Bifunctional fluorinated polymers comprising a plurality of (per)fluoropolyether segments

Patent metadata

Field	Value
Publication number	US-10179836-B2
Application number	US-201515531079-A
Country	US
Kind code	B2
Filing date	Nov 23, 2015
Priority date	Nov 27, 2014
Publication date	Jan 15, 2019
Grant date	Jan 15, 2019

Abstract

A polymer [polymer (P)] comprising a plurality of (per)fluoropolyether (PFPE) segments [segments (S RF )] joined together by hydrogenated (poly)ether segments [segments (S H )], said polymers (P) having two end groups [groups (E)], each group (E) comprising a hydroxy or a leaving group, with the proviso that the hydrogenated (poly)ether segment (S H ) is not a segment of formula —CH 2 OCH 2 OCH 2 — is herein disclosed. Disclosed is also a method for the manufacture of polymer (P) and a polymer obtainable by full or partial fluorination of polymer (P). Polymer (P) and polymers obtainable therefrom by full or partial fluorination can be conveniently used in the manufacture of lubricant compositions or of compositions for imparting hydro-/oleo-repellence to substrates. Said polymers can also be used as intermediates for the manufacture of other polymers or block copolymers.

First claim

The invention claimed is:

1. A polymer (P) comprising a plurality of (per)fluoropolyether (PFPE) segments (S RF ) joined together by hydrogenated (poly)ether segments (S H ), said polymer (P) having two end groups (E), each group (E) comprising a hydroxy or a sulfonate group,
wherein the hydrogenated (poly)ether segments segments (S H ), independently at each occurrence, comply with formula (S H -1):
—R h —O-R h ′—  (S H -I)

wherein (R h ) and (R h ′), equal to or different from one another, are selected from straight or branched divalent alkylene segments, each comprising at least one carbon atom: when (R h ) and (R h ′) comprise more than one carbon atom, they can optionally be interrupted by one or more ethereal oxygen atoms

with the proviso that the hydrogenated (poly)ether segments (S H ) are not segments of formula —CH 2 OCH 2 OCH 2 —.

2. The polymer according to claim 1 complying with formula (P-1):
(E)-(S′ RF )—(S′ H )—(S″ RF )—[(S″ H )—(S′ RF )—(S H )—(S″ RF )] p [(S″ H )—(S′ RF )] q -(E′)  (P-1)

wherein:
(S′ RF ) and (S″ RF ), equal to or different from one another, are (per)fluoropolyether segments (S RF );
(S′ H ) and (S″ H ), equal to or different from one another, are hydrogenated (poly)ether segments (S H );
(E′) is an end group equal to or different from (E);
p is 0 or a positive number and
q is 0 or 1.

3. The polymer according to claim 2 in which:
p is 0 or 1 and
q is 1.

4. The polymer according to claim 2 in which (S RF ) and (S′ RF ) each independently comprise a chain (R f ) having a number average molecular weight ranging from 400 to 5,000 and comprising repeating units (Rº) selected from:
(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, tyre F, Cl, or H,
(iv) —CF 2 CF 2 CF 2 CF 2 O—,
(v) —(CF 2 ) j —CFZ*—O— wherein j is an integer from 0 to 3 and Z* is a group of general formula —OR f *T, wherein R f * 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—, and —CF 2 CF 2 CF 2 CF 2 O—, with each of X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group.

5. The polymer according to claim 2 wherein (E) and (E′) each independently comply with formula (E-1):
—(CH 2 ) m *(OCH 2 CHY*) n *E 1   (E-1)

wherein Y* is hydrogen or methyl, m* is 0 or 1 and n* is 0 or an integer equal to or higher than 1, with the proviso that, when m* is 0, n* is at least 1, and E 1 is a hydroxy group or a leaving group.

