Ring-opening polymerizations using a flow reactor

Patent metadata

Field	Value
Publication number	US-11118008-B2
Application number	US-201816028989-A
Country	US
Kind code	B2
Filing date	Jul 6, 2018
Priority date	Jul 6, 2018
Publication date	Sep 14, 2021
Grant date	Sep 14, 2021

Abstract

Techniques regarding the synthesis of one or more polymers through one or more ring-opening polymerizations conducted within a flow reactor and facilitated by one or more anionic catalysts are provided. For example, one or more embodiments can comprise a method, which can comprise polymerizing, via a ring-opening polymerization within a flow reactor, a cyclic monomer in the presence of one or more anionic organocatalysts.

First claim

What is claimed is:

1. A method, comprising:
polymerizing, via a ring-opening polymerization within a flow reactor, a cyclic monomer in the presence of an anionic organocatalyst, wherein the cyclic monomer is supplied to the flow reactor via a first inlet and the anionic organocatalyst is supplied to the flow reactor via a second inlet, and wherein the organocatalyst is characterized by a chemical structure:

wherein X corresponds to an anion selected from a first group consisting of an oxygen anion, a sulfur anion, and a nitrogen anion;
wherein E corresponds to an atom selected from a second group consisting of an oxygen atom and a sulfur atom;
wherein R 1 corresponds to a first functional group selected from a third group consisting of a first alkyl group and a first aryl group;
wherein R 2 corresponds to a second functional group selected from a fourth group consisting of a second alkyl group and a second aryl group; and
wherein the cyclic monomer is selected from a fifth group consisting of a cyclic carbonate monomer, a substituted cyclic carbonate monomer, a cyclic phospholane monomer, a morpholinone monomer, tetrahydro-2H-pyran-2-thione, oxepane-2-thione, tetrahydrothiopyranone, and 2-thiepanone.

2. The method of claim 1 , wherein the anionic organocatalyst is derived from a chemical reaction between a chemical compound and a chemical base, wherein the chemical base is selected from a fifth group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, phosphazene bases, 1,3,2-diazaphosphorin-2-amin, 2-[(1,1-dimethylethyl)imino]-N,N-diethyl-1,2,2,2,3,4,5,6-octahydro-1,3-dimethyl, 1,3-dihydro-1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, potassium methoxide, potassium hydride, sodium methoxide, and sodium hydride.

3. The method of claim 1 , further comprising:
reacting, via a second ring-opening polymerization within the flow reactor, an intermediate polymer with a second cyclic monomer in the presence of a chemical compound to form a block copolymer, and wherein the intermediate polymer is formed from the polymerizing the cyclic monomer.

4. The method of claim 3 , wherein the reacting comprises protonating the anion via a proton transfer with the chemical compound to form a second anionic organocatalyst, and wherein the second anionic organocatalyst is a catalyst to the second ring-opening polymerization.

5. The method of claim 1 , wherein the ring-opening polymerization is performed at room temperature.

6. A method, comprising:
polymerizing, via a ring-opening polymerization within a flow reactor, a cyclic monomer in the presence of an anionic organocatalyst at room temperature, wherein the anionic organocatalyst is characterized by a chemical structure:

wherein X corresponds to an anion selected from a first group consisting of an oxygen anion, a sulfur anion, and a nitrogen anion;
wherein E corresponds to an atom selected from a second group consisting of an oxygen atom and a sulfur atom;
wherein R 1 corresponds to a first functional group selected from a third group consisting of a first alkyl group and a first aryl group;
wherein R 2 corresponds to a second functional group selected from a fourth group consisting of a second alkyl group and a second aryl group; and
wherein the cyclic monomer is selected from a fifth group consisting of a cyclic carbonate monomer, a substituted cyclic carbonate monomer, a cyclic phospholane monomer, a morpholinone monomer, tetrahydro-2H-pyran-2-thione, oxepane-2-thione, tetrahydrothiopyranone, and 2-thiepanone.

7. The method of claim 6 , wherein the anionic organocatalyst is derived from a chemical reaction between a chemical compound and a chemical base, wherein the chemical base is selected from a fifth group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, phosphazene bases, 1,3,2-diazaphosphorin-2-amin, 2-[(1,1-dimethylethyl)imino]-N,N-diethyl-1,2,2,2,3,4,5,6-octahydro-1,3-dimethyl, 1,3-dihydro-1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene, potassium methoxide, potassium hydride, sodium methoxide, and sodium hydride.

8. The method of claim 6 , further comprising:
reacting, via a second ring-opening polymerization within the flow reactor, an intermediate polymer with a second cyclic monomer in the presence of a chemical compound to form a block copolymer, and wherein the intermediate polymer is formed from the polymerizing the cyclic monomer.

9. The method of claim 8 , wherein the reacting comprises protonating the anion via a proton transfer with the chemical compound to form a second anionic organocatalyst, and wherein the second anionic organocatalyst is a catalyst to the second ring-opening polymerization.

10. A method, comprising:
forming an intermediate polymer by polymerizing, via a ring-opening polymerization within a flow reactor, a cyclic monomer in the presence of an anionic organocatalyst, wherein the anionic organocatalyst is characterized by a chemical structure:

wherein X corresponds to an anion selected from a first group consisting of an oxygen anion, a sulfur anion, and a nitrogen anion;
wherein E corresponds to an atom selected from a second group consisting of an oxygen atom and a sulfur atom;
wherein R 1 corresponds to a first functional group selected from a third group consisting of a first alkyl group and a first aryl group; and
wherein R 2 corresponds to a second functional group selected from a fourth group consisting of a second alkyl group and a second aryl group;

forming a block copolymer by reacting, via a second ring-opening polymerization within the flow reactor, the intermediate polymer with a second cyclic monomer in the presence of a chemical compound, wherein the reacting comprises protonating the anion via a proton transfer with the chemical compound to form a second anionic organocatalyst, and wherein the second anionic organocatalyst is a catalyst to the second ring-opening polymerization.

11. The method of claim 10 , wherein the cyclic monomer is selected from a fifth group consisting of a lactone monomer, a cyclic carbonate monomer, a substituted cyclic carbonate monomer, a cyclic phospholane monomer, a morpholinone monomer, tetrahydro-2H-pyran-2-thione, oxepane-2-thione, tetrahydrothiopyranone, and 2-thiepanone.

12. The method of claim 10 , wherein the anionic organocatalyst is derived from a chemical reaction between a chemical compound and a chemical base, wherein the chemical base is selected from a fifth group consisting of 1,8-diazabicyclo[5.4.0]undec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, phosphazene bases, 1,3,2-diazaphosphorin-2-amin, 2-[(1,1-dimethylethyl)imino]-N,N-diethyl-1,2,2,2,3,4,5,6-octahydro-1,3-dimethyl, 1,3-dihydro-1,3-bis(2,4,6-trimethylphenyl)imidazole.

13. The method of claim 10 , wherein the ring-opening polymerization is performed at room temperature.

Assignees

• IBM
• Univ Leland Stanford Junior

Inventors

• Park Nathaniel H
• Hedrick James L
• Piunova Victoria A
• Zubarev Dmitry
• Jones Gavin O
• Waymouth Robert M
• Lin Binhong

Classifications

• C08G75/26

  Polythioesters · CPC title

• C08G79/04

  Phosphorus linked to oxygen or to oxygen and carbon · CPC title

• C08G67/00

  Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00 · CPC title

• C08G63/685

  containing nitrogen · CPC title

• C08G63/823 Primary

  for the preparation of polylactones or polylactides · CPC title