US009463450B 1  c12)  United States Patent  Shangguan et al.  (10)  Patent No.:  US 9,463,450 Bl  Oct. 11, 2016  (45)  Date of Patent:  (54)  POLYMERIC ACID CATALYSIS  (71)  Applicants:Ning  Shangguan,  Cherry Hill, NJ (US);  Andrew Feiring,  Wilmington, DE  (US);  Ashokkumar B. Shenvi,  Wilmington, DE (US)  (72)  Inventors:  Ning Shangguan,  Cherry Hill, NJ (US);  Andrew Feiring,  Wilmington, DE  (US);  Ashokkumar B. Shenvi,  Wilmington, DE (US)  (73)  Assignee:  Compact Membrane Systems, Inc.,  Newport, DE (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 0 days.  (21)  Appl. No.:  15/078,065  (22)  Filed:  Mar. 23, 2016  (60)  Provisional application No. 62/138,130, filed on Mar.  25, 2015.  (51)  Int. Cl.  (52)  U.S. Cl.  CPC ..............  B0JJ 31/06  (2013.01);  C07C 213100  (2013.01);  C07D 493/04  (2013.01)  ( 58)  Field of Classification Search  CPC ........................................................ B0lJ 31/06  USPC .......................................................... 549/464  See application file for complete search history.  Related U.S. Application Data  15 Claims, No Drawings  (57)  ABSTRACT  OTHER PUBLICATIONS  U.S. PATENT DOCUMENTS  (56)  References Cited  4,935,477 A  7,220,508 B2  2010/0314038 Al  2013/0245219 Al  6/ 1990 Squire  5/2007 Watakabe et al.  12/2010 Tanuma  9/2013 Perry et al.  Harmer, Mark A., et al., Solid Acid Catalysis Using Ion-exchange  Resins, Applied Catalysis A: General 221 (2001) 45-62.  Primary Examiner  - Nizal Chandrakumar  (74)  Attorney, Agent, or Firm  - Jeffrey C. Lew  A highly fluorinated polymer is very useful as an acid  catalyst. The highly fluorinated polymer has at least two  repeating unit types that are the polymerized derivatives of  a perfluorinated cyclic or cyclizable compound and a highly  fluorinated vinyl ether compound having a sulfur containing  functional group. The polymer can be formed by radical  copolymerization of the fluorinated monomers with the  sulfur-containing functional group in sulfonyl fluoride form  (-SO$_{2}$F) that is subsequently converted to sulfonic acid  form (-SO$_{3}$H). The highly fluorinated polymer can be used  to advantage in a solution comprising an aprotic, polar  organic solvent that has a dielectric constant of at least 15  and preferably is free of hydroxyl functional groups. Suit› able solvents are those in which the polymer is soluble to at  least 1 wt  %. Hydroxyl group-containing protic, polar  organic solvents are less preferred. The highly fluorinated  polymer can be an effective heterogeneous catalysts when  used in form of solid, fine particles insolubly suspended in  or in contact with a fluid reaction mass.  C07D 493/00  B0JJ 31/06  C07D 493/04  C07C 213100  (2006.01)  (2006.01)  (2006.01)  (2006.01) 