Polymers for enhanced solubility of nanomaterials, compositions and methods therefor

• US 7,296,576 B2
• Filed: 08/18/2004
• Issued: 11/20/2007
• Est. Priority Date: 08/18/2004
• Status: Active Grant

• Current Assignee: Evermore Applied Materials Corp.
• Original Assignee: Zyvex Performance Materials, LLC
• Inventors: Ait-Haddou, Hassan, Rutkofsky, Marni Loriel
• Primary Examiner(s): Truong; Duc
• Application Number:
  US10/920,877
• Publication Number:
  US 20060041104A1
• Time in Patent Office: 1,189 Days
• Field of Search: 528/397, 528/491, 528/501, 528/503, 528/86, 524/502, 524/881, 524/501
• US Class Current: 528/397
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C08G 61/02 Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• CPC Class Codes: C08J 2365/00 Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08J2307/00 - C08J2357/00, C08J2361/00 take precedence; Derivatives of such polymers
• CPC Class Codes: C08J 5/005 Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/041 Carbon nanotubes
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers

Abstract

Poly(aryleneethynylene) polymers, poly(ferrocenylaryleneethynylene) polymers and poly(ferrocenylethynylene) polymers having properties particularly useful for solubilizing nanomaterials and for effecting subsequent re-solubilization of a solid polymer-solubilized nanomaterial, and compositions and methods thereto are provided.

Claims

1. A method of making a rigid poly(aryleneethynylene) polymer, the polymer having at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2, the method comprising:

coupling a para-diethynyl-(R₁–

R_x)arylene and an (R₁–

R_y)-para-dihaloarylene in the presence of a first polymerization-terminating haloaryl agent,

wherein each R of (R₁–

R_x) and (R₁–

R_y) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R₁–

R_x) and (R₁–

R_y) is a functional group for solubilizing nanomaterial, and

wherein x of (R₁–

R_x) is the maximum number of substituents on the para-diethynyl-(R₁–

R_x)arylene, and y of (R₁–

R_y) is the maximum number of substituents on the (R₁–

R_y)-para-dihaloarylene,

under conditions and for a period of time to produce fluorescence; and

terminating the coupling by addition of a second polymerization-terminating haloaryl agent, the second haloaryl agent having equal or greater activity for coupling as the (R₁–

R_y)-para-dihaloarylene.

2. The method of claim 1 wherein the arylene of the para-diethynyl-(R₁–

R_x)arylene and the arylene of the (R₁–

R_y)-para-dihaloarylene are the same arylene structure.

5. The method of claim 1 wherein the coupling is carried out at a first temperature for a period of time followed by a second temperature for a period of time, wherein the second temperature is greater than the first temperature.

6. The method of claim 5 wherein the first temperature is about room temperature.

7. The method of claim 6 wherein the coupling at about room temperature is for about 10 mm to 1 hour.

8. The method of claim 5 wherein the second temperature is less than about 80°

C.

9. The method of claim 8 wherein the coupling at 80°

C. is for about 24 hours.

10. The method of claim 1 wherein the poly(aryleneethynylene) rigid polymer comprises a poly(phenyleneethynylene) polymer, the para-diethynyl-(R₁–

R_x)arylene comprises a para-diethynyl-(R₁–

R_x)benzene, and the (R₁–

R_y)-para-dihaloarylene comprises a (R₁–

R_y)-para-dihalobenzene.

11. The method of claim 1 wherein the first or second polymerization-terminating haloaryl agent comprises an iodoalkyloxybenzene or a bromoalkyloxybenzene, or a combination thereof.

12. The method of claim 1 wherein the iodoalkyloxybenzene comprises iodoanisole, iodoethoxybenzene, or iodopropoxybenzene, or a combination thereof.

13. The method of claim 1 wherein the bromoalkyloxybenzene comprises bromoanisole, bromoethoxybenzene, or bromopropoxybenzene, or a combination thereof.

14. The method of claim 1 wherein the polydispersity of the polymer is about 1.2 to about 1.8.

15. The method of claim 1 wherein the polydispersity of the polymer is about 1.4 to about 1.6.

16. The method of claim 1 wherein at least one R of (R₁–

R_x) or (R₁–

R_y) is alkoxy or alkyl.

17. The method of claim 10 wherein x is 4, y is 4, one set of para R'"'"'s of(R₁–

R_x) is H and a corresponding set of para R'"'"'s of(R₁–

R_y) is H.

18. The method of claim 10 wherein x is 4, y is 4, one set of para R'"'"'s of(R₁–

R_x) is alkoxy and a corresponding set of para R'"'"'s of(R₁–

R_y) is alkoxy.

19. The method of claim 10 wherein x is 4, y is 4, one set of para R'"'"'s of(R₁–

R_x) is alkyl and a corresponding set of para R'"'"'s of (R₁–

R_y) is alkyl.

20. The method of claim 10 wherein x is 4, y is 4, and each set of para R'"'"'s of (R₁–

R_x) is identical to a corresponding set of para R'"'"'s of(R₁–

R_y).

21. The method of claim 1 wherein the length of the polymer is about 25 nm to about 55 nm.

22. A rigid poly(aryleneethynylene) polymer made by the method of claim 1.

25. A rigid poly(phenyleneethynylene) polymer made by the method of claim 10.

3. A method of making a rigid poly(ferrocenylaryleneethynylene) polymer, the polymer having at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2, the method comprising:

coupling a 1,1′

-diethynyl-(R₁–

R₈)ferrocene and an (R₁–

R_z)-para-dihaloarylene, or coupling a 1,1′

-dihalo-(R₁–

R₈)ferrocene and a para-diethynyl-(R₁–

R_z)arylene, in the presence of a first polymerization-terminating haloaryl agent,

wherein each R of (R₁–

R₈) and (R₁–

R_Z) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R₁–

R₈) and (R₁–

R_z) is a functional group for solubilizing nanomaterial, and

wherein z of (R₁–

R_z) is the maximum number of substituents on the (R₁–

R_z)-para-dihaloarylene,

under conditions for a period of time to produce fluorescence; and

terminating the coupling by addition of a second polymerization-terminating haloaryl agent, the second haloaryl agent having equal or greater activity for coupling as the (R₁–

R_z)-para-dihaloarylene or the 1,1′

-dihalo-(R₁–

R₈)ferrocene.

23. A rigid poly(ferrocenylaryleneethynylene) polymer made by the method of claim 3.

4. A method of making a rigid poly(ferrocenylethynylene) polymer, the polymer having at least one functional group for solubilizing nanomaterial, a length of about 25 nm to about 110 nm, and a polydispersity of less than about 2, the method comprising:

coupling a 1,1′

-diethynyl-(R₁–

R₈)ferrocene and an (R₁–

R₈)-1,1′

-dihaloferrocene in the presence of a first polymerization-terminating haloaryl agent,

wherein each R of (R₁–

R₈) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R₁–

R₈) is a functional group for solubilizing nanomaterial,

wherein corresponding R groups of the 1,1′

-diethynyl-(R₁–

R₈)ferrocene and the (R₁–

R₈)-1,1′

-dihaloferrocene are identical;

under conditions for a period of time to produce fluorescence; and

terminating the coupling by addition of a second polymerization-terminating haloaryl agent, the second haloaryl agent having equal or greater activity for coupling as the (R₁–

R₈)-1,1′

-dihaloferrocene.

24. A rigid poly(ferrocenylethynylene) polymer made by the method of claim 4.