{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,22]],"date-time":"2026-01-22T14:45:04Z","timestamp":1769093104396,"version":"3.49.0"},"reference-count":38,"publisher":"Walter de Gruyter GmbH","issue":"6","funder":[{"DOI":"10.13039\/501100001871","name":"Portuguese Foundation for Science and Technology","doi-asserted-by":"publisher","award":["UIDB\/50011\/2020"],"award-info":[{"award-number":["UIDB\/50011\/2020"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100006111","name":"Minist\u00e9rio da Ci\u00eancia, Tecnologia e Ensino Superior","doi-asserted-by":"publisher","award":["UIDP\/50011\/2020"],"award-info":[{"award-number":["UIDP\/50011\/2020"]}],"id":[{"id":"10.13039\/501100006111","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100008530","name":"European Regional Development Fund","doi-asserted-by":"publisher","award":["21874"],"award-info":[{"award-number":["21874"]}],"id":[{"id":"10.13039\/501100008530","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2020,6,25]]},"abstract":"<jats:title>Abstract<\/jats:title>\n               <jats:p>Lignin obtained by Lignoboost\u00ae procedure from black liquor after kraft pulping of <jats:italic>Eucalyptus globulus<\/jats:italic> wood was characterized and converted into liquid polyols via an innovative and safe procedure using base catalyzed oxyalkylation with propylene carbonate (PC). The effect of four catalysts, Potassium carbonate (K<jats:sub>2<\/jats:sub>CO<jats:sub>3<\/jats:sub>), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), dicyanodiamide (DICY), and 1,4-diazabicyclo [2.2.2] octane (DABCO) was evaluated in terms of lignin polyol yield and weight gain. The ensuing polyols were also characterized by fourier transform infrared (FTIR), <jats:sup>1<\/jats:sup>H NMR, <jats:sup>13<\/jats:sup>C NMR, and size exclusion chromatography (SEC) to determine the degree of the substitution (DS), degree of polymerization (DP), and the molecular weight, respectively. Only a minor proportion of PC (<jats:italic>ca.<\/jats:italic> 3\u201315%) was converted to propylene glycol\/homooligomers as revealed by high performance liquid chromatography (HPLC). All catalysts promoted preferential derivatization of lignin phenolic OH groups by oxypropyl moieties. The maximum average DP of propylene oxide chains in oxyalkylated Lignoboost\u00ae kraft lignin (oKL) was 1.85 per one phenylpropane unit (PPU) using DBU. Conversely, the DP of oKL using DICY was very low (0.27\/PPU). DICY\u2019s catalytic activity seems to be jeopardized due to the formation of unreactive adducts with lignin. The oKL obtained using DBU, DABCO, and K<jats:sub>2<\/jats:sub>CO<jats:sub>3<\/jats:sub> have potential to be used as polyols in the production of polyurethanes as the corresponding hydroxyl number (I<jats:sub>OH<\/jats:sub>) is in the range of 198\u2013410\u00a0mg KOH g<jats:sup>\u22121<\/jats:sup>.