Next Article in Journal
A Kinetic Approach in the Evaluation of Radical-Scavenging Efficiency of Sinapic Acid and Its Derivatives
Previous Article in Journal
Synthesis, X-ray Single Crystal Structure, Molecular Docking and DFT Computations on N-[(1E)-1-(2H-1,3-Benzodioxol-5-yl)-3-(1H-imidazol-1-yl)propylidene]-hydroxylamine: A New Potential Antifungal Agent Precursor
Previous Article in Special Issue
Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane) Copper Complex Grafted Solid Catalyst for Oxidative Polymerization of 2,6-Dimethylphenol
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Editorial

Renewable Green Platform Chemicals for Polymers

1
Department of Materials Science and Engineering, Monash University, Clayton, VIC 3800, Australia
2
PPG Australia, McNaughton Rd, Clayton, VIC 3168, Australia
3
School of Chemistry, Monash University, VIC 3800, Australia
*
Authors to whom correspondence should be addressed.
Molecules 2017, 22(3), 376; https://doi.org/10.3390/molecules22030376
Submission received: 21 February 2017 / Revised: 21 February 2017 / Accepted: 22 February 2017 / Published: 28 February 2017
(This article belongs to the Special Issue Frontier in Green Chemistry Approaches)
This Special Issue covered topics in the field of Green Chemistry. One of the 12 principles in Green Chemistry is “Safer Solvents and Auxiliaries” which is reasonably covered in this Special Issue and examples are shown using ionic liquids [1], water [2], and a solvent-free system [3]. Another principle, “Catalysis”, is also covered, showing that novel heterogeneous catalysts can be used in various reactions [4,5,6]. Non-covalent derivatives that can be applied to proceed “Less Hazardous Chemical Syntheses” are presented by one of the founders of Green Chemistry (J.C. Warner) in this Special Issue [7].
The principle “Use of Renewable Feedstocks” is not well covered in this Special Issue but it is important, especially for the green polymer syntheses. In the modern world, the polymer plays a ubiquitous role. Our day-to-day life is completely pervaded by polymers, most of which are derived from petrochemical sources. The continuously increasing demand for fossil fuels and associated environmental concerns has led research to identify alternative materials which are renewable, green and sustainable in terms of resourcing, production and end-use-applications. Biomass, from both land and sea, seems to be the most promising alternative to petrochemical-based resources in terms of renewability, production and impact on the environment [8].
To date, different types of renewable resources have been reported which can be used to make polymers, and some of their end products are already commercialized using natural polymers such as cellulose and its derivatives, silk, cotton, chitin and chitosan [9]. There are some other examples which also seem promising to assist in dealing with the challenges of renewable polymer productions. Itaconic acid (IA) is a naturally occurring organic compound which is non-toxic and is a promising renewable source for the synthesis of bio-based polymers [10]. By using the functional carboxylic acid groups, it can be modified or copolymerized into different polymers such as epoxy, amide, polyesters etc. Itaconic acid also has a double bond which can undergo free radical polymerization to produce both homo- and co-polymers with other monomers. Previously, itaconic acid was obtained by the distillation of citric acid but currently it can be produced industrially by the fermentation of carbohydrates, such as glucose, using Aspergillus terreus [11]. It can also be used as a platform chemical to produce chemicals such as itaconic diamide, itaconic anhydride, 2-methyl-1,4-butanediol, 2-methyl-1,4-butanediamine from which different polymers can be obtained [12]. Another important bio-based platform chemical is 5-hydroxymethyl furfural (HMF) (derived from hexoses, mainly fructose). HMF and its derivatives such as 2,5-furandicarboxylic acid (FDCA) have been listed as a “Top 10+4” bio-based chemical evaluated by U.S Department of Energy (DOE) [13]. HMF is considered as a strong platform chemical as it can be converted into different sustainable chemicals such as alkoxymethylfurfurals, 2,5-furandicarboxylic acid, 5-hydroxymethylfuroic acid (furanic derivatives) etc., and levulinic acid, adipic acid, 1,6-hexanediol, caprolactum and caprolactone (non-furanic derivatives) which can be used to make different polymers [14]. FDCA is found to be good replacement of terephthalic acid and is already being used commercially along with ethylene glycol to make 100% bio-based polyester [15]. The chemical structure of glycerol makes it a very interesting platform chemical for conversion into other chemicals and it can also be used directly in polycondensation reactions to make polyesters [16]. Depending on the modification, it can be converted into huge numbers of chemicals, such as tartronic acid, hydroxyethanoic acid and hydroxypyruvic acid (by oxidation reaction) for polyester synthesis; ethylene glycol, 1,2-propandiol and 1,2-propanediol (by hydrogenolysis reaction) for polyester and polyurethane synthesis; glycerol dimethacrylate (by transesterification reaction) for polyacrylate synthesis [17]. 3-Hydroxypropanoic acid (HPA) is also an interesting platform chemical which can be derived from glucose by enzymatic catalysis or fermentation. The bifunctionality of this chemical allows it to be be used to synthesize different platform chemicals for polymers by simple chemical transformation. It can be converted into 1,3-propanediol, malonic acid and 3-hydroxypropylamide for polyesters, and glycerol dimethylacrylate and glycidol for acrylates and epoxies [18]. HPA can be coupled with other acids to produce polyesters such as polytrimethylene terephthalate which has huge applications in fiber industries [19]. HPA can itself undergo a polycondensation reaction to form poly(3-hydroxypropanoic acid) which has a melting temperature of 77 °C and glass transition temperature of −22 °C. Levulinic acid (4-oxopentanoic acid) can be produced from lignocellulose waste at a low cost and is considered to be an important platform chemical because of its reactive nature [20]. Levulinic acid esters are used in food industries, as solvents and as plasticizers. It can be converted into 4-hydroxy pentanoic acid through hydrogenation reaction and 1,4-pentanediol which can be used to make polyesters [21]. α-Methylene-γ-valerolactone, which can be derived from levulinic acid, can undergo free radical polymerization and is thought to be an alternative to methylmethacrylate (MMA) [22].
There are other different platform chemicals such as lactides, and 1,4-diacids such as succinic and fumaric acids, glutamic and glucaric acids and sorbitols which can be converted into their corresponding counterparts with appropriate functional group modification, then transformed into the respective polymers [23]. Still, challenges remain in terms of the production of platform chemicals for polymers at large scale with low cost and sustainable conditions.

