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WO2021097532A1 - Inhibiteurs de corrosion organiques - Google Patents

Inhibiteurs de corrosion organiques Download PDF

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Publication number
WO2021097532A1
WO2021097532A1 PCT/AU2020/051259 AU2020051259W WO2021097532A1 WO 2021097532 A1 WO2021097532 A1 WO 2021097532A1 AU 2020051259 W AU2020051259 W AU 2020051259W WO 2021097532 A1 WO2021097532 A1 WO 2021097532A1
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Prior art keywords
alkyl
heteroalkyl
alkenyl
heteroalkenyl
hydrogen
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English (en)
Inventor
Maria Forsyth
Anthony Emil SOMERS
Mahdi Ghorbani MOUSAABADI
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Deakin University
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Deakin University
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Priority claimed from AU2019904419A external-priority patent/AU2019904419A0/en
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Publication of WO2021097532A1 publication Critical patent/WO2021097532A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C59/58—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23F11/167—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives

Definitions

  • the present disclosure generally relates to organic corrosion inhibitors, and to 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 organic corrosion inhibitors, and to compositions, formulations, coatings, and methods of making and use thereof.
  • the organic corrosion inhibitors of the present disclosure comprise onium cations and aromatic carboxylate anions.
  • the aromatic carboxylate groups can provide counter anions for the onium cations, which can provide organic corrosion inhibitors effective for providing various properties including corrosion inhibition.
  • a method for inhibiting corrosion on a substrate by providing one or more coatings on the substrate, wherein at least one coating comprises an organic corrosion inhibitor comprising onium cation groups and aromatic carboxylate counter-anion groups.
  • a coating comprising an organic corrosion inhibitor for inhibiting corrosion on a substrate, wherein the organic corrosion inhibitor comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • a coated metal substrate comprising a metal substrate coated with one or more coating layers, wherein at least one of the coating layers comprises an organic corrosion inhibitor, and wherein the organic corrosion inhibitor comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • a coating applied to an optionally coated substrate wherein the coating comprises or consists of:
  • additives selected from a solvent, an organic film former, a curing agent, an adhesion promoter, an inorganic filler, a wetting agent, and an organic crosslinker.
  • a coating system comprising:
  • one or more corrosion protection layers located between (i) and (ii) comprising an organic corrosion inhibitor, wherein the organic corrosion inhibitor comprises onium cation groups and aromatic carboxylate counteranion groups.
  • an organic corrosion inhibitor comprising or consisting of an aromatic carboxylate of Formula 1 and an onium cation:
  • X is an optionally linked carboxylate anion group
  • the onium cations are quaternary onium cations.
  • the onium cations are selected from ammonium cation groups, pyridinium cation groups, imidazolium cation groups, pyrazolium cation groups, pyrrolidinium cation groups, and phosphonium cation groups.
  • the onium cations are quaternary ammonium cations.
  • the onium cations are ammonium cation groups of Formula 2a: wherein
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl.
  • a coating composition comprising an organic corrosion inhibitor, wherein the organic corrosion inhibitor comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • the coating composition is a curable coating composition comprising or consisting of an organic film former and an organic corrosion inhibitor, wherein the organic corrosion inhibitor comprises onium cation groups and aromatic carboxylate counter-anion groups.
  • a process for preparing a coating system comprising: applying the organic corrosion inhibitor or composition thereof 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 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 1 shows Tafel plots at pH 7 for mild steel immersed in the control solution and the inhibitor (CTA-4OHcinn) solution.
  • Figure 2 shows Nyquist plots of mild steel immersed for 2 h in the control solution ( Figure 2(a)) and the inhibitor (CTA-4OHcinn) solution ( Figure 2(b)).
  • Figure 3 shows Bode plots of mild steel immersed for 2 h in the control solution ( Figure 3(a)) and the inhibitor (CTA-4OHcinn) solution ( Figure 3(b)).
  • Figure 4 shows phase angle plot of mild steel immersed for 2 h in the control solution ( Figure 4(a)) and the inhibitor (CTA-4OHcinn) solution ( Figure 4(b)).
  • Figure 5 shows cyclic polarisation curves of mild steel immersed for 2 h in the control solution ( Figure 5(a)) and the inhibitor (CTA-4OHcinn) solution ( Figure 5(b)).
  • Figure 6 shows images of mild steel following immersion for 2 h in the control solution ( Figure 6(a)) and the inhibitor (CTA-4OHcinn) solution ( Figure 6(b)).
  • Figure 7(a) shows SEM image of mild steel immersed for 12 days in inhibitor solution.
  • Figure 7(b) shows the EDS analysis of zone 1 and zone 2.
  • Figure 8 shows trend of Nyquist plot for mild steel immersed for 2 h in control solution ( Figure 8(a)) and inhibitor (CTA-4OHcinn) solution ( Figure 8(b)).
  • Figure 9 shows 2 h time trend of the Bode and phase angle plot for mild steel immersed for 2 h in control solution ( Figure 9(a)) and the inhibitor (CTA-4OHcinn) solution ( Figure 9(b)).
  • Figure 10 shows optical images of the surface of mild steel with AS1030 samples with the corrosion product intact after immersion at pH 7 for 24 h in control solution ( Figure 10(a) and Figure 10(b)) and inhibitor solution ( Figure 10(c)).
  • Figure 11 shows SEM and mapping images after corrosion production removal of the surface of mild steel samples immersed in inhibitor solution at pH 7 after 24 h, including a selected pit (Figure 11(a)), Fe map (Figure 11(b)), oxygen map (Figure 11(c)), and chloride map (Figure 11(d)).
  • Figure 12 shows EDX spectra for spots 1 and 2 in Figure 11.
  • Figures 13a-e shows XPS elemental analysis following immersion testing results at various times for CTA-4OHcinn as a corrosion inhibitor.
  • Figure 14 shows the deconvolution of the XPS region scans for oxygen, iron, and nitrogen at the different immersion times for CTA-4OHcinn as a corrosion inhibitor.
  • Figure 15 shows Tafel plots for the control solution and inhibitor solution for CTA-4Etocinnas a corrosion inhibitor according to one example of the present disclosure.
  • Figure 16 shows optical images of the sample immersed for 24 h in control solution ( Figure 16(a)) and inhibitor solution ( Figure 16(b)) for CTA-4Etocinn as a corrosion inhibitor according to one example of the present disclosure.
  • Figure 17 shows the SEM image of mild steel after 24 h of immersion in control ( Figure 17(b)) and the inhibitor ( Figure 17(a)) solutions for CTA-4Etocinn as a corrosion inhibitor according to one example of the present disclosure.
  • Figure 18 shows a higher magnification image of one of these deposits, accompanied by elemental information from EDX analysis of the sites labelled for CTA- 4Etocinn as a corrosion inhibitor according to one example of the present disclosure.
  • Figure 19 shows (a) Tafel plots for a control solution and inhibitor solution after 30 minutes immersion and (b) Tafel plots for a control solution and inhibitor solution after 24 hours immersion, for 10 mM CTA-4Etocinn and 10 mM CTA-4OHcinn as corrosion inhibitors with and without ethanol according to one example of the present disclosure.
  • Figure 20 shows (a) Tafel plots for the control solution and both inhibitor solutions after 30 minutes immersion and (b) shows the Tafel plots for the control solution and both inhibitor solutions after 24 hours immersion, for 10 mM CTA-4Etocinn and 10 mM CTA-4OHcinn as corrosion inhibitors with 6.5% ethanol according to one example of the present disclosure.
  • Figure 21 shows Tafel plots for 10 mM CTA-4Etocinn inhibitor solution with 6.5% ethanol in 0.01M NaCl at pH 7 after 30 minutes and 24 hours of immersion.
  • Figure 22 shows (a) Tafel plots for control solution and inhibitor solution after 30 minutes immersion at pH2, (b) Tafel plots for the control solution and inhibitor solution after 24 hours immersion at pH2, and (c) combined Tafel plots comparing the effect between 30 minute and 24 hour immersions, for 0.1 mM CTA-4Butcinn as a corrosion inhibitor according to one example of the present disclosure at pH 2.
  • Figure 23 shows optical images of the sample immersed at pH2 for 24 h in control solution ( Figure 23(a)(i) and (ii) at different magnification) and inhibitor solution ( Figure 23(b)) for 0.1 mM CTA-4Butcinn as a corrosion inhibitor according to one example of the present disclosure.
  • Figure 24 shows the SEM image of mild steel after 24 h of immersion at pH2 in control ( Figure 24(b)) and the inhibitor ( Figure 24(a)) solutions for 0.1 mM CTA- 4Butcinn as a corrosion inhibitor according to one example of the present disclosure.
