Ring-opening polymerizations using a flow reactor

Patent metadata

Field	Value
Publication number	US-11286341-B2
Application number	US-202017018520-A
Country	US
Kind code	B2
Filing date	Sep 11, 2020
Priority date	Jul 6, 2018
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

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 thiourea anion to synthesize a homopolymer, wherein the ring-opening polymerization has a residence time within the flow reactor of greater than or equal to 0.006 seconds and less than or equal to 3.5 seconds.

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 N,N′-di[3,5-di(trifluoromethyl)phenyl]thiourea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[3-(trifluoromethyl)phenyl] thiourea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-phenylthiourea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea, 1-phenyl-3-[3-(trifluoromethyl)phenyl] thiourea, N,N′-diphenylthiourea, and 1-cyclohexyl-3-phenylthiourea.

4. The method of claim 3 , wherein the thiourea 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 thiourea 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 functional group selected from a thiourea group.

7. The method of claim 6 , wherein the reacting comprises protonating the thiourea 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 system comprising:
a flow reactor that houses a stream of chemical reactants to facilitate a polymerization;
a memory that stores computer executable components; and
a processor, operably coupled to the memory, and that executes the computer executable components stored in the memory, wherein the computer executable components comprise:
an analysis component, operatively coupled to the processor, that controls a parameter of the flow reactor based on a characteristic of a homopolymer produced by the polymerization, wherein the chemical reactants comprise a cyclic monomer and an organocatalyst comprising a thiourea anion, wherein the polymerization is a ring-opening polymerization having a residence time within the flow reactor of greater than or equal to 0.006 seconds and less than or equal to 3.5 seconds.

10. The system of claim 9 , 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.

11. The system of claim 9 , wherein the flow reactor comprises a sensor that detects the characteristic, wherein the parameter affects a polymerization condition of the polymerization.

12. The system of claim 11 , wherein the polymerization condition is selected from a group consisting of a flow rate of the stream, a turbulence of the stream within the flow reactor, and an amount of chemical reactants comprised within the stream.

13. The system of claim 9 , wherein the analysis component controls the parameter via cloud computing environment.

14. A method, comprising:
forming a polyester homopolymer by a ring-opening polymerization of a cyclic monomer in the presence of an organocatalyst comprising a thiourea anion, wherein the ring-opening polymerization is performed at a residence time within a flow reactor of greater than or equal to 0.006 seconds and less than or equal to 3.5 seconds.

15. The method of claim 14 , wherein the cyclic monomer is a lactone monomer.

16. A method, comprising:
forming a polycarbonate homopolymer by a ring-opening polymerization of a cyclic monomer in the presence of an organocatalyst comprising thiourea anion, wherein the ring-opening polymerization is performed at a residence time within a flow reactor of greater than or equal to 0.006 seconds and less than or equal to 3.5 seconds.

17. The method of claim 16 , 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

• B01J2219/002

  inside the reactor · CPC title

• B01J2219/00164

  controlling the flow · CPC title

• C08G64/205

  characterised by the apparatus used · CPC title

• C08G63/785 Primary

  characterised by the apparatus used · CPC title

• B01J19/0013

  Controlling the temperature of the process · CPC title