The resin fully polymerizes (cures) during this process forming the thermoset polymer matrix. The gel time is an important parameter to take into consideration when resins are formulated, because it determines the resins reactivities. The kettle is kept under continuous agitation. where X1, X2, and X3 are the values of L(%), [F/(P+L)], and [S/(P+L)], respectively after normalization to the interval [-1,1]. 2004 and2005; Yang et al. The sodium hydroxide (0.1 N) was used to adjust the pH to 3.5. Para tertiary butylphenol formaldehyde resin, https://en.wikipedia.org/w/index.php?title=Phenol_formaldehyde_resin&oldid=982843590, Chemicals that do not have a ChemSpider ID assigned, Articles containing unverified chemical infoboxes, Creative Commons Attribution-ShareAlike License, This page was last edited on 10 October 2020, at 18:16. The partial substitution of phenol by fillers or extenders is one way to reduce the price of these resins. DOI: 10.1002/app.1983.070280209. Intratec offers professional, easy-to-understand reports examining Phenol-Formaldehyde Resins production. The prepared hydroxymethylated lignin was copolymerized with phenol and formaldehyde at 80 ºC in a glass flask equipped with a condenser, a thermometer to control temperature, and an overhead stirrer. 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. The most common application of Phenol-Formaldehyde Resins is in adhesives for bonding wood products, especially those desired for exterior plywood. Available Variants : Resin for Magnesia-Carbon Bricks - PROREZ 7015; Resin for Blast Furnace Tap-hole Mass - PROLAC ABC The base material choice depends on the intended application of the finished product. 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. “Organosolv wheat straw lignin as a phenol substitute for green phenolic resins,” BioResources 11(3), 5797-5815. One of its important applications is as an adhesive for wood-based panels manufacturing. 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. 10.1021/bk-1989-0385.ch005, Alonso, M. V., Rodriguez, J. J., Oliet, M., Rodriguez, F., Garcia, J., and Gilarranz, M. A. Bands at 2937 cm-1 and 2846 cm-1 are the consequence of in-plane and out-of-plane stretching of aliphatic -CH2-. 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. Formation of phenol-formaldehyde resins. Novolac is a type of formaldehyde phenol resin. In any case, the final pH of the synthesized resol resins can be corrected by addition of base or acid solution. The prepared resins were characterized according to gel time, solids content, viscosity, and free formaldehyde.The values for these parameters must be in agreement with commercial resins specifications applied for plywood. Preparation and Characterization of Phenol-Formaldehyde Resins Modified with Alkaline Rice Straw Lignin, Nour-Eddine El Mansouri,b,c,* Qiaolong Yuan,a and Farong Huanga,*, Keywords: Adhesives; Hydroxymethylation; Lignin; Phenol formaldehyde; Wood panels. 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. However the second type of catalyst achieves almost complete methanol conversion. DOI:10.1016/j.ijbiomac.2014.10.020, Khan, M. A., and Ashraf, S. M. (2005). “Lignins for phenol replacement in novolac-type phenolic formulations. “The isolation and characterization of lignin of kenaf fiber,” Journal of Applied Polymer Science 114(3), 1896-1901. 1999). Ma, Z., Li, S., Qiao, W., and Ren, S. (2016). 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. Finally, 10 mL of a hydroxylamine-hydrochloride solution (10%, w/w) was added. “Preparation and performance of lignin-phenol-formaldehyde adhesives,” International Journal of Adhesion and Adhesives64, 163-167. 3. “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. This lignin was purified by its treatment with sulfuric acid (1%) several times and washed extensively with hot water to remove the inorganic substances and solubilize the residual sugars (El Mansouri et al.2006 and 2011a).The formaldehyde (35to40% aqueous solution) and phenol (99%), used in this work were purchased from Sigma Aldrich and used as received. Structure of PF resin and lignin (Forss and Fuhrmann 1979). 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. 2016; Tachon et al. At this point the resin is a 3-dimensional network, which is typical of polymerised phenolic resins. Bakelite was patented on December 7, 1909. The first part of the reaction, at around 70 °C, forms a thick reddish-brown tacky material, which is rich in hydroxymethyl and benzylic ether groups. 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. The resin fully polymerizes (cures) during this process. 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. DOI: 10.1002/app.29881, Yang, S., Wen, J. L., Yuan, T. Q., and Sun, R. C. (2014). PF resins are manufactured in batch process. 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. The polymerization is brought to completion using acid-catalysis such as sulfuric acid, oxalic acid, hydrochloric acid and rarely, sulfonic acids. DOI: 10.1021/acssuschemeng.8b00369, Jung, S., Joo, H., Jin, E., Song, Y., and Bae, H. (2015). 3) shows that for L=35%, the pH increased with increase of (S/PL) molar ratio. J. G. Ferguson, W. E. Grutzner, D. C. Koehler, 2001; El Mansouri et al. FTIR spectroscopy analysis showed that the spectra of LPF resins were structurally similar to that of the unmodified PF resin. The structural differences and similarities between the prepared resins were determined by FTIR spectroscopy. FTIR spectroscopy was employed to characterize the structure of the lignin raw material and the prepared modified phenolic resins. Used as the basis for Bakelite, PFs were the first commercial synthetic resins (plastics). All rights reserved. 2. Our formaldehyde (CAS 50-00-0) and urea formaldehyde concentrate 85% are produced via DB Western technology. Phenolic resins are found in myriad industrial products. The resin fully polymerizes (cures) during this process forming the thermoset polymer matrix. Estimated response surface for gel time at [F/(P+L)]=2.2, L(%) vs.[S/(P+L)]. Sellers, T., Lora, J. H., and Okuma, M. (1994). “Structures, and reactivities with formaldehyde, of some acetosolv pine lignins,” Journal of Wood Chemistry and Technology 19(4), 357-378. Production of Phenol-formaldehyde Adhesives from Catalytic Pyrolysis Oil Angela M. Akude Utah State University Follow this and additional works at: https://digitalcommons.usu.edu/etd Part of the Biological Engineering Commons Recommended Citation Akude, Angela M., "Production of Phenol-formaldehyde Adhesives from Catalytic Pyrolysis Oil" (2017). None reported. A glass flask equipped with a condenser, a thermometer, and an overhead stirrer was charged with the above solution, and then formaldehyde aqueous solution was added according to the molar ratios of formaldehyde to lignin of1.0. Phenol formaldehyde resins (PF) or phenolic resins are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde. 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. Novolaks (or novolacs) are phenol-formaldehyde resins with a formaldehyde to phenol molar ratio of less than one. This resin is also produced by substituting methylphenols in place of phenols. 2820 Faucette Dr., Campus Box 8001Raleigh, NC 27695. 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. Phenol-formaldehyde is degraded by the white rot fungus Phanerochaete chrysosporium. “Use of a methylolated softwood ammonium lignosulfonate as partial substitute of phenol in resol resins manufacture,” Journal of Applied Polymer Science 94(2), 643-650. 2017).There are several modification methods such as demethylation, reduction, oxidation, and hydrolysis that have been studied to improve the reactivity of lignin as well as to produce phenolic compounds from lignin (Hu et al. “Waste liquors from cellulosic industries.4. Another use of phenolic resins is the making of Duroplast, used in the Trabant automobiles. (2004). Table 5.Analysis of Variance for Viscosity at 25 °C, Fig. Lignins are currently produced by several pulping and ethanol processes, but only lignosulfonates and kraft lignin are available in large quantities (Gosselink et al. It is a thermosetting phenol formaldehyde resin, formed from a condensation reaction of phenol with formaldehyde. 4. (2006). DOI: 10.3390/molecules22111850, Tachon, N., Benjelloun-Mlayah, B., and Delmas, M. (2016). 1997; Alonso et al. 1999; Alonso et al. However, phenol-formaldehyde resin may be used for particleboard produced for exterior applications. (2007). “Characterization and phenolation of biorefinery technical lignins for lignin-phenol-formaldehyde resin adhesive synthesis,” RSC Advances 4(101), 57996-58004. 2001).The band observed at 1386 cm-1 in LPF is attributed to lignin, which is assigned to C-O of syringyl unit present in lignin. 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. 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. 