WO2021160788A1

WO2021160788A1 - Methods for reducing or preventing colloids adhesion and/or fouling on different substrates, compositions, and copolymers useful therefor

Info

Publication number: WO2021160788A1
Application number: PCT/EP2021/053431
Authority: WO
Inventors: Gilda Lizarraga; Jaime HUTCHISON; Sananda CHANDA; Avinash SHIVANANDAREDDY
Original assignee: Solvay Sa
Priority date: 2020-02-12
Filing date: 2021-02-12
Publication date: 2021-08-19

Abstract

Methods for reducing or preventing colloids adhesion and/or fouling on different substrates, compositions, and copolymers useful therefor 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 having repeating units derived from at least one zwitterionic monomer, typically at least one betaine monomer, and repeating units derived from at least one carboxylic acid or carboxylic acid anhydride containing monomer; wherein said substrate is selected from metal substrates, metal-containing substrates, silicate substrates and concrete substrates.

Description

METHODS FOR REDUCING OR PREVENTING COLLOIDS ADHESION AND/OR FOULING ON DIFFERENT SUBSTRATES, COMPOSITIONS, AND COPOLYMERS USEFUL THEREFOR

Field of the Invention

The present invention relates to the field of reducing or preventing colloids adhesion and/or fouling on different substrates, and copolymers useful therefor.

Background

5 In general, 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

10 diverse, ranging from fouling of ship hulls, natural surfaces in the marine environment, fouling of heat-transfer components in heating and cooling systems through ingredients contained in the cooling water, fouling of metal tools and components in the metal industry, for example, in metal working, like cutting and drilling, among other examples. Fouling materials are also diverse and

15 include materials such as colloids.

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,

20 the adherence of colloidal living material, including but not limited to 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. In the industrial sector, biofilms cause corrosion, reduce heat exchange in exchangers and give rise to flow resistance in tubes and

25 pipes. In the health sector, it is acknowledged that biofilm formation could be the source of many cases of nosocomial diseases, particularly if the biofilm fixes on surgical materials or in air conditioning or refrigeration systems. Thus, there is an ongoing need for new or improved methods and compositions for reducing or preventing colloids adhesion and/or fouling.

Summary of the Invention

In a first aspect, 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.

In a second aspect, 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.

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.

In a third aspect, 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.

In a fourth aspect, 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.

Detailed Description

As used herein, the terms “a”, “an”, or “the” means “one or more” or “at least one” unless otherwise stated.

As used herein, the term “comprises” includes “consists essentially of’ and “consists of.” The term “comprising” includes “consisting essentially of’ and “consisting of.”

Throughout the present disclosure, various publications may be incorporated by reference. Should the meaning of any language in such publications incorporated by reference conflict with the meaning of the language of the present disclosure, the meaning of the language of the present disclosure shall take precedence, unless otherwise indicated.

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.

As used herein, 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. In some cases, the adherence of 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.

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.

In accordance with the present invention, 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.

Without wishing to be bound to theory, 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. For instance, 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.

In an embodiment, 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.

As the steric bulk of polymer chains, and the hydration layer formed around hydrophilic functions on the polymer chains of the copolymer used, results in a repulsive barrier the presence of biocide is not required. In some embodiments, because biofilm formation is reduced or prevented by what is believed to be a repulsive barrier, the composition is free of biocide. In other embodiments, the composition contains some biocide. When 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.

Accordingly, the copolymer of the present invention is not a biocide.

The method described herein makes use of 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 embodiment, the composition is free of vinylpyrrolidone homopolymer or copolymer. The 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. For example, 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).

In an embodiment, the copolymer (ZW-CA) is a block copolymer, branched copolymer, or statistical copolymer.

In a preferred embodiment, the copolymer (ZW-CA) is a statistical copolymer.

Unless otherwise indicated, 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). There is no particular limitation to the molar mass of the copolymer. However, 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). As used herein, zwitterionic monomer (A) refers to monomer capable of polymerization . Generally, 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.

