Environmentally Friendly o–Cresol–Furfural–Formaldehyde Resin as an Alternative to Traditional Phenol–Formaldehyde Resins for Paint Industry
<p>Negative ion mode ESI-MS mass spectrum for o–cresol–furfural resin at a molar ratio of 1:1.3, in the presence of 0.21 wt.% Na<sub>2</sub>CO<sub>3</sub> at 120–150 °C after a condensation reaction of 34 h.</p> "> Figure 2
<p>Reaction scheme of the condensation of o–cresol and furfural.</p> "> Figure 3
<p>Reaction scheme of activation of o–cresol–furfural resin with hydroxymethylene groups.</p> "> Figure 4
<p>ESI-MS mass spectrum in negative ion mode for the o–cresol–furfural–formaldehyde resin.</p> "> Figure 5
<p>FT-IR spectrum of unmodified o–cresol–furfural–formaldehyde resin.</p> "> Figure 6
<p>Possible structures along with the numbered carbon atoms (red wavy lines indicate possible attachment sites for subsequent molecules).</p> "> Figure 7
<p><sup>1</sup>H NMR spectrum of o–cresol–furfural–formaldehyde resin.</p> "> Figure 8
<p>Structures of furfurals with –CH<sub>2</sub>–OH and –CH<sub>2</sub>–O– groups attached.</p> "> Figure 9
<p>Partial HSQC spectrum showing the signals of methyl groups and protons of –CH– linkage (C<sub>8</sub>–H): ortho-ortho (o-o), ortho-para (o-p) and para-para (p-p).</p> "> Figure 10
<p>Partial HSQC spectrum showing the signals of hydroxymethylene groups, dimethylene ether bridges, protons and signals of –CH<sub>2</sub>–OH and –CH<sub>2</sub>–O– groups attached to furfural.</p> "> Figure 11
<p>DSC thermogram of unmodified o–cresol–furfural–formaldehyde resin.</p> "> Figure 12
<p>Mass spectrum of ESI-MS in negative ion mode for the o–cresol–furfural–formaldehyde resin etherified with n-butanol, in the presence of malonic acid used as a catalyst.</p> "> Figure 13
<p>Mass spectrum of ESI-MS in negative ion mode for o–cresol–furfural–formaldehyde resin etherified with n-butanol in the presence of oxalic acid used as a catalyst.</p> "> Figure 14
<p>FT−IR spectra of o–cresol–furfural–formaldehyde resin, unmodified and after modification with n-butanol: (<b>A</b>) range 4000–2500 cm<sup>−</sup><sup>1</sup>; (<b>B</b>) range 1700–600 cm<sup>−</sup><sup>1</sup>.</p> "> Figure 15
<p>The <sup>1</sup>H NMR spectrum of o–cresol–furfural–formaldehyderesin: (<b>A</b>) unmodified and (<b>B</b>) modified with n-butanol.</p> "> Figure 16
<p>DSC thermograms of o–cresol–furfural–formaldehyde resin modified with n−butanol.</p> "> Figure 17
<p>ESI-MS mass spectrum in negative ion mode for resin o–cresol–furfural–formaldehyde resin after etherification reaction with 2-ethylhexanol in the presence of malonic acid used as a catalyst.</p> "> Figure 18
<p>ESI-MS mass spectrum in negative ion mode for resin o–cresol–furfural–formaldehyde resin after etherification reaction with 2-ethylhexanol in the presence of oxalic acid used as a catalyst.</p> "> Figure 19
<p>FT-IR spectraof o–cresol–furfural–formaldehyde resin unmodified and modified with 2-ethylhexanol: (<b>A</b>) range 4000–2500 cm<sup>−</sup><sup>1</sup>; (<b>B</b>) range 1700–600 cm<sup>−</sup><sup>1</sup>.</p> "> Figure 19 Cont.
