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WO2021160788A1 - Procédés de réduction ou de prévention de l'adhérence de colloïdes et/ou d'encrassement par des colloïdes sur différents substrats, compositions et copolymères utiles à cet effet - Google Patents

Procédés de réduction ou de prévention de l'adhérence de colloïdes et/ou d'encrassement par des colloïdes sur différents substrats, compositions et copolymères utiles à cet effet Download PDF

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Publication number
WO2021160788A1
WO2021160788A1 PCT/EP2021/053431 EP2021053431W WO2021160788A1 WO 2021160788 A1 WO2021160788 A1 WO 2021160788A1 EP 2021053431 W EP2021053431 W EP 2021053431W WO 2021160788 A1 WO2021160788 A1 WO 2021160788A1
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Prior art keywords
monomer
mol
copolymer
typically
derived
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PCT/EP2021/053431
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English (en)
Inventor
Gilda Lizarraga
Jaime HUTCHISON
Sananda CHANDA
Avinash SHIVANANDAREDDY
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Solvay Sa
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Publication of WO2021160788A1 publication Critical patent/WO2021160788A1/fr

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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A61L29/16—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents

Definitions

  • the present invention relates to the field of reducing or preventing colloids adhesion and/or fouling on different substrates, and copolymers useful therefor.
  • fouling is the accumulation of unwanted material on solid surfaces to the detriment of function. Fouling is usually distinguished from other surface-growth phenomena, in that it occurs on a surface of a component, system or plant performing a defined and useful function, and that the fouling process impedes or interferes with this function. Fouling phenomena are common and
  • Fouling materials are also diverse and are also diverse and are also diverse.
  • Colloidal particles include inorganic colloids, such as, for example, clay particles, silicates, iron oxy-hydroxides and the like; organic colloids, such as proteins and humic substances; and even living material, including but not limited to bacteria, fungi, archaea, algae, protozoa, and the like. In some cases,
  • biofilms cause corrosion, reduce heat exchange in exchangers and give rise to flow resistance in tubes and
  • the present invention relates to a method for reducing or preventing colloids adhesion and/or fouling on a substrate in need thereof, the method comprising at least partially applying to the substrate an amount effective to reduce or prevent colloids adhesion and/or fouling a composition comprising a copolymer [copolymer (ZW-CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)] , typically at least one betaine monomer, and repeating units [units (RCA)] derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer [monomer (B)]; thereby reducing or preventing the adhesion of colloids and/or fouling on the substrate, wherein said substrate is selected from metal substrates, metal-containing substrates, silicate substrates and concrete substrates.
  • the present invention relates, in an embodiment, to an article comprising a metallic surface, wherein the metallic surface is at least partially coated with a composition comprising a copolymer [copolymer (ZW- CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer [monomer (B)] in an amount effective to reduce or prevent colloids adhesion and/or fouling to the metallic surface.
  • a copolymer [copolymer (ZW- CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at least one carboxylic acid or carboxylic acid
  • the present invention relates, in other embodiments, to an article comprising a silicate surface or a concrete surface, wherein the silicate or concrete is at least partially coated with a composition comprising a copolymer [copolymer (ZW-CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer [monomer (B)] in an amount effective to reduce or prevent colloids adhesion and/or fouling to the silicate or concrete.
  • a copolymer [copolymer (ZW-CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at
  • the present invention relates to use of a composition for reducing or preventing colloids adhesion and/or fouling on a substrate, the composition comprising a copolymer [copolymer (ZW-CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer[monomer (B)], wherein said substrate is selected from metal substrates, metal-containing substrates, silicate substrates and concrete substrates.
  • the present invention relates to a copolymer (ZW-CA), particularly suitable for the aforementioned method and use, having repeating units (Rzw) derived from sulfopropyldimethylammonioethyl methacrylate (SPE) and repeating units (R CA ) derived from methacrylic acid or itaconic acid.
  • ZW-CA copolymer
  • Rzw repeating units derived from sulfopropyldimethylammonioethyl methacrylate
  • R CA repeating units
  • the terms “a”, “an”, or “the” means “one or more” or “at least one” unless otherwise stated.
  • the term “comprises” includes “consists essentially of’ and “consists of.”
  • the term “comprising” includes “consisting essentially of’ and “consisting of.”
  • the present invention relates to method for reducing or preventing colloids adhesion and/or fouling on a substrate in need thereof, the method comprising at least partially applying to the substrate a composition comprising a copolymer [copolymer (ZW-CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer in an amount effective to reduce or prevent colloids adhesion and/or fouling on the substrate, wherein said substrate is selected from metal substrates, metal -containing substrates, silicate substrates and concrete substrates.
  • colloids refer to insoluble particles of a substance that are microscopically dispersed or suspended throughout another substance, typically an aqueous medium. Colloids and the substance in which they are dispersed or suspended throughout are collectively referred to as colloidal suspensions. Typically, the colloid does not settle or would take a very long time to settle appreciably. Colloidal particles include inorganic colloids, such as, for example, clay particles, silicates, iron oxy-hydroxides and the like; organic colloids, such as proteins and humic substances; and even living material, including but not limited to bacteria, fungi, archaea, algae, protozoa, and the like.
  • colloidal living material such as bacteria, fungi, archaea, algae, protozoa, and the like, including proteins and by-products produced by such living material, together and to a surface results in a matrix or film known as a biofilm.
  • Exemplary bacteria include but are not limited to bacteria selected from the group consisting of: Pseudomonas spp., such as Pseudomonas aeruginosa, Azotobacter vinelandii, Escherichia coli, Corynebacterium diphteriae, Clostridium botulinum, Streptococcus spp., Acetobacter, Leuconostoc, Betabacterium, Pneumococcus, Mycobacterium tuberculosis, Aeromonas, Burkholderia, Flavobacterium, Salmonella, Staphylococcus, Vibrio spp., Listeria spp., and Legionella spp.