<\/jats:p>","DOI":"10.1515\/hf-2019-0274","type":"journal-article","created":{"date-parts":[[2020,6,2]],"date-time":"2020-06-02T08:50:33Z","timestamp":1591087833000},"page":"567-576","source":"Crossref","is-referenced-by-count":19,"title":["Effect of different catalysts on the oxyalkylation of eucalyptus Lignoboost\u00ae kraft lignin"],"prefix":"10.1515","volume":"74","author":[{"given":"Fernanda R.","family":"Vieira","sequence":"first","affiliation":[{"name":"CICECO- Institute of Materials and Department of Chemistry , University of Aveiro , 3810-193 , Aveiro , Portugal"}]},{"given":"Ana","family":"Barros-Timmons","sequence":"additional","affiliation":[{"name":"CICECO- Institute of Materials and Department of Chemistry , University of Aveiro , 3810-193 , Aveiro , Portugal"}]},{"given":"Dmitry V.","family":"Evtuguin","sequence":"additional","affiliation":[{"name":"CICECO- Institute of Materials and Department of Chemistry , University of Aveiro , 3810-193 , Aveiro , Portugal"}]},{"given":"Paula C. R.","family":"Pinto","sequence":"additional","affiliation":[{"name":"RAIZ , Forest and Paper Research Institute , Quinta de S. Francisco, 3801-501 , Eixo , Portugal"}]}],"member":"374","published-online":{"date-parts":[[2020,6,2]]},"reference":[{"key":"2023033118331908227_j_hf-2019-0274_ref_001","doi-asserted-by":"crossref","unstructured":"Akil, Y., Lorenz, D., Lehnen, R., and Saake, B. (2016). Safe and non-toxic hydroxyalkylation of xylan using propylene carbonate. Eur. Polym. J. 77: 88\u201397, https:\/\/doi.org\/10.1016\/j.eurpolymj.2016.02.010.","DOI":"10.1016\/j.eurpolymj.2016.02.010"},{"key":"2023033118331908227_j_hf-2019-0274_ref_002","doi-asserted-by":"crossref","unstructured":"Alves, M., Grignard, B., Gennen, S., Detrembleur, C., Jerome, C., and Tassaing, T. (2015). Organocatalytic synthesis of bio-based cyclic carbonates from CO2 and vegetable oils. RSC Adv. 5: 53629\u201353636, https:\/\/doi.org\/10.1039\/C5RA10190E.","DOI":"10.1039\/C5RA10190E"},{"key":"2023033118331908227_j_hf-2019-0274_ref_003","unstructured":"ASTM D4662-08 (2011). Standard Test Methods for Testing Polyurethane Raw Materials: Determination of acid and alkalinity numbers of polyols. ASTM International, Philadelphia, USA."},{"key":"2023033118331908227_j_hf-2019-0274_ref_004","doi-asserted-by":"crossref","unstructured":"Baghernejad, B. (2010). 1,4- Diazabicyclo[2.2.2]octane (DABCO) as a useful catalyst in organic synthesis. Eur. J. Chem. 1: 54\u201350, https:\/\/doi.org\/10.5155\/eurjchem.1.1.54-60.2.","DOI":"10.5155\/eurjchem.1.1.54-60.2"},{"key":"2023033118331908227_j_hf-2019-0274_ref_005","doi-asserted-by":"crossref","unstructured":"Cateto, C.A., Barreiro, M.F., Rodrigues, A.E., Brochier-Salon, M.C., Thielemans, W., and Belgacem, M.N. (2008). Lignins as macromonomers for polyurethane synthesis: a comparative study on hydroxyl group determination. J. Appl. Polym. Sci. 109: 3008\u20133017, https:\/\/doi.org\/10.1002\/app.28393.","DOI":"10.1002\/app.28393"},{"key":"2023033118331908227_j_hf-2019-0274_ref_006","doi-asserted-by":"crossref","unstructured":"Cateto, C.A., Barreiro, M.F., Rodrigues, A.E., and Belgacem, M.N. (2009). Optimization study of lignin oxypropylation in view of the preparation of polyurethane rigid foams. Ind. Eng. Chem. Res. 48: 2583\u20132589, https:\/\/doi.org\/10.1021\/ie801251r.","DOI":"10.1021\/ie801251r"},{"key":"2023033118331908227_j_hf-2019-0274_ref_007","doi-asserted-by":"crossref","unstructured":"Duval, A. and