In some embodiments, 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

- sulfopropyldimethylammonioethyl (meth)acrylate,

- sulfoethyldimethylammonioethyl (meth)acrylate,

- sulfobutyldimethylammonioethyl (meth)acrylate,

- sulfohydroxypropyldimethylammonioethyl (meth)acrylate,

- sulfopropyldimethylammoniopropylacrylamide,

- sulfopropyldimethylammoniopropylmethacrylamide,

- sulfohydroxypropyldimethylammoniopropyl(meth)acrylamide, - sulfopropyldiethylammonio ethoxyethyl methacrylate. b) heterocyclic betaine monomers, typically

- sulfobetaines derived from piperazine,

- 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,

- 1 -vinyl-3 -(3 -sulfopropyl)imidazolium betaine; c) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl allylics, typically sulfopropylmethyldiallylammonium betaine; d) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl styrenes; e) betaines resulting from ethylenically unsaturated anhydrides and dienes; f) phosphobetaines of formulae

; and g) betaines resulting from cyclic acetals, typically

((dicyanoethanolate)ethoxy)dimethylammoniopropylmethacrylamide. In some preferred embodiments, units (Rzw) are derived from at least one monomer (A) selected from the list consisting of

- sulfopropyldimethylammonioethyl acrylate,

- sulfopropyldimethylammonioethyl methacrylate (SPE),

- sulfopropyldimethylammoniopropyl acrylamide,

- sulfopropyldimethylammoniopropyl methacrylamide,

- sulfohydroxypropyldimethylammonioethyl acrylate,

- sulfohydroxypropyldimethylammonioethyl methacrylate (SHPE),

- sulfohydroxypropyldimethylammoniopropyl acrylamide (AHPS),

- sulfohydroxypropyldimethylammoniopropyl methacrylamide (SHPP)

- l-(3-Sulphonatopropyl)-2-vinylpyridinium (2SPV), and

- l-(3-Sulphonatopropyl)-4-vinylpyridinium (4SPV).

In some more preferred embodiments, units (Rzw) are derived from at least one monomer (A) selected from the list consisting of

- sulfopropyldimethylammonioethyl acrylate,

- sulfopropyldimethylammonioethyl methacrylate (SPE),

- l-(3-Sulphonatopropyl)-2-vinylpyridinium, and

- l-(3-Sulphonatopropyl)-4-vinylpyridinium.

In some even more preferred embodiments, 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).

Generally, 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. Preferably, monomer (B) is selected from the list consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride. More preferably, 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.

In some preferred embodiments, 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.

In some more preferred embodiments, 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.

In some other preferred embodiments, 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.

Generally, 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. In an embodiment, 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. Generally, 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. In an embodiment, 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.

In some embodiments, 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. Preferably, 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).

Still in some preferred embodiments, 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.

When, 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. Besides, 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. For example, 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). Just for the sake of example statistical copolymer 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. Still for the sake of example statistical copolymer poly(maleic anhydride-stat- 3 -(dimethyl(4-vinylbenzyl)ammonio)propane-l -sulfonate) can be prepared by free radical copolymerization in water of maleic anhydride and dimethyl (4-vinylbenzyl)ammonio)propane-l -sulfonate initiated by 4, 4’- azobis(4-cyanovaleric acid (ACVA).

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:

- sulfopropyldimethylammonioethyl methacrylate, sold by Raschig under the name RALLTMER SPE

- sulfoethyldimethylammonioethyl methacrylate,

- sulfobutyldimethylammonioethyl methacrylate:

the synthesis of which is described in the paper “Sulfobetaine zwitterionomers based on n-butyl acrylate and 2-ethoxyethyl acrylate: monomer synthesis and copolymerization behavior”, Journal of Polymer Science, 40, 511-523 (2002), - sulfohydroxypropyldimethylammonioethyl methacrylate,

and other hydroxyalkyl sulfonates of dialkylammonium alkyl acrylates or methacrylates, acrylamido or methacrylamido of formulae below:

