Volume 3 • Issue 3 • 1000e123
J Biotechnol Biomater
ISSN: 2155-952X JBTBM, an open access journal
Editorial Open Access
Biotechnology & Biomaterials
Argyropoulos, J Biotechnol Biomater 2013, 3:3
http://dx.doi.org/10.4172/2155-952X.1000e123
*Corresponding author: Dimitris S Argyropoulos, Department of Chemistry and
Forest Biomaterials, North Carolina State University, Raleigh, NC, USA, E-mail:
dsargyro@ncsu.edu
Received September 12, 2013; Accepted September 13, 2013; Published
September 19, 2013
Citation: Argyropoulos DS (2013) Towards Thermoplastic Lignin Polymers:
Progress in the Utilization of Kraft Lignin for the Synthesis of Heat Stable Polymer
Melts. J Biotechnol Biomater 3: e123. doi:10.4172/2155-952X.1000e123
Copyright: © 2013 Argyropoulos DS, et al. This is an open-access article
distributed under the terms of the Creative Commons Attribution License, which
permits unrestricted use, distribution, and reproduction in any medium, provided
the original author and source are credited.
Towards Thermoplastic Lignin Polymers: Progress in the Utilization of Kraft
Lignin for the Synthesis of Heat Stable Polymer Melts
Dimitris S Argyropoulos
1,2
*
1
Department of Chemistry and Forest Biomaterials, North Carolina State University, Raleigh, NC, USA
2
Most eforts to utilize lignin have been limited by various
factors that impart in it characteristics that deine it as an unreliable
precursor to polymer production. his is because lignin (and
more speciically technical lignin) ofers relatively unpredictable
polymerization characteristics, depending upon its source and the
degree of deligniication to which the plant materials were subjected.
More speciically, the highly functional character of lignin (i.e. rich in
phenolic and aliphatic OH groups, as well as reactive benzylic carbons),
induces a variety of potential polymerization sites and heat instability
in such materials. Both factors promote gelation processes under
polymerization conditions or when the temperature increases close
to, and/or above the glass transition temperature (Tg). In addition, the
relatively low molecular weight (a few thousands) for lignin derived
from commercial pulping and bioreinery operations makes lignin
unsuitable for higher end applications, such as high performance, heat
stable engineering thermoplastic applications.
he work of our group at NCSU has focused at providing a detailed
molecular understanding of the way the polymeric properties of krat
lignin and its derivatives are afected by their thermal treatments.
his information was then correlated with the polymeric properties
of the materials (glass transition temperature (Tg), molecular weight
characteristics, and thermal stability), for a series of selectively and
progressively derivatized sotwood krat lignin samples [1]. Sotwood
krat lignin was shown to be highly susceptible to thermally induced
reactions that cause its molecular characteristics to be severely altered
with the concomitant formation of irreversible crosslinking with no
thermoplastic processing possibilities. However, by fully methylating
the phenolic OH groups [2], from within the structure of sotwood
krat lignin, the thermal stability of these materials was seen to be
dramatically enhanced and their Tg’s reduced [1]. Optimum thermal
stability and melt cycling was observed with the fully methylated
derivatives. he accumulated data is aimed at providing the foundations
for a rational design of single or multi-component lignin-based
thermoplastic materials with reproducible polymeric properties when
thermally processed in a number of manufacturing cycles [1-3].
Furthermore, we have been able to create polyarylene (ether
sulfone)-krat lignin copolymers synthesized by a base catalyzed
stepwise copolymerization of suitably functionalized, fractionated
krat lignin with 4,4’-Dilourodiphenyl Sulfone ( DFDPS) in an aprotic
solvent at elevated temperatures (Scheme 1) [3].
he beneits of incorporating DFDPS within krat lignin are
apparent in the TGA thermograms of the copolymer shown in Figure
1. hermally stable polymer melts exceeding 300°C are apparently
attainable [3].
Conclusions and Overall Outlook
his efort ofers novel avenues at creating reactive lignin materials
that are stabilized and rendered better suited for industrial applications.
It provides methods for creating lignins of controlled and modulated
characteristics, exhibiting thermal and polymerization stabilities. Such
thermal properties and stable molecular weight distributions of lignins
and copolymers produced from commercial lignins provides a means
for beneicially modulating the properties of an otherwise intractable
bio-polymer.
References
1. Cui C, Sadeghifar H, Sen S, Argyropoulos DS (2013) Toward thermoplastic
Figure 1: TGA of kraft lignin and its DFDPS copolymer.
S F F
O
O
Ar OH L
DMSO/toluene
-H
2
O
Ar O
-
Na
+
L
Ar O
-
L
S
F
F
O
O
O
Ar L
-
S
F
F
O
O
O
Ar
L
-
S
F
F
O
O
Ar L
O
-
S
F
F
O
O
O
Ar L
-
S F
O
O
O Ar L
-X
-
Ar OH L
= Lignin molecule with phenolic -OH end group
NaOH
Scheme 1: Copolymerization of kraft lignin with diluorodiphenylsulfone
(DFDPS).
Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia