c12)  United States Patent  Lin et al.  (10)  Patent No.:  US 8,993,793 Bl  Mar.31,2015  (45)  Date of Patent:  (54)  MULTIFUNCTIONAL MESOPOROUS SILICA  CATALYST  (75)  Inventors:  Victor Shang-Yi Lin,  Ames, IA (US);  Show-Ling Lee,  legal representative,  Ames, IA (US);  Chih-Hsiang Tsai,  Ames, IA (US);  Hung-Ting Chen,  Ames, IA (US);  Marek Pruski,  Ames,  IA (US);  Takeshi Kobayashi,  Ames, IA  (US)  (73)  Assignee:  Iowa State University Research  Foundation, Inc.,  Ames, IA (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 405 days.  (21)  Appl. No.:  13/361,613  (22)  Filed:  Jan.30,2012  (60)  Provisional application No. 61/441,076, filed on Feb.  9, 2011.  (51)  Int. Cl.  (52)  U.S. Cl.  CPC .  CllC 3/003  (2013.01);  CllC 3/00  (2013.01);  B0JJ 31/1633  (2013.01);  C07C 67108  (2013.01)  USPC ............  554/174;  554/170; 554/168; 502/158  ( 58)  Field of Classification Search  None  See application file for complete search history.  18 Claims, 4 Drawing Sheets  (57)  ABSTRACT  OTHER PUBLICATIONS  Related U.S. Application Data  (56)  References Cited  U.S. PATENT DOCUMENTS  C07C 51143  CllC 3/00  B0JJ 31/16  C07C 67108  (2006.01)  (2006.01)  (2006.01)  (2006.01)  Alvaro, M. et al., N afion -functionalized mesoporous MCM-41 silica  shows high activity and selectivity for carboxylic acid esterification  and Rriedel-Crafts acylation reactions, 2005, Journal of Catalysis,  vol. 231, pp. 48-55. *  Mbaraka,  I.K.,  et  al.,  Organosulfonic  acid-functionalized  mesoporous silicas fortheesterificationoffatty acid, 2003, Journal of  Catalysis, vol. 219, pp. 329-336.*  Mbaraka, I.K., et al., Design of mltifunctionalized mesoporous sili› cas for esterification of fatty acid, 2005, Journal of Catalysis, vol.  229, pp. 365-373. *  Mbaraka, I.K., et al., Acidic Mesoporous Silica for the catalytic  conversion of fatty acids in beef tallow, 2006, Ind. Eng. Chem. Res.,  vol. 45, pp. 3022-3028.*  Han, L. et al., Synthesis and characterization of the amphoteric amino  acid bifunctional Mesoporous Silica, 2007, Chem Mater. vol. 19, pp.  2860-2867.*  Funatomi, T., et al., Pentafluorophenylammonium triflate (PFPAT):  an efficient , practical, and cost-effective catalyst for esterificaitn,  thioesterificatin, transesterification, and mcrolactone formation,  2006, Green Chemistry, vol. 8, pp. 1022-1027.*  Wakasugi, K., et al., Diphenylammonum triflate (DPAT): efficeint  catalyst for esterificatin ofcarboxylic acids and for transesterification  of carboxylic esters with nearly equimolar amounts of alcohol, 2000,  Tetrahedron Letters, vol. 41, pp. 5249-5252.*  (Continued)  Primary Examiner  - Yate K Cutliff  (74)  Attorney, Agent, or Firm  - Schwegman Lundberg &  Woessner, P.A.  The present invention provides bifunctional silica mesopo› rous materials, including mesoporous silica nanoparticles  ("MSN"), having pores modified with diarylammonium tri› flate and perfluoroaryl moieties, that are useful for the acid› catalyzed esterification of organic acids with organic alco› hols.  US008993 793B 1  350  ~300  E- t 250  z  LU  5 200  LU  0::  LL 150  0::  LU  Ei  100  ~  :::,  t-- 50  0  CATA  CATC  CATO AMBERLYST-15 NAFION  CATALYST  BLANK  7,122,688 B2 * 10/2006 Lin et al.  554/169 