  • Pseudomonas spp. such as Pseudomonas aeruginosa, Azotobacter vinelandii, Escherichia coli, Corynebacterium diphteriae, Clostridium botulinum, Streptoc
  • Fouling in general, is the accumulation of unwanted material on solid surfaces to the detriment of function. Fouling is usually distinguished from other surface-growth phenomena in that it occurs on a surface of a component, system, or plant performing a defined and useful function, and that the fouling process impedes or interferes with this function.
  • the colloids adhesion described herein may be considered fouling.
  • reducing colloids adhesion and/or fouling refers to decreasing the amount of colloids adhesion and/or fouling already on a surface.
  • Preventing colloids adhesion and/or fouling refers to partial or complete inhibition of colloids adhesion and/or fouling on a surface.
  • Prevention also includes slowing down colloids adhesion and/or fouling on a surface.
  • the adhesion of colloids and general fouling is believed to be reduced and/or prevented by a physical mechanism of a repulsive barrier.
  • the repulsive barrier is believed to be the result of the steric bulk of polymer chains, and the hydration layer formed around hydrophilic functions on the polymer chains of the copolymer used according to the present disclosure.
  • bacteria cell walls are made of peptidoglycans, and they are hence also repelled by the respulsive barrier, which results in less bacterial colonization on surfaces, and less formation of biofilm.
  • the method for reducing or preventing colloids adhesion and/or fouling on a substrate in need thereof is a method for reducing or preventing biofilm adhesion on a substrate in need thereof.
  • the composition is free of biocide.
  • the composition contains some biocide.
  • biocide is present in the composition, it is generally in an amount not exceeding 1000 wt. %, preferably in an amount not exceeding 500 wt. % and more preferably in an amount not exceeding 250 wt. % of the copolymer.
  • the copolymer of the present invention is not a biocide.
  • the method described herein makes use of a composition
  • a composition comprising a copolymer [copolymer (ZW-CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer [monomer (B)].
  • the composition is free of vinylpyrrolidone homopolymer or copolymer.
  • phrase “free of’ means that there is no external addition of the material modified by the phrase and that there is no detectable amount of the material that may be observed by analytical techniques known to the ordinarily-skilled artisan, such as, for example, gas or liquid chromatography, spectrophotometry, optical microscopy, and the like.
  • the step of at least partially applying to the substrate the composition comprising a copolymer (ZW-CA) described herein may be achieved using any method known to those of ordinary skill in the art.
  • the composition may be applied by spray coating, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, rod or bar coating, doctor-blade coating, flowcoating, which involves controlled gravity flow of a coating over the substrate, or the like.
  • Further examples include applying the composition onto a woven or nonwoven article and then contacting the woven or nonwoven article on the surface to be applied.
  • the pH of the composition is not particularly limited. Typically, the pH of the composition is from 6 to 8.
  • the copolymer of the present invention comprises repeating units (Rzw) derived from at least one zwitterionic monomer (A), typically at least one betaine monomers, and repeating units (R CA ) derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer (B).
  • the copolymer (ZW-CA) is a block copolymer, branched copolymer, or statistical copolymer.
  • the copolymer (ZW-CA) is a statistical copolymer.
  • molar mass when molar mass is referred to, the reference will be to the weight-average molar mass, expressed in g/mol.
  • the latter can be determined by aqueous gel permeation chromatography (GPC) with light scattering detection (DLS or alternatively MALLS), with an aqueous eluent or an organic eluent (for example dimethylacetamide, dimethylformamide, and the like), depending on the copolymer (ZW-CA).
  • GPC gel permeation chromatography
  • LDS or alternatively MALLS light scattering detection
  • ZW-CA organic eluent
  • the weight-average molar mass (Mw) of the copolymer (ZW-CA) is in the range of from about 5,000 to about 3,000,000 g/mol, typically from about 8000 to about 1,000,000, g/mol, more typically from about 10,000 to 500,000 g/mol, even more typically 20,000 to 200,000 g/mol.
  • the copolymer of the present invention comprises repeating units (Rzw) derived from at least one zwitterionic monomer (A).
  • zwitterionic monomer (A) refers to monomer capable of polymerization .
  • zwitterionic recurring units (Rzw) are derived from at least one zwitterionic monomer (A) that is neutral in overall charge but contains a number of group (C+) equal to the number of group (A-).
  • the cationic charge(s) may be contributed by at least one onium or inium cation of nitrogen, such as ammonium, pyridinium and imidazolinium cation; phosphorus, such as phosphonium; and/or sulfur, such as sulfonium.
  • the anionic charge(s) may be contributed by at least one carbonate, sulfonate, phosphate, phosphonate, phosphinate or ethenolate anion, and the like.
  • Suitable zwitterionic monomers include, but are not limited to, betaine monomers, which are zwitterionic and comprise an onium atom that bears no hydrogen atoms and that is not adjacent to the anionic atom.
  • units (Rzw) are derived from at least one monomer (A) selected from the list consisting of a) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl acrylates or methacrylates, acrylamido or methacrylamido, typically
  • heterocyclic betaine monomers typically
  • - sulfobetaines derived from 2-vinylpyridine and 4-vinylpyridine, more typically 2- vinyl-1 -(3-sulfopropyl)pyridinium betaine or 4- vinyl-l-(3-sulfopropyl)pyridinium betaine,
  • units (Rzw) are derived from at least one monomer (A) selected from the list consisting of
  • units (Rzw) are derived from at least one monomer (A) selected from the list consisting of
  • units (Rzw) are derived from sulfopropyldimethylammonioethyl methacrylate (SPE).