Av\u00e9rous, L. (2016). Oxyalkylation of condensed tannin with propylene carbonate as an alternative to propylene oxide. Sustain. Chem. Eng. 4: 3103\u20133112, https:\/\/doi.org\/10.1021\/acssuschemeng.6b00081.","DOI":"10.1021\/acssuschemeng.6b00081"},{"key":"2023033118331908227_j_hf-2019-0274_ref_008","doi-asserted-by":"crossref","unstructured":"Duval, A. and Av\u00e9rous, L. (2017). Cyclic carbonates as safe and versatile etherifying reagents for the functionalization of lignins and tannins. Sustain. Chem. Eng. 5: 7334\u20137343, https:\/\/doi.org\/10.1021\/acssuschemeng.7b01502.","DOI":"10.1021\/acssuschemeng.7b01502"},{"key":"2023033118331908227_j_hf-2019-0274_ref_009","doi-asserted-by":"crossref","unstructured":"Evtiouguina, M., Barros-Timmons, A., Cruz-Pinto, J.J., Neto, C.P., Belgacem, M.N., and Gandini, A. (2001). Oxypropylation of cork and the use of the ensuing polyols in polyurethane formulations. Biomacromolecules 3: 57\u201362, https:\/\/doi.org\/10.1021\/bm010100c.","DOI":"10.1021\/bm010100c"},{"key":"2023033118331908227_j_hf-2019-0274_ref_010","doi-asserted-by":"crossref","unstructured":"Evtuguin, D.V., Andreolety, J.P., and Gandini, A. (1998). Polyurethanes based on oxygen-organosolv lignin. Eur. Polym. J. 34: 1163\u20131169, https:\/\/doi.org\/10.1016\/s0014-3057(97)00245-0.","DOI":"10.1016\/S0014-3057(97)00245-0"},{"key":"2023033118331908227_j_hf-2019-0274_ref_011","doi-asserted-by":"crossref","unstructured":"Evtuguin, D.V., Neto, C.P., Silva, A.M.S., Domingues, P.M., Amado, F.M.L., Robert, D., and Faix, O. (2001). Comprehensive study on the chemical structure of dioxane lignin from plantation Eucalyptus globulus wood. J. Agric. Food Chem. 49: 4252\u20134261, https:\/\/doi.org\/10.1021\/jf010315d.","DOI":"10.1021\/jf010315d"},{"key":"2023033118331908227_j_hf-2019-0274_ref_012","doi-asserted-by":"crossref","unstructured":"Figueiredo, P., Lintinen, K., Hirvonen, J.T., Kostiainen, M.A., and Santos, H.A. (2018). Properties and chemical modifications of lignin: towards lignin-based nanomaterials for biomedical applications. Prog. Mater. Sci. 93: 233\u201369, https:\/\/doi.org\/10.1016\/j.pmatsci.2017.12.001.","DOI":"10.1016\/j.pmatsci.2017.12.001"},{"key":"2023033118331908227_j_hf-2019-0274_ref_013","doi-asserted-by":"crossref","unstructured":"Gao, Y. and Yunzhao Y. (2002). The synergistic effect of dicyandiamide and resorcinol in the curing of epoxy resins. J. Appl. Polym. Sci. 89: 1869\u20131874, https:\/\/doi.org\/10.1002\/app.12316.","DOI":"10.1002\/app.12316"},{"key":"2023033118331908227_j_hf-2019-0274_ref_014","unstructured":"Glasser, W.G. and Hsu, O.H.H. (1977). Polyurethane intermediates and products and methods of producing same from lignin, US Patent number: 4017474."},{"key":"2023033118331908227_j_hf-2019-0274_ref_015","unstructured":"G\u00fcthner, T., Mertschenk, B., and Schulz, B. (2012). Guanidine and derivatives. In:Ullmann\u2019s encyclopedia of industrial chemistry, Vol. 17, Wiley-VCH, Germany, pp. 182\u2013185."