Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/24—Polysulfonates
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
• • 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
• • 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
  • C25D3/16—Acetylenic compounds

Definitions

• R and R are from the group of oxymethylene and oxyethylene, m and m are each an integer of 01, n and n are each an integer of 1-2, and y is an integer of at least 1.
• This invention relates to novel condensation reaction products of a naphthosultone and an acetylenically unsaturated glycol, and more especially to new and improved nickel electroplating baths containing such condensation reaction products, as additives, novel compositions containing the condensation reaction products herein and especially well suited as brightener additives for the baths, and an improved method for electroplating nickel involving the use of the new baths herein. Additionally, this invention relates to the condensation reaction products per se, and a novel method for the preparation of such products.
• One object of this invention is to provide new and improved nickel electroplating baths for providing bright nickel deposits.
• Another object is to provide novel condensation reaction products of .a naphthasultone, for instance a 1,8-naphthosultone, with an acetylenically unsaturated glycol, eminently well suited as a brightener additive for nickel electroplating baths.
• a further object is to provide new compositions containing such new condensation reaction products and especially well suited as brightener additives for nickel electroplating baths.
• a further object is to provide a new and improved process for the preparation of the novel condensation reaction products herein.
• An additional object is to provide an improvement in the method for electroplating nickel.
• the naphthosultone herein is the inner anhydride of the corresponding hydroxynaphthalene sulfonic acid.
• the 1,8-naphthosult0ne is the inner anhydride of l-hydroxynaphthalene-8-sulfonic acid
• the 1,7-naphthosultone is the inner anhydride of 1-hydroxynaphthalene-7-sulfonic acid.
• the 1,8-naphth0sultone has the formula:
• the condensation reaction is carried out with the naphosulfone and acetylenically unsaturated glycol present in at least those amounts required to stoichiometrically react to form the condensation reaction product herein.
• the naphthosultone and acetylenically-unsaturated glycol are reacted together in equimolar portions to form the condensation reaction product.
• the prior nickel plating baths which are improved upon by the present invention contain water as solvent or continuous phase, and a water-soluble compound of nickel, for instance a nickel salt such as the sulfate, sulfamate or fluoborate of nickel.
• a water-soluble compound of nickel for instance a nickel salt such as the sulfate, sulfamate or fluoborate of nickel.
• these acid baths usually contain chloride ions to enable anode corrosion, boric acid, a stabilizer for the bath, one or more levelling agents, and one or more depressants of surface tension or wetting agents.
• the novel condensation reaction product or products of naphthosultones and heterocyclic aromatic compounds containing one or more five-membered heterocyclic rings including at least one ring nitrogen atom and one or more labile hydrogen atoms can be added to the bath as levelling agent.
• levelling agents are disclosed and claimed in copending US. patent application Ser. No. 492,266, entitled, Nickel Electrodepositing Baths and Novel Condensation Reaction Products as Levelling Agents Therefor, filed Oct. 1, 1965.
• the condensation reaction product herein has a molecular structure including one or more units of the formula:
• the bath sation reaction. 5 comprises at least one bath-compatible condensation reac- When butynediol, e.g.
• 2-butyne-l,4-diol is the glycol tion product compound of a sultone, for example the naphcondcnsed with the naphthosultone, the product obtained tho-1,8 sultone, with the acetylenically unsaturated has a molecular structure including one or more units of glycol, i.e. the glycol as such, e.g. a butynediol, or a the formula: derivative of the unsaturated glycol and especially the hishydroxyethylether of the butynediol, in a proportion of --S02 0 CH CH preferably from about 0.05 to about 2 g./l.
• Such a bath is preferably operated as follows:
• the naphthosultone herein is illustrated by the following (4) current density of amps/(1mg, optimally 7 equatlon: amps/dm. for a bath temperature of 65 C.
• the novel condensation reaction product herein can be I added to the plating bath either as such or when in solution in an inert, i.e. non-reactive with respect to the con- HO-(CHg)nOECGHiOH stituents of the plating bath, liquid solvent.
• exemplary of the inert liquid solvent is water.
• any inert liquid solvent which is compatible with the electroplating bath L I can be utilized.
• the proportions of the condensation re- OCH;)OEC-GH3 ⁇ O- action product in such additive agent composition can be k j varied over wide limits, and do not form a part of this H 0 invention. It will suffice to point out that with higher smaller quantities of such addition agent composition are y required to be added to the bath to obtain the desired concentration therein of such product, than when lower concentrations of the condensation reaction product are present in the additive agent composition.
• reaction products herein comprises, in its broader aspects,
• Acetylenically-unsaturated glycols suitable for the conheating a mixture of the naphthosultone and the acetydensation reaction herein include the mono-acetylenically lenically unsaturated glycol to an elevated reaction temunsaturated glycols and especially those having 4-8 inperature below 95 C., and maintaining the mixture at elusive carbon atoms per molecule, for instance the buthe reaction temperature until its viscosity increases aptynediols, e.g.
