In this work, crude glycerol liquefaction of lignins produced in the pulp and paper industry, as well as an organosolv lignin (sugarcane bagasse), was studied with the ultimate aim of preparing bio-based polyols for polyurethane (PU) preparation. This is a proposed strategy to valorise the by-products of biodiesel and lignocellulose biorefineries. Size-exclusion chromatography revealed that the lignins behave differently during liquefaction based on a ranging product molecular weight (MW). The MW of the liquefaction products was concluded to be related to the phenolic and aliphatic hydroxyl group content of the respective lignins, as well as the removal of glycerol and monoacylglycerol during liquefaction. Lignin was modified to yield mostly a solid-phase product. Fourier transform infrared spectroscopy suggests that crude glycerol constituents like glycerol and fatty acid esters are bound to lignin during liquefaction through formation of ether and ester bonds. Liquefaction yield further also varied with lignin type. The liquefaction products were effectively employed as bio-based polyols to prepare PU.
LiuCWangXLinFet al.Structural elucidation of industrial bioethanol residual lignin from corn stalk: a potential source of vinyl phenolics. Fuel Process Technol2018; 169: 50–57.
2.
RagauskasAJBeckhamGTBiddyMJet al.Lignin valorization: improving lignin processing in the biorefinery. Science2014; 344(6185): 1246843.
3.
HuSJLuoXLLiYB. Polyols and polyurethanes from the liquefaction of lignocellulosic biomass. Chem Sus Chem2014; 7(1): 66–72.
4.
GadhaveRVMahanwarPAGadekarPT. Lignin-polyurethane based biodegradable foam. Open J Polym Chem2018; 8(01): 1.
5.
DuvalALawokoM. A review on lignin-based polymeric, micro- and nano-structured materials. React Funct Polym2014; 85: 78–96.
6.
AhvaziBWojciechowiczOTon-ThatTMet al.Preparation of lignopolyols from wheat straw soda lignin. J Agric Food Chem2011; 59(19): 10505–10516.
7.
KühnelISaakeBLehnenR. Oxyalkylation of lignin with propylene carbonate: influence of reaction parameters on the ensuing bio-based polyols. Ind Crops Prod2017; 101: 75–83.
8.
LeeJHLeeEY. Biobutanediol-mediated liquefaction of empty fruit bunch saccharification residues to prepare lignin biopolyols. Bioresour Technol2016; 208: 24–30.
9.
HuSJLiYB. Two-step sequential liquefaction of lignocellulosic biomass by crude glycerol for the production of polyols and polyurethane foams. Bioresour Technol2014; 161: 410–415.
10.
KühnelISaakeBLehnenR. Comparison of different cyclic organic carbonates in the oxyalkylation of various types of lignin. React Funct Polym2017; 120: 83–91.
11.
GoszKKosmelaPHejnaAet al.Biopolyols obtained via microwave-assisted liquefaction of lignin: structure, rheological, physical and thermal properties. Wood Sci Technol2018; 52(3): 599–617.
12.
LaurichesseSHuilletCAverousL. Original polyols based on organosolv lignin and fatty acids: new bio-based building blocks for segmented polyurethane synthesis. Green Chem2014; 16(8): 3958–3970.
13.
MahmoodNYuanZSSchmidtJet al.Depolymerization of lignins and their applications for the preparation of polyols and rigid polyurethane foams: a review. Renewable Sustainable Energy Rev2016; 60: 317–329.
14.
JasiukaitytėEKunaverMCrestiniC. Lignin behaviour during wood liquefaction-characterization by quantitative 31P, 13C NMR and size-exclusion chromatography. Catal Today2010; 156(1-2): 23–30.
15.
XueBLWenJLXuFet al.Polyols production by chemical modification of autocatalyzed ethanol-water lignin from Betula alnoides. J Appl Polym Sci2013; 129(1): 434–442.
16.
LinLZNakagameSYaoYGet al.Liquefaction mechanism of β-O-4 lignin model compound in the presence of phenol under acid catalysis Part 2. Reaction behavior and pathways. Holzforschung2001; 55(6): 625–630.
17.
de OliveiraDRNogueiraIdMMaiaFJNet al.Ecofriendly modification of acetosolv lignin from oil palm biomass for improvement of PMMA thermo-oxidative properties. J Appl Polym Sci2017; 134(46): 45498.
18.
LeeSHYoshiokaMShiraishiN. Liquefaction of corn bran (CB) in the presence of alcohols and preparation of polyurethane foam from its liquefied polyol. J Appl Polym Sci2000; 78(2): 319–325.
19.
ThielemansWWoolRP. Lignin esters for use in unsaturated thermosets: lignin modification and solubility modeling. Biomacromolecules2005; 6(4): 1895–1905.
20.
NadjiHBruzzeseCBelgacemMNet al.Oxypropylation of lignins and preparation of rigid polyurethane foams from the ensuing polyols. Macromol Mater Eng2005; 290(10): 1009–1016.
21.
CatetoCABarreiroMFRodriguesAEet al.Optimization study of lignin oxypropylation in view of the preparation of polyurethane rigid foams. Ind Eng Chem Res2009; 48(5): 2583–2589.
22.
LuoXGeXCuiSet al.Value-added processing of crude glycerol into chemicals and polymers. Bioresour Technol2016; 215: 144–154.
23.
LeeJHLeeJHKimDKet al.Crude glycerol-mediated liquefaction of empty fruit bunches saccharification residues for preparation of biopolyurethane. J Ind Eng Chem2016; 34: 157–164.
24.
KimKHYuJHLeeEY. Crude glycerol-mediated liquefaction of saccharification residues of sunflower stalks for production of lignin biopolyols. J Ind Eng Chem2016; 38: 175–180.
25.
MullerLCMarxSVoslooHCM. Polyol preparation by liquefaction of technical lignins in crude glycerol. J Renewable Mater2017; 5(1): 67–80.
26.
LeeJHLeeEY. Preparation of biopolyol from empty fruit bunch saccharification residue using glycerol and PEG#300-mediated liquefaction for application to bio-polyester and bio-polyurethane production. J Wood Chem Technol2017; 37(4): 283–293.
27.
XueBLWenJLSunRC. Producing lignin-based polyols through microwave-assisted liquefaction for rigid polyurethane foam production. Materials2015; 8(2): 586–599.
KurimotoYTakedaMKoizumiAet al.Mechanical properties of polyurethane films prepared from liquefied wood with polymeric MDI. Bioresour Technol2000; 74(2): 151–157.
FarisAHIbrahimMNMRahimAAet al.Preparation and characterization of lignin polyols from the residues of oil palm empty fruit bunch. Bioresources2015; 10(4): 7339–7352.
32.
MahmoodNYuanZSSchmidtJet al.Preparation of bio-based rigid polyurethane foam using hydrolytically depolymerized Kraft lignin via direct replacement or oxypropylation. Eur Polym J2015; 68: 1–9.
33.
JinYQRuanXMChengXSet al.Liquefaction of lignin by polyethyleneglycol and glycerol. Bioresour Technol2011; 102(3): 3581–3583.
34.
UptonBMKaskoAM. Strategies for the conversion of lignin to high-value polymeric materials: review and perspective. Chem Rev2016; 116(4): 2275–2306.
35.
XieJQiJHseCYet al.Effect of lignin derivatives in the bio-polyols from microwave liquefied bamboo on the properties of polyurethane foams. Bioresources2014; 9(1): 578–588.
36.
XuFSunJXSunRCet al.Comparative study of organosolv lignins from wheat straw. Ind Crops Prod2006; 23(2): 180–193.
37.
ASTM International. ASTM Standard test methods for testing polyurethane raw materials: Determination of hydroxyl numbers of polyols. West Conshohocken: ASTM D4274-11; ASTM International, 2011.
38.
RingenaOLebiodaALehnenRet al.Size-exclusion chromatography of technical lignins in dimethyl sulfoxide/water and dimethylacetamide. J Chromatogr A2006; 1102(1-2): 154–163.
39.
GavrilovMMonteiroMJ. Derivation of the molecular weight distributions from size exclusion chromatography. Eur Polym J2015; 65: 191–196.
ChenFGLiJ. Aqueous gel permeation chromatographic methods for technical lignins. J Wood Chem Technol2000; 20(3): 265–276.
43.
ZhuWZWestmanGThelianderH. Investigation and characterization of lignin precipitation in the LignoBoost process. J Wood Chem Technol2014; 34(2): 77–97.
44.
AndrianovaAAYeudakimenkaNALilakSLet al.Size exclusion chromatography of lignin: the mechanistic aspects and elimination of undesired secondary interactions. J Chromatogr A2017; 1534: 101–110.
45.
LangeHRulliFCrestiniC. Gel permeation chromatography in determining molecular weights of lignins: critical aspects revisited for improved utility in the development of novel materials. ACS Sustainable Chem Eng2016; 4(10): 5167–5180.
46.
SunJXSunXFSunRCet al.Inhomogeneities in the chemical structure of sugarcane bagasse lignin. J Agric Food Chem2003; 51(23): 6719–6725.
47.
SulaevaIZinovyevGPlankeeleJMet al.Fast track to molar-mass distributions of technical lignins. Chem Sus Chem2017; 10(3): 629–635.
48.
BaumbergerSAbaecherliAFaschingMet al.Molar mass determination of lignins by size-exclusion chromatography: towards standardisation of the method. Holzforschung2007; 61(4): 459–468.
49.
WangKBauerSSunRC. Structural transformation of Miscanthus x giganteus Lignin Fractionated under Mild Formosolv, Basic Organosolv, and Cellulolytic Enzyme Conditions. J Agric Food Chem2012; 60(1): 144–152.
50.
VillaverdeJJLiJBEkMet al.Native lignin structure of miscanthus x giganteus and its changes during acetic and formic acid fractionation. J Agric Food Chem2009; 57(14): 6262–6270.
51.
AbdelkafiFAmmarHRousseauBet al.Structural analysis of Alfa grass (Stipa tenacissima L.) lignin obtained by acetic acid/formic acid delignification. Biomacromolecules2011; 12(11): 3895–3902.
52.
TolbertAAkinoshoHKhunsupatRet al.Characterization and analysis of the molecular weight of lignin for biorefining studies. Biofuels, Bioprod Biorefin2014; 8(6): 836–856.
53.
GellerstedtG. Softwood kraft lignin: raw material for the future. Ind Crops Prod2015; 77: 845–854.
54.
TejadoAPenaCLabidiJet al.Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis. Bioresour Technol2007; 98(8): 1655–1663.
55.
Jasiukaitytė-GrojzdekEKunaverMCrestiniC. Lignin structural changes during liquefaction in acidified ethylene glycol. J Wood Chem Technol2012; 32(4): 342–360.
56.
Sequeiros EcheverriaA. Conversion of lignin to value added chemicals. PhD Thesis, UPV/EHU, 2016.
57.
GaoLPZhengGYZhouYHet al.Improved mechanical property, thermal performance, flame retardancy and fire behavior of lignin-based rigid polyurethane foam nanocomposite. J Therm Anal Calorim2015; 120(2): 1311–1325.
58.
BoeriuCGBravoDGosselinkRJAet al.Characterisation of structure-dependent functional properties of lignin with infrared spectroscopy. Ind Crops Prod2004; 20(2): 205–218.
59.
Monteil-RiveraFPhuongMYeMWet al.Isolation and characterization of herbaceous lignins for applications in biomaterials. Ind Crops Prod2013; 41: 356–364.
