Identification of Known and Novel Monomers for Poly(hydroxyurethanes) from Biobased Materials

Sourcing
polymers from biobased materials is desirable for a transition
to a more sustainable world. However, finding new monomers sourced
from biobased molecules requires extensive experimental effort, due
to the fact that most biomolecules lack the functional groups or properties
needed to serve as a monomer in a particular polymeric system without
chemical modification. Here, we demonstrate a computational screening
method to obtain monomers of a nonisocyanate polyurethane (NIPU),
polyhydroxyurethane (PHU), from biomolecules. Our method generates
candidate monomers from a list of 15 selected biobased starting molecules
by performing chemical transformations that are standard to chemical
catalysis and organic synthesis on these starting molecules and then
screening the results for molecules with moieties that can be used
as monomers for a PHU. Product molecules from two generations of reaction,
a total number of 22,571, were analyzed automatically to identify
molecules that have two or more epoxy or cyclic carbonate functional
groups as candidates for further derivatization. These 21 candidate
molecules were then subjected to another two generations of reaction,
producing a set of 17,913 additional molecules. Further scrutiny of
this set for desired functional groups characterizing PHUs and querying
against the PubChem database were carried out, and 15 known molecules
that are commercially available were identified, with the desirable
features that they are predicted to be derived from biobased starting
molecules in four or fewer steps. Moreover, molecule space generated
from this process was primarily comprised of molecules that were not
known to PubChem, indicating the framework also has the ability to
generate novel candidate monomers that originate from biobased starting
points.