Accepted Manuscript

Title: Lignin-derivatives based polymers, blends and

composites: A review
Author: Amina Naseem Shazia Tabasum Khalid Mahmood
Zia Mohammad Zuber Muhammad Ali Aqdas Noreen
PII:
DOI:
Reference:

S0141-8130(16)31169-2
http://dx.doi.org/doi:10.1016/j.ijbiomac.2016.08.030
BIOMAC 6411

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International Journal of Biological Macromolecules

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21-6-2016
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9-8-2016

Please cite this article as: Amina Naseem, Shazia Tabasum, Khalid Mahmood Zia,
Mohammad Zuber, Muhammad Ali, Aqdas Noreen, Lignin-derivatives based polymers,
blends and composites: A review, International Journal of Biological Macromolecules
http://dx.doi.org/10.1016/j.ijbiomac.2016.08.030
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Lignin-derivatives based polymers, blends and composites: A review

Amina Naseema, Shazia Tabasum*,a, Khalid Mahmood Ziaa, Mohammad Zubera, Muhammad
Alib, Aqdas Noreena
a

Institute of Chemistry, Government College University, Faisalabad 38030, Pakistan

Department of Biotechnology, Government College University, Faisalabad 38030-Pakistan

Corresponding author:
Tel.: +92 300 6603967;
Fax: +92 041-9200671
E-mail address: shazia.shazia.qasim@gmail.com (S. Tabasum)

Lignin-derivative based polymers, blends and composites: A state of the art review

Highlights:

Human history mainly relies on the biopolymers,

Derivatives of lignin like sulfonate, phenolic, organosolv, kraft and sodium sulfonate
lignin have good mechanical, chemical and physical properties.

Functionalizations by lignin are very appropriate for the development of well-designed

materials

The review sheds a light on lignin derivatives based materials with potential applications.

Lignin-derivative based polymers, blends and composites: A review

ABSTRACT:
Lignin and lignin derivatives biopolymers have several properties, such as high thermal
stability, antioxidant, biodegradability, antimicrobial actions, adhesive properties, etc., and thus
they can be extensively used in wide range of areas. Although human history mostly depend on
the biopolymers, however derivatives of lignin such as sulfonate, phenolic, organosolv, Kraft and
sodium sulfonate lignin have good mechanical and physicochemical properties. Well-designed
materials such as coatings and paints, manufacturing of plastics and resins, for rubber packaging,
for fuel production etc., can be obtained by the functionalizations of chemically modified lignin.
Considering multi purposes properties of the lignin and lignin derivatives and extensive

industrial applications of derivatives, this review sheds a light on lignin derivatives based
materials with their prospective applications. All the technical scientific issues have been
addressed highlighting the recent advancement.
Key words: Lignin-derivatives, lignin-blends, lignin-composites
List of Abbreviations
DSC
Differential Scanning Calorimetry
SEM
Scanning Electron Microscopy
FT-IR
Fourier Transform Infrared Spectrophotometry
NMR
Nuclear Magnetic Resonance
TGA
Thermogravimetric Analysis
PSD
Particle Size Distribution
AAS
Atomic Absorption Spectroscopy
GCMS
Gas ChromatographyMass Spectrometry
HSQC
Heteronuclear Single Quantum Correlation Spectroscopy,
HPLC
High Performance Liquid Chromatography
PCFC
Pyrolysis Combustion Flow Calorimetry
STEM
Scanning Transmission Electron Microscopy
cone-FTIR
Cone Calorimeter Coupled Infrared Spectroscopy
HPAEC
High Performance Anion Exchange Chromatography
GPC
Gel Permeation Chromatography
XRD
X-ray Diffraction
TCD
Thermal Conductivity Detector
DSL
Dynamic Light Scattering
MALDI-TOF Matrix-Assisted Laser Desorption/ionization Time-of-Flight Mass Spectrometry
MS
PLS
Partial Least Square
GC-TCD
Gas Chromatograph and Thermal Conductivity Detector.
EIS
Electrochemical Impedance Spectroscopy
SDSPAGE
Sodium Dodecyl Sulfate Polyacrylamide Gel Electrophoresis
HRMS
High Resolution Mass Spectrometers
XPS
X-ray Photoelectron Spectrometer
FID
Flame Ionization Detector
Py/TMAHPyrolysis/Tetramethyl Ammonium Hydroxide-Gas Chromatography/Mass
GC/MS
Spectrometry
TD GCMS
Thermal Desorption Gas Chromatography Mass Spectrometry
ICP-MS
Inductively Coupled Plasma Mass Spectrometry
PCFC
Pyrolysis Combustion Flow Calorimeter
XPS
X-ray Photoelectron Spectroscopy
PANI
Polyaniline
CPs
Conducting Polymers
GQDs
Graphene Quantum Dots
PEG
Polyethylene Glycol
4

PVA
POMA
APS
PAN
DFDPS
PU
BBL
ROP
LPF
ERPF
BPHMF
CO
NBR

Polyvinyl Alcohol
Poly(o-methoxyaniline)
Ammonium Per Sulfate
Poly Acrylonitrile
Difluorodi-Phenyl Sulfone
Polyurethane
Biobutanol Lignin
Ring Opening Polymerization
Lignin Phenol Formaldehyde
Ethanol Residue Modified Phenol Formaldehyde
Bio Phenol HydroxyMethyl Furfural
Castor Oil
Nitrile Butadiene Rubber

Contents
1.

2.

Introduction:
1.1

Sources of lignin

1.2

Classification of lignin:

1.3

Properties of Lignin

1.4

Applications of Lignin

Lignin Blends
2.1

Proteinlignin blends:

2.2

Starchlignin blends:

3.

Drawbacks of Lignin

4.

Derivatization of lignin

5.

4.1

Decomposition of lignin (involves breaking of lignin)

4.2

Using lignin as extracted from the plant:

4.3

Functionalization of lignin biopolymer:

Synthetic polymers functionalized by lignin derivatives

5.1

Lignosulfonate based polymers:

5

6.

5.2

Kraft Lignin based polymers:

5.3

Lignocellulose based polymers:

5.4

Lignophenol based polymers:

5.5

Sodium-lignosulfonate based polymers:

5.6

Organosolv lignin based polymers:

Conclusion and future trends:

References:
1. Introduction:
Lignin resulting from the Latin term lignum meaning wood[1] is the second most rich renewable
natural resource next to cellulose. It is a biopolymer having a highly branched 3-D structure, that
contains the different functional groups, namely hydroxyl (OH), methoxyl, carbonyl (C=O) and
carboxyl(COOH) moieties. [2-6]. It is the important part of all the vascular plants and takes part
in the formation of cell wall after deposition of the cellulose (40-50%), hemicelluloses(15-25%)
and polysaccharides [3,7]. Lignin is essentially a structural material that gives the rigidity and
strength to cell walls and makes up 15-40 wt% of the dry matter of woody plants [8,9]. Lignin
with natural hydrophobicity has phenolic macromolecule, made up of three main phenyl propane
units (monolignols) (Fig. 1a) namely, coniferyl alcohol (G), sinapyl alcohol (S) and minor
amounts of p-coumaryl alcohol (H), which cross together by a series of characteristic linkages
such as CC and COC bonds, linked via dehydrogenation reactions [1,2,10-12]. The
monolignol units when built-in into the lignin polymer are called guaiacyl (G), syringyl (S), and
p-hydroxyphenyl (H) units [1,13,14].
Natural lignin is a high molecular weight polymer consisting of phenyl propanol units [4,15],
heterogeneous in nature and two types of linkages are present one, is condensed linkages (e.g.5-5
6

and -1 linkages) and other is ether linkages (e.g., -O-4 and -O-4) (Fig. 1b) [4,16]. The
percentage of ether linkages in softwood lignin is 56% and hardwood lignin is 72% [17]. Lignin
can be extracted by different methods (enzymatic,chemical and mechanical). For example sulfite
process, soda process, Kraft proces, hydrolysis lignin and etc.[1,3,4,8].
Fig.1 (a) Monolignols in lignin [1]; (b) Representative structure of lignin [4]
1.1 Sources of lignin: Lignin can be attained from various renewable raw materials for example,
sugar cane, bagasse, pine or cedar trees, and wood [18,19]. The hardwoods contain lower
amount of lignin and softwoods have the larger ones.
1.2 Classification of lignin:
Lignin is classified into three major groups depending on its origin:
I. Softwood lignin, known as guaiacyl lignin, consist of coniferyl alcohol and trace amounts of
sinapyl alcohol-derived units. Pine is the example of softwood.
II. Hardwood lignin, it also contains of both coniferyl alcohol and sinapyl alcohol but in
different ratios, known as guaiacyl-syringyl lignin. For example maple.
III. Grass lignin, termed as guaiacyl-syringyl lignin, contains major amounts of structural
elements derived from p-coumaryl alcohol (H) [13,20].
Two types of lignin have been produced from lignocellulosic materials:
A: Sulfur-containing lignin, obtained from commercial chemical pulping processes.
B: Sulfur-free lignin obtained from cellulosic ethanol production processes [4]
1.3 Properties of Lignin
Natural lignin is colourless or pale yellow but on treatment with acid or alkali, its color changes
to brown or dark brown [1,21]. Variation of monolignol content in plant sources yields
multiplicity in both the physical and the chemical properties of the resulting lignin materials

