Ethylenically crosslinkable fluorinated polymer additives for architectural coatings

Patent metadata

Field	Value
Publication number	US-10696850-B2
Application number	US-201615569118-A
Country	US
Kind code	B2
Filing date	Apr 28, 2016
Priority date	Apr 30, 2015
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

The present invention comprises a crosslinkable polymer compound comprising a fluorinated Unit A, an optional hydrophilic Unit B, an optional acidic or neutralized acid Unit C, a crosslinkable pendant olefin group-containing Unit D, and an optional hydrophobic alkyl Unit E. Such polymeric compounds are useful as coatings additives such that, when the coating is applied to a substrate, the additive compound is allowed to first migrate to the surface and subsequently crosslink to form a durable oil-, dirt-, and water-repellent surface.

First claim

What is claimed is:

1. A crosslinkable polymer compound comprising the repeat Units A and D, and optionally comprising one or more of Units B, C, or E, in any order:

wherein
R f is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens —O—, —CH 2 —, —CFH—, or combinations thereof;
A is O, S, or N(R′), wherein R′ is H or an alkyl of from 1 to 4 carbon atoms;
Q is a straight chain, branched chain or cyclic structure of alkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups;
v is 0 or 1;
R 1 is H or CH 3 ;
R 2 is independently selected from H or an alkyl of 1 to 4 carbon atoms;
Z is a hydrophilic group selected from a hydroxyl-terminated straight or branched alkyl of 1 to 10 carbons; hydroxyl-, hydroxyalkyl-, thiol-, or amine-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units; thiol-terminated straight or branched alkyl of 1 to 10 carbons; or an amine-containing straight or branched alkyl of 1 to 10 carbons;
M is H, HN(R 5 ) 3 , Na, Li, Cs, K, or mixtures thereof;
R 5 is H or an alkyl or hydroxyalkyl of 1 to 12 carbon atoms;
R 3 is a straight or branched alkyl chain of 2 to 30 carbons having 1 to 15 olefinic units, or mixtures thereof;
Y is selected from CH 2 O—, —C(O)O—, —OC(O)—, —R 6 OC(O)—, or —C(O)OR 6 OC(O)—;
R 6 is a straight or branched alkylene of 1 to 10 carbons;
R 4 is a straight chain, branched chain, or cyclic structure alkyl group of 1 to 30 carbons;
Unit A is present in an amount of 10 to 60 mol %;
Unit B is present in an amount of 0 to 89 mol %;
Unit C is present in an amount of 0 to 89 mol %;
Unit D is present in an amount of 1 to 90 mol %; and
Unit E is present in an amount of 0 to 89 mol %;

wherein the sum of monomer repeat units is equal to 100%; and
wherein Unit D is formed from oleic (meth)acrylate, linoleic (meth)acrylate, oleic ethyl (meth)acrylate, CH 3 C(═CH 2 )C(O)OCH 2 CH 2 OC(O)C 7 H 14 CH═CHCH 2 CH═CHC 5 H 11 , ricinoleic (meth)acrylate, erucic (meth)acrylate, palmitoleic (meth)acrylate, CH 3 C(═CH 2 )C(O)OCH 2 CH 2 OC(O)C 7 H 14 CH═CHCH 2 C 6 H 13 , vaccenic (meth)acrylate, eicosenoic (meth)acrylate, eladic (meth)acrylate, nervonic (meth)acrylate, pinolenic (meth)acrylate, arachidonic (meth)acrylate, eicosapentaenoic (meth)acrylate, docosahexanoic (meth)acrylate, eicosadienoic (meth)acrylate, or docosatetranoic (meth)acrylate.

2. The compound of claim 1 , having a number average molecular weight M n of about 1500 to about 30,000 Daltons.

3. The compound of claim 1 , wherein Unit C is in the range of about 1 to about 60 mol %.

4. The compound of claim 1 , where R f is a straight or branched-chain perfluoroalkyl group of 2 to 6 carbon atoms.

5. The compound of claim 1 , wherein one of Units B, C, or E is at least 0.1 mol %.

6. The compound of claim 1 , wherein Unit D is in the range of about 2 to about 40 mol %.

7. The compound of claim 1 , said compound further comprising a residue from a hydrophilic chain transfer agent of formula (I)
(V—X—S) g H 2-g ,  (I)

wherein
g is 1 or 2
X is a linear or branched alkylene of 1 to 4 carbon atoms, optionally substituted with one or more hydrophilic functional groups selected from hydroxyl, carboxyl, or amine; and
V is a hydrophilic functional group selected from hydroxyl, carboxyl, thiol, or amine.

