Monomer Design Strategies to Create Natural Product-Based Polymer Materials Cite This: Nat
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Natural Product Reports REVIEW Monomer design strategies to create natural product-based polymer materials Cite this: Nat. Prod. Rep.,2017,34,433 Samantha L. Kristufek, Kevin T. Wacker, Yi-Yun Timothy Tsao, Lu Su and Karen L. Wooley* Covering: 2010–Aug. 2016 In an effort towards enhancing function and sustainability, natural products have become of interest in the field of polymer chemistry. This review details the blending of chemistries developed through synthetic organic chemistry and polymer chemistry. Through synthetic organic chemical transformations, such as functional group interconversion, a protection/deprotection series, or installation of a functional group, Received 4th November 2016 various designs towards novel, synthetic, bio-based polymer systems are described. This review covers DOI: 10.1039/c6np00112b several classifications of natural products – oils and fatty acids, terpenes, lignin, and sugar derivatives – rsc.li/npr focusing on exploring monomers prepared by one or more synthetic steps. 1. Introduction – the power of synthetic organic chemistry to 4.4 Vanillin monomers transform materials science 4.5 Ferulic acid 2. Oils and fatty acids 4.6 Eugenol 2.1 Introduction – oils and fatty acids 4.7 Creosol 2.2 Saturated fatty acids 4.8 Sinapyl alcohol derivatives 2.3 Monounsaturated fatty acids: polymerization through 5. Sugar derivatives carboxylic acid-derived functional groups 5.1 Introduction – sugar derivatives 2.4 Monounsaturated fatty acids: polymerization through 5.2 Mono-substituted monomers and corresponding alkene-derived functional groups glycopolymers 2.5 Monounsaturated fatty acids: polymerization through 5.3 Di-substituted monomers and corresponding polymers both acid- and alkene-derived functional groups 6. Conclusions and future directions 2.6 Polyunsaturated fatty acids 7. Acknowledgements 2.7 Algae oil 8. References 3. Terpenes 3.1 Introduction – terpenes 3.2 Limonene 1. Introduction – the power of 3.3 Tulipalin A synthetic organic chemistry to 3.4 Pinene 3.5 Carvone and menthone transform materials science 3.6 Resin acids In what has been coined as the age of scalability in organic 3.7 Terpinene and phellandrene chemistry,1 the development of scalable transformations for 3.8 Camphor natural products and their derivatives is more important than 3.9 Linear terpenes ever in materials science. The practicality of using functional- 4. Lignin ized natural products for polymerization is more of a reality as 4.1 Introduction – lignin syntheses and isolation techniques become more concise. The 4.2 Vanillin ever expanding chemical toolbox of novel reactions is also 4.3 Vanillin dimers powerful for monomer synthesis. Whether it is the synthesis of a natural product with inherent polymerizable groups from readily-available starting materials or the functionalization of Department of Chemistry, Department of Chemical Engineering, Department of Materials Science & Engineering, Texas A&M University, College Station, Texas an isolated compound, scalability is the key to creating 77842-3012, USA. E-mail: [email protected] sustainable society-enhancing polymeric materials. While this This journal is © The Royal Society of Chemistry 2017 Nat. Prod. Rep.,2017,34,433–459 | 433 Natural Product Reports Review review focuses on the functionalization of naturally-derived materials and their derivatives as the monomer units. Bio- compounds, introducing sustainability in the syntheses of based materials are dened by the ASTM: “amaterialisan polymeric materials encompasses a vast scope of topics organic material in which carbon is derived from a renewable including greener solvents2 or catalyst design.3,4 resource via biological processes. Bio-based materials include Implementing the use of natural products for the replace- all plant and animal mass derived from CO2 recently xed via ment of petrochemical-based monomers has the potential to photosynthesis, per denition of a renewable resource”.5 decrease the dependence on fossil fuels and increase the Specically, the introduction of bio-based materials leads to number of material applications of more renewable resources. the potential to remove some petrochemical-based compo- One way of expanding the content of natural products in nents and take advantage of the renewability of natural polymeric materials is through the incorporation of bio-based products. There are several examples of naturally-sourced monomers currently on the market, such as Coca-Cola natural sourcing part of the poly(ethylene terephthalate) in plastic Samantha L. Kristufek obtained bottle production.6 In another example, the naturally-derived her B.S. in Chemistry in 2011 compound, isosorbide, is being utilized by