  • the present disclosure describes the following various non-limiting examples, which relate to investigations undertaken to identify alternative and improved corrosion inhibitors including organic corrosion inhibitors.
  • the organic corrosion inhibitors, 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, and/or improved barrier protection from water. It was surprisingly found that a coating composition comprising an organic corrosion inhibitor could provide an effective coating on a substrate with properties including at least one of corrosion inhibition and 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 Unless otherwise indicated, the terms “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%.
  • 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. 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.
  • Preferred 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.
  • Preferred alkynyl groups include ethynyl, 1 -propynyl and 2-propynyl.
  • heteroalkyl includes both straight-chained, branched, and cyclic alkyl groups with one or more heteroatoms (e.g. 1-3) independently selected from S, O, and N with both unsubstituted and substituted alkyl groups. 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. Examples of “heteroalkyl” as used herein 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- or polyvalent.
  • heteroarylalkyl means a group comprising a heteroalkyl and aryl according to 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[2.2.1]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 1.
  • aromatic is used interchangeably with “aryl” to refer to an aromatic group, regardless of the valency of aromatic group.
  • the terms “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 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 -CO 2 H 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.
  • linker group e.g. divalent linking group such as an alkyl, heteroatom, or heteroalkyl
  • linker group e.g. divalent linking group such as an alkyl, heteroatom, or heteroalkyl
  • the present disclosure provides various organic corrosion inhibitors comprising onium cation groups and aromatic carboxylate counter-anion groups.
  • the onium cation groups and aromatic carboxylate counter-anion groups can coordinate together to form an ionic compound, for example a salt.
  • the ionic compound e.g. salt
  • the organic corrosion inhibitor may be an ionic liquid.
  • the organic corrosion inhibitors may be provided by any combination of Onium Cation Groups and Aromatic Carboxylate Groups as described below or herein.
  • 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.
  • the onium cations are quaternary onium cations.
  • the onium cations are nitrogen cations, such as ammonium cations.
  • the quaternary onium cations are quaternary onium nitrogen cations, for example quaternary cations selected from ammonium cation groups, pyridinium cation groups, imidazolium cation groups, pyrazolium cation groups, and pyrrolidinium cation groups.
  • the quaternary onium cations are quaternary ammonium cation groups.
  • the onium cations may be selected from any of the onium cations of Formula 2a, 2b, 2c, or 2d: wherein 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. Each alkyl or alkenyl may be optionally substituted, or optionally interrupted by one or more heteroatoms selected from O, N and S.
  • 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. In another example, R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 , are each independently selected from alkyl and heteroalkyl. In another example, R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 , are each independently selected from hydrogen and alkyl. In another example, R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 , are each independently selected from alkyl.
  • the onium cations are selected from quaternary onium nitrogen cations of Formula 2a: wherein
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, arylalkyl, heteroaryl, and heteroarylalkyl, and wherein two or more groups may j oin together to provide an aromatic or aliphatic ring.
  • Each alkyl or alkenyl may be optionally substituted, or optionally interrupted by one or more heteroatoms selected from O, N and S.
  • the groups R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, and heteroalkenyl.
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen, alkyl, and heteroalkyl.
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen and alkyl.
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from alkyl and heteroalkyl.
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from alkyl.
  • the onium cation of Formula 2a is cetrimonium.
  • the aromatic carboxylate group provides a counter anion to the cation groups in the organic corrosion inhibitor.
  • the aromatic carboxylate group may be an optionally linked, optionally substituted, monocyclic 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.
  • the 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.
  • 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 1-12 alkyl, wherein 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 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-C2-8alkyl.
  • R 1 and R 5 are hydrogen, and R 2 , R 3 , and R 4 , are each independently selected from hydrogen and O-C 3-6 alkyl, wherein at least one of R 2 , R 3 , and R 4 , is selected from O-C 3-6 alkyl.
  • 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 1-12 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 3-6 alkyl.
  • 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 and O-C 1-12 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 and O-C 1-12 heteroalkenyl.
  • R 3 is O-C 1-12 alkyl, O-C 1-12 alkyl, or O-C 3-8 alkyl.
  • R 1 and R 5 are hydrogen, and at least one of R 2 , R 3 , and R 4 , is selected from O-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 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 2-8 alkyl.
  • R 1 and R 5 are hydrogen, and at least one of R 2 , R 3 , and R 4 , is selected from O-C 3-6 alkyl.
  • 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 1-12 alkyl.
