EP3033363A1 - Procédés de polymérisation en émulsion - Google Patents

Procédés de polymérisation en émulsion

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Publication number
EP3033363A1
EP3033363A1 EP14771210.3A EP14771210A EP3033363A1 EP 3033363 A1 EP3033363 A1 EP 3033363A1 EP 14771210 A EP14771210 A EP 14771210A EP 3033363 A1 EP3033363 A1 EP 3033363A1
Authority
EP
European Patent Office
Prior art keywords
acid
water soluble
chitosan
stabilizer
emulsion polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14771210.3A
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German (de)
English (en)
Inventor
Martin Jakob
Jonas KÖNECKE
Karlheinz Rockel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese Sales Germany GmbH
Original Assignee
Celanese Emulsions GmbH
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Filing date
Publication date
Application filed by Celanese Emulsions GmbH filed Critical Celanese Emulsions GmbH
Publication of EP3033363A1 publication Critical patent/EP3033363A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • 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
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the present invention relates to methods of emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of an aqueous phase comprising a water soluble chitosan salt and at least one co-stabilizer.
  • the present invention also relates to an aqueous dispersion prepared by emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of an aqueous phase comprising a water soluble chitosan salt and at least one co- stabilizer.
  • the present invention further relates to emulsion polymers and adhesives, binders or coatings containing the emulsion polymers.
  • Emulsion polymerization is a free-radical polymerization that is generally conducted in the presence of at least one monomer, at least one stabilizer, an initiator, and a continuous phase, typically water.
  • the stabilizer may be an emulsifier or protective colloid, used to prevent agglomeration of particles within the emulsion and to affect viscosity and rheology.
  • Protective colloids are preferably water-soluble and non-ionic. Known protective colloids include natural polymers, modified-natural polymers, and synthetic polymers.
  • Chitosan is a linear polysaccharide containing randomly distributed ⁇ -(1 - 4) linked D-glucosamine and N-acetyl-D glucosamine. It is produced through the deacetylation of chitin, the structural element in the exoskeleton of crustaceans. Chitosan is abundant in nature, is biodegradable, and has low potential for toxicity. Chitosan has been used in the agricultural, medical, and winemaking fields. See, for example, U.S. Pub. Nos. 2006/0171999 and 2002/0143081 .
  • chitosan has not been pursued as an emulsion polymerization stabilizer. Instead, chitosan is added after polymerization.
  • U.S. Pat. No. 5,01 1 ,864 discloses a water absorbent latex polymer produced by the process of combining a foamed latex polymer product with both a water absorbent polymer and chitin, and drying that blend to form a foamable latex polymer containing both water absorbent polymer and chitin.
  • 7,736,423 teaches an aqueous composition for outdoor, indoor, fagade and roof paints having a biocidal action.
  • the composition comprises chitosan, chitosan derivatives, or combinations thereof, and is formed by mixing silver nitrate and chitosan to an aqueous dispersion.
  • WO 2012/015863 teaches a low-formaldehyde binder composition for increasing wet and dry tensile strength of a nonwoven substrate, including an aqueous vinyl acetate ethylene copolymer dispersion employing a nonionic, cationic or amphoteric dispersion stabilizer, chitosan, and one or more surfactants not including the dispersion stabilizer.
  • the chitosan is added to the copolymer dispersion after the copolymer dispersion is formed. Similar additions of chitosan after the formation of a polymer are taught in U.S. Pat. No. 8,349,343.
  • a chitosan derivative that may be used for its stabilizing properties during emulsion polymerization and that is retained with the polymer for use in end products.
  • the present invention is directed to a method of emulsion polymerization of at least one ethylenically unsaturated monomer selected from the group consisting of esters of ethylenically unsaturated monocarboxylic and dicarboxylic acids, vinyl esters, C2-C4 olefins, vinyl halides, and vinyl aromatics, the method comprising: a) forming an aqueous phase comprising conducting the emulsion polymerization in the presence of an aqueous phase comprising: i) a water soluble chitosan salt having a degree of deacetylation of chitosan of less than 95 mol.%; and ii) at least one co-stabilizer.
  • the water soluble chitosan salt may be prepared by converting chitosan to a water soluble salt in the presence of water and a chitosan salt forming acid.
  • the chitosan salt forming acid may be selected from the group consisting of C1 -C18 monocarboxylic acids (such as formic acid, acetic acid and propionic acid or higher acids, acetylsalicylic acid, amino acids, adipic acid, ascorbic acid, aspartic acid, citric acid, iminodiacetic acid, itaconic acid, maleamic acid, fumaric acid, glyoxylic acid, glycolic acid, glutamic acid, glutaric acid, lactic acid, maleic acid, malonic acid, N-acetylglycine, nicotinic acid, 2-pyrrolidone-5-carboxylic acid, pyruvic acid, salicylic acid, succinamic acid, succinic acid, tartaric acid, thioacetic acid,
  • the aqueous phase may further comprise a water soluble chain transfer agent.
  • the water soluble chain transfer agent is a co-acid used to form the chitosan salt.
  • the pH of the aqueous phase may be less than 5.
  • the at least one co-stabilizer may be present in an amount from 0.01 to 20 wt.%, based on the total weight of the at least one monomer.
  • the co-stabilizer may be an emulsifier and/or a protective colloid having a neutral or positive charge.
  • the co- stabilizer may be selected from the group consisting of polyvinyl alcohols, modified polyvinyl alcohols, polyethylene glycols, polyvinyl acetals, polyvinylpyrrolidones, polysaccharides or modified polysaccharides in water soluble form, proteins and other polymers of natural origin, synthetic polymers; polyurethane stabilizers, nonionic emulsifiers and cationic emulsifiers.
  • the co- stabilizer is polyvinyl alcohol.
  • the aqueous phase may comprise at least 0.2 wt.% water soluble chitosan salt, or from 0.2 to 5 wt.% water soluble chitosan salt based on the total weight of the at least one monomer.
  • the water soluble chitosan salt may be selected from the group consisting of chitosan acetate, chitosan propionate, chitosan lactate and other salts with solubility of greater than or equal to 1 % in aqueous solution.
  • the chitosan salt used in the aqueous phase may have a viscosity of less than 1000 mPa » s in 1 % aqueous solution.
  • the emulsion polymerization may be performed in the presence of an initiator.
  • the initiator may be present in an amount of at least 0.05 wt.%, based on the total weight of the at least one monomer.
  • the initiator may be a thermal initiator or a redox initiator.
  • the initiator may be a persulfate.
  • the emulsion polymerization may be performed in the presence of a functional co-monomer.
  • the emulsion polymerization may be performed at a temperature from 30 to 100°C and at a pressure from 10 to 10,000 kPa.
  • the emulsion polymer formed by the method described herein may be used in an adhesive, binder or coating.
  • the emulsion polymer may also be used in agricultural coating formulations, in pharmaceutical or medical formulations, and/or in formulations for treating waste water.
  • the present invention is directed to an aqueous dispersion prepared by emulsion polymerization of at least one ethylenically unsaturated monomer selected from the group consisting of esters of ethylenically unsaturated monocarboxylic and dicarboxylic acids, vinyl esters, C2-C4 olefins, vinyl halides, and vinyl aromatics, wherein the emulsion polymerization is conducted in the presence of an aqueous phase comprising a water soluble chitosan salt and a co-stabilizer.
  • the aqueous dispersion may comprise from 20 to 70% solids.
  • the aqueous dispersion may have a pH of less than 5 or of less than 4.
  • the present invention is directed to an emulsion polymer prepared by emulsion polymerization of at least one ethylenically unsaturated monomer selected from the group consisting of esters of ethylenically unsaturated monocarboxylic and dicarboxylic acids, vinyl esters, C2-C4 olefins, vinyl halides, and vinyl aromatics, wherein the emulsion polymerization is conducted in the presence of an aqueous phase comprising a water soluble chitosan salt having a degree of deacetylation of chitosan of less than 95 mol.% and at least one co-stabilize.
  • the present invention is directed to an adhesive, binder or coating containing the emulsion polymer prepared by emulsion polymerization of at least one ethylenically unsaturated monomer selected from the group consisting of esters of ethylenically unsaturated monocarboxylic and dicarboxylic acids, vinyl esters, C2-C4 olefins, vinyl halides, and vinyl aromatics, wherein the emulsion polymerization is conducted in the presence of an aqueous phase comprising: i) a water soluble chitosan salt having a degree of deacetylation of chitosan of less than 95 mol.% and a co-stabilizer.
  • an aqueous phase comprising: i) a water soluble chitosan salt having a degree of deacetylation of chitosan of less than 95 mol.% and a co-stabilizer.
  • this invention relates to emulsion polymerization conducted in the presence of a water soluble chitosan salt, and products produced therefrom.
  • this invention relates to emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of an aqueous phase formed by combining a water soluble chitosan salt with at least one co-stabilizer.
  • the water soluble chitosan salt may have a degree of deacetylation of chitosan of less than 95 mol.%.
  • the at least one ethylenically unsaturated monomer may be selected from the group consisting of esters of ethylenically unsaturated monocarboxylic and dicarboxylic acids, vinyl esters, C2-C4 olefins, and vinyl aromatics.
