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# c12) United States Patent 

# Lin et al. 

# (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. 

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(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. 

## (56) References Cited 

7,122,688 B2 * 10/2006 Lin et al. 554/169 

## Related U.S. Application Data 

## U.S. PATENT DOCUMENTS 

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# (10) Patent No.: US 8,993,793 Bl 

# Mar.31,2015 (45) Date of Patent: 

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.* 

Primary Examiner - Yate K Cutliff 

(74) Attorney, Agent, or Firm - Schwegman Lundberg & Woessner, P.A. 

## (57) ABSTRACT 

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 

## OTHER PUBLICATIONS 

## 18 Claims, 4 Drawing Sheets 

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