Synthesis of linear polyethyleneimine by living anionic polymerization

Patent metadata

Field	Value
Publication number	US-10011683-B2
Application number	US-201715405915-A
Country	US
Kind code	B2
Filing date	Jan 13, 2017
Priority date	Jan 14, 2016
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

Disclosed herein are methods for the productions of linear polyethyleneimine using living anionic polymerization of appropriately functionalized aziridine monomers.

First claim

What is claimed is:

1. A process for synthesizing a linear polyethyleneimine comprising:
combining a compound of Formula (I):

with a compound of Formula (II)

wherein
R 1 and R 2 are either both 2-nitrophenyl, or R 1 and R 2 are different and are each selected from C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl, or substituted or unsubstituted phenyl;
and an anionic initiator selected from a compound of Formula (IIIa) or (IIIb):
R 3 -M 1   (Formula IIIa)

or
(R 3 ) 2 -M 2   (Formula IIIb)

wherein
M 1 comprises Li, Na, K, Rb, or Cs;
M 2 comprises Mg or Ca;

R 3 is selected from the group consisting of C 1 -C 12 alkyl group, C 6 -C 12 aryl, —CN, —OR 4 , —NR 4 2 , PR 4 2 ; R 4 , when present, is in each case independently selected from hydrogen, C 1 -C 12 alkyl, C 6 -C 12 aryl, SO 2 R 1 , and SiR 3
in a suitable solvent to give a linear polyethyleneimine of Formula (IV):

wherein n+m is an integer greater than 100.

2. The process of claim 1 , further comprising the step of removing the sulfonyl groups to give a linear polyethyleneimine of Formula (V)

3. The process according to claim 1 , wherein the anionic initiator comprises LDA, KHDMS, LiHDMS, NaHDMS, LiTMP, Na t OBu, K t OBu.

4. The process according to claim 1 , wherein n+m is an integer greater than 200.

5. The process according to claim 1 , wherein n+m is an integer greater than 400.

6. The process according to claim 1 , wherein n+m is an integer greater than 600.

7. The process according to claim 1 , wherein R 1 and R 2 are both 2-nitrophenyl.

8. The process according to claim 1 , wherein R 1 and R 2 are different and are each selected from C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl, or substituted or unsubstituted phenyl.

9. The process according to claim 8 , wherein R 1 is methyl R 2 is C 4 alkyl.

10. The process according to claim 9 , wherein R 2 is sec-butyl.

11. A linear polyethyleneimine, characterized by a M n >5,000; a polydispersity of no more than 1.10, further characterized in that the polyethyleneimine does not contain any amide functional groups.

12. The linear polyethyleneimine according to claim 11 , having a M n >10,000.

13. The linear polyethyleneimine according to claim 11 , having a M n >20,000.

Assignees

• Univ Alabama

Inventors

• Rupar Paul A
• Reisman Louis
• Mbarushimana Pierre Canisius

Classifications

• C08G73/0206

  Polyalkylene(poly)amines · CPC title

• C08G73/0213 Primary

  Preparatory process · CPC title