(per)fluoropolyether polymers

Patent metadata

Field	Value
Publication number	US-10442893-B2
Application number	US-201615743139-A
Country	US
Kind code	B2
Filing date	Jul 7, 2016
Priority date	Jul 9, 2015
Publication date	Oct 15, 2019
Grant date	Oct 15, 2019

Abstract

The present invention relates to novel (per)fluoropolyether polymers and their use as lubricants, in particular for Magnetic Recording Media (MRM).

First claim

The invention claimed is:

1. A polymer (P), wherein polymer (P) is selected from the group consisting of:
polymers (P N ) comprising:
one (per)fluoropolyether chain (R pf ) and
at least one chain (C) comprising at least one hydroxy group and at least one amino group,
wherein chain (R pf ) is a chain of formula —(CFX) a O(R f )(CFX') b −, wherein
a and b, equal or different from each other, are equal to or higher than 1;
X and X′, equal or different from each other, are —F or —CF 3 , provided that when a and/or b are higher than 1, X and X′ are —F; and
(R f ) comprises repeating units R°, said repeating units being independently selected from the group consisting of:
 (i-a) —CF(CF 3 )O—;
 (ii-a) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —CF 3 ;
 (iii-a) —CF 2 CF 2 CF 2 O—;
 (iv-a) —CF 2 CF 2 CF 2 CF 2 O—;
 (v-a) —(CF 2 ) j —CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula —O—R( f-a )—T, wherein R (f-a) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being selected from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, —CF 2 CF 2 CF 2 CF 2 O—, with each of each of X being independently F or CF 3 and T being a C 1 —C 3 perfluoroalkyl group; and

polymers (P N *) comprising
at least two (per)fluoropolyether chains (R pf ), each chain (R pf ) having two chain ends, wherein:
said at least two chains (R pf ) are linked together at one chain end through a divalent chain (*C*) comprising at least one hydroxy group and at least two amino groups, and
at least one of said at least two chains (R pf ) bears on its opposite chain end a monovalent chain (C*) comprising at least one hydroxy group and at least one amino group; and
wherein each chain (R pf ) is independently a chain of formula —(CFX) a O(R f )(CFX′) b —, wherein
a and b, equal or different from each other, are equal to or higher than 1;
X and X′, equal or different from each other, are —F or —CF 3 , provided that when a and/or b are higher than 1, X and X′ are —F;
(R f ) comprises repeating units R°, said repeating units being independently selected from the group consisting of:
 (i) —CFXO—, wherein X is F or CF 3 ;
 (ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —F;
 (iii) —CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, is F, Cl, or H;
 (iv) —CF 2 CF 2 CF 2 CF 2 O—; and
 (v) —(CF 2 ) j —CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula —O—R (f-a) —T, wherein R( f-a ) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being selected from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, —CF 2 CF 2 CF 2 CF 2 O—, with each of each of X being independently F or CF 3 and T being a C 1 —C 3 perfluoroalkyl group.

2. The polymer (P) according to claim 1 , wherein in said polymer (P N *), said chains (R pf ) are bonded to the nitrogen atom of the amino groups of chain (*C*) and of chain (C*) via a group (B),
said group (B) being a divalent alkyl chain comprising from 1 to 20 carbon atoms, said alkyl chain being optionally interrupted by at least one oxygen atom and/or optionally substituted with at least one hydroxy group and/or with a perfluoroalkyl group comprising from 1 to 3 carbon atoms.

3. The polymer (P) according to claim 1 , wherein said polymer (P N *) comprises two chains (R pf ) and chain (*C*) comprises two amino groups.

4. The polymer (P) according to claim 1 , said polymer (P N *) complying with the following formula (P-I):
T-(R pf )—(B*)—(*C*)—(B*)—(R pf )—(B*)—(C*)  (P-I)

wherein
(R pf ) is a chain of formula —(CFX) a O(R f )(CFX′) b —;
wherein
a and b, equal or different from each other, are equal to or higher than 1;
X and X′, equal or different from each other, are —F or —CF 3 , provided that when a and/or b are higher than 1, X and X′ are —F;
(R f ) comprises repeating units R°, said repeating units being independently selected from the group consisting of:
(i) —CFXO—, wherein X is F or CF 3 ;
(ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —F;
(iii) —-CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, are F, Cl, H;
(iv) —CF 2 CF 2 CF 2 CF 2 O—; and
(v) —(CF 2 ) j —CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula —O —R( f-a )—T, wherein R( f-a ) is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being selected from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 —, —CF 2 CF 2 CF 2 CF 2 O—, with each of each of X being independently F or CF 3 and T being a C 1 —C 3 perfluoroalkyl group

(B*) is a divalent alkyl chain comprising from 1 to 20 carbon atoms, said alkyl chain being optionally interrupted by at least one oxygen atom and/or optionally substituted with at least one hydroxy group and/or with a perfluoroalkyl group comprising from 1 to 3 carbon atoms;
(*C*) is a linear or branched alkyl chain comprising from 1 to 10 carbon atoms, and being optionally interrupted by at least one heteroatom selected from N, O and S and/or by a 5- to 10-membered aromatic moiety optionally comprising one or more heteroatoms and optionally substituted with a linear or branched alkyl chain comprising from 1 to 6 carbon atoms, said aromatic moiety and/or said alkyl chain being optionally substituted with at least one hydroxy group;
(C*) is a linear or branched alkyl chain comprising from 1 to 20 carbon atoms, said alkyl chain being optionally interrupted by one or more heteroatoms and being optionally substituted with a 5- to 10-membered aromatic moiety, or a 5- to 10-membered aromatic moiety optionally substituted with a linear or branched alkyl chain comprising from 1 to 6 carbon atoms, wherein said alkyl chain or said a 5- to 10-membered aromatic moiety further comprising at least one hydroxy group and at least one amino group; and
T is selected from the group comprising —H, —F, —Cl, a straight or branched perfluoroalkyl group comprising from 1 to 3 carbon atoms, and chain —(B*)—(C*).

5. A process for the manufacture of polymer (P N ) according to claim 1 , said process comprising:
reacting at least one PFPE alcohol with a compound bearing at least one sulfonic group to obtain a sulfonic PFPE ester, and
reacting the sulfonic PFPE ester with at least one organic amine to obtain polymer (P N ).

6. The process according to claim 5 , wherein the organic amine is an organic aliphatic or aromatic compound comprising at least one primary or secondary amine group.

7. A process for the manufacture of at least one polymer (P N *) according to claim 1 , said process comprising:
reacting at least one PFPE alcohol with a compound bearing at least one sulfonic group to obtain a sulfonic PFPE ester,
reacting the sulfonic PFPE ester with at least one polyamine to obtain a PFPE- oligomer comprising at least two chains (R pf ),
optionally purifying the PFPE-oligomer, and
reacting the PFPE-oligomer with at least one monoamine to obtain polymer (P N *).

8. The process of claim 7 , wherein reacting the sulfonic PFPE ester with at least one polyamine is performed in the presence of an excess of sulfonic PFPE ester.

9. A lubricant for magnetic recording media (MRM) comprising at least one polymer (P) according to claim 1 .

Assignees

• Solvay Specialty Polymers It

Inventors

• Valsecchi Roberto
• Picozzi Rosaldo
• Simeone Giovanni

Classifications

• C08G65/335

  containing phosphorus · CPC title

• C08G65/3351

  having phosphorus bound to carbon and hydrogen · CPC title

• C08G65/33306

  acyclic · CPC title

• C08G65/007 Primary

  containing fluorine · CPC title

• C10M107/38

  containing halogen · CPC title