  • each of R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is O-C 3-6 alkyl.
  • X is a carboxyl ate 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, Ci- i2heteroalkyl, O-C 1-12 alkyl, and O-C 1-12 heteroalkyl.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, halo,
  • Y is an onium cation. In another example, Y may be selected from any of the onium cations as described herein.
  • an organic corrosion inhibitor may comprise or consist of an onium cation and an aromatic carboxylate of Formula 1: wherein
  • X is a carboxylate anion group
  • R 1 and R 5 are hydrogen
  • the onium cations may be selected from ammonium cation groups, pyridinium cation groups, imidazolium cation groups, pyrazolium cation groups, and pyrrolidinium cation groups.
  • the onium cations may be quaternary onium cations.
  • the onium cations may be quaternary ammonium cations.
  • ammonium cation groups may be of Formula 2a: wherein
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, and wherein two or more groups may j oin together to provide an aromatic or aliphatic ring.
  • Each alkyl or alkenyl may be optionally substituted, or optionally interrupted within one or more heteroatoms selected from O, N and S.
  • R 6 , R 7 , R 8 , and R 9 are each independently selected from alkyl, alkenyl, heteroalkyl, heteroalkenyl and wherein two or more groups may join together to provide an aromatic or aliphatic ring.
  • Each alkyl or alkenyl may be optionally substituted, or optionally interrupted within one or more heteroatoms selected from O, N and S.
  • 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.
  • the organic corrosion inhibitor is provided by an ionic compound formed by an aromatic carboxylate counter-anion of Formula 1 and an onium cation of Formula 2a:
  • Formula 1 and Formula 2 may be provided by any individual embodiments thereof as described herein.
  • X may be an optionally linked carboxylate anion group
  • R 1 and R 5 may be hydrogen
  • Table 3 provides further specific examples of cation and anion
  • a composition may comprise or consist of one or more organic corrosion inhibitors according to any embodiments or examples thereof as described herein, and optionally one or more additives.
  • the composition may be a coating composition such as a curable coating composition.
  • a curable coating composition may comprise or consist of an organic fdm former, one or more organic corrosion inhibitors according to any embodiments or examples thereof as described herein, and optionally one or more additives.
  • the composition may be a liquid formulation.
  • a composition comprising or consisting of one or more solvents, one or more organic corrosion inhibitors according to any embodiments or examples thereof as described herein, and optionally one or more additives.
  • the optional additives may also be provided according any of the embodiments or examples as described below.
  • the organic corrosion inhibitor may be a solid, for example provided as a suspension in the liquid formulation.
  • the composition may be a solid formulation.
  • a composition comprising or consisting of one or more solvents, one or more organic corrosion inhibitors according to any embodiments or examples thereof as described herein, and optionally one or more additives.
  • the optional additives may also be provided according any of the embodiments or examples as described below.
  • compositions and formulations may be used for introduction or dosing into a pipe or conduit for providing corrosion protection.
  • an oil or gas pipe or conduit may be dosed with a formulation comprising the organic corrosion inhibitor.
  • a water tank such as a bilge water tank, which may be dosed with a formulation comprising the organic corrosion inhibitor.
  • the compositions and formulations may be used in various industrial applications, for example water treatment processes, or industrial processes having acidic or low pH environments.
  • organic film former comprises or consists of one or more polymeric constituents.
  • the organic film former may comprise one or more organic corrosion inhibitors according to any embodiments or examples thereof as described herein.
  • Any polymeric constituents may consist of any polymers (e.g. copolymers) or polymerizable components, such as reactive monomers (e.g. resins) that can form polymers in the coatings.
  • the polymeric constituents may consist of polymers, copolymers, resins, monomers and comonomers.
  • Some examples of polymeric constituents include any one or more of polyolefins, polyurethanes, polyacrylic acids, polyacrylates, polyethers, polyesters, polyketides, polyamides, or any copolymers 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, copolymers, 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 organic corrosion inhibitor (in wt % of the total composition or coating) may comprise between about 1 and 50, 5 and 45, or 10 and 30.
  • the organic corrosion inhibitor (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 organic corrosion inhibitor (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 organic corrosion inhibitor (in wt % of the organic film former) may be in a range provided by any two of these upper and/or lower values.
  • compositions or formulations 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.
  • 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 siloxane.
  • 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 organic corrosion inhibitor and one or more optional additive may be dissolved or otherwise dispersed in a solvent to obtain the 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.
