Polyol Preparation by Liquefaction of Technical Lignins in Crude Glycerol

Polyol preparation by liquefaction of technical lignins in crude glycerol

Louis C. Muller1, Sanette Marx1, Hermanus C.M. Vosloo2

1Energy systems, School of Chemical and Minerals Engineering, North-West University, Private Bag X6001, Potchefstroom 2520, South Africa

2Research Focus Area for Chemical Resource Beneficiation: Catalysis and Synthesis Research Group, North-West University, Private Bag X6001, Potchefstroom 2520, South Africa

SUPPLEMENTARY MATERIAL

TABLE S1 Signal assignment of the 1H NMR lignin spectra

δ (ppm) / Assignment / Reference
Organosolv lignin:
7.3-7.6 / Aromatic protons in positions 2 and 6 of p-hydroxyphenyl structures / Seca et al. [1]
6.6-6.8 / Aromatic protons in syringyl and guaiacyl structures / Xu et al. [2]
4.8-5.0 / Hβ in β-O-4 structures / Xu et al. [2]
4.2 / HƔ in β-O-4 structures / Sun et al. [3]
1.9-2.1 / Methyl or methylene protons adjacent to double bonds or carbonyl groups / Marchessault et al. [4]
lignin acetoxy groups / Ralph et al. [5]
0.8-1.5 / Aliphatic protons in lignin or xylans / Xu et al. [2]
Kraft lignin:
8.5 / Phenolic protons / Fernandez-Costas et al. [6]
6.6-6.9 / Aromatic protons in syringyl and guaiacyl structures / Sun et al. [3]
4.0-4.8 / Hβ,HƔ in β-O-4 structure / Sun et al. [3]
0.8-1.7 / Aliphatic protons / Sun et al. [3]
Lignosulphonate
6.6-6.7 / Aromatic protons in syringyl and guaiacyl structures / Sun et al. [3]
4.0-5.0 / Hα, Hβ, HƔ in β-O-4 structure / Zhou et al. [7]
0.8-1.8 / Aliphatic protons in lignin or contaminants / Fernandez-Costas et al. [6]
General
3.7 / Methoxy / Xu et al. [2],
Hu et al. [8]
3.4 / Water / Gottlieb et al. [9]
3.2 / Methanol (impurity)
2.5 / DMSO
2.1 / Acetone (impurity)

TABLE S2 Quantitative 31P NMR OH analysis: Approximate integration ranges [10-12]

Functional group / RII (ppm) / RI (ppm)
Aliphatic OH / 145.30-150.80 / Primary: 132.0-133.6
Secondary: 133.7-138.0
Internal standard (Cyclohexanol) / 145.00-145.30 / 133.6-133.7
Condensed phenolic / 143.30-145.00 & 140.30-142.00
Syringyl / 142.00-143.30
Guaiacyl / 138.55-140.30
p-Hydroxyphenyl / 137.30-138.55
Carboxylic acids / 133.70-135.60

TABLE S3 Signal assignment of the crude glycerol and polyol 1H NMR spectra

δ (ppm) / Assignment / Reference
5.3 / Olefinic protons
1,3-DAG OH / Miyake et al. [13]
Nebel et al. [14]
Sustere et al. [15]
4.5 / Ethanol OH
Glycerol primary and secondary OH / SDBSWeb [16]
Nebel et al. [14]
4.0 / -CH2O- in FAEE and TAG / Rosset et al. [17]
3.95, 3.88 / Glycerol CH and CH2 in MAG and DAGa / Sustere et al. [15]
3.43 / Water
Ethanol CH2
Glycerol CH / Fernandez-Costas et al. [6]
SDBSWeb [16]
Sustere et al. [15]
3.23-3.38 / Glycerol CH and CH2 / Nebel et al. [14]
2.7 / Divinyl methylene / Miyake et al. [13]
2.5 / DMSO / Fernandez-Costas et al. [6]
2.25 / α-Carbonyl methylene / Monteiro et al. [18]
2.07 / Acetone (impurity) / Gottlieb et al. [9]
2.0 / Allyl methylene / Miyake et al. [13]
1.85 / Acetic acid CH3
Methylene adjacent to triple bond in fatty acids / Gottlieb et al. [9]
AOCS [19]
1.5 / β-Carbonyl methylene / Monteiro et al. [18]
1.2-1.3 / Methylene protons on saturated carbon / Miyake et al. [13]
1.15 / FAEE ethoxy CH3 / Guzatto et al. [20]
1.04 / Ethanol CH3 / SDBSWeb [16]
0.8 / Terminal methyl / Monteiro et al. [18]
aMAG and DAG additionally have numerous signals in the range 3.2 – 5.0 ppm which overlaps with the other signals listed above.

TABLE S4 Signal assignment of the crude glycerol and polyol 31P NMR RII spectra

δ (ppm) / Assignment / Reference
148.20 / 1,2-Diacylglycerol / Spyros and Dais [21]
148.02 / 2-Monoacylglycerol / Nagy et al. [22]
147.65 / 1-Monoacylglycerol (CH2) / Christophoridou and Dais [23]; Nagy et al. [24]
147.36-147.39 / Primary OH in glycerol / Nagy et al. [22]
146.70 / 1,3-Diacylglycerol / Spyros and Dais [21]
146.65 / Ethanol / Nagy et al. [22]
146.43-146.45 / 1-Monoacylglycerol (CH) / Nagy et al. [22]
146.32 / Secondary OH in glycerol / Christophoridou and Dais [23]
134.72-134.74 / Fatty acids / Lucas-Torres et al. [25]

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