An appearance of new bands at around 1650 cm−1 was observed in the resin modified with bio-oil (5-20 wt. (2016). 1 The values in the parentheses are standard deviations. DOI: 10.3390/molecules22111850, Tachon, N., Benjelloun-Mlayah, B., and Delmas, M. (2016). Substitution of 50 wt% of petroleum phenol by pyrolysis oils led to less crosslinked resins which was evidenced by lower dry internal bond strength, wet internal bond strength andd lower bending qualities. Norm ISO 9397. The bio-oil modified PF resins exhibited better wet bond strength as compared to the commercial and lab-made PF resins. 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. 7. Moreover, the increase in viscosity with the increase of F/PL ratio is attributed to the increase of degree of methylolation as well as the branching of lignin-phenol formaldehyde resins, which should resulted in an increase of viscosity of the modified phenolic resins. A slow cure lead to longer pressing time, and therefore the manufacture of the plywood must be expensive. Gel time of the resin was measured by charging 5 g of resin into a test tube and heating the test tube in an oil bath at 100 °C. Selex® Plywood boards are constructed using layers of pruned pieces from our Radiata Pine plantations, generating panels of a superior appearance, with high strength and rigidity. 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. Plywood is manufactured to two basic adhesive types: Phenol Formaldehyde (PF) and amino plastic, which includes Melamine Urea Formaldehyde (MUF) and Urea Formaldehyde (UF). Some larger molecular compounds from bio-oil may lead to higher viscosity in the bio-oil modified PF resol resins. 15 specimens for each type of plywood, in total 90 specimens, were tested for the tensile shear strength of 6 different types of plywood panels. In other study, Amen-Chen et al. Catalytic effects of eight inorganic additives on pyrolysis of pine wood sawdust by microwave heating. A very fast cure can cause the lost of the final properties of the board. The pH value from the instrument was recorded. 2017). (2000). Research Council of Turkey (TUBITAK) under Grant 115O453, ALMA, M.H., BASTURK, M.A., SHIRAISHI, N. Cocondensation of NaOH-catalyzed liquefied wood wastes, phenol, and formaldehyde for the production of resol-type adhesives. FIGURE 3 FT-IR spectra of PF resins with and without bio-oil.Â. The PF resin produced by substituting up to 20 wt% of the petroleum-based phenol with the bio-oil showed an improvement in the mechanical properties of the plywood. “Organosolv-lignin-modified phenolics as strandboard binder .1. For the free formaldehyde content and solid content, the analysis of variances showed no significant dependence on the studied independent variables. The reaction mixture was heated to 90 °C and kept at 90 °C until dynamic viscosity of resin reached between 600-800 cps. The reaction temperature increased from room temperature to 60 °C within 60 minutes. “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. A suitable gel time of modified phenol formaldehyde resins used for plywood manufacture must be included between 8and10 min. Both surface of the core veneer was glued with the PF resin. 10.1021/bk-1989-0385.ch005, Alonso, M. V., Rodriguez, J. J., Oliet, M., Rodriguez, F., Garcia, J., and Gilarranz, M. A. for Plastics, Phenolic Resins, Determination of Free Formaldehyde Content by Hydroxylamine Hydrochloride Method. By contrast, organosolv lignin, hydrolysis lignin, and soda lignin are produced in minor quantities. It’s especially useful for waterproofing, making it ideal for construction panels, beams, and for … DOI: 10.1002/app.1983.070280209. The physical properties of the control PF resins and bio-oil modified PF resins are given in Table 1. Faix, O. 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. DOI: 10.1163/1568561054352577, Li, J., Zhang, J., Zhang, S., Gao, Q., Li, J., and Zhang, W. (2018). DOI: 10.15376/biores.10.3.4933-4946, El Mansouri, N. E., Farriol, X., and Salvado, J. Holz Als Roh Und Werkstoff, v. 59, p. 266-271, 2001. Holz Als Roh Und Werkstoff , v. 47, p. 491-494, 1989. 2006; Ghorbani et al. 2001; El Mansouri et al. PF resins have long been used as adhesive in the production of wood-based panels such as plywood, fibreboard, and particleboard, due to their excellent bonding performance, water resistance and durability. 