Azo-Derived Symmetrical Trithiocarbonate for Unprecedented RAFT Control.

Area of Science:

• Polymer Chemistry
• Materials Science

Background:

• Reversible-deactivation radical polymerization (RDRP) is crucial for synthesizing polymers with controlled architectures.
• Developing efficient chain transfer agents is key to achieving high molecular weights and low dispersities.

Purpose of the Study:

• To introduce a novel trithiocarbonate, Bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP), as a superior agent for RAFT polymerization.
• To demonstrate the synthesis of a well-defined triblock copolymer using TTC-bCP and characterize its properties.

Main Methods:

• Synthesis of TTC-bCP from 2,2'-azobis(2-methylpropionitrile) (AIBN).
• Preparation of a methyl methacrylate-n-butyl acrylate-methyl methacrylate triblock copolymer via RAFT polymerization.
• Characterization of the copolymer's molar mass, dispersity, and rheological properties.

Main Results:

• TTC-bCP was synthesized efficiently, featuring an excellent leaving group for RAFT polymerization.
• A high-molar-mass (Mn ≈ 135 kg mol-1) triblock copolymer was prepared with exceptional control (Đ = 1.04).
• Rheological analysis revealed thermoplastic elastomer behavior with a stable rubbery plateau up to 120 °C.

Conclusions:

• TTC-bCP represents a significant advancement in RAFT polymerization agents.
• The developed method allows for the controlled synthesis of advanced polymer materials with desirable properties.
• The resulting triblock copolymers exhibit potential for high-performance elastomer applications.