EP0610236B1 - Process for making nickel-plated castings - Google Patents

Process for making nickel-plated castings Download PDF

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Publication number
EP0610236B1
EP0610236B1 EP92919740A EP92919740A EP0610236B1 EP 0610236 B1 EP0610236 B1 EP 0610236B1 EP 92919740 A EP92919740 A EP 92919740A EP 92919740 A EP92919740 A EP 92919740A EP 0610236 B1 EP0610236 B1 EP 0610236B1
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Prior art keywords
alkyl
ammonium compounds
general formula
cyclic ammonium
brighteners
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German (de)
French (fr)
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EP0610236A1 (en
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Alfred Oftring
Bernd Burkhart
Volker Schwendemann
Klaus Glaser
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18—Heterocyclic compounds

Definitions

  • the present invention relates to an improved process for the production of nickel-plated moldings by electrodeposition of nickel from aqueous acid baths which contain, as essential components, one or more nickel salts, one or more inorganic acids and one or more brighteners.
  • Such brighteners which are generally divided into primary brighteners (“brighteners”) and secondary brighteners (“brighteners”), are usually used as a combination of several of these agents in order to increase the effect.
  • DE-B 11 91 652 (2) describes mono- or polynuclear heterocyclic nitrogen bases of the aromatic type in quaternized form such as pyridinium salts, e.g. 2-pyridinium-1-sulfatoethane, as a leveling agent, i.e. Brightener, described for acidic galvanic nickel baths. These agents are used together with conventional basic gloss agents such as benzene-m-disulfonic acid, diaryl disulfimides or sulfonamides.
  • pyridinium salts e.g. 2-pyridinium-1-sulfatoethane
  • Brightener i.e. Brightener
  • DD 81 548 (3) and DD 108 777 (4) describe pyridinium acetic acid derivatives of the general formula II in which R9 is hydrogen, alkyl or alkenyl, described as a brightener for the electrodeposition of nickel layers.
  • cyclic ammonium compounds of the general formula III in which R10 represents hydrogen, methyl, ethyl, propyl, iso-propyl, carboxyl or aliphatic carboxyl ester, R11 denotes hydrogen, methyl, carboxyl or aliphatic carboxyl ester, R12 denotes the residue of an aliphatic alcohol, q denotes the number 0, 1 or 2 and Y ⁇ stands for hydroxide or halide, described as a brightener in galvanic baths for the deposition of nickel.
  • alkenyl sulfonic acids such as sodium vinyl sulfonate or sodium allylsulfonate are usually used as brighteners in combination with other brighteners such as propargyl alcohol, 2-butyne-1,4-diol, propyne sulfonic acid or 3-pyridinium propyl sulfonate.
  • a disadvantage of the agents known from the prior art is the generally relatively high use concentration in the nickel electrolyte baths used.
  • the invention was therefore an improved process for the production of nickel-plated moldings using brighteners which, with better or at least the same gloss formation as, for example, 2-pyridinium-1-sulfatoethane, 3-pyridinium-propylsulfonate or compounds of the general formulas II or III in a lower concentration need to be used as a task.
  • C1 to C4 alkyl radicals for R1 and R2 and for possible substituents on the heterocyclic ring system and on the phenyl nucleus are n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially Consider methyl and ethyl.
  • alkyl-substituted heterocyclic ring systems for I are: 2-, 3- or 4-methylpyridinium, 2-, 3- or 4-ethylpyridinium, 3- or 4-n-propylpyridinium, 3- or 4-iso-propylpyridinium, 3- or 4-n-butylpyridinium, 4-tert-butylpyridinium, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylpyridinium, 3-methyl-4-isopropylpyridinium, 4-tert-butyl-3-methylpyridinium, 2-, 3-, 4-, 5-, 6-, 7- or 8-methylquinolinium and 1-, 3-, 4-, 5-, 6-, 7- or 8-methylisoquinolinium.
  • Unsubstituted pyridinium is preferred.
  • C1 to C12 alkyl radicals for R3 for example, in addition to the C1 to C4 alkyl radicals mentioned above, n-amyl, iso-amyl, sec.-amyl, tert.-amyl, neopentyl, n-hexyl, n- Heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl and n-dodecyl.
  • C1 to C4 alkyl radicals are preferred.
  • Suitable C5- to C8-cycloalkyl radicals for R3 are in particular cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl and ethylcyclohexyl. Of these, cyclopentyl and cyclohexyl are preferred.
  • Suitable C7- to C12-phenylalkyl groups for R3 are, for example, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-phenylprop-2-yl, 4-phenylbutyl, 2,2-dimethyl- 2-phenylethyl, 5-phenylamyl, 6-phenylhexyl and especially benzyl.
  • the substitution scheme is ortho, meta or preferably para, in the case of disubstituted phenyl radicals the substituents are mainly in the 2,4-position, for example in the case of 2,4-xylyl.
  • a degree of substitution of 1 is preferred in the presence of substituents.
  • unsubstituted phenyl is particularly preferred.
  • C1 to C4 alkoxy radicals here are in particular methoxy and ethoxy, but also n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy.
  • C1 to C4 alkoxycarbonyl groups for example, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, sec.-butoxycarbonyl, tert.-butoxycarbonyl, but especially ethoxycarbonyl and methoxycarbonyl.
  • halogen atom here includes fluorine, iodine, but especially bromine and especially chlorine.
  • the radical R1 is preferably hydrogen, methyl or ethyl, the radical R2 is preferably hydrogen.
  • m preferably represents a number from 0 to 8, in particular 0 to 5.
  • Suitable n-valent anions X are the customary inorganic or organic anions which normally promote water solubility, in particular chloride, bromide, fluoride, sulfate, hydrogen sulfate, methanesulfonate, trifluoromethanesulfonate, 2-hydroxyethanesulfoant, p-toluenesulfonate, nitrate, tetrafluoroborate, Perchlorate, 1-hydroxyethane-1,1-diphosphonate, dihydrogen phosphate, hydrogen phosphate, phosphate, formate, acetate, oxalate and tartrate.
  • cyclic ammonium compounds of the general formula Ib in which the variables m, n and X ⁇ have the meanings given above and R5 denotes C7- to C12-phenylalkyl or phenyl, which can be substituted by one or two C1- to C4-alkyl radicals.
  • cyclic ammonium compounds of the general formula If in which the variables R1, R2, R3, m, n and X ⁇ have the meanings given above.
  • cyclic ammonium compounds I used according to the invention can advantageously be implemented by reacting the corresponding precursor of the general formula IV in which Z represents a nucleofugic leaving group, preferably chlorine or bromine, with a heterocycle of the general formula V. and, if desired, then exchange the anion Z ⁇ for X ⁇ .
  • Z represents a nucleofugic leaving group, preferably chlorine or bromine
  • reaction of components IV and V is advantageously carried out in an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture thereof.
  • an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture thereof.
  • the reaction can also be carried out in water or in a single-phase or two-phase mixture of water and one or more organic solvents, preferably polar organic solvents.
  • a customary phase transfer catalyst can be used. It is usually carried
  • the cyclic ammonium compounds I have the effect character of secondary brighteners, they are preferably used in combination with further, normally primary brighteners, if appropriate also with one or more further secondary brighteners.
  • the primary brighteners are, for example, vinylsulfonic acid or allylsulfonic acid sodium salts
  • the secondary brighteners are, for example, 2-butyne-1,4-diol or propargyl alcohol.
  • aqueous acidic nickel electrolyte baths used one or usually more nickel salts, e.g. nickel sulfate and nickel chloride, one or more inorganic acids, preferably boric acid and sulfuric acid, the compounds I alone or preferably in combination with other customary gloss agents as well as optionally other customary auxiliaries and additives in the concentrations customary for this purpose, e.g. Wetting agents and pore prevention agents.
  • nickel salts e.g. nickel sulfate and nickel chloride
  • inorganic acids preferably boric acid and sulfuric acid
  • Common aqueous acidic nickel electrolytes (“Watts electrolytes”) have the following basic composition: 200 to 350 g / l NiSO4 ⁇ 7 H2O 30 to 150 g / l NiCl2 ⁇ 6 H2O 30 to 50 g / l H3BO3.
  • the pH of the electrolyte baths is usually between 3 and 6, preferably between 4 and 5.
  • a strong mineral acid preferably sulfuric acid, is expediently used to set this pH.
  • the compounds I are present in the electrolyte baths in low concentrations, generally between 0.04 and 0.5 g / l, preferably between 0.1 and 0.3 g / l.
  • concentrations of other customary brighteners are normally in the range from 0.1 to 10 g / l, in particular 0.1 to 2.0 g / l.
  • the nickel electrolyte baths described above can be used to produce nickel coatings on molded parts made of steel, but also on molded parts made of other materials, for example brass, which have been pretreated as usual. This is usually done at temperatures of 30 to 80 ° C, preferably 40 to 60 ° C.
  • the compounds I used according to the invention are distinguished by an extraordinarily high level of gloss. As a rule, they achieve a stronger shine than with the usual brighteners at a significantly lower dosage in the nickel electrolyte baths.
  • the title compound was prepared analogously to Example 1 from pyridine and 2-bromoethyl acetate in a yield of 81%.
  • the title compound was prepared analogously to Example 1 from pyridine and 2-bromobutyric acid methyl ester in a yield of 85%.
  • the title compound was prepared analogously to Example 1 from pyridine and pentyl 2-bromopropionate in a yield of 79%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-bromo-crotonic acid ethyl ester in a yield of 70%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-bromocrotonic acid methyl ester in a yield of 71%.
  • the title compound was prepared analogously to Example 1 from pyridine and benzyl bromoacetate in a yield of 80%.
  • the title compound was prepared analogously to Example 1 from pyridine and 3-chloropropionate in a yield of 86%.
  • the title compound was prepared analogously to Example 1 from pyridine and isopropyl 4-chloroacetoacetate in a yield of 71%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid tert-butyl ester in a yield of 73%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid methyl ester in a yield of 74%.
  • the title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid ethyl ester in a yield of 70%.
  • the title compound was prepared analogously to Example 1 from pyridine and 2-bromoethyl methyl ether in a yield of 69%.
  • the aqueous nickel electrolyte used had the following composition: 300 g / l NiSO47 H2O 60 g / l NiCl2 ⁇ 6 H2O 45 g / l H3BO3 2 g / l saccharin 0.8 g / l vinyl sulfonic acid sodium salt xg / l brightener according to table 0.5 g / l of a fatty alcohol derivative of the formula C12H25 / C14H29-O- (CH2CH2O) 2-SO3Na as a wetting agent The pH of the electrolyte was adjusted to 4.2 with sulfuric acid.
  • Brass sheets were used, which were degreased cathodically in an alkaline electrolyte by the usual methods before the coating with nickel.
  • the nickel was deposited in a 250 ml Hull cell at 55 ° C. and a current of 2A over a period of 10 minutes.
  • the sheets were then rinsed with water and dried with compressed air.
  • comparison compounds C and D are known from (3) and (4) and the comparison compound E is known from (5).