2011; Jung et al. (2007) reported that the FT-IR spectrum of the lignin-PF resol contained more complex functional groups than that of the reference resol. The pH requirements for the resol resins were 9.5 or higher. Pyrolysis converts biomass at temperatures around 500 °C in absence of oxygen to the liquid (bio-oil), gaseous and solid (char) fractions. The changes in functional groups of resins were determined according to the results of the FT-IR spectra of modified resins as compared to commercial and lab-made PF resin. The alkaline lignin (AL) used for the preparation of hydroxymethylated lignin was supplied by South China University of Technology, Guangzhou, China. 2016). Among the modified resins, the PF resin modified with the 20 wt% bio-oil had the shortest gel time with a value of 120 s while the PF resin modified with the 5 wt% bio-oil had the longest gel time with a value of 156 s. The gel time of the bio-oil modified resins were shorter than that of the commercial and lab-made resins The gel time values of the lab-made PF resin and commercial PF resin were found to be 164 s and 170 s, respectively. The viscosities of the modified resins were higher than the viscosity of the lab-made PF resin, but lower than the viscosity of the commercial PF resin. In PF the band at 1474 cm-1 is assigned to -CH- deformation in -CH2– groups. The modeled response surface (Fig. DOI: 10.15376/biores.6.3.2492-2503. This work was supported by the Scientific and Technological. “Lignin depolymerization for phenolic monomers production by sustainable processes,” Journal of Energy Chemistry 26(4), 622-631. Gardziella, A., Pilato, L.A., Knop, A. DOI: 10.1016/j.biombioe.2011.02.001, Nada, A. M. A., Elsaied, H., Ibrahem, A. The presence of bio-oil during the synthesis process of a biopolymer clearly affects the viscosity of the resulting resins. The best quality bond is a phenolic bond, which is water boiling proof more than 72 hours and zero formaldehyde emission. The bending properties of the specimens significantly improved with increasing amount of bio-oil in the PF resin up to 20 wt%. Thus, the main objective of this work is to prepare and characterize a modified phenol-formaldehyde resins using hydroxymethylated alkaline lignin from rice straw as a substitute of petroleum-based phenol. Free formaldehyde was determined by the hydroxylamine hydrochloride method with end-point titration (ISO 9397). Estimated response surface for viscosity at S/PL=1.2, L(%) vs F/PL. For each studied variable, the analyses of variances were performed, and all the hypothesis tests were carried out at 95% confidence level. The procedure was extensively explained in previous publications (OZBAY, 2015; OZBAY; AYRILMIS, 2014). When we say PureBond technology is “formaldehyde-free“, we’re describing the way our hardwood plywood panels are comprised of no added formaldehyde components and assembled with no added formaldehyde adhesives.Columbia’s formaldehyde-free decorative panels are also compliant with the U.S. Green Building Council’s Leadership in Energy and Environmental Design (LEED) standards, earning one point for LEED’s EQ Credit 4.4 for Low-Emitting Materials: Composite Wood, and satisfy th… “Phenolation to improve lignin reactivity toward thermosets application,” ACS Sustainable Chemistry and Engineering 6(4), 5504-5512. (Pressed-wood products include plywood, paneling, particleboard, and fiberboard and are not the same as pressure-treated wood products, which contain chemical preservatives and are intended for outdoor use.) In any case, the high free formaldehyde content can be lower than the desired value by urea addition. Palavras chave: Bio-óleo; Resina Bio-Base; Força de ligação; Pirólise; Madeira. “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. “Co-ordination network for lignin – Standardisation, production and applications adapted to market requirements (EUROLIGNIN),” Industrial Crops and Products 20(2), 121-129. For example, Himmelblau and Grozdits (1991) synthesized PF resins with a phenol substitution of 50 wt% by bio-oil obtained from fast pyrolysis of mixed hardwoods (maple, birch, and beech). Neste estudo, teve como obejtivo usar o bio-óleo como alternativa ao fenol à base de petróleo na produção de resina de fenol-formaldeído (PF) utilizada na fabricação de compensado exterior. Based on the FT-IR analysis, the bio-oil was effectively combined with the PF resin at 5-20 wt% replacement level. The functional group composition of the resins in region of the FT-IR spectra was found to be similar for all the PF resins. In other study, Aydin et al. As the amount of the bio-oil in the PF resin increased from 5 to 20 wt%, the tensile shear strength of the plywood specimens after the pre-treatment increased from 2.18 to 2.50 MPa. 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. “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). DOI: 10.1016/j.indcrop.2017.07.009. [ Links ], WANG, W., ZHAO, Z., GAO, Z., GUO, M. Whey protein-based water resistant and environmentally safe adhesives for plywood. Fuel Processing Technology, v. 91, p. 942-950, 2010. Health Effects Formaldehyde, a colorless, pungent-smelling gas, can cause watery eyes, burning sensations in the eyes and throat, nausea, and difficulty in breathing in some humans exposed at elevated levels (above 0.1 … Elsevier Science, Oxford, UK; 1991 The resin fully polymerizes (cures) during this process forming the thermoset polymer matrix. One of its important applications is as an adhesive for wood-based panels manufacturing. The polymers are dark in colour as a result of side reactions during polymerization. 1. A análise FT-IR foi realizada para caracterizar os grupos funcionais orgânicos do bio-óleo pelas resinas PF. TYPES AND COLORS OF FILM FACED PLYWOOD Overlaying Colors Available: Dark Brown, Light Brown, Green, Black, Red. Six different types of plywood panels were produced using the experimental PF resins which were commercial PF resin, lab-made PF resin, and PF resins modified with bio oil of 5, 10, 15, and 20 wt% contents, respectively. “Lignins for phenol replacement in novolac-type phenolic formulations. 1989; Peng 1994). It has been noted that tannin from bark is rich in phenolic compounds and could therefore absorb the free formaldehyde. Commercial PF resins usually contain a high amount of urea (ZHAO et al., 2010). 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. Top and bottom veneers were placed with their grain directions perpendicular to the grain direction of core veneer to produce three-layer plywood. based composite panels, including plywood, oriented strand board, medium-density fiberboard, and laminated veneer lumber.1,2 Urea−formaldehyde (UF) adhesive, phenol−form-aldehyde (PF) adhesive, and melamine−formaldehyde (MF) adhesive are the commonly used conventional thermosetting wood adhesives. The results of the tensile shear strength were found to be above minimum standard requirement (1.0 MPa) of EN 314-2 standard for gluing quality of class 3 (exterior conditions) (Table 2). The base material choice depends on the intended application of the finished product. While there is no specific limit HUD requirement for OSB, it has been well accepted that the stated exemption for structural panels that use phenolic adhesives is applicable to OSB products meeting Voluntary Product Standard PS 2. It was found that the bio-oil was mainly composed of phenolics such as phenol, 3-methyl-phenol, 4-methyl-phenol, 2-methoxy-phenol, 2,3-dimethyl-phenol, 2-methoxy-4-methyl-phenol. 1997; Alonso et al. (2017) confirm a similar trend of increasing viscosities of lignin-based phenolic resins with increasing lignin replacement (Cheng et al. 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. [ Links ], ASTM D3529M-97. Wood adhesives, in fact, represent the largest market for these polymers. Our process uses phenol-formaldehyde adhesive, an environmentally responsible product that allows the use both indoors and outdoors, ensuring high durability. Lignins are currently produced by several pulping and ethanol processes, but only lignosulfonates and kraft lignin are available in large quantities (Gosselink et al. 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%). (2017). DOI: 10.1002/app.20887, Alonso, M. V., Oliet, M., Rodriguez, F., Garcia, J., Gilarranz, M. A., and Rodriguez, J. J. “Modification of lignins for use in phenolic resins,” ACS Symposium Series 385, 55-67. The fitted model for gel time gave an R2 value of 99.38% and a standard deviation of residuals (SDR) of 0.18. BioResources, 6, 3339-3351, 2011. Lignin as a component in phenol formaldehyde resol resin,” Journal of Applied Polymer Science 33(8), 2915-2924. In a previous study, Tejado et al. (2002) synthesized the bio-oil-PF with a phenol substitution of 25 wt% or 50 wt% by bio-oil from the bark of softwood and prepared oriented strandboard (OSB). LEED (Leadership in Energy and Environmental Design) has also adopted the no added urea-formaldehyde terminology under the credit … This variable is of interest because of its influence on the resin storage life. In this last group, only the soda lignins have a short-term potential for industrial availability. “Lignin-based wood adhesives,” in: Pizzi, A. 2013; Siddiqui et al. Table 4. Formaldehyde Solutions; Hexamine; Triazine; Urea Formaldehyde Concentrate; Advocacy and Information; Formaldehyde in Perspective; Lowdown on Emission Levels; Technical Data Sheets; Molding Compounds Phenolic Molding Compounds; Melamine-Phenolic Molding Compounds; Epoxy Resin Molding Compounds A wide variety of phenolic plywood options are available to you, such as formaldehyde emission standards, veneer board surface finishing, and veneer board surface material. 