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Synthesis of phenolic resins by substituting phenol with modified spruce kraft lignin

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Abstract

In this study, a commercial kraft lignin (KL) was used as the raw material to prepare phenolic resin (PF) based on a detailed analysis of its molecular structure. To further increase the viscosity of the phenolic resins and improve their environmental performance, demethylated and hydroxymethylated KL (DKL and HKL) were also prepared and used to produce DKLPF and HKLPF. Compared with the methoxy content of KL, that of DKL was lower by 39.34%, and the alcoholic hydroxyl contents of HKL were higher by 59.39%. Therefore, the increased active sites on the benzene ring of DKL promote the hydroxymethylation reaction, and HKL adds more methylol groups, which is more conducive to the condensation reaction to produce PF. The synthesis process and properties of the lignin-based PF with high phenol substitution rates were investigated. The results showed that the maximum substitution rates of KL, DKL, and HKL to replace phenol to prepare phenolic resin were 70%, 50%, and 30% (w/w). The viscosity, free formaldehyde content, and other important indices of LPF meet the requirements of the GB/T14732-2017 standard. Besides, as the substitution rate of phenol by lignin increases, the viscosity of DKLPF and HKLPF performance is higher. When the 30% (w/w) phenol was replaced by lignin, the adhesive strengths of KLPF, DKLPF, and HKLPF all reached the maximum, and the trend of adhesive strengths was KLPF < DKLPF < HKLPF.

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References

  • Ahvazi B, Cloutier E, Wojciechowicz O, Ngo TD (2016) Lignin profiling: a guide for selecting appropriate lignin as precursors in biomaterials development. ACS Sustain Chem Eng 4(10):5090–5105

    Article  CAS  Google Scholar 

  • Aini N, Othman N, Hussin MH, Sahakaro K, Hayeemasae N (2019) Hydroxymethylation-modified lignin and its effectiveness as a filler in rubber composites. Processes 7(5):315–336

    Article  CAS  Google Scholar 

  • Alonso MV, Oliet M, Pérez JM, Rodríguez F, Echeverría J (2004) Determination of curing kinetic parameters of lignin–phenol–formaldehyde resol resins by several dynamic differential scanning calorimetry methods. Thermochim Acta 419:161–167

    Article  CAS  Google Scholar 

  • Alvaro T, Cristina P, Jalel L, Juan ME, Iñaki M (2007) Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis. Biores Technol 98:1655–1663

    Article  Google Scholar 

  • Argyropoulos D (1994) Quantitative phosphorus-31 NMR analysis of six soluble lignins. J Wood Chem Technol 14(1):65–82

    Article  CAS  Google Scholar 

  • Chai Y, Liu J, Zhao Y, Zhao Y, Yan N (2016) Characterization of modified phenol formaldehyde resole resins synthesized in situ with various boron compounds. Ind Eng Chem Res 55(37):9840–9850

    Article  CAS  Google Scholar 

  • Chen Y, Gong XW, Yang GS, Li Q, Zhou N (2019) Preparation and characterization of a nanolignin phenol formaldehyde resin by replacing phenol partially with lignin nanoparticles. RSC Adv 9:29255–29262

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Chen Y, Zhang H, Zhu Z, Fu S (2020) High-value utilization of hydroxymethylated lignin in polyurethane adhesives. Int J Biol Macromol 152:775–785

    Article  CAS  PubMed  Google Scholar 

  • Effendi A, Gerhauser H, Bridgwater AV (2008) Production of renewable phenolic resins by thermochemical conversion of biomass: a review. Renew Sustain Energy Rev 12:2092–2116

    Article  CAS  Google Scholar 

  • Fleckenstein M, Biziks V, Mai C, Holger M (2018) Modification of beech veneers with lignin phenol formaldehyde resins in the production of laminated veneer lumber (LVL). Eur J Wood Products 76:843–851

    Article  CAS  Google Scholar 

  • Gilca IA, Ghitescu RE, Puitel AC, Popa VI (2014) Preparation of lignin nanoparticles by chemical modification. Iran Polym J 23(5):355–363

