EP0000107B1 - Metallic or metallised article coated with a polyphenylene oxide film carrying reactive groups, its electrochemical preparation and its use - Google Patents

Metallic or metallised article coated with a polyphenylene oxide film carrying reactive groups, its electrochemical preparation and its use Download PDF

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Publication number
EP0000107B1
EP0000107B1 EP78400001A EP78400001A EP0000107B1 EP 0000107 B1 EP0000107 B1 EP 0000107B1 EP 78400001 A EP78400001 A EP 78400001A EP 78400001 A EP78400001 A EP 78400001A EP 0000107 B1 EP0000107 B1 EP 0000107B1
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Prior art keywords
metallised
metallic
film
polyphenylene oxide
formula
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German (de)
French (fr)
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EP0000107A1 (en
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Jacques Emile Dubois
Minh-Chau Pham
Pierre Camille Lacaze
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Bpifrance Financement SA
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Agence National de Valorisation de la Recherche ANVAR
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to polyphenylene oxide films comprising reactive groups and their preparation by electrochemical means.
  • the invention relates more particularly to new polymers comprising reactive chemical groups and which are prepared electrolytically and deposited in the form of films on metal surfaces.
  • the object of the present invention is to carry out, by the electrolytic polymerization process mentioned above, the synthesis of reactive polymers which is characterized by the presence, in each link of their chain, of functional groups capable of reacting according to a chemical reaction specific.
  • the invention relates more particularly to the polymer films obtained from monomers of formula (I) in which - (CH 2 ) n ⁇ R represents a formyl, acetyl, propionyl, benzoyl, 3-oxo butyl, hydroxymethyl, carboxymethyl aminoethyl or anilinomethyl.
  • the polymers of the invention therefore have as reactive functional group a carbonyl, hydroxy, carboxy or amino group per unit.
  • the polymer films are prepared by anodic oxidation of the monomeric phenols (I) in an alcoholic and strongly basic electrolytic bath.
  • the polymers formed are deposited directly on the anode, where appropriate a conductive substrate - or made conductive - which it is desired to coat with a thin layer of polymer.
  • the alcohols usable for the bath are lower alcohols, such as methanol, ethanol, propanol or isopropanol, or a mixture of lower alcohol and polyol such as glycol or glycerol.
  • the strong bases can be, for example, sodium or potassium hydroxide, or else sodium amide. Their concentration can be from 0.05 to 1 M, preferably 0.1 to 0.3 M to ensure the smooth running of the electrolysis.
  • the monomeric phenol is used at concentrations of at least 6 g / l of electrolyte, preferably from 12 to 25 g / l.
  • the anode or the conductive substrate to be covered by the polymer of the invention can consist of most common metals such as iron, silver, nickel, chromium, copper, gold, platinum , etc., or their alloys.
  • the electrolysis is carried out in a tank (for example made of steel) in the usual way at room temperature with an initial output voltage of the generator of the order of 10 Volt and an initial current density of 0.1 to 1 A / dm 2 .
  • the polymer film quickly forms on the surface of the anode (or of the substrate) and a total covering, generally obtained between 5 to 30 minutes, can be detected when the current becomes very weak.
  • the substrate coated with the polymer film is washed with water and then with alcohol in order to remove the residual traces of base, of phenol monomer and of any secondary products.
  • the polymer films obtained according to the invention are homogeneous, continuous, uniform. thin (300 to 3500 A depending on the polymer) insoluble in water and alcohols, very adherent and hydrophilic depending on the reactive group they contain.
  • Electrolysis of a solution of 0.62 g (0.1 M) of metahydroxybenzyl alcohol and 0.6 g of sodium hydroxide (0.3 M) in 50 cm 3 of methyl alcohol is carried out using as solid copper anode before a surface of 12 cm 2 .
  • a potential difference ⁇ V 0.94 volts is applied relative to a saturated calomel electrode (DHW).
  • a film having a thickness of 2500 A is obtained, measured with a Tolansky interference device mounted on a Leitz metalloplan microscope.
  • the polymer films were treated with characteristic chemical agents to verify the presence and reactivity of the functional chemical groups.
  • the polymers comprising the carbonyl group were treated with an ethanolic solution of 1% of 2,4-dinitro-phenyl-hydrazine (2,4 DNPH) and of 2% of concentrated HCl; the electrodes were soaked for 5 minutes in this boiling solution and then washed in ethanol by ultrasonic stirring.
  • the polymers comprising the hydroxy or amino group have been treated with acetyl chloride.
  • the polymer films of the invention as well as the films treated with the chemical agents were identified by multiple-reflection IR spectroscopy and / or by ESCA (Electron Spectroscopy for Chemical Analysis).
  • the polymer films of the invention can be used for the grafting of various materials reacting on these functions.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Description

La présente invention a pour objet des films d'oxydes de polyphénylène comportant des groupes réactifs et leur préparation par voie électrochimique.The present invention relates to polyphenylene oxide films comprising reactive groups and their preparation by electrochemical means.

