) and R b is methyl (-CH3).
  • ureido means a group with the following structure:
  • a “carbodiimide” means a group with the following structure:
  • R is an alkyl group.
  • at least one water soluble Chain Transfer Agent (“CTA”) (D) inlcudes but not limited to, dibenzyl trithiocarboante (DBTTC), 1-phenylprop-2-yl phenyldithioacetate; 1 -phenylethyl phenyldithioacetate, cumyl phenylditioacetate, 2- phenylprop-2-yl dithiobenzoate; 1-phenylprop-2-yl p-bromodithiobenzoate; 1 -phenylethyl dithiobenzoate; 2-cyanoprop-2-yl dithiobenzoate; 4-cyanopentanoic acid dithiobenzoate; 1- acetoxyethyl dithiobenzoate; hexakis(thiobenzoylthiomethyl)benzene; 1,4- bis(thiobenzoylthiomethyl)benzene; 1,2,4,5-
  • CTA water
  • the at least one water soluble Chain Transfer Agent (“CTA”) (D) may account for, based on the total dry weight of the waterborne macro-RAFT agent, 1 to 30 wt %, preferably 1 to 20 wt %, more preferably 0.1 to 10.0 wt %.
  • the waterborne macro-RAFT agent may have a structure of Formula II:
  • Poly(A x -co-B y )-b-Poly(Cz) Formula II wherein it is synthesized with: i) 30 to 90 mol % (A) a water soluble monoethylenically unsaturated monomer which may contain at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid, or its salt thereof; ii) 1 to 60 mol % (B) a water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group selected from a diacetone group, an acetoacetoxyl group, a ureido group, an oxazoline group, an epoxy group, and a carbodiimide group; iii) 1 to 50 mol % (C) unsaturated hydrophobic monomers, selecting from n-butyl acrylate, styrene, ethyl
  • the waterborne macro-RAFT agent may have a structure of Formula II:
  • Poly(A x -co-B y )-b-Poly(Cz) Formula II wherein it is synthesized with: i) 35 to 85 mol % (A) a water soluble monoethylenically unsaturated monomer which may contain at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid, or its salt thereof; ii) 1 to 50 mol % (B) a water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group selected from a diacetone group, an acetoacetoxyl group, a ureido group, an oxazoline group, an epoxy group, and a carbodiimide group; iii) 5 to 45 mol % (C) unsaturated hydrophobic monomers, selecting from n-butyl acrylate, styrene, ethyl
  • the waterborne macro-RAFT agent may have a structure of Formula II:
  • Poly(A x -co-B y )-b-Poly(Cz) Formula II wherein it is synthesized with: i) 40 to 85 mol % (A) a water soluble monoethylenically unsaturated monomer which may contain at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid, or its salt thereof; ii) 3 to 45 mol % (B) a water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group selected from a diacetone group, an acetoacetoxyl group, a ureido group, an oxazoline group, an epoxy group, and a carbodiimide group; iii) 10 to 40 mol % (C) unsaturated hydrophobic monomers, selecting from n-butyl acrylate, styrene, ethyl
  • the waterborne macro-RAFT agent may have a structure of Formula II:
  • Poly(A x -co-B y )-b-Poly(Cz) Formula II wherein it is synthesized with: i) 40 to 80 mol % (A) a water soluble monoethylenically unsaturated monomer which may contain at least one functional group selected from a carboxylic acid group, a carboxylic acid anhydride group, a sulfonic acid group, a phosphoric acid, or its salt therefore; ii) 3 to 40 mol % (B) a water soluble monoethylenically unsaturated monomer with at least one crosslinkable functional group selected from a diacetone group, an acetoacetoxyl group, a ureido group, an oxazoline group, an epoxy group, and a carbodiimide group; iii) 15 to 35 mol % (C) unsaturated hydrophobic monomers, selecting from n-butyl acrylate, styrene, ethyl
  • x + y shall be larger than z (i.e. x + y > z), for all the embodiments.
  • the polymerization process for obtaining block copolymers are proceeded in aqueous phase, it is a typical polymerization-induced self-assembly (PISA) process.
  • PISA polymerization-induced self-assembly
  • monomer A, monomer B, initiator and small RAFT agent are water-soluble.
  • monomer C By adding monomer C, the block copolymer drives self-assembly in aqueous phase.
  • the final assemblies may have a particle size in the range of 55 to 250 nm, preferably in the range of 75 to 200 nm.
  • the waterborne macro-RAFT agent has been used in emulsion polymerization.
  • many polymerizable monomers known to the skilled person in the art in the field of emulsion polymerization may be used. It’s surprising that the emulsion polymer synthesized with the waterborne macro-RAFT agent has good stability, high solid content and a size range of 100 - 300 nm.
