Polymeric material with surface microdomains

• US 8,062,729 B2
• Filed: 07/11/2007
• Issued: 11/22/2011
• Est. Priority Date: 01/14/2005
• Status: Expired due to Fees

• Current Assignee: Ndsu-Research Foundation
• Original Assignee: Ndsu-Research Foundation
• Inventors: Majumdar, Partha S., Webster, Dean C.
• Primary Examiner(s): Higgins; Gerard
• Application Number:
  US11/827,446
• Publication Number:
  US 20090017288A1
• Time in Patent Office: 1,595 Days
• Field of Search: 428/141, 428/156, 428/195.1, 428/423.1, 428/447, 528/26, 528/28, 528/33, 528/60, 528/66
• US Class Current: 428/141
• CPC Class Codes: C08G 18/4277 Caprolactone and/or substituted caprolactone
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: Y10T 428/24355 Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

A polymeric material may be prepared by reacting a composition that includes polyol, polyisocyanate, and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate, wherein the polymeric material has a surface which includes raised microdomains.

Claims

1. A cross-linked polymeric material prepared by reacting a composition comprising:

a solvent component; and

polymer reactants comprising;

polyol;

polyisocyanate; and

hydroxy functional polyorganosiloxane;

wherein the solvent component comprises a solvent combination selected from one of the following combinations;

(a) butyl acetate, methyl n-amyl ketone and ethyl 3-ethoxypropionate;

(b) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate and toluene;

(c) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate and isopropanol;

(d) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate, toluene and isopropanol;

(e) butyl acetate and methyl n-amyl ketone;

(f) butyl acetate, methyl n-amyl ketone and toluene;

(g) butyl acetate, methyl n-amyl ketone, toluene and isopropanol;

(h) butyl acetate and ethyl 3-ethoxypropionate;

(i) butyl acetate, ethyl 3-ethoxypropionate and toluene;

(j) butyl acetate, ethyl 3-ethoxypropionate and isopropanol; and

(k) butyl acetate, ethyl 3-ethoxypropionate, toluene and isopropanol; and

wherein the cross-linked polymeric material has a surface including raised microdomains and a surrounding polymer matrix, wherein the raised microdomains are more hydrophobic than the surrounding polymer matrix and the average diameter of the raised microdomains is about 0.1 micron to 5 microns; and

the composition includes about 5 to 12 wt %, based on the total solids content of the cross-linked polymeric material, of the hydroxy functional polyorganosiloxane.

2. The cross-linked polymeric material of claim 1 wherein the surface of the cross-linked polymeric material retains the raised microdomains after being exposed to water for 14 days.

3. The cross-linked polymeric material of claim 1 wherein the hydroxy functional polyorganosiloxane comprises hydroxy functional polydimethylsiloxane.

4. The cross-linked polymeric material of claim 3 wherein the hydroxy functional polyorganosiloxane has an average hydroxyl equivalent weight of about 200 to 800.

5. The cross-linked polymeric material of claim 1 wherein the polyol comprises polyol having at least three hydroxy groups.

6. The cross-linked polymeric material of claim 1 wherein the polyol comprises polycaprolactone polyol.

7. The cross-linked polymeric material of claim 1 wherein the polyisocyanate comprises polyisocyanate having at least three isocyanate groups.

8. The cross-linked polymeric material of claim 1 wherein the raised microdomains have an average height of about 0.01 microns to 0.2 micron.

9. The cross-linked polymeric material of claim 1 wherein the raised microdomains have an average spacing of about 0.5 microns to 10 microns.

10. The cross-linked polymeric material of claim 1 wherein the composition further comprises a pot life extender, which includes 24-pentanedione.

11. The cross-linked polymeric material of claim 1 wherein the surface has a microdomain density of about 0.1 to 1.5 microdomains/micron².

20. A substrate comprising a surface coated with the cross-linked polymeric material of claim 1.

21. The cross-linked polymeric material of claim 1 wherein the raised microdomains are polyorganosiloxane rich microdomains and the surrounding polymer matrix is a polyurethane rich matrix.

24. The cross-linked polymeric material of claim 1 wherein the hydroxy functional polyorganosiloxane comprises polyhydroxy functional polyorganosiloxane.

34. The cross-linked polymeric material of claim 1, wherein the hydroxy functional polyorganosiloxane comprises polyhydroxy functional polyorganosiloxane;

the polyisocyanate comprises isophorone based polyisocyanate; and

the polyol comprises polycaprolactone polyol.

35. The cross-linked polymeric material of claim 1, wherein the hydroxy functional polyorganosiloxane comprises hydroxy alkyl functional polydimethylsiloxane;

the polyisocyanate comprises isophorone-based polyisocyanate having at least three isocyanate groups; and

the polyol comprises polycaprolactone polyol having at least three hydroxy groups.

12. A cross-linked polymeric material prepared by reacting a composition comprising:

a solvent component; and

polymer reactants comprising;

polycaprolactone polyol;

polyisocyanate; and

hydroxy functional polyorganosiloxane;

wherein the polycaprolactone polyol includes polyol having at least three hydroxy groups and the polyisocyanate includes isocyanate having at least three isocyanate groups;

the solvent component comprises a solvent combination selected from one of the following combinations;

(a) butyl acetate, methyl n-amyl ketone and ethyl 3-ethoxypropionate;

(b) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate and toluene;

(c) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate and isopropanol;

(d) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate, toluene and isopropanol;

(e) butyl acetate and methyl n-amyl ketone;

(f) butyl acetate, methyl n-amyl ketone and toluene;

(g) butyl acetate, methyl n-amyl ketone, toluene and isopropanol;

(h) butyl acetate and ethyl 3-ethoxypropionate;

(i) butyl acetate, ethyl 3-ethoxypropionate and toluene;

(j) butyl acetate, ethyl 3-ethoxypropionate and isopropanol; and

(k) butyl acetate, ethyl 3-ethoxypropionate, toluene and isopropanol; and

the cross-linked polymeric material has a surface including raised microdomains and a surrounding polymer matrix;

wherein the average diameter of the raised microdomains is about 0.1 micron to 5 microns and being the raised microdomains are more hydrophobic than the surrounding polymer matrix; and

the composition includes about 5 to 12 wt %, based on the total solids content of the cross-linked polymeric material, of the hydroxy functional polyorganosiloxane.

