In a recent publication in the journal Nature Communications, a team of researchers led by Prof.

Gert-Jan Gruter from the Industrial Sustainable Chemistry group has taken a significant stride
towards the development of fully bio-based, rigid polyesters.

They have introduced a straightforward yet innovative synthesis strategy to overcome the
inherent low reactivity of secondary diols derived from bio-based sources. This advancement has
led to the creation of polyesters with excellent mechanical and thermal properties, as well as high
molecular weights. This approach facilitates the production of robust and long-lasting bio-based
plastics using readily available building blocks.

The research featured in the Nature Communications paper was conducted as part of the
RIBIPOL project, which received funding from the Dutch Research Council NWO, with
contributions from industry players such as LEGO and Avantium. LEGO's involvement is linked
to their pursuit of sustainable alternatives to fossil-derived plastics for their building bricks,
while Avantium is interested in applications involving bottles and films. The paper's lead author
is Ph.D. student Daniel Weinland, who completed his studies on October 27th. The RIBIPOL
project includes a total of five Ph.D. students, two of whom have recently defended their theses.

Crucial Role of Rigidity

Generally, polyester plastics are synthesized from small molecules known as dialcohols and
diacids. These monomers are combined in a condensation reaction, forming a lengthy polymer
chain with alternating molecular building blocks. The resulting macroscopic material properties
are influenced by both the number of building blocks within the polymer chain and the intrinsic
characteristics of the monomers.

The rigidity of the monomers is particularly crucial for creating firm, strong, and durable
plastics. Among potential bio-based monomers, the glucose-derived dialcohol isosorbide stands
out due to its highly rigid molecular structure and existing industrial availability.

Nonetheless, isosorbide's reactivity is relatively low, and over the past two decades, crafting
useful isosorbide-based polyesters has proven challenging. Achieving sufficiently long polymer
chains (for desired ductility) while incorporating substantial amounts of isosorbide (for strength
and durability) has been a significant obstacle.

Introducing Aryl Alcohol Incorporation

Weinland and his colleagues in the RIBIPOL project have overcome this hurdle by introducing
aryl alcohol into the polymerization process. This inclusion triggers the in situ formation of
reactive aryl esters, substantially enhancing end group reactivity during polycondensation—the
final stage of polyester synthesis. This innovation is particularly crucial because isosorbide's low
reactivity traditionally hinders chain growth during melt polyesterification. As a result, they have
successfully produced high molecular weight materials with significant fractions of the bio-
based, rigid secondary diol, even up to 100 mol%.

For the first time, they have managed to produce high molecular weight poly(isosorbide
succinate), a type of polyester derived from isosorbide and succinic acid. These resulting robust
plastics exhibit superior heat resistance compared to existing materials like PET, which is
especially relevant for processes such as bottle washing at temperatures up to 85°C. The
isosorbide-based polymers also showcase promising barrier and mechanical properties that
surpass those of common fossil-based materials.
The newly introduced polymerization approach outlined in the paper is characterized by its
operational simplicity and reliance on standard polyester synthesis equipment. It is suitable for
both established and innovative polyester compositions. The researchers anticipate the
exploration of previously unattainable polyester compositions based on monomers with low
reactivity, as well as the application of similar techniques to other polymer classes like
polyamides and polycarbonates.