DE2544729A1 - 1-HYDROXY PROPENE (2,3) SULPHONIC ACID (3) COMPOUNDS AND THE METHOD FOR THEIR MANUFACTURE - Google Patents

Description

Our reference: O. Z. 31 599 WB / Be 6700 Ludwigshafen, October 2, 1975

1-Hydroxy-propen- (2,3) -sulfonic acid - (?) - compounds and Process for their manufacture

The invention "relates to the new 1-hydroxy-propen- (2,3) -sulfonic acid- (3) and their metal salts and a method for their Manufacturing.

It is from Ulimann's Encyclopedia of Technical Chemistry, Volume ΐβ, Page 571 known that 1-hydroxypropanesulfonic acid can be reacted of allyl alcohol with potassium hydrogen sulfite in the presence of tert-butyl perbenzoate in the form of the potassium salt or by Implementation of acrolein and sodium hydrogen sulfite and hydrogenation of the alkali metal salt formed of sulfopropanal is obtained.

1-Hydroxy-propen- (2,3) -sulfonic acid- (3) and its salts have been used so far not yet described.

There were now the new 1-hydroxy-propen- (2,3) sulfonic acid compounds the formula

CH ₀ - CH = CH - S - RI, OH 0

where R is a hydroxyl group or the radical -OY and Y is the equivalent of a metal atom mean found.

It has also been found that 1-hydroxy-propene (2,3) sulfonic acid compounds the formula

CH ₀ - CH = CH - S - R ¹ Ia, ι 2 ι,

OH 0

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where R is a hydroxyl group or the radical -OZ and Z is an alkali atom or the equivalent of an alkaline earth atom, advantageously obtained when chloropropanesulfonic acid compounds are used formula

CH ₀ - CH - CH ₀ - S - R ² II, Cl Cl 0

2
where R is a hydroxyl group or a chlorine atom or the radical -OZ and Z is an alkali atom or the equivalent of an alkaline earth atom, with alkali hydroxide and / or alkaline earth hydroxide at a temperature of 100 to 160 ° C to give l-hydroxy-propen (2,3) sulfonates of the formula

CH ₀ - CH = CH - S - OZ III, OH 0

wherein Z has the aforementioned meaning, and in a second step the substances III with acidic compounds for 1-Hydroxy-propen- (2, j5) -sulfonic acid- (j5) of the formula

CH ₀ - CH - CH - S - OH IV, OH 0

implements.

In the case of using 1,2-dichloropropanesulfonic acid chloride, the reaction can be carried out and sodium hydroxide can be represented by the following formulas:

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? ° 2 ^C1 -3 NaCl

CH ₀ -CH-CH ₀ + 4 NaOH -4 CH ₀ -CH = CH-SO ^ Na

t C t C · O TT λ! C. J?

Cl Cl ~ ⁿ 2 ^u OH

+ HCl -NaCl

CH ₂ -CH = CH ₂ -SO ₃ H OH

In view of the state of the art, the method according to the invention provides a simple and economical starting point of easily accessible starting materials, the new l-hydroxy-propen- (2,3) -sulfonic acid compounds in good yield and purity. It was surprising that both in the saponification and in the preparation of the acid, the substance III and the substance IV can be obtained in high yield and the formation of by-products, e.g. monohydroxy-monochloropropanesulfonic acid salts or l-monochloro-3-propenylsulphonic acid chloride, l-monochloro-3-propenylsulphonic acid Salts, 2-monochloro-l-propenylsulfonic acid chloride or corresponding sulfonic acid salts, saturated condensation products, e.g. with ether bridges, with several chlorine and / or hydroxyl groups and accordingly also unsaturated condensation products with one or more double bonds or triple bonds, is avoided to a significant extent. The starting chloropropanesulfonic acid compound can by reacting 1,2-dichloropropane with sulfur dioxide and chlorine to form chloropropanesulfonic acid chlorides and optionally in a second step by hydrolysis of the chlorides obtained with water at elevated temperature to chloropropanesulfonic acids. It's from of greater technical interest, that obtained as a by-product in the synthesis of propylene oxide by the chlorohydrin process To utilize 1,2-dichloropropane in this economical way.

