(Per)fluoropolyether polymers and use thereof

Patent metadata

Field	Value
Publication number	US-11525070-B2
Application number	US-201816643359-A
Country	US
Kind code	B2
Filing date	Jul 30, 2018
Priority date	Sep 1, 2017
Publication date	Dec 13, 2022
Grant date	Dec 13, 2022

Abstract

The present invention relates to novel (per)fluoropolyether (PFPE) polymers, to a process for their manufacture and to their use as additives in coating compositions.

First claim

The invention claimed is:

1. A (per)fluoropolyether polymer (P) comprising at least one (per)fluoropolyoxyalkylene chain (R pf ) having two chain ends, wherein at least one of said chain ends bears at least one group of formula -B-(E) t , wherein:
t is an integer equal to or higher than 2;
B is a group complying with the following formula (B-I):

wherein
R1, R2 and R5, identical to or different from each other, are a linear or cyclic aliphatic group comprising 6 carbon atoms, optionally substituted with one or more linear or branched alkyl groups having from 1 to 3 carbon atoms, or a 6-membered aromatic group, optionally substituted with one or more linear or branched alkyl groups having from 1 to 3 carbon atoms,
R3 and R4 are each individually a hydrogen atom or together form a group of formula —C(═O)—,
n is an integer from 1 to 4,
symbol (*) indicates the bond to said chain (R pf ), and
each symbol (§) indicates the bond to said moiety E; and
E is a moiety of formula (E-I):
—[OCH(CH 3 )CH 2 ] z —R U   (E-I)

wherein
z is in an integer from 1 to 15,
(R U ) is an unsaturated moiety.

2. The polymer (P) according to claim 1 , wherein said chain (R pf ) is a chain of formula
—(CFX) z1 O(R f )(CFX′) z2 -D-O—

wherein
z1 and z2, 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;
D is a hydrogenated alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms;
(R f ) comprises repeating units R o , 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—;
(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 X being independently F or CF 3 and T being a C 1 -C 3 perfluoroalkyl group.

3. The polymer (P) according to claim 1 , wherein said moiety (R U ) is selected from the group consisting of:
(R U -I) —O—C(═O)—CR H ═CH 2
(R U -II) —O—C(═O)—NH—CO—CR H ═CH 2
wherein
R H is H or a linear or branched C 1 -C 6 alkyl group.

4. The polymer (P) according to claim 1 , wherein said group (B) complies with one of the following formulae (B-I-i) to (B-I-v):

wherein
symbol (*) indicates the bond to said chain (R pf ) and
each of symbols (§) indicates the bond to a group of formula (E-I).

5. The polymer (P) according to claim 1 , wherein said polymer (P) complies with the following formula (P-I):
T-(R pf )-B-[(E-I)] t   (P-I)

wherein
(R pf ), (B), (E-I) and t are as defined in claim 1 and
T is a neutral group selected from: —H, —F, —Cl and linear or branched perfluoroalkyl groups comprising from 1 to 3 carbon atoms; or a group of formula (T-I):
-D*-O-(B)-[(E-I)] t*   (T-I)

wherein
B and (E-I) have the same meanings defined in claim 1 ,
D* is a hydrogenated alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms, and
t* has the same meaning defined for tin claim 1 .

6. A process for the synthesis of polymer (P) as defined in claim 1 , said process comprising:
(I) contacting at least one polyisocyanate compound (NCO) with at least one compound (U) of formula
H—[OCH(CH 3 )CH 2 ] z —R U   (U)

wherein R U is an unsaturated moiety and z is an integer from 1 to 15, wherein the ratio between the equivalents of said compound (NCO) and of said compound (U) is higher than 1;
(II) contacting the compound obtained in step (I) with at least one polymer (PFPE-OH), wherein polymer (PFPE-OH) is at least one (per)fluoropolyether polymer comprising a (per)fluoropolyoxyalkylene chain having two chain ends, wherein at least one of said chain ends comprises a hydroxy group, thus obtaining said polymer (P).

7. The process according to claim 6 , wherein said compound (NCO) is obtained from the reaction of at least three molecules of the same diisocyanate compound, which react together to form a linear or cyclic molecule comprising at least three isocyanate groups.

8. The process according to claim 7 , wherein said compound (NCO) comprises at least four isocyanate groups.

9. The process according to claim 6 , wherein said compound (NCO) comprises three isocyanate groups and is represented by at least one of the following formulae (I) to (IV):

or wherein said compound (NCO) comprises four isocyanate groups and is represented by the following formula (V):

10. The process according to claim 6 , wherein the equivalent ratio between said compound (NCO) and said compound (U) is from 1.1 to 2.

11. The process according to claim 6 , wherein said step (II) is performed in the presence of a fluorinated solvent.

12. A composition (C) comprising at least one polymer (P) as defined in claim 1 and at least one solvent selected from: ketones; esters; organic solvents containing in the molecule an ester-ether group; and mixtures thereof.

13. The composition (C) according to claim 12 , said composition (C) further comprising at least one UV-curable component, such that the amount of said polymer (P) in said composition (C) is from 0.01 to 8 wt. %, based on the total weight of said composition (C).

14. A method for providing a transparent coating onto at least one surface of a plastic substrate, said method comprising:
contacting at least one surface of at least one plastic substrate with polymer (P) as defined in claim 1 ; and
curing said polymer (P) onto said at least one surface.

15. The method according to claim 14 , wherein the plastic substrate is selected from the group consisting of: polyethylene terephthalate (PET), polycarbonate (PC), polyvinyl chloride (PVC), thermoplastic olefin (TPO), thermoplastic polyurethane (TPU), polypropylene (PP), acrylonitrile butadiene styrene (ABS) and polyamides (PA).

16. The polymer (P) according to claim 1 , wherein:
t is an integer from 2 to 3;
n is an integer from 1 to 2.

17. The polymer (P) according to claim 2 , wherein z1 and z2, equal or different from each other, are from 1 to 3.

18. The polymer (P) according to claim 3 , wherein R H is H or a linear or branched C 1 -C 3 alkyl group.

19. The process according to claim 7 , wherein said diisocyanate compound is selected from the group consisting of: hexamethylene diisocyanate; isophorone diisocyanate; xylylene diisocyanate; hyd

Assignees

• Solvay Specialty Polymers It

Inventors

• Fontana Simonetta Antonella
• Puppo Antonio
• Guarda Pier Antonio

Classifications

• C08F290/147 Primary

  Polyurethanes; Polyureas · CPC title

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title

• C09D175/16

  having terminal carbon-to-carbon unsaturated bonds · CPC title

• C08G18/673

  containing two or more acrylate or alkylacrylate ester groups · CPC title

• C08F283/006

  on to polymers provided for in C08G18/00 (C08F283/004 takes precedence) · CPC title