Functional Polymers and Polymeric Materials From Renewable Alpha-Unsaturated Gamma-Butyrolactones

Abstract

Sustainable chemistry requires application of green processes and often starting materials originate from renewable resources. Biomass-derived monomers based on five-membered γ-butyrolactone ring represent suitable candidates to replace sources of fossil origin. α-Methylene-γ-butyrolactone, β-hydroxy-α-methylene-γ-butyrolactone, and β-and γ-methyl-α-methylene-γ-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).

RDRP (Meth)acrylic Homo and Block Polymers from Lignocellulosic Sugar Derivatives

“…[ 85 ] MBL has been homopolymerized via radical, anionic, group transfer and coordination polymerizations in a similar manner to methacrylates. [ 86 ] The FRP of MBL produced polymers with a higher service temperature ( T g ≈ 190 °C) than those from PMMA (≈110 °C) due to the rigid lactone ring, which also provides the polymer with a good durability and a good refractive index.…”

Production and Polymerization of Biobased Acrylates and Analogs

“…The polymerization of methylene butyrolactones has been widely studied and led to several reviews. [ 16,381–386 ] Interest in this field has been sparked by the potential biosourcing of these monomers, associated with their numerous potential applications as fibers, films, low‐pressure laminating resins, [ 156 ] dental composites, [ 387 ] tougheners, [ 388 ] coatings, [ 389 ] optical fibers, [ 390 ] polymeric electrolytes, [ 391 ] thermoplastic elastomers, [ 392 ] superabsorbents, [ 393 ] or pressure‐sensitive adhesives. [ 394 ] Herein, we review the polymerization of MBL, γ‐MMBL, β‐MMBL, and other methylene butyrolactones in successive paragraphs.…”

Advances, Challenges, and Opportunities of Poly(γ-butyrolactone)-Based Recyclable Polymers

“…GBL derivatives (thermodynamic parameters) and the corresponding polymers (reaction conditions and properties) were summarized in Table . α-Methylene-γ-butyrolactone (MBL) (Δ H ° p = −5.9 kJ mol –1 , Δ S ° p = −40.1 J mol –1 K –1 , T c = −126 °C (1 M), ROP) is found naturally in tulips, which is the simplest member of the sesquiterpene lactone family. − MBL is a biomass-sourced bifunctional monomer, which enabled the postfunctionalization. However, due to the highly reactive exocyclic CC bond and a highly stable five-membered γ-butyrolactone, chemoselectivity between ROP and vinyl-addition polymerization (VAP) was a long-term challenge .…”