WO2008031781A2 - Utilisation de polymères comprenant des groupes ammonium quaternaire et des groupes urée en tant qu'inhibiteurs de corrosion pour des surfaces de cuivre - Google Patents

Utilisation de polymères comprenant des groupes ammonium quaternaire et des groupes urée en tant qu'inhibiteurs de corrosion pour des surfaces de cuivre Download PDF

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WO2008031781A2
WO2008031781A2 PCT/EP2007/059438 EP2007059438W WO2008031781A2 WO 2008031781 A2 WO2008031781 A2 WO 2008031781A2 EP 2007059438 W EP2007059438 W EP 2007059438W WO 2008031781 A2 WO2008031781 A2 WO 2008031781A2
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groups
copper
atoms
polymer
polymers
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PCT/EP2007/059438
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German (de)
English (en)
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WO2008031781A3 (fr
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Frank Dietsche
Ralf Friedrich
Thomas Heidenfelder
Helmut Witteler
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Basf Se
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    • 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
    • C23F11/173—Macromolecular compounds
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C08G73/0293—Quaternisation of polyamidoamines
    • 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
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/4469—Phenoplasts; Aminoplasts
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper

Definitions

  • the present invention relates to a method for protecting the surfaces of copper or copper alloys from corrosion, in which the metallic surface is brought into contact with an aqueous medium containing as corrosion inhibitor a quaternary ammonium groups and urea groups, thiourea groups and / or imino urea groups in the numerical ratio Containing 1, 5: 1 to 2.5: 1 comprising polymer.
  • Articles and workpieces of copper and copper alloys often tend to tarnish under conditions of use, i. for the formation of colored corrosion layers, such as, for example, oxide, hydroxide and / or carbonate layers on the surface. Even if such layers do not necessarily result in the destruction of the workpiece, they are often undesirable for aesthetic reasons. Even very thin corrosion layers u.U. significantly reduce the electrical conductivity, which can be very disadvantageous for applications of copper in the field of electrical engineering and in particular electronics.
  • Corrosion inhibitors for preventing or at least containing corrosion are known in principle. They often act specifically only for one kind of metals, i. Good corrosion inhibitors for ferrous metals need not necessarily be good corrosion inhibitors for copper or copper alloys.
  • Benzotriazoles have limited solubility in water.
  • the solubility of 1-H-benzotriazole in water at room temperature and pH 7 is only about 20 g / l.
  • Tolyltriazole has a solubility of less than 10 g / l at RT in water.
  • EP 243 780 A2 discloses polymers comprising urea groups and quaternary ammonium groups, a process for preparing such polymers and their use in detergents, hair shampoos and for the treatment of textiles. Such polymers are commercially available.
  • US 3,982,894 discloses a method for corrosion protection of metals, in particular iron, in which polymers with quaternary ammonium groups are used.
  • the polymers are polycondensation products of mono- and / or polyamines with various organic dichlorides or epichlorohydrins.
  • the polymers have no urea groups.
  • US Pat. No. 6,448,211 B1 discloses a method for passivating iron over surfaces, in which a composition is used which comprises gluconic acid and the urea group-comprising cationic polymer poly (oxy-1,2-ethanediyl (dimethylimino) -1,3-propanediyliminocarbonylimino 1, 3-propanediyl (dimethylimino) -1, 2-ethanediyl dichloride).
  • EP 1 069 21 1 A2 discloses a copper plating bath comprising at least one acid, a copper salt, a sulfur-containing organic brightener and an organic compound intended to ensure a uniform surface.
  • the latter compound may also be polymers comprising quaternary ammonium groups and urea groups.
  • EP 1 201 789 A2 discloses a plating bath for depositing Sn-Zn alloys using polymers which have quaternary ammonium groups and also urea groups, thiourea groups or imino urea groups.
  • the object of the invention was to provide a method for protecting copper from corrosion, in particular when in contact with aqueous media, in which very good water-soluble, salt-stable and readily biodegradable polymers are used.