Abstract

The production of nickel-plated castings by the galvanic separation of nickel from aqueous-acid baths containing as the essential component one or more nickel salts, one or more inorganic acids and one or more brighteners, in which the brighteners used are cyclic ammonium compounds (I) in which the N atom is a component of a pyridine, quinoline or isoquinoline ring system which can also carry one or two C1 to C4-alkyl-substituted constituents and: R?1 and R2¿ are hydrogen or C¿1? to C4-alkyl; A is a group of the formula -CO-R?3¿, -CO-O-R3, -CO-CH?2-CO-O-R3¿ or -O-R3, wherein: R3 is C1 to C12-alkyl, C5 to C8-cycloalkyl, C7 to C4-alkyl radicals, C1 to C4-alkoxy radicals, halogen atoms, hydroxyl groups, phenyl radicals or C1 to C4-alkoxy carbonyl groups; m is a number from 0 to 10; n is a number from 2 to 4; and p is 0 or 1, and X- is an n-valent inorganic or organic anion promoting water-solubility; with the proviso that if p = 0 and A = -CO-O-C¿1? - C12-alkyl, m may not be 1, 2 or 3 and in the same case R?1¿ is not hydrogen if m = 0.

Description

Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung vernickelter Formteile durch galvanisches Abscheiden von Nickel aus wäßrig-sauren Bädern, die als wesentliche Bestandteile ein oder mehrere Nickelsalze, eine oder mehrere anorganische Säuren und ein oder mehrere Glanzmittel enthalten.The present invention relates to an improved process for the production of nickel-plated moldings by electrodeposition of nickel from aqueous acid baths which contain, as essential components, one or more nickel salts, one or more inorganic acids and one or more brighteners.

Ein Teil der hierbei als Glanzmittel eingesetzten Substanzen sind neue Stoffe. Deshalb betrifft die Erfindung weiterhin diese neuen Stoffe.Some of the substances used as glossing agents here are new substances. Therefore, the invention further relates to these new substances.

Es ist bekannt, daß saure Nickelelektrolyte in geringer Menge organische Substanzen enthalten müssen, wenn bei der galvanischen Nickelabscheidung eine glänzende, duktile und an der Oberfläche ebene Abscheidung des Metalls erzielt werden soll. Derartige Glanzmittel, die man in der Regel in primäre Glanzmittel ("Glanzträger") und sekundäre Glanzmittel ("Glanzbildner") unterteilt, werden üblicherweise als Kombination aus mehreren dieser Mittel eingesetzt, um die Wirkung zu steigern.It is known that acidic nickel electrolytes must contain a small amount of organic substances if a shiny, ductile and even metal deposition is to be achieved in the electrodeposition of nickel. Such brighteners, which are generally divided into primary brighteners ("brighteners") and secondary brighteners ("brighteners"), are usually used as a combination of several of these agents in order to increase the effect.

In der Literaturstelle "Praktische Galvanotechnik", Eugen G. Lenze Verlag, Saulgau, 4. Auflage 1984, Seite 268 bis 271 (1) werden Substanzklassen für übliche Glanzmittel für Nickelelektrolyte beschrieben. Eine Einteilung in primäre und sekundäre Glanzmittel und Einebner wird zwar getroffen, es wird aber gleichzeitig darauf hingewiesen, daß diese Einteilung nicht immer eindeutig vorgenommen werden kann. Als glanzerzeugende Substanzklassen werden genannt:

  • Sulfonimide, z.B. Benzoesäuresulfimid
  • Sulfonamide
  • Benzolsulfonsäuren, z.B. Mono-, Di- und Tribenzolsulfonsäure
  • Naphthalinsulfonsäuren, z.B. Mono-, Di- und Trinaphthalinsulfonsäure
  • Alkylsulfonsäuren
  • Sulfinsäure
  • Arylsulfonsulfonate
  • aliphatische Verbindungen mit Ethylen- und/oder Acetylenbindungen, z.B. Butindiol
  • ein- und mehrkernige stickstoffhaltige Heterocyclen, welche noch weitere Heteroatome wie Schwefel oder Selen enthalten können
  • Cumarin
  • Amine und quaternäre Ammoniumverbindungen als Einebnungsmittel
  • Saccharin.
In the reference "Practical Electroplating", Eugen G. Lenze Verlag, Saulgau, 4th edition 1984, pages 268 to 271 (1), classes of substances for conventional brighteners for nickel electrolytes are described. A division into primary and secondary gloss agents and levelers is made, but at the same time it is pointed out that this division cannot always be made clearly. The following are mentioned as gloss-producing substance classes:
  • Sulfonimides, for example benzoic acid sulfimide
  • Sulfonamides
  • Benzenesulfonic acids, eg mono-, di- and tribenzenesulfonic acid
  • Naphthalenesulfonic acids, e.g. mono-, di- and trinaphthalenesulfonic acid
  • Alkylsulfonic acids
  • Sulfinic acid
  • Aryl sulfone sulfonates
  • aliphatic compounds with ethylene and / or acetylene bonds, for example butynediol
  • mononuclear and polynuclear nitrogen-containing heterocycles, which can also contain further heteroatoms such as sulfur or selenium
  • Coumarin
  • Amines and quaternary ammonium compounds as leveling agents
  • Saccharin.

In der DE-B 11 91 652 (2) werden ein- oder mehrkernige heterocyclische Stickstoffbasen vom aromatischen Typ in quaternisierter Form wie Pyridiniumsalze, z.B. 2-Pyridinium-1-sulfatoethan, als Einebnungsmittel, d.h. Glanzmittel, für saure galvanische Nickelbäder beschrieben. Diese Mittel werden zusammen mit üblichen Grundglanzmitteln wie Benzol-m-disulfonsäure, Diaryldisulfimiden oder Sulfonamiden verwendet.DE-B 11 91 652 (2) describes mono- or polynuclear heterocyclic nitrogen bases of the aromatic type in quaternized form such as pyridinium salts, e.g. 2-pyridinium-1-sulfatoethane, as a leveling agent, i.e. Brightener, described for acidic galvanic nickel baths. These agents are used together with conventional basic gloss agents such as benzene-m-disulfonic acid, diaryl disulfimides or sulfonamides.

In der DD 81 548 (3) und der DD 108 777 (4) werden Pyridiniumessigsäurederivate der allgemeinen Formel II

Figure imgb0001

in der R⁹ Wasserstoff, Alkyl oder Alkenyl bedeutet, als Glanzbildner für die galvanische Abscheidung von Nickelschichten beschrieben.DD 81 548 (3) and DD 108 777 (4) describe pyridinium acetic acid derivatives of the general formula II
Figure imgb0001
in which R⁹ is hydrogen, alkyl or alkenyl, described as a brightener for the electrodeposition of nickel layers.

In der FR-A 2 292 057 (5) werden cyclische Ammoniumverbindungen der allgemeinen Formel III

Figure imgb0002

in der R¹⁰ für Wasserstoff, Methyl, Ethyl, Propyl, iso-Propyl, Carboxyl oder aliphatischen Carboxylester steht, R¹¹ Wasserstoff, Methyl, Carboxyl oder aliphatischen Carboxylester bezeichnet, R¹² den Rest eines aliphatischen Alkohols bedeutet, q die Zahl 0, 1 oder 2 bezeichnet und Y⊖ für Hydroxid oder Halogenid steht, als Glanzbildner in galvanischen Bädern für die Abscheidung von Nickel beschrieben.FR-A 2 292 057 (5) cyclic ammonium compounds of the general formula III
Figure imgb0002
in which R¹⁰ represents hydrogen, methyl, ethyl, propyl, iso-propyl, carboxyl or aliphatic carboxyl ester, R¹¹ denotes hydrogen, methyl, carboxyl or aliphatic carboxyl ester, R¹² denotes the residue of an aliphatic alcohol, q denotes the number 0, 1 or 2 and Y ⊖ stands for hydroxide or halide, described as a brightener in galvanic baths for the deposition of nickel.

In der Praxis werden üblicherweise als Glanzbildner Alkenylsulfonsäuren wie Natriumvinylsulfonat oder Natriumallylsulfonat in Kombination mit anderen Glanzbildnern wie Propargylalkohol, 2-Butin-1,4-diol, Propinsulfonsäure oder 3-Pyridinium-propylsulfonat verwendet.In practice, alkenyl sulfonic acids such as sodium vinyl sulfonate or sodium allylsulfonate are usually used as brighteners in combination with other brighteners such as propargyl alcohol, 2-butyne-1,4-diol, propyne sulfonic acid or 3-pyridinium propyl sulfonate.

Nachteilig bei den aus dem Stand der Technik bekannten Mitteln ist allerdings die in der Regel relativ hohe Einsatzkonzentration in den verwendeten Nickelelektrolyt-Bädern.A disadvantage of the agents known from the prior art, however, is the generally relatively high use concentration in the nickel electrolyte baths used.

Der Erfindung lag daher ein verbessertes Verfahren zur Herstellung vernickelter Formteile unter Verwendung von Glanzbildnern, die bei besserer oder zumindest gleicher Glanzbildung wie bei beispielsweise 2-Pyridinium-1-sulfatoethan, 3-Pyridinium-propylsulfonat oder Verbindungen der allgemeinen Formeln II oder III in geringerer Konzentration eingesetzt zu werden brauchen, als Aufgabe zugrunde.The invention was therefore an improved process for the production of nickel-plated moldings using brighteners which, with better or at least the same gloss formation as, for example, 2-pyridinium-1-sulfatoethane, 3-pyridinium-propylsulfonate or compounds of the general formulas II or III in a lower concentration need to be used as a task.

Demgemäß wurde ein Verfahren zur Herstellung vernickelter Formteile durch galvanisches Abscheiden von Nickel aus wäßrig-sauren Bädern, die als wesentliche Bestandteile ein oder mehrere Nickelsalze, eine oder mehrere anorganische Säuren und ein oder mehrere Glanzmittel enthalten gefunden, welches dadurch gekennzeichnet ist, daß man als Glanzmittel cyclische Ammoniumverbindungen der allgemeinen Formel I

Figure imgb0003

in der das N-Atom Bestandteil eines Pyridin-, Chinolin- oder Isochinolin-Ringsystemes ist, welches zusätzlich ein oder zwei C₁- bis C₄-Alkylsubstituenten tragen kann,

