(Per)fluoropolyether polymers

Patent metadata

Field	Value
Publication number	US-10899883-B2
Application number	US-201716469633-A
Country	US
Kind code	B2
Filing date	Dec 12, 2017
Priority date	Dec 14, 2016
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

Abstract

The present invention relates to a novel process for the synthesis of (per)fluoropolyether polymers and to certain novel (per)fluoropolyether polymers. The present invention also relates to the use the (per)fluoropolyether polymers thus obtained, as intermediate compounds for the manufacture of further polymers suitable for use as lubricants, notably for magnetic recording media (MRM).

First claim

The invention claimed is:

1. A process (P FOR ) for the synthesis of at least one polymer (PFPE FOR ), said polymer (PFPE FOR ) comprising a perfluoropolyether backbone having two chain ends, wherein at least one chain end comprises at least one group selected from linear or branched perfluoroalkyl group comprising from 1 to 6 carbon atoms, —OC(═O)F and —C(═O)F,
said process (P FOR ) comprising:
(I) contacting at least one compound (F), wherein compound (F) is a perfluoro compound comprising at least two acyl-fluoride groups with at least one compound (H), wherein compound (H) is a hydrogenated compound comprising at least two fluoroformate groups, to provide a polymer (FH) comprising a partially fluorinated polyether backbone having two chain ends,
wherein said backbone comprises recurring unit(s) derived from said at least one compound (F) alternately arranged with recurring unit(s) derived from said at least one compound (H), and
wherein at least one of said chain ends comprises at least one group selected from —OC(═O)F and —C(═O)F; and
(II) contacting said polymer (FH) obtained in step (I) with a source of fluorine, to provide at least one polymer (PFPE FOR ).

2. The process according to claim 1 , wherein:
said compound (F) is a compound of formula:
F—(O═)C—R f —C(═O)—F

wherein R f is a divalent, perfluoro linear or branched alkyl chain, wherein said alkyl chain comprises from 1 to 10 carbon atoms and is optionally interrupted by one or more oxygen atoms; and/or
said compound (H) is a compound of formula:
F—(O═)CO—R H —OC(═O)—F

wherein R H is a divalent linear or branched alkyl chain, wherein said alkyl chain comprises from 2 to 10 carbon atoms and is optionally interrupted by one or more oxygen atoms.

3. The process according to claim 1 , wherein, in polymer (PFPE FOR ), said backbone is linked at its opposite sides to one chain end via a sigma bond or a linking chain (L) comprising at least one moiety R f and/or at least one moiety R F , wherein
said moiety R f is a divalent, perfluoro linear or branched alkyl chain, wherein said alkyl chain comprises from 1 to 10 carbon atoms and is optionally interrupted by one or more oxygen atoms, and
said moiety R F is a divalent linear or branched perfluoro alkylene chain comprising from 2 to 10 carbon atoms and optionally interrupted by one or more oxygen atoms.

4. The process according to claim 1 , wherein, in polymer (PFPE FOR ), said backbone comprises a recurring unit complying with formula (PFPE FOR-b ):
—[CF 2 R f CF 2 —OR F O] y* —  (PFPE FOR-b )

wherein
R f is a divalent, perfluoro linear or branched alkyl chain, wherein said alkyl chain comprises from 1 to 10 carbon atoms and is optionally interrupted by one or more oxygen atoms,
R F is a divalent linear or branched perfluoro alkylene chain comprising from 2 to 10 carbon atoms and optionally interrupted by one or more oxygen atoms, and
y* is an integer selected such that the average number molecular weight of the backbone of polymer (PFPE FOR ) as determined by NMR analysis is from 282 to 70-000.

5. The process according to claim 1 , wherein polymer (PFPE FOR ) complies with one of formulae (PFPE FOR-1 ) to (PFPE FOR-6 ):
F—C(═O)—R f CF 2 —OR F O—[CF 2 R f CF 2 —OR F O] y* —CF 2 R f C(═O)F  (PFPE FOR-1 )

F—C(═O)O—R F —O[CF 2 R f CF 2 —OR F O] y* —C(═O)F  (PFPE FOR-2 )

F—C(═O)—R f —CF 2 O—R F —O[CF 2 R F O] y* —C(═O)F  (PFPE FOR-3 )

T-R f —CF 2 O—R F —O[CF 2 R f CF 2 —OR F O] y* —C(═O)F  (PFPE FOR-4 )

T-R f —CF 2 O—R F —O[CF 2 R f CF 2 —OR F O]y*—CF 2 R f C(═O)F  (PFPE FOR-5 )

T-R f CF 2 —OR F O—[CF 2 R f CF 2 —OR F O] y* —CF 2 R f -T  (PFPE FOR-6 )

wherein
R f is a divalent, perfluoro linear or branched alkyl chain, wherein said alkyl chain comprises from 1 to 10 carbon atoms and is optionally interrupted by one or more oxygen atoms,
R F is a divalent linear or branched perfluoro alkylene chain comprising from 2 to 10 carbon atoms and optionally interrupted by one or more oxygen atoms,
y* is an integer selected such that the average number molecular weight of the backbone of the polymer as determined by NMR analysis is from 282 to 70000, and
T is a neutral group selected in the group comprising fluorine atom and linear or branched perfluoroalkyl chain comprising from 1 to 6 carbon atoms.