8. A composition comprising
(a) a coating base selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and
(b) a crosslinkable polymer compound comprising Units A and D, and optionally comprising one or more of Units B, C, or E, in any order:

wherein
the composition comprises coating base (a) in an amount of from about 95 to 99.98% and crosslinkable polymer compound (b) in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b);
R f is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens —O—, —CH 2 —, —CFH—, or combinations thereof;
A is O, S, or N(R′), wherein R′ is H or an alkyl of from 1 to 4 carbon atoms;
Q is a straight chain, branched chain or cyclic structure of alkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups;
v is 0 or 1;
R 1 is H or CH 3 ;
R 2 is independently selected from H or an alkyl of 1 to 4 carbon atoms;
Z is a hydrophilic group selected from a hydroxyl-terminated straight or branched alkyl of 1 to 10 carbons; hydroxyl-, hydroxyalkyl-, thiol-, or amine-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units;
thiol-terminated straight or branched alkyl of 1 to 10 carbons; or an amine-containing straight or branched alkyl of 1 to 10 carbons;
M is H, HN(R 5 ) 3 , Na, Li, Cs, K, or mixtures thereof;
R 5 is H or an alkyl or hydroxyalkyl of 1 to 12 carbon atoms;
R 3 is a straight or branched alkyl chain of 2 to 30 carbons having 1 to 15 olefinic units, or mixtures thereof;
Y is selected from —CH 2 O—, —C(O)O—, —OC(O)—, —R 6 OC(O)—, or —C(O)OR 6 OC(O)—;
R 6 is a straight or branched alkylene of 1 to 10 carbons;
R 4 is a straight chain, branched chain, or cyclic structure alkyl group of 1 to 30 carbons;
Unit A is present in an amount of 10 to 60 mol %;
Unit B is present in an amount of 0 to 89 mol %;
Unit C is present in an amount of 0 to 89 mol %;
Unit D is present in an amount of 1 to 90 mol %; and
Unit E is present in an amount of 0 to 89 mol %;

wherein the sum of monomer repeat units is equal to 100%; and
wherein Unit D is formed from oleic (meth)acrylate, linoleic (meth)acrylate, oleic ethyl (meth)acrylate, CH 3 C(═CH)C(O)OCH 2 CH 2 OC(O)C 7 H 14 CH═CHCH 2 CH═CHC 5 H 11 , ricinoleic (meth)acrylate, erucic (meth)acrylate, palmitoleic (meth)acrylate, CH 3 C(═CH 2 )C(O)OCH 2 CH 2 OC(O)C 7 H 14 CH═CHCH 2 C 6 H 13 , vaccenic (meth)acrylate, eicosenoic (meth)acrylate, eladic (meth)acrylate, nervonic (meth)acrylate, pinolenic (meth)acrylate, arachidonic (meth)acrylate, eicosapentaenoic (meth)acrylate, docosahexanoic (meth)acrylate, eicosadienoic (meth)acrylate, or docosatetranoic (meth)acrylate.

9. The composition of claim 8 , further comprising (c) a fatty acid compound in an amount of about 0.001 to 1% by weight, based on the total weight sum of (a)+(b)+(c).

10. The composition of claim 8 , where the crosslinkable polymer compound (b) has a number average molecular weight M n of about 1500 to about 30,000 Daltons.

11. The composition of claim 8 , where Unit C is in the range of about 1 to about 60 mol %.

12. The composition of claim 8 , where R f is a straight or branched-chain perfluoroalkyl group of 2 to 6 carbon atoms.

13. The composition of claim 8 , where the coating base is a water-dispersed coating selected from an aqueous acrylic latex paint.

14. The composition of claim 8 , where the coating base comprises an additive selected from TiO 2 , clays, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate,

Assignees

• Chemours Co Tt Llc
• Chemours Co Fc Llc

Inventors

• Raghavanpillai Anilkumar
• Hughes James J
• Franco Vincent
• Crompton Jr John Russell
• Rosen Brad M
• Lee Hau-Nan
• Ober Michael Henry
• Wu Dan Qing

Classifications

• C09D7/65

  macromolecular (C09D7/41-C09D7/48 take precedence) · CPC title

• C09D5/1687 Primary

  Use of special additives · CPC title

• C08L2201/54

  Aqueous solutions or dispersions · CPC title

• C09D133/16 Primary

  Homopolymers or copolymers of esters containing halogen atoms · CPC title

• C08F220/24

  containing perhaloalkyl radicals · CPC title