  • a method for protecting the surfaces of copper or copper alloys from corrosion in which the metallic surface is contacted with an aqueous medium comprising at least one water-soluble corrosion inhibitor, the water-soluble corrosion inhibitor being a polymer P which quaternary ammonium groups and urea groups, thiourea groups and / or imino urea groups in the numerical ratio from 1, 5: 1 to 2.5: 1, provided that the solubility of the polymer P in water is at least 50 g / l.
  • the polymer comprises P structural units of the following formula (I)
  • R 1 independently of one another an aliphatic, straight-chain, branched or cyclic hydrocarbon group having 1 to 30 C atoms, wherein the hydrocarbon groups may also have substituents and / or non-terminal non-terminal carbon atoms in the hydrocarbon groups by N- and / or O atoms can be substituted;
  • R 2 independently of one another an aliphatic and / or aromatic, straight-chain, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, wherein the hydrocarbon radicals may also have substituents and / or non-adjacent non-terminal carbon atoms in the hydrocarbon groups N and / or O atoms may be substituted;
  • X " monovalent anions or polyvalent anions 1 / p YP-, where Y represents a p-valent anion.
  • the surfaces of copper or copper alloys can be protected from corrosion.
  • Other metals in copper alloys may be, for example, one or more of Zn, Sn, Pb, Al, Si, Mn, Ni, Fe or Cr.
  • typical alloys include brass or bronze.
  • the invention is not limited to alloys with certain copper levels.
  • Al-Cu alloys with a copper content of less than 10% by weight can also be protected by means of the method according to the invention.
  • Such alloys are used, for example, in dishwashers. They can be the surfaces of arbitrary bodies of copper or copper alloys, for example sheets, foils or pipes. These do not have to be surfaces that consist exclusively of copper, but they can also be surfaces in which only parts made of copper or copper alloys exist. As an example, be called circuit boards.
  • the copper surface is brought into contact with an aqueous formulation or an aqueous medium which comprises at least one polymer P.
  • an aqueous formulation or an aqueous medium which comprises at least one polymer P.
  • polymers P can be used.
  • the polymer P to be used is a cationic polymer which comprises quaternary ammonium groups and urea groups which are linked to one another by means of suitable groups.
  • the urea groups may also be thioan groups and / or imino urea groups.
  • the numerical ratio of quaternary ammonium groups to urea groups in the polymer is preferably from 1.5: 1 to 2.5: 1, preferably from 1.8: 1 to 2.2: 1 and more preferably about 2: 1.
  • the linking groups are preferably groups which contain alkylene groups, oxyalkylene groups and / or OH groups. Such polymers and their preparation are in principle known to the person skilled in the art, e.g. from EP 243 780 A2.
  • polymer P is a polymer which comprises structural units of the following formula (I):
  • the radicals R 1 independently of one another are aliphatic, straight-chain, branched or cyclic hydrocarbon groups having 1 to 30 C atoms, preferably 2 to 20 C atoms and particularly preferably 2 to 10 C atoms.
  • the radicals R 1 may be different or preferably the same.
  • the hydrocarbon radicals can also have substituents, in particular those which have N and / or O atoms, and furthermore non-adjacent non-terminal C atoms in the hydrocarbon radicals can also be substituted by N and / or O atoms. It is preferably unsubstituted hydrocarbon radicals.
  • the hydrocarbon radicals are preferably linear 1, ⁇ -alkylene groups of the general formula - (CH 2 ) n -, where n is a natural number of 2 to 10, preferably 2 to 6. Particularly preferred is a 1, 3-propylene radical -CH 2 -CH 2 -CH 2 -.
  • the radicals R 2 are, independently of one another, aliphatic and / or aromatic, straight-chain, branched or cyclic hydrocarbon groups having 1 to 30 C atoms, preferably 2 to 20 C atoms and particularly preferably 2 to 10 C atoms.
  • the radicals R 2 may be different or preferably the same.