L'invention concerne plus particulièrement de nouveaux polymères comportant des groupes chimiques _réactifs et qui sont préparés par voie électrolytique et déposés sous forme de films sur des surface métalliques.The invention relates more particularly to new polymers comprising reactive chemical groups and which are prepared electrolytically and deposited in the form of films on metal surfaces.

La polymérisation par oxydation électrolytique du phénol et de certains de ses dérivés ainsi que le dépôt sur des surfaces métalliques des films polymères obtenus sont connus d'après le brevet des Etats-Unis d'Amérique N° 2.961.384. Par ailleurs, l'obtention de films polymères à partir de phénols disubstitués en positions 2 et 6 et leur dépôt électrolytique sur des métaux tels que le fer, le cuivre et le nickel sont décrits dans le brevet francais N° 74.16158. Ces couches polymères sont très adhérentes, hydrophobes et uniformes et trouvent leur application dans la protection des métaux.The polymerization by electrolytic oxidation of phenol and some of its derivatives as well as the deposition on metal surfaces of the polymer films obtained are known from United States patent No. 2,961,384. Furthermore, the production of polymer films from phenols disubstituted in positions 2 and 6 and their electrolytic deposition on metals such as iron, copper and nickel are described in French patent No. 74.16158. These polymer layers are very adherent, hydrophobic and uniform and find their application in the protection of metals.

Bien entendu, les divers polymères ainsi obtenus ne comportent pas de groupes réactifs. Certains auteurs ont cependant réussi à introduire des groupes chimiques réactifs dans des films polymères par des méthodes physiques élaborées. Dans un tel cas, des groupes carbonyles ont été introduits sur le surface du polymère (polypropylène) par action de l'oxygène après une irradiation de la surface par UV ou électrons (K. KATO, J. of Applied Polymer Science, 19 (1975), p. 951­-957). On a également pu introduire des groupes NH2 par le procédé de la décharge électrique. (J. R. Hollahan et Coll. J. Appl. Polym. Science, 13, (1969), p. 807). Les rares groupes réactifs ainsi introduits dans les films sont distribués au hasard et par ailleurs les films ont tendance à vieillir en raison du grand nombre d'espèces radicalaires piégées (M. MILLARD, Synthesis of Organic Polymer Films in Plasmas, Chap. V. p. 177, dans technics and Application of Plasma Chemistry. J. H. HOLLAHAN et A. T. BELL, 1974, J. WILEY).Of course, the various polymers thus obtained do not contain reactive groups. Some authors have however succeeded in introducing reactive chemical groups into polymer films by sophisticated physical methods. In such a case, carbonyl groups have been introduced onto the surface of the polymer (polypropylene) by the action of oxygen after irradiation of the surface by UV or electrons (K. KATO, J. of Applied Polymer Science, 19 (1975). ), pp. 951-957). It was also possible to introduce NH 2 groups by the method of electric discharge. (JR Hollahan and Coll. J. Appl. Polym. Science, 13, (1969), p. 807). The rare reactive groups thus introduced into the films are distributed at random and in addition the films tend to age due to the large number of radical species trapped (M. MILLARD, Synthesis of Organic Polymer Films in Plasmas, Chap. V. p 177, in technics and Application of Plasma Chemistry, JH HOLLAHAN and AT BELL, 1974, J. WILEY).

Le but de la présente invention est de réaliser, par le procédé de polymérisation électrolytique mentionné ci-dessus, la synthèse de polymères réactifs qui se caractérise par la présence, dans chaque maillon de leur chaîne, de groupes fonctionnels capables de réagir selon une réaction chimique spécifique.The object of the present invention is to carry out, by the electrolytic polymerization process mentioned above, the synthesis of reactive polymers which is characterized by the presence, in each link of their chain, of functional groups capable of reacting according to a chemical reaction specific.

Les films polymères de l'invention sont obtenus à partir de phénols répondant à la formule

Figure imgb0001
dans laquelle

  • R représente un groupe acyle de 1 à 7 atoms de carbone, un groupe hydroxy, carboxy, alcoxycarbonyle, amino, alkylamino ou phénylamino, et
  • n est un nombre entier, qui peut être nul dans le cas où R rest un groupe acyle.
The polymer films of the invention are obtained from phenols corresponding to the formula
Figure imgb0001
 in which
  • R represents an acyl group of 1 to 7 carbon atoms, a hydroxy, carboxy, alkoxycarbonyl, amino, alkylamino or phenylamino group, and
  • n is an integer, which can be zero in the case where R remains an acyl group.

L'invention concerne plus particulièrement les films polymères obtenus à partir de monomères de formule (I) dans laquelle ―(CH2)n―R représente un groupe formyle, acétyle, propionyle, benzoyle, oxo-3 butyle, hydroxyméthyle, carboxyméthyle aminoéthyle ou anilinométhyle.The invention relates more particularly to the polymer films obtained from monomers of formula (I) in which - (CH 2 ) n ―R represents a formyl, acetyl, propionyl, benzoyl, 3-oxo butyl, hydroxymethyl, carboxymethyl aminoethyl or anilinomethyl.

Les polymères de l'invention comportent donc comme groupe fonctionnel réactif un groupe carbonyle, hydroxy, carboxy ou amino par motif.The polymers of the invention therefore have as reactive functional group a carbonyl, hydroxy, carboxy or amino group per unit.

Selon l'invention les films polymères sont préparés par oxydation anodique des phénols monomères (I) dans un bain électrolytique alcoolique et fortement basique. Les polymères formés se déposent directement sur l'anode, le cas échéant un substrat conducteur - ou rendu conducteur - que l'on désire revêtir d'une mince couche de polymère.According to the invention, the polymer films are prepared by anodic oxidation of the monomeric phenols (I) in an alcoholic and strongly basic electrolytic bath. The polymers formed are deposited directly on the anode, where appropriate a conductive substrate - or made conductive - which it is desired to coat with a thin layer of polymer.

Les alcools utilisables pour le bain sont des alcools inférieurs, tels que le méthanol, éthanol, propanol ou isopropanol, ou un mélange d'alcool inférieur et de polyol tel que le glycol ou le glycérol.The alcohols usable for the bath are lower alcohols, such as methanol, ethanol, propanol or isopropanol, or a mixture of lower alcohol and polyol such as glycol or glycerol.

Les bases fortes peuvent être par exemple l'hydroxyde de sodium ou de potassium, ou bien l'amidure de sodium. Leur concentration peut être de 0,05 à 1 M, de préférence 0,1 à 0,3 M pour assurer le bon déroulement de l'électrolyse.The strong bases can be, for example, sodium or potassium hydroxide, or else sodium amide. Their concentration can be from 0.05 to 1 M, preferably 0.1 to 0.3 M to ensure the smooth running of the electrolysis.

Le phénol monomère est utilisé à des concentrations d'au moins 6 g/I d'électrolyte, de préférence de 12 à 25 g/I.The monomeric phenol is used at concentrations of at least 6 g / l of electrolyte, preferably from 12 to 25 g / l.

Par ailleurs il est recommandé de prévoir environ 3 g de monomère par dm2 de substrat à revêtir.Furthermore, it is recommended to provide approximately 3 g of monomer per dm 2 of substrate to be coated.

L'anode ou le substrat conducteur devant être recouvert par le polymère de l'invention peut être constitué par la plupart des métaux courants tels que le fer, l'argent, le nickel, le chrome, le cuivre, l'or, le platine, etc., ou leurs alliages.The anode or the conductive substrate to be covered by the polymer of the invention can consist of most common metals such as iron, silver, nickel, chromium, copper, gold, platinum , etc., or their alloys.

L'électrolyse est effectuée dans une cuve (par exemple en acier) de manière habituelle à température ambiante avec une tension de sortie initiale du générateur de l'ordre de 10 Volt et ne densité de courant initiale de 0,1 à 1 A/dm2. Le film polymère se forme rapidement sur la surface de l'anode (ou du substrat) et un recouvrement total, obtenu en général entre 5 à 30 minutes, peut être décelé lorsque le courant devient très faible.The electrolysis is carried out in a tank (for example made of steel) in the usual way at room temperature with an initial output voltage of the generator of the order of 10 Volt and an initial current density of 0.1 to 1 A / dm 2 . The polymer film quickly forms on the surface of the anode (or of the substrate) and a total covering, generally obtained between 5 to 30 minutes, can be detected when the current becomes very weak.