    Article  CAS  Google Scholar 

  • Gravitis J, Abolins J, Tupciauskas R, Veveris A (2010) Lignin from steam-exploded wood as binder in wood composites. J Environ Eng Landsc Manage 18(2):75–84

    Article  Google Scholar 

  • Hu LH, Pan H, Zhou YH, Hes CY, Liu CG, Zhang BF (2014) Chemical groups and structural characterization of lignin via thiol-mediated demethvlation. J Wood Chem Technol 34(2):122–134

    Article  CAS  Google Scholar 

  • Hussin MH, Rahim AA, Ibrahim MNM, Brosse N (2013) Physicochemical characterization of alkaline and ethanol organosolv lignins from oil palm (Elaeis guineensis) fronds as phenol substitutes for green material applications. Indus Crops Prod 49:23–32

    Article  CAS  Google Scholar 

  • Khan MA, Ashraf SM (2005) Development and characterization of a lignin-phenol-formaldehyde wood adhesive using coffee bean shell. J Adh Ence Technol 19(6):493–509

    Article  CAS  Google Scholar 

  • Li JJ, Wang W, Zhang SF, Gao Q, Zhang W, Li JZ (2016) Preparation and characterization of lignin demethylated at atmospheric pressure and its application in fast curing biobased phenolic resins. RSC Adv 6(71):67435–67443

    Article  CAS  Google Scholar 

  • Li M, Yoo CG, Pu Y, Ragauskas AJ (2017) 31P NMR chemical shifts of solvents and products impurities in biomass pretreatments. ACS Sustain Chem Eng 6(1):1265–1270

    Article  Google Scholar 

  • Li N, Li Y, Yoo CG, Yang X, Lin X, Ralph J, Pan X (2018) An uncondensed lignin depolymerized in the solid state and isolated from lignocellulosic biomass: a mechanistic study. Green Chem 20(18):4224–4235

    Article  CAS  Google Scholar 

  • Li NZ, Chen ZG, Zhang YF (2019) Preparation and characterization of phenol formaldehyde resin adhesives modified by the phenolic lignin. Chem Indus for Prod 39:95–101

    Google Scholar 

  • Lin ZX, Ouyang XP, Yang DJ, Deng YH, Qiu XQ (2010) Effect of hydroxvmethylation of lignin on the properties of lignin-phenol-formaldehyde resins. World Sci-Tech RandD 32:348–351

    Google Scholar 

  • Ma Y, Zhao X, Chen X, Wang Z (2011) An approach to improve the application of acid-insoluble lignin from rice hull in phenol-formaldehyde resin. Colloids Surf, A 377(1–3):284–289

    Article  CAS  Google Scholar 

  • Malutan T, Nicu R, Popa VI (2008) Contribution to the study of hydroxymethylation reaction of alkali lignin. BioResources 3(1):13–20

    CAS  Google Scholar 

  • Mohamad Ibrahim MN, Ghani AM, Nen N (2007) Formulation of lignin phenol formaldehyde resins as a wood adhesive. Malaysian J Anal Sci 11(1):213–218

    Google Scholar 

  • Okamoto T, Takeda H, Funabiki T, Takatani M, Hamada R (1996) Fundamental studies on the development of lignin-based adhesives, I. catalytic demethylation of anisole with molecular oxygen. React Kinet Catal Lett 58(2):237–242

    Article  CAS  Google Scholar 

  • Qiao W, Li S, Guo G, Han S, Ren S, Ma Y (2015) Synthesis and characterization of phenol-formaldehyde resin using enzymatic hydrolysis lignin. J Ind Eng Chem 21:1417–1422

    Article  CAS  Google Scholar 

  • Springer SD, He J, Chui M, Little RD, Foston M, Butler A (2016) Peroxidative oxidation of lignin and a lignin model compound by a manganese SALEN derivativef. ACS Sustain Chem Eng 4(6):3212–3219

    Article  CAS  Google Scholar 

  • Stücker A, Schütt F, Bodo S, Ralph L (2016) Lignins from enzymatic hydrolysis and alkaline extraction of steam refined poplar wood: utilization in lignin-phenol-formaldehyde resins. Ind Crops Prod 85:300–308