As starting materials come l ^ -Dichlor ^ -propanesulfonic acid, his Alkali and alkaline earth salts, expediently the sodium or calcium salt, and l, 2-dichloro-3-propanesulfonic acid chloride into consideration. They are with the alkali hydroxide, preferably potassium hydroxide and especially sodium hydroxide and / or alkaline earth hydroxide,

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preferably calcium or barium hydroxide, in stoichiometric Amount or in excess, preferably in a ratio of 4 to 4.5 moles of alkali metal hydroxide or 2 to 2.5 moles of alkaline earth metal hydroxide converted per mole of 1,2-dichloropropanesulfonic acid compound «The implementation is at a temperature of 100 to 160 ° C, preferably from 105 to 140 ° C, without pressure or under pressure, discontinuously or preferably carried out continuously. As a rule, the starting material is advantageous in the presence of water in an amount of ΊβΟ to 300 percent by weight, based to the Chlorpropansulfonsaureverbindungen II, to implement, appropriate using 40 to 10 percent strength by weight, aqueous alkali or alkaline earth solutions, in particular corresponding Caustic soda.

The reaction can be carried out as follows: A mixture of starting material II and alkali lye is kept at the reaction temperature for 2 to 6 hours ₀ B ₀ formamide or dimethylformamide, isolated from the reaction mixture.

From the aforementioned l-hydroxy-propen- (2,3) -sulfonate- (3) III is obtained by reaction with acidic compounds in a stoichiometric amount or in excess, preferably in an amount from 1 to 1.3 *, in particular from 1 to 1.05 equivalents of acidic compounds per mole of substance III l-hydroxy-propen- (2,3) -sulfonic acid- (3). The reaction is generally carried out at a temperature of from 10 to 50, preferably from 15 to 25 ^° C., without pressure or under pressure, continuously or batchwise be used. Instead of monobasic acids, it is also possible to use equivalent amounts of polybasic acids. For example, the following acids are suitable; Hydrogen chloride, hydrogen bromide, hydrogen iodide, perchloric acid, sulfuric acid, phosphoric acid, nitric acid; acidic ion exchangers! or corresponding mixtures. The acids can be used in concentrated form, as a mixture with one another and / or with a solvent, in particular water. An aqueous reaction is preferred

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ORIGINAL INSPECTED

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Medium, expediently in the presence of 15 Ms 40 mol of water per mol Starting material II or III "

Particularly preferred acidic compounds are mineral acids such as hydrochloric acid, expediently in the form of 10 to 35 percent by weight, aqueous solutions »

The reaction can be carried out as follows: A mixture of starting material III and water is passed continuously at the reaction temperature through a column reactor filled with the exchanger. Accordingly, it can be the aforementioned mixture together with the exchanger, or one of the aforementioned acids also discontinuously during 120 to 150 minutes at the reaction temperature "From keep the continuous discharge or the reaction mixture of batchwise reaction, the end product in a conventional manner, for" B _o by Evaporation, isolated.

From the free acid, expediently in the form of the aqueous solution, by reaction with metal compounds, e.g. with metal hydroxides, Metal oxides or metal salts such as chlorides or nitrates, the corresponding metal salts are produced. The reaction mixture for the preparation of the free acid is expediently used and the crude end product is separated off by filtration off and mixed it with the metal compound and expediently 15 to 35 moles of water per mole of end product IV. Preferred metal salts of the end products IV are those of the metals of groups Ia, Ha, lib, VIIIb of the Periodic Table (D'Ans-Lax, Taschenbuch für Chemist and physicist (Springer, Berlin, 1967), volume 1, page 63); in particular the nickel, cobalt, cadmium, zinc, mercury, sodium, potassium or magnesium salt.

