Polyurea macromer and latexes thereof

Patent metadata

Field	Value
Publication number	US-9783669-B2
Application number	US-201514942202-A
Country	US
Kind code	B2
Filing date	Nov 16, 2015
Priority date	May 22, 2013
Publication date	Oct 10, 2017
Grant date	Oct 10, 2017

Abstract

The present invention is a composition comprising a) a stable aqueous dispersion of polymer particles having one or more structural units of i) a polyurea macromer; and ii) an acrylate, a methacrylate, a vinyl ester, or a styrene monomer, or a combination thereof; and/or b) an aqueous mixture of a i) polyurea macromer polymer particles; and b) acrylate, methacrylate, vinyl ester, or styrenic polymer particles, or a combination thereof, wherein the polyurea macromer is characterized by the following formula I:

where A 1 , A 2 , R 1 , R 2 , and R 3 are as defined herein. Compositions prepared using the compound of the present invention can be used to form coatings with excellent balance of low temperature film formation, hardness, and flexibility.

First claim

The invention claimed is:

1. A composition comprising
a) a stable aqueous dispersion of polymer particles having one or more structural units of i) a polyurea macromer; and ii) an acrylate, a methacrylate, a vinyl ester, or a styrene monomer, or a combination thereof; and/or
b) an aqueous mixture of i) polyurea macromer particles and ii) acrylate, methacrylate, vinyl ester, or styrenic polymer particles, or a combination thereof, wherein the polyurea macromer is characterized by the following formula I:

wherein n is 1 to 20;
R 1 is 1,6-hexanediyl,

wherein the dotted lines represent the points of attachment;
R 2 and R 3 are each independently C 2 -C 10 linear or branched alkanediyl groups, benzenediyl groups, benzenedimethanediyl groups, or cyclohexanediyl groups;
X and Y are independently O or NR 4 , wherein R 4 is H or C 1 -C 6 -alkyl, with the proviso that at least one of X and Y is NH;
at least one of A 1 and A 2 comprise carboxylic acid functionalized groups selected from the group consisting of:
—C(O)—(Z) m —R 5 ; —CH 2 CH(OH)(CH 2 ) p COOH; and —CR 7 ═CH—C(O)—O—(CH 2 ) p COOH;
wherein each R 5 is independently

with the proviso that when one of A 1 and A 2 does not contain carboxylic acid functional groups, the non-carboxylic acid functionalized group is selected from the group consisting of:
—CH 2 CH(OH)R 6 ; —CR 7 ═CH—C(O)—O—(CH 2 ) p R 8 ; —C(O)—Y′—(CH 2 ) p R 9 ; and —CH 2 —CH 2 —C(O)—O—R 10 ; wherein
each R 6 is independently —CH 2 -acrylate or —CH 2 -methacrylate;
each R 7 is independently H or CH 3 ;
each R 8 is independently an acrylate group or a methacrylate group;
each R 9 is independently an acrylate group or a methacrylate group;
each R 10 is independently H or —CH 2 CH═CH 2 ;
each R 11 is independently a linear or branched C 1 -C 15 alkyl group;
Y′ is O or NR 4 ;
m is 0 or 1;
Z is a remnant of a nucleophile; and
each p is independently from 2 to 6.

2. The composition of claim 1 wherein X and Y are each NH; n is from 2 to 10; and the polymer particles comprise from 2 to 30 weight percent structural units of the polyurea macromer and from 70 to 98 weight percent of structural units of the acrylate, the methacrylate, or the styrene, or a combination thereof, wherein A 1 and A 2 are each independently:
—C(O)—(Z) m —R 5 ; —CH 2 CH(OH)R 6 ; —CR 7 ═CH—C(O)O(CH 2 ) p R 8 ; —C(O)—Y′—(CH 2 ) p R 9 ; or —CH 2 CH 2 —C(O)—O—R 10 .

3. The composition of claim 2 wherein
R 1 is

and R 2 and R 3 are each independently linear or branched C 3 -C 10 -alkanediyl groups.

