Two homopolyesters and a series of novel random copolyesters
were
synthesized from two bio-based diacid esters, dimethyl 2,5-furandicarboxylate,
a well-known renewable monomer, and dimethyl 2,2′-bifuran-5,5′-dicarboxylate,
a more uncommon diacid based on biochemical furfural. Compared to
homopolyesters poly(butylene furanoate) (PBF) and poly(butylene bifuranoate)
(PBBf), their random copolyesters differed dramatically in that their
melting temperatures were either lowered significantly or they showed
no crystallinity at all. However, the thermal stabilities of the homopolyesters
and the copolyesters were comparable. Based on tensile tests from
amorphous film specimens, it was concluded that the elastic moduli,
tensile strengths, and elongation at break values for all copolyesters
were similar as well, irrespective of the furan:bifuran molar ratio.
Tensile moduli of approximately 2 GPa and tensile strengths up to
66 MPa were observed for amorphous film specimens prepared from the
copolyesters. However, copolymerizing bifuran units into PBF allowed
the glass transition temperature to be increased by increasing the
amount of bifuran units. Besides enhancing the glass transition temperatures,
the bifuran units also conferred the copolyesters with significant
UV absorbance. This combined with the highly amorphous nature of the
copolyesters allowed them to be melt-pressed into highly transparent
films with very low ultraviolet light transmission. It was also found
that furan–bifuran copolyesters could be as effective, or better,
oxygen barrier materials as neat PBF or PBBf, which themselves were
found superior to common barrier polyesters such as PET.
The functionalization
of inexpensive potato protein concentrate
(PPC) is presented as a simple and easily scalable method to produce
bio-based superabsorbent powders. Five nontoxic acylating agents were
evaluated at different reaction temperatures for solvent-free acylation
of the protein. The best results were obtained for succinic anhydride
(SA) and a reaction temperature of 140 °C. These conditions resulted
in efficient functionalization that provided formation of a useful
network, which allowed high uptake of fluids and little material disintegration
during the uptake, that is, due to protein hydrolysis during the functionalization.
The SA-acylated PPC showed increased water and saline swelling capacities
of 600 and 60%, respectively, as compared to untreated PPC. The acylated
potato protein also showed a saline liquid holding capacity of approximately
50% after centrifugation at 1230 rpm for 3 min, as well as a significant
blood swelling capacity of 530%. This blood swelling represents more
than 50% of that of a commercial fossil-based superabsorbent (SAP)
used for blood absorption in sanitary health products. The swelling
properties of these inexpensive protein-based acylated materials highlight
their potential as sustainable SAP materials (from industrial side-streams)
in applications such as daily care products that are currently dominated
by fossil-based SAPs.
Virgin biopolymers are often brittle and therefore need the addition of plasticizers to obtain the required mechanical properties for practical applications, for example, in bags and disposable kitchen items. In this article, based on a combined experimental and modeling approach, it is shown that it is possible to rank molecules with respect to their plasticization efficiency (depression in glass transition temperature with PVT data and reduced stiffness and strength) by using molecular dynamics simulations. Starch was used as the polymeric matrix material due to its promising potential as a sustainable, eco-friendly, biobased replacement for fossil-based plastics. Three polyols (glycerol, sorbitol, and xylitol), two ethanolamines (tri-and diethanolamine), and glucose were investigated. The results indicate that molecular simulations can be used to find the optimal plasticizer among a set of candidates or to design/identify better plasticizers in a complex polymer system. Glycerol was the most efficient of the six plasticizers, explained by it forming the least amount of hydrogen bonds, having the shortest hydrogen bond lifetimes and low molecular rigidity. Hence, not only was it possible to rank plasticizers, the ranking results could also be explained by the simulations.
Phthalate derivative plasticizers used in poly(vinyl chloride) (PVC) processing have been a subject of concern because of their possible toxicity. Hence, there is a growing interest toward new, nontoxic, "green" plasticizers. In this work, the performances of biobased plasticizers including esters of succinic, levulinic, oleic, and adipic acids were compared in reference to the conventional plasticizer bis(2-ethylhexyl) phthalate (aka dioctyl phthalate or DOP). For this purpose, molecular dynamics (MD) simulations were used to determine polymer/plasticizer interactions and to predict thermomechanical properties of polymer mixtures. The variation of glass temperatures (T g ) of the systems was investigated, and the stabilities of the polymer/ plasticizer mixtures were compared through the Flory−Huggins solubility parameter. The mechanical properties were investigated through nonequilibrium MD simulations. Young's modulus and yield strength values were predicted through stress−strain curves. The results suggest that succinic acid derivatives have the potential to replace phthalate derivatives due to their good solubility in PVC and their effectiveness in reducing the T g .
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