Après l'électrolyse, le substrat revêtu du film polymère est lavé à l'eau puis à l'alcool afin d'éliminer les traces résiduelles de base, de phénol monomère et des produits secondaires éventuels.After the electrolysis, the substrate coated with the polymer film is washed with water and then with alcohol in order to remove the residual traces of base, of phenol monomer and of any secondary products.

Les films polymères obtenus selon l'invention sont homogènes, continus, uniformes. de faible épaisseur (300 à 3500 A selon le polymère) insolubles dans l'eau et les alcools, très adhérents et hydrophiles selon le groupe réactif qu'ils comportent.The polymer films obtained according to the invention are homogeneous, continuous, uniform. thin (300 to 3500 A depending on the polymer) insoluble in water and alcohols, very adherent and hydrophilic depending on the reactive group they contain.

Les exemples suivants illustrent l'invention.The following examples illustrate the invention.

Exemple 1Example 1 Polymère de l'alcool métahydroxybenzylique ou poly(oxyde de hydroxyméthyl-2 phénylène-1,4)Polymer of metahydroxybenzyl alcohol or poly (2-hydroxymethyl-1,4-phenylene oxide)

On effecture l'électrolyse d'une solution de 0,62 g (0,1 M) d'alcool métahydroxybenzylique et 0,6 g d'hydroxyde de sodium (0,3 M) dans 50 cm3 d'alcool méthylique en utilisant comme anode du cuivre massif avant une surface de 12 cm2. On applique une différence de potentiel ΔV = 0,94 volt par rapport à une électrode de calomel saturé (ECS). La densité de courant est initialement i, = 2 mA/cm2 et tombe à if= 0,5 mA/cm2 au bout de t = 40 minutes.Electrolysis of a solution of 0.62 g (0.1 M) of metahydroxybenzyl alcohol and 0.6 g of sodium hydroxide (0.3 M) in 50 cm 3 of methyl alcohol is carried out using as solid copper anode before a surface of 12 cm 2 . A potential difference ΔV = 0.94 volts is applied relative to a saturated calomel electrode (DHW). The current density is initially i, = 2 mA / cm 2 and drops to i f = 0.5 mA / cm 2 after t = 40 minutes.

On obtient un film ayant une épaisseur de 2500 A mesuré avec un appareil interférentiel Tolansky monté sur un microscope métalloplan Leitz.A film having a thickness of 2500 A is obtained, measured with a Tolansky interference device mounted on a Leitz metalloplan microscope.

Exemple 2Example 2 Polymère de l'acide o-hydroxyphénylacétique ou poly(oxyde de carboxyméthyl-2 phénylène-1,4)Polymer of o-hydroxyphenylacetic acid or poly (2-carboxymethyl-1,4-phenylene oxide)

De la même manière que dans l'exemple 1, on effectue l'électrolyse d'une solution de 0,76 g (0,1 M) d'acide salicylique et 0,6 g de NaOH dans 50 cm3 d'alcool méthylique, en utilisant comme anode un miroir de fer (fer évaporé sur une plaque de verre) et en appliquant une tension de ΔV = 0,85 V/ECS

Figure imgb0002
On obtient un film polymère ayant 1200 A d'épaisseur.In the same way as in Example 1, the electrolysis of a solution of 0.76 g (0.1 M) of salicylic acid and 0.6 g of NaOH in 50 cm 3 of methyl alcohol is carried out. , using an iron mirror as anode (iron evaporated on a glass plate) and applying a voltage of ΔV = 0.85 V / DHW
Figure imgb0002
 A polymer film having 1200 A thickness is obtained.

