Isocyanates, derivatives, and processes for producing the same

Patent metadata

Field	Value
Publication number	US-11814360-B2
Application number	US-201816753591-A
Country	US
Kind code	B2
Filing date	Oct 4, 2018
Priority date	Oct 5, 2017
Publication date	Nov 14, 2023
Grant date	Nov 14, 2023

Abstract

The present invention is directed to processes for producing isocyanates and isocyanate derivatives from epoxide and carbon monoxide reagents. In preferred embodiments, the processes include a step for providing carbonylation of an epoxide reagent with a carbon monoxide reagent to produce a beta-lactone intermediate. In certain preferred embodiments, further carbonylation of a beta-lactone intermediate produces a succinic anhydride intermediate. The processes of the present invention include steps for rearranging beta-lactone intermediates and/or succinic anhydride intermediates to produce isocyanate products and/or isocyanate derivatives. In certain preferred embodiments, the isocyanate products may be copolymerized with polyol oligomers to provide polyurethane products.

First claim

What is claimed is:

1. A process for producing an isocyanate product comprising the steps:
a. carbonylation of an epoxide reagent with a carbon monoxide reagent to produce a beta-lactone intermediate;
b. combining the beta-lactone intermediate with a nucleophile to produce an amide ring-opened intermediate or to produce an hydroxamic acid ring-opened intermediate; and
c. contacting an amide ring-opened intermediate with a caustic base reagent in the presence of a halogen reagent to produce the isocyanate product or rearranging the hydroxamic acid ring-opened intermediate to produce the isocyanate product.

2. The process from claim 1 further comprising contacting the isocyanate product with an alcohol to produce a carbamate isocyanate derivative.

3. The process from claim 1 further comprising contacting the isocyanate product with water to produce an amine isocyanate derivative.

4. The process from claim 1 further comprising contacting the isocyanate product with a primary amine to produce a urea isocyanate derivative.

5. A process for producing an isocyanate product comprising the steps:
a. carbonylation of an epoxide reagent with a carbon monoxide reagent to produce a beta-lactone intermediate;
b. contacting the beta-lactone intermediate with a catalyst to produce an organic acid intermediate;
c. reacting the organic acid intermediate with an azide reagent to produce an acyl azide intermediate; and

d. thermally decomposing the acyl azide intermediate to produce the isocyanate product.

6. The process from claim 5 further comprising contacting the isocyanate product with an alcohol to produce a carbamate isocyanate derivative.

7. The process from claim 5 further comprising contacting the isocyanate product with water to produce an amine isocyanate derivative.

8. The process from claim 5 further comprising contacting the isocyanate product with a primary amine to produce a urea isocyanate derivative.

9. A process for producing a diisocyanate product comprising the steps:
a. carbonylation of an epoxide reagent with a carbon monoxide reagent to produce a beta-lactone intermediate;
b. carbonylation of the beta-lactone intermediate with a carbon monoxide reagent to produce a succinic anhydride intermediate;
c. combining the succinic anhydride intermediate with a nucleophile to produce an amide intermediate; and
d. rearranging the amide intermediate in the presence of a halogen reagent with a caustic base reagent to produce the diisocyanate product.

10. The process from claim 9 wherein the amide intermediate is a diamide.

11. The process from claim 9 further comprising contacting the diisocyanate product with an alcohol to produce a carbamate diisocyanate derivative.

12. The process from claim 9 further comprising contacting the diisocyanate product with water to produce an amine diisocyanate derivative.

13. The process from claim 9 further comprising contacting the diisocyanate product with a primary amine to produce a urea diisocyanate derivative.

14. A process for producing an aromatic isocyanate product comprising the steps:
a. carbonylation of an epoxide reagent with a carbon monoxide reagent to produce a beta-lactone intermediate;
b. carbonylation of the beta-lactone intermediate with a carbon monoxide reagent to produce a succinic anhydride intermediate;
c. oxidizing the succinic anhydride intermediate to provide an unsaturated four carbon intermediate;
d. contacting the unsaturated four carbon intermediate with furan to provide a cyclohexene ring intermediate;
e. combining the cyclohexene ring intermediate with a nucleophile to produce an amide intermediate; and
f. rearranging the amide intermediate in the presence of a halogen reagent with a caustic base reagent to produce the aromatic isocyanate product.

15. The process from claim 14 further comprising the steps:
a. dehydrating the cyclohexene ring intermediate to form a disubstituted benzene ring intermediate;
b. combining the disubstituted benzene ring intermediate with a nucleophile to produce an amide intermediate; and
c. rearranging the amide intermediate in the presence of a halogen reagent with a caustic base reagent to produce the aromatic isocyanate product.

16. The process from claim 15 further comprising contacting the aromatic isocyanate product with an alcohol to produce a carbamate aromatic isocyanate derivative.

17. The process from claim 15 further comprising contacting the aromatic isocyanate product with water to produce an amine aromatic isocyanate derivative.

18. The process from claim 15 further comprising contacting the aromatic isocyanate product with a primary amine to produce a urea aromatic isocyanate derivative.

19. A process for producing an aromatic isocyanate product comprising the steps:
a. carbonylation of an epoxide reagent with a carbon monoxide reagent to produce a beta-lactone intermediate; and
i b. reacting said beta-lactone intermediate with a furan reagent to produce an aromatic dicarboxylic acid intermediate;
i c. reacting said aromatic dicarboxylic acid intermediate with an acyl chloride to produce a chlorocarbonyl intermediate;
i d. reacting said chlorocarbonyl intermediate with a hydroxylamine to produce an aromatic hydroxamic acid intermediate; and

i e. rearranging said aromatic hydrocamic acid intermediate to produce the aromatic isocyanate product, or
ii b. rearranging said beta-lactone intermediate to produce an acrylic acid intermediate;
ii c. reacting said acrylic acid intermediate with an isoprene intermediate to produce a cyclohexene-carboxylic acid intermediate;
ii d. dehydro-aromatization of said cyclohexene-carboxylic acid intermediate to produce an aromatic dicarboxylic acid intermediate;
ii e. reacting said aromatic dicarboxylic acid intermediate with an acyl chloride to produce a chlorocarbonyl intermediate;
ii f. reacting said chlorocarbonyl intermediate with a hydroxylamine to produce an aromatic hydroxamic acid intermediate; and
ii g. rearranging said aromatic hydrocamic acid intermediate to produce the aromatic isocyanate product.

20. A process for producing a polyurethane product comprising
copolymerizing the diisocyanate product of claim 9 with a polyol oligomer to produce the polyurethane product.

Assignees

• Novomer Inc

Inventors

• Kulikov Oleg
• Sookraj Sadesh H
• Vakil Utpal Mahendra
• Goodrich Matthew

Classifications

• C07D305/12 Primary

  Beta-lactones · CPC title

• C07C263/00

  Preparation of derivatives of isocyanic acid · CPC title

• C07C263/12

  from or via nitrogen analogues of carboxylic acids, e.g. from hydroxamic acids, involving a Hofmann, Curtius or Lossen-type rearrangement (C07C209/56 takes precedence) · CPC title

• C07C265/00

  Derivatives of isocyanic acid · CPC title

• C07D305/08

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring atoms · CPC title