  • This invention also relates to an aqueous dispersion prepared by emulsion polymerization of at least one ethylenically unsaturated monomer, wherein the emulsion polymerization occurs in the presence of a water soluble chitosan salt and a co-stabilizer.
  • This invention further relates to an adhesive, binder or coating composition containing the emulsion polymer prepared by the emulsion polymerization methods described herein.
  • the present invention provides an industrially feasible emulsion polymerization method using a water soluble chitosan salt as a stabilizer.
  • the first step in the emulsion polymerization method is the formation of an aqueous phase comprising a water soluble chitosan salt and at least one co-stabilizer.
  • aqueous phase comprising a water soluble chitosan salt and at least one co-stabilizer.
  • the water soluble chitosan salt may be selected from the group consisting of chitosan acetate, chitosan propionate, chitosan lactate, and other chitosan salts having a solubility of greater than or equal to 1 % in aqueous solution.
  • the water soluble chitosan salt may be prepared by converting chitosan to a water soluble salt in the presence of water and a chitosan salt forming acid.
  • Methods for converting chitosan to a chitosan salt are disclosed in U.S. Pat. Nos. 2,040,979 and 2,040,880, the entire contents and disclosures of which are hereby incorporated by reference.
  • the chitosan salt forming acid may be an organic acid or an inorganic acid. In some embodiments, the chitosan salt forming acid is an organic acid.
  • the chitosan salt forming acid may be selected from the group consisting of acetic acid, propionic acid, higher carboxylic acids, acetylsalicylic acid, amino acids, adipic acid, ascorbic acid, aspartic acid, citric acid, iminodiacetic acid, itaconic acid, formic acid, maleamic acid, fumaric acid, glyoxylic acid, glycolic acid, glutamic acid, glutaric acid, lactic acid, maleic acid, malonic acid, N-acetylglycine, nicotinic acid, nicotinic acid, 2-pyrrolidone-5-carboxylic acid, pyruvic acid, salicylic acid, succinamic acid, succinic acid, tartaric acid, thioacetic acid, thiolactic acid, sulfonyldiacetic acid, thiodiacetic acids and thioglycolic acids, and combinations thereof.
  • the water soluble chitosan salt may have a degree of deacetylation of less than 95 mol.%, e.g., less than 93 mol.%. In terms of ranges, the water soluble chitosan salt may have a degree of acetylation from 75 to 95 mol.%, e.g., from 75 to 93 mol.%.
  • the water soluble chitosan salt may have a water solubility from 0.5 to 5 %.
  • the water soluble chitosan salt may be provided in solution and may have a viscosity at 1 wt.% strength at 20°C of less than 1000 mPa » s, e.g., less than 500 mPa s or less than 100 mPa s. In terms of ranges, the viscosity at 1 wt.% strength at 20°C may range from 1 to 1000 mPa-s, e.g., from 10 to 500 mPa-s or from 20 to 100 mPa-s. The molecular weight of the water soluble chitosan salt may be selected to achieve this viscosity.
  • the water soluble chitosan salt solution may have a pH of less than 5.
  • the water soluble chitosan salt may be added to water (e.g., demineralized) in a single charge or in multiple charges.
  • the aqueous phase may comprise at least 0.2 wt.% water soluble chitosan salt, based on the total weight of the at least one monomer, e.g., at least 0.5 wt.%, at least 1 wt.%, at least 2 wt.%, or at least 3 wt.%.
  • the aqueous phase may comprise from 0.2 to 5 wt.% water soluble chitosan salt, based on based on the total weight of the at least one monomer, e.g., from 0.5 to 4 wt.% or from 1 to 3 wt.%.
  • the aqueous phase further comprises at least one co-stabilizer.
  • the co-stabilizer is an emulsifier and/or a protective colloid having a positive or neutral charge.
  • the co-stabilizer is selected from the group consisting of polyvinyl alcohols, modified polyvinyl alcohols, polyethylene glycols, polyvinyl acetals, polyvinylpyrrolidones, polysaccharides or modified polysaccharides in water soluble form, proteins and other polymers of natural origin, synthetic polymers; polyurethane stabilizers, nonionic emulsifiers, cationic emulsifiers and combinations thereof.
  • the co-stabilizer may be present from 0.01 to 20 wt.%.
  • nonionic emulsifiers include, but are not limited to, acyl, alkyl, oleyl, and alkylaryl oxyethylates. These products are available commercially, for example, under the name Genapol®, Emulsogen® or Lutensol®.
