Polyisocyanates from fused bicyclic polyols and polyurethanes therefrom

• US 10,550,210 B2
• Filed: 06/26/2018
• Issued: 02/04/2020
• Est. Priority Date: 10/15/2012
• Status: Active Grant

• Current Assignee: Iowa State University Research Foundation Incorporated (Iowa State University)
• Original Assignee: Iowa State University Research Foundation Incorporated (Iowa State University)
• Inventors: Chen, Jason Shih-Hao, Kessler, Michael Richard, Zenner, Michael Dennis
• Primary Examiner(s): Boyle, Robert C
• Application Number:
  US16/018,148
• Publication Number:
  US 20180298023A1
• Time in Patent Office: 588 Days
• CPC Class Codes: B60L 53/20 characterised by converters located in the vehicle
• CPC Class Codes: C07C 2602/36 the rings having more than two atoms in common
• CPC Class Codes: C07D 493/04 Ortho-condensed systems
• CPC Class Codes: C08F 122/20 Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C08G 18/3218 containing cyclic groups having at least one oxygen atom in the ring
• CPC Class Codes: C08G 18/771 oxygen
• CPC Class Codes: C08L 2201/50 Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
• CPC Class Codes: C08L 75/08 from polyethers
• CPC Class Codes: C09J 135/02 Homopolymers or copolymers of esters C09J135/06, C09J135/08 take precedence
• CPC Class Codes: C09J 4/00 Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• CPC Class Codes: H04B 2203/5425 improving S/N by matching impedance, noise reduction, gain control
• CPC Class Codes: H04B 3/548 the power on the line being DC arrangements for feeding power H04L12/10; extracting feeding power from signals H04L25/02
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y02T 10/7072 Electromobility specific charging systems or methods for batteries, ultracapacitors, supercapacitors or double-layer capacitors
• CPC Class Codes: Y02T 90/14 Plug-in electric vehicles

Abstract

The present invention is directed to polyisocyanates and polyurethanes derived therefrom. In various embodiments, the present invention provides polyisocyanates, methods of making the polyisocyanates from fused bicyclic alcohols, polyurethanes, and methods of making the polyurethanes from the polyisocyanates.

Claims

1. A method of making a polyisocyanate, comprising:

a) contacting

a compound having the structure

2. The method of claim 1, wherein m=n=1.

3. The method of any one of claim 1, wherein the acid anhydride is succinic anhydride.

4. The method of any one of claim 1, wherein the acyl halide generator is at least one of thionyl chloride, thionyl bromide, phosphorous pentachloride, phosphorus pentabromide, cyanuric fluoride, phosgene, diphosgene, triphosgene, oxalyl chloride, phosphorus tribromide, phosphorus trichloride, and phosphoryl chloride.

5. The method of any one of claim 1, wherein the azide generator is at least one of sodium azide, trimethylsilyl azide, triethylsilyl azide, lithium azide, potassium azide, tetrabutylammonium azide, tert-butyldimethylsilyl azide, and tert-butyldiphenylsilyl azide.

6. The method of any one of claim 1, wherein contacting the polyacyl halide with an azide generator provides a polyacyl azide having the structure of Formula (I) wherein R″

=—

C(O)N₃, wherein the polyacyl azide undergoes a Curtius rearrangement to provide the polyisocyanate.

7. The method of any one of claim 1, wherein the contacting the polyacyl halide and the azide generator is performed in a biphasic solution comprising at least an aqueous phase and an organic phase and optionally further comprising a phase transfer catalyst.

8. The method of claim 1, wherein R′

is unsubstituted.

9. The method of claim 1, wherein R′

is —

CH₂—

CH₂—

.

10. The method of claim 1, wherein rings A and B are unsubstituted with the exception of the ester substituents including R′

and R″

.

11. The method of claim 1, wherein m=n=1, and one of the ester substituents including R′

and R″

is alpha to at least one carbon atom shared by rings A and B.

12. The method of claim 1, wherein each of rings A and B is a tetrahydrofuran ring, wherein each carbon atom shared by rings A and B has an oxygen atom alpha thereto.

13. The method of claim 1, wherein the polyisocyanate having the structure of Formula (I) is:

14. The method of claim 1, wherein the polyisocyanate having the structure of Formula (I) is:

15. The method of claim 1, wherein the polyisocyanate having the structure of Formula (I) is:

16. The method of claim 1, wherein the polyisocyanate having the structure of Formula (I) is:

17. The method of claim 1, wherein the polyisocyanate having the structure of Formula (I) is:

18. The method of claim 1, wherein the polyisocyanate having the structure of Formula (I) is:

19. The method of claim 1, wherein the polyisocyanate having the structure of Formula (I) is:

20. The method of claim 1, wherein e polyisocyanate having the structure of Formula (I) is: