Pulp and Paper Fundamental Research Symposia Proceedings. The molar ratios of sodium hydroxide to phenol-modified alkaline lignin and the formaldehyde to phenol-modified alkaline lignin were from 1.0 to 1.4, and 1.8 to 2.6, respectively. Lignin as a component in phenol formaldehyde resol resin,” Journal of Applied Polymer Science 33(8), 2915-2924. The same dependency of gel time on lignin content and [S/(P+L)] molar ratio was reported by Alonso and Vázquez (Vázquez et al. A slow cure lead to longer pressing time, and therefore the manufacture of the plywood must be expensive. Contact information a: Key Laboratory of Specially Functional Polymeric Materials and Related Technology of Ministry of Education, School of Materials Science and Engineering, East China University of Science & Technology, 130 Meilong Road, Shanghai 200237. The bands at 1120 cm-1 is characteristic of aromatic C-H in S units of lignin molecule and the C-O of primary alcohol at 1044 cm-1. (1983). RESI-SET ® liquid resins are specifically designed for the foundry no-bake process.. All rights reserved. The reaction of phenol or substituted phenol with an aldehyde, such as formaldehyde, in the presence of an acidic or basic catalyst is used to prepare phenolic resins. In this last group, only the soda lignins have a short-term potential for industrial availability. July 25, 1989 VA Specialty paper manufacturing; release of phenolic resin and methanol from process vessel. In fact, the incorporation of a large amount of lignin with a high molecular weight is the main reason for increasing the molecular weight of final resin, thus resulting in higher viscosities for lignin-phenol formaldehyde resins. The results obtained for solid content were between 41 and 45%. DOI: 10.15376/biores.6.3.2647-2662, El Mansouri, N.-E., Yuan, Q., and Huang, F. (2011b). Available Variants : Resin for Magnesia-Carbon Bricks - PROREZ 7015; Resin for Blast Furnace Tap-hole Mass - PROLAC ABC 10.1021/bk-1989-0385.ch005, Alonso, M. V., Rodriguez, J. J., Oliet, M., Rodriguez, F., Garcia, J., and Gilarranz, M. A. The base material choice depends on the intended application of the finished product. The alkaline lignin (AL) used for the preparation of hydroxymethylated lignin was supplied by South China University of Technology, Guangzhou, China. J. G. Ferguson, W. E. Grutzner, D. C. Koehler, The alkaline lignins have been reported to be the most adequate to formulate phenol formaldehyde resins because they are structurally similar to phenol–formaldehyde resins and contain large molecules that allow quick gelation (Forss and Fuhrmann 1979; Allan et al. DOI: 10.15376/biores.6.3.2492-2503. This lignin was produced by ShangDong QuanMing Paper Making Co. Ltd. by the alkaline process using sodium hydroxide and Na2CO3from rice straw. Fig. Phenolic resins are also used for making exterior plywood commonly known as weather and boil proof (WBP) plywood because phenolic resins have no melting point but only a decomposing point in the temperature zone of 220 °C (428 °F) and above. Analysis of variance (Table 5) showed that viscosity was significantly influenced by all the studied parameters, and the cross-terms (L(%))*[F/(P+L)] and[F/(P+L)]*[S/(P+L)] at the p=0.05 significance level. Sometimes people select fibre reinforced phenolic resin parts because their coefficient of thermal expansion closely matches that of the aluminium used for other parts of a system, as in early computer systems (2016). However, modified resins with gel time near to 10min can be considered and tested for plywood manufacturing if they present low free formaldehyde content. Estimated response surface for pH at L(%)=35%, F/PL vs S/PL. “Kraft lignin depolymerization in an ionic liquid without a catalyst,” BioResources 10(3), 4933-4946. Lignin–Adhesive Research for Wood Composites, Forest and Wildlife Research Center. The negative charge is delocalised over the aromatic ring, activating sites 2, 4 and 6, which then react with the formaldehyde. The band at 1269 cm-1is attributed to in-plane vibration of C-O of the phenolic group present in PF and LPF. In the case of free formaldehyde content, within the range of the three studied variables, the obtained values for formaldehyde content were lower than 0.2%, which is the maximum value acceptable for environmental reasons. Lignin powder was slowly added to NaOH solution, keeping the pH of the mixed solution between 12 and 13 for better dissolution of the lignin powder, which was facilitated by vigorous stirring with an overhead stirrer. Phenol-formaldehyde resins, as a group, are formed by a step-growth polymerization reaction that can be either acid- or base-catalysed. Flexural and compressive mechanical properties,” Journal of Applied Polymer Science 107(1), 159-165. Table 1. Lignin is a good candidate to replace phenol in the phenol formaldehyde resins’ formulation because (a) its polyphenolic structure is similar to that of phenolic resin (Fig. Norambuena, M., Vidal, C., Carrasco, L., Reyes, P., Parra, C., Contreras, D., and Teixeira Mendonça, R. (2016). 