    Article  Google Scholar 

  • Tejado A, Pena C, Labidi J, Mondragon I (2007) Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis. Biores Technol 98(8):1655–1663

    Article  CAS  Google Scholar 

  • Teodor M, Raluca N, Popa VI (2007) Contribution to the study of hydroxymetylation reaction of alkali lignin. BioResources 3(1):13–20

    Google Scholar 

  • Vishtal A, Kraslawski A (2011) Challenges in industrial applications of technical lignins. BioRes 6(3):3547–3568

    Article  Google Scholar 

  • Wang H, Eberhardt TL, Wang C, Gao S, Pan H (2019) Demethylation of alkali lignin with halogen acids and its application to phenolic resins. Polymers 11(11):1771–1787

    Article  CAS  PubMed Central  Google Scholar 

  • Wu SB, Zhan HY (2001) Characteristics of demethylated wheat straw soda lignin and its utilization in lignin-based phenolic formaldehyde resins. Cellul Chem Technol 35(3):253–262

    Google Scholar 

  • Xia CL, Guo TF, Xu YZ, Wang CP (2016) Preparation and structural characterization of hydroxymethylated lignin assisted by microwave irradiation. Biomass Chem Eng 50:12–16

    Google Scholar 

  • Xie S, Sun Q, Pu Y, Lin F, Sun S, Wang X, Ragauskas AJ (2017) Advanced chemical design for efficient lignin bioconversion. ACS Sustain Chem Eng 5(3):2215–2223

    Article  CAS  Google Scholar 

  • Xu YR, Guo LF, Zhang HN, Zhai HM, Ren H (2019) Research status, industrial application demand and prospects of phenolic resin. RSC Adv 9(50):28924–28935

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Zhang W, Ma YF, Wang CP, Li S, Zhang M, Chu FX (2013a) Preparation and properties of lignin-phenol-formaldehyde resins based on different biorefinery residues of agricultural biomass. Ind Crops Prod 43:326–333

    Article  Google Scholar 

  • Zhang W, Ma YF, Xu YZ, Wang CP, Chu FX (2013b) Lignocellulosic ethanol residue-based lignin-phenol-formaldehyde adhesive. Int J Adh Adhesiv 40:11–18

    Article  Google Scholar 

  • Zhang HN, Ren H, Zhai HM (2021) Analysis of phenolation potential of spruce kraft lignin and construction of its molecular structure model. Ind Crops Prod 167:113506

    Article  CAS  Google Scholar 

  • Zhao LW, Griggs BF, Chen CL, Hse CY (1994) Utilization of softwood kraft lignin as adhesive for the manufacture of reconstituted wood. J Wood Chem Technol 14(1):127–145

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The project was supported by the foundation (No. KF 201803) of state key laboratory of biobased material and green papermaking, Qilu University of Technology, Shandong Academy of Sciences. The authors are also grateful for the support of the National Key Basic Research Program of China (No. 202010298105Y). The work was also supported by the Nanjing Forestry University Outstanding Youth Fund (No. NLJQ 2015-5). The research did not receive any specific Grant from funding agencies in the public, commercial, or not-for profit sectors.

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Authors and Affiliations

  1. State Key Laboratory of Biobased Material and Green Papermaking, Key Laboratory of Pulp and Paper Science and Technology of Shandong Province/Ministry of Education, Qilu University of Technology, Shandong Academy of Sciences, Jinan, 250353, China

    Qi Liu, Fangong Kong & Hao Ren

  2. Jiangsu Provincial Key Lab of Pulp and Paper Science and Technology, NanJing Forestry University, NanJing, 210037, Jiangsu Province, China

    Qi Liu, Yanru Xu, Hao Ren & Huamin Zhai

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  1. Qi Liu
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Correspondence to Hao Ren.

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Liu, Q., Xu, Y., Kong, F. et al. Synthesis of phenolic resins by substituting phenol with modified spruce kraft lignin. Wood Sci Technol 56, 1527–1549 (2022). https://doi.org/10.1007/s00226-022-01408-8

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  • DOI: https://doi.org/10.1007/s00226-022-01408-8

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