  • Organic Crosslinker based on wt % of composition
  • the coating and composition as described herein may also include an organic crosslinker.
  • the organic crosslinker may be incorporated into the 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 composition comprises between 1 and 15 wt % crosslinker.
  • 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
  • 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.
  • Anti-foaming agents may include BKY®-014, BKY®-1640. Anti-Corrosion Reagents
  • 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 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 ⁇ m in size to enable them to refract light, for example within light wavelengths of between about 0.4 and 0.7 ⁇ m.
  • 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 layer provided by the compositions as described herein may form part of a coating system.
  • a coating system may be provided comprising:
  • Suitable substrates include metals and metal alloys (e.g. steel or aluminium), and composites.
  • At least one coating layer provided on a substrate comprising or consisting of an organic corrosion inhibitor according to any embodiments or examples thereof as described herein.
  • a coating may be applied to an optionally coated substrate, wherein the coating comprises or consists of:
  • 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 organic corrosion inhibitor according to any embodiments or examples thereof as described herein.
  • 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 organic corrosion inhibitor according to any embodiments or examples thereof as described herein or coating composition thereof, 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 coating layer provides effective adhesion on the coated substrate and between any primer, intermediate or post coating layers if present on the coating.
  • 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 the organic corrosion inhibitor 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.
  • Reagents p-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 ATR-FTIR
  • 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.
  • IE inhibitor efficiencies
  • 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-ethyloxycinnamic acid which may also referred to as para-ethoxy coumaric acid
  • p-Coumaric acid 100 mmol
  • KOH 300 mmol
  • KI cat., 20 mol
  • the solution cool down to the room temperature and ethyl bromide (100 mmol) was added and the reaction mixture was stirred at reflux temperature for a further 24 h.
  • the solution cool down to the room temperature and acidified with concentrated HC1. The pH was monitored by pH paper until acidified.
  • the precipitate was filtered and washed with deionised water (DI) 4-5 times and recrystallized from a mixture of ethanol/water (75/25). The collected precipitate was dried under vacuum for 48 h at 50 °C, to yield the title compound.
  • DI deionised water
  • para-4-butyloxycinnamic acid which may also be referred to as para-butoxy 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. Then the solution cool down to the room temperature and butyl bromide (1 mol) was added and the reaction mixture was refluxed for a further 24 hours. The solution cool down to the room temperature and acidified with concentrated HC1. The pH was monitored by pH paper until acidified. The solvent was removed and the precipitate was acidified with concentrated HC1.
  • 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. Then the solution cool down to the room temperature and hexyl bromide (1 mol) was added and the reaction mixture was refluxed for a further 24 hours. The solution cool down to the room temperature and acidified with concentrated HC1. The pH was monitored by pH paper until acidified..
  • 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.
  • N-methyl diethanolammonium para-4-hydroxy-cinnamate which may also be referred to as N-methyl diethanolammonium p-coumarate
  • N-methyl diethanolammonium p-coumarate An exemplary synthesis of N-methyl diethanolammonium para-4-hydroxy- cinnamate, which may also be referred to as N-methyl diethanolammonium p-coumarate, is provided as follows. N-methyl diethanolamine and p-coumaric acid were weighed and mixed in an equimolar amount. The product was obtained instantly as a viscous liquid. 1 H NMR (300 MHz, DMSO) ⁇ 7.50, 7.47, 7.42, 6.81, 6.78, 6.31, 6.26, 5.58, 3.51, 3.49,
  • Anion exchange resin Amberlist A-26 (OH form) was used in order to obtain bromide exchange for the p-coumarate anion in N-methyl N-ethyl diethanolammonium bromide.
  • a column was filled with the aforementioned resin.
  • p-Coumaric acid aqueous solution, 0.01M was passed through the column. The acid-based reaction with hydroxides occurred, resulting in the retention of the p-coumarate anion in the resin and the displacement of the formed water together with the eluted solution.
  • N-methyl N-ethyl diethanolammonium bromide solution was passed through the column containing the A- 26 (R-p-coumarate form), and 2-(dimethyl ethanol amino)ethyl methacrylate p- coumarate was obtained after evaporation of methanol. The product was obtained as a viscous liquid.
