Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides

• US 5,710,328 A
• Filed: 11/27/1995
• Issued: 01/20/1998
• Est. Priority Date: 11/27/1995
• Status: Expired due to Term

• Current Assignee: Eastman Chemical Company, Research Triangle Institute
• Original Assignee: Eastman Chemical Company
• Inventors: Spivey, James Jerry, Zoeller, Joseph Robert, Tustin, Gerald Charles, Gogate, Makarand Ratnakav
• Primary Examiner(s): Geist, Gary
• Assistant Examiner(s): Keys, Rosalynd
• Application Number:
  US08/562,860
• Time in Patent Office: 785 Days
• Field of Search: 562/599
• US Class Current: 562/599
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/41 Silicon
• CPC Class Codes: B01J 2523/47 Titanium
• CPC Class Codes: B01J 2523/51 Phosphorus
• CPC Class Codes: B01J 2523/55 Vanadium
• CPC Class Codes: B01J 27/198 Vanadium
• CPC Class Codes: C07C 51/083 from carboxylic acid anhydrides
• CPC Class Codes: C07C 51/567 by reactions not involving carboxylic acid anhydride groups
• CPC Class Codes: C07C 53/122 Propionic acid
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid

Abstract

Disclosed is a process for the preparation of α,β-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

Claims

1. Process for the preparation of α

,β

-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium and phosphorus.

2. Process according to claim 1 for the preparation of an α

,β

-unsaturated carboxylic acid having the formula ##STR6## which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride having the formula ##STR7## at a temperature of 150°

to 500°

C. in the presence of a vanadium-phosphorus mixed oxide catalyst wherein the vanadium;

phosphorus atomic ratio is in the range of about 1;

0.1 to 1;

50 and wherein R¹ is hydrogen, alkyl of up to about 20 carbon atoms, alkenyl of up to about 20 carbon atoms, or aryl of 6 to 10 carbon atoms.

3. Process for the preparation of an α

,β

-unsaturated carboxylic acid having the formula ##STR8## which comprises contacting in the gas phase formaldehyde or a source of formaldehyde with a carboxylic anhydride having the formula ##STR9## at a temperature of 250°

to 350°

C. in the presence of a catalyst comprising the oxides of vanadium, silicon and phosphorus having the formula (excluding oxygen);

space="preserve" listing-type="equation">V.sub.x Si.sub.w P.sub.y

in which the ratio of x;

w;

y is in the range of about 1;

8-12;

2-4; and

wherein R¹ is hydrogen or methyl.