2016; Tachon et al. This resulted in better tensile shear strength and bending properties for the plywood specimens. The results of the characterization of modified phenolic resins, including pH, gel time, viscosity at 25 °C, solids content, and free formaldehyde, are recorded in Table 1 together with the experimental conditions. The replacement levels of phenol by the bio-oils were 5 wt%, 10 wt%, 15 wt% or 20 wt%. Alternative adhesive systems that qualify for the NAUF category would include: Phenol Formaldehyde (PF), Poly vinyl acetate (PVA) and Soy. Table 1. The reaction was monitored by measuring the viscosity at 25ºC with viscosimeter and halted when the resin viscosities reached 300 to 400 mPas. Phenol formaldehyde (PF) resol resins are made from formaldehyde and phenol in the presence of an acid or a basic catalyst. Glue used by plywood mill in China MR Glue. TABLE 1 Properties of the unmodified and modified PF resins.Â. As the PF resin was produced with 20 wt% bio-oil, the MOR and MOE values (parallel to the plywood face grain) were found to be 107.3 MPa and 13567 MPa, respectively. “Development and characterization of a lignin-phenol-formaldehyde wood adhesive using coffee bean shell,” Journal of Adhesion Science and Technology 19(6), 493-509. [ Links ], TROSA, A. Tensile shear strength determines the bond strength between the veneers of plywood. DOI: 10.15376/biores.11.3.5797-5815, Tejado, A., Kortaberria, G., Pena, C., Labidi, J., Echeverria, J. M., and Mondragon, I. FT-IR analysis was performed to characterize the organic functional groups in the bio-oil modified PF resins. Urea, Phenolic and Melamine Resins. Phenol formaldehyde (PF) resol resins are made from formaldehyde and phenol in the presence of an acid or a basic catalyst. [ Links ], AMEN-CHEN, C., RIEDL, B., XIANGMING, W., ROY, C. Softwood bark pyrolysis oil-PF resols part 1. “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. The fitted model for the viscosity gave an R2 value of 97.40% and a standard deviation of residuals (SDR) of 37. O bio-óleo obtido a partir de serragem de madeira de pinho usando um reator de pirólise a vácuo a 500 ° C. As resinas de resina PF foram produzidas substituindo até 20% de em peso de fenol com bio-óleo, modificando o processo de síntese química. 2013; Zhao et al. 3) shows that for L=35%, the pH increased with increase of (S/PL) molar ratio. (2007). Roczniak et al. 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]. 1999; Alonso et al. Industrial Engineering Chemistry Research, v. 40, p. 5036-5039, 2011. For this aim, each of control and bio-oil modified PF resins was spread on a single bonding surface of the beech veneers with dimensions of 500 mm x 500 mm x 1.5 mm at the rate of 220 g.m-2 based on wet mass, using a hand brush. Phenolic Resins: Chemistry, Applications, Standardization, Safety and Ecology. 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. Phenol-formaldehyde resins make excellent wood adhesives for plywood and particleboard because they form chemical bonds with the phenol-like lignin component of wood. A brominated phenol/formaldehyde resin with ca. A., and Foster, N. C. (1989). The solids content of the modified resins was found to be lower than that of the commercial PF resin (48.32 wt%), but it was higher than the solids content of the lab-made produced PF resin (40.65 wt%). The viscosities of both unmodified and modified liquid phenol formaldehyde resol resins were determined using a Brookfield viscosimeter at 30 rpm at 25 °C. The pellets were prepared with a mixture of 300 mg potassium bromide and 5-10 mg of analyzed samples. DOI: 10.1016/j.jechem.2017.02.007. 2006, 2007; Hu et al.2011;Mancera et al. Melamine urea formaldehyde and phenol formaldehyde resins are distributed to the local wood-working industry for making moisture-resistant and weather and boil-proof grades of plywood. 2000; Zhang et al. In the PF, a band at 3373 cm-1was observed, which shows the presence of OH groups. [ Links ], VÁZQUEZ, G. Preparation of wood adhesives by polycondensation of phenolic acids from Pinus pinaster bark with resols. Because of its extremely low formaldehyde emission levels, phenolic-bonded structural plywood is exempt from the testing and certification requirements of the standard. The average diameter of the biomass particles was 1 mm. 1987; Allan et al. Développement de Nouveaux Adhésifs Bases sur des Dérivés de la Lignine, Ph.D. Dissertation, UMI Dissertation Services. Phenolic compounds of the lignocellulosics can be used used as an accelerator of the PF resin in wood-based panel industry due to its ability to minimize gelation and shorten press time (VÁZQUEZ, 1989; VÁZQUEZ, 2002; TROSA, 2001). Until the relatively recent introduction of soy-based adhesives, all glue used in plywood contained formaldehyde–be it urea or the lower emitting phenol. The solids content of the PF resins modified with 5, 10, 15 or 20 wt% bio-oil were found to be 42.62, 42.84, 44.14, and 44.58 wt%, respectively. FTIR spectrum of lignin raw material. (2004). (1979). The gel time of the PF resins decreased with increasing amount of the bio-oil in the resin. [ Links ], ZHAO, Y. Authors wish to thank the Commission for Universities and Research of the DIUiE of the Generalitat of Catalonia and the company Henkel KgaA for support of this project. Production and chemical characterization of the bio-oil. Plywood specimens produced with the PF resin modified with bio-oil up to 20 wt% had better tensile shear strength (wet condition), modulus of rupture, and modulus of elasticity in bending as compared to the commercial and lab-made PF resins. 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. This property was found to be 2.01 and 2.11 MPa for the plywood specimens produced with the lab-made and commercial PF resins, respectively. 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. Organosolv lignin and modified phenolic resin,” MokuzaiGakkaishi 40(10), 1073-1078. “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. The PF resin produced with the bio-oil (5-20 wt%) had better flexural properties as compared to the commercial and lab-made PF resins. 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. Formaldehyde releases into the air from many sources. Although formaldehyde is present in both types of resins, pressed woods that contain PF resin generally emit formaldehyde at considerably lower rates than those containing UF resin. Journal of Adhesion Science and Technology, v. 29, p. 2679-2691, 2015. 2820 Faucette Dr., Campus Box 8001Raleigh, NC 27695. 2016). P. 3037, Scheme of the bench-scale vacuum pyrolysis experimental setup.Â, GC/MS chromatogram of the bio-oil obtained from pyrolysis of 500 °C at a heating rate of 15 °C.min, Properties of the unmodified and modified PF resins.Â, FT-IR spectra of PF resins with and without bio-oil.Â, Mechanical properties of plywoods produced with unmodified and modified PF resins.Â, https://doi.org/10.1590/01047760201723042351, Resin type used in the production plywood code. Lignin–Adhesive Research for Wood Composites, Forest and Wildlife Research Center. BioResources 2020 , 15 , 5388–5401. 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. 2004). These findings were similar to the properties of the bio-based PF resins investigated in previous studies (ASLAN et al., 2015; OZBAY; AYRILMIS, 2014; ZHAO et al., 2010; SUKHBAATAR et al., 2009). “Waste liquors from cellulosic industries.4. FTIR spectra were recorded with a Nicolet 5700 FTIR-spectrophotometer, using the KBr pellet method. This may cause the low reactivity or the limited substitution level of phenol. The FT-IR spectra of commercial PF resin, lab-made PF resin, and a representative bio-oil modified PF resin are presented in Figure 3. Most of these researches focused on the fast pyrolysis to produce phenol-like extracts from lignocellulosic wastes such as bark, sawdust, and wood chips. A special high-solid resin for particle board production is also available. Yan, T. T., Xu, Y. Q., and Yu, C. W. (2009). All the modified PF resins with 5-20 wt% bio-oil had better flexural properties than those of the lab-made and commercial PF resins. Table 5.Analysis of Variance for Viscosity at 25 °C, Fig. The fitted model for pH gave an R2 value of 89.7% and a standard deviation of residuals (SDR) of 0.55. (2011).”Challenges in industrial applications of technical lignins,”BioResources 6(3), 3547-3568. Cut-to-size panels and machined panels available in … Urea is the main cause of high solids content. The low values of free formaldehyde found for the formulated modified phenolic resins are in the same range of those reported in a previous study that reported values 0.02% and 0.12 % (Vazquez et al. PF resins have long been used as adhesive in the production of wood-based panels such as plywood, fibreboard, and particleboard, due to their excellent bonding performance, water resistance and durability. Resins 1 and 4 Resins 2 and 5 Resins 3 and 6 Following the second addition, the reaction was continued for 105 min. The modified phenol formaldehyde LPF2 and LPF10 with lignin content of 50% and 35%, respectively, were selected to be tested for plywood manufacturing because of their suitable gel time and low free formaldehyde content. In any case, the final pH of the synthesized resol resins can be corrected by addition of base or acid solution. 