WO2021097531A1 - Inhibiteurs de corrosion polyioniques - Google Patents

Inhibiteurs de corrosion polyioniques Download PDF

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Publication number
WO2021097531A1
WO2021097531A1 PCT/AU2020/051258 AU2020051258W WO2021097531A1 WO 2021097531 A1 WO2021097531 A1 WO 2021097531A1 AU 2020051258 W AU2020051258 W AU 2020051258W WO 2021097531 A1 WO2021097531 A1 WO 2021097531A1
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WIPO (PCT)
Prior art keywords
alkyl
heteroalkyl
alkenyl
heteroalkenyl
polymerizable
Prior art date
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PCT/AU2020/051258
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English (en)
Inventor
Maria Forsyth
Anthony Emil SOMERS
David Mecerreyes
Esther UDABE
Original Assignee
Deakin University
University Of The Basque Country
Basque Center For Macromolecular Design And Engineering, Polymat Fundazioa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from AU2019904421A external-priority patent/AU2019904421A0/en
Application filed by Deakin University, University Of The Basque Country, Basque Center For Macromolecular Design And Engineering, Polymat Fundazioa filed Critical Deakin University
Publication of WO2021097531A1 publication Critical patent/WO2021097531A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C07C57/42—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings having unsaturation outside the rings
    • C07C57/44—Cinnamic acid
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
    • C07C59/52—Unsaturated compounds containing hydroxy or O-metal groups a hydroxy or O-metal group being bound to a carbon atom of a six-membered aromatic ring
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    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/18—Salts thereof
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F112/26—Nitrogen
    • C08F112/28—Amines
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    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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    • C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/06—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
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    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/167—Phosphorus-containing compounds
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    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
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    • C08F2/00—Processes of polymerisation
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    • 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
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Definitions

  • the present disclosure generally relates to polyionic corrosion inhibitors, polymerizable ionic compounds, and cured reaction products, compositions, formulations, coatings, and methods of making and use thereof.
  • Protective coatings used to prevent corrosion typically provide at least one of barrier protection, sacrificial (galvanic) protection and corrosion inhibition, in which each disrupt the electrochemical reaction causing corrosion.
  • Barrier protection acts to prevent migration of electrolytes, sacrificial pigments corrode preferentially to that of the surface being protected, and corrosion inhibitors act in various mechanisms to prevent corrosion including reactions to passivate metal surfaces by forming thin inert films on metal surfaces.
  • Coating systems may contain various resins, solvents, additives, and/or pigments, that provide corrosion protection to substrates.
  • Coating systems are designed for coating onto substrates to provide a protective layer having good mechanical properties such as adhesion, impact resistance and ductility, and which may also include additional corrosion inhibitors for added corrosion protection.
  • Corrosion inhibitors may be provided as pigments including inorganic pigments, organic pigments and metallic pigments.
  • Inorganic pigments include various metal phosphates, molybdates, and silicates, such as zinc molybdate.
  • Organic pigments include various aromatic acids and carbon based polymers including graphite and conducting polymers such as polyaniline.
  • Metallic pigments include metal salts such as metallic zinc, which typically acts as a sacrificial pigment.
  • the present disclosure relates to polyionic corrosion inhibitors, polymerizable ionic compounds, and to cured reaction products, compositions, formulations, coatings, and methods of making and use thereof.
  • the polymerizable ionic compounds of the present disclosure provide polyionic corrosion inhibitors comprising onium cations and aromatic carboxylate anions.
  • the polymerizable ionic compounds comprise at least one polymerizable group, which can be provided on the onium cation and/or aromatic carboxylate anion.
  • the aromatic carboxylate groups provide counter anions for the onium cations of the polymerizable ionic compounds, and have been found effective for providing polymerizable ionic compounds and cured reaction products thereof in the form of polyionic corrosion inhibitors that provide various properties including corrosion inhibition.
  • the polymerizable ionic compounds or polyionic corrosion inhibitors can be provided as polymerizable ionic liquids or polyionic liquids.
  • a method for inhibiting corrosion on a substrate by providing one or more coatings on the substrate, wherein at least one coating comprises a polymerizable ionic compound (PIC) or a cured reaction product thereof, and wherein the PIC comprises onium cation groups and aromatic carboxylate counter anion groups.
  • PIC polymerizable ionic compound
  • a coating comprising a polymerizable ionic compound (PIC) or a reaction product thereof for inhibiting corrosion on a substrate, wherein the PIC comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • PIC polymerizable ionic compound
  • a coated metal substrate comprising a metal substrate coated with one or more coating layers, wherein at least one of the coating layers comprises a polymerizable ionic compound (PIC) or a reaction product thereof, wherein the PIC comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • PIC polymerizable ionic compound
  • a coating applied to an optionally coated substrate wherein the coating comprises or consists of:
  • PIC polymerizable ionic compound
  • a coating system comprising:
  • one or more corrosion protection layers located between (i) and (ii) comprising a polymerizable ionic compound (PIC) or a reaction product thereof, wherein the PIC comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • PIC polymerizable ionic compound
  • a polymerizable ionic compound (PIC) or reaction product thereof comprising or consisting of an optionally polymerizable aromatic carboxylate of Formula 1 and an optionally polymerizable onium cation:
  • X is an optionally linked carboxylate anion group
  • the optionally polymerizable onium cations are optionally polymerizable quaternary onium cations.
  • the onium cations may be selected from ammonium cation groups, pyridinium cation groups, imidazolium cation groups, pyrazolium cation groups, pyrrolidinium cation groups, and phosphonium cation groups, which may be optionally polymerizable.
  • the optionally polymerizable onium cations are optionally polymerizable quaternary ammonium cations.
  • the polymerizable ionic compound is a polymerizable ionic liquid (PIL).
  • PIL polymerizable ionic liquid
  • the polymerizable group is selected from an epoxy, acrylamide, acrylate, and vinyl.
  • the onium cation groups are optionally polymerizable ammonium cation groups of Formula 2a.
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl, and wherein at least one of R 6 , R 7 , R 8 , and R 9 , is a polymerizable group.
  • a curable coating composition comprising or consisting of an organic film former, wherein the organic film former comprises or consists of a polymerizable ionic compound (PIC) or a cured reaction product thereof, wherein the PIC comprises onium cation groups and aromatic carboxylate counter-anion groups, and wherein at least one polymerizable group is provided on at least one group selected from the onium cation groups and aromatic carboxylate counter-anion groups.
  • PIC polymerizable ionic compound
  • a process for preparing a coating system comprising: applying the PIC, cured reaction product or coating composition according to any aspects, embodiments or examples as described herein, to an optionally coated substrate; and optionally applying one or more post coating layer to the coating present on the optionally coated substrate.
  • X is a carboxylic acid or carboxylate group
  • Lx is an optional group being a divalent linking group selected from alkyl, alkenyl, heteroalkyl, and heteroalkenyl;
  • composition of matter, group of steps or group of compositions of matter shall be taken to encompass one and a plurality (i.e. one or more) of those steps, compositions of matter, groups of steps or groups of compositions of matter.
  • Figure 1A-B provide a schematic of a coating preparation on mild steel containing 20 weight % of polymerizable ionic compounds according to some examples of the present disclosure.
  • Figure 2 is an Electrochemical Impedance Spectra (EIS) for a coated steel specimen immersed in 1M NaCl solution for 24 hours; black - control coating without any polymerizable ionic compounds; red - coating with 20 weight % [p-OHcoum]MA polymerizable ionic compound according to one example of the present disclosure; blue- coating with 20 weight % [p-O(C6H13)coum]MA polymerizable ionic compound according to another example of the present disclosure. Larger impedance signifies greater corrosion inhibition and better barrier properties.
  • EIS Electrochemical Impedance Spectra
  • Figures 3A-C show a time evolution of EIS bode plots for control coating and coatings containing 20 weight % [pOHcoum]MA and [pOC6H13]MA polymerizable ionic compounds according to two examples of the present disclosure immersed in NaCl aqueous solution. The highest impedance shown is the coating containing [pOC 6 H 13 ]MA polymerizable ionic compound.
  • Figure 4 shows images of coated specimens after 20hr immersion in NaCl aqueous solutions. Top image with coating containing 20 weight % [p-OHcoum]MA, middle image with coating containing 20 weight % [p-O(C 4 H 9 )coum]MA, bottom image with coating containing 20 weight % [p-O(C 6 H 13 )coum]MA polymerizable ionic compound according to some examples of the present disclosure
  • Figure 5A provides a schematic of polymerizable ionic compounds according to some examples of the present disclosure tested in UV cured coatings at a level of 20 weight %.
  • Figure 5B(i) shows EIS bode impedance plots for UV cured coatings containing 20 weight % of the different polymerizable ionic compounds (PIC) according to some examples of the present disclosure compared with the control coating.
  • PIC polymerizable ionic compounds
  • Figure 5B(ii) shows coatings on AS 1020 mild steel containing 20% of [p- 0[C 6 H 13 )coum]MA, [p-O[C6H13)coum]IM, [p-O[C 6 H 13 )coum]AN and [p- 0[C 6 H 13 )coum]PY and control immersed in sodium chloride aqueous solution after 20 h.
  • Figure 5C shows Nyquist plots after 24 hours immersion of the coatings in NaCl aqueous solution. Same data is provided as the Bode plots in Figure 5B above but in a different format.
  • Figures 6A & 6B provides a schematic of the preparation (Figure 6A) and EIS bode impedance plots ( Figure 6B) for UV cured coatings containing 20 weight % of the anionic polymerizable ionic compound [p-O(MEM)coum] according to one example of the present disclosure compared with the control coating.
  • Figure 7 provides a representation of an immersion of mild steel 1020 surface in an aqueous solution containing the polymerizable ionic compounds according to some examples of the present disclosure.
  • Figure 8A shows Tafel plots of AS 1020 mild steel in control and aqueous solutions containing the polymerizable ionic compounds according to some examples of the present disclosure.
