New Insights into Lignin Modification during Chlorine Dioxide Bleaching Sequences (IV): The Impact of Modifications in the (EP) and (EOP) Stages on the D1 Stage

Abstract

Peroxide‐reinforced extractions ((EP) or (EOP)) of D₀ pulps lower both post‐extraction kappa numbers and Klason lignins more than either E or (EO). An oxygen‐reinforced extraction (EO) results in lower kappa numbers, but affords comparable Klason lignins as an E stage (～1.2% lignin). Quinonoid structures in (EO) stocks are similar to those of the D₀ pulps (1.7 mmol/g lignin). Peroxide inclusion in EP and EOP appeared to eliminate both quinonoid and muconic acid moieties. These observations were confirmed with (EP) treatment of reference pulps (periodate or periodate‐peracetic acid) that contain significant levels of either quinones or muconic entities. The D₁ bleachability order, from easiest to hardest, was D₀(EOP)>D₀(EP)≈D₀(EO)>D₀E. An identical order was found for how quickly the yellow chromophores (b* value) are eliminated. All extracted pulps, regardless of the type of extraction employed, approach a common D₁ asymptotic brightness (～86 ISO) and b* value (～4.2) when excess ClO₂ is applied. The main difference among these pulps was how quickly the asymptotic limits are approached as a function of ClO₂ consumed. The bleachability study indicates that various extracted pulps have similar residual D₁ chromophores limiting the brightness ceiling.     

New Insights into Lignin Modification during Chlorine Dioxide Bleaching Sequences (III): The Impact of Modifications in the (EO) versus E Stage on the D1 Stage

Abstract

Chlorine dioxide delignification (D₀) modifies kraft residual lignin by oxidizing phenolic groups to both quinone and muconic acid structures. Alkaline extraction (E), in addition to removing solubilized lignin, converts quinone moieties to polyphenols. These polyphenols are easily oxidized by oxygen in an (EO) stage or by ClO₂ in a D₁ stage to hydroxyquinones (～1.8 mmol/g lignin). Pulps treated by D₀E consume considerably more ClO₂ in the D₁ than D₀(EO), and have lower bleachability, as was quantified by a simple bleaching model. Both D₀E and D₀(EO) pulps approach a common brightness ceiling (～83 ISO) when excess ClO₂ is applied. Examination of the post‐D₁ b* values indicates that D₀E and D₀(EO) also have similar asymptotic b* values (～6), indicating that both pulps have similar residual chromophores. Hydroxyquinone structures appear to be eliminated in the D₁ stage for D₀(EO) pulps, and at high ClO₂ levels for D₀E pulps.     

Characterization of Residual Lignins Isolated from Unbleached and Semibleached Softwood Kraft Pulps

Abstract

Residual lignins in an unbleached and a semibleached softwood (Pinus taeda L.) kraft pulp were isolated by enzymatic hydrolysis of polysaccharides in the pulps. After purification, the residual lignins were characterized. A dissolved lignin was also isolated from the alkaline extraction spent liquor by acidification and characterized.

Results of the characterization indicate that extensive degradation of residual lignin in kraft pulp occurred during the first two stages of bleaching. The results also strongly support the previous finding that stable covalent linkages between residual lignins and carbohydrates in pulp any be the most probable cause for the residual lignins to resist delignification during kraft pulping and prebleaching.     

Characterization of the Residual Kraft Pulp Lignin In Situ by Sulfite Treatments

Abstract

The O₂ delignification of kraft pulps from Norway spruce was shown having a significant impact on the reactivity of the residual pulp lignin as revealed from their responses to sulfite treatments at pH 7.5. A substantial higher ratio of lignin sulfonation to the phenolic hydroxyl group content of residual pulp lignin was observed for the O₂ -delignified kraft pulps (～ 0.8) as compared to a value of ～ 0.3 for the unbleached samples and ～ 1 for the spruce wood lignin. Under the prevailing sulfite treatment conditions, the sulfonation would be largely attributed to the phenolic lignin component and the etherified structures containing an α -carbonyl or -unsaturated group. The contribution from the latter units, evaluated by a borohydride pretreatment of pulps prior to the sulfite treatment, can only account for approximately 15% of the sulfonation observed for the O₂ -delignified sample. Thus, the nature of phenolic structures in the O₂ -delignified pulps was more similar to that of the wood lignin than that of the kraft pulps.     

