GB1578168A - Pyridyl alkylsulphonic acid derivatives and their use in electroplating baths - Google Patents
Pyridyl alkylsulphonic acid derivatives and their use in electroplating baths Download PDFInfo
- Publication number
- GB1578168A GB1578168A GB931877A GB931877A GB1578168A GB 1578168 A GB1578168 A GB 1578168A GB 931877 A GB931877 A GB 931877A GB 931877 A GB931877 A GB 931877A GB 1578168 A GB1578168 A GB 1578168A
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- GB
- United Kingdom
- Prior art keywords
- pyridyl
- acid betaine
- methyl
- ethanesulfonic acid
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 125000004076 pyridyl group Chemical group 0.000 title claims abstract description 21
- 238000009713 electroplating Methods 0.000 title claims abstract description 12
- 239000002253 acid Substances 0.000 title abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- -1 alkali metal salt Chemical class 0.000 claims abstract description 15
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 100
- 229960003237 betaine Drugs 0.000 claims description 50
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- QKHOXQJNDCOOCU-UHFFFAOYSA-M [Na+].N1=C(C=CC=C1)C(C)S(=O)(=O)[O-] Chemical compound [Na+].N1=C(C=CC=C1)C(C)S(=O)(=O)[O-] QKHOXQJNDCOOCU-UHFFFAOYSA-M 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- AKLOQBSHNNYBRY-UHFFFAOYSA-M sodium;2-hydroxybutane-1-sulfonate Chemical compound [Na+].CCC(O)CS([O-])(=O)=O AKLOQBSHNNYBRY-UHFFFAOYSA-M 0.000 claims description 6
- 125000006277 halobenzyl group Chemical group 0.000 claims description 5
- UNXCZDNUXJJWHY-UHFFFAOYSA-M sodium;2-hydroxypropane-1-sulfonate Chemical compound [Na+].CC(O)CS([O-])(=O)=O UNXCZDNUXJJWHY-UHFFFAOYSA-M 0.000 claims description 5
- LSPPRHYSWKZGRZ-UHFFFAOYSA-M sodium;3-hydroxybutane-1-sulfonate Chemical compound [Na+].CC(O)CCS([O-])(=O)=O LSPPRHYSWKZGRZ-UHFFFAOYSA-M 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000005394 methallyl group Chemical group 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 101000654316 Centruroides limpidus Beta-toxin Cll2 Proteins 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000000354 decomposition reaction Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VQRBXYBBGHOGFT-UHFFFAOYSA-N 1-(chloromethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CCl VQRBXYBBGHOGFT-UHFFFAOYSA-N 0.000 description 3
- LFYCNCNFPPSEHG-UHFFFAOYSA-N 1-pyridin-2-ylethanesulfonic acid Chemical compound OS(=O)(=O)C(C)C1=CC=CC=N1 LFYCNCNFPPSEHG-UHFFFAOYSA-N 0.000 description 3
- GFJMOZYIDADKLJ-UHFFFAOYSA-N 5-bromo-2-chloro-3-methoxypyridine Chemical compound COC1=CC(Br)=CN=C1Cl GFJMOZYIDADKLJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 3
- 229940043264 dodecyl sulfate Drugs 0.000 description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical class CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RLHYTSTWIJTQAV-UHFFFAOYSA-M sodium;1-pyridin-4-ylethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(C)C1=CC=NC=C1 RLHYTSTWIJTQAV-UHFFFAOYSA-M 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- RNASMWVEQFLFSS-UHFFFAOYSA-N 1-pyridin-4-ylethanesulfonic acid Chemical compound OS(=O)(=O)C(C)C1=CC=NC=C1 RNASMWVEQFLFSS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229940081974 saccharin Drugs 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 235000019204 saccharin Nutrition 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical group ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- AVYIOHJNFRTXIT-UHFFFAOYSA-N 1-methylpyridin-1-ium-3-sulfonate Chemical compound C[N+]1=CC=CC(S([O-])(=O)=O)=C1 AVYIOHJNFRTXIT-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DDLBHIIDBLGOTE-UHFFFAOYSA-N 3-chloro-2-hydroxypropane-1-sulfonic acid Chemical class ClCC(O)CS(O)(=O)=O DDLBHIIDBLGOTE-UHFFFAOYSA-N 0.000 description 1
- RTTNOHLFPFFOCA-UHFFFAOYSA-N 3-hydroxybutane-1-sulfonic acid Chemical compound CC(O)CCS(O)(=O)=O RTTNOHLFPFFOCA-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- DVECLMOWYVDJRM-UHFFFAOYSA-N pyridine-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CN=C1 DVECLMOWYVDJRM-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- VZPUIKDUJMGHMI-UHFFFAOYSA-M sodium;pyridin-2-ylmethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC1=CC=CC=N1 VZPUIKDUJMGHMI-UHFFFAOYSA-M 0.000 description 1
