Renewable polymers from lignin via copper-free thermal click chemistry

Han, Yanming; Yuan, Liang; Li, Gaiyun; Luo-hua, Huang; Qin, Tefu; Chu, Fuxiang; Tang, Chuanbing

doi:10.1016/j.polymer.2015.12.010

Cited by 77 publications

(64 citation statements)

References 61 publications

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“…With RHBL g-oxCA in hand, we decided to couple the newly introduced carboxylic acids with aniline 10,a sw ef elt this represented af lexible approach to grafting onto the lignin backbone that complemented other recent reports from our group and others. [5,[46][47][48][49][50][51][52] Initially, model 11 was synthesized from 9 and 10 to aid characterization of the final lignin (Scheme 1). RHBL g-oxCA was then coupled with 10 by using EDC, Et 3 Na nd HOBt at RT for 24 h( Lignin general procedure D).…”

Section: Tempo-mediated Formation Of B-o-4 G-carboxylic Acid-substitumentioning

confidence: 99%

Selective Primary Alcohol Oxidation of Lignin Streams from Butanol‐Pretreated Agricultural Waste Biomass

Panovic

Lancefield

Phillips³

et al. 2019

ChemSusChem

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Chemically modified lignins are important for the generation of biomass‐derived materials and as precursors to renewable aromatic monomers. A butanol‐based organosolv pretreatment has been used to convert an abundant agricultural waste product, rice husks, into a cellulose pulp and three additional product streams. One of these streams, a butanol‐modified lignin, was oxidized at the γ position to give a carboxylic acid functionalized material. Subsequent coupling of the acid with aniline aided lignin characterization and served as an example of the flexibility of this approach for grafting side chains onto a lignin core structure. The pretreatment was scaled up for use on a multi‐kilogram scale, a development that enabled the isolation of an anomeric mixture of butoxylated xylose in high purity. The robust and scalable butanosolv pretreatment has been developed further and demonstrates considerable potential for the processing of rice husks.

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Section: Tempo-mediated Formation Of B-o-4 G-carboxylic Acid-substitumentioning

confidence: 99%

Selective Primary Alcohol Oxidation of Lignin Streams from Butanol‐Pretreated Agricultural Waste Biomass

Panovic

Lancefield

Phillips³

et al. 2019

ChemSusChem

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“…The spectra are thus not only very rich in information but the technique is also simple to operate, fast and widely available. Indeed, also for lignin characterization, FTIR analysisi sc ommonly used in a qualitative fashion,f or example, to identify different functional groups; [25][26][27][28] however,d ue to the complex patterns and severe peak overlap,i ti ss eldom used to extract detailed structural information in aw ay that, for example, NMR spectroscopy does. Nor is it often used for quantitative measurements, although Schultz and Glasserh ave demonstrated some successi nt his direction.…”

Section: Introductionmentioning

confidence: 99%

Linkage Abundance and Molecular Weight Characteristics of Technical Lignins by Attenuated Total Reflection‐FTIR Spectroscopy Combined with Multivariate Analysis

Lancefield

Constant

Peinder³

et al. 2019

ChemSusChem

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Lignin is an attractive material for the production of renewable chemicals, materials and energy. However, utilization is hampered by its highly complex and variable chemical structure, which requires an extensive suite of analytical instruments to characterize. Here, we demonstrate that straightforward attenuated total reflection (ATR)‐FTIR analysis combined with principle component analysis (PCA) and partial least squares (PLS) modelling can provide remarkable insight into the structure of technical lignins, giving quantitative results that are comparable to standard gel‐permeation chromatography (GPC) and 2D heteronuclear single quantum coherence (HSQC) NMR methods. First, a calibration set of 54 different technical (fractionated) lignin samples, covering kraft, soda and organosolv processes, were prepared and analyzed using traditional GPC and NMR methods, as well as by readily accessible ATR‐FTIR spectroscopy. PLS models correlating the ATR‐FTIR spectra of the broad set of lignins with GPC and NMR measurements were found to have excellent coefficients of determination ( R 2 Cal.>0.85) for molecular weight ( M n , M w ) and inter‐unit abundances (β‐ O ‐4, β‐5 and β‐β), with low relative errors (6.2–14 %) as estimated from cross‐validation results. PLS analysis of a second set of 28 samples containing exclusively (fractionated) kraft lignins showed further improved prediction ability, with relative errors of 3.8–13 %, and the resulting model could predict the structural characteristics of an independent validation set of lignins with good accuracy. The results highlight the potential utility of this methodology for streamlining and expediting the often complex and time consuming technical lignin characterization process.

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“…Alkyne‐functionalized lignin macromonomers, as presented above, were used by Han et al . to obtain lignin‐based polymers through copper‐free, thermally induced, azide–alkyne click cycloaddition at 130 °C by applying different synthetic strategies (Figure ).…”

Section: Synthesis Of Aromatic Polymeric Materials Through Click Reacmentioning

confidence: 99%

“…Han et al. used the abovementioned 5‐hexinoyl chloride to esterify aliphatic OH groups of polycaprolactone (PCL) and PLA chain‐extended lignin . Chain‐extended derivatives of lignin possess flexible aliphatic chains, which counterbalance the rigidity provided by the neat lignin aromatic backbone; thus improving the mechanical properties of the materials prepared with such lignin derivatives.…”

Section: Introduction Of Clickable Groups Onto Aromatic Macromersmentioning

confidence: 99%

Clicking Biobased Polyphenols: A Sustainable Platform for Aromatic Polymeric Materials

et al. 2018

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Lignin, tannins, and cashew nut shell liquid are considered the main sources of aromatic-based macromolecules. They represent an abundant alternative feedstock for the elaboration of aromatic chemicals and polymers, with a view to replacing some fossil-based fractions. Located in different tissues of plants, these compounds, with a large diversity and structural complexity, have, to date, been considered as byproducts derived from fractionation-separation industrial processes with low added value. In the last decade, the use of click chemistry as a tool for the synthesis of controlled macromolecular architectures has seen much development in fundamental and applied research for a wide range of applications. It could represent a valid solution to overcome the main limitations encountered in the chemical modification of natural sources of chemicals, with an environmentally friendly approach to create new substrates for the development of innovative polymers and materials. After a brief description of the main aromatic biopolymers, including the main extraction techniques, along with their structure and their properties, this Review describes chemical modifications that have mainly been focused on natural polyphenols, with the aim of introducing clickable groups, and their further use for the synthesis of biobased materials and additives. Special emphasis is given to several as-yet unexplored chemical features that could contribute to further fundamental and applied materials science research.

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Renewable polymers from lignin via copper-free thermal click chemistry

Cited by 77 publications

References 61 publications

Selective Primary Alcohol Oxidation of Lignin Streams from Butanol‐Pretreated Agricultural Waste Biomass

Selective Primary Alcohol Oxidation of Lignin Streams from Butanol‐Pretreated Agricultural Waste Biomass

Linkage Abundance and Molecular Weight Characteristics of Technical Lignins by Attenuated Total Reflection‐FTIR Spectroscopy Combined with Multivariate Analysis

Clicking Biobased Polyphenols: A Sustainable Platform for Aromatic Polymeric Materials

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