The ultrastructure of spruce kraft pulps studied by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS)

Surface properties of spruce (Picea abies) kraft pulps cooked for different times and further OD₀E₁D₁E₂D₂-bleached were investigated with atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). A rough correlation between the increasing relative amount of the fibrillar surface structure in AFM images and increasing O/C atomic ratio in XPS-spectra was found with proceeding delignification. At the end of cooking (120 min) only about 1/3 of the fibre surface consisted of cellulose. The detailed analysis of the relative peak areas of the different C1s components in the XPS-spectra indicated that the granules at the beginning of cooking at 170 °C consisted mainly of lignin and extractives. The analysis also showed that different steps of the bleaching sequence were quite specific in removing structural components. Furthermore, the lignin removal was shown not to result automatically in increased fraction of exposed cellulose surface, but could also lead in increased relative amount of surface extractives. Evidence for the high surface content of hemicelluloses for the D2-stage sample was observed. Hemicelluloses with both fibrillar and amorphous morphology were found to be present.     

THE INFLUENCE OF THE BLEACHING MEDIUM ON CHLORINE DIOXIDE DELIGNIFICATION

Chlorine dioxide delignification (D₀) stages performed in 90% ethanol resulted in post-D₀ kappa numbers that were 2 to 2.5 units lower than those performed in water. In spite of the reduction in kappa number, various gravimetric and UV spectroscopic techniques for measuring residual lignin indicated that the ethanol medium did not significantly enhance D₀ stage lignin removal. Differences in post-D₀ kappa numbers between the ethanol-based and aqueous systems were ascribed to how the bleaching medium affects ClO₂ oxidation of residual lignin. Ethanol-based D₀ stages resulted in an oxidized lignin that contains fewer muconic acid structures and more quinone structures than the aqueous-based systems. Indirect evidence from sodium hydrosulfite reduction implied that quinone moieties consume less KMnO₄ than aromatic structures in lignin during the kappa number test.     

Polyoxometalate catalyzed ozonation of chemical pulps in organic solvent media

Polyoxometalate (POM) catalyzed ozonation of chemical pulps in organic solvent media was found to be particularly effective and selective environmentally benign bleaching approach providing a way for substantial increase in pulp brightness, viscosity and degree of delignification in comparison with other ozone-based bleaching techniques. A series of tested low-boiling polar aprotic and protic organic solvents showed a well-defined capacity for ozonation improvement in the presence of Keggin-type heteropolyanion [PMo₇V₅O₄₀]⁸⁻ (HPA-5). Even moderate solvent proportion of 6% (w/w) in the reaction solution caused additional gain in brightness up to 3.4% ISO with simultaneous increase in pulp viscosity up to 8.8% and lignin removal up to 18.9% after HPA-5 catalyzed ozonation (0.8% O₃; 0.5 mM HPA), as compared with the control solvent-free process. An aqueous acetone solution was found to be the preferred reaction medium in terms of pulp brightening and delignification. Under optimized conditions, the POM-catalyzed ozonation of eucalypt kraft pulp in acetone/water solution showed remarkable brightness improvement by 15.1% ISO with additional lignin removal by 39.4% and increase in intrinsic viscosity by 3% in comparison with pulp bleached in water media.     

Quantification of Lignin and Hexenuronic Acid in Bleached Hardwood Kraft Pulps: A New Calibration Method for UVRR Spectroscopy and Evaluation of the Conventional Methods

Abstract

Lignin content determination is an important task when pulp bleaching is studied. However, none of the conventional methods were developed for bleached pulps and therefore they are accurate mainly for unbleached pulps. This article describes a new, rapid method to determine lignin and hexenuronic acid contents of bleached hardwood kraft pulps based on UV resonance Raman (UVRR) spectroscopy. The lignin contents of pulp samples were determined from the aromatic band heights of the UVRR spectra. Therefore the measurements gave the content of aromatic lignin in pulp, and did not include extensively oxidized lignin structures. The method was applicable for hardwood kraft pulps with lignin content less than 1%. The measured lignin content correlated linearly with the kappa number. The lignin content (% on pulp) equaled 0.15κ+0.16. The constant 0.16 was presumably caused by the incomplete oxidation of the lignin in the kappa number determination. Klason lignin or total lignin determinations were not accurate for these kinds of pulps. Hexenuronic acid content was simultaneously determined from the UVRR band height of unsaturated C?O and C?C structures. The linear correlation of this band with hexenuronic acid indicated that the content of other unsaturated structures was constant in all the pulps, was proportional to the hexenuronic acid content of the pulps, or was insignificantly low. When compared to conventional methods, the UVRR spectroscopic method is fast, requires little sample and pretreatment, and the procedure has good repeatability. In addition, the accuracy of this technique increases with decreasing lignin content (<1%) making it a very attractive method for bleaching studies.     

