Zwitterionic derivatives of (per)fluoropolyethers

Patent metadata

Field	Value
Publication number	US-2018312631-A1
Application number	US-201515528025-A
Country	US
Kind code	A1
Filing date	Nov 18, 2015
Priority date	Nov 19, 2014
Publication date	Nov 1, 2018
Grant date	—

Abstract

(Per)fluoropolyether polymers comprising a (per)fluoropolyether chain having two ends, wherein one or both ends comprise one or more zwitterionic groups at one or both polymer ends, methods for their manufacture and uses thereof are herein disclosed. The polymers can be used in particular for protecting materials in contact with biological fluids or fluids containing biological material from contamination by organic compounds therein contained.

First claim

1 . A polymer comprising a (per)fluoropolyether chain (R f ) having two ends, wherein one or both ends comprise(s) at least one zwitterionic group (Z w ).

2 . The polymer according to claim 1 wherein one or both ends comprise one zwitterionic group (Z w ).

3 . The polymer according to claim 1 wherein chain (R f ) is a straight or branched fully or partially fluorinated polyoxyalkylene chain that 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—,
(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 X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group.

4 . The polymer according to claim 1 wherein the zwitterionic group (Z w ) is:
a straight or branched alkyl group, optionally partially unsaturated and optionally containing at least one heteroatom and containing a cationic and an anionic group or
a 5- to 7-member optionally partially unsaturated cycloaliphatic ring or a 5- to 7-member aromatic ring, optionally containing one or more heteroatoms and optionally substituted with one or more halogens, straight or branched C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups containing a cationic and an anionic group.

5 . The polymer according to claim 1 wherein the zwitterionic group (Z w ) is linked to chain (R f ) via a spacer group (S p ) that is a straight or branched divalent alkylene chain comprising at least 2 carbon atoms, interrupted by one or more heteroatoms or functional groups independently selected from one or more of —S—, —O—, —NR 1 —, —C(O)NR 1 — wherein R 1 is H or straight or branched C 1 -C 4 alkyl, —C(O)—, —C(O)O—, —C(O)S—, —NH(CO)NH—, —NH(CS)NH—, or —OC(O)NH—, or by a phenyl ring optionally substituted with one or more halogens, straight or branched C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups.

6 . The polymer according to claim 5 complying with formula (P-I):
A-O—R f —S p —Z w   (P-I)

wherein: R f , S p , and —Z W are as defined in claim 5 and
A is S p —Z W or is a C 1 -C 3 haloalkyl group.

7 . The polymer according to claim 1 wherein the zwitterionic group is selected from formulae (Z w -1) and (Z w -2):
-Cat 1 + —S 1zw -An −   (Z w -1)

wherein:
Cat 1 + represents NR′R″, wherein R′ and R″, equal to or different from one another, represent C 1 -C 6 straight or branched alkyl;
S 1 is a bond or a straight or branched divalent alkylene chain comprising 1 to 10 carbon atoms, optionally comprising one or more double bonds and/or comprising one or more cycloaliphatic or aromatic rings;
An − represents an anionic group selected from —SO 3 —, —OP(O)(OH)O − , —COO— and —O − , with the proviso that, when An − is —O − , S 1zw is a bond;

wherein:
A zw represents a heterocycloaliphatic or aromatic ring that comprises Cat′ + and from 4 to 6 carbon atoms;
Cat′ + represents a quaternary nitrogen;
k′ is 0 or 1, with the proviso that k′ is 0 when A zw is an aromatic ring;
R zw represents a C 1 -C 4 alkyl or C 1 -C 4 alkoxy group;
y′ is 0 or an integer from 1 to 3 if A zw comprises 4 carbon atoms or from 1 to 5 if A zw comprises 6 carbon atoms;
S 2zw represents a covalent bond or a C 1 -C 4 straight or branched alkyl chain;
An′ − is an anionic group selected from —SO 3 − , —OP(O)(OH)O − and —COO − .

8 . The polymer according to claim 7 , wherein the zwitterionic group complies with formula (Z w -1) wherein R′ and R″ are both methyl, S 1zw is a straight alkylene chain comprising 1 to 10 carbon atoms and An − represents a carboxylate anion.

9 . The polymer according to claim 7 , wherein the zwitterionic group is a group of formula (Z w -2a) or (Z w -2b):

10 . The polymer according to claim 1 wherein the spacer group complies with any one of formulae (S p -I)-(S p -IX):
—CFXCH 2 [OCH 2 CH(J)] x —S p *—;  (S p -I)

—CFXC(O)O—S p **—;  (S p -II)

—CFXC(O)NR 1 —S p **—;  (S p -III)

—CFXCH 2 [OCH 2 CH(J)] x O—CH 2 CH(OH)CH 2 NR 1 —S p **—;  (S p -IV)

—CFXCH 2 —[OCH 2 CH(J)] x O—C(O)NHR 2 NHC(O)NR 1 —S p **—;  (S p -V)

—CFXCH 2 —[OCH 2 CH(J)] x O—C(O)NHR 2 NHC(O)O—S p **—;  (S p -VI)

—CFXCH 2 —[OCH 2 CH(J)] x —OCH 2 C(O)NH—S p **—;  (S p -VII)

—CFXCH 2 —[OCH 2 CH(J)] x CH 2 C(O)O—S p **—;  (S p -VIII)

—CFXCH 2 [OCH 2 CH(J)] x —O—Ar hal —O—S p **—  (S p -IX)

wherein:
J is independently selected from hydrogen, methyl and ethyl;
x is 0 or a positive number ranging from 1 to 10;
R 1 is H or straight or branched C 1 -C 4 alkyl;
R 2 is a C 1 -C 6 straight or branched divalent alkylene chain or a cycloaliphatic or aromatic ring, optionally substituted with one or more C 1 -C 4 straight or branched alkyl groups;
S p * is a bond or a straight or branched divalent alkylene chain comprising from 2 to 20 carbon atoms, optionally comprising one or more double bonds and/or one or more heteroatoms and/or functional groups and/or cycloaliphatic or aromatic rings;
S p ** is a straight or branched divalent alkylene chain comprising from 2 to 20 carbon atoms, optionally comprising one or more double bonds and/or one or more heteroatoms and/or functional groups and/or cycloaliphatic or aromatic rings;
Ar hal is an aromatic ring substituted with at least one halogen atom.

11 . The polymer according to claim 10 wherein X is F and J is H.

12 . The polymer according to claim 10 wherein the spacer is selected from:
a spacer of formula (S p -Ia):
—CF 2 CH 2 (OCH 2 CH 2 ) x —S p *—  (S p -Ia)

wherein x is 1 or 2 and S p * is a covalent bond;
a spacer of formula (S p -IIIa):
—CF 2 C(O)NH—S p **—; and  (S p -IIIa)

a spacer of formula (S p -IIIb):
—CF 2 C(O)NCH 3 —S p **—  (S p -IIIa)

wherein S p ** is a straight alkylene chain of formula —(CH 2 ) 3 —.

13 . A composition comprising one or more polymers according to claim 1 in admixture with one or more curable resins.

14 . The composition according to claim 13 wherein the one or more curable resin is independently selected from polysiloxane resins acrylic resins, polyurethane resins and epoxyamine resins.

15 . The polymer according to claim 6 wherein A selected from —CF 3 , —CF 2 Cl, —CF 2 CF 2 Cl, —C 3 F 6 Cl, —CF 2 Br, —CF 2 CF 3 , —CF 2 H and —CF 2 CF 2 H.

Assignees

• Solvay Specialty Polymers It

Inventors

• Guarda Pier Antonio
• Fontana Simonetta Antonella

Classifications

• C08G65/3346

  having sulfur bound to carbon and oxygen · CPC title

• C08G2650/50

  containing nitrogen, e.g. polyetheramines or Jeffamines(r) · CPC title

• C08G65/3322

  acyclic · CPC title

• C08G65/3328

  heterocyclic · CPC title

• C08G65/33306

  acyclic · CPC title