Scheme 2. Possible structural modification of the dimethacrylate derived from oleic acid and ethylene glycol (Scheme 1) includes variation of both the linking moiety R and the substituents R1, R2, R3, as well as R4resulting in numerous possible bio-based dimethacrylates that may differ in the properties of both monomers and polymers made of them e. g. by photoinitiated polymerization. The efficiency of both processes, monomer manufacturing and polymer formation as well as the properties of the crosslinked polymer materials obtained are important for selection of the new materials for application.
APPLICATION POTENTIAL
Aspects for introduction of new starting materials in existing production processes for manufacturing of new products include availability and current economic affordability of the new raw material, efficiency of the manufacturing processes for both the product, e. g. monomer and further material derived of the product, e. g. crosslinked material. Furthermore, the manufacturing processes should agree with the principles of green chemistry.[20] Quantification of the efficiency of manufacturing processes includes for example the energy balance, atom economy, yield, reaction mass efficiency, process mass intensity, and environmental factor.[21-26]Moreover, the new products should address to gaps existing on the market or may be replacements showing improved properties relative to existing products. Though fossil resources are limited, partial or complete substitution of the fossil resources will be necessary sooner or later. Therefore, the new bio-based dimethacrylate described in the reference[12] is going to contribute to this topic. The new journal Applied Research was selected for publication of the scientific results obtained regarding the new bio‐based dimethacrylate manufacturing and photocrosslinking resulting in hydrophobic crosslinked films to draw attention particularly for the use in practice. Here, the new highly hydrophobic material received from the dimethacrylate alone or in the presence of a bio-based methacrylate comonomer comprising an aromatic structure possesses huge potential. The two long alkyl substituents, which are available in each segment of the crosslinked polymer, contribute to the high hydrophobicity of the material derived from the bio-based dimethacrylate. Furthermore, the high hydrophobicity of the material makes it attractive for applications in corrosion protection e. g. of metal surfaces. At the present time, fluorinated polymers are commonly used to increase the hydrophobicity of surfaces although their manufacture has a negative impact on the environment.[27] Nowadays, substitution of fluorine comprising materials has received increased priority to solve this environmental issue. Here, the new bio-based dimethacrylate (Scheme 1) and a modified structure of the bio-based dimethacrylate e. g. as shown in Scheme 2, respectively, may become interesting alternatives to the currently used fluorinated polymers. 3D Printing can be seen as an additional application field where these monomers could receive additional attraction.[28-32] Particular manufacture of prothesis for medical uses or dental restauration addresses interesting challenges.[31,32]
The journal Applied Research together with its broad interested readership has accelerated scientific research in diverse fields, which strongly relate to application aspects. This covers applied research in industry for improving existing products and production processes as well as for the development of new products whose production proceeds in existing manufacturing plants. These facts may contribute to accelerate the transfer of recently obtained scientific results and newly developed products to manufacturing processes and making it feasible to bring new products to the market. Furthermore, the application aspects of the papers published in the journal Applied Research are going to widen the visual field of researchers working at institutes and universities. Moreover, this may encourage these researchers to include application aspects in their own work as well. The idea of applied research is deep-seated in research institutes such as Fraunhofer Institutes and Universities of Applied Sciences in Germany. The journalApplied Research may become the favorite journal for publication of scientific results focusing on application aspects derived from fundamental research. In addition, this journal represents a valuable source to provide recent research results with applied aspects for teaching in master and doctoral courses focusing on sustainable and green aspects.
References
[1] R. J. Henry, “Evaluation of plant biomass resources available for replacement of fossil oil”, Plant Biotechnology Journal2010 , 8 , 288-293.
[2] K. Hill, “Fats and oils as oleochemical raw materials”,J. Oleo. Sci. 2001 , 50 , 433-444.
[3] A. S. Carlsson, J. L. Yilmaz, A. G. Green, S. Stymne, P. Hofvander, “Replacing fossil oil with fresh oil – with what and for what?”, Eur. J. Lipid Sci. Technol. 2011 , 113 , 812 - 831.