R¹ und R²
für Wasserstoff oder C₁- bis C₄-Alkyl stehen,
A
eine Gruppierung der Formel -CO-O-R³, -CO-CH₂-CO-O-R³, -O-CO-R³ oder -O-R³ bezeichnet, wobei
R³
C₁- bis C₁₂-Alkyl, C₅- bis C₈-Cycloalkyl, C₇- bis C₁₂-Phenylalkyl oder Phenyl, welches durch ein oder zwei C₁- bis C₄-Alkylreste, C₁- bis C₄-Alkoxyreste, Halogenatome, Hydroxylgruppen, Phenylreste oder C₁- bis C₄-Alkoxycarbonylgruppen substituiert sein kann, bedeutet,
m
für eine Zahl von 0 bis 10,
n
für eine Zahl von 1 bis 4 und
p
für 0 oder 1 stehen und
X⊖
ein n-wertiges anorganisches oder organisches Anion, welches die Wasserlöslichkeit fördert, bezeichnet,
mit der Maßgabe, daß für den Fall p=0 und A = -CO-O-C₁-C₁₂-Alkyl m nicht den Wert 1, 2 oder 3 annehmen darf und R¹ für den gleichen Fall ungleich Wasserstoff ist, falls m den Wert 0 annimmt,
einsetzt.Accordingly, a process has been found for the production of nickel-plated moldings by electrodeposition of nickel from aqueous acid baths which contain one or more nickel salts, one or more inorganic acids and one or more brightening agents as essential constituents, which is characterized in that a brightening agent is used cyclic ammonium compounds of the general formula I
Figure imgb0003
in which the N atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two C₁ to C₄ alkyl substituents,
R1 and R2
represent hydrogen or C₁- to C₄-alkyl,
A
denotes a grouping of the formula -CO-O-R³, -CO-CH₂-CO-O-R³, -O-CO-R³ or -O-R³, where
R³
C₁ to C₁₂ alkyl, C₅ to C₈ cycloalkyl, C₇ to C₁₂ phenylalkyl or phenyl, which is substituted by one or two C₁ to C₄ alkyl radicals, C₁ to C₄ alkoxy radicals, halogen atoms, hydroxyl groups, phenyl radicals or C₁- until C₄-alkoxycarbonyl groups can be substituted means
m
for a number from 0 to 10,
n
for a number from 1 to 4 and
p
stand for 0 or 1 and
X ⊖
denotes an n-valent inorganic or organic anion which promotes water solubility,
with the proviso that for the case p = 0 and A = -CO-O-C₁-C₁₂-alkyl m must not have the value 1, 2 or 3 and R¹ is not hydrogen in the same case if m is 0 assumes
starts.

Als C₁- bis C₄-Alkylreste für R¹ und R² sowie für mögliche Substituenten am heterocyclischen Ringsystem und am Phenylkern kommen n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl und vor allem Methyl und Ethyl in Betracht.As C₁ to C₄ alkyl radicals for R¹ and R² and for possible substituents on the heterocyclic ring system and on the phenyl nucleus are n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially Consider methyl and ethyl.

Als alkylsubstituierte heterocyclische Ringsysteme für I seien beispielhaft genannt:
2-, 3- oder 4-Methylpyridinium,
2-, 3- oder 4-Ethylpyridinium,
3- oder 4-n-Propylpyridinium,
3- oder 4-iso-Propylpyridinium,
3- oder 4-n-Butylpyridinium,
4-tert.-Butylpyridinium,
2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-Dimethylpyridinium,
3-Methyl-4-isopropylpyridinium,
4-tert.-Butyl-3-methylpyridinium,
2-, 3-, 4-, 5-, 6-, 7- oder 8-Methylchinolinium und
1-, 3-, 4-, 5-, 6-, 7- oder 8-Methylisochinolinium.Examples of alkyl-substituted heterocyclic ring systems for I are:
2-, 3- or 4-methylpyridinium,
2-, 3- or 4-ethylpyridinium,
3- or 4-n-propylpyridinium,
3- or 4-iso-propylpyridinium,
3- or 4-n-butylpyridinium,
4-tert-butylpyridinium,
2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylpyridinium,
3-methyl-4-isopropylpyridinium,
4-tert-butyl-3-methylpyridinium,
2-, 3-, 4-, 5-, 6-, 7- or 8-methylquinolinium and
1-, 3-, 4-, 5-, 6-, 7- or 8-methylisoquinolinium.

Bevorzugt wird unsubstituiertes Pyridinium.Unsubstituted pyridinium is preferred.

Als geradkettige oder verzweigte C₁- bis C₁₂-Alkylreste für R³ kommen beispielsweise neben der oben aufgeführten C₁- bis C₄-Alkylresten n-Amyl, iso-Amyl, sek.-Amyl, tert.-Amyl, Neopentyl, n-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, iso-Nonyl, n-Decyl, n-Undecyl und n-Dodecyl in Betracht. Bevorzugt werden hiervon C₁- bis C₄-Alkylreste.As straight-chain or branched C₁ to C₁₂ alkyl radicals for R³, for example, in addition to the C₁ to C₄ alkyl radicals mentioned above, n-amyl, iso-amyl, sec.-amyl, tert.-amyl, neopentyl, n-hexyl, n- Heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl and n-dodecyl. Of these, C₁ to C₄ alkyl radicals are preferred.

Als C₅- bis C₈-Cycloalkylreste für R³ kommen insbesondere Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Methylcyclopentyl, Dimethylcyclopentyl, Methylcyclohexyl, Dimethylcyclohexyl und Ethylcyclohexyl in Betracht. Bevorzugt werden hiervon Cyclopentyl und Cyclohexyl.Suitable C₅- to C₈-cycloalkyl radicals for R³ are in particular cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl and ethylcyclohexyl. Of these, cyclopentyl and cyclohexyl are preferred.

Als C₇- bis C₁₂-Phenylalkylgruppen für R³ eignen sich beispielsweise 1-Phenylethyl, 2-Phenylethyl, 1-Phenylpropyl, 2-Phenylpropyl, 3-Phenylpropyl, 2-Phenylprop-2-yl, 4-Phenylbutyl, 2,2-Dimethyl-2-phenylethyl, 5-Phenylamyl, 6-Phenylhexyl und vor allem Benzyl.Suitable C₇- to C₁₂-phenylalkyl groups for R³ are, for example, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-phenylprop-2-yl, 4-phenylbutyl, 2,2-dimethyl- 2-phenylethyl, 5-phenylamyl, 6-phenylhexyl and especially benzyl.

Bei Verwendung monosubstituierter Phenylreste für R³ ist das Substitutionsschema ortho, meta oder vorzugsweise para, bei disubstituierten Phenylresten stehen die Substituenten vor allem in 2,4-Position, z.B. bei 2,4-Xylyl. Es wird bei Vorhandensein von Substituenten ein Substitionsgrad von 1 bevorzugt. Besonders bevorzugt wird jedoch unsubstituiertes Phenyl.When using monosubstituted phenyl radicals for R³, the substitution scheme is ortho, meta or preferably para, in the case of disubstituted phenyl radicals the substituents are mainly in the 2,4-position, for example in the case of 2,4-xylyl. A degree of substitution of 1 is preferred in the presence of substituents. However, unsubstituted phenyl is particularly preferred.

Als C₁- bis C₄-Alkoxyreste kommen hierbei insbesondere Methoxy und Ethoxy, daneben aber auch n-Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, sec.-Butoxy und tert.-Butoxy in Betracht.As C₁ to C₄ alkoxy radicals here are in particular methoxy and ethoxy, but also n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy.

Als C₁- bis C₄-Alkoxycarbonylgruppen dienen hierbei beispielsweise n-Propoxycarbonyl, iso-Propoxycarbonyl, n-Butoxycarbonyl, iso-Butoxycarbonyl, sec.-Butoxycarbonyl, tert.-Butoxycarbonyl, vor allem aber Ethoxycarbonyl und Methoxycarbonyl.As C₁ to C₄ alkoxycarbonyl groups, for example, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, iso-butoxycarbonyl, sec.-butoxycarbonyl, tert.-butoxycarbonyl, but especially ethoxycarbonyl and methoxycarbonyl.

Der Begriff Halogenatom umfaßt hierbei Fluor, Jod, vor allem aber Brom und insbesondere Chlor.The term halogen atom here includes fluorine, iodine, but especially bromine and especially chlorine.

Der Rest R¹ steht vorzugsweise für Wasserstoff, Methyl oder Ethyl, der Rest R² bedeutet vorzugsweise Wasserstoff.The radical R¹ is preferably hydrogen, methyl or ethyl, the radical R² is preferably hydrogen.

m steht vorzugsweise für eine Zahl von 0 bis 8, insbesondere 0 bis 5.m preferably represents a number from 0 to 8, in particular 0 to 5.