  • ethoxylated mono-, di-, and tri-alkylphenols (EO degree: 3 to 80, alkyl substituent radical: C 4 to C12) and also ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: Cs to C36), especially C12-C14 fatty alcohol (3-80)ethoxylates, C13C15 oxo-process alcohol (3-80)-ethoxylates, C16C18 fatty alcohol (1 1 - 80)ethoxylates, C10 oxo-process alcohol (3-80)ethoxylates, Ci 3 oxo-process alcohol (3-80)ethoxylates, polyoxyethylenesorbitan monooleate with 20 ethylene oxide groups, copolymers of ethylene oxide and propylene oxide with a minimum ethylene oxide content of 10% by weight, the polyethylene oxide (4-80) ethers of oleyl alcohol, and the polyethene oxide (4-80) ethers of nony
  • Cationic emulsifiers include, but are not limited to, alkyl quaternary ammonium salts and alkyl quaternary phosphonium salts such as: alkyl trimethyl ammonium chloride, dieicosyldimethyl ammonium chloride; didocosyldimethyl ammonium chloride; dioctadecyldimethyl ammonium chloride; dioctadecyldimethyl ammonium methosulphate; ditetradecyldimethyl ammonium chloride and naturally occurring mixtures of above fatty groups, e.g.
  • di(hydrogenated tallow) dimethyl ammonium chloride di(hydrogenated tallow) dimethyl ammonium methosulphate; ditallow dimethyl ammonium chloride; and dioleyldimethyl ammonium chloride.
  • useful stabilizers include, but are not limited to cationically modified polyvinyl alcohol), cationically modified starch.
  • Specific cationic emulsifiers include alkyl trimethyl ammonium chlorides, such as cetyl trimethyl ammonium chloride and lauryl trimethyl ammonium chloride
  • the amount of emulsifiers, based on the total weight of the least one monomer is typically up to 10%, preferably 0.1 % to 6.0%, more preferably 0.5% to 5.0%, and very preferably 1 .0% to 4.0% by weight.
  • protective colloids include polyvinyl alcohols; polyvinyl acetals; polyvinylpyrrolidones; polysaccharides in water-soluble form, such as starches (amylose and amylopectin), modified starches, celluloses and their carboxymethyl, methyl, hydroxyethyl, and hydroxypropyl derivatives, in particular cationic or electroneutral derivatives, proteins, such as casein or caseinate, soy protein, gelatin; lignosulfonates; synthetic polymers such as poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxyl-functional co-monomer units, poly(meth)acrylamide, polyvinylsulfonic acids, and water-soluble copolymers thereof; melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, styrene-maleic acid copolymers and vinyl ether-
  • the protective colloid is polyvinyl alcohol.
  • Suitable polyvinyl alcohols possess degrees of hydrolysis from 60 to 100 mol%, preferably from 70 to 99 mol%, and viscosities of the 4% strength aqueous solutions at 20° C. of 2-70 mPa * s, more particularly 30 to 60 mPa s.
  • polyvinyl alcohol i.e., polyvinyl alcohol composed only of vinyl alcohol groups and residual vinyl acetate groups
  • copolymeric and/or functionalized polyvinyl alcohols examples being reaction products of polyvinyl alcohol with diketene or with types of polyvinyl alcohols that carry carboxyl groups, thiol groups, formamido groups, amino groups, arylamino groups, sulfate groups, sulfonate groups, phosphonate groups, quaternary ammonium groups, and other functional groups, such as partially acetalized polyvinyl alcohols.
  • Mixtures of protective colloids may also be used.
  • protective colloids are used, their amount, based on the total weight of the at least one monomer, may range from 0.01 to 20 wt.%, e.g., from 0.1 to 15 wt.% or from 2 to 10 wt.%.
  • the aqueous phase may comprise additional components, including chain transfer agents.
  • the chain transfer agent may be selected from the group consisting of monofunctional and multifunctional thiols and alkyl halides and other compounds known to be active in free radical chain transfer methods such as 2,4- diphenyl-4-methyl-1 -pentene.
  • Suitable thiols include but are not limited to: C2-C8 alkyl thiols such as dodecane thiol.
  • Thiol- containing oligomers may also be used such as oligo(cysteine) or an oligomer which has been post-functionalized to give a thiol group(s), such as oligoethylene glycolyl (di)thio glycolate, thiopropionic acid and esters thereof such as butyl-3-mercaptopropionate and octyl-3- mercaptopropionate,.
  • thiols include linear or branched alkylthiols such as dodecyl mercaptan, thio alcohols such as thioethanol, thio alkyl esters such as octyl-3-mercaptopropionate and thio acids such as thio lactic acid.
  • Xanthates, dithioesters, and dithiocarbonates may also be used, such as cumyl phenyldithioacetate.
  • More preferred chain transfer agents comprise: thiolactic acid, thioglycolic acid, thioglycerol, thioethanol, cysteine and cysteamine.
