Polyisocyanates from fused bicyclic polyols and polyurethanes therefrom

Patent metadata

Field	Value
Publication number	US-10550210-B2
Application number	US-201816018148-A
Country	US
Kind code	B2
Filing date	Jun 26, 2018
Priority date	Oct 15, 2012
Publication date	Feb 4, 2020
Grant date	Feb 4, 2020

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.

First claim

We claim:

1. A method of making a polyisocyanate, comprising:
a) contacting
a compound having the structure

 and
an acid anhydride having the structure

to provide a polyacid having the structure of Formula (I)

wherein R″ is —C(O)OH;

b) contacting the polyacid and an acyl halide generator, to provide a polyacyl halide having the structure of Formula (I) wherein R″ is —C(O)X, wherein X is halide; and
c) contacting the polyacyl halide and an azide generator, under conditions suitable to yield a polyisocyanate having the structure of Formula (I) wherein R″ is —NCO;
wherein fused rings A and B are each independently selected from (C 5 -C 10 )cycloalkyl and (C 2 -C 10 )heterocyclyl,
m and n are each independently 1-8,
R′ is selected from the group consisting of (C 2 -C 10 )alkanylene, (C 2 -C 10 )alkenylene, and (C 2 -C 10 )alkynylene, wherein R′ is unsubstituted or substituted, and
fused rings A and B are each independently unsubstituted or substituted.

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)N 3 , 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 —CH 2 —CH 2 —.

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:

Assignees

• Univ Iowa State Res Found Inc

Inventors

• Chen Jason Shih-Hao
• Kessler Michael Richard
• Zenner Michael Dennis

Classifications

• B60L53/20

  characterised by converters located in the vehicle · CPC title

• C07C2602/36

  the rings having more than two atoms in common · CPC title

• C08L2201/50

  Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C · CPC title

• C09J4/00

  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 title

• H04B3/548

  the power on the line being DC (arrangements for feeding power H04L12/10; extracting feeding power from signals H04L25/02) · CPC title