单体混合物一步合成嵌段共聚物的重复单元/序列/拓扑的多维控制《Journal of the American Chemical Society》

Multidimensional Control of Repeating Unit/Sequence/Topology for One-Step Synthesis of Block Polymers from Monomer Mixtures

Xiaochao Xia, Tianle Gao, Feng Li, Ryota Suzuki, Takuya Isono*, and Toshifumi Satoh*

J. Am. Chem. Soc. 2022, XXXX, XXX, XXX-XXX

Publication Date: September 23, 2022

https://doi.org/10.1021/jacs.2c06860

Abstract

Synchronously and thoroughly adjusting the chemical structure difference between two blocks of the diblock copolymer is very useful for designing materials but difficult to achieve via self-switchable alternating copolymerization. Here, we report self-switchable alternating copolymerization from a mixture of two different cyclic anhydrides, epoxides, and oxetanes, where a simple alkali metal carboxylate catalyst switches between ring-opening alternating copolymerization (ROCOP) of cyclic anhydrides/epoxides and ROCOP of cyclic anhydrides/oxetanes, resulting in the formation of a perfect block tetrapolymer. By investigating the reactivity ratio of these comonomers, a reactivity gradient was established, enabling the precise synthesis of block copolymers with synchronous adjustment of each unit’s chemical structure/sequence/topology. Consequently, a diblock tetrapolymer with two glass transition temperatures (Tg) can be easily produced by adjusting the difference in chemical structures between the two blocks.

SUBJECTS:

• Copolymerization,

• Copolymers,

• Ethers,

• Monomers,

• Polymers