- sulfopropyl dimethyl ammoni opropyl acryl ami de, the synthesis of which is described in the paper “Synthesis and solubility of the poly(sulfobetaine)s and the corresponding cationic polymers: 1. Synthesis and characterization of sulfobetaines and the corresponding cationic monomers by nuclear magnetic resonance spectra”, Wen-Fu Lee and Chan- Chang Tsai, Polymer, 35 (10), 2210-2217 (1994), - sulfopropyl dimethylammoniopropylmethacrylamide, sold by Raschig under the name SPP: - sulfopropyldiethylammonio ethoxyethyl methacrylate:

the synthesis of which is described in the paper “Poly(sulphopropylbetaines): 1. Synthesis and characterization”, V. M. Monroy Soto and J. C. Galin, Polymer, 1984, Vol. 25, 121-128; b) heterocyclic betaine monomers, typically:

- sulfobetaines derived from piperazine having any one of the following structures

the synthesis of which is described in the paper “Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165- 2173 (1994), and other hydroxyalkyl sulfonates derived from piperazine of formulae below:

- 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. Gonzalez, J. Cardoso, O. Manero and V. M. Monroy, J. Mater. Res., 5 (3), 654-657 (1990), and other hydroxyalkyl sulfonates derived from 2-vinylpyridine and 4vinylpyridine of formulae below:

- 1 -vinyl-3 -(3 -sulfopropyl)imidazolium betaine: the synthesis of which is described in the paper “Aqueous solution properties of a poly(vinyl imidazolium sulphobetaine)”, J. C. Salamone, W. Volkson, A.P. Oison, S.C. Israel, Polymer, 19, 1157-1162 (1978), and corresponding 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 “Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165- 2173 (1994), and other hydroxyalkyl sulfonates of dialkylammonium alkyl styrenes of formulae below

e) betaines resulting from ethylenically unsaturated anhydrides and dienes, typically compounds having any one of the following structures:

the synthesis of which is described in the paper “Hydrophobically Modified Zwitterionic Polymers: Synthesis, Bulk Properties, and Miscibility with Inorganic Salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165-2173 (1994), f) phosphobetaines having any one of the following structures:

the synthesis of which are disclosed in EP 810239 B1 (Biocompatibles, Alister et ah); g) betaines resulting from cyclic acetals, typically

((dicyanoethanolate)ethoxy)dimethylammoniumpropylmethacrylamide: the synthesis of which is described by M-L. Pujol-Fortin et al. in the paper entitled “Poly(ammonium alkoxydicyanatoethenolates) as new hydrophobic and highly dipolar poly(zwitterions). 1. Synthesis”, Macromolecules, 24, 4523-4530 (1991).

Suitable monomers comprising hydroxyalkyl sulfonate moieties from which can be derived units (Rzw) 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:

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:

The expression “derived from” which puts recurring units (Rzw) in connection with a monomer is intended to define both recurring units (Rzw) directly obtained from polymerizing the said monomer, and the same recurring units (Rzw) obtained by modification of an existing polymer.

Accordingly, 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). Similar modification was described in WO2008125512 with sodium 3 -chloropropane-1 -sulfonate in place of CHPSNa: Finaly, recurring units (Rzw) 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. Exemplary synthetic steps are shown below:

Similarly, 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.

The 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.

In the method according to the present invention, the composition is applied to the substrate in an amount effective to reduce or prevent colloids adhesion and/or fouling. As used herein, the 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. In an embodiment, 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/m², typically from 0.001 to 50 mg/m², of the surface applied.

It has been discovered, surprisingly, that 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. Accordingly, the substrate, typically in need of reduction or prevention of colloids adhesion and/or fouling is a metal or metal-containing substrate. Typically, the metal is selected from the group consisting of iron, cast iron, copper, brass, aluminum, titanium, carbon steel, stainless steel, and alloys thereof.

It has been discovered, surprisingly, that applying to the metal or metal- containing substrate a composition comprising a copolymer (ZW-CA) as described herein not only reduces or prevents the adhesion of colloids and/or fouling on the metal or metal-containing substrate but also decreases the corrosion rate of said metal or metal -containing substrate when submitted to corrosive conditions. Without wishing to be bound to theory, the corrosion rate is believed to be reduced through the formation of a coating or passivation layer involving adsorbed copolymer (ZW-CA) according to the invention which prevents access of the corrosive compounds to the metal or metal-containing substrate. Accordingly copolymer (ZW-CA) according to the invention is considered to behave as a corrosion inhibitor.

In general, surprisingly, 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.

