Waxes from Long-Chain Aliphatic Difunctional Monomers

[Image: see text] Petrochemical polyethylene waxes (M(n) = 800–8000 g/mol for commercial Ziegler waxes) as additives, lubricants, and release agents are essential to numerous products and production processes. The biodegradability of this class of compounds when unintentionally released to the environment is molar mass dependent and subject to ongoing discussions, and alternatives to conventional polyethylene waxes are desirable. By employing bottom-up and top-down approaches, that is nonstoichiometric A(2) + B(2) polycondensation and chain scission, respectively, linear waxes with multiple in-chain ester groups as biodegradation break points could be obtained. Specifically, waxes with 12,12 (WLE-12,12, WLE = waxes linear ester) and 2,18 (WLE-2,18) carbon atom linear ester repeat unit motifs were accessible over a wide range of molar masses (M(n) ≈ 600–10 000 g/mol). In addition to the molar mass, the type of end group functionality (i.e., methyl ester, hydroxy, or carboxylic acid end groups) significantly impacts the thermal properties of the waxes, with higher melting points observed for carboxylic acid end groups (e.g., T(m) = 83 °C for carboxylic acid-terminated WLE-12,12 with M(n,NMR) = 1900 g/mol, T(m) = 92 °C for WLE-2,18 with M(n,NMR) = 2200 g/mol). A HDPE-like orthorhombic crystalline structure and rheological properties comparable to a commercial polyethylene wax suggest WLE-12,12 and WLE-2,18 are viable biodegradable and biosourced alternatives to conventional, petrochemical polyethylene waxes.