  • Trihexyltetradecylphosphonium-para-4-hydroxy-cinnamate A stirred solution of trihexyltetradecylphosphonium chloride (20 mmol, 10.38 g) in toluene (25 mL) was treated with a solution of para-4-hydroxy-cinnamic acid (20 mmol, 3.28 g) in warm DI water (50 ml) at room temperature for 3 h. Then, NaOH (20 mmol, 0.8 g) was added and the reaction mixture was stirred at room temperature for
  • control solution a 0.01 M NaCl solution
  • inhibitor solution a 10 mM CTA-4OHcinn and 0.01 M NaCl solution
  • Figure 1 shows the Tafel plots for the control solution ( Figure 1(a)) and inhibitor solution ( Figure 1(b)).
  • Table 4 shows corrosion current densities (i ⁇ or), corrosion potential (E C on), and inhibition efficiency of CTA-4OHcinn as extracted from Tafel plots in Figure 1.
  • Table 4. Corrosion Potential ( E corr ), Corrosion Current Density (icon), and Inhibitor Efficiency (IE) at pH 7.
  • the results demonstrate that CTA-4OHcinn at 10 mM concentration significantly reduced the corrosion process in comparison with the control sample.
  • CTA-4OHcinn shifted the E corr towards more anodic potentials, from -553 mV for the control to -200 mV.
  • the first set of analyses highlighted the impact of the corrosion inhibitor on mild steel, with an efficiency of 95%.
  • the Tafel plots ( Figure 1) display transient current fluctuations. This may correspond to the breakdown and re-creation of a passivate film on the metal surface.
  • Figure 2(a) shows an almost constant impedance where the arc is below 1000 ohm. cm 2 at all times, in the imaginary axis.
  • Figure 2(b) shows an increasing trend on the impedance, reaching a maximum value of 16000 ohm. cm 2 in the imaginary axis.
  • Figure 3 shows the Bode plot for the sample immersed in the control solution (Figure 3(a)) and inhibitor solution (Figure 3(b)).
  • Figure 3(a) shows a slight decrease at lower frequencies
  • Figure 3(b) shows a clear increase in the impedance against time, which is more notorious at lower frequencies.
  • Figure 4 shows the phase angle plots of the sample immersed in the control solution (Figure 4(a)) and saturated inhibitor solution (Figure 4(b)).
  • Figure 4(a) shows that the maximum phase angle of the control solution is below 40°, and it shifts to lower frequencies against time.
  • Figure 4(b) shows that as time goes by, the maximum phase angle increases, reaching a maximum value of 68°. There is also a broadening with time on the curve peak of the maximum phase angle.
  • the phase angle of the inhibitor test presents two peaks, each one representing a time constant.
  • Figure 5 shows the cyclic polarization curves as a result of the CPP test on the sample immersed in the control solution and the inhibitor solution.
  • the control solution test presents a smooth cathodic curve without sharp changes, and a resulting corrosion potential around -0.410 V.
  • the inhibitor solution test its anodic curve occurs at lower currents than the control test, which results in a shit of the corrosion potential to more noble values.
  • the results also show a sudden increase in the current at a potential around 0.3 V. This critical point is the pitting potential.
  • the reverse polarization of the inhibitor test shows a more noble corrosion potential than the original.
  • Figure 6 shows the images of the sample immersed for 24 h in control solution ( Figure 6(a)) and inhibitor solution ( Figure 6(b)).
  • the sample immersed in control solution showed a significant metal dissolution on approximately 50% of its surface with some oxide deposits.
  • the sample immersed in inhibitor solution showed only two pits surrounded by oxide material.
  • Figure 7(a) shows the SEM image of mild steel after 12 days of immersion in inhibitor solution.
  • Figure 7(b) shows the elemental composition, from the EDS analysis of the sections indicated in the SEM image.
  • the EDS analysis shows a significant difference in the composition between the film (blue frame) and the exposed metal (green frame).
  • the film is composed of 39% carbon, while the exposed metal is mostly iron. There is no evidence of pitting corrosion or metal dissolution on the exposed iron surface.
  • Figure 11 shows a pit surrounded by corrosion product with a background mostly clear of corrosion. From the mapping, it can be seen that O and Cl are concentrated around the pit. This is due to the formation of corrosion product, such as FeOH and the formation of FeCl 2 . Generally Fe(OH)2 can form more easily than FeCl 2 due to its energy formation, however the activity of chloride specie is able to affect the cathodic mechanisms. This result is due to adsorbed CT specie on the interface layer where Fe-Cl forms.
  • FIG. 13 shows the atomic composition of oxygen, carbon, iron, nitrogen, and chlorine as a function of immersion time, as determined by the XPS elemental analysis.
