Alkenyl (perfluoroalkyl) phosphinic acids

Patent metadata

Field	Value
Publication number	US-RE48165-E
Application number	US-201516289925-A
Country	US
Kind code	E1
Filing date	Sep 25, 2015
Priority date	Oct 17, 2014
Publication date	Aug 18, 2020
Grant date	Aug 18, 2020

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.

First claim

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.

Assignees

• Merck Patent Gmbh

Inventors

• Ignatyev Nikolai (Mykola)
• Schulte Michael
• Koppe Karsten
• Bilir Vural
• Frank Walter

Classifications

• C22B3/42

  by ion-exchange extraction · CPC title

• C08F112/14

  substituted by hetero atoms or groups containing heteroatoms · CPC title

• C07F9/302 Primary

  Acyclic unsaturated acids · CPC title

• C07F9/304

  Aromatic acids (P-C aromatic linkage) · CPC title

• C08L43/02

  Homopolymers or copolymers of monomers containing phosphorus · CPC title