Mitsubishi from Penn State Erie, The Beh- Chemical7 in polycarbonate materials. Both academic and rend College in Erie, Pennsylva- industrial research have made great strides in the area of bio- nia. She moved to Texas A&M based materials, however, the myriad natural products University and obtained a Ph.D. generate boundless directions for the synthesis of polymeric under the direction of Professor materials. Karen L. Wooley in 2017, where Beyond the replacement of petrochemical-based materials, she worked on the synthesis of the synthesis of novel materials from natural products has the poly(phenolic carbonate)s and potential to yield novel reactions/methodologies, and ultimately cross-linked epoxy networks from the natural starting material Dr Lu Su obtained her B.S. in quercetin for advanced engi- neering applications. She is currently a postdoctoral researcher 2009 in Northwestern Poly- under the direction of Professor Frank Caruso at The University of technical University and then Melbourne. completed her Ph.D. in polymer chemistry and physics under the supervision of Professor Ming Kevin T. Wacker obtained his B.A. Jiang in 2014 at Fudan University in Chemistry in 2013 from in Shanghai, China. Her Ph.D. Washington University in Saint research was on glycopolymer- Louis, in Saint Louis, Missouri. based self-assembly chemistry. He moved to Texas A&M Univer- She moved to Texas A&M sity in 2013 to pursue a Ph.D. University in 2014 to undertake under the supervision of a postdoctoral position under the Professor Karen L. Wooley, where direction of Professor Karen L. Wooley, where she is currently he is currently working on the working on the synthesis of poly(D-glucose carbonate)s towards development of natural product- biomedical applications. based polymers, particularly from neolignans, for potential biomedical and engineering Karen L. Wooley received a B.S. applications. in Chemistry from Oregon State University in 1988 and a Ph.D. in polymer/organic chemistry from Yi-Yun Timothy Tsao obtained Cornell University in 1993. She his B.S. in Chemistry in 2012 began as an Assistant Professor from National Taiwan University at Washington University in St. in Taipei, Taiwan. In 2013, he Louis in 1993, was promoted in joined the group of Professor 1999 to Full Professor, and was Karen L. Wooley at Texas A&M installed as a James S. McDon- University to pursue his Ph.D., nell Distinguished University and he is working on the devel- Professor in Arts & Sciences in opment of DNA-analog polymeric 2006. In 2009, Karen relocated to materials for novel degradable Texas A&M University, undertaking a position as the W. T. Doherty- polymer-based nanostructures. Welch Chair in Chemistry, and being awarded the title of University Distinguished Professor in 2011. 434 | Nat. Prod. Rep.,2017,34,433–459 This journal is © The Royal Society of Chemistry 2017 Review Natural Product Reports lead to materials with emergent, unforeseen properties. The introduction of new functionalities, therefore, synthetic routes sheer chemical, structural, and stereochemical diversity of from natural oils to synthetic monomers can lead to new natural products compared to petrochemicals from which properties of the corresponding polymeric materials, to allow polymers are synthesized greatly lends itself toward the devel- them to be utilized in demanding applications. opment of these potentially new processes and materials from The main structural component of oils is triglyceride, which bio-based sources. Designing bio-based monomers requires consists of glycerol and fatty acids,21–24 and further functional innovation to maintain high percentages of biomass in the groups in addition to the carboxylic and alkene groups of the materials, which can be introduced through developing new fatty acids are desirable, for the aim of developing new mono- chemistry. For example, Hoye and co-workers explored the mers and decreasing the reliance on petrochemical sources. Diels–Alder (DA) reaction of itaconic anhydride with various Hence, examples of chemical modication based on the furans through a study of the kinetic and thermodynamic carboxylic group and/or double bond of fatty acids that enables properties of the reaction.8 The compounds developed through the synthesis of a variety of monomers for the development of this novel chemistry can later be utilized in the polymerizations polymers25 will be discussed. Fatty acid composition depends of several different polymer classes. on the source of oils (Table 1),26 and they can be classied as Regardless of the rationalization for the use of natural saturated, monounsaturated, and polyunsaturated fatty acids. products in materials science applications, each natural In this section, fatty acids from common natural resources such product is initially limited in its potential nal application,