Ring‐Opening Metathesis Polymerization of Biomass‐Derived Levoglucosenol

Abstract

The readily available cellulose‐derived bicyclic compound levoglucosenol was polymerized through ring‐opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass‐derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High‐molar‐mass polyacetals with apparent weight‐average molar masses of up to 100 kg mol−1 and dispersities of approximately 2 were produced despite the non‐living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 °C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment.

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

“…[8] Its alcohol derivative levoglucosenol (2,S cheme 1), on the other hand, was found to polymerize through ring-opening olefin metathesis polymerization (ROMP) to yield an amorphous thermoplastic polyacetal. [8] Levoglucosenol should, on af irst glance,a lso polymerize via the acetal functionality through cationic ring-opening polymerization (CROP). In fact, molecules with similar or related structures,t hat is,a nhydrosugars [9] and bicyclic ketals, [10] have been polymerized successfully through Lewis acid-catalyzed CROP.H owever,a ttempts to polymerize levoglucosenol (2)t hrough CROP failed.…”

“…CROP of 3 would then give the linear unsaturated polyacetal 4 with the proposed chemical structure shown in Scheme 1, which is potentially degradable [11] and could be further modified or crosslinked. [12] It is worth being mentioned that 3,l ike its precursor 2, [8] can also be polymerized through ROMP (preliminary data, not shown).…”

Cellulose‐Derived Functional Polyacetal by Cationic Ring‐Opening Polymerization of Levoglucosenyl Methyl Ether

“…[8] Its alcohol derivative levoglucosenol (2,S cheme 1), on the other hand, was found to polymerize through ring-opening olefin metathesis polymerization (ROMP) to yield an amorphous thermoplastic polyacetal. [8] Its alcohol derivative levoglucosenol (2,S cheme 1), on the other hand, was found to polymerize through ring-opening olefin metathesis polymerization (ROMP) to yield an amorphous thermoplastic polyacetal.…”

“…In fact, molecules with similar or related structures,t hat is,a nhydrosugars [9] and bicyclic ketals, [10] have been polymerized successfully through Lewis acid-catalyzed CROP.H owever,a ttempts to polymerize levoglucosenol (2)t hrough CROP failed. [12] It is worth being mentioned that 3,l ike its precursor 2, [8] can also be polymerized through ROMP (preliminary data, not shown). CROP of 3 would then give the linear unsaturated polyacetal 4 with the proposed chemical structure shown in Scheme 1, which is potentially degradable [11] and could be further modified or crosslinked.…”

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

“…[5][6][7] Theinstallation of adisulfide,phosphate,oracetal unit into 7and 8-membered cycloolefin derivatives results in degradable materials,b ut the monomers cannot homopolymerize to high molecular weights due to reduced ring strain. [11] The most successful strained monomer to date is Kiesslings bicyclico xazinone system, which features an easily modified synthetic handle for introducing fluorophores and bioactive epitopes ( Figure 1B). [11] The most successful strained monomer to date is Kiesslings bicyclico xazinone system, which features an easily modified synthetic handle for introducing fluorophores and bioactive epitopes ( Figure 1B).…”