The novel compounds which can be prepared by the process of the invention I and Ia are valuable starting materials for the production of pesticides, plasticizers, solvents, Leather greasing agents, detergents, lubricating oils, synthetic resins, lubricants. They are aids in electroplating and starting materials for the production of such auxiliaries.

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They are particularly brighteners for electroplating baths, preferably nickel baths _β It has hitherto been known aqueous acidic nickel baths of reducing the grain sizes and increase the gloss, the leveling, the brightness and elasticity of the nickel precipitate to the galvanized workpieces benzene, naphthalene, saccharin, p -Toluenesulfonylamide (Ulimann's Encyclopedia of Industrial Chemistry, Volume 7, Page 832) to be added. In addition, unsaturated compounds such as allyl alcohol, butynediol, allyl urea, acrylic acid, arylsulfamides, arylsulfimides and unsaturated amines have already been described as brightening additives, which, although they result in a finer grain of the nickel deposit, cannot prevent embrittlement and darkening, especially in places with low current densities »Saturated aliphatic carboxylic acids, on the other hand, are known to be ineffective when used as a gloss additive. In contrast to these known compounds, there is a significant improvement in terms of gloss, brightness and color of the deposited metal layer, high hardness, great ductility, insensitivity to contamination by foreign metals, application range, leveling, reduction of the formation of spots and streaks, graininess and brittleness of the nickel surfaces Prevention of pore formation is achieved by adding the end products I to the galvanic nickel baths. Amounts of 0.05 to 2, in particular 0.1 to 1 percent by weight, based on the total weight of the liquid in the galvanic bath, are preferred End materials I in electroplating baths are the reduced scarring on the underside of the treated workpieces, the suppression of hydrogen development that leads to such scarring, more effective nickel plating with low and very high current densities, with extremely high nickel chloride centrations, and a more even nickel deposition in workpieces with irregular surfaces and the resulting different current densities. A method of working with higher bath concentrations of other inorganic and organic substances, which are deposited preferentially over nickel and usually lead to staining and a reduction in gloss, is also used without these difficulties of the end products I possible.

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The free sulfonic acids IV and their nickel, cobalt, sodium, potassium or magnesium salt are preferably used. The end products I can be used alone or together with other nickel brighteners such as acetylene compounds, e.g. butynediol, or pyridinium compounds, Z ₀ B ₀ quinaldinium bromide, in the nickel baths. If brighteners known to date such as arylsulfamides and arylsulfimides, arylsulfonic acids are also used, there is a synergistic effect by increasing the gloss effect while avoiding the disadvantages such as staining, graininess and brittleness of the nickel surfaces, which can be observed when these compounds are used alone the dihexyl ester, can have an advantageous effect in the presence of oily impurities by preventing the formation of grease or foam scars.

The end products I according to the invention can be useful as additives for the corrosion protection of steel, brass, zinc, aluminum alloys and magnesium alloys and to achieve shiny, hard, very ductile, leveling nickel coatings for printing plates, cutting and embossing tools, nickel foils, nickel tapes , Nickel tubes, mesh plates, automobile bumpers, watch dials, optical items can be used. As a rule, the nickel baths are acidic electrolytes, for example bright nickel baths and semi-bright nickel baths such as the Watts bath, nickel chloride bath, nickel fluorate bath, sulfamate bath. Watts baths with 250 to 500 grams per liter of nickel sulfate, 30 to 75 grams per liter of nickel chloride, 20 to βΟ grams per liter of boric acid are preferred. The usual electroplating conditions for nickel electrolytes are expediently adhered to, preferably temperatures from 45 to 65 ^° C., current densities from 3 to 100, advantageously 4 to 10 Amp / dm, goods movement from 4 to 6 ra / min, pH from 2.5 to 5 * 8, preferably 3 * 5 to 4.5. Cast anodes, rolled nickel anodes, electrolyte nickel anodes or nickel anodes, also in the form of pelletized shaped bodies, with an anode bag, may be considered as anodes. Regarding single

