IP Library Granted Patent US 10,738,153
Granted Patent B2
US 10,738,153 · App. 16/029,025 · Granted Aug 11, 2020

Ring-opening polymerizations using a flow reactor

Inventors: Nathaniel H. Park (San Jose, CA); James L. Hedrick (Pleasanton, CA); Victoria A. Piunova (Los Gatos, CA); Dmitry Zubarev (San Jose, CA); Gavin O. Jones (San Jose, CA); Robert M. Waymouth (Palo Alto, CA); Binhong Lin (Stanford, CA)
Assignees: INTERNATIONAL BUSINESS MACHINES CORPORATION; THE BOARD OF TRUSTEES OF THE LELAND STANFORD JUNIOR UNIVERSITY
C08G64/085
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Quick Facts
Patent No.
US 10,738,153
App. No.
16/029,025
Granted
Aug 11, 2020
Kind
B2
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.

Claims (34)

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.

Assignments (3)
CONFIRMATORY LICENSE Recorded Sep 25, 2019
From: STANFORD UNIVERSITY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 050483/0461 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2018
From: PARK, NATHANIEL H.; HEDRICK, JAMES L.; PIUNOVA, VICTORIA A.; ZUBAREV, DMITRY; JONES, GAVIN O.
To: INTERNATIONAL BUSINESS MACHINES CORPORATION
Reel/Frame 046282/0913 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2018
From: WAYMOUTH, ROBERT M.; LIN, BINHONG
To: THE BOARD OF TRUSTEES OF THE LELAND STANFORD JUNIOR UNIVERSITY
Reel/Frame 046282/0990 →
Continuity (1)
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