(45)  Date of Patent:  Jan.6,2015  (IO)  Patent No.:  US 8,927,766 B2  c12)  United States Patent  Barnicki et al.  (54)  HYDROCARBOXYLATION OF METHYLENE  DIPROPIONATE IN THE PRESENCE OF A  PROPIONIC ACID AND A HOMOGENEOUS  CATALYST  (75)  Inventors:  Scott Donald Barnicki,  Kingsport, TN  (US);  Robert Thomas Hembre,  Johnson  City, TN (US);  Stephen Neal Falling,  Kingsport, TN (US)  (73)  Assignee:  Eastman Chemical Company,  Kingsport, TN (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 176 days.  (21)  Appl. No.:  13/431,402  (22)  Filed:  Mar. 27, 2012  (51)  Int. Cl.  C07C 51112  C07C 59/06  (2006.01)  (2006.01)  (52)  U.S. Cl.  CPC ......................................  C07C 51112  (2013.01)  USPC ...........................................  562/518;  562/579  ( 58)  Field of Classification Search  CPC ................................ C07C 51/12; C07C 59/06  See application file for complete search history.  FOREIGN PATENT DOCUMENTS  OTHER PUBLICATIONS  (57)  ABSTRACT  24 Claims, No Drawings  U.S. PATENT DOCUMENTS  (56)  References Cited  (65)  Prior Publication Data  2,152,852  A  4/1939 Loder  2,153,064  A  4/1939 Larson  2,211,624  A  8/1940 Loder et al.  2,211,625  A  8/1940 Loder  2,298,138  A  10/1942 Loder  2,436,209  A  2/1948 Elgin  2,443,482  A  6/1948 Shattuck  3,333,924  A  8/1967 Hazen et al.  3,751,453 A  8/1973 Kurkov et al.  3,754,028  A  8/1973 Lapporte et al.  3,801,627  A  4/1974 Kurkov et al.  3,859,349  A  1/1975 Cody  3,911,003  A  10/1975 Suzuki  3,927,078 A  12/1975 Lapporte et al.  3,948,977 A  4/1976 Suzuki  3,948,986 A  4/1976 Suzuki  4,016,208 A  4/1977 Suzuki  4,052,452 A  10/1977 Scardigno et al.  4,087,470 A  5/1978 Suzuki  4,112,245 A  9/1978 Zehner et al.  4,128,575 A  12/1978 Leupold et al.  4,136,112 A  1/1979 Bakshi  4,140,866 A  2/1979 Nielsen  4,153,809 A  5/1979 Suzuki  4,228,305 A  10/1980 Suzuki  4,275,234 A  6/1981 Bani el et al.  4,291,007 A  9/1981 Baniel  4,308,397 A  12/1981 Suzuki  4,366,333  A  12/1982 Wilkes  4,409,395  A  10/1983 Miyazaki et al.  4,431,486 A  2/1984 Balmat  4,440,734 A  4/1984  4,501,917 A  2/1985  4,691,048 A  9/1987  4,824,997  A  4/1989  4,935,102  A  6/1990  4,966,658  A  10/1990  4,990,629  A  2/1991  5,026,927  A  6/1991  5,210,335  A  5/1993  5,214,219 A  5/1993  5,276,181 A  1/1994  5,423,955  A  6/1995  5,455,372  A  10/1995  5,723,662  A  3/1998  5,932,772  A  8/1999  5,952,530  A  9/1999  6,252,121 Bl  6/2001  6,291,725 Bl  9/2001  6,294,700 Bl  9/2001  6,303,829 Bl  10/2001  6,307,108 Bl  10/2001  6,307,109 Bl  10/2001  6,307,110 Bl  10/2001  6,310,260 Bl  10/2001  6,376,723 B2  4/2002  7,122,698 B2  10/2006  7,164,040 B2  1/2007  7,223,885 B2  5/2007  Kougioumoutzakis  Schmidt et al.  Hugues et al.  Macfarlane et al.  Berg  Berg  Souma  Andrews et al.  Schuster et al.  Casale et al.  Casale et al.  Berg  Hirai et al.  Ebmeyer et al.  Argyropoulos et al.  Argyropoulos et al.  Argyropoulos et al.  Chopade et al.  Kane! et al.  Kane! et al.  Argyropoulos et al.  Kane! et al.  Argyropoulos et al.  Argyropoulos et al.  Drent et al.  Yoshida et al.  Kuroda et al.  Van Krieken  DE  EP  EP  EP  GB  GB  GB  IL  JP  JP  3133353 C2  3/1983  0 114 657 Bl  3/1987  0 676 239 A2  10/1995  1679331 Al  7/2006  508383 A  6/1939  1499245 A  1/1978  2179337 A  7 /1986  89044 A  3/1993  56100741 A  8/1981  56131546 A  10/1981  Disclosed is a process for the production and purification of  glycolic acid or glycolic acid derivatives by the carbonylation  of methylene dipropionate in the presence of a homogeneous  acid catalyst and propionic acid. This invention discloses  hydrocarboxylations and corresponding homogeneous acid  catalyst and glycolic acid separations. The homogeneous acid  catalyst is readily separated from the hydrocarboxylation  reaction effluent and recycled and the propionic acid is  readily removed from the glycolic acid and the propionic acid  is recycled.  Primary Examiner  - Paul A Zucker  (74)  Attorney, Agent, or Firm  - Jennifer R. Knight  Asci et al, Journal of Chemical Engineering Data, 2009, 54, pp.  2791-2794.*  (Continued)  (Continued)  (Continued)  US008927766B2  US 2013/0261329 Al  Oct. 3, 2013 