- IOIFBRXXRABJET-UHFFFAOYSA-M sodium;pyridin-4-ylmethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC1=CC=NC=C1 IOIFBRXXRABJET-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- NJPKYOIXTSGVAN-UHFFFAOYSA-K trisodium;naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(S([O-])(=O)=O)=CC2=CC(S(=O)(=O)[O-])=CC=C21 NJPKYOIXTSGVAN-UHFFFAOYSA-K 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/32—Sulfur atoms
- C07D213/34—Sulfur atoms to which a second hetero atom is attached
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Pyridine Compounds (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The novel pyridylalkylsulphonic acid betaines of the general formula I <IMAGE> in which the substituents are as defined in Claim 1, are obtained by reacting a 2- or 4-pyridylalkylsulphonic acid or an alkali metal salt thereof with a suitable quaternising agent which is capable of introducing the substituent R on the ring nitrogen atom of the pyridyl group. The compounds of the formula (I) usually give an extremely uniform and flat nickel coating of outstanding ductility, when it is used as additive for conventional nickel electroplating baths. The compounds can be used in the nickel baths either alone or in combination with other additives which promote brightness or levelling.
Description
(54) NOVEL PYRIDYL ALKYLSULPHONIC ACID DERIVATIVES
AND THEIR USE IN ELECTROPLATING BATHS
(71) We, CILAG CHEMIE A.G., a Swiss Body Corporate, of Hochstrasse 209, Schaffhausen, Switzerland, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
The present invention relates to certain novel pyridyl alkyl sulfonic acid betaines useful as additives to nickel electroplating baths.
Pyridyl sulfonic acids or pyridyl alkyl sulfonic acids as additives to nickel plating baths have been reported. United States Patent No 2,839,456, describes the use of 4-pyridyl ethane sulfonic acid, in combination with other additives, as a brightener. Although 2- and 4-pyridine ethane sulfonic acids do improve the luster of deposited nickel layers, they do not influence their levelling. United States Patent No 3,444,056 mentions certain quaternary compounds of pyridine-3-sulfonic acid as levellers and brighteners. The
N-methyl-pyridine-3-sulfonic acid betaine and N-allyl-pyridine-3-sulfonic acid betaine mentioned in this patent are, however, not fully satisfactory. The nickel deposits turn lusterless and brittle with a too low ampere hour load per liter of nickel bath. This behavior of the bath cannot be prevented by any of the regeneration methods employed in electroplating. The compounds of the present invention produce a highly levelled nickel deposit of excellent ductility in a far more constant bath.
The present invention provides pyridyl alkyl sulfonic acid betaines of the general formula:
in which the substituent -(CH2)nSO3e' is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a methyl; methallyl; CH2COOH; sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; halobenzyl; loweralkylbenzyl or benzyl group substituted with the group:
wherein the substituent -(CH2)nSO8 is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2.
For the purposes of nomenclature, the aforementioned groups: sodium 2hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate and sodium 3hydroxybutylsulfonate may also be denoted as 3-Na-sulfo-2-hydroxypropyl, 4-Na-sulfo-2 hydroxybutyl and 4-Na-sulfo-3-hydroxybutyl, respectively.
By the term "loweralkyl" as used herein is meant an aliphatic hydrocarbon with from 1 to 4 carbon atoms; and by the term "halo" is meant fluorine, chlorine and bromine, that is, those halogens with an atomic weight of less than 80.
The pyridyl alkyl sulfonic acid betaines (I) of the present invention are conveniently prepared by quaternization of an appropriate 2- or 4-pyridyl alkyl sulfonic acid (II-a) or its alkali metal salt (II-b), preferably the sodium salt:
wherein the substituent -(CH2)nSO3(H,Z) is in the 2- or 4-position of the pyridyl ring and n is 1 or 2. Quaternization is accomplished by using an appropriate quaternizing agent suitable for introducing the aforementioned R-substituent on the ring nitrogen of the pyridyl group, such as, dimethyl sulfate, methallyl chloride, sodium chloroacetate, an appropriate benzyl halide or an appropriately substituted haloloweralkyl, as more fully described and exemplified hereinafter. The compounds of formulae (II-a) and (II-b) are obtained from known procedures in the art, for example, by reaction between 2- or 4-vinylpyridine and sodium bisulfite according to J. Am. Chem. Soc., 69, 2465 (1947) for the preparation of the ethyl sulfonic acids or by reaction between appropriate haloalkyl pyridines and sodium sulfite.