  • the chain transfer agent may be a co-acid, e.g., an acid in addition to the acid used to convert the chitosan into a water soluble chitosan salt.
  • the chain transfer agent is thiolactic or thioglycolic acid.
  • the chain transfer agent may be present from 0.001 to 2 parts, based on the total weight of the at least one monomer, e.g., from 0.005 to 1 parts or from 0.01 to 0.8 parts.
  • the aqueous phase may have a pH of less than 5, e.g., less than 4. In terms of ranges, the pH may range from 1 to 5, e.g., from 2 to 5 or from 3 to 4.
  • the pH of the aqueous phase may be adjusted after the addition of the water soluble chitosan salt, monomers, co-stabilizers and any other components that may affect the pH of the aqueous phase. If necessary, the pH may be adjusted by adding a buffer, such as sodium acetate, sodium citrate, disodium phosphate, and other known buffers. In some embodiments, the buffer may be sodium acetate.
  • the pH of the aqueous phase may also be adjusted by adding alkali hydroxides, carbonates or hydrogen carbonates, carboxylic acids like formic acid or other strong organic or inorganic acids until a pH of less than 5, e.g., less than 4 is reached.
  • the at least one ethylenically unsaturated monomer may be selected from the group consisting of esters of ethylenically unsaturated monocarboxylic and dicarboxylic acids, vinyl esters, C2-C4 olefins, vinyl halides, and vinyl aromatics.
  • Suitable vinyl esters include the vinyl esters of monocarboxylic acids containing from one to eighteen carbon atoms. Examples of these esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl decanoate, Additional vinyl esters may include vinyl esters of saturated branched monocarboxylic acids having 5 to 15 carbon atoms in the acid radical, vinyl esters of VersaticTM acids, vinyl esters of relatively long-chain saturated or unsaturated fatty acids such as vinyl laurate, vinyl stearate, and also vinyl esters of benzoic acid and of substituted derivatives of benzoic acid, such as vinyl p-tert-butylbenzoate or isopropenyl acetate. In some specific embodiments, the vinyl ester is vinyl acetate.
  • Another group of monomers which can be used is formed by aliphatic, monoolefinically or diolefinically unsaturated, optionally halogen-substituted hydrocarbons, such as ethene, propene, 1 -butene, 2-butene, isobutene, conjugated C 4 -Cs dienes, such as 1 ,3-butadiene, isoprene, chloroprene, and vinyl halides including vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride.
  • optionally halogen-substituted hydrocarbons such as ethene, propene, 1 -butene, 2-butene, isobutene, conjugated C 4 -Cs dienes, such as 1 ,3-butadiene, isoprene, chloroprene, and vinyl halides including vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride
  • a further group of monomers which can be used is formed by esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids, preferably esters of ⁇ , ⁇ -ethylenically unsaturated C3-C8 monocarboxylic or dicarboxylic acids, with preferably C1-C18 alkanols and more particularly with Ci-Cs alkanols or with Cs-Cs cycloalkanols.
  • the esters of the dicarboxylic acids may be monoesters or, preferably, diesters.
  • Ci-Cs alkanols are methanol, ethanol, n- propanol, isopropanol, 1 -butanol, 2-butanol, isobutanol, tert-butanol, n-hexanol, and 2-ethylhexanol.
  • suitable cycloalkanols are cyclopentanol or cyclohexanol.
  • esters of acrylic acid, of methacrylic acid, of crotonic acid, of maleic acid, of itaconic acid, of citraconic acid or of fumaric acid such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 1 -hexyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, di-n-methyl maleate or fumarate, di-n- ethyl maleate or fumarate, di-n-propyl maleate or fumarate, di-n-butyl maleate or fumarate, diisobutyl maleate or fumarate, di-n-pentyl maleate or fumarate, di-n- hexyl maleate or fumarate, dicyclohex
  • a yet further group of monomers may be formed from alkenyl aromatics, e.g., monoalkenyl aromatics. Examples include styrene, vinyltoluene, vinylxylene, a-methylstyrene or o-chlorostyrene.
  • the monomer composition may include at least one co-monomer, e.g., a functional co-monomer.
