Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties

Abstract

Hybrid monomer design is shown to be a powerful approach to develop robust circular plastics without yielding to common property trade-offs by hybridizing parent monomer structures to an offspring monomer that can unify conflicting (de) polymerizability and performance properties.

Chemically recyclable polyesters from CO2, H2, and 1,3-butadiene

“…Polymers containing heteroatoms in their backbones, 5 , 6 , 7 especially polyesters, 8 , 9 , 10 featured with readily cleavable carboxylic ester backbone linkages, are excellent candidates for recycling. Therefore, making new polyesters from CO 2 and cheap bulk chemicals as co-feedstocks, especially large-volume olefins, such as ethylene and 1,3-butadiene, that can be derived from biomass, has long been pursued over the past several decades.…”

O‐to‐S Substitution Enables Dovetailing Conflicting Cyclizability, Polymerizability, and Recyclability: Dithiolactone vs. Dilactone

“…To address this energyintensive challenge and depolymerizability/performance trade-off,f used-ring gBL derivatives were developed to improve polymerizability and polyester crystallinity but still maintain the full chemical recyclability (Figure 1). [6] Similar advances are achieved using bridged-ring [5,7] or geminaldimethyl-substituted [8] thiolactone monomers.T hese strategies are highly effective in specific cases,b ut they each rely on specifically designed monomers,t hereby limiting their generality.A dditionally,t op roduce crystalline recyclable polymers requires either stereocomplexation of enantiomers of chiral polymers in astoichiometric ratio or the burdensome and exquisite stereoselective polymerization of the racemic monomer. [6a,9] As ac onsequence,m ore general strategies for designing chemically recyclable polymers that defy aforementioned tradeoffs between the monomerscyclizability and polymerizability and the polymersd epolymerizability and properties are highly required.…”

Chemically recyclable polymer materials: polymerization and depolymerization cycles

“…Using the same bridged ring strategy, bridged [3.2.1]bicyclic lactone, 6-oxabicyclo[3.2.1]octan-7-one (BiL), has been shown to be both polymerizable and depolymerizable (Scheme 17). 145 In order to reduce epimerization, the polymerization used metal catalysts (La, Y) instead of organocatalyst (TBD). Combined La[N(SiMe 3 ) 2 ] 3 with the co-initiator BnOH, the polymerization at room temperature in toluene with [BiL]/[La]/ [BnOH] = 300/1/3 gave 92% conversion after 8 h, delivering the corresponding polymer with a M n of 13.1 kg mol −1 and narrow dispersity of 1.10.…”