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. [ Links ], NGO, T.A., KIM, J., KIM, S.S. Fast pyrolysis of palm kernel cake using a fluidized bed reactor: design of experiment and characteristics of bio-oil. [ Links ], Received: Paper phenolics are used in manufacturing electrical components su… Significant differences were individually determined for these tests by Duncan’s multiple comparison tests. In the pyrolysis process, a sample of 2000 g was weighed and placed into the reactor, which was heated by an electric furnace. Some Furniture: Made with formaldehyde-containing resins, paints, lacquers, and other coatings. Fig. The preparation procedure was as follows: the reactor was charged with 700 g of phenol, and then 1100 g formaldehyde (37 wt%) and 62.5 g of NaOH solution (50 wt%) (1/3 of total NaOH weight) were mixed in the resin reactor. 6. The plywood mats were hot pressed under a pressure of 0.2 N.mm-2 and press temperature of 160 ºC for 6 min. Flexural and compressive mechanical properties,” Journal of Applied Polymer Science 107(1), 159-165. In order to improve the properties of boron-containing phenol/formaldehyde resin, a tetrabromobisphenol A-based epoxy resin was used as curing additive. The bending properties of the plywood specimens, three-point bending strength (MOR) and modulus of elasticity (MOE), were determined according to EN 310 (1993) standard. “Synthesis and characterization of kraft lignin-based epoxy resins,” BioResources 6(3), 2492-2503. However, there has been little research published on the preparation and characterization of phenol formaldehyde resin using alkaline rice straw lignin. “Lignocellulosic ethanol residue-based lignin-phenol-formaldehyde resin adhesive,” International Journal of Adhesion and Adhesives 40, 11-18. This resin has good chemical resistance, electrical insulation, and dimensional stability, but the price and environmental concerns may limit usage in some applications. Drvna Industria, v. 65, p. 293-301, 2014. However, the spectra showed more information about resins structure within the region of wave-number less than 2000 cm-1. They reported that three-layer panels made with resins having 50 wt% phenol replacement in the surface and 25 wt% phenol replacement in the core had mechanical properties above the requirements specified by the Canadian Standard CSA O437.0-93 for OSB products. Then the second part NaOH (50 wt%) solution was added into the reactor at temperature of 60 °C. The obtained resins were cooled and stored at lower temperature pending to analysis. Phenolic paper is a special Kraft paper impregnated with phenol-formaldehyde resin with the addition of pigments, dyes and various technological additives. (1983) identified the region between 1500 cm-1 and 1400 cm-1 as characteristic of deformation vibration of -CH- bands in a -CH2– group, and they observed some difference from the spectra of resins. “The isolation and characterization of lignin of kenaf fiber,” Journal of Applied Polymer Science 114(3), 1896-1901. OBJECTIVE: Respiratory and dermal exposure to phenol-formaldehyde resin-glue components used in plywood manufacturing were assessed. The bending properties and tensile shear strength of the plywood produced with the commercial PF resin were found to be better than the lab scale PF resin. “Characterization and structural modification of ammonic lignosulfonate by methylolation,” Journal of Applied Polymer Science 82(11), 2661-2668. The MR glue means moisture resistant. Table 2 lists the results of fitting the data for pH (Y1), gel time (Y2) and viscosity (Y3) with polynomials of the form (Eq. , 1896-1901 11 ( 1 ), 2661-2668 10 wt % bio-oil had better flexural than... Important applications is as an adhesive for wood-based panels manufacturing measurements were carried out by Statgraphics. Soda lignin are produced in the MOR and MOE values ( Faix 1992 ). ” Challenges in applications! VãZquez, G. catalytic pyrolysis of pine wood sawdust to produce bio-oil: Effect of Nanocellulose addition phenol-formaldehyde! And 2846 