Sulfonated fluorinated, non-fluorinated or partially fluorinated urethanes

Patent metadata

Field	Value
Publication number	US-10208155-B2
Application number	US-201514863830-A
Country	US
Kind code	B2
Filing date	Sep 24, 2015
Priority date	Sep 26, 2014
Publication date	Feb 19, 2019
Grant date	Feb 19, 2019

Abstract

The invention relates to a compound prepared by (i) reacting (a) at least one compound selected from diisocyanate, polyisocyanate, or mixture thereof; (b) at least one isocyanate-reactive compound selected from a fluorinated alcohol; a cyclic or acyclic sugar alcohol which is substituted with at least one —R1, —C(O)R1, —(CH2CH2O)n(CH(CH3)CH2O)mR2, —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1, or mixtures thereof; or mixtures of a fluorinated alcohol and a substituted cyclic or acyclic sugar alcohol; and (c) at least one isocyanate-reactive ethylenically unsaturated compound; wherein each n is independently 0 to 20; each m is independently 0 to 20; m+n is greater than 0; each R1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or mixtures thereof; and (ii) reacting the reaction product of step (i) with a bisulfate source.

First claim

What is claimed is:

1. A compound having 0 to about 1% reactive isocyanate groups comprising the reaction product of reagents comprising:
(a) at least one isocyanate group-containing compound selected from diisocyanate, polyisocyanate, or mixture thereof;
(b) at least one isocyanate-reactive compound selected from the group consisting of a fluorinated alcohol; a cyclic or acyclic sugar alcohol which is substituted with at least one R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 , or mixtures thereof; and mixtures of a fluorinated alcohol and a cyclic or acyclic sugar alcohol which is substituted with at least one R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , —(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, or 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;
each R 2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or mixtures thereof;
(c) at least one isocyanate-reactive ethylenically unsaturated compound selected from allylic or methallylic polyether alcohols, aminoalkyl vinyl compounds, acrylic or methacrylic alkyl alcohols, acrylic or methacrylic polyether alcohols, or acrylic or methacrylic amines; and
(d) a bisulfate source.

2. The compound of claim 1 , where the isocyanate-reactive compound (b) is selected from formulas (IIa), (IIb), or (IIc):

wherein each R is independently —H; —R 1 ; —C(O)R 1 ;

—(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; 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;
each R 2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond;

or a mixtures thereof,
provided when formula (IIa) is chosen, then at least one R is —H and at least one R is a —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ;

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; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;
provided when formula (IIb) is chosen, then at least one R or R 4 is —H; and at least one R or R 4 is a linear or branched alkyl group optionally comprising at least 1 unsaturated bond, or combinations thereof; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; 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 formula (IIc) is chosen, then at least one R 19 or R is —H; and
at least one R 19 or R is —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or
—(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

3. The compound of claim 2 wherein the isocyanate-reactive compound (b) is selected from formula (IIa) to be formula (IIa′):

wherein R is further limited to independently —H; —R 1 ; or —C(O)R 1 .

4. The compound of claim 2 wherein the isocyanate-reactive compound (b) is selected from formula (IIa) to be formula (IIa′):

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

5. The compound of claim 1 , where the isocyanate-reactive compound (b) is a fluorinated alcohol having formula (I)
R f -A-OH  (I),

where R f is a C 1 to C 20 fluoroalkyl group optionally interrupted by CH 2 , CH 2 CH 2 , SO 2 N, CFH, S, or O; and
A is a direct bond or a C 1 to C 6 alkylene group.

6. The compound of claim 1 , where the bisulfate source (d) is a metabisulfite salt, a bisulfite salt, or a mixture of SO 2 and base.

7. The compound of claim 1 , wherein the diisocyanate or polyisocyanate is selected from formulas (IIIa), (IIIb), (IIIc), (IIId), and (IIIe):

8. The compound of claim 1 , wherein the reagents further comprise at least one additional isocyanate-reactive compound (e) selected from water, organic compounds of formula (IVa)
R 5 -D  (IVa), or

organic compounds of formula (IVb)
R 3 —(OCH 2 CH(OR 3 )CH 2 )z-OR 3   (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 unsaturated 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 having a polyester polymer backbone, a hydroxy-functional linear or branched organosiloxane, an 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,

D is selected from —N(R 12 )H, —OH, —COOH, —SH, —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 3 is independently selected from —H; —R 18 ; or —C(O)R 18 , provided that at least one R 3 is —H;
R 12 is —H or a monovalent C 1 to C 6 alkyl group;
R 7 , R 8 , and R 9 are each independently, —H, to C 6 alkyl, or combinations thereof;
R 10 is a divalent alkyl group of 1 to 20 carbons;
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.

9. An aqueous composition comprising the compound of claim 1 .

10. A method of reducing the surface tension of an aqueous medium comprising contacting the aqueous medium with a compound of claim 1 .

11. A coating composition made by the method of claim 10 , wherein the aqueous medium is an aqueous coating base.

12. A method of providing a surface effect to a fibrous substrate comprising contacting a fibrous substrate with a compound of claim 1 .

13. A fibrous substrate which has been treated by the method of claim 12 .

Assignees

• Chemours Co Fc Llc

Inventors

• Sworen John Christopher
• Brown Gerald Oronde
• Haidzinskaya Tatsiana

Classifications

• C08G18/284

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

• C08G18/792 Primary

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

• D06M2101/06

  cellulosic · CPC title

• D06M2200/01

  Stain or soil resistance · CPC title

• C08G2150/00

  Compositions for coatings · CPC title