[4] P. Intasian, K. Prakinee, A. Phintha, D. Trisrivirat, N. Weeranoppanant, T. Wongnate, P. Chaiyen, “Enzymes, In Vivo Biocatalysis, and Metabolic Engineering for Enabling a Circular Economy and Sustainability”, Chem. Rev. 2021 , 121 , 10367 - 10451.
[5] H. Sardon, D. Mecerreyes, A. Basterretxea, L. Avérous, C.Jehanno, “From Lab to Market: Current Strategies for the Production of Biobased Polyols”, ACS Sustainable Chem. Eng. 2021 ,9 , 10664 - 10677.
[6] L. Vevere, A. Fridrihsone, M. Kirpluks, U. Cabulis, “A Review of Wood Biomass-Based Fatty Acids and Rosin Acids Use in Polymeric Materials”, MDPI Polymers 2020 , 12 , 2706, doi:10.3390/polym12112706.
[7] W. Maaßen, S. Oelmann, D. Peter, W. Sowald, N. Willenbacher, M. A. R. Meier, “Novel Insights into Pressure-Sensitive Adhesives Based on Plant Oils”, Macromol. Chem. Phys. 2015 , 216 , 1609-1618.
[8] S. Walther, N. Strehmel, M. Schlörholz, B. Strehmel, V. Strehmel, “Photopolymerization of Functionalized Monomers Derived from Oleic Acid”, Journal of Photopolymer Science and Technology2016 , 29 , 123-132.
[9] S. Walther, B. Strehmel, V. Strehmel, “Functionalization of an alkyd resin with (meth)acrylate groups for photoinitiated polymerization”, Prog. Org. Coat. 2018 , 125 , 316-324. https://doi.org/10.1016/j.porgcoat.2018.08.028.
[10] B. Sanay, B. Strehmel, V. Strehmel, “Green Approach of Photoinitiated Polymerization Using Monomers Derived from Oleic Acid and Ionic Liquid”, ChemistrySelect 2019 , 4 , 10214-10218, DOI: 10.1002/slct.201902661.
[11] C. Veith, F. Diot-Néant, S. A. Miller, F. Allais, “Synthesis and polymerization of bio-based acrylates: a review”, Polym. Chem. 2020 , 11 , 7452-7470.
[12] B. Sanay, B. Strehmel, V. Strehmel, “Manufacturing and photocrosslinking of a new bio‐based dimethacrylate resulting in hydrophobic crosslinked films”, Appl. Res. 2021 , e202100003. doi.org/10.1002/appl.202100003.
[13] V. Strehmel, D. Strunk, M. Heinz, S. Walther, “A Green Step to New Monomers and Their Polymerization”, ChemistrySelect2020 , 5 , 12109 - 12114, doi.org/10.1002/slct.202002526.
[14] M. Heinz, M. Kepkow, N. Theofel, B. Strehmel, V. Strehmel, “Synthesis and photoinitiated cationic polymerization of epoxidized phenylpropanoid and α-pinene derivatives”, Sustainable Chemistry and Pharmacy 2022 , 29 , 100766. https://doi.org/10.1016/j.scp.2022.100766.
[15] Y. Liu, B. Zhong, A. Lawal, “Recovery and utilization of crude glycerol,
a biodiesel byproduct”, RSC Adv. 2022 , 12 , 27997-28008. DOI: 10.1039/d2ra05090k.
[16] H. Yue, Y. Zhao, X. Ma, J. Gong, “Ethylene glycol: properties, synthesis, and applications”, Chem. Soc. Rev. 2012 ,41 , 4218–4244.
[17] A. Wang, T. Zhang, “One-Pot Conversion of Cellulose to Ethylene Glycol with Multifunctional Tungsten-Based Catalysts”,Acc. Chem. Res. 2013 , 46 , 1377-1386.
[18] F. G. Calvo-Flores, J. A. Dobado, J. Isac-García, F. J. Martín-Mertínez, “Lignin and Lignane as Renewable Raw Materials”, John Wiley & Sons 2015 , Chichester, UK.
[19] N. Strehmel, D. Strunk, V. Strehmel, “White Birch Trunk Extracts as a Source of Organic Compounds”, ChemistrySelect2017 , 2 , 9607 – 9619.
[20] J. Horvath, P. T. Anastas, “Innovations and Green Chemistry,”Chem. Rev. 2007 , 107 , 2169-2173.