  • Figure 8B shows corrosion potentials (E corr ), corrosion current density (i corr ), Tafel anodic and cathodic slopes ( ⁇ a and ⁇ c) of the control and aqueous solutions containing the polymerizable ionic compounds according to some examples of the present disclosure.
  • Figure 9 shows Nyquist plots for AS 1020 mild steel immersed in the control and aqueous solutions containing the polymerizable ionic compounds according to some examples of the present disclosure after 0 h and 24 h.
  • Figure 10 shows optical microscopy images and electrochemical impedance spectra for AS 1020 mild steel immersed in the control and aqueous solutions containing the polymerizable ionic compounds according to some examples of the present disclosure up to 24 h.
  • Figure 11 shows scanning electron microscopy (SEM) images of AS 1020 mild steel after an exposure of 24 h in control solution and aqueous solutions containing the polymerizable ionic compounds according to some examples of the present disclosure.
  • the present disclosure describes the following various non-limiting examples, which relate to investigations undertaken to identify alternative and improved polymeric based corrosion inhibitors including polymerizable ionic compounds.
  • the polymerizable ionic compounds, cured reaction products, compositions, coatings, and coated substrates thereof in the present disclosure can provide corrosion inhibition, and in some aspects, embodiments or examples, additional properties such as antimicrobial properties, formulation processability, or improved barrier protection from water.
  • a coating composition comprising a polymeric ionic compound could provide an effective coating on a substrate with properties including at least one of corrosion inhibition, and in some embodiments and examples antimicrobial resistance.
  • the coating compositions and coatings as described herein have been found suitable for various uses, and in particular use in protecting metal based infrastructure and conduits from corrosion in marine environments and/or oil and gas industry.
  • first, second, etc. are used herein merely as labels, and are not intended to impose ordinal, positional, or hierarchical requirements on the items to which these terms refer. Moreover, reference to a “second” item does not require or preclude the existence of lower-numbered item (e.g., a “first” item) and/or a higher-numbered item (e.g., a “third” item).
  • the phrase “at least one of’, when used with a list of items means different combinations of one or more of the listed items may be used and only one of the items in the list may be needed. The item may be a particular object, thing, or category.
  • “at least one of’ means any combination of items or number of items may be used from the list, but not all of the items in the list may be required.
  • “at least one of item A, item B, and item C” may mean item A; item A and item B; item B; item A, item B, and item C; or item B and item C.
  • “at least one of item A, item B, and item C” may mean, for example and without limitation, two of item A, one of item B, and ten of item C; four of item B and seven of item C; or some other suitable combination.
  • range format is included for convenience and should not be interpreted as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range, unless specifically indicated. For example, description of a range such as from 1 to 5 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 5, from 3 to 5 etc., as well as individual and partial numbers within the recited range, for example, 1, 2, 3, 4, 5, 5.5 and 6, unless where integers are required or implicit from context. This applies regardless of the breadth of the disclosed range. Where specific values are required, these will be indicated in the specification.
  • curable or “cured” is descriptive of a material or composition that has or can be cured (e.g. polymerized or crosslinked) by heating to induce polymerization and/or crosslinking; irradiating with actinic irradiation to induce polymerization and/or crosslinking; and/or by mixing one or more components to induce polymerization and/or crosslinking. "Mixing can be performed, for example, by combining two or more parts and mixing to form a homogeneous composition. Alternatively, two or more parts can be provided as separate layers that intermix (e.g., spontaneously or upon application of shear stress) at the interface to initiate polymerization.
  • substantially free generally refers to the absence of that compound or component in the composition other than any trace amounts or impurities that may be present, for example this may be an amount by weight % in the total composition of less than about 1%, 0.1%, 0.01%, 0.001%, or 0.0001%.
  • the compositions as described herein may also include, for example, impurities in an amount by weight % in the total composition of less than about 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.01%, 0.001%, or 0.0001%.
  • (meth)acrylate refers to acrylate, methacrylate, or combinations thereof.
  • (meth)acrylic refers to acrylic, methacrylic, or combinations thereof.
  • (meth)acryl refers to acryl, methacryl, or combinations thereof.
  • alkyl includes straight-chained, branched, and cyclic alkyl groups and includes both unsubstituted and substituted alkyl groups. Unless otherwise indicated, the alkyl groups typically contain from 1 to 20 carbon atoms. The alkyl groups may for example contain carbon atoms from 1 to 12, 1 to 10, or 1 to 8. The alkyl groups may for example contain carbon atoms from 2 to 12, 2 to 10, or 2 to 8. Examples of “alkyl” as used herein include, but are not limited to, methyl, ethyl, n-propyl.
  • alkyl groups may be mono- or polyvalent.
  • halo or halogen, whether employed alone or in compound words such as haloalkyl, means fluorine, chlorine, bromine or iodine.
  • haloalkyl means an alkyl group having at least one halogen substituent, the terms “alkyl” and “halogen” being understood to have the meanings outlined above.
  • the term “monohaloalkyl” means an alkyl group having a single halogen substituent, the term “dihaloalkyl” means an alkyl group having two halogen substituents and the term “trihaloalkyl” means an alkyl group having three halogen substituents.
  • Examples of monohaloalkyl groups include fluoromethyl, chloromethyl, bromomethyl, fluoromethyl, fluoropropyl and fluorobutyl groups; examples of dihaloalkyl groups include difluoromethyl and difluoroethyl groups; examples of trihaloalkyl groups include trifluoromethyl and trifluoroethyl groups.
  • alkenyl encompasses both straight and branched chain unsaturated hydrocarbon groups with at least one carbon-carbon double bond.
  • alkenyl groups include ethenyl, propenyl, butenyl, pentenyl and hexenyl. Further examples of alkenyl groups include ethenyl, 1 -propenyl, 2-propenyl and but-2-enyl.
  • alkynyl encompasses both straight and branched chain unsaturated hydrocarbon groups with at least one carbon-carbon triple bond.
  • alkynyl groups include ethynyl, propynyl, butynyl, pentynyl and hexynyl. Further examples of alkynyl groups include ethynyl, 1 -propynyl and 2-propynyl.
  • heteroalkyl includes both straight-chained, branched, and cyclic alkyl groups interrupted with one or more heteroatoms (e.g. 1-3) independently selected from S, O, and N.
  • the heteroalkyl may be unsubstituted or substituted. Unless otherwise indicated, the heteroalkyl groups typically contain from 1 to 20 carbon atoms.
  • the heteroalkyl groups may for example contain carbon atoms from 1 to 12, 1 to 10, or 1 to 8.
  • the heteroalkyl groups may for example contain carbon atoms from 2 to 12, 2 to 10, or 2 to 8.
  • heteroalkyl examples include, but are not limited to, methoxy, ethoxy, propoxy, 3,6-dioxaheptyl, 3-(trimethylsilyl)-propyl, 4- dimethylaminobutyl, and the like. Unless otherwise noted, heteroalkyl groups may be mono-, di- or polyvalent.
  • heteroarylalkyl means a group comprising a heteroaryl and alkyl according to the meanings and any examples independently thereof as described herein.
  • heteroalkenyl includes both straight-chained, branched, and cyclic alkenyl groups as described herein with one or more heteroatoms (e.g. 1-3) independently selected from S, O, and N with both unsubstituted and substituted alkenyl groups. Unless otherwise indicated, the heteroalkenyl groups typically contain from 1 to 20 carbon atoms. The heteroalkenyl groups may for example contain carbon atoms from 1 to 12, 1 to 10, or 1 to 8. Unless otherwise noted, heteroalkenyl groups may be mono- or polyvalent.
  • the terms “carbocyclic” and “carbocyclyl” represent a ring system wherein the ring atoms are all carbon atoms, e.g., from 3 to 20 carbon ring atoms, and which may be aromatic, non-aromatic, saturated, or unsaturated.
  • the terms encompass single ring systems, e.g. cycloalkyl groups such as cyclopentyl and cyclohexyl, aromatic groups such as phenyl, and cycloalkenyl groups such as cyclohexenyl, as well as fused- ring systems such as naphthyl and fluorenyl.
  • heterocyclic and “heterocyclyl” represent an aromatic or a non-aromatic cyclic group of carbon atoms wherein from one to three of the carbon atoms is/are replaced by one or more heteroatoms independently selected from nitrogen, oxygen or sulfur.
  • a heterocyclyl group may, for example, be monocyclic or polycyclic, and contain for example from 3 to 20 ring atoms. In a bicyclic heterocyclyl group there may be one or more heteroatoms in each ring, or only in one of the rings. Examples of heterocyclyl groups include piperidinyl, tetrahydrofuranyl, tetrahydropyranyl, pyridyl, pyrimidinyl and indolyl.
  • cycloalkyl represents a ring system wherein the ring atoms are all carbon atoms, e.g., from 3 to 20 carbon ring atoms, and which is saturated.
  • a cycloalkyl group can be monocyclic or polycyclic.
  • a bicyclic group may, for example, be fused or bridged.
  • monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl and cyclopentyl.
  • Other examples of monocyclic cycloalkyl groups are cyclohexyl, cycloheptyl and cyclooctyl.
  • bicyclic cycloalkyl groups include bicyclo[2.2. l]hept-2-yl.
  • an “aromatic” group means a cyclic group having 4m+2 p electrons, where m is an integer equal to or greater than E
  • aromatic is used interchangeably with “aryl” to refer to an aromatic group, regardless of the valency of aromatic group.
  • aromatic carbocyclyl or “aromatic carbocycle” represent a ring system which is aromatic and in which the ring atoms are all carbon atoms, e.g. having from 6-14 ring atoms.
  • An aromatic carbocyclyl group may be monocyclic or polycyclic. Examples of aromatic carbocyclyl groups include phenyl, naphthyl and fluorenyl. Polycyclic aromatic carbocyclyl groups include those in which only one of the rings is aromatic, such as for example indanyl.