  • the emulsion polymerization in the present invention may apply at least one hydrophobic monoethylenically unsaturated monomer may be selected from, but not limited to, (meth)acrylate monomers, (meth)acrylonitrile monomers, styrene monomers, vinyl alkanoate monomers, monoethylenically unsaturated di-and tricarboxylic ester monomers or a mixture thereof.
  • the (meth)acrylate monomers may be Ci-Ci9-alkyl (meth)acrylates, for example, but not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate (i.e.
  • the styrene monomers may be unsubstituted styrene or Ci-Ce-alkyl substituted styrenes, for example, but not limited to, styrene, a-methylstyrene, ortho-, meta- and paramethylstyrene, ortho-, meta- and para-ethylstyrene, o,p-dimethylstyrene, o,p-diethylstyrene, ispropylstyrene, o-methyl-p-isopropylstyrene or any mixture thereof.
  • the vinyl alkanoate monomers may be vinyl esters of C2-Cn-alkanoic acids, for example, but not limited to, vinyl acetate, vinyl propionate, vinyl butanoate, vinyl valerate, vinyl hexanoate, vinyl versatate or a mixture thereof.
  • the monoethylenically unsaturated di-and tricarboxylic ester monomers may be full esters of monoethylenically unsaturated di-and tricarboxylic acids, for example, but not limited to, diethyl maleate, dimethyl fumarate, ethyl methyl itaconate, dihexyl succinate, didecyl succinate or any mixture thereof.
  • one or more Ci-Ci2-alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene or a mixture thereof is chosen as the at least one hydrophobic monoethylenically unsaturated monomer.
  • the at least one hydrophobic monoethylenically unsaturated monomer may be in an amount of at least 70 wt %, all based on the total weight of all monomers used in the emulsion polymerization.
  • the emulsion polymerization in the present invention may apply at least one additional hydrophilic monoethylenically unsaturated monomer may be monoethylenically unsaturated monomers containing at least one functional group selected from, but not limited to, a group consisting of carboxyl, carboxylic anhydride, sulfonic acid, phosphoric acid, hydroxyl and amide.
  • the hydrophilic monoethylenically unsaturated monomer include, but are not limited to, monoethylenically unsaturated carboxylic acids, such as (meth)acrylic acid, itaconic acid, fumaric acid, citraconic acid, sorbic acid, cinnamic acid, glutaconic acid and maleic acid; monoethylenically unsaturated carboxylic anhydrides, such as itaconic acid anhydride, fumaric acid anhydride, citraconic acid anhydride, sorbic acid anhydride, cinnamic acid anhydride, glutaconic acid anhydride and maleic acid anhydride; monoethylenically unsaturated amides, such as (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethylacrylamide (DMA), 2- hydroxyethyl (meth)acrylamide, dimethylaminoethylmethacrylamide; hydroxyalkyl esters of mono
  • acrylic acid, methacrylic acid, acrylamide or a mixture thereof is the preferred at least one water soluble monoethylenically unsaturated monomer.
  • the hydrophilic monoethylenically unsaturated monomer can be in an amount of at least 0.1 % by weight and no more than 20.0 % by weight, preferably no more than 15 % by weight, more preferably no more than 10.0 % by weight, and mostly preferably no more than 5.0 % by weight, based on the total weight of all monomers used in the emulsion polymerization.
  • the monomers for the synthesis of the polymer emulsion may further comprise one or more crosslinking monomers.
  • the crosslinking monomers can be chosen from, but not limited to, di- or poly-isocyanates, polyaziridines, polycarbodiimide, polyoxazolines, glyoxals, malonates, triols, epoxy molecules, organic silanes, carbamates, diamines and triamines, hydrazides, carbodiimides and multi-ethylenically unsaturated monomers.
  • suitable crosslinking monomers include, but not limited to, glycidyl (meth)acrylate, N- methylol(meth)acrylamide, (isobutoxymethyl)acrylamide, vinyltrialkoxysilanes such as vinyltrimethoxysilane; alkylvinyldialkoxysilanes such as dimethoxymethylvinylsilane; (meth)acryloxyalkyl-trialkoxysilanes such as (meth)acryloxyethyltrimethoxysilane, (3- acryloxypropyl)trimethoxysilane and (3-methacryloxypropyl)trimethoxysilane; allyl (meth)acrylate, diallyl phthalate, 1,4-butylene glycol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, divinyl benzene or any mixture thereof.