[21] P. Anastas, N. Eghbali, “Green Chemistry: Principles and Practice”, Chem. Soc. Rev. 2010 , 39 , 301-312.
[22] A. D. Curzons, D. J. C. Constable, D. N. Mortimera, V. L. Cunninghamb, “So you think your process is green, how do you know? – Using principles of sustainability to determine what is green – a corporate perspective”, Green Chem. 2001 , 3 , 1–6.
[23] J. Andraos, “Unification of Reaction Metrics for Green Chemistry: Applications to Reaction Analysis”, Org. Process Res. Dev. 2005 , 9 , 149-163 and Additions & Corrections 519.
[24] C. Jimenez-Gonzalez, C. S. Ponder, Q. B. Broxterman, J. B. Manley, ”Key Green Engineering Research Areas for Sustainable Manufacturing: A Perspective from Pharmaceutical and Fine Chemicals Manufacturers”, Org. Process Res. Dev. 2011 , 15 , 912-917.
[25] M. J. Climent, A. Corma, S. Iborra, M. Mifsud, A. Velty, ”New one-pot multistep process with multifunctional catalysts: decreasing the E factor in the synthesis of fine chemicals”, Green Chem.2010 , 12 , 99-107.
[26] R. A. Sheldon, “The E factor 25 years on: the rise of green chemistry and sustainability”, Green Chem. 2017 ,19 , 18–43.
[27] R. Lohmann, I. T. Cousins, J. C. DeWitt, J. Glüge, G. Goldenman, D. Herzke, A. B. Lindstrom, M. F. Miller, C. A. Ng, S. Patton, M. Scheringer, X. Trier, Z. Wang, ”Are Fluoropolymers Really of Low Concern for Human and Environmental Health and Separate from Other PFAS?” Environ. Sci. Techn. 2020 , 54 , 12820-12828.
[28] Y. Chen, J. Zhang, X. Liu, S. Wang, J. Tao, Y. Huang, W. Wu, Y. Li, K. Zhou, X. Wei, S. Chen, X. Li, X. Xu, L. Cardon, Z. Qian, M. Gou, ”Noninvasive in vivo 3D bioprinting”, Sci. Adv. 2020 ,6 , eaba7406.
[29] A. Bagheri, J. Jin, ”Photopolymerization in 3D Printing”,ACS Appl. Polymer Materials 2019 , 1 , 593-611.
[30] S. C. Ligon, R. Liska, J. Stampfl, M. Gurr, R. Mülhaupt, ”Polymers for 3D Printing and Customized Additive Manufacturing”,Chem. Rev. 2017 , 117 , 10212-10290.
[31] J. W. Stansbury, M. J. Idacavage, ”3D printing with polymers: Challenges among expanding options and opportunities”, Dent. Mat.2016 , 32 , 54-64.
[32] A. Dawood, M. B. Marti, V. Sauret-Jackson, A. Darwood, ”3D printing in dentistry”, Br. Dent. J. 2015 , 219 , 521-529.
ACKNOWLEDGMENT
Open Access funding enabled and organized by Projekt DEAL.
CONFLICT OF INTEREST
The authors declare no conflict of interest.
AUTHORS BIOGRAPHY
Veronika Strehmel accepted her professorship for Organic Chemistry focusing on Macromolecular Chemistry at the Niederrhein University of Applied Sciences in 2010. Beside Polymer Chemistry andPolymerization Technology , she has taught Green Organic and Polymer Chemistry . Furthermore, she has been private lecturer for Polymer Chemistry at the University of Potsdam since 2007, where she has taught Photopolymerization . As a member of the Institute for Coatings and Surface Chemistry of the Niederrhein University of Applied Sciences, her research has focused on ionic liquids as well as on monomers and polymers based on renewable resources. Prior to this, after completing her PhD at the Technical University of Merseburg, she pursued both applied research (Leuna Company; Fraunhofer Institute for Applied Polymer Research) and fundamental research (Stanford University; Martin-Luther University Halle-Wittenberg, where she received her habilitation in Polymer Chemistry in 2000; Institute for Thin Film Technology and Microsensorics; University of Potsdam).
Picture: Veronika Strehmel