Improved glycol acylation process with water-tolerant metal triflates

Patent metadata

Field	Value
Publication number	US-2017008902-A1
Application number	US-201415102346-A
Country	US
Kind code	A1
Filing date	Dec 11, 2014
Priority date	Dec 19, 2013
Publication date	Jan 12, 2017
Grant date	—

Abstract

A method for acid-catalyzed acylation of an isohexide is described. The method can enable direct alcohol acylation with carboxylic acids. In particular, the method involves reacting an isohexide and an excess of carboxylic acid, in the presence of a water-tolerant Lewis acid catalyst. Water-tolerant Lewis acid catalysts can furnish relatively high diester yields (e.g., ≧55%-60%) at lower catalyst loads. This feature, among others, is highly desirable for cost savings, and can improve process economics.

First claim

1 ) A method for acid-catalyzed acylation of an isohexide, comprising contacting an isohexide with an excess of carboxylic acid in the presence of a water-tolerant Lewis acid catalyst at a reaction temperature and for a time sufficient to produce a mixture of corresponding ester derivatives of isohexide, wherein said isohexide is transformed to said ester derivatives at a conversion rate of ≧50 wt. %.

2 ) (canceled)

3 ) The method according to claim 1 , wherein said reaction temperature ranges from about 150° C. to about 250° C.

4 ) The method according to claim 3 , wherein said reaction temperature ranges from 170° C. to 220° C.

5 ) The method according to claim 1 , wherein said reaction time is less than about 24 hours.

6 ) The method according to claim 5 , wherein said reaction time is between about 1-12 hours.

7 ) (canceled)

8 ) The method according to claim 1 , wherein said isohexide conversion rate is from about 55% to 100%.

9 ) The method according to claim 8 , wherein said isohexide conversion rate is about 60% to about 98%.

10 ) The method according to claim 1 , wherein said ester product mixture contains isohexide diesters at a yield of at least ≧5 wt. % relative to the isohexide content.

11 ) The method according to claim 10 , wherein said yield of isohexide diester ranges from about 50% to about 85% relative to the isohexide content.

12 ) The method according to claim 11 , wherein said yield of diester is about 70% to about 75% relative to the isohexide content.

13 ) The method according to claim 1 , wherein said isohexide is at least one of isosorbide, isomannide, and isoidide.

14 ) The method according to claim 1 , wherein said carboxylic acid is selected from the group consisting of an alkanoic, alkenoic, alkyonoic, and aromatic acid, having a carbon chain length ranging from C 2 -C 26 .

15 ) The method according to claim 1 , wherein said carboxylic acid is present in about 2-fold to about 10-fold molar excess relative to the isohexide.

16 ) The method according to claim 15 , wherein said carboxylic acid is present in about 3-fold molar excess relative to the isohexide.

17 ) The method according to claim 1 , wherein said water-tolerant Lewis acid catalyst is either a homogenous or a heterogenous catalyst.

18 ) The method according to claim 1 , wherein said Lewis acid catalyst is a water-tolerant metal triflate, selected the group consisting of: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprodium, holmium, erbium, ytterbium, lutetium, gallium, scandium, bismuth, hafnium, mercury iron, nickel, copper, zinc, thallium, tin, and indium triflate, or a combination thereof.

19 ) The method according to claim 18 , wherein said the metal triflate is at least one of: hafnium, gallium, scandium, and bismuth triflate.

20 ) The method according to claim 1 , wherein said metal triflate is present in an amount of catalyst loading that ranges from about 0.0001 mol. % to about 10 mol. % of the isohexide.

21 ) The method according to claim 20 , wherein said metal triflate is present in an amount of catalyst loading that ranges from about 0.001 mol. % to about 0.01 mol. % relative to the isohexide content.

22 ) The method according to claim 1 , wherein said acid-catalyzed acylation is performed in a single reaction vessel as a biphasic system.

23 ) The method according to claim 22 , wherein said biphasic system is composed of a denser sugar alcohol in a lower phase layer and a carboxylic acid in an upper phase layer in said single reaction vessel.

24 ) The method according to claim 23 , wherein said sugar alcohol is transformed into said isohexide and migrates into a single phase with said carboxylic acid.

25 ) A method of preparing an ester of an isohexide comprising: providing a sugar alcohol in a single reaction vessel with an excess of carboxylic acid in the presence of a water-tolerant Lewis acid catalyst; melting said sugar alcohol to form a biphasic system, in which said molten sugar alcohol and Lewis acid catalyst are in a lower phase and said carboxylic acid is in an upper phase; dehydrating said sugar alcohol in its own phase to form an isohexide; migrating said isohexide along with said Lewis acid catalyst into said carboxylic acid phase, in which said isohexide contacts with said carboxylic acid at a reaction temperature and for a time sufficient to produce a mixture of corresponding ester derivatives of said isohexide.

Assignees

• Archer Daniels Midland Co

Inventors

• Stensrud Kenneth
• Hagberg Erik
• Rockafellow Erin
• Howard Stephen

Classifications

• B01J31/0232

  also containing elements or functional groups covered by B01J31/0201 - B01J31/0228 (perfluorinated sulfonyl compounds or moieties B01J31/0224; perfluorosulfonic acids B01J31/0227) · CPC title

• C07D493/04 Primary

  Ortho-condensed systems · CPC title

• B01J23/08

  of gallium, indium or thallium · CPC title

• B01J23/18

  Arsenic, antimony or bismuth · CPC title

• B01J23/06

  of zinc, cadmium or mercury · CPC title