  • the monomers could further include other suitable polymerizable compounds, which include, but not limited to, olefins, such as ethylene, propene, cloropropene, butene, 1-decene; dienes, such as butadiene, isoprene, cloroprene, norbornadiene; N-vinyl compounds, such as N-vinyl- 2-pyrrolidone (NVP), N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N- methyl acetamide and N-vinyl caprolactam.
  • olefins such as ethylene, propene, cloropropene, butene, 1-decene
  • dienes such as butadiene, isoprene, cloroprene, norbornadiene
  • N-vinyl compounds such as N-vinyl- 2-pyrrolidone (NVP), N-
  • Surfactants may also be polymerizable surfactants, also called a reactive surfactant, containing at least one ethylenically unsaturated functional group.
  • Suitable polymerizable surfactants include, but are not limited to, allyl polyoxyalkylene ether sulfate salts such as sodium salts of allyl polyoxyethylene alkyl ether sulfate, allyl alkyl succinate sulfonate salts, allyl ether hydroxyl propanesulfonate salts such as sodium salts, polyoxyethylene styrenated phenyl ether sulfate salts such as ammonium salts, for example DKS Hitenol® AR 1025 and DKS Hitenol® AR 2020, polyoxyethylene alkylphenyl ether sulfate ammonium salts, polyoxyethylene allyloxy nonylphenoxypropyl ether, and phosphate acrylates such as SI POM ER® PAM 100, phosphate
  • surfactant-free emulsion polymerization Such a process is referred to as “surfactant-free emulsion polymerization” and the resulted emulsion polymer is usually termed as “surfactant-free emulsion polymer”.
  • An organic base and/or inorganic base may be added into the polymerization system as a neutralizer during the polymerization or after the completion of such process.
  • Suitable neutralizers include, but are not limited to, inorganic bases such as ammonia, sodium/potassium hydroxide, sodium/potassium carbonate or a combination.
  • Organic bases such as dimethyl amine, diethyl amine, triethyl amine, monoethanolamine, triethanolamine, or a mixture thereof can also be used as the neutralizer.
  • sodium hydroxide, ammonia, dimethylaminoethanol, 2-amino-2-methyl-1-propanol or any mixture thereof are preferable as the neutralizer useful for the polymerization process.
  • pH of the final polymer emulsion shall be in the range of 5.0 to 10.0, preferably in the range of 5.0 to 8.0.
  • the polymer latex could be further formulated with crosslinkers.
  • Suitable crosslinkers may include, but not limited to, dihydrazide, such as, oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and/or isophthalic dihydrazide or mixture thereof.
  • dihydrazide such as, oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and/or isophthalic dihydrazide or mixture thereof.
  • Particular preferences are adipic
  • Suitable compounds containing hydroxylamine groups or oxime ether groups are specified for example in WO 9325588.
  • Other suitable crosslinkers can be the compounds containing amino groups include ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimines, partly hydrolyzed polyvinylformamides, cyclohexanediamine, and xylylenediamine or mixture thereof.
  • AMPS 2-Acrylamido-2-methylpropane-sulfonic acid
  • NaHCCh Sodium hydrogen carbonate
  • SPS Sodium persulfate
  • BA n-Butyl acrylate
  • Styrene (noted as “St”), from (Sigma-Aldrich)
  • MMA Methyl methacrylate
  • 2-Ethylhexyl acrylate (noted as “2-EHA”), from (Sigma-Aldrich)
  • Adipic acid dihydrazide (noted as “ADH”), from (Sigma-Aldrich)
  • St, BA, 2-EHA, MMA and VAc were purified by a basic aluminium oxide column.
  • GPC Gel Permeation Chromatography
  • PMMA poly(methyl methacrylate)
  • PSt polystyrene
  • DLS results were recorded at 25 °C on a Malvern Zetasizer Nano equipment comprising an avalanche photodiode (APD) detector.
  • the sample was measured at a concentration of 0.3 - 0.5 mg mL -1 in DI water by using a 4 mW He-Ne laser at a wavelength of 633 nm.
  • the measurement gives an average value of the second order cumulant analysis (mean of fits), i.e. Z average.
  • the "mean of fits" is an average, intensity-weighted hydrodynamic particle diameter in nm.
  • the monomer conversion was determined by 1 H NMR.
  • the 1 H NMR spectra were recorded on 400 MHz Bruker instrument.
  • DMSO-cfe (62.50), D2O (64.70) and MeOD (63.30) were used as the solvents for the NMR analysis, and the chemical shift was calibrated using tetramethylsilane (TMS) as the internal standard.
  • TMS tetramethylsilane
  • Latex films were prepared under room temperature for 2 weeks (temperature: 23 °C; humidity: 50 %).
  • the targeting films were prepared with dimensions of 1 mm thickness.