  • Suitable functional co-monomers may include acrylic and methacrylic acids, esters of methacrylic acid, half esters of maleic acid (e.g., monoethyl, monobutyl or monooctyl maleate), beta carboxy ethyl acrylate, (meth)acrylamide, ⁇ , ⁇ -dimethyl acrylamide, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, N-methylol(meth)acrylamide, N-vinylpyrrolidinone, and N-vinyl formamide), glycidyl monomers like glycidyl methacrylate, N-(2,3-epoxy)-propylacryl amide, N-(2,3-epoxy)-propylmethacryl amide, 4-acrylamidophenylglycidyl ether, 3- acrylamidophenylglycidyl ether, 4-methacrylamidophenylglycidyl ether, 3- meth
  • a further group of functional co-monomers may be formed of amino group bearing co-monomers including aminoethyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 4-amino-n-butyl acrylate, 4-amino-n-butyl methacrylate, 2-(N-methylamino)ethyl acrylate, 2-(N-methylamino)ethyl methacrylate, 2-(N-ethylamino)ethyl acrylate, 2-(N-ethylamino)ethyl methacrylate, 2-(N-n-propylamino)ethyl acrylate, 2-(N-n-propylamino)ethyl methacrylate, 2-(N-iso- propyl-amino)ethyl acrylate, 2-(N-iso-propylamino)ethyl methacrylate, 2-(N-tert.- but
  • a further group of functional co-monomers may be formed of cationic co-monomers including 2-(N,N,N-trimethylammonium)ethyl acrylate chloride, 2- (N, N, N- trimethylammonium)ethyl methacrylate chloride, 2-(N-methyl-N,N- diethylammonium)ethyl acrylate chloride, 2-(N-methyl-N,N-diethylammonium)ethyl methacrylate chloride, 2-(N-methyl-N,N-di-n-propylammonium)ethyl acrylate chloride, and 2-(N-methyl-N,N-di-n-propylammonium)ethyl methacrylate chloride.
  • a further group of functional co-monomers is formed of carbonyl group bearing co- monomers like diacetone acrylamide and diacetone methacryl amide.
  • the functional co-monomers provide additional stabilization and/or have moieties that can crosslink with functional groups of other monomers, the free amino groups or other groups of the chitosan salt, and other compounds.
  • electroneutral or cationic functional co-monomers as stabilizers and epoxy group (glycidyl groups), n-methylol groups, their ethers or other groups such as carbonyl group bearing monomers as crosslinking co-monomers.
  • the amount of the co-monomer, based on the total weight of all monomers, is, at least 0 wt.%, at least 0.5 wt.%, at least 2 wt.%, or at least 5 wt.%.
  • all monomers may comprise from 0 to 10 wt.% of the co- monomer, based on the total weight all monomers, e.g., from 0.05 to 10 wt.% or from 1 to 5wt.%.
  • the emulsion polymer described herein is produced by free radical emulsion polymerization of the desired monomer or monomers together in the presence of an aqueous medium containing the chitosan salt and the co- stabilizer(s) in the presence of an initiator.
  • the initiator may be a thermal initiator or a redox initiator.
  • Suitable initiators may include hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide, isopropyl cumyl hydroperoxide, persulfates of potassium, of sodium and of ammonium, peroxides of saturated monobasic aliphatic carboxylic acids having an even number of carbon atoms and a C8-C12 chain length, tert- butyl hydroperoxide, di-tert-butyl peroxide, diisopropyl percarbonate, azoisobutyronitrile, acetylcyclohexanesulfonyl peroxide, tert-butyl perbenzoate, tert-butyl peroctanoate, bis(3,5,5- trimethyl)hexanoyl peroxide, tert-butyl perpivalate, hydroperoxypinane, p- methane hydroper
  • the abovementioned compounds can also be used within redox systems, using transition metal salts, such as iron(ll) salts, or other reducing agents.
  • Transition metal salts such as iron(ll) salts, or other reducing agents.
  • the initiator is a persulfate, such as a water- soluble persulfate, e.g., ammonium persulfate or sodium persulfate.
  • the initiator may be present in an amount of at least 0.02 wt.%, based on the total weight of the at least one monomer, e.g., at least 0.5 wt.% or at least 0.2 wt.%.
  • the water soluble chitosan salt may either be provided as a pre-prepared solution from the market or may be obtained as a chitosan powder that is converted to a water soluble chitosan salt.
  • the powder is added to water (e.g., demineralized water) and a chitosan salt forming acid to form a solution.
  • water e.g., demineralized water
  • the weight ratio between the chitosan and the chitosan salt forming acid may be from 1 :1 to 1 .2:1 , preferably 1 .1 1 :1 in case of acetic acid.
  • other weight ratios may be used, as determined by the stoichiometry of the chitosan salt to be formed.
  • the solution may be heated, e.g., up to 100°C or 75°C, and held at the heated temperature for up to 4 hours, e.g., from 1 to 3 hours or for approximately 2 hours.
  • the solution may then be cooled to room temperature and filtered through a sieve.
  • the active content and viscosity of the solutions may then be measured.
  • the active content of the solution may range from 0.1 to 10%, e.g., from 1 to 5% or from 1 .5 to 4.5%.
