Stereocomplexed Poly(Limonene Carbonate): A Unique Example of the Cocrystallization of Amorphous Enantiomeric Polymers

Abstract

Abstract:We report the cocrystallization of the regio-and stereoregular chiral copolymer poly(limonene carbonate). To the best of our knowledge, this marks the first example of an amorphous, enantiomerically pure polymer that becomes crystalline upon stereocomplexation with its complementary enantiomer. By analyzing X-ray powder diffraction data, we propose a packing model in which sheets of enantiopure chains interdigitate with layers of the opposite enantiomer, forming a "steric zipper".

Recent Progress in Sustainable Polymers Obtained from Cyclic Terpenes: Synthesis, Properties, and Application Potential

“…[99] Powder XRD data showed ap acking modelw ith a" steric zipper", which meantt hat sheetso fe nantiopure chainsi nterdigitated with layers of the other enantiomer.T he use of LO for polyaddition reactions is explainedi n the next section.…”

CO2-fixation into cyclic and polymeric carbonates: principles and applications

“…[289][290][291] More recently, increasing attention has been given to the use of bio-based epoxides for the synthesis of cyclic and polymeric carbonates by reaction with CO 2 . Among these, limonene oxide and limonene dioxide 87,234,238,239,247,260,292 can be produced through the wellstudied epoxidation of (R)-(+)-limonene, a naturally occurring terpene that is extracted from e.g. citrus peels (generated as abundant waste of the juice extraction from orange and other citrus fruits).…”

Polymers of Limonene Oxide and Carbon Dioxide: Polycarbonates of the Solar Economy

“…In 2015, along with Auriemma and co-workers in Italy, Coates reported also the first example of co-crystallization of two amorphous enantiomeric polymers in two specular polymeric chains (Scheme 1) by precipitating a 1:1 mixture of regio-and stereoregular amorphous PLC copolymers, namely poly(1S,2S,4R-limonene carbonate) (PSLC) and poly(1R,2R,4Slimonene carbonate (PRLC), dissolved in n-hexane. [16] The replacement of an oil-derived oxirane with a terpene-based epoxide such as 1,2 limonene oxide, configurates as a drop-in solution similar to those highly desirable in the chemical industry when dealing with new catalytic productions proposed by researchers to renew synthetic processes in use. [17] The same holds true for the oxidation protocol proposed by Kleij, in which limonene oxide is copolymerized with CO2 with a binary catalyst system comprised of an aminotriphenolate Al(III) complex combined with bis-triphenylphosphine iminium chloride (PPNCl) to access different grades of PLC with molecular weights ranging from 1.3 to 15.1 kg/mol.…”