  • aryl or “aromatic” group or moiety includes 6-18 ring atoms and can contain optional fused rings, which may be saturated or unsaturated.
  • aromatic groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl.
  • the aromatic group may optionally contain 1-3 heteroatoms such as nitrogen, oxygen, or sulfur and can contain fused rings.
  • aromatic group having heteroatoms include pyridyl, furanyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl, and benzthiazolyl.
  • the aromatic group may be mono- or polyvalent.
  • the “aromatic” group may be a monocyclic aromatic group, for example a benzene group that may be unsubstituted or substituted.
  • arylalkyl means a group comprising an aryl and an alkyl according to the meanings and any examples independently thereof as described herein.
  • aromatic heterocycle or “aromatic heterocyclyl” represent an aromatic cyclic group of carbon atoms wherein from one to three of the carbon atoms is/are replaced by one or more heteroatoms independently selected from nitrogen, oxygen or sulphur, e.g. having from 5-14 ring atoms.
  • aromatic heterocyclyl is used interchangeably with ‘heteroaryl”.
  • An aromatic heterocyclyl group may be monocyclic or polycyclic. Examples of monocyclic aromatic heterocyclyl groups (also referred to as monocyclic heteroaryl groups) include furanyl, thienyl, pyrrolyl, imidazolyl, pyridyl and pyrimidinyl.
  • polycyclic aromatic heterocyclyl groups include benzimidazolyl, quinolinyl and indolyl.
  • Polycyclic aromatic heterocyclyl groups include those in which only one of the rings is an aromatic heterocycle.
  • cyano represents a -CN moiety
  • hydroxyl represents a -OH moiety
  • alkoxy represents an -O-alkyl group in which the alkyl group is as defined supra. Examples include methoxy, ethoxy, n-propoxy, iso-propoxy, and the different butoxy, pentoxy, hexyloxy and higher isomers.
  • aryloxy represents an -O-aryl group in which the aryl group is as defined supra. Examples include, without limitation, phenoxy and naphthoxy.
  • carboxyl represents a -CO2H moiety.
  • nitro represents a -NO2 moiety
  • fused means that a group is either fused to another ring system or unfused, and “fused” refers to one or more rings that share at least two common ring atoms with one or more other rings. Fusing may be provided by one or more carbocyclic or heterocyclic rings, as defined herein, or be provided by substituents of rings being joined together to form a further ring system.
  • the fused ring may be a 5, 6 or 7-membered ring of between 5 and 10 ring atoms in size.
  • the fused ring may be fused to one or more other rings, and may for example contain 1 to 4 rings.
  • substituted means that a functional group is either substituted or unsubstituted, at any available position.
  • substituted as referred to above or herein may include, but is not limited to, groups or moieties such as halogen, hydroxyl, alkyl, or haloalkyl.
  • the present disclosure provides various polymerizable ionic compounds (PIC) comprising onium cation groups and aromatic carboxylate counter-anion groups.
  • the onium cation groups and aromatic carboxylate counter-anion groups can coordinate to form a polymerizable ionic compound (PIC) or a cured reaction product thereof.
  • PIC polymerizable ionic compound
  • the cured reaction product is also referred to herein as a polymerized ionic compound (PZIC).
  • PZIC polymerized ionic compound
  • the onium cation groups and aromatic carboxylate counter-anion groups can coordinate in the cured polymer PZIC.
  • at least one polymerizable group is provided on a group selected from the onium cation groups and aromatic carboxylate counter-anion groups.
  • the polymerizable ionic compound (PIC) is a polymerizable ionic liquid (PIL).
  • PIC polymerizable ionic liquid
  • PZIC polymerized ionic liquid
  • the cured reaction product or PZIC can comprise a polymer chain containing a plurality of the onium cation groups covalently linked within and/or along the polymer chain, and wherein the aromatic carboxylate counter-anion groups provide counter-ions for the onium cation groups.
  • the cured reaction product or PZIC can comprise a polymer chain containing a plurality of the aromatic carboxylate counter-anion groups covalently linked within and/or along the polymer chain, and wherein the onium cation groups provide counter-ions for the aromatic carboxylate counter-anion groups.
  • the cured reaction product or PZIC can comprise a first polymer chain containing a plurality of the onium cation groups covalently linked within and/or along the first polymer chain, and a second polymer chain containing a plurality of the aromatic carboxylate counter-anion groups covalently linked within and/or along the second polymer chain, and wherein the aromatic carboxylate counter-anion groups provide counter-ions for the onium cation groups.
  • the cured reaction product or PZIC can comprise a polymer chain containing a plurality of the onium cation groups covalently linked as individual pendant groups along the polymer chain, and wherein the aromatic carboxylate counter-anion groups provide counter-ions for the onium cation groups.
  • the cured reaction product or PZIC can comprise a polymer chain containing a plurality of the aromatic carboxylate counter-anion groups covalently linked as individual pendant groups along the polymer chain, and wherein the onium cation groups provide counter-ions for the aromatic carboxylate counter-anion groups.
  • the cured reaction product or PZIL can comprise a first polymer chain containing a plurality of the onium cation groups covalently linked as individual pendant groups along the first polymer chain, and a second polymer chain containing a plurality of the aromatic carboxylate counter-anion groups covalently linked as individual pendant groups along the second polymer chain, and wherein the onium cation groups provide counter-ions for the aromatic carboxylate counter-anion groups.
  • the optionally polymerizable onium cations may be optionally polymerizable quaternary onium cations.
  • the optionally polymerizable onium cations may be selected from ammonium cation groups, pyridinium cation groups, imidazolium cation groups, pyrazolium cation groups, pyrrolidinium cation groups, and phosphonium cation groups.
  • the onium cations do not contain a polymerizable group, such as in some examples when a polymerizable group is provided on an aromatic carboxylate counter-anion group.
  • the onium cations may be quaternary onium nitrogen cations, for example cations selected from ammonium cation groups, pyridinium cation groups, imidazolium cation groups, pyrazolium cation groups, and pyrrolidinium cation groups.
  • the onium cations are polymerizable.
  • an onium compound may comprise one or more polymerizable groups according to any embodiments or examples as described herein.
  • the onium cations may be selected from any of the onium cations of Formula 2a, 2b, 2c, or 2d:
  • R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, and a polymerizable group, and wherein the alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, are optionally substituted with one or more hydroxyl groups.
  • the onium cations of Formula 2a, 2b, 2c, or 2d are quaternary onium cations.
  • R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 may be each independently selected from alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, and a polymerizable group.
  • the groups R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, and a polymerizable group.
  • R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from hydrogen, alkyl, and heteroalkyl, and a polymerizable group.
  • at least one of R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is a polymerizable group.
  • one of R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 is a polymerizable group.
  • the groups R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl.
  • the groups R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl.
  • R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from hydrogen, alkyl, and heteroalkyl.
  • the onium cations are selected from onium nitrogen cations of Formula 2a:
  • A is a polymerizable group selected from an optionally linked epoxy, acrylamide, acrylate, and vinyl group;
  • R 6 , R 7 , and R 8 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl, wherein two or more groups may join together to provide an aromatic or aliphatic ring, and wherein the alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl, are optionally substituted with one or more hydroxyl groups.
  • A may be an aryl comprising a polymerizable group.
  • the groups R 6 , R 7 , and R 8 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, and aryl.
  • R 6 , R 7 , and R 8 are each independently selected from hydrogen, alkyl, heteroalkyl, and aryl.
  • R 6 , R 7 , and R 8 are each independently selected from hydrogen and alkyl.
  • R 6 and R 7 are each independently selected from hydrogen and alkyl, and R 8 is an optionally substituted aryl.
  • the onium cation of Formula 2a is cetrimonium.
  • the onium cations are selected from onium nitrogen cations of Formula 2b:
  • R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, and a polymerizable group, and wherein the alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, are optionally substituted with one or more hydroxyl groups.
  • the groups R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from hydrogen, alkyl, heteroalkyl, and a polymerizable group. In some examples of any of the onium cations of Formula 2b, the groups R 6 , R 7 , R 8 , R 9 , and R 10 , are each independently selected from hydrogen, alkyl, and a polymerizable group. In some examples of any of the onium cations of Formula 2b, the groups R 6 , R 7 , R 9 , and R 10 , are each selected from hydrogen and alkyl, and R 8 is a polymerizable group.
  • the groups R 6 , R 7 , R 8 , R 9 , and R 10 are each independently selected from hydrogen and alkyl.
  • the alkyl and heteroalkyl groups may be optionally substituted with hydroxyl.
  • the onium cations are selected from quaternary onium nitrogen cations of Formula 2c:
  • R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, and a polymerizable group, and wherein the alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, are optionally substituted with one or more hydroxyl groups.
  • the groups R 6 , R 7 , R 8 , R 9 , and R 10 , and R 11 are each independently selected from hydrogen, alkyl, heteroalkyl, and a polymerizable group. In some examples of any of the onium cations of Formula 2c, the groups R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 , are each independently selected from hydrogen, alkyl, and a polymerizable group.
  • the groups R 6 , R 7 , R 8 , R 9 , and R 10 are each selected from hydrogen and alkyl, and R 11 is a polymerizable group. In some examples of any of the onium cations of Formula 2c, the groups R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 , are each independently selected from hydrogen and alkyl. The alkyl and heteroalkyl groups may be optionally substituted with hydroxyl.
  • the onium cations are selected from quaternary onium nitrogen cations of Formula 2d:
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, and a polymerizable group, and wherein the alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, are optionally substituted with one or more hydroxyl groups.
  • the groups R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen, alkyl, heteroalkyl, and a polymerizable group. In some examples of any of the onium cations of Formula 2d, the groups R 6 , R 7 , R 8 , and R 9 , are each independently selected from hydrogen, alkyl, and a polymerizable group. In some examples of any of the onium cations of Formula 2d, the groups R 6 , R 7 , and R 9 , are each selected from hydrogen and alkyl, and R 8 is a polymerizable group.
