Precision synthesis of sustainable thermoplastic elastomers from lysine‐derived monomers

Abstract

Novel renewable thermoplastic elastomers were synthesized by sequential polymerization of lysine‐ and itaconic acid‐derived monomers. Ring‐opening polymerization of lysine‐based O‐carboxyanhydride monomer using diethylene glycol as an initiator gave well‐defined α,ω‐dihydroxy functionalized lysine‐derived polyesters. The Mn of these polyesters increased with the monomer conversion while retaining relatively narrow molecular weight distributions. Based on the successful controlled polymerization and esterification of α,ω‐dihydroxy with 2‐bromoisobutyryl bromide, the resultant Br‐PL‐Br macroinitiator was used for the atom transfer radical polymerization of N‐phenylitaconimide (PhII). Three poly(N‐phenylitaconimide)‐b‐polyester‐b‐poly(N‐phenylitaconimide) triblock copolymers were prepared containing 12 − 25 mol% PPhII, as determined by 1H NMR spectroscopy. The properties of the obtained triblock copolymer are evaluated as high‐performance and renewable thermoplastic elastomer materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 349–355

Physical Behavior of Triblock Copolymer Thermoplastic Elastomers Containing Sustainable Rosin-Derived Polymethacrylate End Blocks

“…The manufacturing and disposal of petroleum-derived products have undesired environmental impacts, which promote development of TPEs from sustainable sources. , Recently, enormous research efforts have focused on sustainable triblock copolymer-based TPEs. For example, fatty acid or vegetable oil-derived polyacrylates, , plant-based poly­(δ-decalactone), − plant-oil-derived polymyrcene, amino acid-derived polyesters, and mint-derived poly­(menthide) , were found to be appropriate replacements for the rubbery midblock due to their low glass transition temperature ( T g ). The development of sustainable glassy end blocks has emphasized lactide and lactone derivatives. − Some other studies include glassy end blocks composed of tulip-derived poly­(α-methylene-γ-butyrolactone), bicyclic sugar-derived poly­(methacrylic isosorbide), salicylic acid-derived poly­(acetylsalicylic ethyl methacrylate), terpene-derived poly­(α-methyl- p -methylstyrene), and glucose-derived poly­(glucose-6-acrylate-1,2,3,4-tetraacetate) …”

“…9,10 Recently, enormous research efforts have focused on sustainable triblock copolymer-based TPEs. For example, fatty acid or vegetable oil-derived polyacrylates, 11,12 plant-based poly(δ-decalactone), 13−15 plant-oil-derived polymyrcene, 16 amino acid-derived polyesters, 17 and mint-derived poly-(menthide) 18,19 were found to be appropriate replacements for the rubbery midblock due to their low glass transition temperature (T g ). The development of sustainable glassy end blocks has emphasized lactide and lactone derivatives.…”

Toward Green Atom Transfer Radical Polymerization: Current Status and Future Challenges

“…[ 87 ] Fully biobased TPEs were achieved from various bioderived monomers (e.g., lysine, itaconate, and furfural) by combining ATRP and click chemistry or ROMP. [ 88 ] Copolymer compositions were optimized to obtain desired, up to 700% elongations. [ 88a ]…”

Synthesis of Sustainable Polyesters via Organocatalytic Ring‐Opening Polymerization of O‐carboxyanhydrides: Advances and Perspectives

“…Because of the structural similarity between α‐amino acids and α‐hydroxy acids, much effort has been made to prepare new OCAs from amino acids. So far, OCAs can be furnished from lactic acid, [ 44,45 ] mandelic acid, [ 31,46 ] phenylalanine, [ 29,31 ] serine, [ 47 ] malic acid, [ 48 ] glutamic acid, [ 18 ] tyrosine, [ 33,49,50 ] and lysine [ 51,52 ] (Figure 1B). In general, recrystallization is sufficient to achieve pure OCA monomers.…”