To prepare the formula (I) compounds in which R is methyl, the precursor (II-a) or (II-b) is reacted with dimethyl sulfate as the quaternizing agent, generally utilizing a slight stoichiometric excess of the latter. Elevated temperatures may be employed to enhance the rate of reaction. Since dimethyl sulfate is a liquid at ambient temperatures, the use of an additional organic solvent for the quaternization reaction is normally unnecessary. The reaction may be illustrated as follows:
To prepare the formula (I) compounds in which R is CH2COOH, approximately equimolar amounts of the precursor (II-b) and haloacetic acid in the form of an alkali metal salt, for example, sodium (III) in an aqueous solvent are reacted, preferably under reflux conditions. The reaction mixture containing the so-formed alkali metal salt is then cooled and treated with a suitable mineral acid, e.g., hydrochloric acid, to convert the salt (IV) to its corresponding acid form (V). The foregoing reaction may be illustrated as follows:
The compounds of formula (I) wherein R is halobenzyl or loweralkylbenzyl are prepared in similar fashion. The precursor (II-b) is reacted with an appropriate benzyl halide (VI), e.g., halobenzyl chloride or loweralkylbenzyl chloride, in water, preferably under reflux conditions. After cooling and treatment with mineral acid, the desired N-benzyl substituted Droduct (VII is ohtained.
R' =H, halo, loweralkyl
The compounds of formula (I) wherein R is methylallyl may be similarly quaternized, as described above for R as a benzyl group, except that methallyl chloride is used as the quaternizing agent.
The compounds of formula (I) wherein R is sodium 2-hydroxypropylsulfonate, sodium 2-hydroxybutylsulfonate or sodium 3-hydroxybutylsulfonate are obtained by quaternizing (II-b) with an appropriate halo-hydroxyalkyl sulfonic acid in sodium salt form, as illustrated below by sodium 2-hydroxypropylsulfonate (X).
To prepare the compounds of formula (I) wherein R is benzyl substituted with the group:
a,a'-dichloroxylol (o-, m- or p-form) is reacted with at least two stoichiometric equivalents of the precursor (II-b) in an aqueous solvent. Elevated temperatures are advantageously employed to enhance the rate of reaction. Upon completion of the reaction and subsequent cooling of the reaction mixture, followed by treatment with mineral acid, the desired products are obtained through conventional recovery techniques. The foregoing quaternization can be illustrated with a,a'-dichloro-p-xylene as follows:
The compounds of formula (I) produce a highly levelled nickel deposit of excellent ductility when used as additives for the electro-deposition of nickel coatings in conventional galvanic nickel baths. These compounds are suitable for use in galvanic nickel baths either alone or in combination with other luster-promoting or levelling additives. For example, an optimum luster is obtained in combination with such generally known brighteners as saccharin, diarylsulfonimides, naphthalene trisulfonic acids or sulfonates or acetylenic compounds, such as propargyl alcohol. The latter compound is especially useful in enhancing the levelling effect of the compounds of the invention. Furthermore, the compounds of the invention may be used in conjunction with conventional wetting agents such as, for example, sodium lauryl sulfate or with other ionized or non-ionized agents that decrease surface tension. The galvanic baths may also contain conventional buffering agents, such as boric acid or tartrates.
The galvanic bath comprises an acidic solution of a nickel salt, preferably nickel sulfate, nickel sulfamate, nickel fluoborate, nickel chloride or nickel acetate. Mixtures of such salts are also suitable. Typical of the nickel galvanic baths in which the compounds (I) of the invention may be employed are those described in United States Patent No 3,444,056. The compounds of the invention may be advantageously used in concentrations ranging from 0.05 gram per liter (g/l) to 2.0 g/l of bath, although from 0.1 to 0.5 g/l is preferred. Other preferred parameters are a bath temperature of about 50 to 60"C, a pH of about 3.5 to 5.0 most preferably 4.5, and a current density ranging from 1 to 10 amp/dm2. The bath may be mechanically or air stirred. If it is air stirred, the use of a non-foamy agent is recommended.