  • the groups R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen and alkyl.
  • the alkyl and heteroalkyl groups may be optionally substituted with hydroxyl.
  • a polymerizable group (Pz) may be provided on the onium cation groups and/or aromatic carboxylate counter-anion groups.
  • a reference to “optionally polymerizable” refers to a cation and/or anion group that may or may not have a polymerizable group as a substituent thereon according to any embodiments or examples as described herein.
  • One or more polymerizable groups may be provided on the same group, which may for example have two separate substituents selected from a polymerizable group.
  • the onium cation groups comprise a polymerizable group
  • the aromatic carboxylate counter-anion groups do not comprise a polymerizable group.
  • the aromatic carboxylate counter-anion groups comprise a polymerizable group, and the onium cation groups do not comprise a polymerizable group.
  • the polymerizable groups (Pz) may be selected from an epoxy, acrylamide, acrylate, and vinyl.
  • the polymerizable groups may be an unsaturated ethylene group, for example a group comprising a terminal vinyl group (e.g. styrene).
  • Pz is a methacrylate group.
  • the polymerizable group (Pz) may be linked to the cation or anion groups by a divalent linking group (Lz), which for example may be depicted as -Lz-Pz.
  • the linking groups (Lz) may comprise a group selected from an ester, amide, urea, urethane, ether, carbonate, alkyl, heteroalkyl, aryl, alkylaryl, and heteroaryl.
  • the linking groups may be selected from alkyl and heteroalkyl groups, which may be optionally interrupted by a group selected from an ester, amide, urea, urethane, ether, and carbonate.
  • the aromatic carboxylate group provides a counter anion in the PIC to the cation groups.
  • the aromatic carboxylate group may be an optionally linked, optionally substituted, monocylic or polycyclic aromatic (Ar) group.
  • the counter- anion group may be provided by its respective conjugate acid, which in-situ may form the carboxylate anion.
  • aromatic (Ar) group for example benzene, may be further optionally substituted at one or more of its ring atoms, such as meta, ortho and/or para substituted with respect to the carboxylate substituent.
  • an optional substituent of the aromatic group may be a polymerizable group.
  • the aromatic carboxylate group is a group of Formula 1:
  • X is an optionally linked carboxylate group.
  • X may be defined as -Lx-X wherein Lx is an optional linking group and X is the carboxylate anion moiety.
  • the aromatic carboxylate groups may be of Formula la:
  • X is a carboxylate group.
  • Lx is an optional divalent linking group, which may be selected from alkyl, alkenyl, heteroalkyl, and heteroalkenyl.
  • R 1 and R 5 are hydrogen, and R 2 , R 3 , and R 4 , are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, O-alkyl, O-alkenyl, O- heteroalkyl, and O-heteroalkenyl.
  • R 1 and R 5 are hydrogen, and at least one of R 2 , R 3 , and R 4 , is selected from O-alkyl, O- alkenyl, O-heteroalkyl, and O-heteroalkenyl.
  • R 1 to R 5 may each be independently selected from hydrogen, O-alkyl and O-heteroalkyl, wherein at least one of R 2 , R 3 , and R 4 , is selected from O-alkyl and O-heteroalkyl.
  • R 1 , R 2 , R 4 , and R 5 can be hydrogen and R 3 can be selected from O-alkyl and O-heteroalkyl.
  • R 1 and R 5 are hydrogen, and R 2 , R 3 , and R 4 , are each independently selected from hydrogen and O-C 1-12 alkyl, wherein at least one of R 2 , R 3 , and R 4 , is O-C 1-12 alkyl.
  • R 1 and R 5 are hydrogen, and R 2 , R 3 , and R 4 , are each independently selected from hydrogen and O-C 2-12 alkyl, wherein at least one of R 2 , R 3 , and R 4 , is selected from O-C 2-12 alkyl.
  • R 1 and R 5 are hydrogen, and R 2 , R 3 , and R 4 , are each independently selected from hydrogen and O-C 2-8 alkyl, wherein at least one of R 2 , R 3 , and R 4 , is selected from O-C 2-8 alkyl.
  • R 1 and R 5 are hydrogen, and R 2 , R 3 , and R 4 , are each independently selected from hydrogen and O-C3-6alkyl, wherein at least one of R 2 , R 3 , and R 4 , is selected from O-C3-6alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 1-12 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 2-12 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 3-6 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are each independently selected from hydrogen and alkyl, and R 3 is a polymerizable group.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is a polymerizable group.
  • X is a carboxylic acid or carboxylate group
  • Lx is an optional divalent linking group selected from alkyl, alkenyl, heteroalkyl, and heteroalkenyl;
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, halo, hydroxyl, C 1-12 alkyl, C 1-12 alkenyl, C 1-12 heteroalkyl, C 1-12 heteroalkenyl, O-C 1-12 alkyl, O- C 1-12 alkenyl, O-C 1-12 heteroalkyl, O-C 1-12 heteroalkenyl, and a polymerizable group.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, halo, hydroxyl, C 1-12 alkyl, C 1-12 alkenyl, C 1-12 heteroalkyl, C 1-12 heteroalkenyl, O-C 1-12 alkyl, O- C 1-12 alkenyl, O-C 1-12 heteroalkyl, O-C 1-12 heteroalkenyl, and a polymerizable group.
  • R 3 is O-C 1-12 alkyl, O-C 1-12 alkyl, or O-C 3-8 alkyl.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, halo, hydroxyl, C 1-12 alkyl, C 1-12 alkenyl, C 1-12 heteroalkyl, C 1-12 heteroalkenyl, O-C 1-12 alkyl, O-C 1-12 alkenyl, O-C 1-12 heteroalkyl, and O-C 1-12 heteroalkenyl.
  • R 1 and R 5 are hydrogen, and at least one of R 2 , R 3 , and R 4 , is selected from O-C 1-12 alkyl.
  • R 1 and R 5 are hydrogen, and at least one of R 2 , R 3 , and R 4 , is selected from O-C 2-12 alkyl.
  • R 1 and R 5 are hydrogen, and at least one of R 2 , R 3 , and R 4 , is selected from O-C 2-8 alkyl.
  • R 1 and R 5 are hydrogen, and at least one of R 2 , R 3 , and R 4 , is selected from O-C3-6alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 1-12 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 2-12 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 3-6 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are each independently selected from hydrogen and alkyl, and R 3 is a polymerizable group.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is a polymerizable group.
  • X is a carboxylate group
  • Lx is an optional linking group selected from alkyl, alkenyl, heteroalkyl, and heteroalkenyl;
  • Y is a cation
  • R 4 and R 8 are hydrogen
  • R 5 , R 6 , and R 7 are each independently selected from hydrogen, C 1-12 alkyl, C 1- 12 heteroalkyl, O-C 1-12 alkyl, O-C 1-12 heteroalkyl, and a polymerizable group.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, halo, hydroxyl, C 1-12 alkyl, C 1-12 alkenyl, C 1-12 heteroalkyl, C 1-12 heteroalkenyl, O-C 1-12 alkyl, O- C 1-12 alkenyl, O-C 1-12 heteroalkyl, O-C 1-12 heteroalkenyl, and a polymerizable group.
  • Y is an onium cation. In another example, Y may be selected from any of the onium cations as described herein.
  • a polymerizable ionic compound (PIC) or reaction product thereof may comprise or consist of optionally polymerizable onium cations and an optionally polymerizable aromatic carboxylate of Formula 1:
  • X is a carboxylate anion group
  • R 1 and R 5 are hydrogen
  • the polymerizable onium cations for the PIC may be selected from ammonium cation groups, pyridinium cation groups, imidazolium cation groups, pyrazolium cation groups, and pyrrolidinium cation groups.
  • the polymerizable onium cations for the PIC may be selected from polymerizable quaternary onium cations.
  • the polymerizable onium cations for the PIC may be selected from polymerizable quaternary ammonium cations.
  • the polymerizable ammonium cation groups for the PIC may be of Formula 2a(i). wherein
  • A is an optionally linked polymerizable group
  • R 6 , R 7 , and R 8 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl, wherein each alkyl, alkenyl, heteroalkyl, and heteroalkenyl is optionally substituted, e.g. with halo or hydroxyl groups.
  • the polymerizable ammonium cation groups for the PIC may be of Formula 2a(ii) wherein are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl, each of which may be optionally substituted, for example with one or more hydroxyl groups;
  • R 9a is hydrogen or methyl; and n is an integer of 1 to 6, for example an integer of 1 to 3.
  • An organic corrosion inhibitor or ionic compound may be provided according to any combination of “Onium Cation Groups” with “Aromatic Carboxylate Groups” as described individually above for each of those groups.
  • a corrosion inhibitor may be provided by an ionic compound or cured reaction product thereof formed by an optionally polymerizable aromatic carboxylate counter-anion of Formula 1 and an optionally polymerizable onium cation of Formula 2a as described herein:
  • a coating comprising a cured reaction product of a polymerizable ionic compound (PIC) comprising an aromatic carboxylate compound of Formula 1 and a polymerizable ammonium compound of Formula 2a(i):
  • PIC polymerizable ionic compound
  • X may be an optionally linked carboxylate anion group
  • A may be an optionally linked polymerizable group
  • R 6 , R 7 , and R 8 may each be independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl.
  • the onium group is a polymerizable ammonium group
  • the quaternary onium cation groups in the cured reaction product the quaternary onium c
  • Formula 3 L 2 may be an optional divalent linking group to the polymer chain.
  • the divalent linking group may be selected from alkyl, alkenyl, heteroalkyl, and heteroalkenyl, for example.
  • R 6 , R 7 , and R 8 may each be independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl.
  • the onium cation is a substituted ammonium cation.
  • the substituted ammonium cation may be provided with a free radically polymerizable group, such as a methacrylate group.