6. The polymer according to claim 2 complying with formula (P-1 Λ):
(E)-(S′ RF )—(R h )O(R h ′)—(S″ RF )-[(R h ′)O(R h )—(S′ RF )—R h OR h ′—(S″ RF )] p —[(R h ′)O(R h )—(S′ RF )] q -(E′)  (P-1Λ)

wherein:
(E) and (E′), equal to or different from one another, comply with formula —CH 2 E 1 , wherein E 1 is selected from hydroxy, nonaflate, triflate and tosylate;
(S′ RF ) and (S″ RF ) are straight (per)fluoropolyether segments respectively comprising a chain (R f ) and a chain (R′ f ) complying with formula (R f -III):
—(CF 2 CF 2 O) a1 (CF 2 O) a2 —  (R f -III)

wherein:
a1, and a2 are integers >0 such that the number average molecular weight is between 400 and 4,000, with the ratio a2/a1 being generally comprised between 0.2 and 5, said chains (R f ) and (R′ f ) optionally differing in their molecular weight;
(R h ) and (R h ′) are both —CH 2 — or one is —CH 2 — and the other one is —CH 2 CH 2 OCH 2 —;
p is 0 or 1 and q is 1.

7. A method for the manufacture of a polymer as defined in claim 1 , said method comprising reacting:
a (per)fluoropolyether diol having an average functionality of at least 1.98 (Diol-1) with
a (per)fluoropolyether diol having an average functionality of at least 1.98 and whose hydroxy end groups are activated to nucleophilic substitution as sulfonic esters (Diol-1*) in the presence of an inorganic or organic base.

8. A method for the manufacture of a polymer, said method comprising treating a polymer of claim 1 with a fluorinating agent.

9. A method for the manufacture of polymers or block co-polymers comprising using a polymer of claim 1 as intermediate for the manufacture of polymers or block-copolymers.

10. A method of lubricating a surface, said method comprising applying a polymer of claim 1 to a surface to be lubricated.

11. A method of imparting hydro-/olco-repellence to a substrate, said method comprising applying to a substrate a polymer of claim 1 .

12. A lubricant, composition comprising a polymer of claim 1 in admixture with lubricants.

13. A composition for imparting hydro-/oleo-repellence to a substrate, said composition comprising a polymer of claim 1 in admixture with surface-treating agents.

14. The polymer according to claim 1 complying with formula (P-1):
(E)-(S′ RF )—(S′ H )—(S″ RF )—[(S″ H )—(S′ RF )—(S′ H )—(S″ RF )] p [(S″ H )—(S′ RF )] q -(E′)  (P-1)

wherein:
(S′ RF ) and (S″ RF ) each independently comprise a chain (R f ) having a number average molecular weight ranging from 400 to 5,000 and comprising repeating units (Rº) selected from:
(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, or H,
(iv) —CF 2 CF 2 CF 2 CF 2 O—,
(v) —(CF 2 ) j —CFZ*—O— wherein j is an integer from 0 to 3 and Z* is a group of general formula-OR f *T, wherein R f * 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—, and —CF 2 CF 2 CF 2 CF 2 O—, with each of X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group;

(S H ), (S′ H ) and (S″ H ), equal to or different from one another, comply with formula (S H -1):
—R h —O—R h ′—  (S H -1)

wherein (R h ) and (R h ′), equal to or different from one another, are selected from straight or branched divalent alkylene segments, each comprising at least one carbon atom; when (R h ) and (R h ′) comprise more than one carbon atom, they can optionally be interrupted by one or more ethereal oxygen atoms
(E) and (E′) each independently comply with formula (E-1):
—(CH 2 ) m *(OCH 2 CHY*) n *E 1   (E-1)

wherein Y* is hydrogen or methyl, m* is 0 or 1 and n* is 0 or an integer equal to or higher than 1, with the proviso that, when m* is 0, n* is at least 1, and E 1 is a hydroxy group or a leaving group;
p is 0 or 1 and
q is 1.

Assignees

• Solvay Specialty Polymers It

Inventors

• Tonelli Claudio Adolfo Pietro
• Barbieri Solange
• Wlassics Ivan
• Bragante Letanzio
• Marchionni Giuseppe

Classifications

• C08G2650/48

  containing fluorine, e.g. perfluropolyethers · CPC title

• C08G65/007 Primary

  containing fluorine · CPC title

• C08G65/3344

  containing oxygen in addition to sulfur · CPC title

• C08G81/024

  Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G · CPC title

• C08G65/334

  containing sulfur · CPC title