Preparation of carbon fibers from a lignin copolymer with polyacrylonitrile

Abstract In this study, we have developed an economically viable and technologically sound process for the production of low-cost carbon fibers (CFs) made of lignin copolymer with acrylonitrile (AN). Initially, lignin, a by-product of the pulp and paper industry, is copolymerized with AN in dimethysulfoxide (DMSO) by the radical copolymerization. The resulting copolymer was confirmed by a Fourier transform infrared (FT-IR), 13C, and 1H nuclear magnetic resonance (NMR) spectroscopy, showing the presence of the C N group of polyacrylonitrile (PAN) co-eluting with ether, hydroxyl, and aromatic groups that are attributed to lignin. This provided evidence that a PAN–lignin copolymer was synthesized. Using a wet-spinning process, the PAN–lignin copolymers are then spun into fibers with an average tensile strength of 2.41 gf/den, a tensile strain of 11.04%, and a modulus of 22.92 gf/den. The CFs are prepared by the subsequent thermal treatment of the spun fibers. Differential scanning calorimeter (DSC) analysis of the PAN–lignin copolymer-based spun fibers displays a downshifted exothermic peak at 285.83 compared with the homopolymer PAN-based as-spun fibers, which provides evidence that lignin is cooperated with the oxidative stabilization reactions. The stabilized fibers are carbonized by heating from room temperature to 800 °C in a nitrogen atmosphere. This study shows the potential for a number of recycled and renewable polymers to be incorporated into wet-spun fibers for production of CF feedstocks, thereby reducing the supply cost using the current commercial technology.

[1]  C. S. Sipaut,et al.  Preparation and characterization of a newly water soluble lignin graft copolymer from oil palm lignocellulosic waste , 2010 .

[2]  P. Gérardin,et al.  Graft Copolymerization of Acrylic Acid onto Sawdust Using KMnO4 as Initiator , 1998 .

[3]  W. Zhang,et al.  Characterization on oxidative stabilization of polyacrylonitrile nanofibers prepared by electrospinning , 2007 .

[4]  Satoshi Kubo,et al.  Lignin-based carbon fibers for composite fiber applications , 2002 .

[5]  M. D’Auria,et al.  Graft copolymers of lignin with electron poor alkenes , 2003 .

[6]  L. Barclay,et al.  Antioxidant Properties of Phenolic Lignin Model Compounds , 1997 .

[7]  N. Morohoshi,et al.  Biodegradable polyurethanes from plant components , 1995 .

[8]  Satoshi Kubo,et al.  Lignin-based Carbon Fibers: Effect of Synthetic Polymer Blending on Fiber Properties , 2005 .

[9]  Y. Uraki,et al.  Preparation of carbon fibers from softwood lignin by atmospheric acetic acid pulping , 1998 .

[10]  F. G. Calvo-Flores,et al.  Lignin as renewable raw material. , 2010, ChemSusChem.

[11]  M. Morshed,et al.  An investigation on the stabilization of special polyacrylonitrile nanofibers as carbon or activated carbon nanofiber precursor , 2009 .

[12]  Bo-Hye Kim,et al.  Process Optimization for Preparing High Performance PAN-based Carbon Fibers , 2009 .

[13]  K. Holtman,et al.  Lignin-based carbon fibers: Oxidative thermostabilization of kraft lignin , 2005 .

[14]  R. Gersonde,et al.  Graft copolymers of lignin with 1-ethenylbenzene. 2. Properties , 1996 .

[15]  Ahmad Fauzi Ismail,et al.  The effect of processing conditions on a polyacrylonitrile fiber produced using a solvent-free free coagulation process , 2008 .

[16]  J. Kadla,et al.  Effect of Organoclay Reinforcement on Lignin-Based Carbon Fibers , 2011 .

[17]  V. A. Medvedev,et al.  Improving Carbon Fibre Production Technology , 2003 .

[18]  F. S. Baker,et al.  On the characterization and spinning of an organic‐purified lignin toward the manufacture of low‐cost carbon fiber , 2012 .

[19]  J. Meister,et al.  Synthesis and properties of several cationic graft copolymers of lignin , 1992 .

[20]  F. Lu,et al.  Free radical-scavenging properties of lignin. , 1998, Nutrition and cancer.

[21]  K. Perepelkin,et al.  Oxidized (Cyclized) Polyacrylonitrile Fibres — Oxypan. A Review , 2003 .

[22]  Chengguo Wang,et al.  Effect of coagulation on the structure and property of PAN nascent fibers during dry jet wet-spinning , 2009 .

[23]  Weijin Liu,et al.  Preparation of conductive polyaniline fibers by a continuous forming-drawn processing routine , 2004 .

[24]  S. Kelley,et al.  Multiphase materials with lignin. VIII. Interpenetrating polymer networks from polyurethanes and polymethyl methacrylate , 1990 .

[25]  J. Meister,et al.  Graft 1-phenylethylene copolymers of lignin. 1. Synthesis and proof of copolymerization , 1991 .

[26]  Wolfgang G. Glasser,et al.  Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials , 2002 .

[27]  Qing Shen,et al.  Lignin‐based activated carbon fibers and controllable pore size and properties , 2011 .

[28]  Tor P. Schultz,et al.  Lignin : historical, biological, and materials perspectives , 1999 .

[29]  C. Fellows,et al.  Value-adding to cellulosic ethanol: lignin polymers. , 2011 .

[30]  V. Verneker,et al.  On coloration of polyacrylonitrile: a NMR study , 1986 .

[31]  K. Sudo,et al.  A new carbon fiber from lignin , 1992 .

[32]  R. Thring,et al.  POLYURETHANES FROM ALCELL@ LIGNIN , 1997 .