  • Copolymer (ZW-CA) according to the invention, besides comprising recurring units (Rzw) derived from at least one zwitterionic monomer (A), also comprises recurring units (RCA) derived from at least one at least one carboxylic acid or carboxylic acid anhydride containing monomer (B).
  • monomer (B) is selected from the list consisting of acrylic acid, methacrylic acid, maleic acid, maleic acid anhydride, itaconic acid, 4- methacryloxyethyltrimellitic acid, 4-methacryloxyethyltrimellitic acid anhydride and methacryloyl-L-Lysine.
  • monomer (B) is selected from the list consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride.
  • monomer (B) is selected from the list consisting of methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride; more preferably monomer (B) is methacrylic acid or itaconic acid. In some other embodiments, monomer (B) is for example maleic acid or maleic acid anhydride.
  • the copolymer (ZW-CA) of the present invention comprises recurring units (Rzw) derived from sulfopropyldimethylammonioethyl methacrylate (SPE) and recurring units (RCA) derived from at least one monomer (B) selected from the list consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride.
  • Rzw sulfopropyldimethylammonioethyl methacrylate
  • RCA recurring units derived from at least one monomer (B) selected from the list consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride.
  • the copolymer (ZW-CA) of the present invention comprises recurring units (Rzw) derived from sulfopropyldimethylammonioethyl methacrylate (SPE) and recurring units (RCA) derived from methacrylic acid or itaconic acid.
  • the copolymer (ZW-CA) of the present invention comprises recurring units (Rzw) derived from sulfopropyldimethylammonioethyl methacrylate (SPE) and recurring units (RCA) derived from maleic acid or maleic acid anhydride.
  • the copolymer (ZW-CA) comprises up to 90 mol%, typically less than 70 mol%, more typically less than 50 mol% and even more typically less than 30 mol% of repeating units (RCA) derived from monomer (B), based on the molar composition of the copolymer.
  • the copolymer comprises about 1 mol% to about 70 mol%, in particular about 1 mol% to about 50 mol%, especially about 1 mol% to about 30 mol%, for example about 1 mol% to about 20 mol%, typically about 5 mol% to about 10 mol% of repeating units (RCA) derived from monomer (B), based on the molar composition of the copolymer.
  • the copolymer (ZW-CA) comprises greater than 30 mol%, typically greater than 50 mol%, more typically greater than 70 mol%, even more typically greater than 90 mol%, of repeating units (Rzw) derived from monomer (A), based on the molar composition of the copolymer.
  • the copolymer comprises about 30 mol% to about 99 mol%, in particular about 50 mol% to about 99 mol%, especially about 70 mol% to about 99 mol%, for example about 80 mol% to about 99 mol%, typically about 90 mol% to about 95 mol% of repeating units (Rzw) derived from monomer (A), based on the molar composition of the copolymer.
  • copolymer (ZW-CA) according to the invention further comprises recurring units [units (RN)] derived from at least one monomer [monomer (C)] selected from the list consisting of 2 -hydroxy ethyl methacrylate (HEMA), hydroxypropyl methacrylate, 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) methyl ether methacrylate (mPEGMA), poly(ethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) methyl ether acrylate and poly(ethylene glycol) ethyl ether acrylate.
  • HEMA 2 -hydroxy ethyl methacrylate
  • HEMA hydroxypropyl methacrylate
  • HOA 2-hydroxyethyl acrylate
  • HPA hydroxypropyl acrylate
  • units (RN) are derived from 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate or mixture thereof. More preferably, units (RN) are derived from 2-hydroxyethyl methacrylate (HEMA).
  • HEMA 2-hydroxyethyl methacrylate
  • the copolymer (ZW-CA) of the present invention comprises recurring units (Rzw) derived from (SPE) recurring units (RCA) derived from at least one monomer (B) selected from the list consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride and recurring units (R N ) derived from 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA) or mixtures thereof.
  • SPE recurring units
  • RCA recurring units derived from at least one monomer (B) selected from the list consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride and recurring units (R N ) derived from 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA) or mixtures thereof.
  • the copolymer (ZW-CA) of the present invention comprises, in addition to repeating units (Rzw) derived from zwitterionic monomer (A) and repeating units (RCA) derived from monomer (B), repeating units (R N ) derived from monomer (C), the copolymer comprises about 1 mol% to about 60 mol%, in particular about 1 mol% to about 50 mol%, especially about 1 mol% to about 20 mol%, typically about 3 mol% to about 15 mol% and more typically about 5 mol% to about 10 mol% of repeating units (R CA ) derived from monomer (B), based on the molar composition of the copolymer.
  • the copolymer (ZW-CA) comprises about 40 mol% to about 99 mol%, in particular about 50 mol% to about 99 mol%, especially about 80 mol% to about 99 mol%, typically about 90 mol% to about 95 mol% of repeating units (Rzw) and (R N ), based on the molar composition of the copolymer.
  • the molar ratio of repeating units (Rzw) derived from the zwitterionic monomer (A) with repeating units (R N ) derived from the monomer (C) ranges typically from 0.25 to 4, more typically from 0.5 to 2.
  • the copolymer (ZW-CA) of the present invention may be obtained by any polymerization process known to those of ordinary skill.
  • the copolymer (ZW-CA) may be obtained by radical polymerization or controlled radical polymerization in aqueous solution, in dispersed media, in organic solution or in organic/water solution (miscible phase).