},{"key":"2023033118331908227_j_hf-2019-0274_ref_016","unstructured":"Ionescu, M. (2005). Chemistry and technology of polyols for polyurethanes. Rapra Technology Limited, Shropshire, UK, pp. 37\u201341."},{"key":"2023033118331908227_j_hf-2019-0274_ref_017","doi-asserted-by":"crossref","unstructured":"Jasiukaityt\u0117-Grojzdek, E., Kunaverf, M., and Crestini, C. (2012). Lignin structural changes during liquefaction in acidified ethylene glycol. J. Wood Chem. Technol. 32: 342\u2013360, https:\/\/doi.org\/10.1080\/02773813.2012.698690.","DOI":"10.1080\/02773813.2012.698690"},{"key":"2023033118331908227_j_hf-2019-0274_ref_018","doi-asserted-by":"crossref","unstructured":"Jin, Y., Ruan, X., Cheng, X., and L\u00fc, Q. (2011). Liquefaction of lignin by polyethyleneglycol and glycerol. Bioresour. Technol. 102: 3581\u20133583, https:\/\/doi.org\/10.1016\/j.biortech.2010.10.050.","DOI":"10.1016\/j.biortech.2010.10.050"},{"key":"2023033118331908227_j_hf-2019-0274_ref_019","doi-asserted-by":"crossref","unstructured":"K\u00fchnel, I., Podschun, J., Saake, B., and Lehnen R. (2015). Synthesis of lignin polyols via oxyalkylation with propylene carbonate. Holzforschung 69: 531\u2013538, https:\/\/doi.org\/10.1515\/hf-2014-0068.","DOI":"10.1515\/hf-2014-0068"},{"key":"2023033118331908227_j_hf-2019-0274_ref_020","doi-asserted-by":"crossref","unstructured":"K\u00fchnel, I., Saake, B., and Lehnen, R. (2017a). Comparison of different cyclic organic carbonates in the oxyalkylation of various types of lignin. React. Func. Polym. 120: 83\u201391, https:\/\/doi.org\/10.1016\/j.reactfunctpolym.2017.09.011.","DOI":"10.1016\/j.reactfunctpolym.2017.09.011"},{"key":"2023033118331908227_j_hf-2019-0274_ref_021","doi-asserted-by":"crossref","unstructured":"K\u00fchnel, I., Saake, B., and Lehnen, R. (2017b). Oxyalkylation of lignin with propylene carbonate: influence of reaction parameters on the ensuing bio-based polyols. Ind. Crop. Prod. 101: 75\u201383, https:\/\/doi.org\/10.1016\/j.indcrop.2017.03.002.","DOI":"10.1016\/j.indcrop.2017.03.002"},{"key":"2023033118331908227_j_hf-2019-0274_ref_022","doi-asserted-by":"crossref","unstructured":"Liu, H., Chung, H. (2017). Lignin-based polymers via graft copolymerization. J. Polym. Sci., Part A: Polym. Chem. 55: 3515\u20133528, https:\/\/doi.org\/10.1002\/pola.28744.","DOI":"10.1002\/pola.28744"},{"key":"2023033118331908227_j_hf-2019-0274_ref_023","doi-asserted-by":"crossref","unstructured":"Lohmeijer, B.G., Pratt, R.P., Leibfarth, F., Logan, J.W., Long, D.A., Dove, A.P., Nederberg, F., Choi, J.,Wade, C., Waymouth, R.M., and Hedrick, J.L. (2006). Guanidine and amidine organocatalysts for ring-opening polymerization of cyclic esters. Macromolecules 39: 8574\u20138583, https:\/\/doi.org\/10.1021\/ma0619381.","DOI":"10.1021\/ma0619381"},{"key":"2023033118331908227_j_hf-2019-0274_ref_024","doi-asserted-by":"crossref","unstructured":"Magina, S., Santos, A.P., and Evtuguin, D.V. (2015). Study on the residual lignin in Eucalyptus globulus sulphite pulp. Holzforschung 69: 513\u2013522, https:\/\/doi.org\/10.1515\/hf-2014-0218.","DOI":"10.1515\/hf-2014-0218"},{"key":"2023033118331908227_j_hf-2019-0274_ref_025","doi-asserted-by":"crossref","unstructured":"Matsuo, J., Nakano, S., Sanda, F., and