Phosphonate and phosphonic acid raft agents and monomers, along with methods of their manufacture and use

Patent metadata

Field	Value
Publication number	US-9683055-B2
Application number	US-201615155719-A
Country	US
Kind code	B2
Filing date	May 16, 2016
Priority date	Sep 12, 2013
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

A RAFT agent is provided that includes a thiocarbonylthio-containing organic compound having a phosphonic end group. The RAFT agent can have the formula:

wherein Z is an organic linkage; R 1 is H or an alkyl group; R 2 is H or an alkyl group; A is O, S, or NH; and R″ is an organic end group. A method is also provided for forming a polymer chain on a surface of a nanoparticle. The method can include: attaching a RAFT agent to the surface of the nanoparticle such that the phosphonic group of the RAFT agent is covalently bonded to the surface of the nanoparticle; and attaching a polymer to the RAFT agent.

First claim

What is claimed:

1. A RAFT agent comprising a thiocarbonylthio-containing organic compound having a phosphonic end group.

2. The RAFT agent as in claim 1 , wherein the phosphonic end group is a phosphonic acid group.

3. The RAFT agent as in claim 1 , having the formula:

where Z is an organic linkage; R 1 is H or an alkyl group; R 2 is H or an alkyl group; A is O, S, or NH; and R″ is an organic end group.

4. The RAFT agent as in claim 3 , wherein R″ comprises an alkyl group terminating with a phenyl end group or a nitrophenyl end group.

5. The RAFT agent as in claim 4 , wherein R″ comprises a benzyl group, a nitrobenzyl group, or a para-methyl benzyl group.

6. The RAFT agent as in claim 3 , wherein R 1 is H or an alkyl group having a formula of C n H 2n+1 , with n being an integer of 1 to 6.

7. The RAFT agent as claim 3 , wherein R 1 is a methyl group, an ethyl group, a propyl group, an iso-propyl group; a butyl group, or a tert-butyl group.

8. The RAFT agent as claim 3 , wherein R 2 is H or an alkyl group having a formula of C n H 2n+1 , with n being an integer of 1 to 6.

9. The RAFT agent as in claim 3 , wherein R 2 is a methyl group, an ethyl group, a propyl group, an iso-propyl group; a butyl group, or a tert-butyl group.

10. The RAFT agent as in claim 3 , wherein the organic linkage of Z comprises an ester group or an ethyl acetate linkage.

11. The RAFT agent as in claim 3 having the formula:

where n is 1 to 10, m is 1 to 10, R 1 is H or an alkyl group; R 2 is H or an alkyl group; A is O, S, or NH; and R″ is an organic end group.

12. The RAFT agent as in claim 3 , wherein R″ is a benzyl group.

13. The RAFT agent as in claim 12 , wherein a nitro group is positioned on the benzyl group.

14. The RAFT agent as in claim 13 , wherein the nitro group is positioned on the benzyl group at the para position.

15. The RAFT agent as in claim 3 , wherein A is O, NH, or S.

16. The RAFT agent as in claim 3 , wherein the RAFT agent is selected from the group consisting of:

17. A salt of the RAFT agent of claim 3 .

18. A method of forming a polymer chain on a surface of a nanoparticle, the method comprising:
attaching the RAFT agent of claim 1 to the surface of the nanoparticle, wherein the phosphonic group of the RAFT agent is covalently bonded to the surface of the nanoparticle; and
attaching a polymer to the RAFT agent.

Assignees

• Univ South Carolina

Inventors

• Benicewicz Brian
• Viswanath Anand
• Green Alexandra Nicole

Classifications

• C07F9/4006

  Esters of acyclic acids which can have further substituents on alkyl · 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

• C07F9/3808

  Acyclic saturated acids which can have further substituents on alkyl · CPC title

• C07C329/00

  Thiocarbonic acids; Halides, esters or anhydrides thereof · CPC title

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title