Perez‐arce, JonatanCenteno‐pedrazo, AnderLabidi, JalelOchoa‐gomez, Jose R.Garcia‐suarez, Eduardo J.2021-02-22Perez‐arce , J , Centeno‐pedrazo , A , Labidi , J , Ochoa‐gomez , J R & Garcia‐suarez , E J 2021 , ' Lignin‐based polyols with controlled microstructure by cationic ring opening polymerization ' , Polymers , vol. 13 , no. 4 , 651 , pp. 1-12 . https://doi.org/10.3390/polym13040651 , https://doi.org/10.3390/polym130406512073-4360researchoutputwizard: 11556/1098Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.Lignin‐based polyols (LBPs) with controlled microstructure were obtained by cationic ring opening polymerization (CROP) of oxiranes in an organosolv lignin (OL) tetrahydrofuran (THF) solution. The control on the microstructure and consequently on the properties of the LBPs such as hydroxyl number, average molecular weight, melting, crystallization and decomposition temperatures, are crucial to determine the performance and application of the derived‐products. The influence of key parameters, for example, molar ratio between the oxirane and the hydroxyl groups content in OLO, initial OL concentration in THF, temperature, specific flow rate and oxirane nature has been investigated. LBPs with hydroxyl numbers from 35 to 217 mg KOH/g, apparent average Mw between 5517 and 52,900 g/mol and melting temperatures from −8.4 to 18.4 °C were obtained. The CROP procedure allows obtaining of tailor‐made LBPs for specific applications in a very simple way, opening the way to introduce LBPs as a solid alternative to substitute currently used fossil‐based polyols.12582905enginfo:eu-repo/semantics/openAccessjournal article10.3390/polym13040651Biomass valorizationControlled microstructureLignin upgradingLignin‐based polyolsGeneral ChemistryPolymers and PlasticsFunding InfoBasque Government (grant KK-2019/00097)Basque Government (grant KK-2019/00097)http://www.scopus.com/inward/record.url?scp=85102352155&partnerID=8YFLogxK