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. Resoles are major polymeric resin materials widely used for gluing and bonding building materials. DOI: 10.1002/app.20887, Alonso, M. V., Oliet, M., Rodriguez, F., Garcia, J., Gilarranz, M. A., and Rodriguez, J. J. In PF the band at 1474 cm-1 is assigned to -CH- deformation in -CH2– groups. The obtained resins were cooled and stored at lower temperature pending to analysis. This product is used in a wide variety of settings and industries, and is one of the oldest synthetic resins around. Similarly, these bands are also present in LPF with 35% and 50% of lignin. DOI: 10.1039/C4RA09595B, Zhao, M., Jing, J., Zhu, Y., Yang, X., Wang, X., and Wang, Z. 247-288. The former of these two gives a complete reaction of oxygen. DOI: 10.1163/1568561054352577, Li, J., Zhang, J., Zhang, S., Gao, Q., Li, J., and Zhang, W. (2018). “Finnish plywood, particleboard, and fiberboard made with a lignin-base adhesive,” Forest Products Journal 29(7), 39-43. The pellets were prepared with a mixture of 300 mg potassium bromide and 5-10 mg of analyzed samples. Treatment of phenol-formaldehyde resin manufacturing wastewater by the electrocoagulation process February 2012 Desalination and water treatment 39(1-3):176-181 Phenolic resin is used as a binder in loudspeaker driver suspension components which are made of cloth. Peng, W. (1994). A., and Foster, N. C. (1989). 2016; Norambuena et al. A., and Yousef, M. A. Allan, G. G., Dalan, J. We manufacture premium Quality Phenol Formaldehyde Resin covering both NOVOLAC and RESOL for Refractory and Foundry Industry. 2011b). 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. This variable is of interest because of its influence on the resin storage life. 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 . Bisphenol-F can further link generating tri- and tetra-and higher phenol oligomers. Moreover, the band at 1474 cm-1is not very intensive in both LPF, which indicates that methylolated lignin molecule incorporates hydroxymethyl groups in the LPF (Nada et al. R. S. Skinner, M. T. Skubiak, and D. H. Wetherell. 1 injured. The higher or lower values indicate a slow or fast curing reaction, respectively. Phenol-formaldehyde resins, as a group, are formed by a step-growth polymerization reaction that can be either acid- or base-catalysed. “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). for Plastics, Phenolic Resins, Determination of Free Formaldehyde Content by Hydroxylamine Hydrochloride Method. [1][2] There are many variations in both production and input materials that are used to produce a wide variety of resins for special purposes. Some of the lignins that have been used in phenolic resins are derived from annual plants such as flax (Tejado et al. “Kraft lignin behavior during reaction in an alkaline medium,” Biomass & Bioenergy 35(5), 2072-2079. 1994; Alonso et al. Fig. In place of phenol itself, they are often produced from cresols (methylphenols). “Kraft lignin depolymerization in an ionic liquid without a catalyst,” BioResources 10(3), 4933-4946. 1989; Sellers et al. (2016). 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. The fitted model for pH gave an R2 value of 89.7% and a standard deviation of residuals (SDR) of 0.55. DOI: 10.1016/j.eurpolymj.2015.03.029, Roczniak, K., Biernacka, T., and Skarzynski, M. (1983). “Sustainable bio-based phenol-formaldehyde resoles using hydrolytically depolymerized kraft lignin,” Molecules 22(11), 1850. DOI: 10.1016/j.indcrop.2017.07.009. 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. (2000). Phenol-formaldehyde resins are heat-resistant and waterproof, though somewhat brittle. DOI: 10.1016/j.indcrop.2018.04.027. The initial reaction in all cases involves the formation of a hydroxymethyl phenol: The hydroxymethyl group is capable of reacting with either another free ortho or para site, or with another hydroxymethyl group. Formaldehyde Resin Phenolic Resin Drilling Fluids Filtration Control Agent Phenol Formaldehyde Resin. Phenolic micro-balloons are used for density control. ), Wood Adhesives Chemistry and Technology, Marcel Dekker, New York, pp. 1987; Allan et al. DOI: 10.1016/j.jechem.2017.02.007. In this video the preparation of a phenol formaldehyde resin is shown. “Structure-property relationships for technical lignins for the production of lignin-phenol-formaldehyde resins,” Industrial Crops and Products 108, 316-326. Phenolic resins account for a large portion of phenol production. 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 modified phenol formaldehyde resins were dissolved in isopropanol-water mixture (2:1, v/v) and hydrochloric acid was added until pH was in the range 2 to 3. The base material choice depends on the intended application of the finished product. Fig. Phenolic Resins: Chemistry, Applications, Standardization, Safety and Ecology. A very fast cure can cause the lost of the final properties of the board. Fig. Persistence Market Research delivers comprehensive information in the global phenolic resins market, in its latest report, which includes global … 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. Article submitted: October 11, 2011; Peer review completed: January 8, 2012; Revised version received and accepted: August 12, 2018; Published: September 7, 2018. Synthetic resin bonded paper, made from phenolic resin and paper, is used to make countertops. 