<p>FT-IR spectraof o–cresol–furfural–formaldehyde resin unmodified and modified with 2-ethylhexanol: (<b>A</b>) range 4000–2500 cm<sup>−</sup><sup>1</sup>; (<b>B</b>) range 1700–600 cm<sup>−</sup><sup>1</sup>.</p> "> Figure 20
<p>The<sup>1</sup>H NMR spectra of resin: (<b>A</b>) unmodified and (<b>B</b>) modified with 2-ethylhexanol.</p> "> Figure 21
<p>DSC thermograms of o–cresol–furfural–formaldehyde resin modified with 2−ethylhexanol in 1st and 2nd runs of heating.</p> "> Figure 22
<p>The coatings obtained from o–cresol–furfural–formaldehyde resins, modified with (<b>A</b>) n-butanol, (<b>B</b>) 2-ethylhexanol, on an acid-resistant plate, after drying at 150 °C for 1 h.</p> ">
Abstract
:1. Introduction
2. Materials and Methods
2.1. Chemicals
2.2. Synthesis and Apparatus
2.2.1. Synthesis of o–Cresol–Furfural Resin
2.2.2. Synthesis of o–Cresol–Furfural–Formaldehyde Resins
2.2.3. Modification of o–Cresol–Furfural–Formaldehyde Resins in Etherification Reaction
2.2.4. Coating Preparation
2.2.5. Analytical Methods
High-Performance Liquid Chromatography (HPLC)
Analysis of Free Formaldehyde
Analysis of Non-Volatile Substances
Viscosity Determination
Electrospray Ionization Mass Spectrometry (ESI-MS)
Nuclear Magnetic Resonance (NMR) Spectroscopy
Fourier Transform Infrared Spectroscopy (FT-IR)
Differential Scanning Calorimetry (DSC)
Gel Permeation Chromatography (GPC)
3. Results and Discussion
3.1. Synthesis of o–Cresol–Furfural Resin
3.2. Synthesis of o–Cresol–Furfural–Formaldehyde Resin
3.3. Etherification of o–Cresol–Furfural–Formaldehyde Resin with n-Butanol
3.4. Etherification of o–Cresol–Furfural–Formaldehyde Resin with 2-Ethylhexanol
3.5. Application-Related Properties
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
- Rivero, G.; Fasce, L.A.; Cerè, S.M.; Manfredi, L.B. Furan resins as replacement of phenolic protective coatings: Structural, mechanical and functional characterization. Prog. Org. Coat. 2014, 77, 247–256. [Google Scholar] [CrossRef]
- Mougel, C.; Garnier, T.; Cassagnau, P.; Sintes-Zydowicz, N. Phenolic foams: A review of mechanical properties, fire resistance and new trends in phenol substitution. Polymer 2019, 164, 86–117. [Google Scholar] [CrossRef]
- Oliveira, F.B.; Gardrat, C.; Enjalbal, C.; Frollini, E.; Castellan, A. Phenol–Furfural Resins to Elaborate Composites Reinforced with Sisal Fibers––Molecular Analysis of Resin and Properties of Composites. J. Appl. Polym. Sci. 2008, 109, 2291–2303. [Google Scholar] [CrossRef]
- Patel, A.U.; Soni, S.S.; Patel, H.S. Synthesis, Characterization and Curing of o–cresol–Furfural Resins. Int. J. Polym. Mater. 2009, 58, 509–516. [Google Scholar] [CrossRef]
- Hirano, K.; Asami, M. Phenolic resins—100 years of progress and their future. React. Funct. Polym. 2013, 73, 256–269. [Google Scholar] [CrossRef]
- Pilato, L. Phenolic resins: 100 Years and still going strong. React. Funct. Polym. 2013, 73, 270–277. [Google Scholar] [CrossRef]
- Tang, K.; Zhang, A.; Ge, T.; Liu, X.; Tang, X.; Li, Y. Research progress on modification of phenolic resin. Mater. Today Commun. 2021, 26, 101879. [Google Scholar] [CrossRef]
- Sarika, P.R. Bio-BasedAlternatives to Phenol and Formaldehyde for the Production of Resins. Polymers 2020, 12, 2237. [Google Scholar] [CrossRef] [PubMed]
- Win, D.T. Furfural—Gold from Garbage. Au J. Technol. 2005, 8, 185–190. [Google Scholar]
- Fink, J.K. Reactive Polymers Fundamentals and Applications; William Andrew Publishing: Norwich, NY, USA, 2005; pp. 1–38. [Google Scholar]