  • polymerizable quaternary onium cations there is provided polymerizable quaternary onium cations.
  • the polymerizable quaternary onium cations may be selected from ammonium cation groups, imidazolium cation groups, anilinium cation groups, and pyridinium cation groups.
  • the link between the ammonium cation and the methacrylate group may have an ester linkage.
  • A is a polymerizable group
  • R 6 , R 7 , and R 8 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl.
  • the anion may be absent of a free radically polymerizable group.
  • Z is a carboxylate anion group
  • L 1 is an alkenyl divalent linking group.
  • R 1 , R 2 , R 4 and R 5 are hydrogen; and R 3 may be selected from a hydroxyl or O-alkyl groups, such as butyloxy or hexyloxy groups.
  • free-radically polymerizable monomers of the onium cation with non-polymerizable aromatic carboxylic anion groups include:
  • the onium cation such as a substituted ammonium cation
  • the ammonium cations may comprise hydrogen and alkyl substituents (e.g. R 9 , R 7 , R 6 and R 8 ), for example C1-8alkyl substituents, which may be optionally substituted.
  • the aromatic carboxylic group comprises a polymerizable group.
  • X is a carboxylate anion group
  • L x is an alkenyl divalent linking group
  • R 1 , R 2 , R 4 and R 5 are each hydrogen
  • R 3 comprises a polymerizable group, such as a methacrylate group optionally linked by an ester or alkyl group.
  • polyionic corrosion inhibitor comprising a non- polymerizable onium cation (i.e. absent of a polymerizable group) and a polymerizable aromatic carboxylate group (i.e. comprising a polymerizable group) is provided below:
  • the polymerizable ionic compound may be a polymerizable ionic liquid (PIL).
  • a composition may comprise or consist of at least one corrosion inhibitor selected from a polyionic corrosion inhibitor and polymerizable ionic compound (PIC) according to any embodiments or examples thereof as described herein, and optionally one or more additives.
  • PIC polymerizable ionic compound
  • a curable coating composition may further comprise or consist of an organic film former, and optionally one or more additives.
  • the organic film former can comprise or consist of a polymerizable ionic compound (PIC) or a cured reaction product thereof according to any aspects, embodiments or examples thereof as described herein.
  • PIC polymerizable ionic compound
  • the curable coating composition may be a liquid formulation comprising or consisting of an organic film former, and optionally one or more additives.
  • the curable coating composition comprises or consists of an organic film former, one or more solvents, and optionally one or more additives, and wherein the organic film former comprises or consists of a polymerizable ionic compound (PIC) or a cured reaction product thereof according to any aspects, embodiments or examples thereof as described herein.
  • PIC polymerizable ionic compound
  • the organic film former and optional additives may also be provided according any of the embodiments or examples as described below.
  • the “organic film former” comprises or consists of a polymerizable ionic compound (PIC) or a cured reaction product thereof according to any aspects, embodiments or examples thereof as described herein, and optionally one or more polymeric constituents.
  • PIC polymerizable ionic compound
  • the organic film former may comprise or consist of a polymerizable onium cation group or compound, and a non-polymerizable aromatic carboxylate counter anion group or compound, each being selected according to any embodiments or examples thereof as described herein, and optionally one or more polymeric constituents.
  • the organic film former may comprise or consist of a polymerizable aromatic carboxylate counter anion group or compound, and a non-polymerizable onium cation group or compound, each being selected according to any embodiments or examples thereof as described herein, and optionally one or more polymeric constituents.
  • the “organic film former” may comprise or further consist of any other polymeric constituents that could be provided in the composition or coating thereof.
  • Any additional polymeric constituents may consist of any polymers (e.g. co-polymers) or polymerizable components, such as reactive monomers (e.g. resins) that can form polymers in the coatings.
  • the polymeric constituents may consist of polymers, co-polymers, resins, monomers and co-monomers.
  • Some examples of polymeric constituents include any one or more of polyolefins, polyurethanes, polyacrylic acids, polyacrylates, polyethers, polyesters, polyketides, polyamides, or any co-polymers thereof.
  • the organic film former does not itself cover any additive as described below (e.g. inorganic filler, or wetting agent etc.).
  • any monomers, co-monomers, resins, co-polymers, and polymers are present in the composition, formulation or coating thereof, then it is understood those prospective constituents are encompassed by the term “organic film former”.
  • the organic film former “consists of’ one or more specified constituents, then it will be appreciated that the absence of a prospective polymeric constituent being explicitly specified in the organic film former means the absence of that polymeric constituent from the composition, formulation or coating thereof. In other words, when the term “consists of’ is used so only those polymeric constituents specified to consist in the organic film former are present in the composition, formulation or coating thereof.
  • the organic film former (in wt % of the total composition or coating) may comprise between about 40 and 99, 50 and 95, or 60 and 90.
  • the organic film former (in wt % of the total composition or coating) may comprise at least 30, 35, 40, 45, 50, 60, 65, 70, 75, 80, 85, 90, 95, or 98.
  • the organic film former (in wt % of the total composition or coating) may comprise less than about 99, 98, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, or 35.
  • the organic film former (in wt % of the total composition or coating) may be in a range provided by any two of these upper and/or lower values.
  • the PIC in wt % of the total composition or coating may comprise between about 1 and 50, 5 and 45, or 10 and 30.
  • the PIC in wt % of the total composition or coating may comprise at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50.
  • the PIC in wt % of the total composition or coating may comprise less than about 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5.
  • the PIC (in wt % of the organic film former) may be in a range provided by any two of these upper and/or lower values.
  • the PIC in wt % of the organic film former may comprise between about 1 and 50, 5 and 45, or 10 and 30.
  • the PIC in wt % of the organic film former may comprise at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50.
  • the PIC in wt % of the organic film former may comprise less than about 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5.
  • the PIC in wt % of the organic film former may be in a range provided by any two of these upper and/or lower values.
  • the polymerizable ionic compound may be a polymerizable ionic liquid (PIL).
  • the coating or coating composition further comprises or further consists of one or more optional additive(s).
  • the additive(s) are usually present in an amount of less than about 15% based on the weight of the composition.
  • the additive(s) are usually present in an amount of less than about 15% based on the weight of the composition or the organic film former.
  • the amount of all additives combined may be provided in an amount of less than about 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, or 0.05%.
  • the additives may be provided in an amount of greater than about 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%.
  • the amount of all additive(s), if present, may be provided in an amount (based on the total weight of composition) of a range between any two of the above values, for example between about 0.01% and 10%, between about 0.05% and 5 %, between about 0.1% and about 3%, or between about 0.5% and 2%.
  • any reference to “substantially free” generally refers to the absence of a compound in the composition other than any trace amounts or impurities that may be present, for example this may be an amount by weight % in the total composition of less than about 1%, 0.1%, 0.01%, 0.001%, or 0.0001%.
  • the compositions as described herein may also include, for example, impurities in an amount by weight % in the total composition of less than about 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.01%, 0.001%, or 0.0001%.
  • the present coating compositions are configured to provide a minimum film forming temperature (MFT) for ambient conditions.
  • MFT minimum film forming temperature
  • the MFT of various coating compositions may be provided at about 0 to 40 °C, 5 to 35 °C, 10 to 30 °C, 15 to 25 °C, or about 20 °C.
  • additives are optional and may be added to further enhance application of the coating compositions and/or further enhance performance characteristics of the completed coating system (e.g. composition, substrate, or coating).
  • suitable additives may include any one or more of the following: i. polymerisation initiators; ii. adhesion promoters; iii. solvents; iv. organic cross-linkers; v. inorganic fillers; vi. wetting agents; vii. rheology modifiers; viii. surfactants; ix. dispersants; x. anti-foaming agents; xi. anti-corrosion reagents; xii. stabilizers; xiii. levelling agents; xiv. pigments; and xv. colorants.
  • composition may be a formulation, such as a liquid formulation, for which the following examples and embodiments may apply.
  • the coating composition can be provided as a coating formulation for commercial and industrial application.
  • a coating formulation can be prepared by dissolving or dispersing the coating compositions, in an appropriate solvent and then mixing them together optionally with one or more additives or dissolving the compositions into a suitable solvent under suitable processing conditions.
  • the coating formulation can be prepared from a multi-part composition which can be pre dissolved in suitable solvents, and which can then be pre-mixed together prior to application of the coating composition to the coated substrate.
  • the coating composition can be formulated into a one-part stable dispersion, which for example would not require premixing before application.
  • the composition as described herein may be a liquid formulation, such as liquid suspension formulation or liquid dispersion formulation.
  • the coating composition may be applied in different physical forms such as a solution, dispersion, suspension, mixture, aerosol, emulsion, paste or combination thereof, solutions or dispersions or emulsions are preferred.
  • a polymerisation initiator may be used.
  • initiator or “polymerisation initiator” refers to a chemical compound that reacts with a monomer to form an intermediate compound which capable of linking successively with a large number of other monomers into a polymeric compound.
  • the terms “initiator” and “polymerisation initiator” may be used interchangeably within the context of this application. Examples of polymerisation initiators include photoinitiators and thermal initiators.
  • polymerisation initiators examples include:
  • the polymerisation initiator may be a photoinitiator.
  • the polymerisation initiator may be a thermal initiator.
  • a free radical initiator may be used, wherein free radicals are generated by chemical and/or radiation means.
  • Several types of compounds can initiate polymerisation reactions by decomposing to form free radicals. These compounds include: azo-containing compounds, carboxylic peroxyacids and peroxyesters, alkyl hydroperoxides, and dialkyl and diacyl peroxides, among others. Examples of initiators have been described (Reference: W. D. Cook, G. B. Guise, eds.
  • an initiator is selected from a peroxide or an aliphatic azo compound.
  • the polymerisation initiator may be provided in the composition in an amount (based on wt % of composition) of at least about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the polymerisation initiator is provided in the composition in an amount (based on wt % of composition) of about 0.1 to 10, 0.5 to 6, 1 to 5, or 2 to 4.
