Synthesis Of Rod-coil Block Copolymers Research Articles

Kumada chain-growth polycondensation as a universal method for synthesis of well-defined conjugated polymers

Kumada chain-growth polycondensation (KCGP) is a novel method for the synthesis of well-defined conjugated polymers. Because the Ni-catalyst can transfer in an intramolecular process to the propagating chain end, the polymerization follows chain-growth mechanism. With this newly developed method, various conjugated polymers, such as polythiophenes, poly(p-phenylene) (PPP), polypyrrole (PPy), and polyfluorene with controlled molecular weights and relatively narrow polydispersities (PDIs), have been prepared. Especially, the polymerizations for poly(3-alkylthiophene)s (P3ATs), PPP, and PPy exhibited quasi-living characteristics, which allows preparing polymer brushes, fully-conjugated block copolymers, and macroinitiators and macro-reactants for the synthesis of rod-coil block copolymers. In the current review, the progress in this new area is summarized.

Synthesis of a Conjugated Macromolecular Initiator for Nitroxide-Mediated Free Radical Polymerization.

Controlled synthesis of rod-coil block copolymers is possible with a new macroinitiator for "living" nitroxide-mediated radical polymerization (NMRP). The synthesis of the new macroinitiator which contains a rodlike, conjugated poly(p-phenylene vinylene) block is described. Electron microscopy imaging indicates microphase separation of the resulting block copolymer when cast from chloroform.

Synthesis of rod-coil block copolymers via end-functionalized poly(p-phenylene)s

This paper describes a new way to synthesize rod-coil block copolymers consisting of poly(p-phenylene) (PPP) as rigid rod and either polystyrene (PS) or poly(ethylene oxide) (PEO) as flexible coil. The Suzuki-coupling of the AB-type monomer 4-bromo-2,5-diheptylbenzeneboronic acid (1) under strictly proton-free conditions leads to the control of PPP endgroups and hence allows the synthesis of a variety of differently end-functionalized poly(p-phenylene)s. The poly(2,5-diheptyl-p-phenylene)-block-polystyrene (7) is then prepared via condensation via condensation of anionically polymerized living polystyrene (6) with α-(4-formylphenyl)-ω-phenyl-poly(2,5diheptyl-p-phenylene) (4). Toluenesulfonic acid catalyzed condensation of α-methyl-ω-amino-poly(oxyethylene) (8) with PPP 4 yields poly(2,5-diheptyl-p-phenylene)-block-poly(ethylene oxide) (9).

Synthesis of rod-coil block copolymers via end-functionalized poly(p-phenylene)s

This paper describes a new way to synthesize rod-coil block copolymers consisting of poly(p-phenylene) (PPP) as rigid rod and either polystyrene (PS) or poly(ethylene oxide) (PEO) as flexible coil. The Suzuki-coupling of the AB-type monomer 4-bromo-2,5-diheptylbenzeneboronic acid (1) under strictly proton-free conditions leads to the control of PPP endgroups and hence allows the synthesis of a variety of differently end-functionalized poly(p-phenylene)s. The poly(2,5-diheptyl-p-phenylene)-block-polystyrene (7) is then prepared via condensation via condensation of anionically polymerized living polystyrene (6) with α-(4-formylphenyl)-ω-phenyl-poly(2,5diheptyl-p-phenylene) (4). Toluenesulfonic acid catalyzed condensation of α-methyl-ω-amino-poly(oxyethylene) (8) with PPP 4 yields poly(2,5-diheptyl-p-phenylene)-block-poly(ethylene oxide) (9).

Synthesis of rod-coil block copolymers via end-functionalized poly(p-phenylene)s

Synthesis of rod-coil block copolymers via end-functionalized poly(p-phenylene)s