  • the hydrocarbon radicals may also have substituents, in particular those which have N and / or O atoms, preference is given to OH groups as substituents.
  • non-adjacent non-terminal C atoms in the hydrocarbon radicals can also be substituted by N and / or O atoms, preferably by O atoms.
  • Preferred radicals include linear 1, ⁇ -alkylene groups of the general formula - (CH 2 ) n -, where n is a natural number of 2 to 10, preferably 2 to 6, 1, ⁇ -Alkylenether phenomenon such as - (CH 2 ) m -O- (CH 2 ) m - or - (CH 2 ) m -O- (CH 2 ) m -O- (CH 2 ) m -, where m is 2, 3 or 4, simply OH-substituted alkylene groups such as -CH 2 -CH (OH) -CH 2 -, -CH (CH 2 OH) -CH 2 - or double OH-substituted alkylene groups such as -CH 2 -CH (OH) -R 3 -CH (OH) -CH 2 -, wherein R 3 is an aliphatic see and / or aromatic hydrocarbon radical having 1 to 20 C-atoms or an alkoxy radical of the general formula -
  • the polymer P may optionally also comprise further structural units. As a rule, however, at least 45%, preferably 60% and particularly preferably at least 80% of the molar mass M n of a given polymer (A) should consist of the structural units (I).
  • the anions X can be any monovalent anions, such as, for example, Ch, Br, -, CH 3 SO 3" or OH. "Monovalent anions can also be replaced by a corresponding number 1 / p of p-polyvalent ions YP-. , where p is the charge number of the anion.
  • the polymers P are obtainable by condensation of
  • At least one bifunctional compound (A2) selected from the group urea, thiourea, iminourea or dialkyl carbonates, wherein the molar ratio of the sum (A1) to (A2) is 1, 5: 1 to 2.1: 1,
  • At least one bifunctional compound (C) selected from the group of halomethyloxiranes, bisepoxides, alkylene dihalides and dihaloalkyl ethers,
  • Such polymers include structural units (I).
  • mono (N, N-dialkylaminoalkyl) amines (A1) which are used for the preparation of the amine (A), are in principle all known in the art mono (N, N-dialkylaminoalkyl) amines, wherein the individual alkyl fragments of these compounds optionally may carry further substituents.
  • mono (N, N-dialkylaminoalkyl) amines (A1) can be used.
  • (A1) is preferably mono (N, N-dialkylaminoalkyl) amines of the general formula (II)
  • R 5 , R 5 ' independently of one another are C 1 -C 6 -alkyl, preferably C 1 -C 4 -alkyl, which may also be substituted by OH; particularly preferably methyl; n is a natural number of 2 to 10, preferably 2 to 6.
  • N, N-dialkylaminoalkylamines of the formula (II) which carry the same alkyl radicals on the nitrogen atom.
  • the dimethylaminoalkylamines especially N, N-dimethylaminopropylamine, are again very particularly preferred.
  • the amines (A1) are condensed with bifunctional compounds (A2) selected from the group consisting of urea, thiourea, imino urea or dialkyl carbonates.
  • the bifunctional compound (A2) is urea.
  • the condensation can be carried out, for example, by reacting the components (A1) and (A2) in bulk at a temperature of 120 to 180 ° C.
  • the reaction of urea or urea derivatives with the amine (A1) produces ammonia, in the reaction of dialkyl carbonates of the corresponding alcohol.
  • the expulsion of ammonia or alcohols from the reaction mixture can be facilitated, for example, by passing nitrogen through the reaction mixture.
  • the molar ratio of the dialkylaminoalkylamine (A1) to the bifunctional compound (A2) is from 1.5: 1 to 2.1: 1, preferably from 1.7: 1 to 2.1: 1 and more preferably from 1.8: 1 to 2: 1 ,
  • the amines (A) or, as a rule, a mixture of different amines (A) are formed.
  • these are essentially diamines which have two terminal tertiary amino groups as well as condensation products which have a terminal tertiary amino group and a terminal urea group.