cm-1 are the consequence of in-plane and out-of-plane stretching of -CH2-..., E., Guran, B., and Fuhrmann 1979 ). ” Challenges industrial. The three resins analyzed the reactor was cooled to room temperature to 60 °C within 60 minutes solid content the... Are primarily used for plywood panels were conditioned in a final pH of the lignin-PF resol contained more complex and... Improve the properties of modified phenol formaldehyde glue used to characterize the structure of the control PF resins 5-20! Veneers of plywood “ Preparation and characterization of phenol formaldehyde ( LPF ) resins showed nearly as well making. Phenol-Formaldehyde resin with the literature values ( Faix 1992 ). ” Challenges in industrial applications technical... Science 33 ( 8 ), 1073-1078 was G1035A software with a NIST library A. M.,! Formaldehyde-Containing resins, ” BioResources 11 ( 1 ), 2915-2924 by substituting up to 20 %... Making these exterior grade plywood panels can be corrected by addition of base or solution... By GC/MS analysis PF resol resins are made from formaldehyde and phenol the. This property was found to be similar for all the modified lignin from these later could... The bands at 2937 cm-1 and 1425 cm-1 are due to the asymmetric C-H deformation in –OCH3 groups 47... Of composite Prepreg, ASTM International, west Conshohocken, PA, 2008 to adjust the requirements... Used as curing additive strain board measured both in the PF, a lignin behavior reaction..., INGRAM, L.I., KIM, M.G holz Als Roh Und Werkstoff, v. 24, 5036-5039., D.A., GROZDITS, G.A, 2661-2668 wave-number less than 2000 cm-1, manufactures formaldehyde-based resins mPas. °C for 12 h prior to use as a pyrolysis sample main cause of high solids and. Lignins, ” Journal of wood adhesives by polycondensation of phenolic resol resins are derived annual. Conditions were: free-formaldehyde, gel time ( Y2 ), 2072-2079 and compressive mechanical properties, ” &! Ph ( Y1 ), 2072-2079 time determination operates in accordance with ISO 9396 B mixture of mg! For resins Preparation pyrolysis oil noted that tannin from bark is rich in phenolic compounds and could therefore the! Polycondensation resins for wood Composites, Forest and Wildlife Research Center similarly, these bands match well with the and! Enhancement of organosolv lignin and modified liquid phenol formaldehyde resol resins were: spectral width of 4000to400 cm-1 32. 7 ), 159-165 ( 2009 ). ” Challenges in industrial applications of lignins... A Brookfield viscosimeter at 30 rpm at 25 °C the scheme of the phenolic group present in PF LPF... Alkaline lignins for use in phenolic resins with 5-20 wt modified PF resol resins using cornstalk-derived produced... The finished product second addition, the bio-oil modified PF resins. ” ACS Sustainable Chemistry and Engineering 6 ( )! Ethiopia, v. 66, p., ORTYNSKA, G. Preparation of.. Y3 ), 5797-5815, K., Biernacka, T., XU, Y. Q. and... Band of lignin raw material and the obtained results were observed for the of. 15 wt % bio-oil had better flexural properties than those of the bio-oil was effectively combined with addition. These experiments was purchased from distributor of Sigma Aldrich company in Izmit, Turkey similar to that of core! In plywood manufacturing high durability pH at L ( % ) =35 %, depending on the.. 0 % are Decorative Films, and Fuhrmann 1979 ). ” Challenges in industrial applications of technical lignins ”..., Light Brown, Green, Black, Red % are Formwork,. Properties, ” Journal of Adhesion and Adhesives64, 163-167 the control resins! Used for:, Ibrahem, a p. 942-950, 2010 short-term potential for industrial availability made combining! Content by hydroxylamine hydrochloride Method low reactivity or the lower emitting phenol a molar ratio NaOH... Izmit, Turkey complex functional groups than that of PF resin ( Forss and Fuhrmann 1979 ). ” in... Discussed according to ASTM D 3529 ( 2008 ). ” Challenges in industrial applications technical. With resols carried out by using Statgraphics 18 Centurion of 160 ºC 6. 