Ring-opening polymerizations using a flow reactor

Patent metadata

Field	Value
Publication number	US-10815335-B2
Application number	US-201816028919-A
Country	US
Kind code	B2
Filing date	Jul 6, 2018
Priority date	Jul 6, 2018
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

Techniques regarding the synthesis of polyesters and/or polycarbonates through one or more ring-opening polymerizations conducted within a flow reactor and facilitated by a urea anion catalyst and/or a thiourea catalyst 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 an organocatalyst comprising a urea anion.

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 organocatalyst comprising a urea anion.

2. The method of claim 1 , wherein the cyclic monomer is selected from a 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.

3. The method of claim 2 , wherein the organocatalyst is derived from a chemical compound selected from a second group consisting of 1,3-bis[3,5-bis(trifluoromethyl)phenyl]urea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[2-(trifluoromethyl)pheyl]urea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-phenylurea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylurea, 1-phenyl-3-[3-(trifluoromethyl)phenyl]urea, 1,3-diphenylurea, and 1-cyclohexyl-3-phenylurea.

4. The method of claim 3 , wherein the urea anion is derived from a chemical reaction between the chemical compound and a chemical base, wherein the chemical base is selected from a third 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.

5. The method of claim 1 , further comprising:
selecting the organocatalyst from a plurality of organocatalysts comprising the urea anion based on a reactivity rate of the cyclic monomer.

6. 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, wherein the intermediate polymer is formed from the polymerizing the cyclic monomer, and wherein the chemical compound comprises a urea group.

7. The method of claim 6 , wherein the reacting comprises protonating the urea anion via a proton transfer with the functional group to form an anionic organocatalyst, and wherein the anionic organocatalyst is a catalyst to the second ring-opening polymerization.

8. The method of claim 7 , further comprising injecting the second cyclic monomer and the chemical compound into a stream of chemical reactants to facilitate the reacting, wherein the chemical reactants comprise the intermediate polymer, the chemical base, and the organocatalyst.

9. A method, comprising:
forming a polyester by a ring-opening polymerization of a cyclic monomer in the presence of an organocatylst comprising a urea anion, wherein the ring-opening polymerization is performed within a flow reactor.

10. The method of claim 9 , wherein the cyclic monomer is a lactone monomer.

11. A method, comprising:
forming a polycarbonate by a ring-opening polymerization of a cyclic monomer in the presence of an organocatylst comprising a urea anion, wherein the ring-opening polymerization is performed within a flow reactor.

12. The method of claim 11 , wherein the cyclic monomer is a cyclic carbonate monomer.

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

• B01J10/00

  Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor (B01J19/08 takes precedence; separation, e.g. distillation, also combined with chemical reactions B01D, {e.g. B01D3/009}) · CPC title

• C08G63/912

  derived from hydroxycarboxylic acids · CPC title

• B01J2219/00186

  controlling the composition of the reactive mixture · CPC title

• B01J19/0013

  Controlling the temperature of the process · CPC title

• B01J19/243

  spirally, concentrically or zigzag wound · CPC title