As used herein, the term “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.

Examples of nesosilicates include, but are not limited to, olivine [(Mg,Fe)₂Si0₄], forsterite (Mg₂Si0₄), fayalite (Fe₂Si0₄), alite [Ca₃((Si0₄)0)], belite (Ca₂Si0₄), andalousite, sillimanite and kyanite [all three are of formula Al₂0(Si0₄)], phenakite, topaz and thaumasite.

Exemplary of sorosilicates are prehnite, hemimorphite [Zn (Si₂Ov)(OH)₂] and compounds of formula CaMg(Si₂Ov).

Cyclosilicates refer to silicates with tetrahedrons that usually link to form rings of three (Si₃0₉) ⁶, four (Si 0i₂) ⁸, six (Si₆0i₈) ¹² or nine (Si₉0₂₇) ¹⁸ units, and include, for example, beryl.

Examples of tectosilicates include, but are not limited to, quartz, cristobalite, tridymite, orthose [K(AlSi₃0₈)], anorthite [Ca(Al₂Si₂0₈)] and celsiane [Ba(Al₂Si₂0₈)].

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 (Si0₃) 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(Si0₃)₂], spodumene [LiAl(Si0₃)₂], wollastonite [Ca(Si0₃)], enstatite [Mg(Si0₃)], hypersthene, hedenbergite, augite, pectolite, diallage, fassaite, spodumene, jeffersonite, aegirine, omphafacite and hiddenite.

Suitable examples of amphiboles include, but are not limited to, calcium amphiboles such as tremolite [Ca₂Mg₅[Si₄On,(OH,F)]₂], actinote [Ca₂(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.

Other suitable crystalline silicates include, but are not limited to, barium silicates, such as BaSi0₃ (barium metasilicate), Ba₂Si₃0₇ (barium disilicate), and Ba₂Si0 (dibarium silicate); calcium silicates, such as CaSi0₃ (monocalcium silicate or wollastonite), Ca₂Si0₄ (dicalcium silicate), and Ca₃Si0₃ (tricalcium silicate); magnesium silicates, such as MgSi0₃ (enstatite), Mg₂Si0₄ (forsterite); aluminum silicates (also “aluminosilicates”), such as halloysite (Al₂Si₂0₅(0H)₄), kaolinite (Al₂Si₂0₅(0H)₄), mullite (aka porcelainite, Al₆Si₂0i₃), muscovite (KAl₂(AlSi₃)Oio(OH)₂), sanidine (KAlSi₃0₈), albite (NaAlSi₃0₈) and anorthite (CaAl₂Si₂0₈). Many crystalline silicates useful for the present invention are ceramics.

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.

Among 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

• bricks, dental porcelain, the composition or which lies in the leucite field in the ternary raw material diagram kaolin/clay-feldspar-quartz, having generally a high feldspar content (typically about 80%) and a low kaolin content (typically less than about 5%), magnesium silicates, including talc-based ceramics which are typically based on the ternary phase diagram MgO-AkCh-SiC , such as steatite, cordierite and forsterite ceramics, and zircon-based ceramics for electrical insulators, ceramics in the system Li₂0-Al₂03-Si02, which have generally low- thermal expansion and can be notably used for thermoshock-resistant tablewares. 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.