Endo, T. (1998). Ring-opening polymerization of cyclic carbonates by alcohol \u2013 acid catalyst. J. Polym. Sci., Part A: Polym. Chem. 36: 2463\u20132471, https:\/\/doi.org\/10.1002\/(SICI)1099-0518(199810)36:14<2463::AID-POLA4>3.0.CO;2-U.","DOI":"10.1002\/(SICI)1099-0518(199810)36:14<2463::AID-POLA4>3.0.CO;2-U"},{"key":"2023033118331908227_j_hf-2019-0274_ref_026","doi-asserted-by":"crossref","unstructured":"Nadji, H., Bruzz\u00e8se, C., Belgacem, M.N., Benaboura, A., and Gandini, A. (2005). Oxypropylation of lignins and preparation of rigid polyurethane foams from the ensuing polyols. Macromol. Mater. Eng. 290: 1009\u20131016, https:\/\/doi.org\/10.1002\/mame.200500200.","DOI":"10.1002\/mame.200500200"},{"key":"2023033118331908227_j_hf-2019-0274_ref_028","doi-asserted-by":"crossref","unstructured":"Pinto, P.C., Evtuguin, D.V., Pascoal Neto, C., and Silvestre, A.J.D. (2002). Behaviour of Eucalyptus globulus lignin during kraft pulping. Part 2. Analysis by NMR, ESI\/MS and GPC techniques. J. Wood Chem. Technol. 22: 109\u2013125, https:\/\/doi.org\/10.1081\/WCT-120013356.","DOI":"10.1081\/WCT-120013356"},{"key":"2023033118331908227_j_hf-2019-0274_ref_029","doi-asserted-by":"crossref","unstructured":"Prozil, S.O., Evtuguin, D.V., Silva, A.M.S, and Lopes, L. P.C. (2014). Structural characterization of lignin from grape stalks (Vitis vinifera L.). J. Agric. Food Chem. 62: 5420\u20135428, https:\/\/doi.org\/10.1021\/jf502267s.","DOI":"10.1021\/jf502267s"},{"key":"2023033118331908227_j_hf-2019-0274_ref_030","doi-asserted-by":"crossref","unstructured":"Rokicki, G. (2000). Aliphatic cyclic carbonates and spiroorthocarbonates as monomers. Prog. Polym. Sci. 25: 259\u2013342, https:\/\/doi.org\/10.1016\/s0079-6700(00)00006-x.","DOI":"10.1016\/S0079-6700(00)00006-X"},{"key":"2023033118331908227_j_hf-2019-0274_ref_031","doi-asserted-by":"crossref","unstructured":"Sadeghifar, H., Cui, C., and Argyropoulos, D.S. (2012). Toward thermoplastic lignin polymers. Part 1. selective masking of phenolic hydroxyl groups in kraft lignins via methylation and oxypropylation chemistries. Ind. Eng. Chem. Res. 51: 16713\u201316720, https:\/\/doi.org\/10.1021\/ie301848j.","DOI":"10.1021\/ie301848j"},{"key":"2023033118331908227_j_hf-2019-0274_ref_032","doi-asserted-by":"crossref","unstructured":"Segura, D.M., Nurse, A.D., Mccourt, A., Phelps, R., and Segura. A. (2005). Chemistry of polyurethane adhesives and sealants. In: Cognard, P. (Ed.). Handbook of adhesives and sealants. Elsevier, Oxford, pp. 102\u2013162.","DOI":"10.1016\/S1874-5695(02)80004-5"},{"key":"2023033118331908227_j_hf-2019-0274_ref_033","doi-asserted-by":"crossref","unstructured":"Sherck, N.J., Kim, H.C., and Won, Y. (2016). Elucidating a unified mechanistic scheme for the dbu-catalyzed ring-opening polymerization of lactide to poly(lactic acid). Macromolecules 49: 4699\u20134713, https:\/\/doi.org\/10.1021\/acs.macromol.6b00621.","DOI":"10.1021\/acs.macromol.6b00621"},{"key":"2023033118331908227_j_hf-2019-0274_ref_034","doi-asserted-by":"crossref","unstructured":"So\u00f3s, L., De\u00e1k, G., K\u00e9ki, S., and