  • the pH of the solution is less than 5, e.g., less than 4.5 and in terms of ranges, may range from 1 to 5, e.g., from 1 .5 to 4.8.
  • the water soluble chitosan salt solution may then be combined with excess water (e.g., demineralized).
  • At least one co-stabilizer may then be added to the water soluble chitosan salt solution to form a suspension.
  • the at least one co- stabilizer may be added in one charge or in sequential charges.
  • the suspension may then be heated to dissolve the at least one co-stabilizer.
  • the heating time and temperature may vary. Generally, the suspension is heated for at least 1 hour, e.g., from 1 hour to 5 hours or for approximately 3 hours, to a temperature from 50°C to 150°C, e.g., from 75°C to 125°C, to form a solution.
  • the solution is then cooled to room temperature. Additional components of the aqueous phase, including a water soluble chain transfer and/or a defoamer may be added to the solution and the pH may then be measured. The pH may be adjusted to achieve a pH of less than 5.
  • the solution may then be transferred to a reactor unit for polymerization, e.g., a reactor unit with a stirring device, temperature control, and feed facilities.
  • the at least one ethylenically unsaturated monomer and any co-monomers are polymerized in a monomer slow-add process.
  • a portion for kick-off reaction may be added in a single charge or in multiple charges.
  • at least a first portion of the at least one ethylenically unsaturated monomer and any co-monomers, and at least a portion of an initiator may be added to the solution.
  • the reaction temperature may range from 50°C to 100°C, e.g., from 65°C to 80°C.
  • At least a second portion of the at least one ethylenically unsaturated monomer, and any co-monomers may then be added to the reactor over a period from 1 to 6 hours, e.g., from 3 to 5 hours. Additional initiator may also be added during this time.
  • the reaction temperature may be held at the pre-determined temperature.
  • a final amount of initiator may be added to the reactor and the temperature may be increased by at least 3°C, e.g., at least 5°C or at least 10°C and held at this temperature from 30 minutes to 2 hours. The reaction temperature is then allowed to decrease to room temperature.
  • the total amount of the at least one ethylenically unsaturated monomer, and/or any co-monomers may be added to the reactor, forming an emulsion and polymerized in a batch process.
  • the at least one ethylenically unsaturated monomer, and/or any co-monomers may be polymerized continuously in a reactor cascade or in a closed loop reactor. Upon completion of the polymerization, the residual monomer content may be lowered using demonomerization. This may be achieved using physical or chemical means. Physical means may include distillation or stripping with an inert gas.
  • Chemical means may include adding a redox initiator system, such as a combination of tert-butyl hydroperoxide and sodium meta bisulfate, a combination of organic peroxides like tert-butyl peroxi- 3,5,5-trimethylhexanoate and disodium 2-hydroxy-2-sulfinatoacetate, or a combination of tert-butyl peroxi-3,5,5-trimethylhexanoate and a mixture of disodium 2-hydroxy-2-sulfinatoacetate with sodium sulfite and disodium 2-hydroxy-2- sulfonatoacetate.
  • the redox initiator system may be added in one charge or in multiple charges over appropriate time periods.
  • the residual monomer content of the polymer may be less than 10,000 ppm, e.g., less than 5,000 ppm or less than 3500 ppm.
  • the emulsion polymer may also be referred to as an aqueous dispersion and may have a solids content from 20 to 70%, e.g., from 50 to 70% or from 50 to 65%.
  • the final emulsion polymer may have a pH of less than 5, e.g., less than 4.5.
  • the emulsion polymers formed by the herein described methods may be used for a variety of purposes in various products, including in the manufacture of paints, including high pigment volume paints and other decorative coatings; adhesives for porous substrates such as wood, paper, paperboard or non-porous substrates such as metals, plastics or glass; binders for plastic substrates such as synthetic resin-bound plasters, paste-form tile adhesives, paste-form sealants, plaster-coated thermal insulation systems, fibrous substrates such as woven or nonwoven products including textiles, apparel in general, papers, scrim, engineered fabrics, glass or other mineral fibers, roofing or flooring materials; construction compositions including cement compositions, fibrous products, caulks and sealants; functional coatings for waterproofing, powders such as redispersible powders for waterproofing, adhesives and the like.
  • the coating composition is applied to the substrate to be coated in a manner dependent on the configuration of the coating composition.
  • the application can, depending on the viscosity and the pigment content of the formulation and on the substrate, be effected by means of rolling, brushing, knife coating, dipping or as a spray.
  • the emulsion polymers formed by the herein described methods may be further used in agricultural applications, including as part of seed coating formulations, pre-harvest or post-harvest coatings for agricultural products like fruits and vegetables, adjuvant for herbicides and may be used in pharmaceutical and medical fields or in waste water treatment.