Exemple 3Example 3 Polymère de la p-hydroxyphényl-2 éthylamine ou poly(oxyde d'aminoéthyl-4 phénylène-1,2)Polymer of p-hydroxyphenyl-2 ethylamine or poly (4-aminoethyl-1,2-phenylene oxide)

  • a) De la même manière que dans l'exemple 1, on effectue l'électrolyse d'une solution méthanolique (50 cm3) de 0,68 g de parahydroxyphényl-2 éthylamine (Tyramine) et de 0,6 g de NaOH en utilisant une anode en cuivre massif de 18 cm2. ΔV=0,5 V/ECS.
    Figure imgb0003
    Le film obtenu a 2500 A d'épaisseur.    a) In the same way as in Example 1, electrolysis is carried out of a methanolic solution (50 cm 3 ) of 0.68 g of 2-parahydroxyphenyl ethylamine (Tyramine) and of 0.6 g of NaOH in using an 18 cm 2 solid copper anode. ΔV = 0.5 V / DHW.
    Figure imgb0003
    The film obtained is 2500 A thick.
  • b) On a répété l'expérience ci-dessus en remplacant l'anode cuivre par un miroir de fer de 8,8 cm2. ΔV = 0,9 V/ECS.
    Figure imgb0004
    b) The above experiment was repeated, replacing the copper anode with an 8.8 cm 2 iron mirror. ΔV = 0.9 V / DHW.
    Figure imgb0004
Exemple 4Example 4 Polymère de N-o-hydroxybenzyl-aniline ou poly(oxyde d'anilino-méthyl-2 phénylène-1,4)Polymer of N-o-hydroxybenzyl-aniline or poly (anilino-methyl-2-phenylene-1,4-oxide)

  • a) On a effectué l'électrolyse de la même manière que dans les exemples précédents mais en faisant varier la différence de potentiel ΔV de 0 à 1,3 V/ECS et en utilisant un miroir de fer de 9 cm2.
    Figure imgb0005
    Epaisseur du film: 3000 A    a) The electrolysis was carried out in the same way as in the previous examples but by varying the potential difference ΔV from 0 to 1.3 V / ECS and using an iron mirror of 9 cm2.
    Figure imgb0005
    Film thickness: 3000 A
  • b) On a répété l'expérience avec du fer massif (7 cm2) et tension constante.
    Figure imgb0006
    b) The experiment was repeated with solid iron (7 cm 2 ) and constant tension.
    Figure imgb0006
Exemple 5Example 5 Polymère de p-hydroxyphényl-4 butanone-24-p-hydroxyphenyl-butanone-2 polymer

  • a) De la même manière que dans les exemples 1 à 3, on effectue l'électrolyse de 0,82 g (0,1 M) de p-hydroxyphényl-4 butanone-2 en utilisant une anode de fer massif de 5 cm2.
    Figure imgb0007
    épaisseur du film: 3 500 A.    a) In the same way as in Examples 1 to 3, the electrolysis of 0.82 g (0.1 M) of p-hydroxyphenyl-4 butanone-2 is carried out using a 5 cm 2 solid iron anode. .
    Figure imgb0007
    film thickness: 3,500 A.
  • b) On utilise une anode d'acier de 10 cm2.
    Figure imgb0008
    b) A 10 cm 2 steel anode is used.
    Figure imgb0008
  • c) On utilise une anode en titane massif de 16 cm2.
    Figure imgb0009
    c) A solid titanium anode of 16 cm 2 is used .
    Figure imgb0009

Dans le tableau 1 suivant sont rassemblés, en plus des exemples précédents, divers phénols substitués qui ont été polymérisés selon l'invention. Toutes les polymérisations ont été suivies in situ par polaromicrotribométrie (PMT) qui permet de détecter les modifications physicochimiques sur la surface métallique (voir par exemple J. E. DUBOIS, P. C. LACAZE, R. COURTEL, C. C. HERMANN, D. MAUGIS, J. of Electrochem. Soc., 122, (1975) p 1454).

Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
 In Table 1 below are collected, in addition to the preceding examples, various substituted phenols which have been polymerized according to the invention. All the polymerizations were followed in situ by polaromicrotribometry (PMT) which makes it possible to detect the physicochemical modifications on the metal surface (see for example JE DUBOIS, PC LACAZE, R. COURTEL, CC HERMANN, D. MAUGIS, J. of Electrochem. Soc., 122, (1975) p 1454).
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013

Les films polymères ont été traités par des agents chimiques caractéristiques pour la vérification de la présence et de la réactivité des groupes chimiques fonctionnels. Les polymères comportant le groupe carbonyle ont été traités par une solution éthanolique de 1 % de dinitro-2,4 phényl-hydrazine (2,4 DNPH) et de 2 % HCI concentré; les électrodes étaient trempées pendant 5 minutes dans cette solution à l'ébullition puis lavées dans de l'éthanol par agitation ultrasonique. Les polymères comportant le groupe hydroxy ou amino ont été traités par du chlorure d'acétyle.The polymer films were treated with characteristic chemical agents to verify the presence and reactivity of the functional chemical groups. The polymers comprising the carbonyl group were treated with an ethanolic solution of 1% of 2,4-dinitro-phenyl-hydrazine (2,4 DNPH) and of 2% of concentrated HCl; the electrodes were soaked for 5 minutes in this boiling solution and then washed in ethanol by ultrasonic stirring. The polymers comprising the hydroxy or amino group have been treated with acetyl chloride.