4. The composition of claim 2 wherein
m is 0; and
R 2 and R 3 are each —CH 2 CH(CH 3 )— groups; and
A 1 and A 2 are independently —C(O)—R 5 .

5. The composition of claim 2 wherein
m is 0; and
at least one of A 1 and A 2 is —CH 2 —CH(OH)R 6 , wherein R 6 is —CH 2 -methacrylate
or —(CH 2 ) p —COOH, wherein p is 2 to 6.

6. The composition of claim 2 wherein at least one of A 1 and A 2 is
—CR 7 ═CH—C(O)—O—(CH 2 ) p R 8 ; wherein R 7 is H, R 8 is a methacrylate group or COOH.

7. The composition of claim 2 wherein at least one of A 1 and A 2 is —C(O)—O—(CH 2 ) p R 9 wherein R 9 is a methacrylate group; or wherein at least one of A 1 and A 2 is —CH 2 —CH 2 —C(O)O—R 10 .

8. The composition of claim 7 wherein one of A 1 and A 2 is —C(O)—O—(CH 2 ) p R 9 wherein R 9 is a methacrylate group; and wherein the other of A 1 and A 2 is —CH 2 —CH 2 —C(O)—O—R 10 .

9. The composition of claim 1 wherein one or both of A 1 and A 2 comprise carboxylic acid functionalized groups selected from the group consisting of:
—C(O)—(Z) m —R 5 ; —CH 2 CH(OH)(CH 2 ) p COOH; and —CR 7 ═CHC(O)O(CH 2 ) p COOH;
wherein R 5 is

with the proviso that when one of A 1 and A 2 does not contain carboxylic acid functional groups, the non-carboxylic acid functionalized group is selected from the group consisting of:
—CH 2 CH(OH)R 6 ; —CR 7 ═CHC(O)O(CH 2 ) p R 8 ; and —C(O)—Y′—(CH 2 ) p R 9 ;
R 6 is —CH 2 -acrylate, or —CH 2 -methacrylate;
R 8 is an acrylate group or a methacrylate group;
R 9 is an acrylate group or a methacrylate group; and
wherein X and Y are each NH; and the polymer particles comprise from 2 to 30 weight percent structural units of the polyurea macromer and from 70 to 98 weight percent of structural units of the acrylate, the methacrylate, or the styrene, or a combination thereof.

10. The composition of claim 9 wherein A 1 and A 2 are each
independently —C(O)(O) m —R 5 ; —CH 2 CH(OH)(CH 2 ) p COOH; or —CR 7 ═CHC(O)O(CH 2 ) p COOH.

11. The composition of claim 10 wherein
m is 0 and n is 2 to 10.

12. The composition of claim 11 wherein
R 1 is

wherein the dotted lines represent the points of attachment; and
R 2 and R 3 are each independently linear or branched C 3 -C 10 -alkanediyl groups.

13. The composition of claim 12 wherein
A 1 and A 2 are each —C(O)—R 5 ;
each R 5 is independently:

14. The composition of claim 9 wherein
m is 0; and
one of A 1 and A 2 is —CH 2 —CH(OH)R 6 , wherein R 6 is —CH 2 -methacrylate or —(CH 2 ) p —COOH.

15. The composition of claim 9 wherein
at least one of A 1 and A 2 is —CH═CHC(O)O(CH 2 ) p COOH.

16. The composition of claim 9 wherein
one of A 1 and A 2 is —C(O)O(CH 2 ) p R 9 , wherein R 9 is a methacrylate group; and the other
of A 1 and A 2 is —C(O)CH 2 CH 2 COOH.

Assignees

• Rohm & Haas
• Dow Global Technologies Llc

Inventors

• Cardoen Gregoire
• Drake Ian J
• Even Ralph C
• Hughes Andrew
• Zhang Tianlan
• Kalantar Thomas H

Classifications

• C08G18/636

  characterised by the presence of a dispersion-stabiliser · CPC title

• C08L2201/54

  Aqueous solutions or dispersions · CPC title

• C08G18/3228

  acyclic · CPC title

• C08F220/18

  with acrylic or methacrylic acids · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title