2. Sellers, T, Jr., (1995). Table 5.Analysis of Variance for Viscosity at 25 °C, Fig. In place of phenol itself, they are often produced from cresols (methylphenols). Table 2. The diagram of the entire experimental protocol is shown in Fig.2. “Fourier transform infrared spectroscopy,” in: Methods in Lignin Chemistry, Li n, S.Y., and Dence, C. W. 2013; Zhao et al. “Modification of lignins for use in phenolic resins,” ACS Symposium Series 385, 55-67. DOI: : 10.1016/j.indcrop.2004.04.015, Hu, L., Pan, H., Zhou, Y., and Zhang, M. (2011). Estimated response surface for gel time at [F/(P+L)]=2.2, L(%) vs.[S/(P+L)]. Since formaldehyde exists predominantly in solution as a dynamic equilibrium of methylene glycol oligomers, the concentration of the reactive form of formaldehyde depends on temperature and pH. To evaluate the feasibility of the achieved lignin replacement, it is necessary to undertake complementary experiments to determine the properties of manufactured plywood from the prepared lignin-based phenolic resins. Encyclopædia Britannica, Inc. They were near to the range of values of the commercial resins used for plywood production, which ranges from 45to47% (Alonso et al. This resin has good chemical resistance, electrical insulation, and dimensional stability, but the price and environmental concerns may limit usage in some applications. Estimated response surface for viscosity at S/PL=1.2, L(%) vs F/PL. Used as the basis for Bakelite, PFs were the first commercial synthetic resins (plastics). for Plastics, Phenolic Resins, Determination of Free Formaldehyde Content by Hydroxylamine Hydrochloride Method. Phenol-formaldehyde (PF) is a thermosetting resin that is widely used in many fields. Chemical Reaction Phenol Formaldehyde resins are prepared by reaction of phenol with formaldehyde in the presence of acidic or basic catalyst. Mancera, C., Ferrando, F., Salvado, J., and El Mansouri, N. E. (2011). When the molar ratio of formaldehyde:phenol reaches one, in theory every phenol is linked together via methylene bridges, generating one single molecule, and the system is entirely crosslinked. Bands at 2937 cm-1 and 2846 cm-1 are the consequence of in-plane and out-of-plane stretching of aliphatic -CH2-. DOI: 10.1002/app.27003, Vázquez, G., Freire, S., Rodríguez-Bona, C., González, J., and Antorrena, G. (1999). Consumers most commonly encounter this substance in the context of a packaged product which includes it, such as MDF, a wood product commonly used in construction. Siddiqui, H., Mahmood, N., Yuan, Z., Crapulli, F., Dessbesell, L., Rizkalla, A., Ray, A., and Xu, C. (2017). In any case, the final pH of the synthesized resol resins can be corrected by addition of base or acid solution. Phenol and formaldehyde are charged into the kettle in specified quantaties. POLYTONETM PF 132 C is a phenol – formaldehyde resin to be mixed with Hexa or Part 2 Catalyst.POLYTONETM PF 132 C (Part 1 + 2) effortlessly penetrates and adheres to the structure of many organic and inorganic fillers and reinforcements which makes it an ideal candidate for various end uses. The kettle is kept under continuous agitation. In the early studies related to the use of lignin for phenolic resins manufacturing, different types of unmodified lignins, which were obtained directly from the pulping liquor, were investigated. The modified lignin from these later methods could partially replace phenol in phenol-formaldehyde resin synthesis. Ghorbani, M., Liebner, F., van Herwijnen, H. W. G., Pfungen, L., Krahofer, M., Budjav, E., and Konnerth, J. (1992). Fernández-Rodríguez, J., Erdocia, X., Sánchez, C., González Alriols, M., and Labidi, J. 2006; Ghorbani et al. DOI: 10.1002/app.26941, Tejado, A., Kortaberria, G., Pena, C., Blanco, M., Labidi, J., Echeverria, J. M., and Mondragon, I. “Waste liquors from cellulosic industries.4. “Modification of ammonium lignosulfonate by phenolation for use in phenolic resins,” Bioresource Technology 96(9), 1013-1018.DOI: 10.1016/j.biortech.2004.09.009, Cheng, S., Yuan, Z., Leitch, M., Anderson, M., and Charles, C. (2013). DOI: 10.1002/app.1987.070330824. The bands at 1455 cm-1 and 1425 cm-1 are due to the asymmetric C-H deformation in –OCH3 groups. © 2020 NC State University. DOI: 10.1080/02773819909349617. “Lignin phenol formaldehyde resoles: The impact of lignin type on adhesive properties,” BioResources 11(3), 6727-6741. DOI: 10.1016/j.jechem.2017.02.007. The acquisition conditions were: spectral width of 4000to400 cm-1, 32 accumulations, and 4-cm-1 resolution. Springer Verlag, Berlin Heidleberg New York. The statistical analysis was carried out by using Statgraphics 18 Centurion. Supplied into the commercial formaldehyde market, it’s also vertically integrated as a raw material into phenolic resin and amino resins production. 