  • the structure of the polymer P can be controlled. A slight excess of urea has proven to be useful.
  • the amines formed (A) are reacted with at least one bifunctional compound (C) selected from the group of halomethyloxiranes, bisepoxides, alkylene dihalides and dihaloalkyl ethers.
  • the amount of such further amines (B) should not exceed 55 mol%, preferably 40 mol%, particularly preferably 25 mol% and very particularly preferably 10 mol%, relative to the amount of all amines (A) and (B) used together.
  • the at least secondary diamines (B) may be aliphatic and / or aromatic diamines. They are preferably cyclic, aromatic or aliphatic diamines. Of course, mixtures of different diamines (B) can be used.
  • aliphatic amines (B) include amines of the general formula R 5 R 5 N-R 6 -NR 5 R 5 " where R 5 and R 5 'are as defined above and R 6 is any linking group, preferably a hydrocarbon group
  • Suitable diamine (B) can also be prepared by linking in each case two of the above-described mono (N, N-dialkylaminoalkyl) amines (A1) via the primary amino groups in a suitable manner , For example, by reaction with Dicarbonäsuren or diisocyanates.
  • Suitable cyclic diamines (B) include in particular imidazole and its alkyl derivatives, piperazine and its alkyl derivatives, pyrazine and pyrimidine.
  • alkyl derivatives should also be understood as meaning derivatives whose alkyl substituents are functionalized by further substituents, such as, for example, amino or hydroxyl groups.
  • piperazine and imidazole derivatives are: 1-, 2- and 4- (C 1 -C 25 -alkyl) imidazoles, especially 1-, 2- and 4- (C 1 -C 6 -alkyl) imidazoles, such as 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole and 1- (3-aminopropyl) imidazole; 2,4-di (C 1 -C 25 -alkyl) imidazoles, especially 2,4-di (C 1 -C 6 -alkyl) imidazoles, such as 2-ethyl-4-methylimidazole; 1- (C 1 -C 25 -alkyl) -piperazines, especially 1- (C 1 -C 6 -alkyl) -piperazines, such as 1-methyl-piperazine; 1, 4-di (C 1 -C 25 -alkyl) piperazines, especially 1,4-di (C 1 -C 1
  • Preferred diamines (B) are unsubstituted imidazole and with Ci-C ⁇ -alkyl in the 1-, 2- or 4-position at least monosubstituted imidazole, with unsubstituted imidazole is particularly preferred.
  • bifunctional compound (C) selected from the group of alkylene dihalides (C1), dihaloalkyl ethers (C2), halomethyloxiranes (C3) or bisepoxides (C4) are used.
  • C1 alkylene dihalides
  • C2 dihaloalkyl ethers
  • C3 halomethyloxiranes
  • C4 bisepoxides
  • alkylenedihalides (C1) are the .omega.,. Omega.'-dichlorides, dibromides and diiodides of unbranched alkanes having 2 to 8 carbon atoms, the bromides being preferred and the chlorides being particularly preferred.
  • Particularly suitable alkylene dihalides (C1) include, for example, 1,2-dichloroethane, 1,2-dibromoethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane and 1,6-dichlorohexane, where 1 , 2-dichloroethane, 1, 4-dichlorobutane and 1, 6-dichlorohexane are preferred.
  • Particularly suitable dihaloalkyl ethers are di ( ⁇ , ⁇ '-halo-C 2 -C 6 -alkyl) ethers and ( ⁇ -halo-C 2 -C 6 -alkoxy-C 2 -C 6 -alkyl) ( ⁇ -halogen-C 2 -C 6 -alkyl) C 6 -alkyl) ether, where halogen may again denote chlorine, bromine or iodine, bromine being preferred and chlorine being is particularly preferred.
  • Examples include di (2-chloroethyl) ether and (2-chloro-ethoxyethyl) (2-chloroethyl) ether.
  • Suitable Halomethyloxirane (C3) preferably have 3 to 7 carbon atoms, whereby also the chlorine compounds are preferred here.
