IMPROVED ALKOXYLATION PROCESS

Abstract

The present invention relates to a method for preparing a fatty-chain high-molecular-weight alkoxylate, comprising treating the reaction medium with an acid having a pK.sub.a of 3.5 or less.

Claims

1-11. (canceled)

12. A process for preparing a compound of formula (I): ##STR00002## where: R represents a linear or branched hydrocarbon-based fatty chain comprising from 8 to 60 carbon atoms; Ak represents an alkylene unit with 2 carbon atoms, 3 carbon atoms, or 4 carbon atoms; and n is an integer from 10 to 250; the process comprising: reacting a compound having formula R-OH, where R is as defined in formula (I), with at least one alkylene oxide, in the presence of a catalyst to produce a reaction medium; treating the reaction medium with an acid having a pK.sub.a of less than or equal to 3.5 to produce a neutralized reaction medium; and recovering the compound of formula (I) by treating the neutralized reaction medium.

13. The process of claim 12, wherein R of formula (I) and formula R-OH represents a linear or branched hydrocarbon-based fatty chain comprising from 8 to 60 carbon atoms, wherein the hydrocarbon-based fatty chain is saturated or unsaturated and optionally includes: one or more saturated rings; or one or more partially unsaturated rings; or one or more completely unsaturated rings; or one or more oxygen atoms in an ether functionality, an alcohol functionality, an acid functionality, or an ester functionality; or any combination of these.

14. The process of claim 12, wherein R of formula (I) represents a linear or branched hydrocarbon-based fatty chain comprising from 8 to 40 carbon atoms, wherein the hydrocarbon-based fatty chain is saturated or unsaturated and optionally includes: one or more saturated rings; or one or more partially unsaturated rings; or one or more completely unsaturated rings; or one or more oxygen atoms in an ether functionality, an alcohol functionality, an acid functionality, or an ester functionality; or any combination of these.

15. The process of claim 12, wherein R of formula (I) represents a linear or branched hydrocarbon-based fatty chain comprising from 10 to 30 carbon atoms, wherein the hydrocarbon-based fatty chain is saturated or unsaturated and optionally includes: one or more saturated rings; or one or more partially unsaturated rings; or one or more completely unsaturated rings; or one or more oxygen atoms in an ether functionality, an alcohol functionality, an acid functionality, or an ester functionality; or any combination of these.

16. The process of claim 12, wherein n of formula (I) is an integer from 15 to 200.

17. The process of claim 12, wherein n of formula (I) is an integer from 18 to 160.

18. The process of claim 12, wherein the compound of the formula R-OH is selected from the group consisting of fatty alcohols, fatty acids, fatty polyacids, alcohol esters, sugar esters, glycerides, fatty-chain phenol derivatives, polyols, and combinations thereof.

19. The process of claim 18, wherein the polyols are selected from the group consisting of sugars, alkyl polyglycosides, polyphenols, and combinations thereof.

20. The process of claim 12, wherein the compound of the formula R-OH is selected from the group consisting of octanoic acid; nonanoic acid; decanoic acid; undecanoic acid; undecylenic acid; dodecanoic acid; tetradecanoic acid; hexadecanoic acid; octadecanoic acid; 9-octadecenoic acid; 9,12-octadecadienoic acid; 9,12,15-octadecatrienoic acid; arachidic acid; arachidonic acid; behenic acid; erucic acid; octanols; nonanols; decanols; undecanols; undecenols; dodecanols; tetradecanols; hexadecanols; octadecanols; oleyl alcohol; sorbitol esters; sorbitan esters; sorbitol ethers; sorbitan ethers; isosorbide monoesters; isomannide monoesters; isoidide monoesters; isosorbide monoethers; isomannide monoethers; isoidide monoethers; hydroxyethyl oleate; cardanol; polyacids; tannins; lignans; lignins and other natural polyols; polyols derived from natural products; and combinations thereof.

21. The process of claim 12, wherein the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof.

22. The process of claim 12, wherein the alkylene oxide is ethylene oxide.

23. The process of claim 12, wherein the catalyst is a basic or alkaline catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium alkoxides, potassium alkoxides, and combinations thereof.

24. The process of claim 23, wherein the basic or alkaline catalyst comprises potassium hydroxide.

25. The process of claim 12, wherein the acid having a pK.sub.a of less than or equal to 3.5 is a mineral Brønsted acid, an organic Brønsted acid, a mineral Lewis acid, or an organic Lewis acid.

26. The process of claim 12, wherein the acid having a pK.sub.a of less than or equal to 3.5 is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, p-toluenesulfonic acid, alkanesulfonic acid, and combinations thereof.

27. The process of claim 12, wherein the acid having a pK.sub.a of less than or equal to 3.5 is selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, isopropanesulfonic acid, n-butanesulfonic acid, isobutanesulfonic acid, sec-butanesulfonic acid, tert-butanesulfonic acid, and combinations thereof.

