Preparation of high molecular weight polymers by direct arylation and heteroarylation
A method for preparing polymers by direct heteroarylation or arylation polycondensation is described herein. The method includes preparing a reaction mixture including at least a monomer to be polymerized, a catalyst and a ligand; heating the reaction mixture; and, optionally, end-capping the reaction mixture.
1. A polymer comprising repeating units of the Formulae (V), (VI) or (VII):
-[A 1 -A 2 ]- (V);
-[A 3 ]- (VI); or
-[A 3 -A 4 ]- (VII),
wherein
A 1 , A 2 , A 3 and A 4 are independently selected from heteroaryl, wherein the heteroatoms are selected from nitrogen, oxygen, and/or sulfur, or is further defined by the formula:
wherein R 17 , R 18 , R 19 , and R 20 are H, CN and C 1-30 alkyl and denotes the point of attachment with the adjacent “A” group;
-[A 3 -A 4 ]- (VII) is a random polymer; and
the polymers of the Formulae (V), (VI) or (VII) have M n values in excess of about 10 kDa and characterized by not comprising organometallic by-products;
with the provisos that when the polymer is -[A 3 ]-, A 3 is not a thienyl group, a 3,4-ethylenedioxythiophene group, a thieno[3,4-c]pyrrole-4,6-dione group or a group of the formula:
wherein R 23 and R 26 are H, CN and C 1-30 alkyl; R 24 and R 25 are C 1-30 alkyl; and denotes the point of attachment with the adjacent “A” group;
when the polymer is -[A 1 -A 2 ]-, A 1 or A 2 is not a group of the formula:
wherein R 8 and R 9 are H, CN and C 1-30 alkyl; and denotes the point of attachment with the adjacent “A” group; when the polymer is -[A 1 -A 2 ]- and comprises a group of the formula:
wherein R 23 and R 26 are H, CN and C 1-30 alkyl; R 24 and R 25 are C 1-30 alkyl; and denotes the point of attachment with the adjacent “A” group; A 1 or A 2 is 5-Octyl-5H-thieno [3,4-c]pyrrole-4,6-dione, 5,5′-dioctyl-4H,4′H- 1,1-bithieno[3,4-c]pyrrole-4,4′, 6,6′(5H,5′H)-tetrone or 3,4-ethylenedioxythiophene.
2. The polymer of claim 1 , wherein heteroaryl comprises at least one thienyl group.
3. The polymer of claim 2 , wherein the at least one thienyl group is fused to a 5-membered or 6-membered heterocyclo group.
4. The polymer of claim 2 , wherein the heteroaryl comprises 2, 3 or 4 thienyl groups.
5. The polymer of claim 1 , wherein the heteroaryl comprises an oxindole group, indigo group or isoindigo group.
6. The polymer of claim 1 , wherein A 1 , A 2 , A 3 and A 4 are independently selected from:
wherein R 1 , R 1′ , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 ,R 18 , R 19 , R 20 ,R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are independently selected from H, CN and C 1-30 alkyl and denotes the point of attachment with the adjacent “A” group.
7. The polymer of claim 1 , characterized by not comprising metals.
8. The polymer of claim 7 , selected from the group consisting of:
wherein n is the number of repeating units in the polymer chain.