Als n-wertige Anionen X kommen die üblichen, normalerweise die Wasserlöslichkeit fördernden anorganischen oder organischen Anionen in Betracht, so vor allem Chlorid, Bromid, Fluorid, Sulfat, Hydrogensulfat, Methansulfonat, Trifluormethansulfonat, 2-Hydroxyethansulfoant, p-Toluolsulfonat, Nitrat, Tetrafluorborat, Perchlorat, 1-Hydroxyethan-1,1-diphosphonat, Dihydrogenphosphat, Hydrogenphosphat, Phosphat, Formiat, Acetat, Oxalat und Tartrat.Suitable n-valent anions X are the customary inorganic or organic anions which normally promote water solubility, in particular chloride, bromide, fluoride, sulfate, hydrogen sulfate, methanesulfonate, trifluoromethanesulfonate, 2-hydroxyethanesulfoant, p-toluenesulfonate, nitrate, tetrafluoroborate, Perchlorate, 1-hydroxyethane-1,1-diphosphonate, dihydrogen phosphate, hydrogen phosphate, phosphate, formate, acetate, oxalate and tartrate.

Hiervon werden ein- oder zweifach (n=1 oder 2) geladene Anionen, vor allem Fluorid, Sulfat, Methansulfonat, Nitrat und Tetrafluoroborat, insbesondere jedoch Chlorid und Bromid bevorzugt.Of these, single or double (n = 1 or 2) charged anions, especially fluoride, sulfate, methanesulfonate, nitrate and tetrafluoroborate, but especially chloride and bromide, are preferred.

In einer bevorzugten Ausführungsform werden cyclische Ammoniumverbindungen der allgemeinen Formel Ia

Figure imgb0004

in der die Variablen R¹, n und X⊖ die oben genannten Bedeutungen haben, R⁴ C₁- bis C₁₂-Alkyl oder C₅- bis C₈-Cycloalkyl bezeichnet und k für O oder eine Zahl von 4 bis 10 steht, mit der Maßgabe, daß R¹ ungleich Wasserstoff ist, falls k den Wert 0 annimmt, eingesetzt.In a preferred embodiment, cyclic ammonium compounds of the general formula Ia
Figure imgb0004
in which the variables R¹, n and X ⊖ have the meanings given above, R⁴ denotes C₁- to C₁₂-alkyl or C₅- to C₈-cycloalkyl and k represents O or a number from 4 to 10, with the proviso that R¹ is not equal to hydrogen, if k assumes the value 0, is used.

In einer weiteren bevorzugten Ausführungsform werden cyclische Ammoniumverbindungen der allgemeinen Formel Ib

Figure imgb0005

in der die Variablen m, n und X⊖ die oben genannten Bedeutungen haben und R⁵ C₇- bis C₁₂-Phenylalkyl oder Phenyl, welches durch ein oder zwei C₁- bis C₄-Alkylreste substituiert sein kann, bezeichnet, eingesetzt.In a further preferred embodiment, cyclic ammonium compounds of the general formula Ib
Figure imgb0005
in which the variables m, n and X ⊖ have the meanings given above and R⁵ denotes C₇- to C₁₂-phenylalkyl or phenyl, which can be substituted by one or two C₁- to C₄-alkyl radicals.

In einer weiteren bevorzugten Ausführungsform werden cyclische Ammoniumverbindungen der allgemeinen Formel Ic

Figure imgb0006

in der die Variabeln R¹, R², R³, m, n und X⊖ die oben genannten Bedeutungen haben, eingesetzt.In a further preferred embodiment, cyclic ammonium compounds of the general formula Ic
Figure imgb0006
in which the variables R¹, R², R³, m, n and X ⊖ have the meanings given above.

In einer weiteren bevorzugten Ausführungsform werden cyclische Ammoniumverbindungen der allgemeinen Formel Id

Figure imgb0007

in der die Variablen R¹, R³, n und X⊖ die oben genannten Bedeutungen haben, eingesetzt.In a further preferred embodiment, cyclic ammonium compounds of the general formula Id
Figure imgb0007
in which the variables R¹, R³, n and X ⊖ have the meanings given above.

In einer weiteren bevorzugten Ausführungsform werden cyclische Ammoniumverbindungen der allgemeinen Formel Ie

Figure imgb0008

in der die Variablen R¹, R³, n und X⊖ die oben genannten Bedeutungen haben, eingesetzt.In a further preferred embodiment, cyclic ammonium compounds of the general formula Ie
Figure imgb0008
in which the variables R¹, R³, n and X ⊖ have the meanings given above.

In einer weiteren bevorzugte Ausführungsform werden cyclische Ammoniumverbindungen der allgemeinen Formel If

Figure imgb0009

in der die Variablen R¹, R², R³, m, n und X⊖ die oben genannten Bedeutungen haben, eingesetzt.In a further preferred embodiment, cyclic ammonium compounds of the general formula If
Figure imgb0009
in which the variables R¹, R², R³, m, n and X ⊖ have the meanings given above.

Die erfindungsgemäß eingesetzten cyclischen Ammoniumverbindungen I lassen sich in vorteilhafter Weise durch Umsetzung der entsprechenden Vorstufe der allgemeinen Formel IV

Figure imgb0010

in der Z eine nucleofuge Abgangsgruppe, vorzugsweise Chlor oder Brom, darstellt, mit einem Heterocyclus der allgemeinen Formel V
Figure imgb0011
und gewünschtenfalls anschließenden Austausch des Anions Z⊖ gegen X⊖ herstellen.The cyclic ammonium compounds I used according to the invention can advantageously be implemented by reacting the corresponding precursor of the general formula IV
Figure imgb0010
in which Z represents a nucleofugic leaving group, preferably chlorine or bromine, with a heterocycle of the general formula V.
Figure imgb0011
and, if desired, then exchange the anion Z ⊖ for X ⊖ .

Die Umsetzung der Komponenten IV und V wird zweckmäßgerweise in einem inerten organischen Lösungsmittel wie Toluol, Xylol, Petrolether, Ligroin, Cyclohexan, Aceton, Tetrahydrofuran, Dioxan, Methanol, Ethanol, iso-Propanol, Essigsäureethylester oder Benzoesäuremethylester oder in einer Mischung hieraus durchgeführt. Man kann die Umsetzung aber auch in Wasser oder in einem einphasigen oder zweiphasigen Gemisch aus Wasser und einem oder mehreren organischen Lösungsmitteln, vorzugsweise polaren organischen Lösungsmitteln, vornehmen. Bei Zweiphasengemischen kann ein üblicher Phasentransferkatalysator eingesetzt werden. Man arbeitet in der Regel bei Temperaturen von 40 bis 130°C, insbesondere bei 60 bis 110°C, und bei Normaldruck.The reaction of components IV and V is advantageously carried out in an inert organic solvent such as toluene, xylene, petroleum ether, ligroin, cyclohexane, acetone, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate or methyl benzoate or in a mixture thereof. However, the reaction can also be carried out in water or in a single-phase or two-phase mixture of water and one or more organic solvents, preferably polar organic solvents. In the case of two-phase mixtures, a customary phase transfer catalyst can be used. It is usually carried out at temperatures from 40 to 130 ° C, in particular at 60 to 110 ° C, and at normal pressure.