Among 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 (Si0₂) 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 (Si0₂), soda (Na₂0) and lime (CaO); soda-lime-silica glass often further comprises one or more additional components, usually in a low amount, in particular A1₂0₃, K₂0 and MgO ; an exemplary soda-lime- silica glass composition is or comprises from 63 % to 81% Si0₂, from 9% to 18% Na₂0, from 7% to 14% CaO, from 0 % to 1.5 % K₂0, from 0 % to 8 % MgO and from 0% to 3% of A1₂0₃ ; soda-lime-silica glass is notably useful for some low-temperature incandescent light bulbs and tablewares, etc. borosilicate glass, which comprises silica (Si0₂) and boron trioxide (B₂0₃) ; borosilicate glass often further comprises one or more additional components, usually in a low amount, in particular Na₂0, K₂0, CaO, MgO and A1₂0₃ ; a first exemplary borosilicate glass composition (Pyrex™-type) is or comprises from 65% to 85% of Si0₂, from 7% to 15% of B₂0₃, from 3% to 9 % of Na₂0, from 0.5% to 7% of A1₂0₃, from 0% to 3% K₂0, 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 Si0₂, from 2% to 10% of B₂0₃, from 5% to 30% of CaO, from 0% to 12% of A1₂0₃, from 0% to 20% of Na₂0, from 0% to 2% K₂0 and from 0% to 15% MgO ; borosilicate glass is notably useful for chemical glassware like reagent bottles, household cookwares, car head lamps and optical components ; lead glass, also known as crystal glass or lead-oxide glass, which comprises silica (Si0₂) and lead oxide (PbO) ; lead glass may further contain notably B₂0₃, A1₂0₃, MgO, ZnO and Zr0₂ ; lead glass may contain or be free of alkali oxide (such as K₂0 and Na₂0) ; aluminosilicate glass, which comprises silica and alumina ; aluminosilicate glass often further comprises one or more additional components, usually in a low amount, in particular CaO, MgO, BaO, B₂0₃, SrO, Na₂0 and K₂0 ; an exemplary aluminosilicate glass composition is or comprises from 45% to 75% Si0₂, from 5% to 30% A1₂0₃, from 10% to 35% of one or more alkaline earth metal oxide(s) and up to 5% of other components such as alkali metal oxides ; and germanium-oxide glass, which comprises silica, alumina and germanium dioxide (Ge0₂).

As used herein, the term “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.

In general, surprisingly, 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.

By concrete is meant 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. By hydraulic cements is meant 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.

Generally, 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.

In some embodiments, 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.

Generally, 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%.

Besides, 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 %.

In some embodiments, the concrete comprises well known admixtures such as setting and hardening admixtures, workability admixtures, and porosity admixtures.

The substrate used according to the present invention is in contact with an aqueous medium. Herein, “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.

In an embodiment, 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. Accordingly, 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.

In an embodiment, 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.

In another aspect, 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. In an embodiment, 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; heating apparatus, typically a hot plate or immersion heater; ceramic (esp. porcelain) sanitary ware, tile, bathtub, toilet, sink, countertop, faucets, or pipes; medical or dental implants; ceramic (esp. porcelain) tools or molds; solar panels; or ceramic (esp. porcelain) decorative articles.

In another embodiment, 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.

Still in an other aspect, 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.

In an embodiment, 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. Thus, in an embodiment of the article, 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.

Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence. Reduction of biofilm adhesion test - Pseudomonas aeruginosa ATCC

9027

The ability of 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).

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

The ability of 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.

Coating of silicate coupons with copolymer (ZW-CA)

Silicate glass coupons (e.g. alkaline earth, boro-aluminosilicate glass, available as Eagle glass cover slides) coated with copolymer (ZW-CA) can be prepared by spin-coating using e.g. a Spin Coater - Laurell WS-650. On a cleaned substrate, 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).

Surface potential measurements on concrete

Surface potential can be measured using Electrokinetic Analyzer for Solid Surface Analysis: SurPASS™ 3 (Anton-Paar). As a substrate for the measurements, concrete coated polycarbonate (polycarbonate cup filled with concrete) CDC coupons (Biosurface Technologies Corporation, Bozeman MT) or borosilicate glass CDC coupons (Biosurface Technologies Corporation, Bozeman MT) is used. The measurements are carried out in 20 mM NaCl solution with pH adjusted to pH 7.9 using 0.05 M NaOH/HCl.

Surface potential measurements on concrete coupons

In this test, the surface charge is first measured for pristine concrete coupons. After the measurements, 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. 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.

With the surface modification with the copolymer (ZW-CA), it is possible to observe a decrease in the surface charge indicating adsorption of the polymer on surface and an increase in surface hydrophilicity as compared to pristine coupons.

Anti-corrosion testing

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 cm² surface area as working electrode; and a platinum wire as counter electrode. Potentiostats/ galvanostats (Biologic) are used to make measurements.

Aggressive/ corrosive water conditions are used for this testing, where LSI (Langelier Saturation Index) is less than 0, and where use temperatures are between room temperature and 80°C.

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.