5) shows that for [S/(P+L)]=1.2 molar ratio, the viscosity increased with increase of lignin content (in lower [F/(P+L)] region) and [F/(P+L)] molar ratio. “Lignins for phenol replacement in novolac-type phenolic formulations, part I: Lignophenolic resins synthesis and characterization,” Journal of Applied Polymer Science 106(4), 2313-2319. 2014; Podschun et al. “Development and characterization of a lignin-phenol-formaldehyde wood adhesive using coffee bean shell,” Journal of Adhesion Science and Technology 19(6), 493-509. Roczniak et al. Obtained polymer is thermoplastic and require a curing agent or hardener to form a thermoset. The fitted model for gel time gave an R2 value of 99.38% and a standard deviation of residuals (SDR) of 0.18. “Preparation and performance of lignin-phenol-formaldehyde adhesives,” International Journal of Adhesion and Adhesives64, 163-167. (2006). release of phenol and formaldehyde from process vessel. Elements. DOI: 10.15376/biores.11.3.6727-6741, Gosselink, R. J. Typically, heat and pressure are used to shape and "cure" the mixture into a finished part. 2015; Fernandez-Rodriguez et al. However, it was reported that lignins present some certain limitations, such as the lower number of reactive sites, low phenolic hydroxyl groups, and the steric impediments. Phenolic laminates are made by impregnating one or more layers of a base material such as paper, fiberglass, or cotton with phenolic resin and laminating the resin-saturated base material under heat and pressure. Under the trade name Bakelite, a phenol-formaldehyde resin was one of the earliest plastics, invented by American industrial chemist Leo Baekeland and patented in 1909. This spectrum is characterized by a broad band of OH stretching located at 3415 cm-1, which is attributed to the hydroxyl groups in phenolic and aliphatic structures, and the bands at 2933 cm-1and 2849 cm-1, arising from CH stretching in the aromatic methoxyl groups and the methyl and meythylene groups of the side chains. Vishtal, A., and Kraslawski, A. 7. Allan, G. G., Dalan, J. For that, the unmodified lignins are relatively reluctant to undergo either self-condensation or condensation with formaldehyde, phenol, or phenol formaldehyde prepolymer (Vázquez et al.1999). (2016). 2004). A polymeric compound obtained by polycondensation of a phenolic compound and an aldehyde compound under acidic or basic conditions generally refers to a resin synthesized from phenol and formaldehyde, and is called a phenol-formaldehyde resin (PF). Structure of PF resin and lignin (Forss and Fuhrmann 1979). Novolac is a type of formaldehyde phenol resin. Phenol formaldehyde resin (resole type) is the most useful thermosetting resin for the manufacture of wood-based panels such as plywood, particleboard, and fiberboard (Nimz 1983; Sellers 1995; Gardziella et al. Novolacs have multiple uses as tire tackifier, high temperature resin, binder for carbon bonded refractories, carbon brakes, photoresists and as a curing agent for epoxy resins. At a temperature greater than 90 °C, it forms methylene and dimethylene amino bridges. “Optimization of experimental variables to modify lignin fromEucalyptus globulus under alkaline catalysis,” BioResources 11(1), 1828-1842. (2005). “Structural modification and characterization of lignosulfonate by a reaction in an alkaline medium for its incorporation into phenolic resins,” Journal of Applied Polymer Science 102(4), 3286-3292.DOI: 10.1002/app.24744, El Mansouri, N. E., Pizzi, A., and Salvado, J. These bands are assigned to C=O stretching in unconjugated ketone and carbonyl bond in ester group or in conjugated p-substituted aryl ketone, respectively (Khan and Ashraf 2005).The absorption bands at 1600 cm-1 and 1500 cm-1are assigned to aromatic ring vibrations. 