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The details of the production of the baths, the implementation of the electrolytic metal deposition, the technique of electroplating and the pre- and post-treatment of the workpieces can be found in Ullmann's Encyclopedia of Technical Chemistry, Volume T, pages 791 to 848 and supplementary volume, pages 433 to 436, and Dettner, Handbuch der Galvanotechnik (Hanser, Munich 1966), especially Volume II, pages 87 to 14l, referenced "

The parts listed in the following examples are parts by weight ο They relate to parts by volume as Kilograms to Liters »

example 1

In a stirred vessel provided with reflux condenser 520 parts of aqueous sodium hydroxide solution (25 percent by weight) were charged and heated to 100 ⁰ C. 100 parts of 1,2-dichloropropanesulfonyl chloride are then slowly run in and the mixture is kept under reflux for 6 hours at 109 ° C. at a pH of 9> 5 °. The mixture is then evaporated and the residue is recrystallized with 200 parts of formamide and the precipitated out Sodium chloride filtered off »69.5 parts of 1-hydroxy-propen (2,3) -sulphonic acid sodium - (- 3) (92 % of theory) with a hydrogenation iodine number (determined according to Ullmanns Encyklopadie der technischen Chemie, Volume J ₁ page) are obtained 546) of 157 »

Example 2

50 parts of sodium (3) l-hydroxy-propen- (2,3) -sulphonic acid prepared analogously to Example 1 are dissolved in 75 parts of water, acidified with 32 parts of hydrochloric acid (36.5 percent by weight) and added for 1 1/2 hours "held 22 ° C then the reaction mixture at 50 ⁰ C under vacuum evaporated in a rotary evaporator, taken up with 120 parts of ethanol, and the end product is filtered off with suction from the precipitated sodium chloride" is obtained 40.3 parts of l-Hydrpxypropen- (2,3) -sulfonsäure- (3) (93.5 % of theory) _ with an acid number of 409 and a hydrogen iodine number of 183 »

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Example 3

The reaction with 258 parts of 1,2-Dichlorpropansulfochlorid analogously to Example 1 and Ij56 parts of calcium hydroxide, suspended in 406 parts of water for 5 hours at 150 ⁰ C in a Druckrührapparat performed "After filtration, the reaction solution cools the mixture to a temperature below from 100 ⁰ C and evaporated to dryness to give the end product and calcium chloride remain as a residue. Recrystallization from alcohol gives 177 parts (92.5 % of theory) of l-hydroxypropene (2,5) sulfonic acid calcium with a melting point of ⁰ ° C. (decomposition) and a hydrogenation iodine number of 160 "

Example 4

-Sulfonsäure- to release the Hydroxypropen- l = (2,3) (3) 100 parts of the end product obtained according to Example 3 are dissolved in 150 parts of water and at 22 ⁰ C in the course of one hour with 125 parts of sulfuric acid (25 weight percent) implemented. Then the precipitated calcium sulfate is filtered off and the reaction mixture is evaporated at 50 ^° C. in a rotary evaporator under vacuum. 83.5 parts (95 % of theory) of 1-hydroxypropene- (2,3) -sulfonic acid- (j5) with an acid number of 403 and a hydrogen death number of 18l are obtained.

Examples 5 to 14 (use)

Polished copper and brass coupons were galvanized at temperatures of 60 ⁰ C a) with (5 m / minute) and b) without agitation. Bath composition of the Watts electrolyte used:

Nickel sulphate 200 g / l

Nickel chloride 50 5 S / 1 Boric acid 55 s / i Sodium salt of sulfo- succinic acid hexyl ester 0, g / l

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The pH value in the Watts bath is 3 * 5 to 4.5 * an electrolyte nickel anode with anode bag, a current density of 0.5 to 12 Amp / dm ² (Hu
lysis time of 10 minutes used.

at the same time 0.5 to 12 Amp / dm (Hull cell) and an electrical

In the following examples, each of the base electrolytes the following additions added:

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example

additive

Amount g / l

Remarks

Sodium salt of

1-hydroxy-propenyl-

sulfonic acid

Benzenesulfonamide

1,4-di (2-hydroxyethoxy) butyne-2

high-gloss nickel layer over a
Current density range of _<Q ^ _{A / dm} 2

7 "12 A / dm

_Q ^ _{A / dm}
slight subsequent chrome plating

0.25

^ (Compare-S equal)

Sodium salt of allylsulfonic acid

in the entire current density range
veiled

_ »7 Sodium salt of allyl · cd (sulfonic acid
^ same)

10

shiny in the current density range from L · 0.5 to

> 12 A / dm, but lower glossj lower ductilityj strongly passive against subsequent chrome plating

1-Hydroxy-propenyl-sulfonic acid sodium salt

shiny in the current density range from <C0.5 to> 12 A / dm ²

9
§ (Ver
> same)

Saccharin

Butyne-2-diol-1,4

Propargyl alcohol

2.5
0.25

0.05

shiny in a current density range of

1.5 A / dm ² to 11 A / dm ² (slight haze in the low current density range) j very low
Ductility and difficult chrome plating

VjJ VJI

at additive lot game g / l 10 Saccharin 2.5 same ν butyne-2-diol-1,4 0.25 Propargyl alcohol 0.05 Copper sulfate (100 ppm)

oo

Remarks

dark spots throughout the current density range

11 Nickel salt of 1-hydroxy
propenylsulfonic acid 2 shiny in
> 12 A / dm ² Current density range of <0, 5 to O12
CD
approx 1,1-dihydroxy-propenyl-
sulfonic acid 2 shiny in
> 12 A / dm ² Current density range of <0, 5 to Ν » Sodium salt of 1,1-di-
hydroxy propenyl sulfone
acid 2 shiny in
> 12 A / dm ² Current density range of <0, 5 to

Nickel salt of the 1,1-di-

hydroxy propenyl sulfone

acid

shiny in the current density range from <0.5 to> 12 A / dm ²

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The Niekelschichten obtained from baths with the inventive Additives obtained are lighter, more elastic and more pleasant in color compared to those of the comparative electrolytes and have a smaller grain size, comparatively no or fewer scars, no spots, focal points or veils on the surfaces of the workpiece and a better leveling and thus a lower layer thickness while at the same time more uniform Deposition on the entire material surface and thus result in less subsequent grinding and polishing work as well as nickel savings.

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Claims (3)

Claims ί 1-Hydroxy-propen- (2,3) -sulfonic acid- (3) compounds of the formula 0 CH ₀ - CH = CH - S - RI, 1 c- ff OH O where R is a hydroxyl group or the radical -OY and Y is the equivalent of a metal atom. 2. Process for the preparation of l-hydroxy-propen- (2,3) -sulfonic acid- (3) compounds the formula CH ₂ - CH = CH - S - R ¹ Ia, OH 0 wherein R is a hydroxyl group or the radical -OZ and Z is an alkali atom or the equivalent of an alkaline earth atom, characterized in that chloropropanesulfonic acid compounds of the formula CH ₀ - CH - CH ₀ - S - R ² II, t d t d | f Cl Cl O wherein R is a hydroxyl group or a chlorine atom or the radical -OZ and Z is an alkali atom or the equivalent of an alkaline earth atom mean with alkali hydroxide and / or alkaline earth hydroxide at a temperature of 100 to 160 ° C to form 1-hydroxypropene (2,3) sulfonates the formula - CH = CH 0 - OZ tf CH ₂ - S.
ff OH O III, where Z has the aforementioned meaning, converts and in one 709816/1187 -, air - ο.ζ. 31 599 - t. second step the substances III with acidic compounds for 1-Hydroxy-propen- (2,3) -sulfonic acid- (j5) of the formula CH ₀ - CH = CH - S - OH IV OH 0 implements. 3. Use of 1-hydroxy-propene (2,3) sulfonic acid (3) compounds the formula CH ₀ - CH = CH - S - RI, 1 d t! OH 0 where R is a hydroxyl group or the radical -OY and Y is the equivalent of a metal atom, as electroplating Aids. BASF Aktiengesellschaft 709816/1187