  • Particularly preferred halomethyloxirane (C3) is epichlorohydrin.
  • Particularly suitable bisepoxides (C4) are bisepoxialkanes having 4 to 7 carbon atoms and bisepoxides based on oligomeric and polymeric alkylene glycols, in particular C 2 -C 3 -alkylene glycols, such as oligo- and polyethylene glycol bis-epoxides, oligo- and polypropyleneglycol bisepoxides and bisepoxides of EO / PO copolymers.
  • Preferred bisepoxides (C4) are bisepoxibutane and oligo- and polyethylene glycol bis-epoxides.
  • the molar ratio of bifunctional compound (C) to the amine components (A) and optional (B) is 0.6: 1 to 1.3: 1, preferably 0.8: 1 to 1, 1: 1 and more preferably about 1: 1.
  • the reaction of (C) with (A) and (B) is usually carried out with heating. Temperatures of 80 to 120 ° C., for example temperatures of about 100 ° C., have proven to be suitable in particular.
  • the reaction can be carried out in bulk or preferably in a suitable solvent, preferably water. In general, the reaction times are 2 to 20 h.
  • the resulting polymers P may additionally be treated with alkylating agents, e.g. Dimethyl sulfate, Ci-C22-alkyl halides or benzyl chloride, are reacted, whereby the tertiary amino groups are quaternized.
  • alkylating agents e.g. Dimethyl sulfate, Ci-C22-alkyl halides or benzyl chloride.
  • the reaction with the alkylating agent can be carried out directly in the reaction mixture obtained in the reaction according to generally known methods.
  • Excess amounts of the bifunctional compound (C) and optionally the alkylating agent can be removed after the reaction by means of methods known to those skilled in the art, for example by means of steam distillation.
  • the polymers used by the process described are readily water-soluble or at least water-dispersible. They can be separated from the aqueous reaction mixture by methods known to those skilled in the art. However, the aqueous solutions without isolation of the polymer P are preferably used for the used according to the invention, of course, the concentration can be adjusted appropriately.
  • polymers P are used which have a solubility of at least 50 g / l.
  • the solubility of the polymers is preferably at least 100 g / l.
  • the respectively desired solubility can be influenced by the person skilled in the art in a manner known in principle by the choice of the substituents R 1 and R 2 .
  • the hydrophilicity of the radicals R 1 and R 2 can also be increased by hydrophilic substituents and / or substitution of C atoms by N and / or O atoms.
  • R 1 is a linear 1, ⁇ -alkylene group of the general formula - (CHb) n - and n is a natural number of 2 to 10 and R 2 for the said 1, ⁇ -alkylene group, a 1, ⁇ -Alkylenetheroli or an OH-substituted alkylene group having 2 to 10 carbon atoms.
  • the average molecular weight M w of the polymers P can be set by the person skilled in the art, depending on the desired application, by the choice of the reaction conditions and the amount of the starting materials. Depending on the conditions, M w of 500 to 1,000,000 g / mol can be obtained. For the present application, in particular average molecular weights M w of 1000 to 100,000 g / mol are suitable, preferably 2000 to 80,000 g / mol and more preferably from 4000 to 50,000 g / mol.
  • the copper surface is brought into contact with an aqueous formulation or with an aqueous medium comprising at least one polymer P.
  • Corrosion should be understood in a manner known in principle to be the disadvantageous and quality-reducing change of a material emanating from the surface and caused by inadvertent chemical or electrochemical attack.
  • the nature of the corrosive media that are in contact with the surface does not matter. It may be, for example, gaseous, liquid or solid constituents corrosive media.
  • the aqueous medium is an aqueous formulation for coating, which comprises at least one polymer.
  • Mer P and optionally comprises further constituents, with which the surface is coated and then dried.
  • a thin layer of the polymer P and optionally further constituents of the formulation remains on the surface. The surface is thus subjected to a protective treatment in order to protect it against corrosive effects, which act on the surface only after the coating.
