Synthesis of cyclic carbonate monomers

Patent metadata

Field	Value
Publication number	US-11034664-B1
Application number	US-202016871733-A
Country	US
Kind code	B1
Filing date	May 11, 2020
Priority date	May 11, 2020
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

Techniques regarding the synthesis of cyclic carbonate monomers are provided. For example, one or more embodiments described herein can comprise a method, which can include cyclizing a functionalized diol monomer with N,N′-carbonyldiimidazole, wherein the cyclizing produces a cyclic carbonate monomer and an imidazole carbamate. The method can also include activating the imidazole carbamate with an acid, wherein the activating promotes cyclization of the imidazole carbamate into the cyclic carbonate monomer.

First claim

What is claimed is:

1. A method, comprising:
cyclizing a functionalized diol monomer with N,N′-carbonyldiimidazole, wherein the cyclizing produces a mixture of a cyclic carbonate monomer and an imidazole carbamate product; and
activating the imidazole carbamate product with an acid, wherein the activating promotes cyclization of the imidazole carbamate product into the cyclic carbonate monomer.

2. The method of claim 1 , wherein the N,N′-carbonyldiimidazole is added to a solution of the functionalized diol monomer over a period of time ranging from greater than or equal to 1 second and less than or equal to 60 minutes.

3. The method of claim 1 , wherein an amount of the N,N′-carbonyldiimidazole added to a solution of the functionalized diol monomer to perform the cyclizing ranges from greater than or equal to 0.1 equivalents and less than or equal to 3 equivalents.

4. The method of claim 1 , wherein the functionalized diol monomer is functionalized 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid.

5. The method of claim 1 , further comprising:
reacting a diol monomer using a base compound, wherein the reacting promotes functionalization of the diol monomer with a substrate having a reactive functional group, wherein the substrate is at least one member selected from the group consisting of an alkyl halide, a benzylic halide, an allylic halide, a sulfonate, a carbonate, an ester, a carbamate, and a phosphonate.

6. The method of claim 5 , wherein the functionalized diol monomer is functionalized 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid.

7. The method of claim 5 , wherein the base compound is at least one compound selected from the group consisting of an amine base, a carbonate base, a phosphate base, a carbonate base, a hydroxide base, and an alkoxide base.

8. The method of claim 1 , wherein the functionalized diol monomer is characterized by a structure selected from the group consisting of

9. A method comprising:
selectively reacting a primary alcohol group of a diol monomer with N,N′-carbonyldiimidazole and an amine base, wherein the selectively reacting forms a carbamate amine salt compound; and
cyclizing the carbamate amine salt compound with an acid, wherein the cyclizing forms a cyclic carbonate monomer.

10. The method of claim 9 , wherein an amount of the N,N′-carbonyldiimidazole added to a solution of the diol monomer to react with the primary alcohol ranges from greater than or equal to 1 equivalents and less than or equal to 3 equivalents.

11. The method of claim 10 , wherein the diol monomer is 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid, wherein the amine base is triethylamine, and wherein the acid is acetic acid.

12. The method of claim 11 , wherein an amount of the amine base added to a solution of the diol monomer to perform the reacting ranges from greater than or equal to 0.5 equivalents and less than or equal to 3 equivalents, and wherein an amount of the acid added to a solution of the carbamate amine salt compound to perform the cyclizing ranges from greater than or equal to 0.1 equivalents and less than or equal to 30 equivalents.

13. The method of claim 10 , further comprising:
purifying the cyclic carbonate monomer via a solid supported acidic resin filtration procedure.

14. The method of claim 10 , wherein the diol monomer is 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid, and wherein the carbamate amine salt compound is characterized by formula 1:

15. The method of claim 9 , further comprising:
functionalizing the cyclic carbonate monomer via an esterification of a carboxyl group of the cyclic carbonate monomer.

16. A method comprising:
adding an amine base and N,N′-carbonyldiimidazole to a solution of a diol monomer, wherein adding the amine base and the N,N′-carbonyldiimidazole forms a carbamate amine salt; and
adding an acid to a solution of the carbamate amine salt, wherein adding the acid forms a cyclic carbonate monomer via cyclization.

17. The method of claim 16 , further comprising:
functionalizing the cyclic carbonate monomer via an esterification of a carboxyl group of the cyclic carbonate monomer.

18. The method of claim 16 , wherein the diol monomer is 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid.

19. The method of claim 16 , wherein the N,N′-carbonyldiimidazole selectively reacts with a primary alcohol group of the diol monomer over a carboxyl group of the diol monomer to form the carbamate amine salt.

Assignees

• IBM

Inventors

• Park Nathaniel H
• Hedrick James L
• Piunova Victoria A
• Arrechea Pedro
• Erdmann Tim

Classifications

• C07D319/06 Primary

  not condensed with other rings · CPC title

• C07D233/60

  with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms · CPC title