Partially fluorinated urethane based coatings

Patent metadata

Field	Value
Publication number	US-10138594-B2
Application number	US-201514852740-A
Country	US
Kind code	B2
Filing date	Sep 14, 2015
Priority date	Sep 26, 2014
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

A compound for imparting water repellency and optionally stain release to substrates wherein the compound is prepared by reacting (a) at least one isocyanate group-containing compound, (b) at least one isocyanate-reactive compound and (c) at least one fluorinated isocyanate-reactive compound.

First claim

The invention claimed is:

1. A compound for imparting water repellency and optionally stain release to substrates wherein the compound is prepared by the process comprising:
reacting (a) at least one isocyanate group-containing compound selected from the group consisting of diisocyanate and polyisocyanate, or mixture thereof; (b) at least one isocyanate-reactive compound selected from the group consisting of cyclic or acyclic sugar alcohol which is substituted with at least two —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ; or mixtures thereof; where the cyclic or acyclic sugar alcohol is selected from a saccharide, reduced sugar, aminosaccharide, aldonic acid, and aldonic acid lactone;

wherein each n is independently 0 to 20;
each m is independently 0 to 20;
m+n is greater than 0;
each R 1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; and
(c) at least one fluorinated isocyanate-reactive compound selected from a fluorinated alcohol, fluorinated thiol, or fluorinated amine.

2. The composition of claim 1 , wherein the at least one isocyanate-reactive compound (b) is selected from Formulas (IIa), (IIb), or (IIc):

wherein each R is independently —H; —R 1 ; —C(O)R 1 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;
each n is independently 0 to 20;
each m is independently 0 to 20;
m+n is greater than 0;
r is 1 to 3;
a is 0 or 1;
p is independently 0 to 2;

provided that a is 0 when r is 3;
each R 1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;
provided when X is Formula (IIa), then at least two R are a —R 1 ; —C(O)R 1 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;
each R 4 is independently —H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ; provided when X is Formula (IIb), then at least two of R or R 4 are a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ; and
each R 19 is —H, —C(O)R 1 , or —CH 2 C[CH 2 OR] 3 , provided when X is Formula (IIc), then at least two of R 19 or R are —C(O)R 1 , or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

3. The composition of claim 1 , wherein the diioscyanate or polyisocyanate is selected from the group consisting of hexamethylene diisocyanate homopolymer, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of formulas (Ia), (Ib), (Ic) and (Id):

4. The composition of claim 1 , wherein the at least one fluorinated isocyanate-reactive compound (c) is at least one compound of the formula
R f -A x -Z—H  (III)

wherein
R f is a C1 to C20 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
X is 0 or 1;
A is (CH 2 ) k , (CH 2 CF 2 ) m (CH 2 ) n , (CH 2 ) o SO 2 N(CH 3 )(CH 2 ) p , O(CF 2 ) 2 (CH 2 ) r , or OCHFCF 2 OE;
Z is O, S, or NH;
m is 1 to 4;
k, n, o, p, and r are each independently 1 to 20; and
E is a C 2 to C 20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C 6 to C 10 aryl group.

5. The composition of claim 4 , where R f is an uninterrupted linear C 2 to C 6 perfluoroalkyl, and x is 1.

6. The composition of claim 1 , wherein further comprising reacting (d) at least one compound selected from water, at least one organic compound of Formula (IVa)
R 5 —X  (IVa),

at least one organic compound of Formula (IVb)
R 15 —(OCH 2 CH(OR 16 )CH 2 ) z —OR 17   (IVb),

or mixtures thereof; wherein
R 5 is selected from a —C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group, a hydroxy-functional C 1 to C 30 linear or branched alkyl, a hydroxy-functional linear or branched C 1 to C 30 polyether, a hydroxy-functional linear or branched polyester, a hydroxy- or amine-functional linear or branched organosiloxane, a thiol-functional C 1 to C 30 linear or branched alkyl, an amine-functional C 1 to C 30 linear or branched alkyl,

wherein
R 7 , R 8 , and R 9 are each independently, —H, —C 1 to C 6 alkyl, or combinations thereof;
R 10 is a divalent alkyl group of 1 to 20 carbons;
X is an isocyanate-reactive group selected from —OH, —C(O)OH, —SH, —NH(R 12 ), —O—(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t —H or —[C(O)]—O—(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t —H;
R 12 is —H or a monovalent C1 to C6 alkyl group;
R 15 , R 16 , and R 17 are each independently a —H; —R 18 ; —C(O)R 18 provided that at least one R 15 , R 16 , or R 17 is a —H;
R 18 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;
z is 1 to 15;
Y is —Cl;
s is an integer of 0 to 50;
t is an integer of 0 to 50; and
s+t is greater than 0.

7. The composition of claim 2 wherein formula (IIa) is further defined as formula (IIa′):

wherein R is independently a —H; —R 1 ; or —C(O)R 1 .

8. The composition of claim 2 wherein formula (IIa) is further defined as formula (IIa′):

wherein R is independently a —H; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

9. The composition of claim 2 wherein (b) is formula (IIb):

10. The composition of claim 2 wherein (b) is formula (IIc):

11. A composition for imparting water repellency and optionally stain release to a substrate comprising an aqueous dispersion of the compound of claim 1 .

Assignees

• Chemours Co Fc Llc
• Chemours Co Fc Llc

Inventors

• Sworen John Christopher
• Brown Gerald Oronde
• Vincenzini Mario
• Kohler Ewa
• Haidzinskaya Tatsiana

Classifications

• C08G18/284

  Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids · CPC title

• C09D175/04

  Polyurethanes · CPC title

• D06M15/576 Primary

  containing fluorine · CPC title

• C08G18/36

  Hydroxylated esters of higher fatty acids · CPC title

• C09D175/06

  from polyesters · CPC title