  • Chitosan powder was slowly added at room temperature to an appropriate amount of demineralized water containing glacial acetic acid to give active contents as listed in table 1 .
  • the weight ratio between chitosan and acetic acid was kept at 1 .1 1 to 1 .
  • the solution was heated up to 75°C and kept for 2 hours at this temperature. After cooling to room temperature, the mixture was filtrated over a 400 ⁇ steel sieve and the active content and viscosity were measured.
  • the pH of these solutions was in the range between 3.8 and 4.2.
  • the solutions were adjusted to 1 wt. % and the viscosity was determined by means of a Brookfield RVT viscometer at 23°C using spindle 2 at 20 rpm. Active content was determined by determining dry matter at 105 °C for 2 hours in a drying oven.
  • the aqueous phases were prepared as follows. To chitosan acetate solution samples A to E, excess parts demineralized water were added according to Table 2, followed by 4.4 parts partially hydrolyzed polyvinyl alcohol with a degree of hydrolysis of 88 mol.% and a viscosity of 18 mPa » s in 4% solution, 4.4 parts partially hydrolyzed polyvinyl alcohol with a degree of hydrolysis of 88 mol-% and a viscosity of 8 mPa » s in 4 % solution, followed by 0.12 parts sodium acetate. The suspension was heated for 3 hours at 80°C to dissolve the polyvinyl alcohols.
  • Example 1 The particle size distribution of Examples 1 to 6 and Comparative Example A was measured using the Mastersizer Micro Plus laser diffraction instrument from Malvern Instruments Ltd. The scatter data were evaluated using the volume-averaged "polydisperse Mie” evaluation provided by Malvern. Brookfield viscosities were measured at 23°C using an RVT viscometer at 20 rpm using the recommended spindle by the manufacturer for the respective viscosity range unless otherwise stated.
  • Example 4 and 5 show that use of thiolactic acid as a co-acid and chain transfer agent 1 ) reduces the viscosity significantly, 2) lowers particle size and 3) allows polymerization using higher amounts of chitosan acetate and higher levels of degrees of deacetylation of the chitosan.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des procédés de polymérisation en émulsion d'au moins un monomère éthyléniquement insaturé effectués en présence d'une phase aqueuse comprenant un sel de chitosane soluble dans l'eau et d'au moins un co-stabilisant. L'invention concerne également une dispersion aqueuse préparée par la polymérisation en émulsion d'au moins un monomère éthyléniquement insaturé effectuée en présence d'un sel de chitosane soluble dans l'eau et d'au moins un co-stabilisant. Le polymère en émulsion peut être compris dans des produits comprenant des adhésifs, des liants, des revêtements, des revêtements agricoles, des formulations pharmaceutiques, des formulations médicales et des formulations de traitement des eaux usées.
EP14771210.3A 2013-09-03 2014-09-02 Procédés de polymérisation en émulsion Withdrawn EP3033363A1 (fr)

Applications Claiming Priority (2)

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US201361872905P 2013-09-03 2013-09-03
PCT/EP2014/068547 WO2015032726A1 (fr) 2013-09-03 2014-09-02 Procédés de polymérisation en émulsion

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Publication number Priority date Publication date Assignee Title
EP3417018A4 (fr) * 2016-03-11 2019-11-06 Georgia-Pacific Nonwovens LLC Chitosane-liant à base de latex en mélange pour étoffes non tissées à haute performance

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US2040979A (en) 1932-07-30 1936-05-19 Edward G Crozier Rolling mill guide
US2040880A (en) 1934-06-21 1936-05-19 Du Pont Process for the preparation of films and filaments and products thereof
EP0228879A3 (fr) * 1985-12-27 1989-07-12 Lion Corporation Procédé de préparation d'un latex polymère ultrafin
US5011864A (en) 1989-11-09 1991-04-30 Hoechst Celanese Corp. Water absorbent latex polymer foams containing chitosan (chitin)
US6573313B2 (en) 2001-01-16 2003-06-03 The Hong Kong Polytechnic University Amphiphilic core-shell latexes
US8226962B2 (en) 2005-01-31 2012-07-24 The Hong Kong Polytechnic University Textiles with chitosan core-shell particles
US7736423B2 (en) 2005-08-29 2010-06-15 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Aqueous composition for outdoor paints, indoor paints, facade paints and roof paints
US20120028527A1 (en) 2010-07-30 2012-02-02 Wacker Chemical Corporation Ultra Low Formaldehyde Binders for Nonwoven Substrates
US9902785B2 (en) * 2011-12-22 2018-02-27 Celanese Sales Germany Gmbh Polymer dispersions, their preparation and use

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