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

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".

Pinenes: Abundant and Renewable Building Blocks for a Variety of Sustainable Polymers

“…Commercial polymers of these compounds,"terpene resins", are normally obtained by Lewis acid-catalyzed polymerization. Importantly,awide variety of other terpene-based polymers have also been described, for example,p olymers based on menthone, [59][60][61][62][63] on related limonene, [64][65][66][67] myrcene, [68,69] carvone [70] (Scheme 1B), and others. Accordingly,a pplications of classical cationic or radical polymerization of pinenes for the preparation of aliphatic cycloolefin polymers have been described for decades [45][46][47][48][49][50][51][52] and also different copolymerizations were studied in detail.…”

Pinene: reichlich vorhandene und erneuerbare Bausteine für eine Vielzahl an nachhaltigen Polymeren

“…a-Pinen und b-Pinen sind die Hauptbestandteile von Te rpentin-Öl( aus Pinien/Kiefern) und ihre Produktion liegt derzeit bei ca. B. Polymere basierend auf Menthon, [59][60][61][62][63] auf dem verwandten Limonen, [64][65][66][67] Myrcene, [68,69] Carvone [70] (Schema 1B)und anderen. [38][39][40][41][42] Diese bicyclischen Verbindungen sind somit die am häufigsten vorkommenden natürlichen Te rpene,d ie aus nicht essbaren Pflanzenteilen in vielen Tonnen erhalten werden kçnnen.…”

“…Wichtigerweise ist auch schon eine große Vielfalt an anderen Terpene-basierten Polymeren beschrieben worden, z. B. Polymere basierend auf Menthon, [59][60][61][62][63] auf dem verwandten Limonen, [64][65][66][67] Myrcene, [68,69] Carvone [70] (Schema 1B)und anderen. [71] Eine nähere Betrachtung der Polymerisationen von diesen und verwandten Te rpenen und ihren Derivaten würde den Rahmen dieses Kurzaufsatzes übersteigen -d iese Studien wurden bereits anderswo detailliert beschrieben.…”

Coordination Polymerization of Renewable 3‐Methylenecyclopentene with Rare‐Earth‐Metal Precursors

“…[1][2][3][4][5] Bioresourced polymers usually have functional groups,which are anticipated to be excellent building blocks for constructing advanced materials.T erpenes including a-pinene, bpinene,l imonene,m yrcene,a nd camphene are ac lass of abundant biomass monomers found in many natural plant oils (Scheme 1), which share the same elementary unit with isoprene,a nd thus become an important monomer reservoir. Therefore,e xploitation of renewable polymers derived mostly or entirely from bioresources has attracted considerable attention from industry and academic sectors.…”

“…Therefore,e xploitation of renewable polymers derived mostly or entirely from bioresources has attracted considerable attention from industry and academic sectors. [1][2][3][4][5] Bioresourced polymers usually have functional groups,which are anticipated to be excellent building blocks for constructing advanced materials.T erpenes including a-pinene, bpinene,l imonene,m yrcene,a nd camphene are ac lass of abundant biomass monomers found in many natural plant oils (Scheme 1), which share the same elementary unit with isoprene,a nd thus become an important monomer reservoir. [1,5,6] Although much effort has been focused on exploring the catalytic chemical processes of terpene, [7] only few reports concern terpene compounds as starting monomers for polymerizations.…”