Ein Teil der als Glanzmittel eingesetzten cyclischen Ammoniumverbindungen I sind neue Stoffe. Deshalb sind weiterhin Gegenstand der vorliegenden Anmleldung cyclische Ammoniumverbindungen der allgemeinen Formel Ig

Figure imgb0012

in der die Variablen

R⁴
C₁- bis C₁₂-Alkyl oder C₅- bis C₈-Cycloalkyl,
k
0 oder eine Zahl von 4 bis 10,
n
eine Zahl von 1 bis 4,
X⊖
ein n-wertiges anorganisches oder organisches Anion, welches die Wasserlöslichkeit fördert, und
R⁶
C₂- bis C₄-Alkyl
bezeichnen.Some of the cyclic ammonium compounds I used as brighteners are new substances. Therefore, cyclic ammonium compounds of the general formula Ig are also the subject of the present application
Figure imgb0012
in the the variables
R⁴
C₁ to C₁₂ alkyl or C₅ to C₈ cycloalkyl,
k
0 or a number from 4 to 10,
n
a number from 1 to 4,
X ⊖
an n-valent inorganic or organic anion, which promotes water solubility, and
R⁶
C₂ to C₄ alkyl
describe.

Weiterhin sind auch Gegenstand der vorliegenden Anmeldung cyclische Ammoniumverbindungen der allgemeinen Formel Ih

Figure imgb0013

in der die Variablen

m
eine Zahl von 0 bis 10,
n
eine Zahl von 1 bis 4,
X⊖
ein n-wertiges anorganisches oder organisches Anion, welches die Wasserlöslichkeit fördert, und
R⁷
C₇- bis C₁₂-Phenylalkyl
bezeichnen.The present application also relates to cyclic ammonium compounds of the general formula Ih
Figure imgb0013
in the the variables
m
a number from 0 to 10,
n
a number from 1 to 4,
X ⊖
an n-valent inorganic or organic anion, which promotes water solubility, and
R⁷
C₇ to C₁₂ phenylalkyl
describe.

Weiterhin sind auch Gegenstand der vorliegenden Anmeldung cyclische Ammoniumverbindungen der allgemeinen Formel Ij

Figure imgb0014

in der die Variablen

R¹
Wasserstoff oder C₁- bis C₄-Alkyl, n eine Zahl von 1 bis 4 und
X⊖
ein n-wertiges anorganisches oder organisches Anion, welches die Wasserlöslichkeit fördert, bezeichnen, und
R⁸
C₃- bis C₁₂-Alkyl, C₅- bis C₈-Cycloalkyl, C₇- bis C₁₂-Phenylalkyl oder Phenyl, welches durch ein oder zwei C₁- bis C₄-Alkylreste, C₁- bis C₄-Alkoxyreste, Halogenatome, Hydroxylgruppen, Phenylreste oder C₁- bis C₄-Alkoxycarbonylgruppen substituiert sein kann, bedeutet.
The present application also relates to cyclic ammonium compounds of the general formula Ij
Figure imgb0014
in the the variables
R¹
Hydrogen or C₁ to C₄ alkyl, n is a number from 1 to 4 and
X ⊖
denote an n-valent inorganic or organic anion which promotes water solubility, and
R⁸
C₃- to C₁₂-alkyl, C₅- to C₈-cycloalkyl, C₇- to C₁₂-phenylalkyl or phenyl, which by one or two C₁- to C₄-alkyl radicals, C₁- to C₄-alkoxy radicals, halogen atoms, hydroxyl groups, phenyl radicals or C₁- until C₄-alkoxycarbonyl groups can be substituted means.

Da die cyclischen Ammoniumverbindungen I den Wirkungscharakter von sekundären Glanzbildnern haben, werden sie vorzugsweise in Kombination mit weiteren, normalerweise primären Glanzbildnern, gegebenenfalls auch mit einem oder mehreren weiteren sekundären Glanzbildnern verwendet. Als primäre Glanzbildner kommen beispielsweise Vinylsulfonsäure- oder Allylsulfonsäure-Natriumsalz, als sekundäre Glanzbildner beispielsweise 2-Butin-1,4-diol oder Propargylalkohol in Frage.Since the cyclic ammonium compounds I have the effect character of secondary brighteners, they are preferably used in combination with further, normally primary brighteners, if appropriate also with one or more further secondary brighteners. The primary brighteners are, for example, vinylsulfonic acid or allylsulfonic acid sodium salts, and the secondary brighteners are, for example, 2-butyne-1,4-diol or propargyl alcohol.

Die verwendeten wäßrig-sauren Nickelelektrolyt-Bäder enthalten ein oder meist mehrere Nickelsalze, z.B. Nickelsulfat und Nickelchlorid, eine oder mehrere anorganische Säuren, vorzugsweise Borsäure und Schwefelsäure, als Glanzmittel die Verbindungen I allein oder vorzugsweise in Kombination mit weiteren üblichen Glanzmitteln sowie gegebenenfalls weitere übliche Hilfsmittel und Zusätze in den hierfür üblichen Konzentrationen, z.B. Netzmittel und Porenverhütungsmittel. Gebräuchlich wäßrig-saure Nickelelektrolyte ("Watts-Elektrolyte") haben die folgende Grundzusammensetzung:
200 bis 350 g/l NiSO₄ · 7 H₂O
30 bis 150 g/l NiCl₂ · 6 H₂O
30 bis 50 g/l H₃BO₃.The aqueous acidic nickel electrolyte baths used one or usually more nickel salts, e.g. nickel sulfate and nickel chloride, one or more inorganic acids, preferably boric acid and sulfuric acid, the compounds I alone or preferably in combination with other customary gloss agents as well as optionally other customary auxiliaries and additives in the concentrations customary for this purpose, e.g. Wetting agents and pore prevention agents. Common aqueous acidic nickel electrolytes ("Watts electrolytes") have the following basic composition:
200 to 350 g / l NiSO₄ · 7 H₂O
30 to 150 g / l NiCl₂ · 6 H₂O
30 to 50 g / l H₃BO₃.

Der pH-Wert der Elektrolyt-Bäder liegt üblicherweise zwischen 3 und 6, vorzugsweise zwischen 4 und 5. Zur Einstellung dieses pH-Wertes dient zweckmäßigerweise eine starke Mineralsäure, vorzugsweise Schwefelsäure.The pH of the electrolyte baths is usually between 3 and 6, preferably between 4 and 5. A strong mineral acid, preferably sulfuric acid, is expediently used to set this pH.

Die Verbindungen I liegen in den Elektrolyt-Bädern in niedrigen Konzentrationen, in der Regel zwischen 0,04 und 0,5 g/l, vorzugsweise zwischen 0,1 und 0,3 g/l, vor. Die Konzentrationen weiterer üblicher Glanzmittel liegen normalerweise im Bereich von jeweils 0,1 bis 10 g/l, insbesondere 0,1 bis 2,0 g/l.The compounds I are present in the electrolyte baths in low concentrations, generally between 0.04 and 0.5 g / l, preferably between 0.1 and 0.3 g / l. The concentrations of other customary brighteners are normally in the range from 0.1 to 10 g / l, in particular 0.1 to 2.0 g / l.

Mit den beschriebenen Nickelelektrolyt-Bädern können vor allem Nickelüberzüge auf Formteilen aus Stahl, daneben aber auch auf Formteilen aus anderen Materialien, beispielsweise Messing, die wie üblich vorbehandelt worden sind, galvanisch erzeugt werden. Hierzu arbeitet man in der Regel bei Temperaturen von 30 bis 80°C, vorzugsweise 40 bis 60°C.The nickel electrolyte baths described above can be used to produce nickel coatings on molded parts made of steel, but also on molded parts made of other materials, for example brass, which have been pretreated as usual. This is usually done at temperatures of 30 to 80 ° C, preferably 40 to 60 ° C.