4) shows that for [F/(P+L)]=2.2 molar ratio, the gel time increased with increase of lignin content at higher level of ([S/(P+L)]=1.4) molar ratio, and decrease with increase of [S/(P+L)] molar ratio at lower level of lignin replacement (L(%)=20%). A total of 11lignin-phenol formaldehyde (LPF) resins, as indicated in Table 1,were prepared by varying the replacement percentage of phenol by hydroxymethylated lignin (%L) between 20and50%, the mass ratio of formaldehyde/(phenol+lignin)[F/(P+ L) between 1.8 and 2.6,and the ratio of sodium hydroxide/(phenol plus lignin)[S/(P+L)] between 1.0 and 1.4.A 2x2x2 factorial design with a three repeated central points was applied in order to quantify the effect of those parameters on the resins properties. studied the effect of benuang (Octomeles sumatrana BN) and duabanga (Duabanga moluccana DB) barks as the filler for phenol-formaldehyde resin (PF) in glulam production. Formaldehyde is to be commercially manufactured on an industrial scale from methanol and air in the presence of a sliver catalyst or the use of a metal oxide catalyst. This is why novolacs (F:P <1) do not harden without the addition of a crosslinking agents, and why resoles with the formula F:P >1 will. 4. “Lignin-based polycondensation resins for wood adhesives,” Journal of Applied Polymer Science 103(3), 1690-1699. 2011b). The base material choice depends on the intended application of the finished product. Phenolic resins account for a large portion of phenol production. A., and Yousef, M. A. 2017). Formaldehyde resin is a synthetic resin product made with formaldehyde as a base ingredient. Phenol-formaldehyde (PF) adhesives are frequently used for the production of particular wood-based composites, such as plywood, laminated veneer lumber, glue laminated timber, fiberboard, and particleboard (Malutan et al .  The phenolic units are mainly linked by methylene and/or ether groups. Exterior plywood, oriented strand boards (OSB), engineered laminated composite lumber (LCL) are typical applications. We manufacture premium Quality Phenol Formaldehyde Resin covering both NOVOLAC and RESOL for Refractory and Foundry Industry. In this research work, modified phenol-formaldehyde resins were prepared using hydroxymethylated alkaline rice straw lignin as a substitute for petroleum-based phenol in the range of 20 to 50% by weight. Synthetic resin bonded paper, made from phenolic resin and paper, is used to make countertops. Our solid RESI-FLAKE ® resins were developed for use in the production of foundry shell molds and cores by the hot-sand process. The obtained mixture was heated to 50ºC and kept at this temperature for 8 h according to the optimum conditions reported in our previous research works on lignin hydroxymethylation (El Mansouri et al. Being thermosets, hydroxymethyl phenols will crosslink on heating to around 120 °C to form methylene and methyl ether bridges through the elimination of water molecules. The most common application of Phenol-Formaldehyde Resins is in adhesives for bonding wood products, especially those desired for exterior plywood. 1) (Forss and Fuhrmann1979), (b) the material comes from renewable resources, and (c) it can be used as a macromolecular material without previous treatment (Nimz 1983; Pang et al. surface materials are transferred to blenders, in which the particles are mixed with resin, wax, and other additives by means of spray nozzles, tubes, or atomizers. ), Wood Adhesives Chemistry and Technology, Marcel Dekker, New York, pp. A test tube equipped with a plunger was filled with 10 g of unmodified and modified phenolic resins and then placed in an oil bath under a constant temperature of 130°C.The resin was mixed at short time intervals and the gel point was reached when the plunger could not be moved up. Paper phenolics are used in manufacturing electrical components such as punch-through boards, in household laminates, and in paper composite panels. One reacts phenol and formaldehyde directly to produce a thermosetting network polymer, while the other restricts the formaldehyde to produce a prepolymer known as volcano which can be moulded and then cured with the addition of more formaldehyde and heat. “Lignocellulosic ethanol residue-based lignin-phenol-formaldehyde resin adhesive,” International Journal of Adhesion and Adhesives 40, 11-18. Resoles are major polymeric resin materials widely used for gluing and bonding building materials. 