Polymers for enhanced solubility of nanomaterials, compositions and methods therefor
View Patent ↗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.
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-(R 1 –R x )arylene and an (R 1 –R y )-para-dihaloarylene in the presence of a first polymerization-terminating haloaryl agent,
wherein each R of (R 1 –R x ) and (R 1 –R y ) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R 1 –R x ) and (R 1 –R y ) is a functional group for solubilizing nanomaterial, and
wherein x of (R 1 –R x ) is the maximum number of substituents on the para-diethynyl-(R 1 –R x )arylene, and y of (R 1 –R y ) is the maximum number of substituents on the (R 1 –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 (R 1 –R y )-para-dihaloarylene.
2. The method of claim 1 wherein the arylene of the para-diethynyl-(R 1 –R x )arylene and the arylene of the (R 1 –R y )-para-dihaloarylene are the same arylene structure.
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-(R 1 –R 8 )ferrocene and an (R 1 –R z )-para-dihaloarylene, or coupling a 1,1′-dihalo-(R 1 –R 8 )ferrocene and a para-diethynyl-(R 1 –R z )arylene, in the presence of a first polymerization-terminating haloaryl agent,
wherein each R of (R 1 –R 8 ) and (R 1 –R Z ) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R 1 –R 8 ) and (R 1 –R z ) is a functional group for solubilizing nanomaterial, and
wherein z of (R 1 –R z ) is the maximum number of substituents on the (R 1 –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 (R 1 –R z )-para-dihaloarylene or the 1,1′-dihalo-(R 1 –R 8 )ferrocene.
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-(R 1 –R 8 )ferrocene and an (R 1 –R 8 )-1,1′-dihaloferrocene in the presence of a first polymerization-terminating haloaryl agent,
wherein each R of (R 1 –R 8 ) is independently H, or a functional group for solubilizing nanomaterial, and at least one R of (R 1 –R 8 ) is a functional group for solubilizing nanomaterial,
wherein corresponding R groups of the 1,1′-diethynyl-(R 1 –R 8 )ferrocene and the (R 1 –R 8 )-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 (R 1 –R 8 )-1,1′-dihaloferrocene.
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-(R 1 –R x )arylene comprises a para-diethynyl-(R 1 –R x )benzene, and the (R 1 –R y )-para-dihaloarylene comprises a (R 1 –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 (R 1 –R x ) or (R 1 –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(R 1 –R x ) is H and a corresponding set of para R's of(R 1 –R y ) is H.
18. The method of claim 10 wherein x is 4, y is 4, one set of para R's of(R 1 –R x ) is alkoxy and a corresponding set of para R's of(R 1 –R y ) is alkoxy.
19. The method of claim 10 wherein x is 4, y is 4, one set of para R's of(R 1 –R x ) is alkyl and a corresponding set of para R's of (R 1 –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 (R 1 –R x ) is identical to a corresponding set of para R's of(R 1 –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 .
23. A rigid poly(ferrocenylaryleneethynylene) polymer made by the method of claim 3 .
24. A rigid poly(ferrocenylethynylene) polymer made by the method of claim 4 .
25. A rigid poly(phenyleneethynylene) polymer made by the method of claim 10 .