  • there is a slight increase in the concentration of oxygen and iron after 2 hours of immersion which could be due to a defect in the protective film, exposing the underlying steel, which could be the result of film breakage.
  • XPS shows the formation of a film on the metal surface whose composition stabilizes in the first 45 minutes. Also, notice that the film capacitance of the metal sample after immersion in 10 mM inhibitor solution reaches a steady-state around the first 40 minutes ( Figure 2). Therefore, the constant composition of the film, as well as the constant capacitance, could indicate the film covers all the metal surface effectively in the first 45 minutes.
  • the signal of iron begins to appear again, which is in agreement with the SEM images of the sample immersed for 24 hours in 10 mM inhibitor solution ( Figure 10), that shows the presence of pits. Also, the presence of nitrogen, confirms the adsorption of the cetrimonium group on the metal surface.
  • Figure 14 shows the deconvolution of the XPS region scans for oxygen, iron, and nitrogen at the different immersion times.
  • the control test shows two peaks which correspond to the hydroxide and oxide states. However, after inhibitor interaction, a third peak appears, which corresponds to an oxygen-carbon single-bond.
  • the green peak represents oxygen double-bonded to a carbon atom as well as hydroxide.
  • the oxide peak (red), decreases with the immersion time up to two hours. However, it appears again after 24 hours, which could be related to the breakdown of the protective film.
  • Figure 14b the green and red peaks correspond to the 2p doublet for the Fe 3+ state. These peaks decrease with the immersion time and eventually disappear almost completely after two hours of immersion.
  • the blue peak corresponds to the elemental iron state, which could indicate the formation of an organic ultrathin layer that does not shield the iron beneath it completely from the X-rays. Since the depth of penetration for XPS analysis is estimated to be 10 nm, this suggests that the oxide/hydroxide layer on the control is greater than 10nm thick, while the protective layer formed with inhibitor present is less than 10 nm thick.
  • the nitrogen Figure 14c
  • two peaks were observed on the inhibitor exposed samples, with the blue peak corresponding to the amino group C-NH 2 of the inhibitor cation, which disappears after two hours of immersion.
  • the red peak it could correspond to a complex formation between the nitrogen atom and the iron surface.
  • control solution (“control solution”), and (b) a 10 mM CTA-4Etocinn and 0.01 M NaCl solution with 6.5% ethanol(“inhibitor solution”).
  • Figure 15 shows the Tafel plots for the control solution and inhibitor solution.
  • Table 5 shows corrosion current densities (i ⁇ or), corrosion potential (E C on), and inhibition efficiency of CTA-4OHcinn as extracted from Tafel plots in Figure 15.
  • Figure 16 shows optical images of the sample immersed for 24 h in control solution ( Figure 16(a)) and inhibitor solution ( Figure 16(b)).
  • the sample immersed in control solution showed a significant metal dissolution on approximately 50% of its surface with some oxide deposits.
  • the sample immersed in the CTA-4Etocinn inhibitor solution showed no obvious signs of corrosion after 24 hours.
  • Figure 17 shows the SEM image of mild steel after 24 h of immersion in control ( Figure 17(a)) and the inhibitor ( Figure 17(b)) solutions. Extensive damage can be seen on the control sample, while small deposits are visible on the inhibitor sample.
  • Figure 18 shows a higher magnification image of one of these deposits, accompanied by elemental information from EDX analysis of the sites labelled.
  • the EDS analysis shows a significant difference in the composition between the general background film (Site 20) and the deposits formed (Sites 18 and 19).
  • the deposits appear to be areas at which corrosion has started and a protective film has formed.
  • the presence of N on these sites indicates the presence of the inhibitor in this protective film.
  • the absence of N in the background film does not mean it is not there, but is below the detection limit of the EDX technique, a more surface sensitive technique such as XPS would be required to confirm, or not, the presence of N.
  • the fact that N consistently showed up on the deposits means that the inhibitor preferentially attaches to these areas and is intimately involved in the protective film that limits the corrosion.
  • CTA-4Etocinn as a corrosion inhibitor was compared with CTA-4OHcinn.
  • Mild steel was immersed at pH 7 for 30 minutes in (a) a 0.01 M NaCl solution with 6.5% ethanol (“control solution/6.5% ethanol”) and without ethanol (“control solution/no ethanol”), and (b) a 10 mM CTA-4Etocinn and 0.01 M NaCl solution with 6.5% ethanol (“inhibitor solution/6.5% ethanol”) and without ethanol (“inhibitor solution/no ethanol”).