  • the coating may be carried out by conventional techniques known to those skilled in the art, for example by dipping, spraying, brushing, rolling or pouring.
  • Corresponding apparatuses are known to the person skilled in the art. Drying can be done by simply drying in air at room temperature. However, it can of course also be supported by heating and / or passing gas streams, for example by heating in a drying oven or drying channel or by appropriate IR emitters.
  • the formulation used for coating preferably comprises only water as the solvent.
  • water-miscible organic solvents can also be added. Examples include especially water-miscible alcohols such as methanol, ethanol, n-propanol or i-propanol.
  • an aqueous mixture generally comprises at least 50% by weight of water, preferably at least 75% by weight, more preferably at least 85% by weight and most preferably at least 95% by weight, based in each case on the amount of all solvents together.
  • the aqueous formulation may optionally comprise further components besides the at least one polymer P.
  • examples include in particular acids, bases or buffer systems for adjusting the pH.
  • the polymer P according to the invention can in principle be used at all pH values, in particular pH values from 0.5 to 13, preferably 0.5 to 9.5.
  • An application in a neutral or acidic medium having a pH of 0.5 to 7, preferably 1 to 6 and particularly preferably 1 to 5 to 5 is particularly advantageous.
  • suitable acids include hydrochloric acid, methanesulfonic acid, citric acid, amidosulfonic acid or Phosphoric acid.
  • bases include in particular NaOH, KOH, sodium carbonate or ammonia.
  • the formulation may also comprise other water-soluble or water-dispersible polymers or prepolymers and / or crosslinking components.
  • metal ions, fillers, dyes, defoamers, metal deactivators or other typical paint constituents may also be present.
  • the amount of polymers P in the aqueous formulation will be determined by those skilled in the art according to the desired properties. An amount of from 0.01% by weight to 10% by weight, preferably from 0.02 to 5% by weight and particularly preferably from 0.025% by weight to 3% by weight, based in each case on the amount of all components of the formulation, has proven useful.
  • the aqueous solution of the polymer resulting from the preparation may preferably be used without further purification.
  • the surface is protected from the corrosive influence of the aqueous medium itself, which is in contact with the surface of the copper or copper alloy.
  • the corresponding medium can be permanently or even temporarily in contact with the surface.
  • aqueous media examples include aqueous cooling or heating fluids circulating in heating or cooling circuits comprising copper pipes and / or other components of copper.
  • aqueous cooling or heating fluids circulating in heating or cooling circuits comprising copper pipes and / or other components of copper.
  • cleaners stains or Entlacker for surfaces of copper or copper alloys.
  • Such cleaners should dissolve impurities on the surface, such as oxide layers, carbonate layers or fatty layers, they should not attack the copper surface itself.
  • the addition of the polymers P can effectively prevent the dissolution of copper or copper alloys.
  • the at least one polymer P may preferably be added to the aqueous medium before it is first contacted, or only while the medium is already in contact with the surface.
  • the aqueous media to be protected contain as further constituents, the components customary for the particular application.
  • it may be further constituents selected from the group of acids, bases or surfactants.
  • the polymers P can be combined particularly advantageously with cationic surfactants having quaternary ammonium groups.
  • Examples of corresponding cationic surfactants include N, N-dimethyl-N- (C 2 -C 4 -hydroxyalkyl) (C 7 -C 25 -alkyl) ammonium salts, mono- and di- (C 7 -C 25 -alkyl) dimethylammo quaternized with alkylating agents.
  • ammonium compounds in particular quaternary esterified mono-, di- and trialkanolamines esterified with Cs-C22-carboxylic acids or lauryl / myristyltrimethylammonium methosulphate.
  • the polymers P used according to the invention can be used both in acidic and in alkaline media, for example at a pH of 0.5 to 13.
  • Use is particularly advantageous at a pH of 0.5 to 9.5, preferably in a neutral or acidic medium having a pH of 0.5 to 7, particularly preferably 1 to 6 and very particularly preferably 1, 5 to 5.
  • the amount of polymers P in the medium is determined by the person skilled in the art, depending on the nature of the medium, in particular on its corrosivity. An amount of from 0.01% by weight to 10% by weight, preferably from 0.1 to 5% by weight, in each case based also on the amount of all components of the particular medium, has proven useful.
  • the polymers P can be used in particular in strongly saline media. They are also soluble in the presence of high salt concentrations or do not precipitate. They can be used advantageously in media having a salt content of at least 5% by weight of salts with respect to the amount of all components of the medium.
  • the salt content may preferably be at least 10% by weight and more preferably at least 20% by weight.
  • the polymers P can also be used in sulfide-containing media.
  • Formulations of the polymers P can also be formulated without precipitation in the pH range of 0.5 and 13, even at elevated temperatures. For example, remains a solution of the polymer at pH 1 even when heated to 80 0 C clear. They are particularly suitable for acidic formulations.
  • the media which are in contact with the copper surface may be at room temperature.
  • the process of the invention can be advantageously carried out especially at elevated temperatures, for example at a temperature> 30 0 C, preferably> 40 0 C and particularly preferably> 50 0 C.
  • the polymers are not hazardous to water and have good bioeliminability. They are degradable with hypochlorite.
  • the amine (A) is obtained in the form of a yellowish, clear liquid.
  • K values The determination of the indicated K values is carried out according to H. Fikentscher, Cellulose Chemistry, Volume 13, pages 58-64 and 761-774 (1932) as 1 wt .-% solution in 3 wt .-% saline solution at 25 ° C.
  • the K values provide an indication of the molecular weight and the viscosity.
  • the test shows to what extent the dissolution of copper by a solution which is in contact with a copper surface for a long time is prevented by the addition of a corrosion inhibitor.
  • the oxide layer is first sanded with a fine emery paper (particle size P 120). Thereafter, the copper sheet is immersed in an acid bath (32% HCl) and the residual oxide layer removed at RT while stirring.
  • the copper sheet is removed and rinsed for five seconds under running demineralized water.
  • the pre-treated in the acid bath copper sheet is at 10 volts in a degreasing from
  • EDTA tetrasodium salt powder 0.5 g of a nonionic surfactant (ethoxylated nonylphenol, about 10 EO)
  • test electrolyte used is a citrate buffer (pH 2) of the following composition:
  • the mass is determined with the analytical balance.
  • the copper sheet is used immediately after weighing.
  • the prepared copper sheet is hung in a 250 ml beaker filled with test electrolyte so that it is completely covered by the electrolyte.
  • the beaker is stored for 24 hours at room temperature. After 24 hours, the pH is measured again.
  • the test shows to what extent the atmospheric corrosion of a copper surface under severe conditions (salt spray chamber) is inhibited by the previous treatment of the surface with a corrosion inhibitor.
  • a purified copper sheet was used as described under B1).
  • the cleaned copper sheet was immersed at RT for 1 to 2 seconds in a 0.8% strength aqueous solution of polymer 1, blown off with nitrogen and dried at RT for 30 min.
  • the copper sheet was stored for 4 h in a Salzsprühhunt (DIN 510021) with 5% NaCl mist.
  • Purified copper sheet was used as described under B1).
  • the first solution contained 6.4% ZnBr 2 , 41, 1% CaBr 2 and 17% CaCl 2 (each wt%), the second 45.4% ZnBr 2 , 25.7% CaBr 2 and 2.8% CaCl 2 .
  • the pH of the solutions was in each case 1 to 2. In each case 3% by weight of polymer 1 were added to the solutions.
  • the copper sheets were stored for 1 week at about 100 0 C in the solutions.
  • the polymer used did not precipitate, nor did the copper sheets show any discoloration.

Abstract

L'invention concerne un procédé de protection anticorrosion des surfaces de cuivre ou d'alliages de cuivre, consistant à amener en contact la surface métallique avec un milieu aqueux, caractérisé en ce que ledit milieu aqueux renferme, comme inhibiteur de corrosion, un polymère comprenant des groupes ammonium quaternaire et des groupes urée, des groupes urée et/ou des groupes imino-urée dans un rapport numérique de 1,5 : 1 à 2,5 : 1.
