Structure‐Performance Guided Design of Sustainable Plasticizers from Biorenewable Feedstocks

The search for more sustainable solutions for plastics production, moving away from petrochemical feedstocks as today's major raw material basis, is a research area of increasing interest. This task goes far beyond the issue of designing greener polymers and their related monomers as tailor‐made plastics require, besides the polymer itself, further components. These additives also need to be switched from typically fossil‐based to bio‐renewable raw materials. One of such necessary components for many applications are plasticizers, and a major application of them is related to polyvinyl chloride (PVC) as one of the leading polymers with a wide range of applications. Typically today‘s plasticizers are based on fossil feedstocks, and some of them such as specific ortho‐phthalates as the most important product class of plasticizers are now subject to restrictions and authorization by the EU's REACH legislation due to their toxicological profile. In this contribution, we report the synthesis and technical evaluation of alternative, novel bicyclic plasticizer candidates, which are fully accessible from renewable feedstocks. In detail, these new plasticizer target molecules are based on the use of the furan‐derivative 2‐methylfuran, maleic anhydride and 2‐ethylhexanol as bio‐based starting materials. The synthetic concept consists of an initial Diels‐Alder reaction with 2‐methylfuran and a subsequent hydrogenation and optional esterification step. The applied reactions are well‐known as economic and sustainable technologies. Thus, not only the starting materials (being of bio‐based origin) but also the selected reaction technologies for the syntheses of the target molecules are sustainable. Furthermore, a range of performance tests enabled an insight into structure‐performance relationships and revealed promising plasticizing properties of this new bio‐based plasticizer generation with, e. g., an attractive solution temperature fulfilling the criterium for a “fast fuser” as well as good compatibility with PVC. Addressing the challenge of switching the raw material basis in plastics production from fossil to bio‐based feedstocks, the synthesis of bicyclic plasticizers, which are accessible from the biorenewable compounds 2‐methylfuran, maleic anhydride and 2‐ethylhexanol, is presented as well as their use in performance tests. Among involved reactions are Diels‐Alder reactions and hydrogenations.