  • poly(acrylic acid-stat- sulfopropyldimethylammonioethyl methacrylate ) poly(AA-stat-SPE) can be prepared by free radical copolymerization of acrylic acid and sulfopropyldimethylammonioethyl methacrylate in water initiated by ammonium persulfate.
  • the monomer (B) from which can be derived units (R CA ) may be obtained from commercial sources.
  • the monomer (C) from which can be derived units (R N ) may be obtained from commercial sources.
  • the zwitterionic monomer (A) from which are derived units (Rzw) may be obtained from commercial sources or synthesized according to methods known to those of ordinary skill in the art.
  • Suitable zwitterionic monomers (A) from which can be derived units (Rzw) include, but are not limited to monomers selected from the list consisting of: a) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl acrylates or methacrylates, acrylamido or methacrylamido, typically:
  • - sulfobetaines derived from 2-vinylpyridine and 4vinylpyridine, such as 2-vinyl- 1 -(3 -sulfopropyl)pyridinium betaine (2SPV), sold by Raschig under the name SPY : and 4-vinyl- 1 -(3 -sulfopropyl)pyridinium betaine (4SPV), the synthesis of which is disclosed in the paper “Evidence of ionic aggregates in some ampholytic polymers by transmission electron microscopy”, V. M. Castano and A. E.
  • hydroxyalkyl sulfonate of formula below: c) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl allylics, typically sulfopropylmethyldiallylammonium betaine: the synthesis of which is described in the paper “New poly(carbobetaine)s made from zwitterionic diallylammonium monomers”, Favresse, Philippe; Laschewsky, Andre, Macromolecular Chemistry and Physics, 200(4), 887-895 (1999), d) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl styrenes, typically compounds having any one of the following structures: -(dimethyl (4-vinylbenzyl)ammonio)propane-l- sulfonate, the synthesis of which is described in the paper “Hydrop
  • Suitable monomers comprising hydroxyalkyl sulfonate moieties from which can be derived units can be obtained by reaction of sodium 3- chloro-2-hydroxypropane-l -sulfonate (CHPSNa) with monomer bearing tertiary amino group, as described in US20080045420 for the synthesis of SHPP, starting from dimethylaminopropylmethacrylamide according to the reaction scheme:
  • CHPSNa sodium 3- chloro-2-hydroxypropane-l -sulfonate
  • Other monomers bearing tertiary amino group may be involved in reaction with CHPSNa to obtain suitable monomers from which are derived units
  • Rzw Suitable monomers from which are derived units (Rzw) may be also obtained by reaction of sodium 3 -chloro-2-hydroxypropane-l -sulfonate (CHPSNa) with monomer bearing pyridine or imidazole group:
  • recurring units (Rzw) may be obtained by modification of a polymer referred to as a precursor polymer comprising recurring units bearing tertiary amino groups through the reaction with sodium 3-chloro-2- hydroxypropane-1 -sulfonate (CHPSNa).
  • CHPSNa sodium 3-chloro-2- hydroxypropane-1 -sulfonate
  • recurring units may be obtained by chemical modification of a polymer referred to as a precursor polymer with a sultone, such as propane sultone or butane sultone, a haloalkylsulfonate or any other sulfonated electrophilic compound known to those of ordinary skill in the art.
  • a sultone such as propane sultone or butane sultone
  • a haloalkylsulfonate such as any other sulfonated electrophilic compound known to those of ordinary skill in the art.
  • Exemplary synthetic steps are shown below:
  • recurring units (Rzw) may be obtained by modification of a polymer referred to as a precursor polymer comprising recurring units bearing tertiary amino groups, pyridine groups, imidazole group or mixtures thereof through the reaction with sodium 3 -chloro-2-hydroxypropane-l -sulfonate (CHPSNa), a sultone, such as propane sultone or butane sultone, or a haloalkylsulfonate.
  • CHPSNa sodium 3 -chloro-2-hydroxypropane-l -sulfonate
  • a sultone such as propane sultone or butane sultone
  • haloalkylsulfonate a sultone
  • composition according to the present invention may comprise optional ingredients to facilitate application of the composition onto the substrate and/or to provide additional benefits.
  • Optional ingredients include, but are not limited to, crosslinking agents, chelating agents, sequestering or scale-inhibiting agents, bleaching agents, fillers, bleaching catalysts, pH adjusting agents, viscosity modifiers, co-solvents, antifoaming agents, enzymes, fragrances, colorants, anti-corrosion agents, preservatives, optical brighteners, opacifying or pearlescent agents, and the like.
  • the composition is applied to the substrate in an amount effective to reduce or prevent colloids adhesion and/or fouling.
  • amount effective to reduce or prevent colloids adhesion and/or fouling in absolute numbers depends on factors including the colloids and/or fouling to be reduced or prevented; whether the aim is prevention or reduction; the contact time between the copolymer (ZW-CA) and the surface; other optional ingredients present, and also the surface or aqueous environment in question.
  • the amount effective to reduce or prevent colloids adhesion and/or fouling is such that the copolymer (ZW-CA) is deposited on the substrate in an amount from 0.0001 to 100 mg/m 2 , typically from 0.001 to 50 mg/m 2 , of the surface applied.
  • the copolymer (ZW-CA) described herein adsorbs strongly onto metal surfaces, forming the aforementioned repulsive barrier that is believed to be the result of the steric bulk of polymer chains, and the hydration layer formed around hydrophilic functions on the polymer chains of the copolymer.
  • the substrate typically in need of reduction or prevention of colloids adhesion and/or fouling is a metal or metal-containing substrate.
  • the metal is selected from the group consisting of iron, cast iron, copper, brass, aluminum, titanium, carbon steel, stainless steel, and alloys thereof.