The Impact of Xylanase and Hot Acid Pretreatment on HexAs in Eucalyptus Kraft Pulp Bleaching

The influence of the presence of hexenuronic acid (HexA) in eucalyptus kraft pulp on the efficiency of D₀EpD₁ was investigated by separately using both commercial cellulase-free xylanase and hot acid pretreatments. In comparison to the xylanase pretreatment, the hot acid pretreatment was more than four-fold effective in removing the HexAs (61%) and concomitantly reduced the kappa number, but resulted in lower viscosity. After subsequent D₀EpD₁ bleaching, the final brightness and its stability were improved remarkably, especially under xylanase pretreatment. At the same brightness of 85% ISO, the xylanase pretreatment reduced the consumption of active chlorine (35.6%) more than the acid pretreatment did (27.5%). The total relative active chlorine savings for the xylanase pretreatment over the acid pretreatment was therefore nearly 23%. The HexA component can be removed considerably in both D₀ and D₁ stages during the D₀EpD₁ bleaching sequence, while only slightly in the Ep stage. The use of xylanase and acid pretreatment both resulted in insignificant physical strength losses for the bleached pulps.     

Strategies to reduce the brightness reversion of industrial ECF bleached Eucalyptus globulus kraft pulp

BACKGROUND: Brightness stability is a key property of bleached chemical pulps and is primarily determined by wood species and bleaching process conditions. Eucalyptus globulus is becoming a very important raw material for hardwood pulp production. In spite of this importance, there is a relative lack of systematic studies in the literature dealing with the subject. This research aims to study the effect of some of the foremost bleaching parameters of a DEDD bleaching sequence as well as the effect of a final P stage (DEDP instead of DEDD) in the brightness stability of bleached E. globulus kraft pulps. RESULTS: The increase of the D₀ stage temperature from 55 °C to 90 °C caused an increase in brightness stability. Increasing the ClO₂ charges from 2.8% to 3.2% also improved significantly the brightness stability. A high H₂SO₄ charge in the D₀ stage (10 kg tonne^?1 pulp) diminished the brightness stability. The combination of H₂O₂ addition to the E stage and ClO₂ reduction in the two final D stages does not affect brightness reversion. Raising the D₂ stage temperature from 65 °C to 82 °C decreased the brightness reversion, while an increase was obtained when the temperature rose above 82 °C. Substitution of the last ClO₂ stage in the DEDD sequence by a H₂O₂ stage (DEDP) significantly reduced the brightness reversion. CONCLUSION: For an existing pulp mill in which the implementation of new technologies to improve brightness reversion is considered, the results obtained showed that brightness stability can be improved without any significant capital investment. Copyright © 2007 Society of Chemical Industry     

Dissolution of Ethylenediamine Pretreated Pulp with High Lignin Content in LiCl/DMSO without Milling

Abstract

Various hardwood and softwood chemical pulps, including those with relatively high lignin content (up to ca. 10.5%), were completely dissolved without milling in lithium chloride/dimethyl sulfoxide (LiCl/DMSO) after a pretreatment with ethylenediamine (EDA). Because milling of the sample is not required, degradation of the cell wall components caused by milling does not take place. After the EDA pretreatment, the crystallinity of the pulps remained as high as the original pulps, although the crystal structure changed. This is the first time that transparent solutions of underivatized pulps with high lignin content were obtained in a simple organic solvent system. Interestingly, even in the case of coarse wood meal (40–80 mesh) about 70% could be dissolved after repeating the dissolving procedure two times. The formation of a pulp–EDA or wood–EDA complex seems to be critical for the dissolution in LiCl/DMSO. The nuclear magnetic resonance (NMR) spectrum of the EDA treated pulp solution had good resolution even though the degree of polymerization (DP) of the cellulose in the pulp is very high.     