  • adhesion promoters may be used.
  • an acid based adhesion promotor for example siloxanes.
  • Other examples of adhesion promoters include silanes, such as R-(CH2)n-Si-(OH)m.
  • the adhesion promoter may be provided in the composition in an amount (based on wt % of composition) of at least about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the adhesion promoter is provided in the composition in an amount (based on wt % of composition) of about 0.1 to 10, 0.5 to 6, 1 to 5, or 2 to 4.
  • the PIC and one or more optional additive may be dissolved or otherwise dispersed in a solvent to obtain the coating composition.
  • the solvent may be a single solvent or a mixture of solvents.
  • Useful solvents include water and/or an organic solvent.
  • Organic solvents can be selected from but not limited to solvents containing groups selected from ketones such as methyl propyl ketone and methyl ethyl ketone; alcohols such an ethanol, isopropanol, tert-butyl alcohol, benzyl alcohol and tetrahydrofurfuryl alcohol; ethers such as glycol ethers, for example di(propylene glycol)dimethyl ether; and/or esters.
  • Organic solvents such as ethylene glycol ethers or propylene glycol ether can be added to assist in reducing the surface tension and improving the wetting and film forming.
  • Dow glycol ethers including CellosolveTM family solvents (such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether), CarbitolTM family solvents (diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether or diethylene glycol monohexyl ether), EcosoftTM and DowanolTM such as propylene glycol propyl ether (PnP), propylene glycol butyl ether (PnB), dipropylene glycol propyl ether (DPnP)dipropylene glycol methyl ether (DPM).
  • Dow glycol ethers including CellosolveTM family solvents (such as ethylene glycol monopropyl ether, ethylene
  • the solvent may be provided in the composition in an amount (based on wt % of composition) of at least about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or 99. In an embodiment, the solvent is provided in the composition in an amount (based on wt % of composition) of about 50 to 99, 80, to 98, 85 to 97, or 90 to 95.
  • the coating and composition as described herein may also include an organic crosslinker.
  • the organic crosslinker may be incorporated into the coating composition prior to application on a coated substrate.
  • Suitable crosslinkers are organic compounds or oligomers comprising of at least two groups capable of reacting with the acid functionalities of the organic polymer. Examples of organic crosslinkers include, but are not limited to aziridine, carbodiimide, epoxy, isocyanate and anhydride.
  • the coating composition comprises between 1 and 15 wt % crosslinker (based on the weight of the PIC, polymer or organic film former component).
  • the coatings and compositions described herein may comprise an optional inorganic filler.
  • the inorganic filler is selected from but not limited to silica, alumina oxide, titania oxide, clays such as Montmorillonite, laponite and layered double hydroxide.
  • the particle size of an inorganic filler varies from micro meter to sub micro meter, and in one embodiment can be from 0.5 to 500 nanometre or from 1 to 100 nm. In one example the particle size is from 1 to 50 nm.
  • Surface finish can be important for the successful application of decorative coatings, and surface wetting agents can provide further advantages to the coatings or coating compositions. Addition of a wetting agent can also be useful in industrial application for improved control of drying time and obtaining a broader operation window.
  • the coating or coating composition as described herein may further include a wetting agent.
  • the wetting agent may be incorporated into the coating composition prior to application on a coated substrate.
  • Suitable wetting agents include, but are not limited to, ethers including glycol ethers (e.g. propylene glycol methyl ether (Dowanol PM) or propylene glycol propyl ether (Dowanol PnP), diprolylene glycol propyl ether (DPnP), propylene glycol butyl ether (PnB), dipropylene glycol butyl ether (DPnB), propylene glycol phenyl ether (PPh)).
  • glycol ethers e.g. propylene glycol methyl ether (Dowanol PM) or propylene glycol propyl ether (Dowanol PnP
  • Dprolylene glycol propyl ether Dprolylene glycol propyl ether
  • PnB propylene glycol butyl
  • Rheology modifiers may include hydroxypropyl methyl cellulose (e.g. Methocell 311), modified urea (e.g. Byk 411, 410), cellulose acetate butyrates (e.g. EastmanTM CAB-551-0.01, CAB-381-0.5, CAB-381-20), and polyhydroxycarboxylic acid amides (e.g. Byk 405).
  • Methocell 311 hydroxypropyl methyl cellulose
  • modified urea e.g. Byk 411, 410
  • cellulose acetate butyrates e.g. EastmanTM CAB-551-0.01, CAB-381-0.5, CAB-381-20
  • polyhydroxycarboxylic acid amides e.g. Byk 405
  • Surfactants may include fatty acid derivatives (e.g. AkzoNobel, Bermadol SPS 2543), quaternary ammonium salts, ionic and non-ionic surfactants.
  • Dispersants may include non-ionic surfactants based on primary alcohols (e.g. Merpol 4481, DuPont) and alkylphenol-formaldehyde-bisulfide condensates (e.g. Clariants 1494).
  • non-ionic surfactants based on primary alcohols (e.g. Merpol 4481, DuPont) and alkylphenol-formaldehyde-bisulfide condensates (e.g. Clariants 1494).
  • Anti-foaming agents may include BKY®-014, BKY®-1640.
  • additional anti-corrosion agents include metal salts including rare earth metals, such as salts of zinc, molybate, and barium (e.g. phosphates, chromates, molybdates, or metaborate of the rare earth metals).
  • Anti-corrosion reagents may include phosphate esters (e.g. ADD APT, Anticor C6), alkylammonium salt of (2- benzothiazolythio), succinic acid (e.g. BASF, Irgacor 153), triazine dithiols, and thiadiazoles.
  • Stabilizers may include various biocides.
  • Levelling agents such as fluorocarbon-modified polymers (e.g. EFKA 3777). Colorants and pigments
  • Colorants may be dyes or pigments and include organic and inorganic dyes such as fluorescents (Royale Pigments and Chemicals LLC) (e.g. to enhance visibility of the reactivation treatment and where it has been applied), fluorescein, and phthalocyanines.
  • Pigments may include organic phthalocyanine, quinaridone, diketopyrrolopyrrole (DPP), and diarylide derivatives and inorganic oxide pigments (for example to enhance visibility and where it has been applied).
  • DPP diketopyrrolopyrrole
  • the addition of small amount of colorants may change the colours of the coating distinguishing from the original substrate and is an useful tool servicing for quality control purpose.
  • the colorant may be a dye.
  • Dyes may be organic, soluble in the surrounding medium, and black or chromatic substances.
  • the optional additives may for example be selected from those as described in the book "Coating Additives” by Johan Bielemann, Wiley-VCH, Weinheim, New York, 1998.
  • the dyes may include organic and inorganic dyes.
  • the dyes may be organic dyes, such as azo dyes (e.g. monoazo such as arylamide yellow PY73, diazo such as diarylide yellows, azo condensation compounds, azo salts such as barium red, azo metal complexes such as nickel azo yellow PG10, benzimidazone).
  • the dyes may be fluorescents (e.g.
  • the colorant may be a UV fluorescent dye.
  • the colorants such as fluorescent dyes could for example be used with UV goggles to look for fluorescence after spraying to insure coverage. It will be appreciated that dyes may be organic soluble for improved compatibility or miscibility with the solvents. Peak absorption may be below about 295 nm, for example, which is the natural cut-on for sunlight.
  • Further examples of fluorescent dyes may include acridine dyes, cyanine dyes, fluorine dyes, oxazine dyes, phenanthridine dyes, and rhodamine dyes.
  • the colorant may be a pigment.
  • Pigments may be in powder or flake-form and can provide colorants which, unlike dyes may be insoluble in the surrounding medium (see “Rompp Lexikon Lacke und Druckmaschine”, Georg Thieme Verlag Stuttgart / New York 1998, page 451). Pigments are typically composed of solid particles less than about 1 pm in size to enable them to refract light, for example within light wavelengths of between about 0.4 and 0.7 pm.
  • the pigments may be selected from organic and inorganic pigments including color pigments, effect pigments, magnetically shielding, electrically conductive, anticorrosion, fluorescent and phosphorescent pigments.
  • Organic pigments may include may include polycyclic pigments(e.g. phthalocyanide such as copper phthalocyanine, anthraquinones such as dibrom anthanthrone, quinacridones such as quinacridone red PV19, dioxazine such as dioxazine violet PV23, perylene, thionindigo such as tetrachloro), nitro pigments, nitroso pigments, quinoline pigments, and azine pigments.
  • the pigments may be inorganic.
  • the inorganic pigments may be selected from carbon black (e.g.
  • pigments used in aerospace paint compositions may include organic phthalocyanine, quinaridone, diketopyrrolopyrrole (DPP), and diarylide derivatives and inorganic oxide pigments (for example to enhance visibility and where it has been applied).
  • a coating formulation comprises an organic film former in about 85-95 wt %, an adhesion promotor in about 1-5 wt %, and a photoinitiator in about 1- 8%, and wherein the organic film former comprises a PIC according to any embodiments or examples thereof in about 10-30 wt % (of the total formulation).
  • the coating composition may comprise an organic film former comprising a PIC, an adhesion promoter and polymerisation initiator: i) an organic film former comprising: a) a PIC: b) polymeric constituents: oxibis(propane-l,2-diyl) diacrylate dipropylen glycols diacrylate trimethylolpropane triacrylate cyclic trimethylolpropane formal acrylate ii) acid based adhesion promotor, for example a silane or siloxane; and iii) polymerization initiator, for example
  • a coating layer provided by the compositions as described herein may form part of a coating system.
  • a coating system may be provided comprising:
  • one or more corrosion protection layers located between (i) and (ii) comprising a polymerizable ionic compound (PIC) or a reaction product thereof, wherein the PIC comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • the corrosion protection layers may comprise or consist of a polymerizable ionic compound (PIC) or a reaction product thereof, or a coating or coating composition thereof, according to any embodiments or examples as described herein.
