US010131736B2  c12)  United States Patent  Richter  (45)  Date of Patent:  Nov. 20, 2018  (IO)  Patent No.:  US 10,131,736 B2  (54)  METHOD FOR ISOCYANATE  MODIFICATION USING CATALYSTS WITH  AN NPN SEQUENCE  (71)  Applicant:  Covestro Deutschland AG,  Leverkusen  (DE)  (72)  Inventor:  Frank Richter,  Leverkusen (DE)  (73)  Assignee:  Covestro Deutschland AG,  Leverkusen  (DE)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 64 days.  (21)  Appl. No.:  15/119,179  (22)  PCT Filed:  Feb. 13, 2015  (86)  PCT No.:  PCT/EP2015/053085  § 371 (c)(l),  (2) Date:  Aug. 16, 2016  (87)  PCT Pub. No.:  WO2015/124503  PCT Pub. Date:  Aug. 27, 2015  (65)  Prior Publication Data  US 2017/0008996 Al  Jan. 12, 2017  (30)  Foreign Application Priority Data  Feb. 18, 2014  (EP) ..................................... 14155524  (51)  Int. Cl.  (52)  U.S. Cl.  CPC ..........  C08G 1811883  (2013.01);  C07F 9/067  (2013.01);  C08G 18102  (2013.01);  C08G  181022  (2013.01);  C08G 181027  (2013.01);  C08G 181092  (2013.01);  C08G 181095  (2013.01);  C08G 181097  (2013.01);  C08G  18173  (2013.01)  (58)  Field of Classification Search  CPC .. C08G 18/1883; C08G 18/02; C08G 18/022;  C08G 18/027; C08G 18/092; C08G  18/095; C08G 18/097  See application file for complete search history.  C08G 18102  C08G 18118  C07F 9/06  C08G 18173  C08G 18109  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  15 Claims, No Drawings  (56)  References Cited  (57)  ABSTRACT  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  Document N_English Translation Dec. 13, 2017.*  The Synthesis of Aliphatic Polyisocyanates Containing Biuret,  Isocyanurate or Uretdione Backbones for use in Coatings, Laas, et  al., J. Prakt Chem., 1994, 336, 185-200.  1,4,2-Diazaphospholidine-3,5-diones and Related Compounds: A  Lecture on Unpredictability in Catalysis, Frank U. Richter, Chem.  Eur. J. 2009, 15, pp. 5200-5202.  D. Wendisch, H. Reiff and D. Dieterich, Die Angewandte  Makromolekulare Chemie 141, 1986, 173-183  (Nr.  2302).  Anhydrous Phosphazenium Fluorides as Sources for Extremely  Reactive Fluoride Ions in Solution, Schwesinger, et al., Chem. Eur.  J. 2006, 12, 438-445.  An Electron-Rich Proazaphosphatrane for Isocyanate Trimerization  to Isocyanurates, Raders, et al., J. Org. Chem. 2010, 75, 5308-5311.  Extremely Base-Resistant Organic Phosphazenium Cations,  Schwesinger, et al, Chem Eur. J. 2006, 12, 429-437.  Primary Examiner  - Michael L Leonard  (74)  Attorney, Agent, or Firm  - Richard P. Bender; John  E. Mrozinski, Jr.  The invention relates to a method for modifying isocyanates,  wherein at least one organic monomer isocyanate having an  NCO functionality  > 1 is oligomerised in the presence of at  least one catalyst, said method being characterised in that the  catalyst comprises at least one specific compound having an  NPN sequence selected from compounds of formula I (for› mula I), and/or from compounds of formula  II (formula II)  where HX represents an acid with a pKa value 2:2, x› represents the anion of an acid with a pKa value 2:2, and n  represents an integer or fractional number between  O  and 20,  wherein  Y represents R$_{12}$(R$_{13}$)N- and/or one or more  substituents of the structure of formula III (formula III) and  wherein R$_{1 }$ to R$_{19 }$ independently represent identical or  different substituents selected from C$_{1 }$-C$_{20 }$ alkyl-, C$_{1 }$-C$_{20 }$ cycloalkyl- and C$_{6}$-C$_{20 }$ aryl groups, or wherein R$_{1 }$ and R$_{2}$ ,  R$_{3 }$ and R$_{4}$ ,  R$_{5 }$ and R$_{6}$ ,  R$_{7 }$ and R$_{8}$ ,  R$_{9 }$ and R$_{10}$, R$_{12 }$and R$_{13}$,  R$_{14 }$ and R$_{15}$, R 16  and R$_{1 7}$ ,  R$_{18 }$ and R$_{19 }$ independently  represent identical or different substituents selected from  C$_{1 }$-C$_{20 }$ alkylene-, C$_{1 }$-C$_{20 }$ cycloalkylene-, C$_{6}$-C$_{20 }$ arylene  groups, and can form a 3- to 12-membered ring with the N  atom joined to the P atom. The invention also relates to the  use of a catalyst of this type.  U.S. PATENT DOCUMENTS  5,260,436 A  5,914,383 A  6,090,939 A  6,107,484 A  2003/0135007 Al  2006/0241300 Al  2015/0025268 Al  11/1993 Verkade et al.  6/ 1999 Richter et al.  7 /2000 Richter et al.  8/2000 Richter et al.  7/2003 Ewald et al.  10/2006 Wessel et al.  1/2015 Richter et al.  CA  CN  CN  2244486 Al  2/1999  102964566 B  3/2013  102964566 B  *  5/2014  (Continued)  4,960,848 A  5,013,838 A  10/ 1990 Scholl et al.  5/ 1991 Scholl 