skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis and Characterization of Lignin-grafted-poly(ε-caprolactone) from Different Biomass Sources

Journal Article · · New Biotechnology
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. for Biological Sciences; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Bioenergy Innovation
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Bioenergy Innovation; Univ. of North Texas, Denton, TX (United States)
  4. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. for Biological Sciences; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Bioenergy Innovation
+ Show Author Affiliations

Modification of lignin with poly(ε-caprolactone) is a promising approach to valorize industrial low-value lignins and to advance the bioeconomy. We have synthesized lignin grafted poly(ε-caprolactone) (lignin-g-PCL) copolymers via ring-opening polymerization of ε-caprolactone with different types of lignins of varying botanical sources (G-type pine lignin, S/G-type poplar lignin, and C-type Vanilla seeds lignin) and lignin extraction methods (Kraft and ethanol organosolv pulping). The lignin-g-PCL copolymer showed remarkably improved compatibility and dispersion in acetone, chloroform, and toluene in comparison to non-modified lignins. The structure and thermal properties of the lignin-g-PCL were investigated using Fourier-transform infrared spectroscopy (FTIR), 31P nuclear magnetic resonance (NMR), 2D heteronuclear single quantum correlation (HSQC) NMR, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Furthermore, we have found that all the technical lignins were reactive to the copolymerization reaction regardless of their plant source and isolation methods. The molecular weights of the synthesized lignin-g-PCL copolymers were positively correlated with the content of aliphatic lignin hydroxyls, suggesting that the copolymerization reaction tends to occur preferentially at the aliphatic hydroxyls rather than the phenolic hydroxyls of lignin. Thermal analyses of the lignin-g-PCL copolymers were studied, and in general, a reduction of melting temperature and crystallinity percentage in comparison to the neat PCL was observed. However, the thermal behavior of lignin-g-PCL copolymers varied depending on the lignin feedstocks employed in the copolymerization reaction.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1712708
Journal Information:
New Biotechnology, Vol. 60; ISSN 1871-6784
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (50)

