Monocapped conductive polymers with alkenyl or alkynyl end groups and block copolymers therefrom
Novel polymer compositions which provide controlled end-group functionalization for polythiophenes including regioregular polythiophenes including alkenyl and alkynyl functionalization. Monocapped polymers are formed and can be converted to block copolymers. Conditions and reagents can be selected to provide more monocapping than dicapping of the polymer. Devices, films, and blends can be prepared.
1. A one-pot method of making a poly(3-substituted thiophene) which is at least 70% monocapped with alkenyl or alkynyl end group comprising (i) preparing a poly(3-substituted thiophene) precursor to form a polymer reaction mixture; and (ii) reacting the precursor in the polymer reaction mixture with an alkenyl or alkynyl Grignard reagent to form in one pot the poly(3-substituted thiophene which is at least 70% monocapped with alkenyl or alkynyl end group, wherein the alkenyl or alkynyl end group comprises from two to five carbon atoms, and wherein the poly(3-substituted thiophene) which is at least 70% monocapped with alkenyl or alkynyl end group is also 20 percent or less dicapped.
2. The method according to claim 1 , wherein the poly(3-substituted thiophene) is at least 86% monocapped with alkenyl or alkynyl end group.
3. The method according to claim 1 , wherein the poly(3-substituted thiophene) is at least 91% monocapped with alkenyl or alkynyl end group.
4. The method according to claim 1 , wherein the poly(3-substituted thiophene) is a poly(3-alkyl thiophene).
5. The method according to claim 1 , wherein the alkenyl or alkynyl end group comprises vinyl, allyl, or ethynyl.
6. The method according to claim 1 , wherein the poly(3-substituted thiophene) which is at least 70% monocapped with alkenyl or alkynyl end group is also 10 percent or less dicapped.
7. The method according to claim 1 , wherein the poly(3-substituted thiophene) which is at least 70% monocapped with alkenyl or alkynyl end group is also 1 percent or less dicapped.
8. The method according to claim 1 , wherein the poly(3-substituted thiophene) is at least 86% monocapped with alkenyl or alkynyl end group and the poly(3-substituted thiophene) is a poly(3-alkyl thiophene).
9. The method according to claim 8 , wherein the alkenyl or alkynyl end group comprises vinyl, allyl, or ethynyl.
10. The method according to claim 8 , wherein the poly(3-substituted thiophene) which is at least 86% monocapped with alkenyl or alkynyl end group is also 1 percent or less dicapped.
11. The method according to claim 1 , wherein the poly(3-substituted thiophene) is at least 90% head-to-tail regioregular.
12. The composition according to claim 1 , wherein the poly(3-substituted thiophene) is at least 98% head-to-tail regioregular.
13. The method according to claim 1 , wherein the poly(3-substituted thiophene) is a regioregular polythiophene.
14. The method of claim 1 , wherein the poly(3-substituted thiophene) precursor is prepared using Grignard metathesis polymerization of one or more 3-substituted thiophene monomers.
15. The method of claim 1 , wherein the precursor is reacted with an alkenyl or alkynyl reagent by quenching the precursor with an excess of Grignard reagent.
16. The method of claim 1 , wherein the reaction of the precursor with the Grignard reagent is followed by treatment with a proton source.
17. The method of claim 1 , wherein the poly(3-substituted thiophene) which is at least 70% monocapped with alkenyl or alkynyl end groups further comprises bromine end groups.