Die erfindungsgemäß eingesetzten Verbindungen I zeichnen sich durch eine außerordentlich hohe Glanzbildung aus. Man erreicht mit ihnen in der Regel einen stärkeren Glanz als mit den üblichen Glanzbildnern bei deutlich niedrigerer Dosierung in den Nickelelektrolyt-Bädern.The compounds I used according to the invention are distinguished by an extraordinarily high level of gloss. As a rule, they achieve a stronger shine than with the usual brighteners at a significantly lower dosage in the nickel electrolyte baths.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1 Herstellung von 2-Pyridiniumbuttersäureethylester-bromidPreparation of 2-pyridinium butyric acid bromide

7,9 g (0,1 mol) Pyridin und 19,5 g (0,1 mol) 2-Brombuttersäureethylester wurden in 40 ml Aceton 6 h unter Rückfluß erhitzt. Danach wurde das Lösungsmittel abdestilliert, der Rückstand mit wenig Aceton gewaschen und im Vakuum bei ca. 0,1 mbar getrocknet. Man erhielt 21,6 g (entsprechend einer Ausbeute 79 %) der Titelverbindung in Form von farblosen Kristallen. Die Reinheit des Produktes lag bei über 99 %.7.9 g (0.1 mol) of pyridine and 19.5 g (0.1 mol) of 2-bromobutyric acid ethyl ester were refluxed in 40 ml of acetone for 6 hours. The solvent was then distilled off, the residue washed with a little acetone and dried in vacuo at about 0.1 mbar. 21.6 g (corresponding to one Yield 79%) of the title compound in the form of colorless crystals. The purity of the product was over 99%.

Beispiel 2Example 2 Herstellung von Essigsäure-2-pyridiniumethylester-bromidPreparation of 2-pyridinium ethyl bromide

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und Essigsäure-2-bromethylester in einer Ausbeute 81 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 2-bromoethyl acetate in a yield of 81%.

Beispiel 3Example 3 Herstellung von 2-Pyridiniumbuttersäuremethylester-bromidPreparation of 2-pyridinium butyric acid methyl ester bromide

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 2-Brombuttersäuremethylester in einer Ausbeute 85 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 2-bromobutyric acid methyl ester in a yield of 85%.

Beispiel 4Example 4 Herstellung von 2-Pyridiniumpropionsäurepentylester-bromidPreparation of 2-pyridiniumpropionic acid pentyl ester bromide

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 2-Brompropionsäurepentylester in einer Ausbeute 79 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and pentyl 2-bromopropionate in a yield of 79%.

Beispiel 5Example 5 Herstellung von 4-Pyridiniumcrotonsäureethylester-bromidPreparation of 4-pyridiniumcrotonic acid ethyl ester bromide

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 4-Bromcrotonsäureethylester in einer Ausbeute von 70 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 4-bromo-crotonic acid ethyl ester in a yield of 70%.

Beispiel 6Example 6 Herstellung von 4-Pyridiniumcrotonsäuremethylester-bromidPreparation of 4-pyridiniumcrotonic acid methyl ester bromide

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 4-Bromcrotonsäuremethylester in einer Ausbeute von 71 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 4-bromocrotonic acid methyl ester in a yield of 71%.

Beispiel 7Example 7 Herstellung von Pyridiniumessigsäurebenzylester-bromidPreparation of benzyl pyridinium bromide

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und Bromessigsäurebenzylester in einer Ausbeute von 80 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and benzyl bromoacetate in a yield of 80%.

Beispiel 8Example 8 Herstellung von 3-Pyridiniumpropionsäurephenylester-chloridProduction of 3-pyridiniumpropionic acid chloride

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 3-Chlorpropionsäurephenylester in einer Ausbeute von 86 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 3-chloropropionate in a yield of 86%.

Beispiel 9Example 9 Herstellung von 4-Pyridiniumacetessigsäure-iso-propylester-chloridPreparation of isopropyl 4-pyridinium acetoacetic acid chloride

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 4-Chloracetessigsäure-iso-propylester in einer Ausbeute von 71 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and isopropyl 4-chloroacetoacetate in a yield of 71%.

Beispiel 10Example 10 Herstellung von 4-Pyridiniumacetessigsäure-tert.-butylester-chloridPreparation of 4-pyridiniumacetoacetic acid tert-butyl ester chloride

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 4-Chloracetessigsäure-tert.-butylester in einer Ausbeute von 73 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid tert-butyl ester in a yield of 73%.

Beispiel 11Example 11 Herstellung von 4-Pyridiniumacetessigsäuremethylester-chloridPreparation of 4-pyridiniumacetoacetic acid methyl ester chloride

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 4-Chloracetessigsäuremethylester in einer Ausbeute von 74 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid methyl ester in a yield of 74%.

Beispiel 12Example 12 Herstellung von 4-Pyridiniumacetessigsäureethylester-chloridPreparation of 4-pyridiniumacetoacetic acid ethyl ester chloride

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 4-Chloracetessigsäureethylester in einer Ausbeute von 70 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 4-chloroacetoacetic acid ethyl ester in a yield of 70%.

Beispiel 13Example 13 Herstellung von 2-Pyridiniumethyl-methylether-bromidPreparation of 2-pyridiniumethyl methyl ether bromide

Die Titelverbindung wurde analog zu Beispiel 1 aus Pyridin und 2-Bromethyl-methylether in einer Ausbeute von 69 % hergestellt.The title compound was prepared analogously to Example 1 from pyridine and 2-bromoethyl methyl ether in a yield of 69%.

AnwendungsbeispieleExamples of use

Die gemäß den Beispielen 1 bis 13 hergestellten Produkte wuren als Glanzmittel in schwach sauren galvanischen Bädern zur Abscheidung von Nickel eingesetzt.The products produced according to Examples 1 to 13 were used as brighteners in weakly acidic galvanic baths for the deposition of nickel.

Der verwendete wäßrige Nickelelektrolyt hatte folgende Zusammensetzung:
300 g/l NiSO₄ · 7 H₂O
60 g/l NiCl₂ · 6 H₂O
45 g/l H₃BO₃
2 g/l Saccharin
0,8 g/l Vinylsulfonsäure-Natriumsalz
x g/l Glanzbildner gemäß Tabelle
0,5 g/l eines Fettalkoholderivates der Formel C₁₂H₂₅/C₁₄H₂₉-O-(CH₂CH₂O)₂-SO₃Na als Netzmittel
Der pH-Wert des Elektrolyten wurde mit Schwefelsäure auf 4,2 eingestellt.The aqueous nickel electrolyte used had the following composition:
300 g / l NiSO₄7 H₂O
60 g / l NiCl₂ · 6 H₂O
45 g / l H₃BO₃
2 g / l saccharin
0.8 g / l vinyl sulfonic acid sodium salt
xg / l brightener according to table
0.5 g / l of a fatty alcohol derivative of the formula C₁₂H₂₅ / C₁₄H₂₉-O- (CH₂CH₂O) ₂-SO₃Na as a wetting agent
The pH of the electrolyte was adjusted to 4.2 with sulfuric acid.

Es wurden Messingbleche verwendet, die vor der Beschichtung mit Nickel in einem alkalischen Elektrolyten nach den üblichen Methoden kathodisch entfettet wurden. Die Nickelabscheidung erfolgte in einer 250 ml-Hull-Zelle bei 55°C und einer Stromstärke von 2A während eines Zeitraumes von 10 Minuten. Anschließend wurden die Bleche mit Wasser gespült und mit Preßluft getrocknet.Brass sheets were used, which were degreased cathodically in an alkaline electrolyte by the usual methods before the coating with nickel. The nickel was deposited in a 250 ml Hull cell at 55 ° C. and a current of 2A over a period of 10 minutes. The sheets were then rinsed with water and dried with compressed air.