The present invention also provides an electroplating bath for electro-depositing levelled and lustrous nickel comprising an electroplating bath which comprises an aqueous acidic solution of at least one nickel salt and at least one additive which is a compound of the formula:
in which the substituent -(CH2),S030 is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2, and R is a methyl; methallyl; CH2COOH; CH2(CH2)CH2SO3Na wherein x is the integer 1 or 2; sodium 2-hydroxypropyl-sulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; benzyl; halobenzyl; loweralkylbenzyl; or benzyl group substituted with the group;
wherein the substituent -(CH2)nSO8 is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2, in a concentration of from 0.05 to 2.0 grams per liter, and preferably, from 0.1 to 0.5 grams per liter. The preferred additives of formula (I) are those wherein R is either benzyl or a benzyl group substituted with the previously described group:
including but not limited to 2-[N-benzylpyridyl-(2)1-ethane sulfonic acid betaine and 1 ,2-bis[2-(2-sulfoethyl)-pyridinium-(1)-methyljbenzene.
The following Examples are intended to illustrate, but not to limit, the scope of the present invention. Example IV, Example V (first two compounds) and Example VI relate to the preparation of certain pyridyl alkyl sulfonic acid betaines which may be used in the electroplating baths of the present invention.
EXAMPLE I
A. 2-[N-carboxymethyl-pyridyl- (2)]-ethanesulfonic acid betaine: 23.3 Grams (0.2 mol) of chloroacetic acid sodium salt, 41.8 g (0.2 mol) of 2-pyridyl ethane sulfonic acid sodium salt and 50 g of water are refluxed for five hours Following cooling down to 20"C, the reaction mixture is treated with 250 g of concentrated hydrochloric acid.
The crystallized sodium chloride is filtered off by suction and the solution is concentrated to dryness under vacuum. The residue is mixed with 350 ml of methanol. The product, 27.5 g of 2-[N-carboxymethyl-pyridyl-(2)]-ethane-sulfonic acid betaine, which crystallizes at room temperature is filtered off by suction and vacuum dried at 1100C; decomposition point: 214"C.
B. 2-[N-carboxymethyl-pyridyl- (4)]-ethane sulfonic acid betaine is obtained in the same way, by employing an equivalent quantity each of 4-pyridyl ethane sulfonic acid sodium salt and chloroacetic acid sodium salt as reactants; decomposition point: 234"C.
C. [N-carboxymethyl-pyridyl-(4)]-methanesulfonic acid betaine is obtained in the same way, by employing an equivalent quantity each of 4-pyridyl methane sulfonic acid sodium salt and chloroacetic acid sodium salt as reactants; decomposition point: 290"C.
EXAMPLE II
A. 2-[N-methyl-pyridyl-(2)]-ethane sulfonic acid betaine: 55 Grams (0.29 mol) of 2-pyridyl ethane sulfonic acid and 40.7 g (0.32 mol) of dimethyl sulfate are heated to 150-155"C. Two hours later the reaction mixture is allowed to cool down to 20"C and a mixture of 40 ml of ethanol and 40 ml of isopropanol are added. After standing for 24 hours, the precipitated crude product is filtered off by suction. After double recrystallization from methanol, the white crystals are vacuum dried at 80"C. The final yield is 16.8 g of 2-[N-methyl-pyridyl-(2)j-ethane sulfonic acid betaine; decomposition point: 2090C.
B. 2-[N-methyl-pyridyl-(4)/-ethane sulfonic acid betaine is prepared in the same manner from equivalent amounts of 4-pyridyl ethane sulfonic acid and dimethyl sulfate.
EXAMPLE 111
A. 2-[N-(2-methylbenzyl)-pyridyl-(2)]-ethane sulfonic acid betaine: 41.8 Grams (0.2 mol) of 2-pyridyl ethane sulfonic acid sodium salt, 28.1 g (0.2 mol) of o-methylbenzyl chloride and 20 g of water and refluxed for 5 hours. The reaction mixture is then allowed to cool down to 2UOC and 250 g of concentrated hydrochloric acid are added.
The precipitated sodium chloride is filtered off by suction and the filtrate concentrated to dryness under vacuum. The residue is mixed with 200 ml of ethanol and the precipitated white crystal mass is filtered off by suction and vacuum dried at 1100C to yield 32 g of 2-[N-(2-methylbenzyl)-pyridyl-(2)]-ethane sulfonic acid betaine; decomposition point: 223 C.