• the naphthosultones herein are prepared by the intraually heating a mixture of the naphthosultone and acetmolecular condensation of the corresponding hydroxyylenically unsaturated glycol, usually in equimolar pornaphthalene sulfonic acid, and the 1,8-naphthosultone is tious, to an elevated temperature below C., preferobtainable in commerce.
• the acetylenically unsaturated 65 ably of the order of 50 C., to effect dissolution of the glycols, the butynediols, are also obtainable in commerce, naphthosultone in the glycol.
• the thus-obtained soluas are the bis-hydroxyethylethers of butynediols. tion is then heated to a reaction temperature above 65 Nickel electroplating baths improved upon by the pres- C.
• ent invention contain, in addition to water as solvent or and the solution maintained at a reaction temperature continuous phase, the following: within the range stated until the solution becomes of a (1) nickel ions, as sulfate, sulfamate, or fluoborate. syrupy consistency which typically requires about 4 hours (2) chloride ions, to permit anode corrosion. time.
• the thus-treated mixture is then cooled to room (3) boric acid. temperature.
• a stabilizer such as saccharine, paratoluenesulfon-
• the following examples further illustrate the invention amide, hexamrnine, or cyanuric acid. but are not restrictive thereof.
• n and n' are each an integer of 1-2, and y is an integer of value of at least 1.
• y is an integer of value of at least 1.
• acetylenically unsaturated glycol e.g. butynediol or the bis-hydroxyethylether of butynediol
• the naphthosultone e.g. 1,8-naphthosultone.
• the mixture is gradually heated to about 50 C. thereby dissolving the 1,8-naphthosultone, and then the mixture is heated to about 80 C. and maintained at that temperature for 4 hours; whereby the viscosity increases until the liquid becomes syrupy.
• the temperature of the mixture is then returned to ambient or room temperature.
• the solution thus obtained is useable directly as a brightener under the conditions cited above.
• those baths containing Compound A give the better results; in particular, nickel electroplating baths containing Compound A produce nickel deposits which are brighter and better levelled at microns thickness than those produced from baths containing Compound B to microns thickness.
• baths containing brighteners of this invention produce extremely brilliant deposits even when quite thin.
• nickel electroplating baths were prepared which were identical to those containing Compound A, but in which the compound was replaced by equivalent quantities of unreacted bis-hydroxyethylether of butynediol and of 1,8-naphthosultone as such (i.e., not subjected to the aforementioned condensation reaction).
• the nickel deposits obtained from such baths were semibright, cloudy and non-levelled, and were of no commercial importance.
• composition comprising a solution in an inert liquid solvent of a compound having a molecular structure including at least one unit of the formula:
• R and R are selected from the group consisting of oxymethylene and oxyethylene and are the same, m and m are each an integer of 0-1,
• R and R are selected from the group consisting of oxymethylene and oxyethylene and are the same,
• n and m are each an integer of 0-1,
• n and n are each an integer of 1-2, and
• y is an integer of value of at least 1.
• composition of claim 2 wherein the compound has a molecular structure including at least one unit of the formula:
• n and n are each an integer of 1-2, and y is an integer of value of at least 1. 4.
• the compound has a molecular structure including at least one unit of the formula:
• R and R' are selected from the group consisting of oxymethylene and oxyethylene and are the same,
• In and m are each an integer of 0-1,
• n and n' are each an integer of 1-2, and
• y is an integer of value of at least 1. said compound being present in the bath in an amount sufficient to impart brightness to the nickel electroplate.
• n and n are each an integer of 12, and y is an integer of value of at least 1.
• the compound has a molecular structure including at least one unit of the formula:
• y is an integer of value of at least 1.
• An aqueous acidic nickel electroplating bath containing a source of nickel ions and as a brightener a compound having a molecular structure including at least one unit of the formula:
• R and R are selected from the group consisting of oxymethylene and oxyethylene and are the same, In and m are each an integer of 0-1, n and n are each an integer of 1-2, and y is an integer of value of at least 1,
• y is an integer of value of at least 1.
• An aqueous acidic nickel electroplating bath containing a source of nickel ions and as a brightener a compound having a molecular structure including at least one unit of the formula:
• R and R are selected from the group consisting of oxymethylene and oxyethylene and are the same, m and m are each an integer of 0-1, n and n are each an integer of 1-2, and y is an integer of value of at least 1, said compound being present in the bath in an amount sufficient to impart brightness to the nickel electroplate.
• the brightener is contained therein in amount of approximately 0.05 to 2 g./l.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Electroplating And Plating Baths Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

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Country Status (8)

Cited By (2)

Citations (2)

• 1964
  • 1964-10-08 FR FR990781A patent/FR1418245A/fr not_active Expired
• 1965
  • 1965-01-12 DE DEP35856A patent/DE1232799B/de active Pending
  • 1965-04-13 NL NL6504674A patent/NL6504674A/xx unknown
  • 1965-04-22 BE BE662877D patent/BE662877A/xx unknown
  • 1965-04-23 GB GB17297/65A patent/GB1089745A/en not_active Expired
  • 1965-04-23 SE SE5313/65A patent/SE305787B/xx unknown
  • 1965-06-08 IL IL23689A patent/IL23689A/xx unknown
  • 1965-10-01 US US500462A patent/US3457146A/en not_active Expired - Lifetime

Patent Citations (2)

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