WO1990010095A1 - Preparations de revetements polymeres utilisees comme agents anticorrosion - Google Patents

Preparations de revetements polymeres utilisees comme agents anticorrosion Download PDF

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Publication number
WO1990010095A1
WO1990010095A1 PCT/AU1990/000075 AU9000075W WO9010095A1 WO 1990010095 A1 WO1990010095 A1 WO 1990010095A1 AU 9000075 W AU9000075 W AU 9000075W WO 9010095 A1 WO9010095 A1 WO 9010095A1
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WO
WIPO (PCT)
Prior art keywords
corrosion
polymer
corrosion inhibiting
species
polymeric coating
Prior art date
Application number
PCT/AU1990/000075
Other languages
English (en)
Inventor
Gordon George Wallace
Original Assignee
Itc Uniadvice Limited
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.)
Filing date
Publication date
Application filed by Itc Uniadvice Limited filed Critical Itc Uniadvice Limited
Publication of WO1990010095A1 publication Critical patent/WO1990010095A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic 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
    • 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

Definitions

  • This invention relates to the corrosion protection of metallic substrates and in particular to corrosion protection achieved by the use of polymeric coatings which contain corrosion inhibiting species and a method of preparation thereof.
  • a sacrificial anode may be employed which preferentially corrodes.
  • an inhibitor which causes precipitation of the corrosion product and consequently inhibition of further corrosion may be used.
  • An example of such an inhibitor is chromate ions.
  • It is an object of the present invention is to provide at least an alternate composition and method for the protection of metal substrates against corrosion.
  • the invention comprises a polymeric coating composition including a polymer incorporating a selective,
  • the corrosion inhibiting species or "inhibitor” may be an organic or inorganic anion and may be incorporated into the polymer coating as a counterion (C ⁇ ).
  • Preferred corrosion inhibiting species include
  • precipitating agents such as chromate ions (CroO) 2- or other complexing agents capable of reacting with the substrate metal, including ethylenediamine-tetraacetic acid (EDTA) or dithiocarbamate.
  • EDTA ethylenediamine-tetraacetic acid
  • species preferably have sufficient mobility to be released from, or redistributed through the polymer. As corrosion commences the species react at sites of corrosion resulting in a blocking of further attack.
  • the polymer coating of this invention may be synthesised from any suitable monomer.
  • the polymer is a conducting polymer.
  • Preferred conducting polymers may be prepared by the process illustrated as follows:-
  • C ⁇ is a corrosion inhibiting species
  • Y + is the cation of the supporting electrolyte salt
  • n is preferably between 2 and 4.
  • the properties of the polymer may be varied by varying the counterion C ⁇ . Following polymerization, C ⁇ may be released by either chemical or electrochemical reduction of the polymer.
  • the invention comprises a method according to the following process for preparing a polymeric coating composition including a polymer incorporating a selectively releasable corrosion inhibiting species:
  • X is preferably selected from the group consisting of -NH, S and O.
  • the coating may be generated either chemically or electrochemically and it is possible to generate the coating on the metal substrate.
  • the polymers of the present invention are:
  • metal substrates including tin oxide or other metal oxides, stainless steel and galvanised surfaces.
  • These polymers are preferably stable and adherent for an extended period after attaching to the
  • conducting polymers (depending on the monomer and counterion employed) are preferably stable to at least 200°C.
  • the conducting polymers are generally flexible materials.
  • the rate of growth of the polymer material is approximately 1 ⁇ m/min. However, in the case of
  • the corrosion inhibiting species is only released at the onset of corrosion and that when corrosion is halted, then the release of the corrosion inhibiting species will cease.
  • the inhibitor is released on demand and the mobility within the polymer ensures it is delivered to the site of corrosion.
  • Fig. 1 is a scanning electronmicrograph of
  • Fig. 2 is an energy dispersive x-ray (EDX) spectrum of polymer coated zincalum
  • Fig. 3 is an electrochemical cell set-up for an inhibitor release experiment
  • Fig. 4 is a U.V. - visible spectrum of Cr(VI)
  • Fig. 5 is a graph of current v time during the
  • Fig. 6 is an interpretation of Tafel plot
  • Polyalanine is another suitable conducting polymeric material.
  • the inhibitor may usually be incorporated directly during electropolymerisation. Chromium is a preferred inhibitor and can be incorporated directly during electropolymerisation providing a surfactant is present. It is believed that the surfactant inhibits the oxidation of the zincalum substrate during
  • Suitable corrosion inhibiting species include phosphate, oxine, oxalate and hydroxy quinoline sulfonic acid.
  • chromate containing layers can be grown on top of a surfactant containing polymeric coating.
  • the thickness of such polymer coatings can be controlled by varying the electroplating time and may be air or oven dryed.
  • these polymers contain a corrosion inhibiting species in addition to the
  • surfactant is short chain or amphiprotic.
  • Potentiodynamic or galvanostatic conditions can be employed during electropolymerisation. Galvanostatic polymer growth is preferred since it has previously been discovered that this results in more consistent polymer growth. Preferable current density is greater than or equal to 0.5 mA/cm 2 . At higher current densities, oxidation of the zincalum substrate occurs.
  • Zincalum has been chosen as a test case and the ability to initiate polymerisation and chemical
  • amphoteric surfactants which would provide the surface active properties and also some ion exchange to
  • Zincalum has been used for demonstration purposes. It has already been shown that such polymers may be coated on to stainless steel and a range of other metal surfaces.
  • substrate oxidation may be inhibited by the use of non-aqueous solvents.
  • a preferred solvent for this purpose is acetonitrile with toluene sulfonate as a supporting electrolyte.
  • An electrocatalyst may also be utilized.
  • Titan facilitate electropolymerisation, reducing the initialisation potential by more than 100 M.V.
  • Triggered release of corrosion inhibitors can be achieved using conducting polymers of the present invention.
  • Conducting polymers are known to release the incorporated counterion upon reduction of the polymer according to:
  • the corrosion inhibitor is released in two phases. Further controlled release of the corrosion inhibitor is also possible.
  • Corrosion rate can be calculated by the following equation:

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

Abstract

La préparation de revêtement polymère décrite contient un polymère dans lequel est incorporée une espèce anticorrosion libérable, sélective. Un procédé servant à empêcher la corrosion de substrats métalliques consiste à incorporer une espèce anticorrosion dans un revêtement polymère, à produire ce revêtement sur un substrat métallique, puis à libérer l'espèce anticorrosion selon les besoins pendant le processus corrodant. Le revêtement polymère est de préférence conducteur et est de préférence constitué par le polymère représenté par la formule (I), où C- représente des contre-ions anticorrosion, tels que de préférence des ions chromate, de l'acide éthylènediamine-tétra-acétique (EDTA), du dithiocarbamate, du phosphate ou de l'oxyne, X représente -NH, S ou O et n est de préférence compris entre 2 et 4. Un procédé de préparation de (I) par oxydation de pyrrol est également décrit.
PCT/AU1990/000075 1989-02-24 1990-02-23 Preparations de revetements polymeres utilisees comme agents anticorrosion WO1990010095A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPJ293589 1989-02-24
AUPJ2935 1989-02-24

Publications (1)

Publication Number Publication Date
WO1990010095A1 true WO1990010095A1 (fr) 1990-09-07

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ID=3773747

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1990/000075 WO1990010095A1 (fr) 1989-02-24 1990-02-23 Preparations de revetements polymeres utilisees comme agents anticorrosion

Country Status (1)

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WO (1) WO1990010095A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2679240A1 (fr) * 1991-07-17 1993-01-22 Centre Nat Rech Scient Procede d'obtention d'une couche mince de polymere d'aniline ou d'heterocycles aromatiques, sur un substrat metallique, par polymerisation et deposition par voie chimique.
EP0619333A2 (fr) * 1993-04-03 1994-10-12 ATOTECH Deutschland GmbH Procédé de revêtement de métaux
WO1995000678A1 (fr) * 1993-06-25 1995-01-05 Zipperling Kessler & Co (Gmbh & Co) Procede de production de materiaux metalliques anticorrosion et materiaux ainsi produits
FR2714077A1 (fr) * 1993-12-21 1995-06-23 Lorraine Laminage Procédé et bain de dépôt électrolytique de polypyrrole sur une surface de métal oxydable par électropolymérisation.
DE102004037542A1 (de) * 2004-08-03 2006-02-23 Chemetall Gmbh Verfahren zum Schützen einer metallischen Oberfläche mit einer korrosionsinhibierenden Beschichtung
US7601280B2 (en) 2002-06-04 2009-10-13 Lumimove, Inc. A Missouri Corporation Corrosion-responsive coating formulations for protection of metal surfaces
CN103304784A (zh) * 2013-06-26 2013-09-18 华东理工大学 一种防腐涂料用易分散聚噻吩的制备方法
RU2722533C1 (ru) * 2019-05-28 2020-06-01 Михаил Леонидович Галкин Клатратный ингибитор коррозии