  • Suitable substrates include metals and metal alloys (e.g. steel or aluminium), and composites.
  • a coated metal substrate may be provided comprising a metal substrate coated with one or more coating layers, wherein at least one of the coating layers comprises a polymerizable ionic compound (PIC) or a reaction product thereof, wherein the PIC comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • PIC polymerizable ionic compound
  • At least one coating layer comprising or consisting of a polymerizable ionic compound (PIC) or a reaction product thereof, or a coating or coating composition thereof, according to any embodiments or examples as described herein.
  • PIC polymerizable ionic compound
  • a coating may be applied to an optionally coated substrate, wherein the coating comprises or consists of:
  • PIC polymerizable ionic compound
  • additives selected from a solvent, a curing agent, an adhesion promoter, an inorganic filler, a wetting agent, and an organic crosslinker.
  • a coated metal substrate comprising a metal substrate coated with one or more coating layers, wherein at least one of the coating layers comprises or consists of an polymerizable ionic compound (PIC) or reaction product thereof according to any embodiments or examples thereof as described herein.
  • PIC polymerizable ionic compound
  • a process for preparing a coating system as described herein may comprise: applying a coating composition according to any embodiments or examples thereof as described herein to an optionally coated substrate to form a coating; and optionally applying at least one post coating layer to the coating present on the optionally coated substrate.
  • a process for preparing a coating system may comprise: applying the PIC, cured reaction product or coating composition according to any aspects, embodiments or examples as described herein, to an optionally coated substrate; and optionally applying one or more post coating layer to the coating present on the optionally coated substrate.
  • the coating composition as described herein can be applied onto a coated substrate to form a coating layer by any method known in the coating industry including spray, drip, dip, roller, brush or curtain coating, especially spray.
  • the dry thickness of the coating depends on the application. In some embodiments, the dry thickness of the coating layer (in microns) is less than about 300, 250, 200, 150, 100, 75, 50, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1. The dry thickness may be in a range provided by any two of these values.
  • the coating layer provides effective adhesion on the coated substrate and between any primer, intermediate or post coating layers if present on the coating.
  • the coating layer is a primer coating.
  • the coating layer may include additional adhesion promoters, such as those described or exemplified herein.
  • any suitable method known to those skilled in the art may be used to assess whether the adhesive linkage between the coating layer and other layers (e.g. coated substrate or post coating layer). Methods may include but are not limited to ASTM and ISO standards.
  • Properties include corrosion inhibition, and may include any one or more of low toxicity, environmentally friendly, good processability, miscibility with coating systems, high stability, and improved barrier protection from water.
  • a process for protecting a substrate from corrosion by applying a polymerizable ionic compound (PIC), or reaction product thereof, or composition thereof according to any embodiments or examples as described herein, to the substrate.
  • the substrate may be a tank, conduit or pipe.
  • the substrate may be used in various industrial applications such as water treatment, or acidic environments.
  • the composition may be a formulation according to any examples as described herein, such as a liquid or solid formulation.
  • the solid or liquid formulation may be introduced or dosed into the tank, conduit or pipe, for example.
  • the polymerizable ionic compound (PIC) may be a polymerizable ionic liquid (PIL).
  • Reagents -Coumaric acid also referred to as para-hydroxy cinnamic acid
  • N-methyldiethanolamine 2-bromoethanol
  • 2-bromoethane 2-(dimethylamino)ethyl methacrylate
  • potassium hydroxide 4-vinylaniline
  • Darocur® Speedcure 73
  • Amberlist® A-26 OH form
  • 1-vinylimidazole was obtained from Sigma Aldrich.
  • 1-Bromobutane and 1-bromohexane were obtained from Acros.
  • Oxybis(propane-l,2- diyl) diacrylate, dipropylene glycol diacrylate, trimethylpropyl triacrylate, cyclic trimethylolpropane formal acrylate, and acid-based adhesion promotors were obtained from Arkema/Sartomer. Mild Steel 1020, NaCl aqueous solution, MiliQ water, methanol and ethanol were used without further purification.
  • NMR spectra were recorded on a Bruker AC-400 spectrometer under the following experimental conditions: spectral width 15 ppm with 32k data points, flip angle 908, relaxation delay of 1 second, digital resolution of 0.24 Hz/pt.
  • DSC spectra were recorded on a DSC Q2000 instrument (TA Instruments) under N2 atmosphere. Samples (5 mg) sealed in aluminium pans were heated from 25 °C to 100 °C at the heating rate of 20 K min 1 then were left at 100 °C for 3 min in order to eliminate the thermal history. Samples were cooled down to -70 °C at the rate of 2 K min -1 and were left at 70 °C for 3 min. Samples were heated again to 100 °C at the rate of 20 K min -1 .
  • ATR-FTIR measurements were performed on Bruker Alpha-P equipment. Spectra were recorded from 350 to 4000 cm 1 at the resolution of 2 cm -1 .
  • a BioLogic VMP3 multi-channel potentiostat and EC Lab VI 0.44 software were used for PP experiments.
  • a three-electrode cell was used with the steel rod as the working electrode, a titanium mesh counter electrode and Ag/AgCl reference electrode.
  • the reference electrode was placed in a Luggin capillary that was positioned close to the working electrode surface.
  • Open Circuit Voltage (OCV) was monitored for 30 min followed by a PP scan at the scan rate of 0.167 mV s -1 , with the scan range of from 150 mV below OCV to 250 mV above OCV. Three PP curves were obtained for each test solution.
  • Corrosion Current Density i corr
  • Corrosion Potential E corr
  • Electrochemical impedance spectroscopy was carried out over a test period of 24 h in order to characterise the electrochemical properties of AS 1020 mild steel electrodes immersed in the control solution, solution containing the inhibitor compound, or solution containing polymer coatings.
  • BioLogic VMP3 multi-channel potentiostat was used for the EIS tests.
  • OCV was monitored over the frequency range of 100 kHz to 10 mHz with 6 points per decade and a sinusoidal amplitude of lOmV. Impedance responses were monitored after each hour.
  • a Leica MZ 7 optical microscope in combination with LAS V4.0 software was used to observe surfaces after 24 h of immersion.
  • SEM Scanning electron microscopy
  • EDS energy-dispersive X-ray spectroscopy
  • para-4-butyloxycinnamic acid which may also be referred to as para-butoxy coumaric acid
  • KOH (3 mol) and KI cat., 20 mol
  • Butyl bromide (1 mol) was added and the reaction mixture was refluxed for a further 24 hours.
  • the solvent was removed and the precipitate was acidified with concentrated HC1.
  • the crude product was filtered, washed with water and recrystallized from a mixture of ethanol/water (75/25).
  • para-4-hexyloxycinnamic acid which may also referred to as para-hexyloxy coumaric acid
  • p-Coumaric acid (1 mol) KOH (3 mol) and KI (cat., 20 mol%) was dissolved in a mixture of ethanol/water (75/25) and refluxed for 1 h.
  • Hexyl bromide (1 mol) was added and the reaction mixture was refluxed for a further 24 hours.
  • the solvent was removed and the precipitate was acidified with concentrated HC1.
  • the crude product was filtered, washed with water and recrystallized from a mixture of ethanol/water (75/25).
  • para-4-ethyloxymethacrylatecinnamic acid which may also be referred to as para-ethyl methacrylate coumaric acid
  • p-Coumaric acid (1 mol) KOH (3 mol) and a catalytic amount of KI were dissolved in a mixture of ethanol/water (75/25%) and refluxed 1 hour.
  • 2-bromoethyl methacrylate (1 mol) was added and the reaction mixture was refluxed for a further 24 hours.
  • the solvent was removed and the precipitate was acidified with concentrated HC1.
  • the crude product was filtered, washed with water and recrystallized from a mixture of ethanol/water (75/25%).
  • the final product was dried under vacuum and obtained as a white powder.
  • N-methyl N-ethyl diethanolammonium bromide was obtained by quatemizing N- methyl diethanolamine using 2-bromoethane as described as follows. N-methyl diethanolamine was treated dropwise with 2-bromoethane at room temperature. After the addition of the 2-bromoethane, the reaction mixture was then stirred for 24 hours at 50 °C. The product was obtained as a solid and purified by dissolving the solid in a minimum amount of methanol and then precipitating the product in a large excess of ethyl acetate. The precipitate was washed three times with ethyl acetate and dried under vacuum at 40 °C. The final product was obtained as a white powder and stored under inert gas until further use. 1 H NMR (400 MHz, D 2 0) d 4.08, 4.07, 4.07, 4.06, 4.05, 4.04, 4.03, 3.59,
  • the crude product was dissolved in a minimum amount of methanol and precipitated in a large excess of ethyl acetate, in order to remove unreacted compounds.
  • the precipitate was washed three times with ethyl acetate and dried under vacuum at 40 °C.
  • the final product was obtained as a white powder and stored under inert gas until further use.
  • 2-(dimethyl ammonium)ethyl methacrylate trans-4- butoxycinnamate which may also be referred to as 2-(dimethyl amino)ethyl methacrylate para-butoxy cinnamate
  • 2-(Dimethyl amino)ethyl methacrylate and 4-butoxycinnamic acid were weighted and mixed in an equimolar amount. The product was obtained instantly as a viscous liquid.
  • An exemplary synthesis of 4-vinylpyridine para-hexyloxy cinnamate is provided as follows. 2-Vinylpyridine and p-hexoxy coumaric acid were weighted and mixed in an equimolar amount. The product was obtained instantly as a viscous liquid.
  • Tetrabutylammonium para-ethyloxy methacrylate triethylammonium salt An exemplary synthesis of tetrabutylammonium para-ethyl methacrylate coumarate is provided as follows. Triethylamine and para-ethyloxy methacrylate coumaric acid were weighted and mixed in an equimolar amount. The product was obtained instantly as a viscous liquid.