Removal of residual lignin of ethanol‐based organosolv pulp by an alkali extraction process

Organosolv pulps usually have high kappa number. This research investigated an alkaline extraction method prior to bleaching for reducing the kappa number of organosolv pulp. Ethanol wheat straw pulp with a kappa number of 58.2 was extracted with 1% NaOH solution. The results show that the ethanol pulp has a large amount of lignin particles on the fiber surface. After 1 min alkali extraction, the kappa number of the ethanol pulp is reduced by 60%, to 22.2, and both the number and the size of the lignin particles on the fiber surface are significantly reduced. In comparison with a further ethanol washing/extraction, the alkali extraction is much more effective in terms of lignin removal. X‐ray photoelectron spectroscopy results show that a thin layer of lignin remained on the fiber surface after alkli extraction, but this did not reduce the internal bond strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Alcell® lignin solubility in ethanol–water mixtures

The lignin solubility in aqueous solutions of different ethanol concentrations was studied. The concept of the solubility parameter was applied to account for the effect of ethanol concentration on the lignin solubility. Experimental results showed that the lignin solubility increased strongly as the ethanol concentration increased from 9.5 to 47.5% then, it increased much more slowly until a maximum was reached at an ethanol concentration of about 70%. Further increase in the ethanol concentration resulted in a slight decrease in the lignin solubility. Based on the lignin molecular formula, the solubility parameter (δ-value) of the ALCELL® lignin was 13.7 (cal/cm³)^1/2. The δ-value of aqueous ethanol solutions of increased ethanol concentration was calculated and was found to decrease continuously from 22.31 (cal/cm³)^1/2 for pure water to 12.08 (cal/cm³)^1/2 for pure ethanol. The effect of ethanol concentration on the solubility of the ALCELL lignin was then explained based on the theory that lignin exhibited the maximum solubility when the δ-value of the solvent was close to that of the ALCELL lignin and the H-bonding capacity of the solutions with different ethanol concentrations was similar. © 1995 John Wiley & Sons, Inc.     

Bioethanol production from bio‐ organosolv pulps of Pinus radiata and Acacia dealbata

Wood chips from Pinus radiata and Acacia dealbata were pretreated with the white‐rot fungi Ceriporiopsis subvermispora and Ganoderma australe, respectively, for 30 days at 27 °C and 55% relative humidity, followed by an organosolv delignification with 60% ethanol solution at 200 °C for 1 h to produce pulps with high cellulose and low lignin content. Biotreatment for 30 days was chosen based on low weight and cellulose losses (lower than 4%) and lignin degradation higher than 9%. After organosolv delignification, pulp yield for P. radiata and A. dealbata pulps was 45–49% and 31–51%, respectively. P. radiata bio‐pulps showed higher glucan (93%) and lower lignin content (6%) than control pulps (82% glucan and 13% lignin). A. dealbata bio‐pulps also showed higher glucan (95%) and lower lignin content (2%) than control pulps (92% glucan and 4% lignin). Pulp suspensions at 2% consistency were submitted either to separate enzymatic hydrolysis and fermentation (SHF) or simultaneous enzymatic saccharification and fermentation (SSF) for bioethanol production. The yeast Saccharomyces cerevisiae was used for fermentation. Glucan‐to‐glucose conversion in the enzymatic hydrolysis of control and bio‐pulps of P. radiata was 55% and 100%, respectively, and it was 100% for all pulp samples case of A. dealbata. The highest ethanol yield (calculated as percentage of theoretical yield) during SHF of P. radiata control and bio‐pulps was 38% and 55%, respectively, and for A. dealbata control and bio‐pulps 62% and 69%, respectively. The SSF of P. radiata control and bio‐pulps yielded 10% and 65% of ethanol, respectively, and 77% and 82% for A. dealbata control and bio‐pulps, respectively. In wood basis, the maximum conversion obtained (g ethanol per kg wood) in SHF was 37% and 51% (for P. radiata and A. dealbata pulps, respectively) and 44% and 65% in SSF (for P. radiata and A. dealbata pulps, respectively) regarding the theoretical yield. The low wood‐to‐ethanol conversion was associated with low pulp yield (A. dealbata pulps), high residual lignin amount (P. radiata pulps) and the low pulp consistency (2%) used for SHF and SSF. Copyright © 2007 Society of Chemical Industry     

