Synthesis and Polymerizability of Atom-Bridged Bicyclic Monomers

Abstract

Abstract:The synthesis and polymerizability of atom-bridged bicyclic monomers was surveyed. The monomers included lactams, ureas, urethanes, lactones, carbonates, ethers, acetals, orthoesters, and amines. Despite widely-varying structures, they almost all polymerized to give polymers with monocyclic rings in the chain. The polymerizations are grouped by mechanism: uncoordinated anionic, coordinated anionic, and cationic.

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

“…Consequently, aliphatic substituents such as methyl-or propyl groups in the γ-position lead to an unfavourable polymermonomer equilibrium and decreased conversion 10,63,64 . However, although several examples have been published, detailed predictions about the polymerizability and polymer-monomer equilibrium of bicyclic lactams are challenging [65][66][67] . For lactam 5-3S, no significant conversion was observed beneath a ratio A/M start of approximately 1:100, whereas even a ratio A/M start as small as 1:1200 (<0.1%) lead to a conversion of over 40% within 1 h for the stereoisomeric lactam 5-3R.…”

High-Tg PLA copolymers via base-catalyzed transesterification of PLA with 2,5,7-trioxabicyclo[2.2.2]octan-6-one

“…Hall and Okada systematically investigated the ROP of bicyclic lactones. [47][48][49][50][51][52][53][54][55] Recently, several other bicyclic lactones have also been synthesized and polymerized to generate high thermally stable polyesters with good mechanical properties and potential closed-loop recycling of monomers (Scheme 1). [55][56][57][58][59] The ROP of oxygen-containing bicyclic lactones (Scheme 1, VI-VIII) exhibits different polymerization behavior.…”

Fully Bio‐based Poly(ketal‐ester)s by Ring‐opening Polymerization of a Bicylcic Lactone from Glycerol and Levulinic Acid

“…[49] Ring-opening polymerization (ROP) of bicyclic lactones is a straightforward method to incorporate ring structures into polyester backbones. [50,51] Recently, we and others synthesized several new bicyclic lactones, and their controlled ROP has enabled the synthesis of high molar mass and high thermally stable polyesters with good mechanical properties and closedloop recycling properties. [52][53][54][55][56][57][58] Here, we show that by synthesizing a bicyclic lactone from LevA and glycerol, conducting the ROP of this monomer under mild conditions, high molar mass poly(ketal-ester) with good thermal properties and enhanced degradability characteristics under acidic conditions can be produced.…”

“…Ring‐opening polymerization (ROP) of bicyclic lactones is a straightforward method to incorporate ring structures into polyester backbones [50,51] . Recently, we and others synthesized several new bicyclic lactones, and their controlled ROP has enabled the synthesis of high molar mass and high thermally stable polyesters with good mechanical properties and closed‐loop recycling properties [52–58] .…”