In case of carbon steel surface treated with copolymer (ZW-CA), it is possible to observe a decrease of corrosion rate compared to untreated carbon steel surface.

The invention will now be illustrated in more detail with reference to the following examples, which are not intended as being limiting. Example 1: Synthesis of a statistical copolymer poly(methacrylic acid- stat-SPE) (poly(MAA-stat-SPE)) in the present invention by conventional radical polymerization (Initiator: 2,2'-Azobis(2- methylpropionamidine)dihydrochloride) V50 - MAA = 10 mol% - SPE = 90 mol%)

In a 500 mL five-neck reactor equipped with a water condenser and a mechanical agitation, are introduced, at room temperature (25°C), 50 g of MilliQ water and degassing started. Meanwhile, the temperature was also increased from room temperature to 60°C. When the temperature reached 60°C, 0.55 g of an aqueous solution of MAA at 50 wt %, 9.67 g of an aqueous solution of SPE at 50 wt% and 113 g of MilliQ water were added. As there was a temperature drop on addition, the temperature was allowed to reach 60°C. On reaching 60°C,

10.75 g of an aqueous V50 solution at 10 wt% was added. Under a nitrogen blanket, were introduced by continuous feeding the remaining 10.48 g of the aqueous MAA solution at 50 wt% and the remaining 183.71 g of the aqueous

SPE solution at 50 wt% over 6 hours. At the end of the feeding, the reaction was pursued for two hours at 60°C.

At the end of the polymerization, a sample was taken for 'H NMR analysis to determine the SPE and MAA monomer conversions. A sample was also taken for gel permeation chromatography (GPC) analysis to determine the number average molar mass Mn, the weight average molar mass Mw and the polydispersity (PDI = polydispersity index).

Example 2: Synthesis of a statistical copolymer poly(methacrylic acid- stat-SPE) (poly(MAA-stat-SPE)) in the present invention by conventional radical polymerization (Initiator: 2,2'-Azobis(2- methylpropionamidine)dihydrochloride) V50 - MAA = 30 mol% - SPE =

70 mol%)

In a 500 mL five-neck reactor equipped with a water condenser and a mechanical agitation, are introduced, at room temperature (25°C), 50 g of MilliQ water and degassing started. Meanwhile, the temperature was also increased from room temperature to 60°C. When the temperature reached 60°C, 1.16 g of an aqueous solution of MAA at 50 wt %, 8.83 g of an aqueous solution of SPE at 50 wt% and 210.56 g of MilliQ water were added. As there was a temperature drop on addition, the temperature was allowed to reach 60°C. On reaching 60°C, 12.63 g of an aqueous V50 solution at 10 wt% was added. Under a nitrogen blanket, were introduced by continuous feeding the remaining 22.16 g of the aqueous MAA solution at 50 wt% and the remaining 167.83 g of the aqueous SPE solution at 50 wt% over 6 hours. At the end of the feeding, the reaction was pursued for two hours at 60°C.

At the end of the polymerization, a sample was taken for H NMR analysis to determine the SPE and MAA monomer conversions. A sample was also taken for gel permeation chromatography (GPC) analysis to determine the number average molar mass Mn, the weight average molar mass Mw and the polydispersity (PDI = polydispersity index).

The results for examples 1 and 2 are summarized in Table 1 below. Table 1

Example 3: Synthesis of a statistical copolymer poly(itaconic acid-stat- SPE) (poly(IA-stat-SPE)) in the present invention by conventional radical polymerization (Initiator: 2,2'-Azobis(2- methylpropionamidine)dihydrochloride) V50, IA = 30 mol% - SPE =

70 mol%)

Monosodium Itaconate (IA-Na) was prepared by dissolving 16.804 g of Itaconic acid (IA) in MiliQ water containing 5.11 g of NaOH.

