IE42004B1

IE42004B1 - Production of alkysulphonates

Info

Publication number: IE42004B1
Application number: IE2545/74A
Authority: IE
Original assignee: Anic Spa
Priority date: 1973-12-20
Filing date: 1974-12-10
Publication date: 1980-05-21
Also published as: BE823394A; JPS5095224A; FR2324623A1; DK660674A; ZA747894B; NL7416738A; DE2460246A1; CA1024161A; FR2324623B1; ES433563A2; NO744593L; IT1045798B; AU7593674A; SE7416079L; CH613943A5; GB1481187A; IE42004L; LU71508A1

Abstract

A novel process for the production of alkylsulphonate compounds is described. In this process, an olefin having a carbon atom number of less than 10 is reacted in a solvent with a bisulphite of an alkali metal. This solvent consists of a mixture of water and at least one alcohol. The reaction proceeds in the presence of oxygen or of an oxygen-containing gas. An initiator is necessary which consists of a transition metal ion, selected from the group comprising the metals of groups I, VII and VIII, preferably from Cu, Mn, Fe and Co. In the above process, yields are virtually quantitative. The compounds obtained can be used in detergent formulations.

Description

This invention, relates to a process for producing ammonium or alkali metal alkyl-sulphonates, which are useful in detergent compositions for instance as wetting agents.

The Complete Specification of our Patent to which the present application is one for a Patent of Addition, describes and claims a process for producing a sulphonate, which comprises reacting at least one olefin with ammonium bisulphite or an alkali metal bisulphite in a solvent medium including water and an alcohol, in the presence of oxygen or a gaseous mixture including oxygen and in the presence of a transition metal compound as promoter, and at a pH in the range from 2 to 8.5 with the proviso that when the reaction is effected at a temperature below 60°C. the pH is in the range from 5.5 to 8.5.

According to the present invention, there is provided a process for producing a sulphonate, which comprises reacting at least one primary olefin containing less than 10 carbon atoms with ammonium bisulphite or an alkali metal bisulphate, in a solvent medium including water and an alcohol, in the presence of oxygen or a gaseous mixture including oxygen and in the presence of a transition metal compound as promoter.

The process of the present invention can be carried or out in a continuous/batch operation. -242004 The primary olefins employed in the process of the present invention can be linear or branched. Examples of suitable olefins are oct-l-ene and hex-l-ene.

Preferably the transition metal of the transition metal compound is selected from the metals belonging to Groups I, VII and VIII of the Periodic Table. More preferably the transition metal is Cu, Fe, Mn or Co. The transition metal compound can be a salt or oxide,; it is preferred to use an oxide of Fe or Mn, for example FegOg, MnOg or Mn^O^.

Preferably the transition metal compound is -4 -2 present in a concentration of from 10 to 10 mole per litre of reaction mixture. More preferably the transition metal compound is present in a concentration of approximately _g mole per litre of reaction mixture.

Advantages are shown by the use of MnOg, since it is soluble in bisulphite solutions and can be recovered quantitatively, by means of filtration, as MngO^ when, at the end of the reaction, the reaction is neutralized under a weak air stream.

Preferably the molar ratio of the ammonium bisulphite or alkali metal bisulphite: the olefin is less (less than 1):1. More preferably the molar ratio of the ammonium bisulphite or alkali metal bisulphite: the olefin is approximately 0.8: 1.

Preferably the ratio by weight of alcohol to water in the solvent mixture is in the range from 1.2:1 to 2.5:1.

More preferably the ratio by weight of alcohol to water in the solvent mixture is approximately 1.9:1. -342004 Alternatively, it is preferred, when the alcohol is isopropyl alcohol, lor the ratio by volume of isopropyl alcohol to water to be approximately 3.5: 1.5.

Preferably the ratio by weight of solvent mixture to primary olefin is in the range from 6:1 to 3:1.

During the reaction, the temperature is preferably kept below the boiling point of water, i.e. less than 100°C, and, for this purpose, use can be made of superatmospheric pressure in order to keep the system in the liquid phase; when the alcohol and water give rise to an azeotropic mixture, the operation may be carried out at the boiling point of the same.

In the case of isopropyl alcohol, the process is preferably carried out at 80°C which is the boiling point of the wateralcohol azeotropic mixture. Use is preferably made of the temperature range from 20 to 90°C, more preferably approximately 80 °C.

An air or oxygen flow is preferably such as to maintain a flow equal to approximately 0.8 litre of oxygen per litre of reaction mixture per hour. The pH is preferably maintained at approximately about 6, but the reaction generally proceeds well at a pH in the range from 8.5 to 2.

Throughout the reaction, good stirring should be adopted in order to allow the emulsification of the olefin. Bisulphite may be formed in situ by reaction SOg and ammonium hydroxide or alkali metal hydroxide.

Other operating conditions are disclosed in the complete specification of the main application. -442004 The following Examples are intended to show the effectiveness of the use of a transition metal catalyst in those reactions starting with an olefin having less than 10 carbon atoms, which, as it is known, have a high degree of inertia towards this type of reaction. Examples 1 and 3 are included for comparative purposes.