60.
StewartDYahiaouiNMcDougallGJet al.Fourier-transform infrared and Raman spectroscopic evidence for the incorporation of cinnamaldehydes into the lignin of transgenic tobacco (Nicotiana tabacum L.) plants with reduced expression of cinnamyl alcohol dehydrogenase. Planta1997; 201(3): 311–318.
61.
ZhongRMorrisonWHIIIHimmelsbachDSet al.Essential role of caffeoyl coenzyme A O-methyltransferase in lignin biosynthesis in woody poplar plants. Plant Physiol2000; 124(2): 563–577.
62.
AuxenfansTCrônierDChabbertBet al.Understanding the structural and chemical changes of plant biomass following steam explosion pretreatment. Biotechnol Biofuels2017; 10(1): 36.
63.
PopescuCMPopescuMCSingurelGet al.Spectral characterization of eucalyptus wood. Appl Spectrosc2007; 61(11): 1168–1177.
64.
El MansouriNESalvadoJ. Analytical methods for determining functional groups in various technical lignins. Ind Crops Prod2007; 26(2): 116–124.
65.
SimonDBorregueroAMde LucasAet al.Valorization of crude glycerol as a novel transesterification agent in the glycolysis of polyurethane foam waste. Polym Degrad Stab2015; 121: 126–136.
66.
SkoogDAHollerFJNiemanTA. Principles of instrumental analysis. 5th ed. Philadelphia: Brooks/Cole, 1998.
67.
CarricoCSFragaTPasaVMD. Production and characterization of polyurethane foams from a simple mixture of castor oil, crude glycerol and untreated lignin as bio-based polyols. Eur Polym J2016; 85: 53–61.
BoeriuCGFitigauFIGosselinkRJAet al.Fractionation of five technical lignins by selective extraction in green solvents and characterisation of isolated fractions. Ind Crops Prod2014; 62: 481–490.
70.
NadjiHDioufPNBenabouraAet al.Comparative study of lignins isolated from Alfa grass (Stipa tenacissima L.). Bioresour Technol2009; 100(14): 3585–3592.
KongjaoSDamronglerdSHunsomM. Purification of crude glycerol derived from waste used-oil methyl ester plant. Korean J Chem Eng2010; 27(3): 944–949.
73.
SujakAMuszynskiSKachel-JakubowskaM. Quality of rapeseed bio-fuel waste: optical properties. Int Agrophys2014; 28(2): 213–218.
74.
GurunathanTRaoCRKNarayanRet al.Synthesis, characterization and corrosion evaluation on new cationomeric polyurethane water dispersions and their polyaniline composites. Prog Org Coat2013; 76(4): 639–647.
75.
IgnatLIgnatMCiobanuCet al.Effects of flax lignin addition on enzymatic oxidation of poly(ethylene adipate) urethanes. Ind Crops Prod2011; 34(1): 1017–1028.
76.
KirpluksMCabulisUIvdreAet al.Mechanical and thermal properties of high-density rigid polyurethane foams from renewable resources. J Renewable Mater2016; 4(1): 86–100.
77.
LiCLuoXLiTet al.Polyurethane foams based on crude glycerol-derived biopolyols: one-pot preparation of biopolyols with branched fatty acid ester chains and its effects on foam formation and properties. Polymer2014; 55(25): 6529–6538.
78.
ZhaoYYanNFengM. Polyurethane foams derived from liquefied mountain pine beetle-infested barks. J Appl Polym Sci2012; 123(5): 2849–2858.
79.
CiobanuCUngureanuMIgnatLet al.Properties of lignin-polyurethane films prepared by casting method. Ind Crops Prod2004; 20(2): 231–241.
ArshanitsaAKruminaLTelyshevaGet al.Exploring the application potential of incompletely soluble organosolv lignin as a macromonomer for polyurethane synthesis. Ind Crops Prod2016; 92: 1–12.
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