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Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized ?-butyrolactones.

ABSTRACT: Multivinyl-functionalized ?-butyrolactones, ?-vinyl-?-methyl-?-methylene-?-butyrolactone (?VMMBL) and ?-allyl-?-methyl-?-methylene-?-butyrolactone (?AMMBL), have been synthesized from biorenewable ethyl levulinate and effectively polymerized by Lewis pairs consisting of an organic N-heterocyclic carbene Lewis base and a strong organo-Lewis acid E(C6F5)3 (E?=?Al, B). This Lewis pair polymerization is quantitatively chemoselective, proceeds exclusively via polyaddition across the conjugated ?-methylene double bond without participation of the ?-vinyl or ?-allyl double bond, and produces high-molecular-weight functionalized polymers with unimodal molecular-weight distributions. The Al-based Lewis pair produces a polymer with approximately 5.5 times higher molecular weight than that produced by the B-based Lewis pair. The resulting vinyl-functionalized polymers are soluble in common organic solvents and stable at room temperature, and can be thermally cured into crosslinked materials.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

SUBMITTER: Gowda RR

PROVIDER: S-EPMC5540837 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones.

Gowda Ravikumar R RR Chen Eugene Y-X EY

Philosophical transactions. Series A, Mathematical, physical, and engineering sciences 20170801 2101

Multivinyl-functionalized γ-butyrolactones, γ-vinyl-γ-methyl-α-methylene-γ-butyrolactone (γVMMBL) and γ-allyl-γ-methyl-α-methylene-γ-butyrolactone (γAMMBL), have been synthesized from biorenewable ethyl levulinate and effectively polymerized by Lewis pairs consisting of an organic N-heterocyclic carbene Lewis base and a strong organo-Lewis acid E(C6F5)3 (E = Al, B). This Lewis pair polymerization is quantitatively chemoselective, proc ...[more]

PMID: 28739962

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Project description:Sustainable chemistry requires application of green processes and often starting materials originate from renewable resources. Biomass-derived monomers based on five-membered ?-butyrolactone ring represent suitable candidates to replace sources of fossil origin. ?-Methylene-?-butyrolactone, ?-hydroxy-?-methylene-?-butyrolactone, and ?- and ?-methyl-?-methylene-?-butyrolactones bearing exocyclic double bond are available directly by isolation from plants or derived from itaconic or levulinic acids available from biomass feedstock. Exocyclic double bond with structural similarity with methacrylates is highly reactive in chain-growth polymerization. Reaction involves the linking of monomer molecules through vinyl double bonds in the presence of initiators typical for radical, anionic, zwitterionic, group-transfer, organocatalytic, and coordination polymerizations. The formed polymers containing pendant ring are characterized by high glass transition temperature (T g > 195°C) and render decent heat, weathering, scratch, and solvent resistance. The monomers can also be hydrolyzed to open the lactone ring and form water-soluble monomers. Subsequent radical copolymerization in the presence of cross-linker can yield to hydrogels with superior degree of swelling and highly tunable characteristics, depending on the external stimuli. The five-membered lactone ring allows copolymerization of these compounds by ring opening polymerization to provide polyesters with preserved methylene functionality. In addition, both the lactone ring and the methylene double bond can be attacked by amines. Polyaddition with di- or multi-amines leads to functional poly(amidoamines) with properties tunable by structure of the amines. In this mini-review, we summarize the synthetic procedures for preparation of polymeric materials with interesting properties, including thermoplastic elastomers, acrylic latexes, stimuli-sensitive superabsorbent hydrogels, functional biocompatible polyesters, and poly(amidoamines).

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Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized ?-butyrolactones.

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Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones.

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