  • Oxybis(propane-l,2-diyl) diacrylate (40% w/w), dipropylene glycol diacrylate (25% w/w), trimetyl propyl triacrylate (13% w/w), cyclic trimethylolpropane formal acrylate (12% w/w), acid based adhesion promotor (3% w/w), Darocur® (Speedcure 73) (5% w/w) and 2-(dimethyl amino)ethyl methacrylate p-coumarate (20% w/w) were added and mixed in a vial.
  • a mild Steel 1020 surface was prepared in order to have a rectangular gap to a depth of 62.5 pm. The gap was filled with the aforementioned mixture and then UV cured.
  • Oxybis(propane-l,2-diyl) diacrylate (40% w/w), dipropylene glycol diacrylate (25% w/w), trimetyl propyl triacrylate (13% w/w), cyclic trimethylolpropane formal acrylate (12% w/w), acid based adhesion promotor (3% w/w), Darocur (Speedcure 73) (5% w/w) and 2-(dimethyl amino)ethyl methacrylate p-butyloxy coumarate (20% w/w), were added and mixed in a vial.
  • a mild Steel 1020 surface was prepared in order to have a rectangular gap to a depth of 62.5 pm. The gap was filled with the aforementioned mixture and it was UV cured.
  • 3.3 Preparation of polymer coating containing 2-(dimethyl amino)ethyl methacrylate p-hexyloxy coumarate
  • Oxybis(propane-l,2-diyl) diacrylate (40% w/w), dipropylene glycol diacrylate (25% w/w), trimetyl propyl triacrylate (13% w/w), cyclic trimethylolpropane formal acrylate (12% w/w), acid based adhesion promotor (3% w/w), Darocur (Speedcure 73) (5% w/w) and 2-(dimethyl amino)ethyl methacrylate p-hexyloxy coumarate (20% w/w) were added and mixed in a vial.
  • a mild Steel 1020 surface was prepared in order to have a rectangular gap to a depth of 62.5 pm. The gap was filled with the aforementioned mixture and it was UV cured.
  • Oxybis(propane-l,2-diyl) diacrylate (40% w/w), dipropylene glycol diacrylate (25% w/w), trimetyl propyl triacrylate (13% w/w), cyclic trimethylolpropane formal acrylate (12% w/w), acid based adhesion promotor (3% w/w), Darocur (Speedcure 73) (5% w/w) and 1 -vinylimidazole para-4-hexyloxycinnamate (20% w/w) were added and mixed in a vial.
  • a mild Steel 1020 surface was prepared in order to have a rectangular gap to a depth of 62.5 pm. The gap was filled with the aforementioned mixture and it was UV cured.
  • Oxybis(propane-l,2-diyl) diacrylate (40% w/w), dipropylene glycol diacrylate (25% w/w), trimetyl propyl triacrylate (13% w/w), cyclic trimethylolpropane formal acrylate (12% w/w), acid based adhesion promotor (3% w/w), Darocur (Speedcure 73) (5% w/w) and 4-vinylaniline para-4-hexyloxycinnamate (20% w/w) were added and mixed in a vial.
  • a mild Steel 1020 surface was prepared in order to have a rectangular gap to a depth of 62.5 pm. The gap was filled with the aforementioned mixture and it was UV cured.
  • Oxybis(propane-l,2-diyl) diacrylate (40% w/w), dipropylene glycol diacrylate (25% w/w), trimetyl propyl triacrylate (13% w/w), cyclic trimethylolpropane formal acrylate (12% w/w), acid based adhesion promotor (3% w/w), Darocur (Speedcure 73) (5% w/w) and 4-vinylpyridine para-hexyloxy cinnamate (20% w/w) were added and mixed in a vial.
  • a mild Steel 1020 surface was prepared in order to have a rectangular gap to a depth of 62.5 pm. The gap was filled with the aforementioned mixture and it was UV cured.
  • Figures 1-5 provides examples where the polymerizable group is on the onium nitrogen cation
  • Figure 6 provides examples where the polymerizable group is on the aromatic carboxylate group.
  • Figure 2 is an Electrochemical Impedance Spectra (EIS) for the coated steel specimens immersed in 1M NaCl solution for 24 hours; black - control coating without any polymerizable ionic compounds; red - coating with 20 weight % [p-OHcoum]MA polymerizable ionic compound (see above Example 2.3.1); blue- coating with 20 weight % [p-O(C 6 H 13 )coum]MA polymerizable ionic compound (see above Example 2.3.4). Larger impedance signifies greater corrosion inhibition and better barrier properties.
  • EIS Electrochemical Impedance Spectra
  • Figures 3A-C show a time evolution of EIS bode plots for control coating and coatings containing 20 weight % [pOHcoum]MA (see above Example 2.3.1) and [pOC 6 H 13 ]MA (see above Example 2.3.4) polymerizable ionic compounds according to two examples of the present disclosure immersed in NaCl aqueous solution.
  • the highest impedance shown is the coating containing [pOC 6 H 13 ]MA (see above Example 2.3.4) polymerizable ionic compound.
  • Figure 4 shows polymer coatings on AS 1020 mild steel containing 20% of [p-OHcoum]MA, 20% of [p-O(C 4 H 9 )coum]MA, and 20% of [ p-O(C 6 H 13 )coum] MA after an immersion of 20h in 0.005 M NaCl. It was observed that [p-OHcoum]MA take water during immersion. On the other hand, increasing the length of the alkyl chain attached to the oxygen of the coumarate anion, the hydrophobicity is increased and so the weight of [p-O(C 4 H 9 )coum]MA and [p-O(C 6 H 13 )coum]MA remained constant.
  • FIG. 5A-D Various polymerizable ionic compounds were prepared where an onium nitrogen cation contained a polymerizable group (see Figures 5A-D and above Examples 2.3.1, 2.3.3, 2.3.4, 2.3.5, 2.3.6, and 2.3.7).
  • the polymerizable ionic compounds were tested as UV cured coatings at a level of 20 weight % of the PIC in the total weight of the coating. In each case the anion is the same but the polymerizable group on the nitrogen cation is modified. A significant impact on improved corrosion performance was shown.
  • Figure 5B(i) shows EIS bode impedance plots for UV cured coatings containing 20 weight % of the different polymerizable ionic compounds (PIC) compared with the control coating.
  • PIC polymerizable ionic compounds
  • the PIC of [p-O[C 6 H 13 )coum]AN provides very high impedances after 24 hours.
  • the PIC of [p-O[C 6 H 13 )coum]IM also shows particularly high impedance values.
  • Figure 5C shows Nyquist plots after 24 hours immersion of the coatings in NaCl aqueous solution. Same data is provided as the Bode plots in Figure 5B(i) above but in different format.
  • the PIC of [p- 0[C 6 H 13 )coum]IM shows highest impedance values and these test demonstrate the significance of the coating barrier and corrosion protection properties on the PIC chemistry.
  • a defect was introduced into a reference UV polymer coating without any inhibitor, and coatings containing 20wt% [p-O[C 6 H 13 )coum]MA, [p-O[C 6 H 13 )coum]IM, [p-O[C 6 H 13 )coum]AN and [p-O[C 6 H 13 )coum]PY, respectively.
  • the coatings were introduced into acidic solutions in order to initiate the corrosion reaction.
  • filiform corrosion pictures of all coatings can be observed after 10 days.
  • the control coating without inhibitors shows a completely rust covered surface.
  • the polymer coatings containing inhibitors passed the scribe test very well showing little to no corrosion propagation. All systems are significantly improved over the control (without any PIC).
  • FIG. 6A & 6B provides a schematic of the preparation ( Figure 6A) and EIS bode impedance plots ( Figure 6B) for UV cured coatings containing 20 weight % of the anionic polymerizable ionic compound [p-O(MEM)coum] according to one example of the present disclosure (see above Example 2.3.8) compared with the control coating. Four orders of magnitude higher impedance is observed.
  • the corrosion inhibition properties of the monomers were evaluated by immersing mild steel AS 1020 foils into an aqueous solution of the ionic monomers. By this method it is expected that the organic ionic compounds may adsorb onto the mild steel surface forming a corrosion inhibition layer as illustrated in the Figure 7.
  • Figure 10 also shows optical images of the mild steel samples immersed in control, [p-O[C 6 H 13 )coum]MA, [p- 0[C 6 H 13 )coum]IM, [p-O[C 6 H 13 )coum]AN and [p-O[C 6 H 13 )coum]PY.
  • the control sample presents a surface covered red rust, while the inhibitor immersed samples are not showing evidence of such corroded areas.
  • the mild steel samples were evaluated using electron microscopy of the surfaces.
  • Mild steel AS 1020 surfaces were analyzed after an immersion of 24 h in 0.01 M NaCl with and without monomeric ionic liquid inhibitors by optical microscopy, scanning electron microscopy and electron diffraction spectroscopy.
  • rust deposits can be observed on the surface immersed in the control solution (optical and scanning electron microscopy images).
  • the surfaces in contact with solutions containing inhibitors do not present rust deposits.
  • EDS analysis confirmed the presence of carbon, oxygen and nitrogen atoms on these surfaces, indicating the creation of an organic inhibiting layer onto the metallic surface.

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Abstract

La présente invention concerne de manière générale des inhibiteurs de corrosion polyioniques comprenant des composés ioniques polymérisables, et des produits de réaction durcis, des compositions, des formulations, des revêtements et des procédés de fabrication et d'utilisation associés. La présente invention concerne également un procédé de d'inhibition de la corrosion sur un substrat. La présente invention concerne des revêtements comprenant un composé ionique polymérisable ou un produit de réaction durci de celui-ci, le composé ionique polymérisable comprenant des groupes cations onium éventuellement polymérisables et des groupes contre-anions carboxylate aromatique éventuellement polymérisables.
PCT/AU2020/051258 2019-11-22 2020-11-20 Inhibiteurs de corrosion polyioniques WO2021097531A1 (fr)

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