EXAMPLE 1 1.20 Grams of NagSgO,- (corresponding to 1.2 moles of NaIISO,p were dissolved in 700 cc of isopropyl alcohol and 300 cc of water in a glass reactor equipped with a stirrer, a Teflon anti-slosh baffle, glass electrode, air bubbler, a charging funnel and a reflux condenser; 200 cc (1.6 moles) of hexene-1 were added and the resulting mixture was buffered by NaOH at pH of 5.5; the mixture was brought to 60°C on a thermostatic bath and air was then bubbled through the mixture at a rate of 4 litres per hour, the bisulphite disappearance was followed iodometrically. The reaction was over after 50 minutes. 160 Grams of dry product were isolated containing 10.5% by weight of Na2SO4· Productivity was equal to 160 Grams per hour per litre.

EXAMPLE 2 The preceding test was repeated but this time it was carried out in the presence of 200 mg of MnOg The reaction was over in 20 minutes 197 Grams of dry product were isolated containing 5.2% by weight Na2SO4. Productivity was equal to 492 Grams per hour per litre. -542004 EXAMPLE 3 The procedure of Example 1 was repeated, except that tho olefin used was octene-1.

The reaction was over in 55 minutes and 175.5 g of dry product were isolaLed containing 11.7% of NagSO^.

Productivity was equal to 160 Grams per hour per litre.

EXAMPLE 4 The procedure of Example 3 was repeated but this time it was carried out in the presence of 200 mg of MnOg. The reaction was over in 20 minutes and 205 g of dry product were isolated containing 4.7% by weight of Na2S0^. Productivity was equal 615 Grams per hour per litre.

Claims

1. What we claim is:1. A process for producing a sulphonate:, which comprises reacting at least one primary olefin containing less than 10 carbon atoms with ammonium bisulphite or an 5 alkali metal bisulphite, in a solvent medium including water and an alcohol, in the presence of oxygen or a gaseous mixture including oxygen and in the presence of a transition metal compound as promoter.

2. A process according to claim 1, wherein the 10 transition metal of the transition metal compound is selected from the metals belonging to Groups I, VII and VIII of the Periodic Table. 3. A process according to claim 2, wherein the transition metal is Cu, Mn, Fe or Co. 15 4. A process according to claim 3, wherein the transition metal compound is an oxide of Mn or Fe.

3. 5. A process according to any preceding claim, wherein the transition metal compound is present in a con-4 -2 centration of from 10 to 10 mole per litre of reaction mixture. -743004 G. Λ process according Lo claim 5, wherein Lhe l.ransi Lion metal compound is present in a concentration of -3 approximately 10 mole per litre of reaction mixture.

4. 7. A process according to any preceding claim, 5 wherein the molar ratio of the ammonium bisulphite or alkali metal bisulphite: the olefin is (less than 1):1.

5. 8. A process according to claim 7, wherein the molar ratio of the ammonium bisulphite or alkali metal bisulphite: the olefin is approximately 0.8: 1. 10

6. 9. A process according to any preceding claim, wherein the ratio by weight of alcohol to water in the solvent mixture is in the range from 1.2:1 to 2.5:1.

7. 10. A process according to claim 9, wherein the ratio by weight of alcohol to water in the solvent mixture is approxi15 mately 1.9:1.

8. 11. A process according to any one of Claims 1 to 8, wherein the alcohol is isopropyl alcohol.

9. 12. A process according to claim 11, wherein the ratio by voluine of isopropyl alcohol to water is approximately -8420 0 4

10. 13. A process according to any preceding claim, wherein the temperature during the reaction is less than 100 °C

11. 14. A process according to claim 13, wherein the temperature is in the range from 20 to 90 °C.

12. 15. A process according to claim 14, wherein Lhe temperature is approximately 80°C.

13. 16. A process according to any preceding claim, wherein the ratio by weight of solvent mixture to primary olefin is in the range from 6:1 to 3:1.

14. 17. A process according to any preceding claim, wherein oxygen is introduced into the reaction mixture at a rate of approximately 0.8 litre of oxygen per litre of reaction mixture per hour.

15. 18. A process according to any preceding claim, wherein the pH of the reaction mixture is in the range from 2 to 8.5.

16. 19. A process according to claim 18, wherein the pH is approximately 6.0.

17. 20. A process according to any preceding claim, wherein the ammonium bisulphite or alkali metal bisulphite is prepared in situ by reacting sulphur dioxide and ammonium hydroxide or an alkali metal hydroxide. -942004

18. 21. Λ process according Lo any preceding claim, wherein Lhe primary olefin is reacted with ammonium bisulphite

19. 22. A procoss substantially as described in either of the foregoing Examples 2 and 4.

20. 23. An alkali metal alkylsulphonate whenever produced by a process according to any one of claims 1 to 20 and 22.

21. 24. An ammonium alkylsulphonate whenever produced by a process according to claim 21.

22. 25. A di(alkali metal)alkylene-l,2-disulphonate whenever produced by a process according to any one of claims 1 to 20 and 22.

23. 26. A detergent composition which includes an alkylsulphonate as claimed in any one of claims 23 to 25.