Facile Synthesis of Helical Rod–Coil Block Polymers by the Combination of ATRP and Pd(II)‐Initiated Isocyanides Polymerizations

A bifunctional initiator containing propargyl bromoisobutyrate and alkyne‐Pd(II) (PBB‐Pd(II)) is designed and synthesized. The propargyl bromoisobutyrate unit of PBB‐Pd(II) can initiate the atom transfer radical polymerization (ATRP) of vinyl monomers, while the Pd(II) complex can initiate the polym...

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Bibliographic Details
Published in:Macromolecular chemistry and physics 2019-04, Vol.220 (8), p.n/a
Main Authors: Liu, Na, Lu, Hao‐Jun, Jiang, Zhi‐Qiang, Lu, Yu‐Bing, Zou, Hui, Zhou, Li, Wu, Zong‐Quan
Format: Article
Language:English
Subjects:
Alkynes
Block copolymers
Chemical synthesis
Coils
Crystallization
Enantiomers
enantioselective crystallization
helices
Monomers
Optical activity
poly(phenyl isocyanide)
Polymerization
Polymers
rod–coil
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Summary:A bifunctional initiator containing propargyl bromoisobutyrate and alkyne‐Pd(II) (PBB‐Pd(II)) is designed and synthesized. The propargyl bromoisobutyrate unit of PBB‐Pd(II) can initiate the atom transfer radical polymerization (ATRP) of vinyl monomers, while the Pd(II) complex can initiate the polymerization of phenyl isocyanides. Both the ATRP and Pd(II)‐mediated isocyanide polymerization are proceeded in living/controlled manner. Thus, combining the two living polymerizations, a series of well‐defined block copolymers bearing rod poly(phenyl isocyanide)s and coil poly(acrylate) segments can be facilely prepared in high yield with tunable composition, controlled molar masses (Mns), and narrow molar mass distributions (Mw/Mns). What is more, benefiting from this synthetic strategy, well‐defined core cross‐linked star polymers are readily synthesized. Optically active block copolymers and star polymers can be facilely obtained by using chiral isocyanide monomers due to the formation of predominated one‐handed helix. The chiral star polymers show excellent enantioselective recognition ability in enantioselective crystallization of racemic compounds. A novel bis‐active catalyst is designed and synthesized to afford the optically active block copolymers with rod–coil structures via the combination of atom transfer radical polymerization and Pd(II)‐initiated isocyanide polymerization. These obtained optically active block copolymers show good performance in enantioselective crystallization and the enantiomeric excess of the induced crystal is up to 80%.
ISSN:1022-1352
1521-3935
DOI:10.1002/macp.201800574