B. 2-[N-(2-methylbenzyl)-pyridyl-(4)]-ethane sulfonic acid betaine is obtained in the same way, by using an equivalent quantity each of 4-pyridyl ethane sulfonic acid sodium salt and o-methylbenzylchloride as reactants; decomposition point: 241"C.
EXAMPLE IV
[N-benzyl-pyridyl-(2)]methane sulfonic acid betaine: 17.3 Grams (0.1 mol) of 2-pyridyl methanesulfonic acid sodium salt, 12.7 g (0.1 mol) of benzylchloride and 13 g of water are refluxed for 2 hours at 100-1050C. The reaction mixture is allowed to cool down to 200C and 100 ml of concentrated hydrochloric acid are added. The precipitated sodium chloride is filtered off and the solution concentrated to dryness. The residue is mixed with 100 ml of ethanol. The precipitated white crystals are filtered off and vacuum dried at 1100C to yield 13.7 g of N-benzyl-pyridyl-(2) methane sulfonic acid betaine; decomposition point: 230"C.
EXAMPLE V
By following the procedures of Examples III and IV, except that equivalent quantities of appropriate reactants are employed, the following respective products are obtained:
2-[N-benzylpyridyl-(2)] ethane sulfonic acid betaine; decomposition point: 198 C.
2-[N-benzylpyridyl-(4)-ethane sulfonic acid betaine; decomposition point: 234 C.
2-[N-(2-chlorobenzyl)-pyridyl-(2)]-ethane sulfonic acid betaine; decomposition point: 2380C.
2-[N-(4-chlorobenzyl)-pyridyl-(2)]-ethane sulfonic acid betaine; decomposition point: 201 C 2-[N-(2-chlorobenzyl)-pyridyl-(4)]-ethane sulfonic acid betaine; decomposition point:
237 C.
EXAMPLE VI
A. 2-[N-(3-Na-sulfopropyl)-pyridyl-(2)]-ethane sulfonic "acid betaine: 4i.8 Grams (0.2 mol) of 2-pyridyl ethane sulfonic acid sodium salt, 30.5 g (0.25 mol) of propansultone, 200 g of methanol and 15 g of water are heated to 65 C for 7 hours. The reaction mixture is then concentrated under vacuum and the residue is mixed with 200 ml of concentrated hydrochloric acid. The precipitated sodium chloride is filtered off and the mother liquor concentrated to dryness. The oily residue is! dissolved in 200 my of methanol and allowed to stand for 2 days. Some 2-pyridyl ethane sulfonic acid, whicE'precipitates within this time, is filtered off and'the filtrate is neutralized with 30% sodium methylate solution (in methanol). A white salt precipitates which is filtered off and vacuum dried at 110 C to yield 17 g of 2-[N-(3-Na-sulfopropyl)-pyridyl-(2)]-ethane sulfonic acid betaine; decomposition point: 228 C B. The procedure of Example VI-A is repeated except that an equivalent amount of butansultone is substituted for the propansultone used therein to yield the corresponding product, 2-[N-(4-Na-sulfobutyl)-pyridyl-(2)]-ethane sulfonic acid betaine.
C. By following the procedure of Example VI-A, except that equivalent amounts of appropriate starting materials are employed as reactant, there are obtained as respective products:
[N-(3-Na-sulfopropyl)-pyridyl-(4)]-methane sulfonic acid betaine; and
2-[N-(4-Na-sulfobutyl)-pyridyl-(4)]-ethane sulfonic arid betaine.
EXAMPLE VII
A. 2-[N-(3-Na-sulfo-2-hydroxypropyl)-pyridyl-(2)]-ethane sulfonic acid betaine: 20.9 Grams (0.1 mol) of 2-pyridyl ethane sulfonic acid sodium salt, 19.7 g (0.1 mol) of 3-chloro-2-hydroxypropyl sulfonic acid-'(1)-sodium salt and 20 ml of water are heated at 95 C for 6 hours. The reaction mixture is then concentrated under vacuum and the residue is mixed with 100 ml of concentrated hydrochloric acid. The insoluble sodium chloride is filtered off and the mother liquor concentrated to dryness. The oily residue is dissolved in 100 ml of methanol and allowed to stand for 2 days. Some 2-pyridyl ethane sulfonic acid, which precipitates within this time, is filtered off and the filtrate is neutralized with 30% sodium methylate solution (in methanol). The precipitated white salt is filtered off and vacuum dried at 110 C to yield 11 g of 2-[n-(3-Na-sulfo-2-hydroxypropyl)-pyridyl-(2)]- ethane sulfonic acid betaine; decomposition point: 183 C.