2008a; Bertaud et al. DOI: 10.1016/j.ijadhadh.2012.08.004. Analysis of Variance for Gel Time, Fig. 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. “Highly efficient de-polymerization of organosolv lignin using a catalytic hydrothermal process and production of phenolic resins / adhesives with the depolymerized lignin as a substitute for phenol at a high substitution ratio,” Industrial Crops & Products 44, 315-322. [3] The phenolic units are mainly linked by methylene and/or ether groups. 2016). 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. “Co-ordination network for lignin – Standardisation, production and applications adapted to market requirements (EUROLIGNIN),” Industrial Crops and Products 20(2), 121-129. Obtained polymer is thermoplastic and require a curing agent or hardener to form a thermoset. The absence of peaks at 1708 cm-1 and 1646 cm-1 is a characteristic of alkali soluble lignin fractions. (2011).”Challenges in industrial applications of technical lignins,”BioResources 6(3), 3547-3568. China; b: Laboratory of Biological Engineering, Faculté des Sciences et Téchniques, Sultan Moulay Slimane University (USMS), Mghila BP.523, Béni-Mellal, 23000, Morocco; c: Department of Chemistry, Polydisciplinary Faculty-USMS, Mghila BP.592, Béni-Mellal, 23000, Morocco; * Corresponding authors:elmansouri.noureddine@gmail.com; fhuanglab@ecust.edu.cn. Développement de Nouveaux Adhésifs Bases sur des Dérivés de la Lignine, Ph.D. Dissertation, UMI Dissertation Services. It has great moisture resistance, low cost and good thermal and flame resistance. 2011; Jung et al. 2006, 2007; Hu et al.2011;Mancera et al. Table 2. 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%). 1 to the Experimental Data for pH (Y1), Gel time (Y2), and Viscosity (Y3), Fig. The acquisition conditions were: spectral width of 4000to400 cm-1, 32 accumulations, and 4-cm-1 resolution. Phenol and formaldehyde are charged into the kettle in specified quantaties. 2004). Mancera, C., Ferrando, F., Salvado, J., and El Mansouri, N. E. (2011). The negative charge is delocalised over the aromatic ring, activating sites 2, 4 and 6, which then react with the formaldehyde. The process of polymerizing the compound is completed by adding acidic catalysts like sulfuric acid, oxalic acid, or sulfonic … The modified lignin from these later methods could partially replace phenol in phenol-formaldehyde resin synthesis. The base material choice depends on the intended application of the finished product. “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. Paper phenolics are used in manufacturing electrical components such as punch-through boards, in household laminates, and in paper composite panels. “Development and characterization of a lignin-phenol-formaldehyde wood adhesive using coffee bean shell,” Journal of Adhesion Science and Technology 19(6), 493-509. “Some properties and chemical-structure of phenolic resins and their derivatives,” Journal of Applied Polymer Science 28(2), 531-542. 2013; Zhao et al. DOI: 10.15376/biores.11.3.5797-5815, Tejado, A., Kortaberria, G., Pena, C., Labidi, J., Echeverria, J. M., and Mondragon, I. Lignin–Adhesive Research for Wood Composites, Forest and Wildlife Research Center. 1). An alkaline catalyst is added to initiate the reaction. This band, appearing at lower frequency, indicates strong hydrogen bonding occurs. Pulp and Paper Fundamental Research Symposia Proceedings. However, modified resins with gel time near to 10min can be considered and tested for plywood manufacturing if they present low free formaldehyde content. A suitable gel time of modified phenol formaldehyde resins used for plywood manufacture must be included between 8and10 min. Phenolic resins are found in myriad industrial products. 7. (2013) and Siddiqui et al. (1992). (2006). “Optimization of experimental variables to modify lignin fromEucalyptus globulus under alkaline catalysis,” BioResources 11(1), 1828-1842. 2017). 2013; Siddiqui et al. Manufacturer of Resin Plant - Phenolic Resin Plant, Polyester Resin Plant, Phenol Formaldehyde Resin Plant and Resin Manufacturing Plant offered by Vinayak Industries, Thane, Maharashtra. 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. DOI:10.15376/biores.11.3.6867-6879. 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. (2008). 2007, 2008), or kenaf (Yan2009), and agricultural waste such as sugar cane bagasse and wheat straw (Hoareau et al. 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.