Les films polymères de l'invention ainsi que les films traités par les agents chimiques ont été identifiés par spectroscopie IR à réflexions multiples et/ou par ESCA (Electron Spectroscopy for Chemical Analysis).The polymer films of the invention as well as the films treated with the chemical agents were identified by multiple-reflection IR spectroscopy and / or by ESCA (Electron Spectroscopy for Chemical Analysis).

Dans le tableau Il suivant sont indiqués les pics caractéristiques des groupes chimiques pour des polymères dont les spectres IR sont bien résolus, tandis que des résultats obtenus en ESCA seront donnés dans le tableau III pour les autres.In Table II below are indicated the characteristic peaks of the chemical groups for polymers whose IR spectra are well resolved, while results obtained in ESCA will be given in Table III for the others.

Dans tous les spectres IR obtenus, la bande correspondant au groupe OH phénolique est complètement absente; par contre le pic caractérisant le groupe polyoxyde apparaît aux environs de 1200 cm-1. La présence de très intenses bandes d'absorption C=O, correspondant soit à la fonction aldéhyde (1700 cm-1) soit cétone (1680 cm-1) prouve que ces groupes restent inattaqués durant l'électrolyse.

Figure imgb0014
Figure imgb0015
 In all the IR spectra obtained, the band corresponding to the phenolic OH group is completely absent; on the other hand, the peak characterizing the polyoxide group appears around 1200 cm -1 . The presence of very intense absorption bands C = O, corresponding either to the aldehyde function (1700 cm -1 ) or ketone (1680 cm -1 ) proves that these groups remain unaffected during electrolysis.
Figure imgb0014
Figure imgb0015

L'analyse ESCA des anodes confirme aussi la présence des polymères sur leur surface. Les spectres C1s mettent en évidence les groupes chimiques distincts par les valeurs des énergies de liaison caractéristiques. On obtient les mêmes résultats pour les dérivés ortho, méta ou para.

Figure imgb0016
ESCA analysis of the anodes also confirms the presence of polymers on their surface. The C 1s spectra show the distinct chemical groups by the values of the characteristic bond energies. The same results are obtained for the ortho, meta or para derivatives.
Figure imgb0016

Compte tenu de la présence d'un groupe chimique réactif sur toute la surface les films polymères de l'invention peuvent être utilisés pour le greffage de diverses matières réagissant sur ces fonctions.Given the presence of a reactive chemical group over the entire surface, the polymer films of the invention can be used for the grafting of various materials reacting on these functions.

Ainsi il est possible de fixer des enzymes ou bien de faire réagir d'autres composés comportant des groupes réactifs, par exemple des chlorures ou anhydrides d'acides sur les films polymères portant un groupe hydroxy ou amine (ce qui permet d'obtenir une surface de poly-ester et respectivement polyamide). Cette propriété permet l'utilisation des films polymères de l'invention comme couches intermédiaires pour la fixation des résines, laques et peintures, notamment sur les métaux auxquels celles-ci adhèrent très mal.Thus it is possible to fix enzymes or else to react other compounds comprising reactive groups, for example chlorides or acid anhydrides on polymer films carrying a hydroxy or amine group (which makes it possible to obtain a surface polyester and polyamide respectively). This property allows the use of the polymer films of the invention as intermediate layers for fixing resins, lacquers and paints, especially on metals to which they adhere very poorly.