B. The procedure of Example VlI-A is followed, except that equivalent amounts of appropriate starting materials are employed as reactants, to yield the following respective products:
2-[N-(4-Na-sulfo-2-hydroxybutyl)-pyridyl-(2) -'ethane sulfonic acid betaine;
2-[N-(4-Na-sulfo-3-hydroxybutyl)pyridyl-(4)]-ethane sulfonic acid betaine; and
[N-(3-Na-sulfo-2-hydroxypropyl)-pyridyl-(4)]-methane sulfonic acid betaine.
EXAMPLE VIII
A. 1, 4-Bis-[2- (2-sulfoethyl)-pyridinium- (1) -methyl7-benzene: 62.8 Grams (0.3 mol) of 2-pyridyl ethane sulfonic acid sodium salt, 17.5 g (0.1 mol) of α,α'-dichloro-p-xylene and 50 g of water are heated to 100-105 C for 4 hours. The reaction mixture is then cooled and 200 g of concentrated hydrochloric acid are added. The precipitated sodium chloride is filtered off and, the filtrate concentrated under vacuum to dryness. 200 Ml of methanol are added to the residue. The precipitated impure crystals are filtered off, dissolved in 120 ml of water at 200C, and again precipitated by adding 480 ml of ethanol. The white crystal mass is filtered off and vacuum dried at 110 C to yield 26 g of 1,4-bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene; decomposition point: > 350 C.
B. In the same manner, except that equivalent amounts of appropriate reactants are employed, there are obtained as respective products:
1,2-bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene; decomposition point: 248 C.
1,3-bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene; decomposition point: 251 C.
1,4-bis-[4-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene; decomposition point: 258 C.
EXAMPLE IX
The following illustrate typical galvanic nickel baths in which the subject compounds of formula (I) may be employed. It is understood that the hereinmentioned subject compounds are not listed for the purpose of limiting the scope of the invention thereto but to exemplify the usefulness of all compounds within formula (I).
A
Nickel sulfate . 7H2O .. ...g/l .. 310
Nickel chloride . 6H2O ...g/l .. 50
Boric Acid . .. . . . ...g/l .. 40
Lauryl sulfate . ...g/l .. 0.2
Saccharin .. .................. ...... . ..g/l .. 2.0 2-[N-benzylpyridyl-(2)]-ethanesulfonic
acid betaine ..g/l .. 0.3 pH . .... . . ........ .. 4.6.
Temperatur . . ... C .......... .. 50-60
Current density . ..amp/dm2.. 1-7
B
Nickel sulfate . 7H2O .. ...g/l .. 310
Nickel chloride . 6H2O ...g/l .. 50
Boric Acid . . ..g/l . 40
Lauryl sulfate ...g/l . 0.2
Saccharin sodium . ...... ..... ..... . ...g/l . 1.0 1,3,6-naphthalene trisulfonic acid sodium
salt .... .................. ...... . ...g/l . 1.0 2-[N-benzylpyridyl-(4)]-ethanesulfonic
acid betaine ..g/l .. 0.3 pH .... . ......... .. 4.6
Temperature .. . ... C........... ..50-60
Current density . . . ampldm- 1-7
C
Nickel sulfate . 7H2O ... ...g/l.. 280
Nickel chloride . 6H2O . . . g/l.. 40
Boric Acid .. . . ...g/l .. 40
Lauryl sulfate ...... . ...g/l.. 0.2
Dibenzylsulfonimide . ...g/l.. . 8.0
Propargyl alcohol ....... ..... ....... . ...g/l .. . 0.04
1,2-bis-[2-(2-sulfoethyl)-pyridinium(1) methyl]-benzene . . . . .g/l . 0.15 pH ..... . . ......... .. 4.6
Temperature . . C .. 50-60
Current density . ...amp/dm2.. 1-7
EXAMPLE X
A. The procedure of Example III-A is followed except that 18 g (0.2 mole) of methallyl chloride is substituted for the o-methylbenzyl chloride used therein to yield, as the final product, 2-[N-(2-methylpropen-2-yl)-pyridyl-(2)]-ethane sulfonic acid betaine, also known as 2-[N-methallyl-pyridyl-(2)]-ethane sulfonic acid betaine, decomposition point: 196 C.