- Depta, M.; Jaszcz, K. Furfural as an alternative for formaldehyde in production of phenolic resins. Przemysł Chem. 2020, 8, 1242–1250. [Google Scholar]
- Cardarelli, F. A Concise Desktop Reference, 3rd ed.; Materials Handbook; Springer International Publishing: Cham, Switzerland, 2018. [Google Scholar]
- Ahujaa, S.; Singh, D. A kinetic model of alkali catalyzed phenol-furfural novalac resinification. Polym. Polym. Compos. 2011, 19, 581–586. [Google Scholar] [CrossRef]
- Liu, J.; Xuan, D.; Chai, J.; Guo, D.; Huang, Y.; Liu, S.; Chew, Y.T.; Li, S.; Zheng, Z. Synthesis and thermal properties of resorcinol–furfural thermosetting resin. ACS Omega 2020, 5, 10011–10020. [Google Scholar] [CrossRef] [PubMed]
- Asaro, L.; Seoane, I.T.; Fasce, L.A.; Cyras, V.P.; Manfredi, L.B. Development of low environmental impact protective coatings based on a furan resin and cellulose nanocrystals. Prog. Org. Coat. 2019, 133, 229–236. [Google Scholar] [CrossRef]
- Liu, F.; Yang, L.; Huang, Y.; Jiang, P.; Li, G.; Jiang, W.; Liu, X.; Fan, Z. Performance of resin bonded sand for magnesium alloy casting. J. Manuf. Process. 2017, 30, 313–319. [Google Scholar] [CrossRef]
- Nakamura, K.; Okuyama, K.; Takase, T. Magnetic properties of magnetic glass-like carbon prepared from furan resin alloyed with magnetic fluid. J. Magn. Magn. Mater. 2017, 425, 43–47. [Google Scholar] [CrossRef]
- Rivero, G.; Pettarin, V.; Vázquez, A.; Manfredi, L.B. Curing kinetics of a furan resin and its nanocomposites. Thermochim. Acta 2011, 516, 79–87. [Google Scholar] [CrossRef]
- Vergara, U.; Sarrionandia, M.; Gondra, K.; Aurrekoetxea, J. Polymerization and curing kinetics of furan resins under conventional and microwave heating. Thermochim. Acta 2014, 581, 92–99. [Google Scholar] [CrossRef]
- Albert, D.F.; Andrews, G.R.; Mendenhall, R.S.; Bruno, J.W. Supercritical mathanol drying as a convenient route to phenolic-furfural aerogels. J. Non-Cryst. Solids 2001, 296, 1–9. [Google Scholar] [CrossRef]
- Teranishi, Y.; Kobayashi, T.; Yasuda, E.; Iwaki, M.; Kakihana, M.; Fukushima, M.; Nakamura, K.; Tanabe, Y. Radiation damages and bubble formation of ion implanted furan-resin-derived carbon. Surf. Coat. Technol. 2005, 196, 216–220. [Google Scholar] [CrossRef]
- Teranishi, Y.; Tanabe, Y.; Kobayashi, T.; Nakamura, K.; Fukushima, M.; Ishizuka, M.; Mitsuo, A.; Uematsu, T.; Isao, N.; Shimizu, K.; et al. Graphitization behavior of the implanted furan-resin-derived carbon. Nucl. Instrum. Methods Phys. Res. B 2009, 267, 1259–1263. [Google Scholar] [CrossRef]
- Cheng, Y.; Sui, G.; Liu, H.; Wang, X.; Yang, X.; Wang, Z. Preparation of highly phenol substituted bio-oil–phenol–formaldehyde adhesives with enhanced bonding performance using furfural as crosslinking agent. J. Appl. Polym. Sci. 2019, 136, 46995. [Google Scholar] [CrossRef]
- Ugryumov, S.A.; Patrakov, R.V. The Use of Furan Oligomers for Modifying Phenol Formaldehyde Resin in Plywood Industry. Polym. Sci. 2011, 4, 38–40. [Google Scholar] [CrossRef]
- Żmihorska-Gotfryd, A. Preparation and properties of glycol-and polyetherol-modified phenol-formaldehyde resins. Polimery 2000, 45, 687–692. [Google Scholar] [CrossRef]
- Knop, A.; Pilato, L.A. Phenolic Resins; Springer: Berlin/Heidelberg, Germany, 1985; p. 48. [Google Scholar]
- ISO 9397; Plastics—Phenolic Resins—Determination of Free-Formaldehyde Content—Hydroxylamine Hydrochloride Method. ISO: Geneva, Switzerland, 1995.