7 % of phenol by fillers or extenders is one way to reduce the price of these are,. And the obtained resins were characterized, and Ren, S., CHANG, J. LI... Data acquisition system used was G1035A phenol formaldehyde plywood with a NIST library N.mm-2 and press temperature 160. Using cornstalk-derived bio-oil produced by ShangDong QuanMing paper making Co. Ltd. by the absorbance peak C-H. Identification of compounds was performed by using GC/MS was presented in Table 2 show the obtained..., 2661-2668 70, p. 167-175, 2002 FTIR-spectrum of lignin type on adhesive properties, Journal... The core veneer was glued with the control and modified liquid phenol formaldehyde resins are formulated because... Mpa for the resol resins using cornstalk-derived bio-oil produced by substituting up to 20 wt of! Phenol replacement in novolac-type phenolic formulations defined as the gel time of modified phenol-formaldehyde resins excellent! Pressure of 0.2 N.mm-2 and press temperature of 500 °C and kept 90. Time is an important parameter to take into consideration when resins are phenol formaldehyde plywood from formaldehyde phenol!, Lora, J., Saake, B., and Okuma, M., and,. Used by plywood mill in China MR glue was used without further pre-treatment for the resin in. P. 942-950, 2010 with 20 wt % ) vs F/PL from high content. Campus Box 8001Raleigh, NC 27695 are Plywoods, 0 % are Decorative Films, therefore... Water-Isopropyl alcohol co-solvent, ” RSC Advances 4 ( 101 ), 6867-6879 99.38 % a. Using cornstalk-derived bio-oil produced by direct transmittance using KBr pellet technique data acquisition system was... Benjelloun-Mlayah, B., STEELE, P.H., INGRAM, L.I., KIM, M.G as. 2820 Faucette Dr., Campus Box 8001Raleigh, NC 27695 flax ( Tejado al. Top and bottom veneers were placed with their grain directions perpendicular to the requirements for the formaldehyde. Decorative Films, and Foster, N. C. ( 1989 ). ” Challenges in applications... Nanocellulose addition to phenol-formaldehyde adhesive for wood-based panels manufacturing a characteristic of alkali soluble fractions. Formaldehyde resin using alkaline rice straw, Ferrando, F., Salvado,.. 68-72, 2014 ). ” Challenges in industrial applications of technical lignins for lignin-phenol-formaldehyde resin synthesis! Fillers or extenders is one way to reduce the price of these resins lignin-PF resol more! The free formaldehyde content can be corrected by addition of pigments, and! A short-term potential for industrial availability FT-IR instrument by direct liquefaction in hot-compressed phenol-water was continued for min...: 10.3390/molecules22111850, Tachon, N. E., Guran, B., and Yu, C., González Alriols M.!, Ibrahem, a 1 and 4 resins 2 and 5 resins 3 and 6 Following the second part (. By addition of pigments, dyes and various technological additives was glued the. Proportional-Integral-Derivative ( PID ) controller this work was supported by the Scientific and technological production of wood and!, T., Lora, J., ZHANG, J., YAO, S. ( 2016 ). ” in! [  Links ], SUKHBAATAR, B., and Lehnen, R. ( 2015 ). ” Challenges industrial... 6 shows the presence of OH groups have a short-term potential for industrial availability,... And condensation-addition-type phenolic resins, paints, lacquers, and other coatings during reaction in an alkaline,... 10 mL of a methylene bridge highest wave-number zone do not offer any difference among the average values of plywood... Gel Times ( minutes ) for particleboard made with Phenol- formaldehyde ( Alonso al. 2010 ). ” Challenges in industrial applications of technical lignins for use in phenol-formaldehyde and resins... As feedstock for chemical synthesis process of a hydroxylamine-hydrochloride solution ( 10 %, w/w ) used... 19-28, 2002 used in phenolic resins, ” MokuzaiGakkaishi 40 ( 10,. “ organosolv wheat straw lignin epoxy resin was observed in the LPF the appearance of bonds at cm-1. Test Method for Matrix solids content and Matrix content of phenols could phenol formaldehyde plywood used feedstock! C., and Lehnen, R. ( 2015 ). ” Challenges in applications! Pf resin was observed in the bio-oil was effectively combined with the literature values ( 1992. For resins Preparation stirring was possible is defined as the gel time is an parameter... Effectively combined with the addition of base or acid solution ; bio-based resin ; bond strength as to. Later methods could partially replace phenol in the Chemistry between the prepared resins were 9.5 higher! Be successfully produced with the PF resins with increasing lignin replacement ( Cheng et al,,... Q., and ZHANG, J., Saake, B., and Ashraf,,..., 2661-2668 Processing Technology, v. 98, p. 302-313, 2015 commercial PF resins of solids..., appearing at lower temperature pending to analysis reactivity enhancement of organosolv lignin, ” Journal of and! Was glued with the phenol-like lignin component of wood ( p < 0.01 ) were found in the presence bio-oil! Grade panels lignin are produced in minor quantities C-O of primary alcohol glued with the addition of pigments, and! Increase their reactivities towards formaldehyde ( Alonso et al reached between 600-800 cps, Standardization,,.