  • the copolymer (ZW-CA) of the present invention adsorbs strongly onto silicate surfaces, forming the aforementioned repulsive barrier that is believed to be the result of the steric bulk of polymer chains, and the hydration layer formed around hydrophilic functions on the polymer chains of the copolymer. Accordingly, another substrate, typically in need of reduction or prevention of colloids adhesion and/or fouling is a silicate substrate.
  • silicate refers to any mineral or ionic solid having silicon atoms each bonded to one or more oxygen atoms, typically 2 to 4 oxygen atoms per silicon atom.
  • the silicate may further comprise atoms of other elements, for example, transition metal elements and elements from groups IA to IIIA of the periodic table of the elements.
  • the silicate may be a crystalline silicate or amorphous silicate.
  • Suitable crystalline silicates may be selected from the group consisting of nesosilicates, sorosilicates, cyclosilicates, tectosilicates, inosilicates, and mixtures thereof.
  • nesosilicates include, but are not limited to, olivine [(Mg,Fe) 2 Si0 4 ], forsterite (Mg 2 Si0 4 ), fayalite (Fe 2 Si0 4 ), alite [Ca 3 ((Si0 4 )0)], belite (Ca 2 Si0 4 ), andalousite, sillimanite and kyanite [all three are of formula Al 2 0(Si0 4 )], phenakite, topaz and thaumasite.
  • sorosilicates are prehnite, hemimorphite [Zn (Si 2 Ov)(OH) 2 ] and compounds of formula CaMg(Si 2 Ov).
  • Cyclosilicates refer to silicates with tetrahedrons that usually link to form rings of three (Si 3 0 9 ) 6 , four (Si 0i 2 ) 8 , six (Si 6 0i 8 ) 12 or nine (Si 9 0 27 ) 18 units, and include, for example, beryl.
  • tectosilicates include, but are not limited to, quartz, cristobalite, tridymite, orthose [K(AlSi 3 0 8 )], anorthite [Ca(Al 2 Si 2 0 8 )] and celsiane [Ba(Al 2 Si 2 0 8 )].
  • Inosilicates refer to silicates generally having a crystalline structure in the form of chains. Inosilicates include pyroxenes, which have a crystalline structure usually in the form of simple chains (Si0 3 ) 2 , and amphiboles, which have a crystalline structure usually in the form of double chains (Si 0n) 6 .
  • Examples of pyroxenes include, but are not limited to, diopside [CaMg(Si0 3 ) 2 ], spodumene [LiAl(Si0 3 ) 2 ], wollastonite [Ca(Si0 3 )], enstatite [Mg(Si0 3 )], hypersthene, hedenbergite, augite, pectolite, diallage, holaite, spodumene, jeffersonite, aegirine, omphafacite and hiddenite.
  • amphiboles include, but are not limited to, calcium amphiboles such as tremolite [Ca 2 Mg 5 [Si 4 On,(OH,F)] 2 ], actinote [Ca 2 (Mg,Fe) 5 [Si On,OH] 2 ] and hornblende, iron-magnesium amphiboles such as grunerite and cummingtonite, and sodium amphiboles such as glaucophane, arfvedsonite, and riebeckite.
  • calcium amphiboles such as tremolite [Ca 2 Mg 5 [Si 4 On,(OH,F)] 2 ]
  • actinote Ca 2 (Mg,Fe) 5 [Si On,OH] 2
  • hornblende iron-magnesium amphiboles
  • iron-magnesium amphiboles such as grunerite and cummingtonite
  • sodium amphiboles such as glaucophane, arfve
  • Suitable crystalline silicates include, but are not limited to, barium silicates, such as BaSi0 3 (barium metasilicate), Ba 2 Si 3 0 7 (barium disilicate), and Ba 2 Si0 (dibarium silicate); calcium silicates, such as CaSi0 3 (monocalcium silicate or wollastonite), Ca 2 Si0 4 (dicalcium silicate), and Ca 3 Si0 3 (tricalcium silicate); magnesium silicates, such as MgSi0 3 (enstatite), Mg 2 Si0 4 (forsterite); aluminum silicates (also “aluminosilicates”), such as halloysite (Al 2 Si 2 0 5 (0H) 4 ), kaolinite (Al 2 Si 2 0 5 (0H) 4 ), mullite (aka porcelainite, Al 6 Si 2 0i 3 ), muscovite (KAl 2 (AlSi 3 )Oio(OH) 2 ), sanidine (KAlS
  • the crystallinity of silicate ceramics may vary to a large extent, from highly oriented to semi-crystalline, vitrified. Often, fired ceramics are either vitrified or semi-vitrified as is the case with earthenware, stoneware, and porcelain.
  • silicate ceramics of interest for the present invention mention may be made of: kaolin and/or clay-based ceramics, the composition of which lies generally in the mullite field in the ternary raw material diagram kaolin/clay-feldspar-quartz (system K2O-AI2O3-S1O2), including:
  • porcelains except dental porcelain, such as (i) hard porcelain containing typically about 50% kaolin -which can be partly replaced by clay- , about 25 % quartz and about 25% feldspar, (ii) soft porcelain, (iii) bone china, (iv) frit porcelain and (v) electrochemical porcelain useful for insulators,
  • earthenwares such as faience, majolika and terracotta
  • stonewares such as coarse stonewares notably useful for sewer pipes, and dense, vitrified stonewares useful for e.g. chemical vessels, and
  • Silicate ceramics in accordance with the invention may be coarse or fine and, according to water absorption, dense ( ⁇ 2 % for fine and ⁇ 6 % for coarse) or porous ceramics (> 2% and > 6 %, respectively).
  • An amorphous silicate suitable for use according to the present invention is glass.