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3812563A (en) * 1963-11-27 1965-05-27 Interchemical Corporation Latices of vinylidine chloride interpolymers and articles coated therewith
US3574072A (en) * 1968-04-03 1971-04-06 Universal Oil Prod Co Polymerization of heterocyclic compounds
AU6362369A (en) * 1968-12-26 1971-05-13 Monsanto Company Novel surface coatings
US4051055A (en) * 1976-12-21 1977-09-27 The Procter & Gamble Company Cleansing compositions
GB1494212A (en) * 1973-12-12 1977-12-07 Peier L Rust converting and protective agent
GB1520027A (en) * 1974-10-25 1978-08-02 Pyrene Chemical Services Ltd Processes for providing protective coatings on metal surfaces
AU8510582A (en) * 1981-06-24 1983-01-06 Amchem Products Inc. Pre-coating anticorrosive composition
US4475957A (en) * 1983-10-17 1984-10-09 Amchem Products, Inc. Coating composition
AU2794584A (en) * 1983-05-14 1984-11-15 Ciba Specialty Chemicals Holding Inc. Corrosion-inhibiting coating compositions
GB2187466A (en) * 1985-05-23 1987-09-09 Inst Mekhaniki Metallopolimern Anticorrosive material
AU2196388A (en) * 1987-09-16 1989-03-16 Dow Chemical Company, The Electrically conductive polymer compositions, processes and polymers useful for preparing the polymer compositions

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3812563A (en) * 1963-11-27 1965-05-27 Interchemical Corporation Latices of vinylidine chloride interpolymers and articles coated therewith
US3574072A (en) * 1968-04-03 1971-04-06 Universal Oil Prod Co Polymerization of heterocyclic compounds
AU6362369A (en) * 1968-12-26 1971-05-13 Monsanto Company Novel surface coatings
GB1494212A (en) * 1973-12-12 1977-12-07 Peier L Rust converting and protective agent
GB1520027A (en) * 1974-10-25 1978-08-02 Pyrene Chemical Services Ltd Processes for providing protective coatings on metal surfaces
US4051055A (en) * 1976-12-21 1977-09-27 The Procter & Gamble Company Cleansing compositions
AU8510582A (en) * 1981-06-24 1983-01-06 Amchem Products Inc. Pre-coating anticorrosive composition
AU2794584A (en) * 1983-05-14 1984-11-15 Ciba Specialty Chemicals Holding Inc. Corrosion-inhibiting coating compositions
US4475957A (en) * 1983-10-17 1984-10-09 Amchem Products, Inc. Coating composition
GB2187466A (en) * 1985-05-23 1987-09-09 Inst Mekhaniki Metallopolimern Anticorrosive material
AU2196388A (en) * 1987-09-16 1989-03-16 Dow Chemical Company, The Electrically conductive polymer compositions, processes and polymers useful for preparing the polymer compositions

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2679240A1 (fr) * 1991-07-17 1993-01-22 Centre Nat Rech Scient Procede d'obtention d'une couche mince de polymere d'aniline ou d'heterocycles aromatiques, sur un substrat metallique, par polymerisation et deposition par voie chimique.
EP0619333A2 (fr) * 1993-04-03 1994-10-12 ATOTECH Deutschland GmbH Procédé de revêtement de métaux
EP0619333A3 (en) * 1993-04-03 1994-11-23 Atotech Deutschland Gmbh Process for coating metals.
WO1995000678A1 (fr) * 1993-06-25 1995-01-05 Zipperling Kessler & Co (Gmbh & Co) Procede de production de materiaux metalliques anticorrosion et materiaux ainsi produits
FR2714077A1 (fr) * 1993-12-21 1995-06-23 Lorraine Laminage Procédé et bain de dépôt électrolytique de polypyrrole sur une surface de métal oxydable par électropolymérisation.
EP0659794A1 (fr) * 1993-12-21 1995-06-28 Sollac Procédé et bain de dépôt électrolytique de polypyrrole sur une surface de métal oxydable par électropolymérisation
US5522981A (en) * 1993-12-21 1996-06-04 Sollac Process and bath for the electrolytic deposition of polypyrrole on an oxidizable metal surface by electro-polymerization
US7601280B2 (en) 2002-06-04 2009-10-13 Lumimove, Inc. A Missouri Corporation Corrosion-responsive coating formulations for protection of metal surfaces
DE102004037542A1 (de) * 2004-08-03 2006-02-23 Chemetall Gmbh Verfahren zum Schützen einer metallischen Oberfläche mit einer korrosionsinhibierenden Beschichtung
CN103304784A (zh) * 2013-06-26 2013-09-18 华东理工大学 一种防腐涂料用易分散聚噻吩的制备方法
RU2722533C1 (ru) * 2019-05-28 2020-06-01 Михаил Леонидович Галкин Клатратный ингибитор коррозии

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