28. The process of claim 27, wherein the acid having a pK.sub.a of less than or equal to 3.5 is methanesulfonic acid.

29. The process of claim 12, wherein the compound of formula (I) is an alkoxylate selected from group consisting of: C.sub.16-C.sub.18 alcohol with 33 OE; C.sub.10 oxo alcohol with 20 OE; C.sub.16-C.sub.18 alcohol with 18 OE; (C.sub.18) oleyl alcohol with 20 OE; stearic acid ethoxylated with 120 OE; rapeseed oil with 20 OE; rapeseed oil with 30 OE; hydrogenated castor oil with 25 OE; hydrogenated castor oil with 20 OE; ester of sorbitan monolaurate with 20 OE; ester of sorbitan monostearate with 20 OE; ester of sorbitan monooleate with 20 OE; and coconut fatty acid with 150 OE.

Description

EXAMPLES

Example 1: Industrial Synthesis of Stearic Acid With 120 OE (According to the Invention)

[0078] An industrial reactor is charged with 287.5 kg (1000 mol) of stearic acid (Radiacid 0417 from Oleon). The acid is melted by heating to 80° C. 2.5 kg of potassium hydroxide (85% KOH, in the form of granules (prills)) are then added. The reaction medium is dried at 110° C. under 40 mmHg (or approximately 5.33 kPa). The reaction medium is then brought to 170° C. 50 kg of ethylene oxide are then introduced at this temperature. When the reaction has started (when a drop in autogenous pressure and a rise in temperature are observed), the introduction of ethylene oxide is continued up to a total of 5280 kg (120 000 mol).

[0079] Once the addition has ended, cooking is carried out bymaintenance at temperature for 30 minutes. The reaction medium is cooled to 105° C. and transferred into a posttreatment reactor. The catalyst is neutralized with 1.25 kg of 80% formic acid in water.

[0080] 0.115% (6.25 kg) of 70% methanesulfonic acid (Arkema) and 0.115% (6.25 kg) of water are then added. The mixture is maintained at 90° C. for 30 minutes. Steam stripping is then carried out at 105-110° C. for 5 hours under reduced pressure of 100 mmHg (i.e. 13.33 kPa). The final product is drained. Impurities of unsaturated ether type are no longer detected, and the final content of acetaldehyde, measured by NMR, is 3 ppm by weight.

Example 2: Effect of the Treatment With MSA (pK.SUB.a = -1.9, Laboratory Test)

[0081] In this example, the procedure is as in example 1, for the preparation of 500 g of stearic acid with 120 OE, by reaction of stearic acid with ethylene oxide, and the reaction catalyst (potassium hydroxide). At the end of the reaction cooking is carried out and the catalyst is neutralized as stated in example 1 with formic acid.

[0082] The acid treatment for controlling the impurities present in the reaction medium is carried out, at 90° C. with stirring and nitrogen inertizing, with 0.115% of 70% MSA (0.58 g) (sold by Arkema) and 0.115% (0.58 g) of water. The mixture is maintained at 90° C. for 30 minutes. A sample analyzed by NMR indicates that the entirety of the impurities of unsaturated ether type have disappeared and that acetaldehyde has formed to a level of 1840 ppm. Nitrogen stripping is carried out at 90° C. for 90 minutes. The final analysis of the product by NMR gives a residual content of acetaldehyde of 230 ppm.

Example 3: Comparative by Treatment With HCOOH (pK.SUB.a = 3.75, Laboratory Test)

[0083] Example 2 above is repeated, replacing the MSA with 80% formic acid in aqueous solution (sold by Vivochem). The mixture is maintained at 90° C. for 30 minutes. A sample analyzed by NMR indicates that the entirety of the impurities of unsaturated ether type are intact and that no acetaldehyde has formed in this case.

[0084] As can therefore be seen, the treatment with a strong acid of pK.sub.a of less than 3.5 is important in order to be able to convert the impurities of ether type into aldehyde functions that are then easily removed by stripping.

Example 4: Industrial Trial of Treatment With MSA

[0085] A new industrial trial is carried out, as in example 1, using MSA to neutralize the catalyst and to treat the impurities of unsaturated ether type. Thus, in an industrial reactor, a batch of 5440 kg of stearic acid with 120 OE is synthesized under the conditions presented in example 1. The total amount of methanesulfonic acid used to neutralize the catalyst and treat impurities of unsaturated ether type is 9.25 kg of 70% MSA, i.e. 0.175% and 0.115% (6.25 kg) of water. After the steam stripping operation at 105-110° C., for 5 hours under reduced pressure of 100 mm of mercury (i.e. 13.33 kPa), the final product is drained. Impurities of unsaturated ether type are no longer detected, and the final content of acetaldehyde, measured by NMR, is 2 ppm.