Cyclopropenium polymers and methods for making the same

Patent metadata

Field	Value
Publication number	US-9758606-B2
Application number	US-201514611166-A
Country	US
Kind code	B2
Filing date	Jan 30, 2015
Priority date	Jul 31, 2012
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

The present invention provides, inter alia, a process for incorporating a cyclopropenium ion into a polymeric system. Processes for making cross-linked polymers, linear polymers, and dendritic polymers, as well as for incorporating a cyclopropenium ion onto a preformed polymer are also provided. Further provided are stable, polycationic compounds, various polymers that contain stable cyclopropenium cations, and substrates containing such polymers. The use of these polymers in water purification systems, antimicrobial coatings, ion-transport membranes, cell supports, drug delivery vehicles, and gene therapeutic vectors are also provided.

First claim

What is claimed is:

1. A process for incorporating a cyclopropenium ion into a polymeric system comprising contacting a functionalized cyclopropenium ion with a functionalized compound capable of reacting with the functional group of the cyclopropenium ion for a period of time and under conditions suitable for the functionalized cyclopropenium and the functionalized compound to react and form a polymeric system that comprises a stable cyclopropenium cation that remains positively charged;
wherein the functionalized cyclopropenium ion is a compound of formula (100):

wherein
X 1-3 are independently selected from the group consisting of Cl and N; and
R 1-4 are independently selected from the group consisting of no atom, amino, aryl, heteroaryl,C 1-10 alkoxy, C 2-10 alkenyloxy, C 2-10 alkynyloxy, C 1-10 alkyl C 3-10 cycloalkyl, C 2-10 alkenyl, C 3-10 cycloalkenyl, C 2-10 alkynyl, halogen, aryloxy, heteroaryloxy, C 2-10 alkoxycarbonyl, C 1-10 alkenylthio, C 2-10 alkynylthio, C 2-10 alkynylthio, C 1-10 alkylsulfonyl, C 1-10 alkylsulfinyl, aryl-C 1-10 alkyl, heteroaryl-C 1-10 alkyl, aryl-C 1-10 heteroalkyl, heteroaryl-C 1-10 heteroalkyl, a phosphorus group, a silicon group and a boron group, wherein R 1 and R 2 or R 3 and R 4 are optionally combined to form a 5 to 8-membered carbocyclic or heterocyclic ring; further wherein the aliphatic or aromatic portions of R 1 and R 2 are optionally substituted with from 1 to 4 substituents selected from the group consisting of halogen, cyano, nitro, C 1-4 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, aryl, C 1-6 alkoxy, C 2-6 alkenyloxy, C 2-6 alkynyloxy,aryloxy, C 2-6 alkoxycarbonyl, C 1-6 alkylthio, C 1-6 alkylsulfonyl, C 1-6 alkylsulfinyl, oxo, imino, thiono, primary amino, carboxyl, C 1-6 alkylamino, C 1-6 dialkylamino, amido, nitrogen heterocycles, hydroxy, thiol and phosphorus.

2. The process according to claim 1 , wherein the polymeric system is selected from the group consisting of linear polymers, branched polymers, cross-linked polymers, and dendritic polymers.

3. The process according to claim 1 , wherein the functionalized cyclopropenium ion is selected from the group consisting of:

optionally together with an appropriate counter ion.

4. The process according to claim 1 , wherein the functionalized cyclopropenium ion is selected from the group consisting of:

wherein
R 1-4 are independently selected from the group consisting of

 and combinations thereof.

5. The process according to claim 1 , wherein the functionalized cyclopropenium ion is selected from the group consisting of:

wherein
R 1-4 are independently selected fromk the group consisting of

 wherein R is hydrogen or methyl;
and combinations thereof.

6. The process according to claim 1 , wherein the functionalized cyclopropenium ion is:

7. The process according to claim 1 wherein the functionalized cyclopropenium ion is:

8. The process according to claim 1 , wherein the functionalized cyclopropenium ion is:

9. The process according to claim 1 , wherein the functionalized cyclopropenium ion is:

10. The process according to claim 1 , wherein the functionalized compound capable of reacting with the functional group of the cyclopropenium ion is a polymer selected from the group consisting of a linear polymer, a branched polymer, a cross-linked polymer, and a dendritic polymer.

11. The process according to claim 10 , wherein the polymer is a homopolymer or a heteropolymer.

12. The process according to claim 11 , wherein the heteropolymer is selected from the group consisting of a random copolymer, a block copolymer, and a graft copolymer.

13. The process according to claim 10 , wherein the backbone of the polymer comprises a group selected from the group consisting of ethylene, propylene, styrene, (meth)acrylate, vinyl chloride, urethane, ethylene terephthalate, ester, amide, norbornene, silicon, oxygen, and combinations thereof.

14. The process according to claim 1 , wherein the cyclopropenium cation incorporated into the polymeric system remains positively charged in a pH range from 0 to greater than 14.

15. The process according to claim 1 , wherein the cyclopropenium cation incorporated into the polymeric system remains positively charged in a pH range from 8 to 13.

16. A process for making a cross-linked polymer comprising contacting an alkene functionalized cyclopropenium ion with a polymer comprising a pendant thiol group, for a period of time and under conditions suitable for the functionalized cyclopropenium ion and the polymer to react and form a cross-linked polymer that comprises a stable cyclopropenium cation that remains positively charged.

17. The process according to claim 16 , which is carried out according to:

18. A process for making a cross-linked polymer comprising contacting a thiol functionalized cyclopropenium ion with a functionalized compound comprising an alkene group, for a period of time and under conditions suitable for the functionalized cyclopropenium ion and the functionalized compound to react and form a cross-linked polymer that comprises a stable cyclopropenium cation that remains positively charged.

19. The process according to claim 18 , which is carried out according to:

20. A process for making a linear polymer comprising contacting a functionalized cyclopropenium ion with a polymerizing agent for a period of time and under conditions suitable for the functionalized cyclopropenium ion to react and to form a linear polymer that comprises a stable cyclopropenium cation that remains positively charged.

21. The process according to claim 20 , further comprising contacting the functionalized cyclopropenium ion with a monomer suitable for forming a copolymer with the functionalized cyclopropenium ion.

22. The process according to claim 20 , which is carried out according to:

wherein

 is a polymer backbone comprising a group selected from the group consisting of ethylene, propylene, styrene, (meth)acrylate, vinyl chloride, ureth

Assignees

• Univ Columbia

Inventors

• Lambert Tristan Hayes
• Campos Luis M
• Bandar Jeffrey
• Dell Emma Jane

Classifications

• C08F212/26

  Nitrogen · CPC title

• C08F112/32

  containing two or more rings · CPC title

• C08F12/26

  Nitrogen · CPC title

• C08F212/08

  Styrene · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title