Lignin Valorization: Improving Lignin Processing in the Biorefinery journal May 2014
Conversion of technical lignins to functional materials with retained polymeric properties journal April 2015
Lignin-derivatives based polymers, blends and composites: A review journal December 2016
Lignin as a UV Light Blocker—A Review journal May 2020
Chemical modification of lignins: Towards biobased polymers journal July 2014
Synthesis of polycaprolactone: a review journal January 2009
Reactive extrusion of polycaprolactone compounds containing wood flour and lignin: Reactive Extrusion of PCL Compounds journal June 2001
Study on Thermal and Mechanical Properties of Biodegradable Blends of Poly(ε-caprolactone) and Lignin journal April 2001
Polymer blends of steam-explosion lignin and poly(ɛ-caprolactone) by high-energy ball milling journal January 2008
Phase Structure and Mechanical Property of Blends of Organosolv Lignin Alkyl Esters with Poly(ε-caprolactone) journal January 2009
Lignin/Poly(ε-Caprolactone) Blends with Tuneable Mechanical Properties Prepared by High Energy Ball-Milling journal June 2010
Engineering highly stretchable lignin-based electrospun nanofibers for potential biomedical applications journal January 2015
Injection-Molded Bioblends from Lignin and Biodegradable Polymers: Processing and Performance Evaluation journal November 2017
Prevention of mold invasion by eco-friendly lignin/polycaprolactone nanofiber membranes for amelioration of public hygiene journal November 2016
Multiphase materials with lignin. 11. Starlike copolymers with caprolactone journal January 1994
Synthesis, thermal properties, rheological and mechanical behaviors of lignins-grafted-poly(ε-caprolactone) journal July 2013
Grafting polycaprolactone onto alkaline lignin for improved compatibility and processability journal December 2019
Non-Einstein Viscosity Phenomenon of Acrylonitrile–Butadiene–Styrene Composites Containing Lignin–Polycaprolactone Particulates Highly Dispersed by High-Shear Stress journal June 2019
Multiphase materials with lignin. XII. Blends of poly(vinyl chloride) with lignin–caprolactone copolymers journal January 1994
Sustainable and Antioxidant Lignin–Polyester Copolymers and Nanofibers for Potential Healthcare Applications journal June 2017
Biodegradable and renewable poly(lactide)–lignin composites: synthesis, interface and toughening mechanism journal January 2015
Strong and biocompatible lignin /poly (3-hydroxybutyrate) composite nanofibers journal April 2018
Construction of sustainable polyurethane-based gel-coats containing poly( ε -caprolactone)-grafted lignin and their coating performance journal July 2018
Lignin, a biomass crosslinker, in a shape memory polycaprolactone network journal September 2019
“Tree to Bone”: Lignin/Polycaprolactone Nanofibers for Hydroxyapatite Biomineralization journal May 2019
Implantable and degradable antioxidant poly(ε-caprolactone)-lignin nanofiber membrane for effective osteoarthritis treatment journal February 2020
Preparation and characterization of Lignin-graft-poly (ɛ-caprolactone) copolymers based on lignocellulosic butanol residue journal November 2015
Nucleation, Crystallization, and Thermal Fractionation of Poly (ε-Caprolactone)-Grafted-Lignin: Effects of Grafted Chains Length and Lignin Content
  • Pérez-Camargo, Ricardo A.; Saenz, Guery; Laurichesse, Stéphanie
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 53, Issue 24 https://doi.org/10.1002/polb.23897
journal September 2015
Effect of ball milling on lignin polyesterification with ε-caprolactone journal April 2015
Conversion of sulfuric acid lignin generated during bioethanol production from lignocellulosic materials into polyesters with ɛ-caprolactone journal June 2011
Poly(ε-caprolactone) chains grafted from lignin, hydroxymethylated lignin and silica/lignin hybrid macroinitiators: Synthesis and characterization of lignin- based thermoplastic copolymers journal April 2019
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals journal June 2010
Novel seed coat lignins in the Cactaceae: structure, distribution and implications for the evolution of lignin diversity journal November 2012
Lignin Structural Modifications Resulting from Ethanol Organosolv Treatment of Loblolly Pine journal January 2010
31 P NMR Characterization of Tricin and Its Structurally Similar Flavonoids journal April 2017
Determination of hydroxyl groups in biorefinery resources via quantitative 31P NMR spectroscopy journal August 2019
Effects of Coumarate 3-Hydroxylase Down-regulation on Lignin Structure journal January 2006
Downregulation of pectin biosynthesis gene GAUT4 leads to reduced ferulate and lignin-carbohydrate cross-linking in switchgrass journal January 2019
Dispersity in polymer science (IUPAC Recommendations 2009) journal January 2009
Application of quantitative 31P NMR in biomass lignin and biofuel precursors characterization journal January 2011
Simultaneous depolymerization and fermentation of lignin into value-added products by the marine protist, Thraustochytrium striatum journal March 2020
Elucidating Structural Characteristics of Biomass using Solution-State 2 D NMR with a Mixture of Deuterated Dimethylsulfoxide and Hexamethylphosphoramide journal April 2016
Inhibitory effects of lignin on enzymatic hydrolysis: The role of lignin chemistry and molecular weight journal August 2018
Effects of organosolv and ammonia pretreatments on lignin properties and its inhibition for enzymatic hydrolysis journal January 2017
NMR Studies Part 3: Analysis of Lignins from Modern Kraft Pulping Technologies journal January 1998
UV spectra of carbonyl-contaiming furan compounds journal May 1973
Perspective on Technical Lignin Fractionation journal May 2020
Fractionation of industrial lignins: opportunities and challenges journal January 2020
Electrospun Polycaprolactone/lignin-based Nanocomposite as a Novel Tissue Scaffold for Biomedical Applications journal January 2017
Engineering PCL/lignin nanofibers as an antioxidant scaffold for the growth of neuron and Schwann cell journal September 2018

Similar Records

Effect of the Lignin Structure on the Physicochemical Properties of Lignin-Grafted-Poly(ε-caprolactone) and Its Application for Water/Oil Separation
Journal Article · Tue Dec 06 00:00:00 EST 2022 · ACS Sustainable Chemistry & Engineering · OSTI ID:1712708
+5 more
Polylactide-Poly(6-methyl-ε-caprolactone)-Polylactide Thermoplastic Elastomers
Journal Article · Wed Nov 14 00:00:00 EST 2012 · Macromolecules · OSTI ID:1712708
Starch/Poly(ε-caprolactone) Graft Copolymers Synthetized by γ-Radiation and Their Application as Compatibilizer in Polymer Blends
Journal Article · Sun Dec 15 00:00:00 EST 2019 · Journal of Polymers and the Environment · OSTI ID:1712708

Related Subjects

59 BASIC BIOLOGICAL SCIENCES
Lignin
polycaprolactone
lignin copolymer
ring-opening polymerization