US 8,927,766  B2  40  39  Example 67  TABLE 12-continued  TABLE 12  TABLE 13  A 50 mL Hastelloy 27 6C high pressure autoclave was fitted  with an impeller, gas inlet tube, sample tube, and thermowell.  The autoclave was heated with a heating block, with tempera- ture control provided by feedback via a thermocouple in the  autoclave thermowell. Pure carbon monoxide gas (>99.9%)  was fed to the autoclave via a high pressure regulator. The  autoclave was charged with 20% W-heteropoly/silica catalyst  (1.48 g) propionic acid (12.28 g, 0.16 mo!) and MDP (14.1 g,  0.08 mo!) and water (1.4 g, 0.08 mo!) and sealed. The auto› clave was secured to the stand and the system was pressurized  with 200 psig nitrogen and vented. This purging procedure  was repeated two times. The autoclave was then purged with  carbon monoxide and pressurized to 200 psig carbon mon- oxide. The temperature in the autoclave was increased to 140°  C. Upon reaching 140°  C., the pressure in the autoclave was  increased to 1,000 psig carbon monoxide. The reaction was  held at these conditions for 2 hours and then cooled to room  temperature and vented. Finally the autoclave was purged  with nitrogen and unloaded. The reaction contents were ana› lyzed by GC. Results are shown in Table 12.  The procedure of Example 67 was repeated using either  MDP/propionic acid or MDA/acetic acid and water at target  equivalents of 1 eq. of MDA(MDP), 2 eq. acetic (propionic)  acid, and 1 eq. water at a reaction pressure ofl 000 psig carbon  monoxide. The examples were run with the solid catalyst and  corresponding loading, at the temperature, and for the hold› ing time shown in Table 12. Calculated yields are also given  in Table 12.  A 50 mL Hastelloy 276C high pressure autoclave was fitted  with an impeller, gas inlet tube, sample tube, and thermowell.  The autoclave was heated with a heating block, with tempera› ture control provided by feedback via a thermocouple in the  autoclave thermowell. Pure carbon monoxide gas (>99.9%)  was fed to the autoclave via a high pressure regulator. The  autoclave was charged with AMBERLYST 36 D catalyst  (1.43 g), propionic acid (12.3 g, 0.166 mo!), MDP (14.1 g,  0.088 mo!), and water (1.5 g, 0.083 mo!) and sealed. The  autoclave was secured to the stand and the system was pres› surized with 200 psig nitrogen and vented. This purging pro› cedure was repeated two times. The autoclave was then  purged with carbon monoxide and pressurized to 500 psig  carbon monoxide. The temperature in the autoclave was  increased to 140°  C. Upon reaching 140°  C., the pressure in  the autoclave was increased to 1,000 psig carbon monoxide.  The reaction was held at these conditions for 2 hours and then  cooled to room temperature and vented. Finally the autoclave  was purged with nitrogen and unloaded. The reaction con- tents were analyzed by GC. The results are shown in Table 13.  Example 84 was repeated with the catalyst and catalyst  loading and amount of propionic acid and water given in  Table 13. Each reaction was run at 1000 psig carbon monox- ide and at the temperature and for the time indicated in Table  13. Yield to desired products and selectivity are also given in  Table 13.  Examples 85-91  Examples 68-83  Examples 84  EX  73 MDA  74 MDA  75 MDA  76 MDA  77 MDA  78 MDA  79 MDA  80 MDA  81 MDP  82 MDP  83 MDP  Hydrocarboxylations ofMetbylene Diacetate (MDA)  or Metbylene Dipropionate (MDP) Catalyzed by  Strongly Acidic Solid Acid Catalysts.  loading temp  time  yield  catalyst  (wt%)  (" C.)  (h)  (%)  SAC-13  9  180  78.8  NafionNR50  5  140  2  69.4  SAC-13  15  160  98.6  polymer-bound pTSA  5  140  2  66  AMBERLYST 36  5  140  2  77  SMOPEX (4% crosslinking)  5  140  3  65  SMOPEX (8% crosslinking)  5  160  2  70  SMOPEX (12% crosslinking)  5  180  2  66  AMBERLYST 36  5  140  2  86  SAC-13  10  140  2  76  SMOPEX (4% crosslinking)  5  140  2  68  EX  67 MDP  68 MDP  69 MDA  70 MDA  71 MDA  72 MDA  Hydrocarboxylations ofMetbylene Diacetate (MDA)  or Metbylene Dipropionate (MDP) Catalyzed by  Strongly Acidic Solid Acid Catalysts.  catalyst  loading temp  time  (wt%)  (°C.) (h)  20% W-heteropoly/silica  SiOiAl2O3  KIO  AMBERLYST 70  SAC-13  SAC-13  5  5  5  5  9  9  140  140  140  140  140  160  2  2  2  2  yield  (%)  6.5  2.0  3.8  18.8  47.8  69.8  Hydrocarboxylations ofMDP  Loading  A3  Water  Temp  Time  Yield  Select.  Ex Catalyst  (wt%)  (eq)  (eq)  ("C.)  (h)  (%)  (%)  84 AMBERLYST 36 D  5  2.0  1.0  140  2  96  96  85  AMBERLYST 36 D  8  0.14  1.1  140  2  89  94  86  AMBERLYST 36 D  5  2.1  140  2  86  96  87  AMBERLYST 36 D  5  1.1  140  2  78  95  88  AMBERLYST 36 D  5  0.15  140  2  72  94  89  AMBERLYST 36 D  5  2  0.05  140  2  2  28  90 AMBERLYST 36 D  5  2  0.05  90  2  3  5  91  AMBERLYST 36 D  5  2  0.5  140  2  16  66 