- ISO 8618; Plastics-Liquid Phenolic Resins—Conventional Determination of Non-Volatile Matter. ISO: Geneva, Switzerland, 1995.
- PN-86/C-89085/06; Epoxy Resins—Methods of Testing—Determination of Viscosity. PKN: Warsaw, Poland, 1986.
- ISO 6286; Molecular Absorption Spectrometry. ISO: Geneva, Switzerland, 1996.
- Ishida, S.; Wakaki, S.; Kato, Y.; Nakamoto, Y. Computational studies of reactions of phenols with aldehydes. J. Ind. Eng. Chem. 1984, 23, 380–383. [Google Scholar] [CrossRef]
- EN ISO 2808; Paints and Varnishes—Determination of Film Thickness. ISO: Geneva, Switzerland, 1999.
- EN ISO 4618; Paints and Varnishes—Bend Test (Conical Mandrel). ISO: Geneva, Switzerland, 2006.
- EN ISO 2409; Paints and Varnishes—Cross-Cut Adhesion. ISO: Geneva, Switzerland, 2013.
- EN ISO 1522; Paints and Varnishes—Hardness by Pendulum Dumping Test. ISO: Geneva, Switzerland, 2008.
- Żmihorska-Gotfryd, A. Coating compositions based on modified phenol-formaldehyde resin and urethane prepolymers. Prog. Org. Coat. 2004, 49, 109–114. [Google Scholar] [CrossRef]
- Regulation, E. 1272/2008,‘Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006. Off. J. Eur. Union 2008, 50, 353. [Google Scholar]
Properties | Parameters |
---|---|
Molar ratio o–cresol–furfural | 1:1.1–2 |
Reaction temperature, °C | 120–150 |
Reaction time, hour | 5–80 |
Free o–cresol content, wt.% | 1.2–8.6 |
Free furfural content, wt.% | 12.3–29.8 |
Physical state | Solid–liquid |
Physicochemical Properties | Parameters |
---|---|
Molar ratio o–cresol–furfural–formaldehyde | 1:0.5–0.8:0.5–0.8 |
Reaction temperature, °C (1st stage/2nd stage) | 120/90 |
Reaction time, hours (1st stage/2nd stage) | 11/2 |
Free o–cresol content, wt.% | 4–14 |
Free furfural content, wt.% | 0–4 |
Free formaldehyde content, wt.% | 1–3 |
Physical state | Solid |
Physicochemical Properties | Parameters |
---|---|
Molar ratio o–cresol–furfural–formaldehyde | 1:0.65:0.65 |
Reaction temperature, °C (1st stage/2nd stage) | 120/90 |
Reaction time, hours (1st stage/2nd stage) | 11/1 |
Free o–cresol content, wt.% | 2.2 |
Free furfural content, wt.% | 0.2 |
Free formaldehyde content, wt.% | <0.1 |
Molecular weight, g/mol | 1245 |
Glass transition temperature, °C | 207 |
Non-volatile mattercontent, wt.% | 98 |
Physical state | Solid |
Functional Group | 13C NMR | 1H NMR | ||
---|---|---|---|---|
Chemical Shift δ [ppm] | Symbol | Chemical Shift δ [ppm] | Symbol | |
–CH3, –CH2- | 29.35–30.46 | C-7, C-19, K–CH2–K | 2.08–2.56 | C7–H3, C19–H3 |
–CH– | 43.79–43.98; 44.40–44.80; 45.20–45.75 | C-8 | 2.08–2.56 | C8–H |
–CH2–O– | 85.72–85.85 | K–CH2–O–CH2–K | 4.37–4.52 | K–CH2–O–CH2–K |
–CH2–OH | 92.30; 92.40 | C-20 | 4.68–4.83 | C20–Ha,b |
–CH2–O– | 92.97–93.70 | F–CH2–O– F–CH2–O–H | 3.57–3.70 | F–CH2–O– F–CH2–O–H |
–CH– in F | 136.80–137.62, 139.66 | C-11, C-12 | 5.68–6.45 | C11–H;C12–H |
–CH– in K | 144.01, 144.11 | C-3, C-5, C-16, C-18 | 6.80 i 6.88 | C3–H;C5–H; C16–H;C18–H |