B. 2-[N(2-methylpropen-2-yl)-pyridyl-(4)]-ethane sulfonic acid betaine, also known as 2-[N-methallyl-pyridyl-(4)1-ethane sulfonic acid betaine, decomposition point: 208 C, is obtained in similar fashion by using an equivalent quantity each of 4-pyridyl ethane sulfonic acid sodium salt and methallyl chloride as reactants.
Claims (25)
1. A pyridyl alkyl sulfonic acid betaine having the general formula:
in which the substituent - (Cll2)nSO30 is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a methyl; methallyl; CH2COOH; sodium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; halobenzyl; loweralkylbenzyl; or benzyl group substituted with the group:
wherein the substituent -(CH2)nSO38 is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2.
2. 2-[N-Carboxymethyl-pyridyl-(2)]-ethanesulfonic acid betaine.
3. 2-[N-Carboxymethyl-pyridyl-(4)]-ethanesulfonic acid betaine.
4. [N-Carboxymethyl-pyridyl-(4)]-methanesulfonic acid betaine.
5. 2-[N-Methyl-pyridyl-(2)]-ethanesulfonic acid betaine.
6. 2-[N-(2-Methylbenzyl)-pyridyl-(2)]-ethanesulfonic acid betaine.
7. 2- N-(2-Methylbenzyl)-pyridyl-(4) -ethanesulfonic acid betaine.
8. 2- N-(2-Chlorobenzyl)-pyridyl-(2) ethanesulfonic acid betaine.
9. 2- N-(4-Chlorobenzyl)-pyridyl-2) -ethanesulfonic acid betaine.
10. 2'- N- 2-Chlorobenzyl)-pyndyl-(4) -ethanesulfonic acid betaine.
11. 2-[N-(3-Na-Sulfo-2-hydroxypropyl)-pyridyl-(2)]-ethanesulfonic acid betaine.
12. 1,4-bis-[2-(2-Sulfoethyl)-pyridinium-(1)-methyl]-benzene.
13. 1,2-bis-[2-(2-Sulfoethyl)-pyridinium-(1)-methyl]-benzene.
14. 1,3-bis-[2-(2-Sulfoethyl)-pyridinium-(1)-methyl]-benzene.
15. 1,4-bis-[4-(2-Sulfoethyl)-pyridinium-(1)-methyl]-benzene.
16. 2-[N-Methallyl-pyridyl-(2)]-ethanesulfonic acid betaine.
17. 2-[N-Methallyl-pyridyl-(4)]-ethanesulfonic acid betaine.
18. A process for preparing a pyridyl alkyl sulfonic acid betaine having the formula:
in which the substituent groups are as defined in claim 1 which process comprises quaternizing, by methods known per se, an appropriate 2- or 4-pyridyl alkyl sulfonic acid
or its alkali metal salt
wherein Z is an alkali metal and the substituent -(CH2)nSO 3(H,Z) is in the 2- or 4-position of the pyridyl ring, and ii is 1 or 2 with an appropriate quaternizing agent to introduce the above defined R substituent onto the ring nitrogen of the pyridyl group.
19. A process for preparing 1,2-bis-[2-(2-sulfoethyl)-pyridinium-(1)-methyl]-benzene, which comprises reacting 2-pyridyl ethanesulfonic acid sodium salt with α,α'-dichloro-o- xylol.
20. A process as claimed in claim 18 substantially as hereinbefore described with reference to any one of Examples I to VI.
21. A pyridyl alkyl sulfonic acid betaine as claimed in claim 1 whenever prepared by a process as claimed in any one of claims 18 to 20.
22. An electroplating bath which comprises an aqueous acidic solution of at least one nickel salt and at least one additive which is a compound of the formula:
in which the substituent -CH)nSO3 is in the 2- or 4-position of the pyridyl ring; n is the integer 1 or 2; and R is a methyl; methallyl; CH2COOH; CH2(CH2)xCH2SO3Na wherein x is the integer 1 or 2; sddium 2-hydroxypropylsulfonate; sodium 2-hydroxybutylsulfonate; sodium 3-hydroxybutylsulfonate; benzyl; halobenzyl; loweralkylbenzyl, or benzyl group substituted with the group:
wherein the substituent -(CH2)nSO3 is in the 2- or 4-position of the pyridyl ring and n is the integer 1 or 2, in a concentration of from 0.05 to 2.0 grams per liter.
23. An electroplating bath as claimed in claim 22 wherein the additive is 1,2-bis-[2-(2sulfoethyl)-pyridinium- (l)-methyl]-benzene which is contained in the bath in a concentration of from 0.1 to 0.5 grams per liter.
