High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation

• US 9,518,001 B1
• Filed: 05/19/2016
• Issued: 12/13/2016
• Est. Priority Date: 05/13/2016
• Status: Active Grant

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Powers, Kevin, Barrett, William, Sullivan, Jeffrey M.
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US15/159,185
• Time in Patent Office: 208 Days
• US Class Current: 1/1
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 57/13 Dicarboxylic acids
• CPC Class Codes: C07C 67/333 by isomerisation; by change of size of the carbon skeleton introduction or elimination of carboxyl groups C07C67/313, C07C67/32
• CPC Class Codes: C07C 67/343 by increase in the number of carbon atoms
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07C 69/675 of saturated hydroxy-carboxylic acids

Abstract

A composition comprising about 97 mole percent or greater of one or more 1,1-dicarbonyl substituted-1-ethylenes and about 3 mole percent or less of one or more 1,1-dicarbonyl substituted-methanes. A process comprising: contacting in a fluid state one or more 1,1-dicarbonyl substituted-1,1 hydroxymethyl-methanes and greater than 200 ppm to about 1000 ppm of one or more strong acids based on the weight of the one or more 1,1-dicarbonyl substituted-1,1 hydroxymethyl-methanes with a zeolite catalyst at a temperature of about 180° C. to about 220° C. for a sufficient time to convert about 96 percent or greater of the one or more 1,1-dicarbonyl substituted-1,1 hydroxymethyl-methanes to one or more 1,1-dicarbonyl substituted-1-ethylenes.

Claims

1. A process comprising:

contacting in a fluid state one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and greater than 200 ppm to about 1000 ppm of one or more strong acids based on the weight of the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes with a zeolite catalyst at a temperature of about 180°

C. to about 220°

C. for a sufficient time to convert about 96 percent or greater of the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes to one or more 1,1-dicarbonyl substituted-1-ethylenes.

2. A process according to claim 1 wherein the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and the one or more strong acids are passed through a fixed bed of zeolite catalyst, a reaction effluent containing one or more 1,1-dicarbonyl substituted-1-ethylenes exits the fixed bed of zeolite catalyst and the one or more 1,1-dicarbonyl substituted-1-ethylenes are isolated from the reaction effluent.

3. A process according to claim 1 wherein the zeolite catalyst contains acid groups.

4. A process according to claim 1 wherein the strong acid is present in an amount of about 300 ppm to 900 ppm and about 98 percent or greater of the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes are converted to one or more 1,1-dicarbonyl substituted-1-ethylenes.

5. A process according to claim 1 wherein the pKa of the strong acid is about 3 to about −

12.

6. A process according to claim 1 wherein the strong acid is one or more mineral acids.

7. A process according to claim 2 wherein the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and the strong acids are contacted with the bed of the zeolite catalyst at a pressure of about 50 to about 200 mmHg.

8. A process according to claim 1 wherein the one or more 1,1-dicarbonyl substituted-1-ethylenes is isolated by separating the reaction effluent into three streams, a light stream comprising water, formaldehyde and one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes;

a heavy stream containing oligomers and polymers and an intermediate stream containing one or more 1,1-dicarbonyl substituted-1-ethylenes and one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes;

distilling the intermediate stream and isolating a product containing 1,1-dicarbonyl substituted-1-ethylenes.

9. A process according to claim 1 wherein the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes are prepared by contacting one or more 1,1-dicarbonyl substituted-methanes with formaldehyde or a source of formaldehyde in the presence of a catalytic amount of one or more trialkylene amines under conditions to prepare a reaction mixture containing one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes and the trialkylene amines are removed from the reaction mixture by evaporation.

10. A process according to claim 9 wherein the concentration of the trialkylene amine in the one or more 1,1-dicarbonyl substituted-1,1-bis (hydroxymethyl)-methanes is less than 1 ppm after the trialkylene amines are removed by evaporation.

11. A process according to claim 9 wherein the one or more 1,1-dicarbonyl substituted-methanes is one or more malonates and the one or more 1,1-dicarbonyl substituted-1-ethylenes is one or more methylene malonates.

12. A process according to claim 1 wherein the product isolated comprises about 97 mole percent or greater of one or more 1,1-dicarbonyl substituted-1-ethylenes and about 3 percent mole percent or less of one or more 1,1-dicarbonyl substituted-methanes.

13. A process according to claim 12 wherein the product isolated comprises 99 percent by weight or greater of one or more 1,1-dicarbonyl substituted-1-ethylenes and 1 percent by weight or less of one or more 1,1-dicarbonyl substituted-methanes.

14. A process according to claim 12 wherein the isolated product contains 1 mole percent or less of an impurity containing a dioxane group, about 1 mole percent or less of any impurity having the alkene group replaced by an analogous hydroxyalkyl group wherein the mole percent is based on the total moles in the 1,1-disubstituted alkene compound.