  • Figure 19a shows the Tafel plots for the control solution and inhibitor solution after 30 minutes immersion
  • Figure 19b shows the Tafel plots for the control solution and inhibitor solution after 24 hours immersion.
  • additional alkyl chain length e.g. from a hydroxy group to an ethoxy group on the aromatic carboxylate anion can increase the corrosion protection on the metallic surface of mild steel alloy.
  • the inventors also found that over time the inhibitor provides increased interaction with the surface of the substrate thereby creating an improved protective film layer evident from the shift of the pitting potential (point of rapid current increase on anodic arm) to a more positive value and increased corrosion inhibition efficiency.
  • FIG. 20a shows the Tafel plots for the control solution and both inhibitor solutions after 30 minutes immersion
  • Figure 20b shows the Tafel plots for the control solution and both inhibitor solutions after 24 hours immersion.
  • the CTA-4Etocinn demonstrates up to approximately 3 orders of magnitude reductions in the current density of the anodic arm, suggesting significant inhibition of the metal oxidation reaction, when compared to the CTA-4OHcinn inhibitor.
  • the icorr value is approximately 1 order of magnitude smaller for the CTA-4Etocinn inhibitor, suggesting a slower corrosion rate when compared to the CTA-4OHcinn inhibitor.
  • Figure 21 shows the Tafel plots for the 10 mM CTA-4Etocinn inhibitor solution with 6.5% ethanol in 0.01M NaCl at pH 7 after 30 minutes and 24 hours of immersion. Over time the inhibitor interaction with the surface of the substrate increases to form a protective film layer and thus moving the pitting potential (point of rapid current increase on anodic arm) to more positive values and increasing the inhibitor efficiency.
  • CTA-4Butcinn as a corrosion inhibitor was investigated. Mild steel was immersed at pH 2 for 24 hours in (a) a 0.01 M NaCl solution with 6.5% ethanol (“control solution”), and (b) a 0.1 mM CTA-4Butcinn and 0.01 M NaCl solution (“inhibitor solution”). Mild steel was immersed at pH 2 for 24 hours in (a) a 0.01 M NaCl solution with 6.5% ethanol (“control solution”), and (b) a 0.1 mM CTA-4Butcinn and 0.01 M NaCl solution (“inhibitor solution”).
  • Figure 22a shows the Tafel plots for the control solution and inhibitor solution after 30 minutes immersion
  • Figure 22b shows the Tafel plots for the control solution and inhibitor solution after 24 hours immersion
  • Figure 22c shows a combined plot comparing the effect between 30 minute and 24 hour immersions.
  • the results demonstrate that CTA-4Butcinn at 0.1 mM concentration reduced the corrosion process in comparison with the control sample. CTA-4Butcinn shifted the E corr towards more anodic potentials. At 30 minutes there is some reduction of the cathodic current densities, suggesting a mixed mode of inhibition, and it appears that this reduction of the cathodic current density may linger after 24 hours.
  • Figure 23 shows optical images of the sample immersed for 24 h in control solution ( Figure 23(a)(i) and (ii)) and inhibitor solution ( Figure 23(b)).
  • the sample immersed in inhibitor solution showed a significant less corrosion, indicating that protection of the alloy surfaces can occur and may suggest organic film formation on the surface of alloy.
  • Figure 24 shows the SEM image of mild steel after 24 h of immersion in control ( Figure 24(b)) and the inhibitor ( Figure 24(a)) solutions. Extensive damage can be seen on the control sample, while small deposits are visible on the inhibitor sample Overall, the results show electrochemical and morphological differences between those samples exposed to the control solution and those samples exposed to the organic corrosion inhibitor solution.

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Abstract

La présente invention concerne d'une manière générale des inhibiteurs de corrosion organiques comprenant des compositions, des formulations, des revêtements, et des procédés de préparation et d'utilisation de ceux-ci. La présente invention concerne également un procédé d'inhibition de la corrosion sur un substrat. La présente invention concerne des revêtements comprenant un inhibiteur de corrosion organique comprenant des groupes de cations onium et des groupes de contre-anions carboxylate aromatique.
PCT/AU2020/051259 2019-11-22 2020-11-20 Inhibiteurs de corrosion organiques Ceased WO2021097532A1 (fr)

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