Acknowledgments

The Guest Editor Kei Saito wishes to thank all the authors for their contributions to this Special Issue, all the reviewers for their work in evaluating the submitted articles and the editorial staff of Molecules.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Potdar, M.K.; Kelso, G.F.; Schwarz, L.; Zhang, C.; Hearn, M.T.W. Recent developments in chemical synthesis with biocatalysts in ionic liquids. Molecules 2015, 20, 16788–16816. [Google Scholar] [CrossRef] [PubMed]
  2. Pinto, J.; Silva, V.L.M.; Silva, A.M.G.; Silva, A.M.S. Synthesis of (E)-2-styrylchromones and flavones by base-catalyzed cyclodehydration of the appropriate β-diketones using water as solvent. Molecules 2015, 20, 11418–11431. [Google Scholar] [CrossRef] [PubMed]
  3. Zhang, Y.; Wang, B.; Zhang, X.; Huang, J.; Liu, C. An efficient synthesis of 3,4-dihydropyrimidin-2(1H)-ones and thiones catalyzed by a novel brønsted acidic ionic liquid under solvent-free conditions. Molecules 2015, 20, 3811–3820. [Google Scholar] [CrossRef] [PubMed]
  4. Saito, K.; Miyamoto, K.; Nanayakkara, S.; Ihara, H.; Hearn, M.T.W. Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane) copper complex grafted solid catalyst for oxidative polymerization of 2,6-dimethylphenol. Molecules 2016, 21, 146. [Google Scholar] [CrossRef] [PubMed]
  5. Maeno, Z.; Mitsudome, T.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. Selective C–C coupling reaction of dimethylphenol to tetramethyldiphenoquinone using molecular oxygen catalyzed by Cu complexes immobilized in nanospaces of structurally-ordered materials. Molecules 2015, 20, 3089–3106. [Google Scholar] [CrossRef] [PubMed]
  6. Garg, B.; Bisht, T.; Ling, Y. Graphene-based nanomaterials as efficient peroxidase mimetic catalysts for biosensing applications: An overview. Molecules 2015, 20, 14155–14190. [Google Scholar] [CrossRef] [PubMed]
  7. Stoler, E.; Warner, J.C. Non-covalent derivatives: Cocrystals and eutectics. Molecules 2015, 20, 14833–14848. [Google Scholar] [CrossRef] [PubMed]
  8. Sheldon, R. Green and sustainable manufacture of chemicals. Green Chem. 2014, 16, 950–963. [Google Scholar] [CrossRef]
  9. Harmsen, P.; Hackmann, M.; Bos, H. Green building blocks of bio-based plastics. Biofuels Bioprod. Biorefin. 2014, 8, 306–324. [Google Scholar] [CrossRef]
  10. Medway, A.; Sperry, J. Heterocycle construction using the biomass-derived building block itaconic acid. Green Chem. 2014, 16, 2084–2101. [Google Scholar] [CrossRef]
  11. Willke, T.; Vorlop, K. Biotechnological production of itaconic acid. Appl. Microbiol. Biotechnol. 2001, 56, 289–295. [Google Scholar] [CrossRef] [PubMed]
  12. Geilen, F.; Engendahl, B.; Harwardt, A.; Marquardt, W.; Klankermayer, J.; Leitner, W. Selective and flexible transformation of biomass-derived platform chemicals by a multifunctional catalytic system. Angew. Chem. Int. Ed. 2010, 49, 5510–5514. [Google Scholar] [CrossRef] [PubMed]