Zsuga, M. (1999). Anionic bulk oligomerization of ethylene and propylene carbonate initiated by bisphenol-A\/base systems. J. Polym. Sci., Part A: Polym. Chem. 37: 545\u2013550, https:\/\/doi.org\/10.1002\/(sici)1099-0518(19990301)37:5<545::aid-pola4>3.0.co;2-t.","DOI":"10.1002\/(SICI)1099-0518(19990301)37:5<545::AID-POLA4>3.0.CO;2-T"},{"key":"2023033118331908227_j_hf-2019-0274_ref_035","doi-asserted-by":"crossref","unstructured":"Taylor, J.E., Bull, S.D., and Williams, J.M.J. (2012). Amidines, isothioureas, and guanidines as nucleophilic catalysts. Chem. Soc. Rev. 41: 2109\u20132121, https:\/\/doi.org\/10.1039\/c2cs15288f.","DOI":"10.1039\/c2cs15288f"},{"key":"2023033118331908227_j_hf-2019-0274_ref_036","unstructured":"Tomani, P.E. (2010). The LignoBoost process. Cellu. Chem. Tech. 44: 53\u201358."},{"key":"2023033118331908227_j_hf-2019-0274_ref_037","doi-asserted-by":"crossref","unstructured":"Tribot, A., Amer M., Alio, M.A., Baynast, H., Delattre, C., Pons, A., Mathias, J.D., Callois, J.M., Vial, C., Michaud, P., et al. (2019). Wood-lignin: supply, extraction processes and use as bio-based material. Eur. Polym. J. 112: 228\u2013240, https:\/\/doi.org\/10.1016\/j.eurpolymj.2019.01.007.","DOI":"10.1016\/j.eurpolymj.2019.01.007"},{"key":"2023033118331908227_j_hf-2019-0274_ref_038","doi-asserted-by":"crossref","unstructured":"Zhang, X., Chen, M., Liu, C., Zhang, A., and Sun, R. (2015). Ring-opening graft polymerization of propylene carbonate onto xylan in an ionic liquid. Molecules 20: 6033\u20136047, https:\/\/doi.org\/10.3390\/molecules20046033.","DOI":"10.3390\/molecules20046033"},{"key":"2023033118331908227_j_hf-2019-0274_ref_039","doi-asserted-by":"crossref","unstructured":"Zhang, X., Kim, Y., Islam, E., Taylor , M., Eberhardt, T.L., Hassan, E.B, Shmulsky, R. (2019). Rigid polyurethane foams containing lignin oxyalkylated with ethylene carbonate and polyethylene glycol. Ind. Crops Prod. 141: 111797, https:\/\/doi.org\/10.1016\/j.indcrop.2019.111797.","DOI":"10.1016\/j.indcrop.2019.111797"}],"container-title":["Holzforschung"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.degruyter.com\/view\/journals\/hfsg\/74\/6\/article-p567.xml","content-type":"text\/html","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/www.degruyter.com\/document\/doi\/10.1515\/hf-2019-0274\/xml","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/www.degruyter.com\/document\/doi\/10.1515\/hf-2019-0274\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,4,1]],"date-time":"2023-04-01T02:08:48Z","timestamp":1680314928000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.degruyter.com\/document\/doi\/10.1515\/hf-2019-0274\/html"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,6,1]]},"references-count":38,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2020,2,28]]},"published-print":{"date-parts":[[2020,6,25]]}},"alternative-id":["10.1515\/hf-2019-0274"],"URL":"https:\/\/doi.org\/10.1515\/hf-2019-0274","relation":{},"ISSN":["1437-434X","0018-3830"],"issn-type":[{"value":"1437-434X","type":"electronic"},{"value":"0018-3830","type":"print"}],"subject":[],"published":{"date-parts":[[2020,6,1]]}}}