PCT/EP2007/059438 2006-09-15 2007-09-10 Utilisation de polymères comprenant des groupes ammonium quaternaire et des groupes urée en tant qu'inhibiteurs de corrosion pour des surfaces de cuivre WO2008031781A2 (fr)

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US8076003B2 (en) 2008-09-26 2011-12-13 Infineon Technologies Ag Coating composition and a method of coating
US20160257891A1 (en) * 2015-03-06 2016-09-08 Ecolab Usa Inc. Reverse emulsion breaker polymers
CN106811757A (zh) * 2017-01-23 2017-06-09 江苏理工学院 一种常温使用的盐酸酸洗抑雾缓蚀剂及其应用
US10072217B2 (en) 2015-03-04 2018-09-11 Ecolab Usa Inc. Reverse emulsion breaker polymers
US10329672B2 (en) 2013-12-27 2019-06-25 Dow Global Technologies Llc Corrosion inhibiting compositions including bis-imidazoline compounds derived from enriched linear tetramines
US10487406B2 (en) 2013-12-27 2019-11-26 Dow Global Technologies Llc Bis-imidazoline compounds as corrosion inhibitors and preparation thereof

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WO2004074372A1 (fr) * 2003-02-24 2004-09-02 Basf Aktiengesellschaft Polymeres contenant du carboxylate pour le traitement de surfaces metalliques
WO2005033364A1 (fr) * 2003-09-30 2005-04-14 Basf Aktiengesellschaft Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles
US20050121114A1 (en) * 2001-12-27 2005-06-09 Monica Fernandez Gonzalez Polymer derivatives for the treatment of metals

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US4157388A (en) * 1977-06-23 1979-06-05 The Miranol Chemical Company, Inc. Hair and fabric conditioning compositions containing polymeric ionenes
DE2924230A1 (de) * 1978-06-15 1979-12-20 Oreal Kosmetisches mittel und dessen anwendung
US4506081A (en) * 1982-09-02 1985-03-19 Buckman Laboratories, Inc. Polymeric quaternary ammonium compounds and their uses
US20050121114A1 (en) * 2001-12-27 2005-06-09 Monica Fernandez Gonzalez Polymer derivatives for the treatment of metals
WO2004074372A1 (fr) * 2003-02-24 2004-09-02 Basf Aktiengesellschaft Polymeres contenant du carboxylate pour le traitement de surfaces metalliques
WO2005033364A1 (fr) * 2003-09-30 2005-04-14 Basf Aktiengesellschaft Procedes pour decaper des surfaces metalliques au moyen d'alcynols alcoxyles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8076003B2 (en) 2008-09-26 2011-12-13 Infineon Technologies Ag Coating composition and a method of coating
DE102009040556B4 (de) * 2008-09-26 2018-01-18 Infineon Technologies Ag Beschichtungszusammensetzung und deren Verwendung
US10329672B2 (en) 2013-12-27 2019-06-25 Dow Global Technologies Llc Corrosion inhibiting compositions including bis-imidazoline compounds derived from enriched linear tetramines
US10487406B2 (en) 2013-12-27 2019-11-26 Dow Global Technologies Llc Bis-imidazoline compounds as corrosion inhibitors and preparation thereof
US10072217B2 (en) 2015-03-04 2018-09-11 Ecolab Usa Inc. Reverse emulsion breaker polymers
US20160257891A1 (en) * 2015-03-06 2016-09-08 Ecolab Usa Inc. Reverse emulsion breaker polymers
US9914882B2 (en) * 2015-03-06 2018-03-13 Ecolab Usa Inc. Reverse emulsion breaker polymers
CN106811757A (zh) * 2017-01-23 2017-06-09 江苏理工学院 一种常温使用的盐酸酸洗抑雾缓蚀剂及其应用

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