Ring-opening polymerizations using a flow reactor

Patent metadata

Field	Value
Publication number	US-10738153-B2
Application number	US-201816029025-A
Country	US
Kind code	B2
Filing date	Jul 6, 2018
Priority date	Jul 6, 2018
Publication date	Aug 11, 2020
Grant date	Aug 11, 2020

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 functionalizing, via a post-polymerization reaction within a flow reactor, a chemical compound by covalently bonding a trimethylsilyl protected thiol to a pendent functional group of the chemical compound in a presence of a catalyst. The pendent functional group can comprise a perfluoroaryl group and a methylene group.

First claim

What is claimed is:

1. A method, comprising:
functionalizing, via a post-polymerization reaction within a flow reactor, a chemical compound by covalently bonding a trimethylsilyl protected thiol to a pendent functional group of the chemical compound in a presence of a catalyst, the pendent functional group comprising a perfluoroaryl group and a methylene group.

2. The method of claim 1 , wherein the catalyst is a salt byproduct of quenching a polymerization reaction that forms the chemical compound, and wherein the chemical compound is a polycarbonate.

3. The method of claim 1 , further comprising:
quenching a ring-opening polymerization reaction that forms the chemical compound, wherein the chemical compound is a polycarbonate, wherein the quenching comprises forming a salt byproduct, and wherein the salt byproduct is the catalyst.

4. The method of claim 3 , wherein the ring-opening polymerization reaction is performed within the flow reactor and comprises polymerizing a cyclic carbonate monomer in the presence of an anionic organocatalyst.

5. The method of claim 4 , wherein the ring-opening polymerization reaction further comprises switching an active catalyst from the anionic organocatalyst to a second anionic organocatalyst by a proton transfer with a neutral chemical compound, wherein the proton transfer neutralizes the anionic organocatalyst and ionizes the neutral chemical compound.

6. A method, comprising:
functionalizing a polycarbonate polymer by reacting a trimethylsilyl protected thiol with the polycarbonate polymer in the presence of a catalyst and within a flow reactor, wherein the polycarbonate polymer comprises a perfluoroaryl group.

7. The method of claim 6 , wherein the perfluoroaryl group is bonded to the polycarbonate polymer via a methylene group.

8. The method of claim 6 , further comprising:
quenching a ring-opening polymerization reaction that forms the polycarbonate polymer, wherein the quenching comprises forming a salt byproduct, and wherein the salt byproduct is the catalyst.

9. The method of claim 8 , wherein the ring-opening polymerization reaction is performed within the flow reactor and comprises polymerizing a cyclic carbonate monomer in the presence of an anionic organocatalyst.

10. The method of claim 9 , wherein the ring-opening polymerization reaction further comprises switching an active catalyst from the anionic organocatalyst to a second anionic organocatalyst by a proton transfer with a neutral chemical compound, wherein the proton transfer neutralizes the anionic organocatalyst and ionizes the neutral chemical compound.

11. A method, comprising:
quenching a ring-opening polymerization reaction with a chemical acid, wherein the ring-opening polymerization reaction forms a polycarbonate, and wherein the quenching comprises forming a salt byproduct; and
functionalizing, via a post-polymerization reaction within a flow reactor, the polycarbonate, wherein the polycarbonate comprises a perfluoroaryl group, and wherein the salt byproduct catalyzes the functionalizing.

12. The method of claim 11 , wherein the perfluoroaryl group is bonded to the polycarbonate via a methylene group.

13. The method of claim 11 , wherein the salt byproduct is a basic salt.

14. The method of claim 11 , wherein the ring-opening polymerization reaction is performed within the flow reactor and comprises polymerizing a cyclic carbonate monomer in the presence of an anionic organocatalyst.

15. The method of claim 14 , wherein the ring-opening polymerization reaction further comprises switching an active catalyst from the anionic organocatalyst to a second anionic organocatalyst by a proton transfer with a neutral chemical compound, wherein the proton transfer neutralizes the anionic organocatalyst and ionizes the neutral chemical compound.

16. A method, comprising:
quenching a ring-opening polymerization to form a salt byproduct; and
functionalizing, by a chemical reaction within a flow reactor, a polycarbonate formed by the ring-opening polymerization by reacting a perfluoroaryl group of the polycarbonate with a trimethylsilyl protected thiol in the presence of the salt byproduct.

17. The method of claim 16 , wherein the salt byproduct is a catalyst to the functionalizing.

18. The method of claim 17 , wherein the quenching is performed within the flow reactor.

19. The method of claim 18 , wherein the ring-opening polymerization comprises polymerizing a cyclic carbonate monomer in the presence of an anionic organocatalyst.

20. The method of claim 19 , wherein the ring-opening polymerization further comprises switching an active catalyst from the anionic organocatalyst to a second anionic organocatalyst by a proton transfer with a neutral chemical compound, wherein the proton transfer neutralizes the anionic organocatalyst and ionizes the neutral chemical compound.

21. A method comprising:
modifying a polycarbonate polymer via a post-polymerization reaction within a flow reactor, wherein the post-polymerization reaction comprises reacting a perfluoroaryl group of the polycarbonate polymer with a trimethylsilyl protected thiol in the presence of a catalyst.

22. The method of claim 21 , wherein the catalyst is a salt byproduct of a quenching of a ring-opening polymerization that formed the polycarbonate polymer.

23. The method of claim 22 , wherein the perfluoroaryl group is bonded to a molecular backbone of the polycarbonate polymer via a methylene group.

24. The method of claim 22 , wherein the ring-opening polymerization is performed within the flow reactor and comprises polymerizing a cyclic carbonate monomer in the presence of an anionic organocatalyst.

25. The method of claim 24 , wherein the ring-opening polymerization further comprises switching an active catalyst from the anionic organocatalyst to a second anionic organocatalyst by a proton transfer with a neutral chemical compound, wherein the proton transfer neutralizes the anionic organocatalyst and ionizes the neutral chemical compound.

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

• C08G64/42 Primary

  Chemical after-treatment · CPC title

• C08G64/081

  containing sulfur · CPC title

• C08G64/085 Primary

  containing silicon · CPC title

• C08G64/10

  containing halogens · CPC title