In a 500 mL five-neck reactor equipped with a water condenser and a mechanical agitation, are introduced, at room temperature (25°C), 146 g of MilliQ water and degassing started. Meanwhile, the temperature was also increased from room temperature to 60°C. When the temperature reached 60°C, 3.837 g of an aqueous solution of IA-Na at 50 wt % and 16.672 g of an aqueous solution of SPE at 50 wt% were added. As there was a temperature drop on addition, the temperature was allowed to reach 60°C. On reaching 60oC, 11.917 g of an aqueous V50 solution at 10 wt% was added. Under a nitrogen blanket, were introduced by continuous feeding the remaining 29.944 g of the aqueous IA-Na solution at 50 wt% and the remaining 150.05 g of the aqueous SPE solution at 50 wt% over 6 hours. At the end of the feeding, the reaction was pursued for two hours (one hour at 60°C and one hour at 90°C).

At the end of the polymerization, a sample was taken for 'H NMR analysis to determine the SPE and IA monomer conversions. A sample was also taken for gel permeation chromatography (GPC) analysis to determine the number average molar mass Mn, the weight average molar mass Mw and the polydispersity.

Example 4: Synthesis of a statistical copolymer poly(itaconic acid-stat- SPE) (poly(IA-stat-SPE)) in the present invention by conventional radical polymerization (Initiator: 2,2'-Azobis(2- methylpropionamidine)dihydrochloride) V50, IA = 50 mol% - SPE =

50 mol%)

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.

In a 500 mL five-neck reactor equipped with a water condenser and a mechanical agitation, are introduced, at room temperature (25°C), 155.3 g of MilliQ water and degassing started. Meanwhile, the temperature was also increased from room temperature to 60°C. When the temperature reached 60°C, 7.33 g of an aqueous solution of IA-Na at 50 wt % and 13.645 g of an aqueous solution of SPE at 50 wt% were added. As there was a temperature drop on addition, the temperature was allowed to reach 60°C. On reaching 60°C, 13.65 g of an aqueous V50 solution at 10 wt% was added. Under a nitrogen blanket, were introduced by continuous feeding the remaining 65.975 g of the aqueous IA-Na solution at 50 wt% and the remaining 122.813 g of the aqueous SPE solution at 50 wt% over 6 hours. At the end of the feeding, the reaction was pursued for two hours (one hour at 60°C and one hour at 90°C). At the end of the polymerization, a sample was taken for H NMR analysis to determine the SPE and IA monomer conversions. A sample was also taken for gel permeation chromatography (GPC) analysis to determine the number average molar mass Mn, the weight average molar mass Mw and the polydispersity (PDI = polydispersity index).

The results for the examples 3 and 4 are summarized in Table 2 below. Table 2

Example 5: Reduction of biofilm adhesion test — Pseudomonas aeruginosa ATCC 9027

The ability of statistical copolymers poly(methacrylic acid-stat-SPE) (poly(MAA-stat-SPE)) and poly(itaconic acid-stat-SPE) (poly(IA-stat-SPE)), made according to Examples 1 and 2, to reduce biofilm adhesion by Pseudomonas aeruginosa ATCC 9027 was evaluated.

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.

To quantify the percent of biofilm reduction, 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. For statistical copolymer poly(methacrylic acid-stat-SPE,(MAA-stat-SPE), the results are summarized in the Tables 3 and 4 below.

Table 3

Table 4

As shown in Tables 3 and 4, reduction greater thant 90% in bright pixels

(biomass) was observed between the control coupon and the treated coupon with statistical copolymer poly(methacrylic acid-stat-SPE), (poly(MAA-stat-SPE)).

For statistical copolymer poly(itaconic acid-stat-SPE), (poly(IA-stat-SPE)), the results are summarized in the Tables 5 and 6 below. Table 5

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)).

Claims

C L A IM S

1. 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 (R_CA)] 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.

2. Method according to claim 1, wherein the monomer (A) is selected from the group consisting of a) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl acrylates or methacrylates, acrylamido or methacrylamido, typically

- sulfopropyldimethylammonioethyl (meth)acrylate,

- sulfoethyldimethylammonioethyl (meth)acrylate,

- sulfobutyldimethylammonioethyl (meth)acrylate, - sulfohydroxypropyldimethylammonioethyl (meth)acrylate,

- sulfopropyl dimethyl ammoni opropyl acryl ami de,

- sulfopropyldimethylammoniopropylmethacrylamide,

- sulfohydroxypropyldimethylammoniopropyl(meth)acrylamide,

- sulfopropyldiethylammonio ethoxyethyl methacrylate. b) heterocyclic betaine monomers, typically

- sulfobetaines derived from piperazine,

- sulfobetaines derived from 2-vinylpyridine and 4-vinylpyridine, more typically l-(3-Sulphonatopropyl)-2-vinylpyridinium or l-(3-Sulphonatopropyl)- 4-vinylpyridinium ,

- lvinyl-3-(3-sulfopropyl)imidazolium betaine; c) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl allylics, typically sulfopropylmethyldiallylammonium betaine; d) alkyl or hydroxyalkyl sulfonates or phosphonates of dialkylammonium alkyl styrenes; e) betaines resulting from ethylenically unsaturated anhydrides and dienes; f) phosphobetaines of formulae

g) betaines resulting from cyclic acetals, typically ((dicyanoethanolate)ethoxy)dimethylammoniopropylmethacrylamide.

3. Method according to claim 2, wherein the monomer (A) is selected from the list consisting of - sulfopropyldimethylammonioethyl acrylate,

- sulfopropyldimethylammonioethyl methacrylate (SPE),

- sulfopropyldimethylammoniopropyl acrylamide,

- sulfopropyldimethylammoniopropyl methacrylamide,

- sulfohydroxypropyldimethylammonioethyl acrylate,

- sulfohydroxypropyldimethylammonioethyl methacrylate (SHPE),

- sulfohydroxypropyldimethylammoniopropyl acrylamide (AHPS),

- sulfohydroxypropyldimethylammoniopropyl methacrylamide (SHPP)

- l-(3-Sulphonatopropyl)-2-vinylpyridinium (2SPV), and

- l-(3-Sulphonatopropyl)-4-vinylpyridinium (4SPV).

4. The method according to any one of claims 1 to 3, wherein 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.

5. The method according to claim 4, wherein monomer (B) is selected from the list consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid and maleic acid anhydride.

6. The method according to any one of claims 1 to 5, wherein 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 derived from monomer (B), based on the molar composition of the copolymer.

7. The method according to any one of claims 1 to 6, wherein 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.

8. The method according to any one of claims 1 to 7, wherein copolymer (ZW-CA) further comprises repeating units [units (R_N)] derived from at least one monomer [monomer (C)] selected from the list consisting of 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate, 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, 4-hydroxybutyl acrylate, poly(ethylene glycol) methacrylate (PEGMA), poly(ethylene glycol) methyl ether methacrylate (mPEGMA), polyethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) methyl ether acrylate and poly(ethylene glycol) ethyl ether acrylate.

9. The method according to claim 8, wherein copolymer (ZW-CA) 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% of repeating units (RCA) derived from monomer (B), based on the molar composition of the copolymer.

10. The method according to claims 8 or 9, wherein 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% of repeating units (Rzw) and (R_N) based on the molar composition of the copolymer,

11. The method according to claim 10, wherein the molar ratio of repeating units (Rzw) with repeating units (R_N) ranges from 0.25 to 4.

12. The method according to any one of claims 1 to 11, wherein copolymer (ZW-CA) is a statistical copolymer the weight-average molar mass (Mw) of which 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.

13. The method according to any one of claims 1 to 12, wherein the substrate is in contact with an aqueous medium.

14. The method according to any one of claims 1 to 13, wherein the copolymer is deposited on the substrate in an amount from 0.0001 to 100 mg/m², typically from 0.001 to 50 mg/m², of the surface applied.

15. The method according to any one of claims 1 to 14, wherein the substrate is a metal or metal-containing substrate, typically wherein the metal is selected from the group consisting of iron, cast iron, copper, brass, aluminum, titanium, carbon steel, stainless steel, and alloys thereof.

16. The method according to any one of claims 1 to 14, wherein the substrate is a silicate or a concrete substrate.

17. 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 (RCA) 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.

18. An article comprising a silicate or a concrete surface, wherein the silicate or 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 (RCA) 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 or the concrete surface.

19. Article according to claim 17, wherein 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.

20. 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 (RCA)] 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.

21. A copolymer having repeating units derived from sulfopropyldimethylammonioethyl methacrylate (SPE) and repeating units derived from methacrylic acid or itaconic acid.