–C– in K | 146.83 | C-1, C-2, C-4, C-6, C-13, C-14, C-15, C-16 | — | — |
–CH– in K | 149.27, 150.80, 152.03, 154.66, 154.74, 156.20, 156.31, 156.86, 156.98, 158.70, 159.36, 159.43, 160.34, 160.29, 161.76 | C-3, C-5, C-16, C-18 | 6.50–7.21 | C3–H;C5–H; C16–H;C18–H |
–C– | 153.64, 153.69, 159.60 | –C– from furfural | — | — |
–CH– in F | 163.39 | C-11, C-12 (from a molecule containing F–CH2–O– and F–CH2–O–H) | 6.23–6.35 | |
–CH– in F | 171.23 | C–10 | 7.25–7.50 | C10–H |
Unnmodifiedresin, wt.% | 20 |
n-butanol, wt.% | 80 |
Acidic environment, pH | 3 |
Reaction temperature, °C | 110 |
Reaction time, hour | 20 |
Physicochemical Properties | Parameters | |
---|---|---|
Catalyst | Malonic Acid | Oxalic Acid |
Free o–cresol content, wt.% | <1.0 | <1.0 |
Free furfural content, wt.% | <1.0 | <1.0 |
Free formaldehyde content, wt.% | <0.1 | <0.1 |
Molecular weight, g/mol | 3402 | 11,389 |
Glass transition temperature, °C | 55 | 53 |
Non-volatile matter content, wt.% | 17.52 | 19.91 |
Viscosity 20 °C, mPa·s | 22.5 | 12.1 |
Unmodified resin, wt.% | 20 |
2-ethylhexanol, wt.% | 80 |
Acidic environment, pH | 2.5 |
Reaction temperature, °C | 110 |
Reaction time, hour | 20 |
Physical and Chemical Properties | Parameters | |
---|---|---|
Catalyst | Malonic Acid | Oxalic Acid |
Free o–cresol content, wt.% | <1.0 | <1.0 |
Free furfural content, wt.% | <0.1 | <0.1 |
Free formaldehyde content, wt.% | <0.1 | <0.1 |
Molecular weight, g/mol | 6394 | 8334 |
Glass transition temperature, °C | 48 | 53 |
Non-volatile matter content, wt.% | 20.57 | 19.91 |
Viscosity 20 °C, mPa·s | 248 | 12.1 |
Physico-Mechanical Properties | o–Cresol–Furfural–Formaldehyde Resin Modified with | |
---|---|---|
n-Butanol | 2-Ethylhexanol | |
Thickness a (dried coating)µm | 18 ± 3 | 20 ± 3 |
Flexibility b (mm) | 6 | 4 |
Cross-cut adhesion c (grades) | 1 | 0 |
Hardness d | 0.89 | 0.81 |
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content. |
© 2024 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Depta, M.; Napiórkowski, S.; Zielińska, K.; Gębura, K.; Niewolik, D.; Jaszcz, K. Environmentally Friendly o–Cresol–Furfural–Formaldehyde Resin as an Alternative to Traditional Phenol–Formaldehyde Resins for Paint Industry. Materials 2024, 17, 3072. https://doi.org/10.3390/ma17133072
Depta M, Napiórkowski S, Zielińska K, Gębura K, Niewolik D, Jaszcz K. Environmentally Friendly o–Cresol–Furfural–Formaldehyde Resin as an Alternative to Traditional Phenol–Formaldehyde Resins for Paint Industry. Materials. 2024; 17(13):3072. https://doi.org/10.3390/ma17133072
Chicago/Turabian StyleDepta, Marta, Sławomir Napiórkowski, Katarzyna Zielińska, Katarzyna Gębura, Daria Niewolik, and Katarzyna Jaszcz. 2024. "Environmentally Friendly o–Cresol–Furfural–Formaldehyde Resin as an Alternative to Traditional Phenol–Formaldehyde Resins for Paint Industry" Materials 17, no. 13: 3072. https://doi.org/10.3390/ma17133072