PROCESS FOR MAKING ETHERS FROM ALKOXIDE ANIONS OR PRECURSORS OF ALKOXIDE ANIONS

• US 20100280277A1
• Filed: 09/22/2008
• Published: 11/04/2010
• Est. Priority Date: 09/26/2007
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies, Inc. (Dow, Inc.)
• Inventors: Mitford, Richard R., Hippler, Jeffrey G., King, Stephen W.
• Granted Patent: US 8,957,256 B2
• Time in Patent Office: Days
• US Class Current: 568/613
• CPC Class Codes: C07C 41/16 by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
• CPC Class Codes: C07C 43/11 Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10

Abstract

Improved methods for making ethers. In particular, an alkoxide can be more effectively converted into an ether by reaction with a hydrocarbyl halide in the presence of a substantial excess of a hygroscopic base such as NaOH. When present in such an unconventional excess, the base serves multiple functions. As a consequence, the alkoxide is extensively converted to the desired ether rapidly at excellent yields. The reaction environment also aids later product isolation. The use of the NaOH rather than Na metal allows the ether product to be separated from water soluble impurities such as salt products, left over base, left over hydrocarbyl halide, formates, etc. by liquid-liquid extraction among aqueous and organic phases.

Claims

1. A method of making an ether, comprising the steps of:

a) reacting an alcohol with at least a 20 molar percent stoichiometric excess of a water-soluble hygroscopic base to form an intermediate product mixture comprising an alkoxide anion, remaining alcohol, and excess base; and

b) in the presence of the excess base and remaining alcohol, adding a hydrocarbyl halide to the intermediate product mixture and reacting the alkoxide anion with the hydrocarbyl halide to form a product mixture comprising an ether.

5. The method of claim 1, wherein the alcohol comprises a terminal ether moiety and step (b) comprises forming an ether comprising said terminal ether moiety and an additional terminal ether moiety.

6. The method of claim 1, wherein the alcohol comprises a monoalkyl ether (poly)oxyalkylene alcohol having from 2 to 10,000 oxyalkylene units.

8. The method of claim 1, further comprising the steps of adding a sufficient amount of water to the product mixture to form an aqueous phase and an organic phase;

separating the phases; and

recovering the ether from the organic phase.

10. The method of claim 1, wherein step (b) is carried out at a temperature below about 75°

C. and in the presence of a decoloring agent.

11. The method of claim 6, wherein steps (a) and steps (b) occur under a non-ambient atmosphere and a positive pressure relative to the ambient.

13. b) The method of claim 1, wherein at least a portion of the excess base is in the form of suspended particles during at least a portion of the reaction between the hydrocarbyl halide and the alkoxide anion.

16. The method of claim 13, wherein at least a portion of step (b) occurs at a temperature below about 75°

C.

2-4. -4. (canceled)

7. (canceled)

9. (canceled)

12. (canceled)

14-15. -15. (canceled)

17-18. -18. (canceled)

19. A method of forming an ether, comprising the steps of:

a) providing a reaction medium comprising suspended particles of a hygroscopic base and an alcohol reactive with the base to form an alkoxide; and

b) reacting the alkoxide with a hydrocarbyl halide in said reaction medium, said reaction occurring in said reaction medium at a temperature at which at least a portion of said particles remain solid during at least a portion of the reaction.

20. A method of making an ether, comprising the steps of:

a) reacting an alcohol with at least a 20 molar percent stoichiometric excess of a water-soluble hygroscopic base to form an intermediate product mixture comprising an alkoxide anion, remaining alcohol, excess base, said reacting occurring at a first temperature; and

b) heating the intermediate product mixture to a second temperature greater than the first temperature;

c) optionally holding the intermediate product mixture at a third temperature greater than the first temperature; and

d) in the presence of the excess base and the remaining alcohol, adding a hydrocarbyl halide to the intermediate product mixture and reacting the alkoxide anion with the hydrocarbyl halide at a fourth temperature to form a product mixture comprising an ether.

21. The method of claim 20, wherein at least two of the second, third and fourth temperatures are substantially the same.

22-25. -25. (canceled)