Filippi Luca, Meier Michael A R
Karlsruhe Institute of Technology (KIT), Institute for Biological and Chemical Systems - Functional Molecular Systems (IBCS-FMS), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (IOC), Materialwissenschaftliches Zentrum (MZE), Straße am Forum 7, 76131, Karlsruhe, Germany.
Macromol Rapid Commun. 2021 Feb;42(3):e2000440. doi: 10.1002/marc.202000440. Epub 2020 Sep 16.
In this work, a straightforward and efficient synthesis approach to renewable non-isocyanate polyurethanes (NIPUs) is described. For this purpose, suitable and renewable carbamate monomers, possessing two double bonds, are synthesized from hydroxamic fatty acid derivatives via the Lossen rearrangement in a one-step synthesis, and sustainable dithiols are synthesized from dialkenes derived from renewable feedstock (i.e., limonene and 1,4-cyclohexadiene). Subsequently, the comonomers are polymerized with the highly efficient thiol-ene reaction to produce NIPUs with M values up to 26 kg mol bearing thioether linkages. The main side product of the Lossen rearrangement, a symmetric urea, can also be polymerized in the same fashion. Important in the view of sustainability, the monomer mixture can also be used directly, without separation. The obtained polymers are characterized by NMR, attenuated total reflection-infrared spectroscopy, differential scanning calorimetry, and size exclusion chromatography.
在这项工作中，描述了一种直接且高效的可再生非异氰酸酯聚氨酯（NIPU）合成方法。为此，通过一步合成中的洛森重排，由异羟肟酸脂肪酸衍生物合成具有两个双键的合适且可再生的氨基甲酸酯单体，并由源自可再生原料（即柠檬烯和1,4 - 环己二烯）的二烯烃合成可持续的二硫醇。随后，通过高效的硫醇 - 烯反应使共聚单体聚合，以生产具有高达26 kg/mol的M值且带有硫醚键的NIPU。洛森重排的主要副产物，一种对称脲，也可以以相同方式聚合。从可持续性角度来看很重要的是，单体混合物也可直接使用，无需分离。所获得的聚合物通过核磁共振、衰减全反射红外光谱、差示扫描量热法和尺寸排阻色谱进行表征。