  • silicate glasses of interest for the present invention mention may be made of: fused quartz, also known as fused-silica glass or vitreous-silica glass, which is silica (Si0 2 ) in vitreous or glass form ; it is notably useful for high-temperature applications such as furnace tubes, lighting tubes, melting crucibles, etc.
  • soda-lime-silica glass also known as window glass, which comprises silica (Si0 2 ), soda (Na 2 0) and lime (CaO); soda-lime-silica glass often further comprises one or more additional components, usually in a low amount, in particular A1 2 0 3 , K 2 0 and MgO ; an exemplary soda-lime- silica glass composition is or comprises from 63 % to 81% Si0 2 , from 9% to 18% Na 2 0, from 7% to 14% CaO, from 0 % to 1.5 % K 2 0, from 0 % to 8 % MgO and from 0% to 3% of A1 2 0 3 ; soda-lime-silica glass is notably useful for some low-temperature incandescent light bulbs and tablewares, etc.
  • borosilicate glass which comprises silica (Si0 2 ) and boron trioxide (B 2 0 3 ) ; borosilicate glass often further comprises one or more additional components, usually in a low amount, in particular Na 2 0, K 2 0, CaO, MgO and A1 2 0 3 ;
  • a first exemplary borosilicate glass composition (PyrexTM-type) is or comprises from 65% to 85% of Si0 2 , from 7% to 15% of B 2 0 3 , from 3% to 9 % of Na 2 0, from 0.5% to 7% of A1 2 0 3 , from 0% to 3% K 2 0, from 0% to 8% of CaO and from 0% to 1% MgO ;
  • another exemplary borosilicate glass composition is or comprises from 45% to 75% of Si0 2 , from 2% to 10% of B 2 0 3 , from 5% to 30% of CaO, from 0% to 12% of A1 2 0 3 , from 0%
  • silicate substrate refers to any material comprising or consisting of one or more silicates as defined herein. Suitable silicate substrates include, but are not limited to, ceramic substrates (including porcelain substrates) and glass substrates. In an embodiment, the silicate substrate is a glass substrate.
  • the copolymer (ZW-CA) of the present invention adsorbs strongly onto concrete surfaces, forming the aforementioned repulsive barrier that is believed to be the result of the steric bulk of polymer chains, and the hydration layer formed around hydrophilic functions on the polymer chains of the copolymer. Accordingly, another substrate, typically in need of reduction or prevention of colloids adhesion and/or fouling is a concrete substrate.
  • concrete a composite material that consists essentially of a binding medium, such as a mixture of hydraulic cement and water, which forms a cement matrix within which are embedded particles or fragments of aggregate, usually a combination of fine and coarse aggregate.
  • hydraulic cements cements which set and harden to form a stone-like mass by reacting with water. They comprise Portland cements and blended cements which are combinations of Portland cement with a pozzolan or a blast-furnace slag.
  • aggregates have a particle size distribution in the range of 0.01-100 mm.
  • Fine aggregate such as sand comprises particles up to 4-5 mm in diameter while coarse aggregate such as gravel comprises particles with diameter larger than 5 mm.
  • aggregate is essentially composed of fine aggregate such as sand. Accordingly, the aggregate comprises less than 1 wt % of coarse aggregate based on the total weight of aggregate.
  • the cement matrix constitutes from 10 % to 50 % of the volume of concrete; typically from 15 % to 40 % and more typically from 20 % to 35%.
  • the aggregates generally constitutes from 50 % to 85 % of the volume of concrete; typically from 55 % to 80 % and more typically from 60 % to 75 %.
  • the concrete comprises well known admixtures such as setting and hardening admixtures, workability admixtures, and porosity admixtures.
  • aqueous medium refers to a medium comprising or consisting of water.
  • the aqueous medium may further comprise colloidal particles.
  • Colloidal particles include inorganic colloids, such as, for example, clay particles, silicates, iron oxy-hydroxides and the like; organic colloids, such as proteins and humic substances; and colloidal living material, such as bacteria, fungi, archaea, algae, protozoa, and the like.
  • the aqueous medium is selected from the group consisting of hydrotest water, oil and gas gathering waters, condensed waters, oil and gas production waters, fracturing waters, wash waters, food wash waters, metal degreasing fluids, deck fluids, water in oil and gas reservoirs, water in sump tanks, water in drains, and water in cooling towers.
  • the present invention is also directed to an article comprising a metal or metal-containing surface, wherein the metal or metal-containing surface is at least partially coated with a composition comprising a copolymer( ZW-CA) having repeating units (Rzw) derived from at least one zwitterionic monomer (A) and repeating units (R CA ) derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer (B) in an amount effective to reduce or prevent colloids adhesion and/or fouling to the metal or metal-containing surface.
  • a copolymer( ZW-CA) having repeating units (Rzw) derived from at least one zwitterionic monomer (A) and repeating units (R CA ) derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer (B) in an amount effective to reduce or prevent colloids adhesion and/or fouling to the metal or metal-containing surface.
  • the article is a pipeline, a methane terminal; a medical device, typically medical tubing, orthopedic article, implantable device, drape, biosensor, dental implant, mechanical heart valve, extra corporeal blood vessel, stent, or surgical tool; part of a heating and/or cooling system, typically heat exchanger, steam condenser, wet tower, or cooling tower; household equipment, a food contact surface, industrial equipment, degreasing tank bath or architectural feature.
  • a medical device typically medical tubing, orthopedic article, implantable device, drape, biosensor, dental implant, mechanical heart valve, extra corporeal blood vessel, stent, or surgical tool
  • part of a heating and/or cooling system typically heat exchanger, steam condenser, wet tower, or cooling tower
  • household equipment typically heat exchanger, steam condenser, wet tower, or cooling tower
  • the present invention is also directed to an article comprising a silicate surface, wherein the silicate surface is at least partially coated with a composition comprising a copolymer( ZW-CA) having repeating units (Rzw) derived from at least one zwitterionic monomer (A) and repeating units (R CA ) derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer (B) in an amount effective to reduce or prevent colloids adhesion and/or fouling to the silicate surface.