  13. Werpy, T.; Peterson, G. Top Value Added Chemicals from Biomass Volume I—Results of Screening for Potential Candidates from Sugars and Synthesis Gas; National Renewable Energy Laboratory: Golden, CO, USA, 2004; pp. 1–66. [Google Scholar]
  14. Putten, R.; van der Waal, J.; Jong, E.; Rasrendra, C.; Heeres, H.; de Vries, J. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. Chem. Rev. 2013, 113, 1499–1597. [Google Scholar] [CrossRef] [PubMed]
  15. Avantium, Danone ink PEF deal. Chemical Week, 2012; 43–44.
  16. Zhou, C.; Beltramini, J.; Fun, Y.; Lu, G. Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals. Chem. Soc. Rev. 2008, 37, 527–549. [Google Scholar] [CrossRef] [PubMed]
  17. Gu, Y.; Jerome, F. Glycerol as a sustainable solvent for green chemistry. Green Chem. 2010, 12, 1127–1138. [Google Scholar] [CrossRef]
  18. Pina, C.; Falletta, E.; Rossi, M. A green approach of chemical building blocks. The case of 3-hydroxypropanoic acid. Green Chem. 2011, 13, 1624–1632. [Google Scholar] [CrossRef]
  19. Zhao, L.; Hu, H.; Shen, J.; Rong, H. The use of polytrimethylene terephthalate/polyester bi-component filament for the development of seamless garments. Text. Res. J. 2013, 83, 1283–1296. [Google Scholar] [CrossRef]
  20. Bozell, J.; Moens, L.; Elliott, D.C.; Wang, Y.; Neuenscwander, G.G.; Fitzpatric, S.W.; Bilski, R.J.; Jarnefeld, J.L. Production of levulnic acid and use as a platform chemical for derived products. Resour. Conserv. Recycl. 2000, 28, 227–239. [Google Scholar] [CrossRef]
  21. Climent, M.; Corma, A.; Iborra, S. Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels. Green Chem. 2014, 16, 516–547. [Google Scholar] [CrossRef]
  22. Vobeck, Z.; Wei, C.; Tauer, K. Poly (α-methylene-γ-valerolactone) 1. Suitable monomer synthesis and radical polymerization studies. Polymer 2015, 74, 262–271. [Google Scholar] [CrossRef]
  23. Isikgor, F.; Becer, R. Lignocellulosic biomass: A sustainable platform for the production of bio-based chemicals and polymers. Poly. Chem. 2015, 6, 4497–4559. [Google Scholar] [CrossRef]

Share and Cite

MDPI and ACS Style

Ray, P.; Smith, C.; Simon, G.P.; Saito, K. Renewable Green Platform Chemicals for Polymers. Molecules 2017, 22, 376. https://doi.org/10.3390/molecules22030376

AMA Style

Ray P, Smith C, Simon GP, Saito K. Renewable Green Platform Chemicals for Polymers. Molecules. 2017; 22(3):376. https://doi.org/10.3390/molecules22030376

Chicago/Turabian Style

Ray, Parijat, Craig Smith, George P. Simon, and Kei Saito. 2017. "Renewable Green Platform Chemicals for Polymers" Molecules 22, no. 3: 376. https://doi.org/10.3390/molecules22030376

Article Metrics

Back to TopTop