TY - JOUR
T1 - Betulin-Based Thermoplastics and Thermosets through Sustainable and Industrially Viable Approaches
T2 - New Insights for the Valorization of an Underutilized Resource
AU - Curia, Silvio
AU - Dautle, Savanna
AU - Satterfield, Barry
AU - Yorke, Kelly
AU - Cranley, Cameron E.
AU - Dobson, Brittany E.
AU - La Scala, John J.
AU - Soh, Lindsay
AU - Gordon, Melissa B.
AU - Stanzione, Joseph F.
N1 - Funding Information:
The studies leading to these results have received funding from the U.S. Army Research Laboratory via Cooperative Agreements W911NF-16-2-0225 and W911NF-14-2-0086. S.C., S.D., B.S., K.Y., and J.F.S. are indebted to Dr. Paul Bertin and Elevance Renewable Sciences Inc. for kindly providing the ODDAc monomer used in this work and also thank Prof. Jonathan Foglein and the Department of Chemistry at Rowan University for providing access and support in the use of the NMR spectrometer. Furthermore, S.C. and J.F.S. acknowledge Waters Corporation and TA Instruments, especially Michael Dowling and Rich Mendelsohn, for their continued support in use of their instruments that we have in the Sustainable Materials Research Laboratory at Rowan University. C.E.C., B.E.D., and M.B.G. gratefully acknowledge Lafayette College and the Excel Scholars Program.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/10/7
Y1 - 2019/10/7
N2 - The use of naturally available building blocks for the preparation of high-performance polymers is attracting increasing interest. Betulin (or betulinol) is a naturally occurring, large, nonaromatic diol with a pentacyclic ring structure that can be extracted in high percentages from the bark of birch trees. Here we demonstrate that betulin can be used to prepare polyesters with exceptional thermal attributes through industrially viable and scalable melt polycondensation reactions. Specifically, betulin-based thermoplastics were synthesized using succinic acid, adipic acid, 1,12-dodecanedioic acid, and 1,18-octadecanedioic acid as comonomers and showed good solubility in common industrial solvents. Additionally, betulin-based polyester thermosets were formulated via the incorporation of glycerol as a cross-linker. A systematic study evaluating the effect of various comonomers on the structure-property relationships of these betulin-derived thermoplastics (Mws ranging from 7500 g mol-1 to about 60,000 g mol-1) and thermosets (E′ at room temperature ranging from 2.0 to 780 MPa) reveals that betulin is a renewable and versatile platform chemical for the preparation of high-performance polymeric materials. Indeed, these materials displayed glass transition temperatures ranging from 20 °C to about 215 °C, thermal stabilities in excess of 300 °C in both N2 and air, and Young's moduli and tensile strengths exceeding 600 MPa and 9 MPa, respectively. These investigations provide new insights into the rational design of approaches toward betulin-based products for high-performance polymer applications.
AB - The use of naturally available building blocks for the preparation of high-performance polymers is attracting increasing interest. Betulin (or betulinol) is a naturally occurring, large, nonaromatic diol with a pentacyclic ring structure that can be extracted in high percentages from the bark of birch trees. Here we demonstrate that betulin can be used to prepare polyesters with exceptional thermal attributes through industrially viable and scalable melt polycondensation reactions. Specifically, betulin-based thermoplastics were synthesized using succinic acid, adipic acid, 1,12-dodecanedioic acid, and 1,18-octadecanedioic acid as comonomers and showed good solubility in common industrial solvents. Additionally, betulin-based polyester thermosets were formulated via the incorporation of glycerol as a cross-linker. A systematic study evaluating the effect of various comonomers on the structure-property relationships of these betulin-derived thermoplastics (Mws ranging from 7500 g mol-1 to about 60,000 g mol-1) and thermosets (E′ at room temperature ranging from 2.0 to 780 MPa) reveals that betulin is a renewable and versatile platform chemical for the preparation of high-performance polymeric materials. Indeed, these materials displayed glass transition temperatures ranging from 20 °C to about 215 °C, thermal stabilities in excess of 300 °C in both N2 and air, and Young's moduli and tensile strengths exceeding 600 MPa and 9 MPa, respectively. These investigations provide new insights into the rational design of approaches toward betulin-based products for high-performance polymer applications.
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U2 - 10.1021/acssuschemeng.9b03471
DO - 10.1021/acssuschemeng.9b03471
M3 - Article
AN - SCOPUS:85073103274
VL - 7
SP - 16371
EP - 16381
JO - ACS Sustainable Chemistry and Engineering
JF - ACS Sustainable Chemistry and Engineering
SN - 2168-0485
IS - 19
ER -