  • DMA measurements were performed by using an Anton Paar MCR302 rheometer with the oscillation mode (strain: 0.05 %; rate: 10 rad/s).
  • a stoichiometric amount of ADH solution was added in each of the latex.
  • the molar ratio of DAAM/ADH is around 2/1.
  • 0.42 g of 10 wt % of ADH aqueous solution was added to 10.0 g of a latex and stirred vigorously to obtain the final composition.
  • the DMA results presented in Table-1 show that all the films made with the composition of ADH in the present invention have the higher storage modulus. More specifically, according to the data listed in Table 2, the DAAM-based RAFT latexes indicate higher storage modulus with respect to non-DAAM containing latex.
  • the resulting polymer latexes are subjected to stability test.
  • Freeze-thaw stability test is performed by exposing the latex samples in a - 5 °C freezer for 24 hours, and then allowing them to thaw at ambient temperature for another 24 h. After each cycle, the latex samples are analysed by visual observation on physical changes, e.g. flow behaviour, coagulum. After 3 cycles, if no significant changes are observed, it is the demonstration that the latex samples can pass the freeze-thaw stability test. P stands for pass and F means failure. And, the freeze-thaw stability test results are listed in Table 3. Table-3 Freeze-Thaw Stability (F/T Stability)

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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)

Abstract

: L'invention divulgue un macro-agent RAFT à base d'eau amphiphile et le procédé de fabrication de latex à l'aide d'un tel macro-agent RAFT à base d'eau amphiphile, ainsi que les compositions de ce dernier. Le macro-agent RAFT à base d'eau amphiphile vivant est préparé en phase aqueuse par la technologie PISA. Le macro-agent RAFT à base d'eau peut être synthétisé avec (A) au moins un monomère à insaturation monoéthylénique soluble dans l'eau, (B) au moins un monomère à insaturation monoéthylénique soluble dans l'eau ayant au moins un groupe fonctionnel réticulable, (C) au moins un monomère hydrophobe à insaturation monoéthylénique, et (D) au moins un agent de transfert de chaîne (« CTA ») soluble dans l'eau. Ce macro-agent RAFT à base d'eau (auto-assemblages) peut être utilisé pour produire un latex sans tensioactif présentant une bonne stabilité et une teneur en solides élevée, qui peut être appliqué dans le domaine des revêtements, des adhésifs, de la fabrication de papier ainsi que dans le domaine du ciment.
PCT/EP2022/082982 2021-12-03 2022-11-23 Préparation de latex sans tensioactif, à teneur élevée en solides, à l'aide d'un macro-agent raft à base d'eau amphiphile fonctionnel WO2023099310A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993025588A1 (fr) 1992-06-13 1993-12-23 Basf Aktiengesellschaft Dispersions ou solutions contenant des composes hydroxylamine utilises comme agents de reticulation
US20170362425A1 (en) * 2016-06-15 2017-12-21 Rhodia Operations High Performance Surfactant Free Latexes for Improved Water Resistance

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993025588A1 (fr) 1992-06-13 1993-12-23 Basf Aktiengesellschaft Dispersions ou solutions contenant des composes hydroxylamine utilises comme agents de reticulation
US20170362425A1 (en) * 2016-06-15 2017-12-21 Rhodia Operations High Performance Surfactant Free Latexes for Improved Water Resistance

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEN SHENG-LI ET AL: "In situsynthesis of block copolymer nano-assemblies by polymerization-induced self-assembly under heterogeneous condition", CHINESE JOURNAL OF POLYMER SCIENCE, CHINESE CHEMICAL SOCIETY AND INSTITUTE OF CHEMISTRY, CAS, BEIJING, vol. 35, no. 4, 10 January 2017 (2017-01-10), pages 455 - 479, XP036129115, ISSN: 0256-7679, [retrieved on 20170110], DOI: 10.1007/S10118-017-1907-8 *
FEIZHOU WANG ET AL: "Synthesis and Redispersibility of Poly(styrene- block - n -butyl acrylate) Core?Shell Latexes by Emulsion Polymerization with RAFT Agent?Surfactant Design", MACROMOLECULES, vol. 48, no. 5, 20 February 2015 (2015-02-20), US, pages 1313 - 1319, XP055653109, ISSN: 0024-9297, DOI: 10.1021/ma502564m *
XU KE ET AL: "Nanoparticle Surface Cross-Linking: A Universal Strategy to Enhance the Mechanical Properties of Latex Films", MACROMOLECULES, vol. 55, no. 13, 29 June 2022 (2022-06-29), US, pages 5301 - 5313, XP093016570, ISSN: 0024-9297, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/acs.macromol.2c00688> DOI: 10.1021/acs.macromol.2c00688 *

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