Zinc-Mediated Allylation-Lactonization One-Pot Reaction to Methylene Butyrolactones: Renewable Monomers for Sustainable Acrylic Polymers with Closed-Loop Recyclability

ACS Polym Au. 2022 Apr 18;2(4):266-274. doi: 10.1021/acspolymersau.2c00001. eCollection 2022 Aug 10.


Despite biomass-derived methylene butyrolactone monomers having great potential in substituting the petroleum-based methacrylates for synthesizing the sustainable acrylic polymers, the possible industrial production of these cyclic monomers is unfortunately not practical due to moderate overall yields and harsh reaction conditions or a time-consuming multistep process. Here we report a convenient and effective synthetic approach to a series of biomass-derived methylene butyrolactone monomers via a zinc-mediated allylation-lactonization one-pot reaction of biorenewable aldehydes with ethyl 2-(bromomethyl)acrylate. Under simple room-temperature sonication conditions, near-quantitative conversions (>90%) can be accomplished within 5-30 min, providing pure products with high isolated yields of 70-80%. Their efficient polymerizations with a high degree of control and complete chemoselectivity were enabled by the judiciously chosen Lewis pair catalyst based on methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) [MeAl(BHT)2] Lewis acid and 3-diisopropyl-4,5-dimethylimidazol-2-ylidene (I i Pr) Lewis base, affording new poly(methylene butyrolactone)s with high thermal stability and thermal properties tuned in a wide range as well as pendant vinyl groups for postfunctionalization. Through the development of an effective depolymerization setup (370-390 °C, ca. 100 mTorr, 1 h, a muffle furnace), thermal depolymerizations of these polymers have been achieved with monomer recovery up to 99.8%, thus successfully constructing sustainable acrylic polymers with closed-loop recyclability.

PMID:36855566 | PMC:PMC9955236 | DOI:10.1021/acspolymersau.2c00001


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