Sequence Controlled Polymers from a Novel β-Cyclodextrin Core.

Area of Science:

• Polymer Chemistry
• Macromolecular Science
• Organic Synthesis

Background:

• Controlled radical polymerization techniques are crucial for designing advanced polymer architectures.
• Single Electron Transfer-Living Radical Polymerization (SET-LRP) offers precise control over polymer growth.
• Developing novel initiators is key to expanding the scope and efficiency of SET-LRP.

Purpose of the Study:

• To synthesize and characterize a novel beta-cyclodextrin-based initiator for SET-LRP.
• To explore efficient synthetic routes for the initiator using click-like reactions.
• To demonstrate the initiator's capability in synthesizing complex polymer structures.

Main Methods:

• Synthesis of the beta-cyclodextrin-based initiator via copper(I)-catalyzed azide-alkyne cycloaddition, nucleophilic thiol-ene, and radical thiol-ene reactions.
• Optimization of the initiator synthesis, identifying radical thiol-ene as the most successful method.
• Application of the initiator in SET-LRP for the polymerization of acrylates.

Main Results:

• Successful synthesis of a beta-cyclodextrin-based SET-LRP initiator.
• Radical thiol-ene reaction identified as the most efficient synthetic pathway.
• Controlled synthesis of 7-arm multiblock copolymers with low dispersities (≤1.12).
• High monomer conversion (≥95%) and rapid polymerization times (under 6.5 h per block).

Conclusions:

• The novel beta-cyclodextrin-based initiator is effective for controlled SET-LRP.
• The developed initiator enables the efficient synthesis of sequence-controlled multiblock copolymers.
• This work advances the development of advanced polymer architectures using sustainable polymerization methods.