13. The cross-linked polymeric material of claim 12 comprising about 10 wt % to 40 wt % polycaprolactone polyol.

14. The cross-linked polymeric material of claim 12 comprising about 30 wt % to 85 wt % of polyisocyanate.

15. The cross-linked polymeric material of claim 12 wherein the polyisocyanate has an average isocyanate equivalent weight of about 150 to 600.

16. The cross-linked polymeric material of claim 12 comprising:

about 20 to 30 wt % of the polycaprolactone polyol which includes polyol having at least three hydroxy groups;

about 50 to 75 wt % of the polyisocyanate, which includes isocyanate having at least three isocyanate groups; and

about 5 to 12 wt % hydroxy functional polydimethylsiloxane.

17. The cross-linked polymeric material of claim 12 wherein the polycaprolactone polyol comprises polycaprolactone triol having an average hydroxyl equivalent weight of about 150 to 200;

the polyisocyanate comprises isophorone diisocyanate based polyisocyanate having an average isocyanate equivalent weight of about 250 to 450; and

the hydroxy functional polyorganosiloxane comprises α

, ω

-bis(3-(2′

-hydroxyethoxy)propyl)-polydimethylsiloxane having an average hydroxyl equivalent weight of about 350 to 700.

18. The cross-linked polymeric material of claim 12, wherein the composition comprises on a solids basis:

about 10 to 40 wt % of the polycaprolactone polyol; and

about 30 to 85 wt % of the polyisocyanate; and

about 5 to 12 wt % hydroxy functional polydimethylsiloxane.

19. The cross-linked polymeric material of claim 12 wherein the surface of the cross-linked polymeric material retains the raised microdomains after being exposed to water for 14 days.

22. The cross-linked polymeric material of claim 12 wherein the raised microdomains are polyorganosiloxane rich microdomains and the surrounding polymer matrix is a polyurethane rich matrix.

23. The cross-linked polymeric material of claim 12 wherein the raised microdomains have an average height of about 0.01 to 0.2 microns.

25. A cross-linked polymeric material prepared by reacting a composition comprising:

a solvent component; and

polymer reactants comprising;

polyol;

polyisocyanate; and

hydroxy functional polyorganosiloxane;

wherein the cross-linked polymeric material has a surface including raised microdomains and a surrounding polymer matrix;

the raised microdomains are more hydrophobic than the surrounding polymer matrix; and

the microdomain density of the surface is about 0.1 to 1.5 microdomains/micron;

the composition includes about 5 to 12 wt %, based on the total solids content of the cross-linked polymeric material, of the hydroxy functional polyorganosiloxane; and

the solvent component comprises a solvent combination selected from one of the following combinations;

(a) butyl acetate, methyl n-amyl ketone and ethyl 3-ethoxypropionate;

(b) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate and toluene;

(c) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate and isopropanol;

(d) butyl acetate, methyl n-amyl ketone, ethyl 3-ethoxypropionate, toluene and isopropanol;

(e) butyl acetate and methyl n-amyl ketone;

(f) butyl acetate, methyl n-amyl ketone and toluene;

(g) butyl acetate, methyl n-amyl ketone, toluene and isopropanol;

(h) butyl acetate and ethyl 3-ethoxypropionate;

(i) butyl acetate, ethyl 3-ethoxypropionate and toluene;

(j) butyl acetate, ethyl 3-ethoxypropionate and isopropanol; and

(k) butyl acetate, ethyl 3-ethoxypropionate, toluene and isopropanol.

26. The cross-linked polymeric material of claim 25 wherein the hydroxy functional polyorganosiloxane comprises polyhydroxy functional polyorganosiloxane.

27. The cross-linked polymeric material of claim 25 wherein the raised microdomains are polyorganosiloxane rich microdomains and the surrounding polymer matrix is a polyurethane rich matrix.

28. The cross-linked polymeric material of claim 27 wherein the raised microdomains have an average diameter of about 0.1 micron to 5 microns.

29. The cross-linked polymeric material of claim 25 wherein the raised microdomains have an average height of about 0.01 microns to 0.2 microns.

30. The cross-linked polymeric material of claim 25 wherein the raised microdomains have an average spacing of about 0.5 microns to 10 microns.

31. The cross-linked polymeric material of claim 25, wherein the surface of the cross-linked polymeric material retains the raised microdomains after being exposed to water for 14 days.

32. The cross-linked polymeric material of claim 25, wherein the raised microdomains have an average diameter of about 0.1 micron to 5 microns;

the surface of the cross-linked polymeric material retains the raised microdomains after being exposed to water for 14 days; and

the polyol comprises polyol having at least three hydroxy groups and/or the polyisocyanate comprises polyisocyanate having at least three isocyanate groups.

33. The cross-linked polymeric material of claim 32, wherein the hydroxy functional polyorganosiloxane comprises polyhydroxy functional polyorganosiloxane.