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