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USRE48165EActiveUtilityPatentIndex 48

Alkenyl (perfluoroalkyl) phosphinic acids

Assignee: MERCK PATENT GMBHPriority: Oct 17, 2014Filed: Sep 25, 2015Granted: Aug 18, 2020
Est. expiryOct 17, 2034(~8.3 yrs left)· nominal 20-yr term from priority
Inventors:IGNATYEV NIKOLAI MYKOLASCHULTE MICHAELKOPPE KARSTENBILIR VURALFRANK WALTER
C22B 3/42C08F 112/14C07F 9/302C07F 9/304C08L 43/02B01J 31/0261B01J 39/04C22B 3/384B01J 20/28047C08F 214/18B01J 41/04C22B 59/00C08F 130/02C08F 261/06C08F 114/18C08F 12/14B01J 20/3085C08F 30/02C08F 230/02B01J 20/3265C07F 9/5316B01J 20/3204B01J 20/103B01J 20/22Y02P10/20B01J 41/13C22B 3/24Y02P10/234C22B 3/0064
48
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Cited by
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References
20
Claims

Abstract

The invention relates to alkenyl(perfluoroalkyl)phosphinic acids, to the preparation and intermediates thereof, to the use thereof as monomers for the preparation of oligomers and/or polymers, to the corresponding oligomers/polymers, to the corresponding support materials comprising the oligomers/polymers, and to the use thereof as ion exchangers, as catalysts or extraction medium and corresponding salts thereof.

Claims

exact text as granted — not AI-modified
The invention claimed is: 
     
       1. A compound of the formula I 
       
         
           
           
               
               
           
         
         where 
         R f  denotes a straight-chain or branched perfluoroalkyl group having 1 to 12 C atoms, 
         A denotes H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms, 
         B denotes —(CR 1 R 2 ) n —, [—(CR 1 R 2 ) m —O—(CR 1 R 2 ) m1 —] m2 , arylene or substituted arylene, 
         X denotes H, F and/or Cl, 
         n denotes an integer from 0 to 20, 
         m denotes an integer from 1 to 20, 
         m 1  denotes an integer from 0 to 8, 
         m 2  denotes an integer from 1 to 20 and 
         R 1  or R 2  each, independently of one another, denote H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms. 
       
     
     
       2. A compound according to  claim 1 , wherein R f  denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms. 
     
     
       3. A compound according to  claim 1 , wherein A and X are identical. 
     
     
       4. A compound according to  claim 1 , wherein B denotes —(CR 1 R 2 ) n —, arylene or substituted arylene. 
     
     
       5. A process for the preparation of a compound of the formula I according to  claim 1 , which comprises:
 a) hydrolysing a compound of the formula II
   (F) x (R f ) 4−x P—B—CX═CX-A  II ,
 
 
 where R f , A, B and X have a meaning indicated in  claim 1  and x denotes 2, to give an intermediate compound of the formula IIIa, 
 
       
         
           
           
               
               
           
         
         where R f , A, B and X have a meaning indicated in formula II, or 
         b) reacting a compound of the formula II
   (F) x (R f ) 4−x P—B—CX═CX-A  II ,
 
 
         where R f , A, B and X have a meaning indicated in  claim 1  and x denotes 2 or 3, with a hexaalkyldisiloxane optionally in the presence of a catalytic amount of water, 
         where the alkyl groups of the hexaalkyldisiloxane each, independently of one another, denote a straight-chain or branched alkyl group having 1 to 4 C atoms, to give an intermediate compound of the formula III, 
       
       
         
           
           
               
               
           
         
         where R f , A, B and X a have a meaning indicated in formula II; and
 then hydrolysing the intermediate compound of formula IIIa or III to obtain a compound of formula I. 
 
       
     
     
       6. A compound of the formula IIIa, 
       
         
           
           
               
               
           
         
         where 
         R f  denotes a straight-chain or branched perfluoroalkyl group having 1 to 12 C atoms, 
         A denotes H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms, 
         B denotes —(CR 1 R 2 ) n —,[—(CR 1 R 2 ) m —O—(CR 1 R 2m1 —] m2 ,arylene or substituted arylene, 
         X denotes H, F and/or Cl, 
         n denotes an integer from 0 to 20, 
         m denotes an integer from 1 to 20, 
         m 1  denotes an integer from 0 to 8, 
         m 2  denotes an integer from 1 to 20 and 
         R 1  or R 2  each, independently of one another, denote H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms. 
       
     
     
       7. A method for the preparation of oligomers or polymers which comprises oligomerizing or polymerizing a compound of  claim 1 . 
     
     
       8. Oligomer or polymer containing polymerised compounds of the formula I, according to  claim 1 , as monomer units. 
     
     
       9. A process for the preparation of oligomers or polymers according to  claim 8 , comprising polymerizing a compound of the formula I, optionally together with further monomers and optionally in the presence of a crosslinking agent. 
     
     
       10. Process according to  claim 9 , wherein the polymerisation is carried out by means of free radicals. 
     
     
       11. Process according to  claim 9  wherein a homo-polymer is prepared. 
     
     
       12. Process according to  claim 9  wherein the polymerisation is carried out without crosslinking agents. 
     
     
       13. Process according to  claim 9  wherein the polymerisation is carried out in, on or at a support material. 
     
     
       14. Composite material comprising a support material and at least one compound according to  claim 1 . 
     
     
       15. An ion exchanger or a Brønsted acid catalyst material comprising a compound of  claim 1  or a polymer or oligomer of a compound of  claim 1 . 
     
     
       16. A method for the extraction of cations of the rare earths from a solution which comprises contacting the solution with a material comprising a compound of  claim 1  or a polymer or oligomer thereof. 
     
     
       17. A salt corresponding to the formula IV, 
       
         
           
           
               
               
           
         
         where the cation Kt + in formula IV denotes an inorganic or organic cation and where
 R f  denotes a straight-chain or branched perfluoroalkyl group having 1 to 12 C atoms, 
 A denotes H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms, 
 B denotes —(CR 1 R 2 ) n —, [—(CR 1 R 2 ) m —O—(CR 1 R 2 ) m1 —] m2 , arylene or substituted arylene, 
 X denotes H, F and/or Cl, 
 n denotes an integer from 0 to 20, 
 m denotes an integer from 1 to 20, 
 m 1  denotes an integer from 0 to 8, 
 m 2  denotes an integer from 1 to 20 and 
 R 1  or R 2  each, independently of one another, denote H, F, Cl or a straight-chain or branched alkyl group having 1 to 12 C atoms. 
 
       
     
     
       18. A polymer or oligomer comprising polymerized units of a salt of  claim 17  as monomer units. 
     
     
       19. Composite material comprising a support material and at least one polymer or oligomer of  claim 8 . 
     
     
       20. Composite material comprising a support material and at least one polymer or oligomer of claim 18.

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