Die folgende Tabelle zeigt die Ergebnisse dieser Versuche. Man erkennt, daß mit den erfindungsgemäßen Glanzbildnern ein stärkerer Glanz erzielt wurde als mit den Glanzbildnern des Standes der Technik, und das zum Teil bei deutlich niedrigerer Dosierung in den Nickelelektrolyt-Bädern.

Figure imgb0015
The following table shows the results of these tests. It can be seen that a greater gloss was achieved with the brighteners according to the invention than with the brighteners of the prior art, and in some cases with a significantly lower dosage in the nickel electrolyte baths.
Figure imgb0015

Die Vergleichsverbindungen C und D sind aus (3) bzw. (4) und die Vergleichsverbindung E ist aus (5) bekannt.The comparison compounds C and D are known from (3) and (4) and the comparison compound E is known from (5).

Claims (11)

  1. A process for producing nickelized shaped articles by electrodeposition of nickel from aqueous acidic baths containing as essential constituents one or more nickel salts, one or more inorganic acids and one or more brighteners, which comprises using brighteners that are cyclic ammonium compounds of the general formula I
    Figure imgb0026
     where the nitrogen atom is part of a pyridine, quinoline or isoquinoline ring system which can additionally carry one or two C₁-C₄-alkyl substituents,
    R¹ and R² are each hydrogen or C₁-C₄-alkyl,
    A is a group of the formula -CO-O-R³, -CO-CH₂-CO-O-R³, -O-CO-R³ or -O-R³, where
    R³ is C₁-C₁₂-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂-phenylalkyl or phenyl which can be substituted by one or two C₁-C₄-alkyl radicals, C₁-C₄-alkoxy radicals, halogen atoms, hydroxyl groups, phenyl radicals or C₁-C₄-alkoxycarbonyl groups,
    m is from 0 to 10, n is from 1 to 4, p is 0 or 1, and
    X⊖ is an n-valent inorganic or organic anion which promotes water solubility,
    with the proviso that for p = 0 and A = -CO-O-C₁-C₁₂-alkyl m must not be 1, 2 or 3 and under the same conditions R¹ must not be hydrogen when m is 0.
  2. A process for producing nickelized shaped articles as claimed in claim 1, wherein the brighteners used are cyclic ammonium compounds of the general formula Ia
    Figure imgb0027
     where the variables R¹, n and X⊖ are each as defined above, R⁴ is C₁-C₁₂-alkyl or C₅-C₈-cycloalkyl, and k is 0 or from 4 to 10, with the proviso that R¹ is not hydrogen when k is 0.
  3. A process for producing nickelized shaped articles as claimed in claim 1, wherein the brighteners used are cyclic ammonium compounds of the general formula Ib
    Figure imgb0028
     where the variables m, n and X⊖ are each as defined above and R⁵ is C₇-C₁₂-phenylalkyl or phenyl which can be substituted by one or two C₁-C₄-alkyl radicals.
  4. A process for producing nickelized shaped articles as claimed in claim 1, wherein the brighteners used are cyclic ammonium compounds of the general formula Ic
    Figure imgb0029
     where the variables R¹, R², R³, m, n and X⊖ are each as defined above.
  5. A process for producing nickelized shaped articles as claimed in claim 1, wherein the brighteners used are cyclic ammonium compounds of the general formula Id
    Figure imgb0030
     where the variables R¹, R³, n and X⊖ are each as defined above.
  6. A process for producing nickelized shaped articles as claimed in claim 1, wherein the brighteners used are cyclic ammonium compounds of the general formula Ie
    Figure imgb0031
     where the variables R¹, R³, n and X⊖ are each as defined above.
  7. A process for producing nickelized shaped articles as claimed in claim 1, wherein the brighteners used are cyclic ammonium compounds of the general formula If
    Figure imgb0032
     where the variables R¹, R², R³, m, n and X⊖ are each as defined above.
  8. A process for producing nickelized shaped articles as claimed in any of claims 1 to 7, wherein in addition to the cyclic ammonium compounds I at least one further brightener is used.
  9. Cyclic ammonium compounds of the general formula Ig
    Figure imgb0033
     where R⁴ is C₁-C₁₂-alkyl or C₅-C₈-cycloalkyl, k is 0 or from 4 to 10, n is from 1 to 4, X⊖ is an n-valent inorganic or organic anion which promotes water solubility, and R⁶ is C₂-C₄-alkyl.
  10. Cyclic ammonium compounds of the general formula Ih
    Figure imgb0034
     where m is from 0 to 10, n is from 1 to 4, X⊖ is an n-valent inorganic or organic anion which promotes water solubility, and R⁷ is C₇-C₁₂-phenylalkyl.
  11. Cyclic ammonium compounds of the general formula Ij
    Figure imgb0035
     where R¹ is hydrogen or C₁-C₄-alkyl, n is from 1 to 4, X⊖ is an n-valent inorganic or organic anion which promotes water solubility, and R⁸ is C₃-C₁₂-alkyl, C₅-C₈-cycloalkyl, C₇-C₁₂-phenylalkyl or phenyl which can be substituted by one or two C₁-C₄-alkyl radicals, C₁-C₄-alkoxy radicals, halogen atoms, hydroxyl groups, phenyl radicals or C₁-C₄-alkoxycarbonyl groups.
EP92919740A 1991-10-30 1992-09-21 Process for making nickel-plated castings Expired - Lifetime EP0610236B1 (en)

Applications Claiming Priority (3)

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DE4135710A DE4135710A1 (en) 1991-10-30 1991-10-30 CYCLIC AMMONIUM COMPOUNDS AND THE USE THEREOF AS A GLOSS AGENT FOR AQUEOUS-ACID GALVANIC NICKEL BATHS
DE4135710 1991-10-30
PCT/EP1992/002180 WO1993009275A1 (en) 1991-10-30 1992-09-21 Process for making nickel-plated castings

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EP0610236B1 true EP0610236B1 (en) 1995-09-20

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WO2004072320A2 (en) * 2003-02-07 2004-08-26 Pavco, Inc. Use of n-allyl substituted amines and their salts as brightening agents in nickel plating baths
WO2008070121A1 (en) * 2006-12-06 2008-06-12 Cornell Research Foundation, Inc. Intermediate duration neuromuscular blocking agents and antagonists thereof
US8592451B2 (en) 2009-03-17 2013-11-26 Cornell University Reversible nondepolarizing neuromuscular blockade agents and methods for their use
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DE1191652B (en) * 1963-05-15 1965-04-22 Dehydag Gmbh Acid galvanic nickel bath
US3206383A (en) * 1964-03-26 1965-09-14 Kappel Mario Electrolyte for use in the galvanic deposition of bright leveling nickel coatings
DE1496833A1 (en) * 1966-12-05 1969-07-17 Henkel & Cie Gmbh Acid galvanic nickel bath
FR2292057A1 (en) * 1974-11-20 1976-06-18 Popescu Francine Bright nickel electroplating bath - contg. pyridinium cpd. as primary brightener for level ductile deposits
US4457934A (en) * 1982-05-01 1984-07-03 Stauffer Chemical Company Insect repellent compounds
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Chemical Abstracts, Band 115, 1991, Banks, Roland Eric et al: "Fluorcarbon derivates of nitrogen. Part 19. Synthesis and mass spectometric analysis of some pyridnium (tetrafluoro-4-pyridy) methylides" Zusammenfassung 158920c, & J. Fluorine Chem., 53(1), 127-142 *

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