Etherification Process

Patent metadata

Field	Value
Publication number	US-2021363084-A1
Application number	US-201816757414-A
Country	US
Kind code	A1
Filing date	Oct 19, 2018
Priority date	Oct 19, 2017
Publication date	Nov 25, 2021
Grant date	—

Abstract

The present invention relates to a process for preparing ethers, particularly unsymmetrical ethers, and preferably ethers suitable for use as base stocks for lubricant compositions. In particular, the process involves the reaction of an α,β-unsaturated aldehyde with a trihydrocarbyl orthoester to form an α,β-unsaturated acetal and conversion of the α,β-unsaturated acetal to an ether through hydrogenation and hydrogenolysis.

First claim

1 . A process for preparing an ether, said process comprising the steps of:
i) contacting an α,β-unsaturated aldehyde with a trihydrocarbyl orthoester to form an α,β-unsaturated acetal; and ii) subjecting the α,β-unsaturated acetal obtained from step i) to hydrogenation and hydrogenolysis to hydrogenate at the α- and β-positions of the α,β-unsaturated acetal and to convert the acetal group to an ether.

2 . The process of claim 1 , wherein the α,β-unsaturated aldehyde is of formula (I):

where R 1 and R 3 are independently selected from H and aliphatic hydrocarbyl; and R 2 is aliphatic hydrocarbyl.

3 . The process of claim 2 , wherein R 1 and R 3 are independently selected from H, C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl and C 4 -C 18 cycloalkyl-substituted-alkyl and R 2 is C 1 -C 18 alkyl, C 3 -C 18 cycloalkyl and C 4 -C 18 cycloalkyl-substituted-alkyl.

4 . The process of claim 1 , wherein the trihydrocarbyl orthoester is of formula (II):

where R 4 is selected from C 4 -C 40 alkyl, C 3 -C 40 cycloalkyl and C 4 -C 40 cycloalkyl-substituted-alkyl and R 5 is selected from H and C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl and C 4 -C 12 cycloalkyl-substituted-alkyl.

5 . The process of claim 1 wherein step i) is conducted in the presence of an acidic catalyst selected from p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid, phosphoric acid, and an acidic ion-exchange resin.

6 . The process of claim 5 , wherein the acidic ion-exchange resin is an acidic macroreticular-type ion-exchange resin or an acidic gel-type ion-exchange resin.

7 . The process of claim 1 , further comprising the preceding step of preparing the α,β-unsaturated aldehyde of formula (I) by an aldol condensation reaction.

8 . The process of claim 1 , further comprising the preceding step of preparing a trihydrocabyl orthoester of formula (II) by reacting a trimethyl orthoester and/or triethyl orthoester with a molar excess of an alcohol of formula R 4 OH in the presence of an acidic catalyst, where R 4 is C 4 -C 40 alkyl, C 3 -C 40 cycloalkyl and C 4 -C 40 cycloalkyl-substituted-alkyl.

9 . The process of claim 8 , wherein the alcohol and orthoester are contacted in a molar ratio of at least 5:1.

10 . The process of claim 8 , wherein the acidic catalyst is selected from sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, hydrochloric acid, phosphoric acid and an acidic ion-exchange resin.

11 . The process of claim 1 , wherein the α,β-unsaturated aldehyde is contacted with the trihydrocarbyl orthoester in step i) at a temperature in the range of from 50° C. to 150° C.

12 . (canceled)

13 . (canceled)

14 . The process of claim 1 , wherein hydrogenation and hydrogenolyis in step ii) is performed in the presence of a hydrogenation catalyst and optionally as a one pot reaction.

15 . The process of claim 14 , wherein the catalyst comprises a metal selected from nickel, palladium, platinum, rhodium, ruthenium, cobalt, copper and combinations thereof.

16 . The process of claim 14 , wherein the catalyst is supported with a support material selected from carbon, silica, alumina, silica-alumina, and aluminosilicate.

17 . The process of claim 1 , wherein hydrogenation and hydrogenolysis in step ii) is conducted at a temperature in the range of from 100° C. to 350° C.

18 . The process of claim 1 , wherein hydrogenation and hydrogenolysis in step ii) is conducted at a pressure of from 1,500 kPa absolute to 30,000 kPa absolute.

19 . (canceled)

20 . The process of claim 1 , wherein the ether formed in the process has a total number of carbon atoms of from 20 to 50.

21 . The process of claim 1 , further comprising blending the ether obtained from the process with one or more additional base stocks and/or one or more lubricant additives into a lubricant composition.

22 . (canceled)

23 . The process of claim 21 , wherein the ether is present in the lubricant composition in an amount of greater than 1% by weight, preferably greater than 5% by weight, more preferably greater than 10% by weight, even more preferably greater than 20% by weight, more preferably still greater than 30% by weight.

24 . The process of claim 21 , further comprising supplying the lubricant composition to a surface for lubrication, such as a surface in an internal combustion engine.

Assignees

• Bp Plc

Inventors

• Deeley Jon
• Armitage Gareth

Classifications

• C07C43/303

  having acetal carbon atoms bound to acyclic carbon atoms · CPC title

• C07C43/04

  Saturated ethers · CPC title

• C07C41/56

  by condensation of aldehydes, paraformaldehyde, or ketones · CPC title

• C07C41/28 Primary

  from acetals, e.g. by dealcoholysis · CPC title

• C07C41/20

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title