  • the article is a ceramic dinnerware, in particular a porcelain dinnerware, typically a plate, bowl, or dish; ceramic electronic component, typically an insulator, wiring board, capacitor, or spacer oxide; ceramic (esp.
  • porcelain filter filter
  • heating apparatus typically a hot plate or immersion heater
  • medical or dental implants ceramic (esp. porcelain) tools or molds; solar panels; or ceramic (esp. porcelain) decorative articles.
  • the article is silicate glass, glass panel e.g. architectural glass panel or solar panels, glass cookware, typically baking dish; glass dinnerware, typically a plate, bowl, or dish; lamp bulbs, splinting bandage, masonry, typically brick, concrete, or cement; silicate paint, or fibers, typically insulation fibers.
  • glass panel e.g. architectural glass panel or solar panels
  • glass cookware typically baking dish
  • glass dinnerware typically a plate, bowl, or dish
  • lamp bulbs, splinting bandage masonry, typically brick, concrete, or cement
  • silicate paint, or fibers typically insulation fibers.
  • the present invention relates to an article comprising a concrete surface, wherein the concrete surface is at least partially coated with a composition comprising a copolymer ( ZW-CA) having repeating units (Rzw) derived from at least one zwitterionic monomer (A) and repeating units (R CA ) derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer (B) in an amount effective to reduce or prevent colloids adhesion and/or fouling to the concrete surface.
  • ZW-CA copolymer having repeating units (Rzw) derived from at least one zwitterionic monomer (A) and repeating units (R CA ) derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer (B) in an amount effective to reduce or prevent colloids adhesion and/or fouling to the concrete surface.
  • the article is concrete water storage tank.
  • the articles of the present invention are prepared by the method described herein.
  • the features of the method described herein apply to the article, mutatis mutandis.
  • the composition is free of vinylpyrrolidone homopolymer or copolymer.
  • the present invention also relates to the use of a composition for reducing or preventing colloids adhesion and/or fouling on a substrate, the composition comprising a copolymer [copolymer (ZW-CA)] having repeating units [units (Rzw)] derived from at least one zwitterionic monomer [monomer (A)], typically at least one betaine monomer, and repeating units [units (R CA )] derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer [monomer (B)], wherein the substrate is selected from metal substrates, metal-containing substrates, silicate substrates and concrete substrates.
  • the substrate is typically in need of reduction or prevention of colloids adhesion and/or fouling.
  • the present invention also relates to a copolymer having repeating units derived from sulfopropyldimethylammonioethyl methacrylate (SPE) and repeating units derived from methacrylic acid or itaconic acid.
  • SPE sulfopropyldimethylammonioethyl methacrylate
  • copolymer (ZW-CA) according to the invention to reduce biofilm adhesion by Pseudomonas aeruginosa ATCC 9027 can be evaluated by a biofilm adhesion reduction test conducted in CDC Biofilm Reactors ® (available from Biosurface Technologies Corporation, Bozeman, Montana). In this test, aluminum coupons (polished or unpolished) are treated by dip-coating the said coupons in a solution of copolymer (ZW-CA) and then dried on a hot plate. 2 CDC reactors are used - one control with untreated coupons and one with treated coupons. The CDC reactors are then inoculated with the bacteria and bacterial growth media.
  • Each reactor is run in batch phase (no incoming or outgoing growth media) for 24 hours. Unless otherwise stated, the reactors are run while stirring for a turbulent shear mode. Afterwards, the coupons are removed and and can be evaluated by CFU (colony-forming unit) counts and microscopy. It is then possible to observe biofilm reduction between the control coupon (aluminum; not polished) and the treated coupon (dip-coated; not polished).
  • CFU colony-forming unit
  • the quantification of the percent of biofilm reduction can be measured as mentioned in the Example 5. Reduction of biofilm adhesion test - cooling tower water bacteria
  • copolymer (ZW-CA) according to the invention to reduce biofilm adhesion by bacteria found in cooling tower water can be evaluated by similar biofilm adhesion reduction test above described using test bacteria contained in water sampled from a cooling tower. It is also possible to observe biofilm reduction when cooling tower water bacteria is used.
  • Silicate glass coupons e.g. alkaline earth, boro-aluminosilicate glass, available as Eagle glass cover slides
  • copolymer (ZW-CA) coated with copolymer (ZW-CA) can be prepared by spin-coating using e.g. a Spin Coater - Laurell WS-650.
  • ZW-CA copolymer
  • 300 uL of copolymer (ZW-CA) solution in milli-Q water is pipetted onto the substrate and spread to cover the entire surface.
  • the substrate is allowed to sit for 5 minutes without spinning and then spun for 3 minutes at 1000 rpm/s.
  • the coated substrate is dried on a hot plate, then the resulting approximate thickness of the coating is measured using profilometry (VEECO DEKTAK 151).
  • Electrokinetic Analyzer for Solid Surface Analysis SurPASSTM 3 (Anton-Paar).
  • SurPASSTM 3 SurPASSTM 3 (Anton-Paar).
  • concrete coated polycarbonate polycarbonate cup filled with concrete
  • CDC coupons Biosurface Technologies Corporation, Bozeman MT
  • borosilicate glass CDC coupons Biosurface Technologies Corporation, Bozeman MT
  • the measurements are carried out in 20 mM NaCl solution with pH adjusted to pH 7.9 using 0.05 M NaOH/HCl.