6. The process according to claim 1 , wherein step (I) comprises adding at least one compound (F-mono), wherein compound (F-mono) is a compound comprising one acyl-fluoride group, and/or at least one compound (H-mono), wherein compound (H-mono) is a compound comprising one fluoroformate group.

7. A perfluoropolyether polymer (PFPE* FOR ) comprising a perfluoropolyether backbone having two chain ends,
wherein:
at least one of said chain end comprises at least one group selected from linear or branched perfluoroalkyl group comprising from 1 to 6 carbon atoms, —OC(═O)F and —C(═O)F, and
said backbone comprises at least one moiety selected from moieties of formulae (Ia) to (If):
—(C 2 F 4 O) a —;  (Ia)

—(C 3 F 6 O) b —;  (Ib)

—(C 4 F 8 O) c —;  (Ic)

—(C 5 F 10 O) d —;  (Id)

—(C 6 F 12 O) e —;  (Ie)

—(C x F 2x O) f —;  (If)

wherein
x is an integer from 7 to 12;
each of a, b, c, d, e and f is independently 0 or an integer, wherein the sum of a, b, c, d, e and f is such that the average number molecular weight of the backbone of the polymer as determined by NMR analysis is from 282 to 70-000;
with the proviso that:
when a is different from 0, at least one of b, c, d, e or f is different from 0,
when b is different from 0, at least one of a, c, d, e or f is different from 0,
when c is different from 0, at least one of a, b, d, e or f is different from 0;

and with the proviso that when said backbone comprises two moieties complying with formulae (Ia) to (If) as defined above, said two moieties are alternately arranged within the backbone.

8. The polymer (PFPE* FOR ) according to claim 7 , wherein said backbone comprises a recurring unit complying with formula (PFPE FOR-b ):
—[CF 2 R f CF 2 —OR F O] y* —  (PFPE FOR-b )

wherein
R f is a divalent, perfluoro linear or branched alkyl chain, wherein said alkyl chain comprises from 1 to 10 carbon atoms and is optionally interrupted by one or more oxygen atom,
R F is a divalent linear or branched perfluoro alkylene chain comprising from 2 to 10 carbon atoms and optionally interrupted by one or more oxygen atoms and
y* is an integer selected such that the average number molecular weight of the backbone of polymer (PFPE FOR ) as determined by NMR analysis is from 282 to 70-000.

9. The polymer (PFPE* FOR ) according to claim 7 , wherein said recurring moieties (Ia) to (Ie) comply with formulae (Ia*) to (Ie*):
—CF 2 CF 2 O—  (Ia*)

—CF 2 CF 2 CF 2 O—  (Ib*)

—CF 2 CF 2 CF 2 CF 2 O—  (Ic*)

—CF 2 CF 2 CF 2 CF 2 CF 2 O—;  (Id*)

—CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O—.  (Ie*)

10. The polymer (PFPE* FOR ) according to claim 7 , wherein polymer (PFPE* FOR ) is selected from polymers of formulae (PFPE* FOR-1 ) to (PFPE* FOR-3 ):
F—C(═O)—R f CF 2 —OR F O—[CF 2 R f CF 2 —OR F O] y* —CF 2 R f C(═O)F  (PFPE* FOR-1 )

F—C(═O)O—R F —O[CF 2 R f CF 2 —OR F O] y* —C(═O)F  (PFPE* FOR-2 )

F—C(═O)—R f —CF 2 O—R F —O[CF 2 R F O] y* —C(═O)F  (PFPE* FOR-3 )

wherein
y* is an integer selected such that the average number molecular weight of the backbone of said polymer (PFPE* FOR ) as determined by NMR analysis is from 282 to 70-000, and each of R f and R F , different from each other, complies with one of formulae (Ia*) to (Ie*):
—CF 2 CF 2 O—  (Ia*)

—CF 2 CF 2 CF 2 O—  (Ib*)

—CF 2 CF 2 CF 2 CF 2 O—  (Ic*)

—CF 2 CF 2 CF 2 CF 2 CF 2 O

Assignees

• Solvay Specialty Polymers It

Inventors

• Galimberti Marco
• Fontana Giovanni
• Valsecchi Roberto
• Tortelli Vito

Classifications

• C10M2213/0606

  used as base material · CPC title

• C08G65/007 Primary

  containing fluorine · CPC title

• C10N2040/18

  in connection with recordings on magnetic tape or disc · CPC title

• C08G65/3312

  acyclic · CPC title

• G11B5/71

  characterised by the lubricant · CPC title