Claims (15)

1. Metallic or metallised object coated with a film of polyphenylene oxide, characterised by the fact that the said film consists of substituted oxyphenylene units of the formula I':
Figure imgb0039
in which:
R denotes an acyl group containing 1 to 7 carbon atoms, a hydroxy, carboxy, alkoxy carbonyl, amino, alkylamino or phenylamino group, and
n is an integer which may be zero in the case where R is an acyl group.
2. An object according to claim 1, characterised by the fact that in the oxyphenylene units of the, formula I', the -(CH2),f-R group denotes a formyl, acetyl, propionyl, benzoyl, 3-oxobutyl, hydroxymethyl, carboxymethyl, aminoethyl or aniline methyl group.
3. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0040
4. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0041
5. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0042
6. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0043
7. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0044
8. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0045
9. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0046
10. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0047
11. A metallic or metallised object coated with a film of polyphenylene oxide consisting of units of the formula:
Figure imgb0048
12. A process for preparing electrolytically a metallic or metallised object coated with a film of polyphenylene oxide such as defined in claim 1, said process characterised in that an anodic oxidation of phenols of formula I
Figure imgb0049
in which the symbols R and n have the same meaning as in claim 1, is carried out in an alcoholic and strongly basic electrolysis bath, the metallic or metallised object serving as the anode.
13. Application of metallic or metallised objects coated with a film of polyphenylene oxide according to any of claims 1 to 11 in the fixing of enzymes.
14. Application of metallic or metallised objects coated with a film of polyphenylene oxide according to any of claims 1 to 11 in the grafting of resins.
15. Application of metallic or metallised objects coated with a film of polyphenylene oxide according to any of claims 1 to 11 in the fixing of lacquers or paints.
EP78400001A 1977-06-10 1978-06-01 Metallic or metallised article coated with a polyphenylene oxide film carrying reactive groups, its electrochemical preparation and its use Expired EP0000107B1 (en)

Applications Claiming Priority (2)

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FR7717851 1977-06-10
FR777717851A FR2393835A1 (en) 1977-06-10 1977-06-10 POLYPHENYLENE OXIDE FILMS CONTAINING REAGENT GROUPS AND THEIR PREPARATION BY ELECTROCHEMICAL METHODS

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EP0000107A1 EP0000107A1 (en) 1978-12-20
EP0000107B1 true EP0000107B1 (en) 1980-07-23

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US4488943A (en) * 1980-11-18 1984-12-18 The United States Of America As Represented By The United States Department Of Energy Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends
US4563263A (en) * 1982-01-15 1986-01-07 Terumo Corporation Selectively permeable film and ion sensor
US4444627A (en) * 1982-02-25 1984-04-24 Formosa Plastics Corporation Prevention of polymer buildup in polymerization reactors using thin organic coatings by electrolysis of phenol
US4432840A (en) * 1982-04-26 1984-02-21 Formosa Plastics Corporation Prevention of polymer buildup in polymerization reactors using thin organic coatings by electrolysis of phenol
US4820790A (en) * 1987-03-13 1989-04-11 Amoco Corporation Chain-extended poly(aryl ether ketones)
DE3816458A1 (en) * 1988-05-13 1989-12-21 Josowicz Mira ULTRAMICROELECTRODE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
DE4128569C1 (en) * 1991-08-28 1992-12-24 Mira Dr.Rer.Nat. Josowicz
GB2262524A (en) * 1991-12-18 1993-06-23 Sandoz Ltd Pharmaceutically active 2-hydroxy-benzylamines
US5739864A (en) * 1994-08-24 1998-04-14 Macrovision Corporation Apparatus for inserting blanked formatted fingerprint data (source ID, time/date) in to a video signal

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US2961384A (en) * 1956-12-27 1960-11-22 American Marietta Co Electrolytic polymerization of phenol
US3226361A (en) * 1961-11-29 1965-12-28 Gen Electric Functional aromatic substituents in polyphenylene oxides
SE350519B (en) * 1967-03-28 1972-10-30 Sumitomo Chemical Co
NL6810338A (en) * 1968-07-19 1970-01-21
US3681285A (en) * 1971-02-24 1972-08-01 Basf Ag Manufacture of colorless high molecular polyphenylene ethers
FR2270338A1 (en) * 1974-05-10 1975-12-05 Anvar Electrolytic coating of conductive substrates - using electrolytic bath contg. 2,6-substd phenol dissolved in e.g. alcohol
US4129555A (en) * 1977-03-23 1978-12-12 General Electric Company Poly-phenylene oxide process employing aminophenol reactants

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DE2860042D1 (en) 1980-11-13
EP0000107A1 (en) 1978-12-20
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FR2393835B1 (en) 1980-02-29
FR2393835A1 (en) 1979-01-05
US4334054A (en) 1982-06-08

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