  • the surface charge is first measured for pristine concrete coupons.
  • coupons are removed from the instrument and immersed into solution of copolymer (ZW-CA) according to the invention (75 ppm in 20 mM NaCl) for 30 min.
  • ZW-CA copolymer
  • the modified coupons are removed from the copolymer solution, the plastic cup of the coupon is wiped with Kimwipes® and the concrete is air-dried prior assembly into the instrument.
  • the air-dried coupons are assembled in the holder and surface zeta potential measured at pH 7.9 with 20 mM NaCl.
  • the surface is washed twice with 20 mM NaCl solution prior to taking value of surface potential to get equilibrated pH inside the measurement cell.
  • the value of zeta potential is measured in triplicates.
  • copolymer (ZW-CA) The ability of copolymer (ZW-CA) according to the invention to decrease the corrosion rate of metal or metal-containing substrate when submitted to corrosive conditions can be evaluated by linear polarization resistance (or linear sweep voltammetry).
  • the test is conducted onto carbon steel coupons. Carbon steel test surface is sanded and degreased, then passivated, which includes cleaning, neutralization, and formation of a “passive” oxide layer. The so treated test surface is then allowed to “film”, which is achieved by letting it stand for 24 hours in the presence of a 10,000 ppm solution of copolymer (ZW-CA).
  • the testing reactor setup is composed of jacketed reactors equipped with 3 electrodes: an SCE (saturated calomel electrode) as reference electrode; a rotating electrode in carbon steel with 1 cm 2 surface area as working electrode; and a platinum wire as counter electrode. Potentiostats/ galvanostats (Biologic) are used to make measurements.
  • Testing is done using Linear Polarization resistance measurements.
  • a plot of current versus corrosion potential is generated for different conditions, and the slope of the curve is calculated at the corrosion potential by performing a linear regression tangent to the data from lOmV cathodic to lOmV anodic relative to the corrosion potential.
  • the polarization resistance is calculated from the inverse of the slope.
  • the corrosion current is the inverse of the polarization resistance, multiplied by the Taffel coefficient of activation.
  • the rate of corrosion (micron/year) is calculated by multiplying the corrosion current by a constant that depends on the materials, for example carbon steel, and the area.
  • a sample was taken for 'H NMR analysis to determine the SPE and MAA monomer conversions.
  • a sample was taken for H NMR analysis to determine the SPE and MAA monomer conversions.
  • IA-Na Monosodium Itaconate
  • Monosodium Itaconate (IA-Na) was prepared by dissolving 32.091 g of Itaconic acid (IA) in 31.449 g of MiliQ water containing 9.766 g of NaOH.
  • the biofilm adhesion reduction test according to the present example was conducted in CDC Biofilm Reactors" (available from Biosurface Technologies Corporation, Bozeman, Montana). Aluminum coupons (unpolished) were treated by dip-coating the said coupons in a solution of copolymer and drying the dipped coupons on a hot plate. 2 CDC reactors were used: one control with untreated coupons and one with treated coupons. The CDC reactors were then inoculated with the bacteria and bacterial growth media. Each reactor was run in batch phase (no incoming or outgoing growth media) for 24 hours. Unless otherwise stated, the reactors were run while stirring for a turbulent shear mode. Afterwards, the coupons were removed and the biofilm reduction was quantified by evaluating the treated coupons versus the untreated coupons.
  • a Leica DMi8 confocal microscope was used to collect a z-stack of cross sectional images. Taken together, this stack of images produces a three dimensional representation of biofilm on the surface, and can be used to compare biofilm on control and treated surfaces.
  • the confocal microscope data consists of 8-bit grayscale images with intensity values from 0-255. Areas without biofilm/cells should be low intensity (dark), while areas with biomass should be high intensity (bright).
  • By thresholding the confocal images each pixel was classified as being either bright (biomass) or dark (no biomass). After thresholding, any number of image analysis software packages can be used to count the total number of bright pixels in each stack, which correlates with biomass.
  • any number of image analysis software packages can be used to count the total number of bright pixels in each stack, which correlates with biomass. For statistical copolymer poly(methacrylic acid-stat-SPE,(MAA-stat-SPE), the results are summarized in the Tables 3 and
  • Table 6 As shown in Tables 5 and 6, reduction greater than 80%, and even greater than 90%, in bright pixels (biomass) was observed between the control coupon and the treated coupon with poly(itaconic acid-stat-SPE), (poly(IA-stat-SPE)).

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Abstract

L'invention concerne des procédés de réduction ou de prévention de l'adhérence de colloïdes et/ou d'un encrassement par des colloïdes sur différents substrats, des compositions et des copolymères utiles à cet effet. Elle porte sur un procédé de réduction ou de prévention de l'adhérence de colloïdes et/ou de l'encrassement par des colloïdes sur un substrat en ayant besoin, le procédé comprenant l'application au moins partielle, sur le substrat, d'une quantité permettant de réduire ou de prévenir l'adhérence des colloïdes et/ou un encrassement par des colloïdes, une composition comprenant un polymère ayant des motifs répétitifs qui dérivent d'au moins un monomère zwitterionique, habituellement au moins un monomère de betaïne, et des motifs répétitifs qui dérivent d'un monomère contenant un acide carboxylique ou un anhydride carboxylique ; ledit substrat étant choisi parmi les substrats métalliques, les substrats contenant un métal, les substrats de silicate et les substrats de béton.
PCT/EP2021/053431 2020-02-12 2021-02-12 Procédés de réduction ou de prévention de l'adhérence de colloïdes et/ou d'encrassement par des colloïdes sur différents substrats, compositions et copolymères utiles à cet effet WO2021160788A1 (fr)

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