247-288. “Fiberboards based on sugarcane bagasse lignin and fibers,” Macromolecular Materials and Engineering 291(7), 829-839.DOI: 10.1002/mame.200600004, Jiang, X., Liu, J., Du, X., Hu, Z., Chang, H. M., and Jameel, H. (2018). The modeled response surface (Fig. Overall, the viscosity values obtained are between 330 and 790 (mPas), and most of the prepared resins have viscosities within the range of 275to425 (mPas) suitable for use in plywood manufacture (Alonso et al. Phenol formaldehyde resins (PF) or phenolic resins are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde. Figure 6 shows the FTIR-spectrum of lignin raw material used for resins preparation. DOI: 10.1039/C4RA09595B, Zhao, M., Jing, J., Zhu, Y., Yang, X., Wang, X., and Wang, Z. The viscosities of both unmodified and modified liquid phenol formaldehyde resol resins were determined using a Brookfield viscosimeter at 30 rpm at 25 °C. (2011).”Challenges in industrial applications of technical lignins,”BioResources 6(3), 3547-3568. Norm ISO 9397. Infrared spectra of lignin-based phenol formaldehyde (LPF) resins showed structural similarity with that of PF resin. Base-catalysed phenol-formaldehyde resins are made with a formaldehyde to phenol ratio of greater than one (usually around 1.5). “Organosolv wheat straw lignin as a phenol substitute for green phenolic resins,” BioResources 11(3), 5797-5815. By contrast, organosolv lignin, hydrolysis lignin, and soda lignin are produced in minor quantities. (1979). Solid content was determined by gravimetry from the weighted amount of resin before and after drying the resin samples at 150 °C for 30 min. Phenol reacts with formaldehyde at the ortho and para sites (sites 2, 4 and 6) allowing up to 3 units of formaldehyde to attach to the ring. At this point the resin is a 3-dimensional network, which is typical of polymerised phenolic resins. “Finnish plywood, particleboard, and fiberboard made with a lignin-base adhesive,” Forest Products Journal 29(7), 39-43. 2011; Jung et al. “Methods to improve lignin’s reactivity as a phenol substitute and as replacement for other phenolic compounds: A brief review, “BioResources 6(3), 3515-3525. 7. FTIR-spectra of (a) PF, (b) LPF with L=35% (LPF10), and (c) LPF with L=50% (LPF2). The Manufacturing Process A. In the PF, a band at 3373 cm-1was observed, which shows the presence of OH groups. 1994; Alonso et al. “Co-ordination network for lignin – Standardisation, production and applications adapted to market requirements (EUROLIGNIN),” Industrial Crops and Products 20(2), 121-129. The structural differences and similarities between the prepared resins were determined by FTIR spectroscopy. Phenolic resins are found in myriad industrial products. The base material choice depends on the intended application of the finished product. Bakelite was patented on December 7, 1909. This variable is of interest because of its influence on the resin storage life. Manufacturer of Resin Plant - Phenolic Resin Plant, Polyester Resin Plant, Phenol Formaldehyde Resin Plant and Resin Manufacturing Plant offered by Vinayak Industries, Thane, Maharashtra. The former of these two gives a complete reaction of oxygen. (ed. Phenol-formaldehyde resins are heat-resistant and waterproof, though somewhat brittle. The sodium hydroxide (0.1 N) was used to adjust the pH to 3.5. Among all of the modification treatments that increase reactive sites in lignin, the phenolation and hydroxymethylation modifications are the most studied and effective for formulation of phenolic resins (Nada et al. There are two main production methods. DOI: 10.3390/molecules22111850, Tachon, N., Benjelloun-Mlayah, B., and Delmas, M. (2016). The analysis of variance reported in Table 3, showed that pH was significantly influenced only by (S/PL) at the p=0.05 significance level. Phenolic laminates are made by impregnating one or more layers of the base material such as paper, fiberglass or carbon with phenolic resin and laminating the resin saturated base material under heat and pressure. The process may be carried out as follows; • A mixture of phenol and formaldehyde are allowed to react in the presence of a catalyst i.e.Oxalic acidandsodium hydroxide. DOI: 10.1016/j.ijadhadh.2015.10.010, Zhang, W., Ma, Y., Xu, Y., Wang, C., and Chu, F. (2013). This resin is also produced by substituting methylphenols in place of phenols. The feature common to all composite processes is the combining of a resin, a curing agent, some type of reinforcing fiber, and in some cases a solvent. The used apparatus for gel time determination operates in accordance with ISO 9396 B. It was developed by the Belgian-American chemist Leo Baekeland in Yonkers, New York, in 1907. The molecular weights are in the low thousands, corresponding to about 10–20 phenol units. Bisphenol-F can further link generating tri- and tetra-and higher phenol oligomers. 2016). This product is used in a wide variety of settings and industries, and is one of the oldest synthetic resins around. The Dutch painting forger Han van Meegeren mixed phenol formaldehyde with his oil paints before baking the finished canvas, in order to fake the drying out of the paint over the centuries. 2004). 6. FTIR spectroscopy analysis showed that the spectra of LPF resins were structurally similar to that of the unmodified PF resin.
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