Ethanol-Modified Supercritical Carbon Dioxide Extraction of the Bioactive Lipid Components of <Emphasis Type="Italic">Camelina sativa</Emphasis> Seed

Camelina sativa seed is an underutilized oil source that attracts a growing interest, but it requires more research on its composition and processing. Its high omega‐3 content and growing demand for clean food processing technologies make conventional oil extraction less attractive. In this study, the effect of extraction methods on the bioactive lipid composition of the camelina seed lipid was investigated, and its bioactive lipid composition was modified at the extraction stage using ethanol‐modified supercritical carbon dioxide (SC‐CO₂). Ethanol‐modified SC‐CO₂ extractions were carried out at varying temperatures (50 and 70 °C), pressures (35 and 45 MPa), and ethanol concentrations (0–10%, w/w), and were compared to SC‐CO₂, cold press, and hexane extraction. The highest total lipid yield (37.6%) was at 45 MPa/70 °C/10% (w/w) ethanol. Phospholipids and phenolic content increased significantly with ethanol‐modified SC‐CO₂ (p < 0.05). SC‐CO₂ with 10% (w/w) ethanol concentration selectively increased phosphatidylcholine (PC) content. Apparent solubility of camelina seed lipids in SC‐CO₂, determined using the Chrastil model, ranged from 0.0065 kg oil/kg CO₂ (35 MPa/50 °C) to 0.0133 kg oil/kg CO₂ (45 MPa/70 °C). Ethanol‐modified SC‐CO₂ extraction allowed modification of the lipid composition that was not possible with the conventional extraction methods. This is a promising green method for extraction and fractionation of camelina seed lipids to separate and enrich its bioactives.     

Estimating Glucan,Xylan, and Methylglucuronic Acids in Kraft Pulps of Eucalyptus globulus Using FT-NIR Spectroscopy and Multivariate Analysis

Abstract

Fourier transform near infrared (FT-NIR) associated with multivariate analysis was used to estimate glucan, xylan, 4-O-Methyl-α -D-glucuronic acid (MeGlcA) content, and pulp yield in kraft pulps of Eucalyptus globulus Labill. Several models were applied to correlate chemical composition in samples with the NIR spectral data by means of principal components regression (PCR) or partial least square (PLS) algorithms. Calibration models were built and validated by using all the spectral data and cross-validation methodology. The r_c ² values for the best calibration models for quantification of glucan, xylan, MeGlcA contents and pulp yield were between 0.71–0.92. The model was validated using a set of external samples. The amount of glucan (64–77%), xylan (12–18%), and MeGlcA (204–363 mmol kg pulp^–1) in pulps were predicted with a root mean square error of prediction (RMSEP) of 0.91%, 0.46%, and 15.21% for glucan, xylan, and MeGlcA, respectively. Pulp yield (in the range of 46–70%) was also predicted with good accuracy with a RMSEP of 1.63%. These results suggest that glucan, xylan, MeGlcA composition, and pulp yield in kraft pulps of E. globulus can be adequately estimated by NIR spectroscopy for laboratory or industrial applications. NIR predictions can also provide useful and cost-effective tools for the rapid screening of large numbers of samples.     

Comparative study of three lignin fractions isolated from mild ball‐milled Tamarix austromogoliac and Caragana sepium

Six lignin fractions from mild ball‐milled Tamarix austromogoliac (TA) and Caragana sepium (CS) were sequentially isolated with 80% dioxane containing 0.05M HCl at 75°C for 4 h, 50% aqueous ethanol containing 1M triethylamine at 70°C for 4 h, and 8% aqueous NaOH at 45°C for 3 h. The results showed that the successive treatments made it possible to isolate lignin from wood with a high yield and purity, in which 89.4 and 90.6% of the original lignin from TA and CS were released, respectively. The lignin fractions isolated with the three‐step method were analyzed with Fourier transform infrared, ¹H‐ and ¹³C‐NMR, alkaline nitrobenzene oxidation, and gel permeation chromatography. It was found that the three lignin fractions isolated from TA were rich in syringyl units, and the molar ratio of the relatively total moles of vanillin, vanillic acid, and acetovanillin to the relatively total moles of syringaldehyde, syringic acid, and acetosyringone decreased from 1: 2.6 to 1 : 3.2 to 1: 3.6 in the lignin preparations, whereas this ratio in the corresponding lignin fractions isolated from CS was found to be 1.4 : 1, 1.1 : 1, and 1 : 1.4, respectively. More importantly, the results revealed that the sequential extractions of the mild ball‐milled TA and CS with 80% acidic dioxane, 50% alkaline ethanol, and 8% aqueous NaOH under the conditions used did not significantly cleave the β–O‐4 and α–O‐4 linkages in lignin macromolecules. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dissolution of Lignin from Kraft Pulp after Treatment with Nitrogen Oxides