24. An electroplating bath as claimed in claim 22 substantially as hereinbefore described with reference to Example IX.
25. An article whenever having a coating of nickel electro-deposited thereon from an electroplating bath as claimed in any one of claims 22 to 24.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66652576A | 1976-03-12 | 1976-03-12 | |
| US05/763,452 US4067785A (en) | 1976-03-12 | 1977-01-27 | Electroplating additives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1578168A true GB1578168A (en) | 1980-11-05 |
Family
ID=27099476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB931877A Expired GB1578168A (en) | 1976-03-12 | 1977-03-04 | Pyridyl alkylsulphonic acid derivatives and their use in electroplating baths |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS52116475A (en) |
| AT (1) | AT361266B (en) |
| BR (1) | BR7701506A (en) |
| CA (1) | CA1072098A (en) |
| CH (1) | CH630355A5 (en) |
| DE (1) | DE2710721A1 (en) |
| ES (1) | ES456723A1 (en) |
| FR (1) | FR2343729A1 (en) |
| GB (1) | GB1578168A (en) |
| IT (1) | IT1083723B (en) |
| NL (1) | NL7702673A (en) |
| SU (1) | SU791230A3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2242200A (en) * | 1990-02-20 | 1991-09-25 | Omi International | Plating compositions and processes |
| EP0752420A1 (en) * | 1995-07-06 | 1997-01-08 | Giuseppe Faranda | Process for the preparation of 1-(3-sulphopropyl)-pyridinium-betaine |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2839456A (en) * | 1956-11-16 | 1958-06-17 | Hanson Van Winkle Munning Co | Electroplating |
| US3336324A (en) * | 1966-06-24 | 1967-08-15 | Cilag Chemie | N-allyl-pyridine-3-sulfonic acid betaine |
| DE1621157A1 (en) * | 1967-08-16 | 1971-05-19 | Riedel & Co | Acid galvanic nickel bath |
| US3821095A (en) * | 1972-09-26 | 1974-06-28 | M & T Chemicals Inc | Zinc electroplating process and electrolyte therefor |
| US3862019A (en) * | 1974-04-26 | 1975-01-21 | R O Hull & Company Inc | Composition of electroplating bath for the electrodeposition of bright nickel |
-
1977
- 1977-03-04 GB GB931877A patent/GB1578168A/en not_active Expired
- 1977-03-10 ES ES456723A patent/ES456723A1/en not_active Expired
- 1977-03-10 IT IT4841677A patent/IT1083723B/en active
- 1977-03-10 JP JP2554577A patent/JPS52116475A/en active Pending
- 1977-03-11 AT AT166477A patent/AT361266B/en not_active IP Right Cessation
- 1977-03-11 DE DE19772710721 patent/DE2710721A1/en not_active Withdrawn
- 1977-03-11 CH CH310777A patent/CH630355A5/en not_active IP Right Cessation
- 1977-03-11 CA CA273,773A patent/CA1072098A/en not_active Expired
- 1977-03-11 NL NL7702673A patent/NL7702673A/en not_active Application Discontinuation
- 1977-03-11 BR BR7701506A patent/BR7701506A/en unknown
- 1977-03-11 SU SU772458751A patent/SU791230A3/en active
- 1977-03-11 FR FR7707349A patent/FR2343729A1/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2242200A (en) * | 1990-02-20 | 1991-09-25 | Omi International | Plating compositions and processes |
| GB2242200B (en) * | 1990-02-20 | 1993-11-17 | Omi International | Plating compositions and processes |
| EP0752420A1 (en) * | 1995-07-06 | 1997-01-08 | Giuseppe Faranda | Process for the preparation of 1-(3-sulphopropyl)-pyridinium-betaine |
Also Published As
| Publication number | Publication date |
|---|---|
| BR7701506A (en) | 1977-11-29 |
| AT361266B (en) | 1981-02-25 |
| IT1083723B (en) | 1985-05-25 |
| FR2343729B1 (en) | 1982-07-02 |
| NL7702673A (en) | 1977-09-14 |
| ES456723A1 (en) | 1978-12-16 |
| JPS52116475A (en) | 1977-09-29 |
| DE2710721A1 (en) | 1977-09-15 |
| CH630355A5 (en) | 1982-06-15 |
| FR2343729A1 (en) | 1977-10-07 |
| CA1072098A (en) | 1980-02-19 |
| SU791230A3 (en) | 1980-12-23 |
| ATA166477A (en) | 1980-07-15 |
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