Process for making ethers from alkoxide anions or precursors of alkoxide anions

• US 8,957,256 B2
• Filed: 09/22/2008
• Issued: 02/17/2015
• Est. Priority Date: 09/26/2007
• Status: Expired due to Fees

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Inventors: King, Stephen W., Hippler, Jeffrey G., Mitford, Richard R.
• Primary Examiner(s): KEYS, ROSALYND ANN
• Application Number:
  US12/680,022
• Publication Number:
  US 20100280277A1
• Time in Patent Office: 2,339 Days
• Field of Search: 568/618, 568/615
• US Class Current: 568/618
• 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 hygroscopic base to form an intermediate product mixture comprising an alkoxide anion and excess base, said reaction occurring under conditions such that the base functions as a scavenger to scavenge by-product water to help drive the reaction toward completion;

b) preheating the intermediate product mixture to a temperature greater than about 110°

C.; and

c) in the presence of the excess base, adding a stoichiometric excess of a hydrocarbyl halide to the pre-heated intermediate product mixture and reacting the alkoxide anion with the hydrocarbyl halide at a temperature greater than about 110°

C. to form a product mixture comprising an ether.

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

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

4. 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.

5. The method of claim 1, wherein a first portion of step (c) comprises reacting the alkoxide anion with the hydrocarbyl halide at a temperature greater than about 110°

C. and a second portion of step (c) occurring after the first portion is carried out at a temperature below about 75°

C. and in the presence of a decoloring agent.

6. The method of claim 3, wherein the steps step (a) and step (c) occur under a non-ambient atmosphere and a positive pressure relative to the ambient.

7. 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 balide and the alkoxide anion.

8. The method of claim 7, wherein a first portion of step (c) comprises reacting the alkoxide anion with the hydrocarbyl halide at a temperature greater than about 110°

C. and a portion of step (c) occurring after the first portion occurs at a temperature below about 75°

C.

11. The method of claim 1, wherein step (d) is carried out in the presence of the hygroscopic base in finely divided solid form.

12. The method of claim 1, wherein the alcohol has the formula ROH wherein R is selected from a straight, linear or branched monovalent moiety other than H.

13. The method of claim 12, wherein the ether is a diether.

9. 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 hygroscopic base to form an intermediate product mixture comprising an alkoxide anion, remaining alcohol, excess base, said reacting occurring at a first temperature, said reaction occurring under conditions such that the base functions as a scavenger to scavenge by-product water to help drive the reaction to completion;

b) heating the intermediate product mixture to a second temperature greater than the first temperature and greater than about 110°

C.;

c) optionally holding intermediate product mixture at a third temperature greater than the first temperature and greater than about 110°

C.; and

d) in the presence of the excess base and the remaining alcohol, adding a stoichiometric excess of a hydrocarbyl halide to the intermediate product mixture and reacting the alkoxide anion with the hydrocarbyl halide at a temperature greater than about 110°

C. to form a product mixture comprising an ether.

10. The method of claim 9, wherein at least two of the second, third and fourth temperatures are substantially the same.