Laboratory experiments show that pretreatment with NO₂ including heating and ripening at 5% consistency and 90°C for 3 hours in the presence of NO₃- and H⁺ led to a dissolution of approximately 50–60% of the lignin in unbleached kraft pulp. Only 5–15% were dissolved when the treatment was terminated after heating to 90°C. An extensive fragmentation of the lignin during the ripening explains the extensive delignification in acid medium.

Fractionated dissolution of the remaining lignin by alkaline extraction gave fractions with small variation in N-contents (2.9–3.4%) and hydrophilicity. The last fraction exhibited the highest sorption of water vapor. The delignification was related to the decrease in molecular size during the pretreatment and during the subsequent alkaline treatments.     

Optimized Catalytic Bleaching Sequences for Eucalyptus Kraft Pulp

Contemporary multi-stage bleaching processes partially remove residual lignin and hexenuronic acid from cellulosic pulps. The reactions in the steps could be faster and consume smaller amounts of chemicals. Catalytic bleaching (H_cat), utilizing hypochlorite (H), triethylenediamine (DABCO) and its derivative N-carboxymethyl triethylenediamine (CM-DABCO), is a new discovery that has the potential to improve the chemical and energetic efficiency of bleaching processes in chemical pulp mills, e.g. through reducing the reaction time of the bleaching processes. The objective of this study was to clarify if new kraft pulp bleaching sequences with initial stage of chlorine dioxide (ClO₂; D) and an intermediate stage of H_cat could provide fully bleached pulps. The bleaching sequences of the studied eucalyptus pulps include D₀E_(OP)H_cat(Q)P and H_catZ/DP, which attained a final brightness of 88 and 89% ISO, respectively. H_catZ/DP showed to be the best sequence for the catalytic bleaching of eucalyptus kraft pulps. This study may open new doors to future bleaching of cellulose pulps with fewer towers and decreased use of chemicals.     

Physicochemical characterization of lignin fractions sequentially isolated from bamboo (Dendrocalamus brandisii) with hot water and alkaline ethanol solution

Nine lignin fractions from bamboo (Dendrocalamus brandisii) were sequentially isolated with hot water at 80, 100, and 120°C for 3 h and 60% aqueous ethanol containing 0.25, 0.5, 1.0, 2.0, 3.0, and 5.0% NaOH at 80°C for 3 h. Molecular weight and purity analysis revealed that the lignin fractions isolated by hot water (L₁, L₂, and L₃) had lower weight-average molecular weights (between 1350 and 1490 g mol⁻¹) and contained much higher amounts of associated hemicelluloses (between 9.26 and 22.29%), while the lignin fractions isolated by alkaline aqueous ethanol (L₄, L₅, L₆, L₇, L₈, and L₉) had higher weight-average molecular weights (between 2830 and 3170 g mol⁻¹) and contained lower amounts of associated hemicelluloses (between 0.63 and 1.66%). Spectroscopy (UV, FTIR, ¹³C-NMR, and HSQC) analysis showed that the bamboo (Dendrocalamus brandisii) lignin was typical grass lignin, consisting of p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) units. The major interunit linkages presented in the alkaline aqueous ethanol extractable bamboo lignin were β-O-4′ aryl ether linkages (about 74.3%), followed by β-β′ resinol-type linkages and β-1′ spirodienone-type linkages (both for 7.8%), together with small amounts of β-5′ phenylcoumaran (6.8%) and p-hydroxycinnamyl alcohols end groups (3.1%). In addition, a small percentage (1.0%) of the lignin side-chain was found to be acetylated at the γ-carbon, predominantly over syringyl units. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012