[8,13]. Molecular masses of isolated lignin are in the range 100020,000 g/mol, but the degree of
polymerization in nature is difficult to estimate, since lignin is consistently fragmented during
extraction and contains numerous types of sub units which repeat randomly [8,22].
On heating lignin to temperatures about 150160C, molecular mass increase takes place
as reported for hardwood Kraft lignin and organosolv lignin [3]. The Tg is another important
parameter which measures the amount of rubbery region in a material and is also an indirect
measure of degree of crosslinking and crystallinity [8]. The Tg of lignin is depends upon the
amount of water and polysaccharides, as well as molecular weight and chemical
functionalization, but generally when Tg will be lower than mobility of the lignin molecules will
be better. It is worth to mention that Tg usually increases with increasing the molecular weight
[8,13].
Lignin has degradable property and in common practice, hydrogenation and oxidation are
the two most common techniques reported used to degrade the lignin [13,23]. Lignin has many
other properties such as high thermal stability [24], antioxidant, biodegradability [25] and
antimicrobial behavior, adhesive properties and relative abundance [1, 13, 26]. Lignin show the
additives properties, dust dispersant and blending properties [1,4].
1.4 Applications of Lignin
Lignin has useful and reasonable adhesive properties, which can be enhanced by variation of
lignin itself. It can be used as rubber intensifier, polyolefin, rubber packing, used in composite
materials and also in the unsaturated polyester and vinyl ester as filler and co-monomer [1,13].
In glass wool building insulation lignin is used as the binder. When the fiber pads are formed,
lignin is applied to hot glass as the ammonium salt solid recovered from the Kraft paper
manufacturing process and allows the glass fibers to bind [1,13,27]. Low levels of lignin and

modified lignin can yield high performance concrete strength and grinding and reduce harm of
external wall due to humidity and acid rain. Additions of alkali lignin to pet and human food as a
fiber source are possible uses of lignin, high nutritional fiber relates with low occurrences of
colon cancer.[28]. Chemically modified lignin has been used as a dispersing agents, flocculent,
thickener or auxiliary agents for coatings, paints etc. Ligno-sulfonate prevents the clumping and
settling of un dissolved particles in suspensions [1,21].
2.

Lignin Blends

Thermoplastic materials containing lignin and protein blended with natural rubber enhanced the
impact resistance as compared to lignin free materials [1, 29]. Lignin blends with polyolefin
were used as a stabilizer against oxidation under UV radiation, to allow the biodegradation of
material [1]. Some bio-molecules based lignin blends have been comprehensively presented in
the literature including, protein, starch etc in the subsequent lines.
2.1

Proteinlignin blends:

Proteins-lignin blends have been used for making plastics and resins. By adding the soda lignin
to soy protein, water absorption of plastics decreased and mechanical properties of soy
protein/glycerol blends improved. Blends containing 50wt% soda lignin showed twice tensile
strength as compared to unblended soy protein [8].
2.2

Starchlignin blends:

Starch-based films used for wrapping materials had low resistance to water by adding the
hydrophobic polymers (lignin) [1, 8].
3.

Drawbacks of Lignin

Lignin changes its properties abruptly when relative moisture changes and is a fragile glass at
common application temperature; 20-25C.The dark brown color is a product of free radicals in

lignin that if bleached away will slowly change and react with atmospheric oxygen. This
property is a main disadvantage for applications of lignin to customer products [30]. Different
technologies for lignin are utilized as a primary source of lignin consumption but it makes little
thermodynamic or financial logic. Such certain limitations of lignin lead towards its
modification. One of the most important advantages of lignin modification is ecological fact.
Such as biodegradability and wood-like closed CO2 loop. The global CO2 balance is affected
considerably by burning fossil energy carries, but lignosulfonate prepared by ARBOFORM
method has the same biodegradability as wood and it can be burned with neutrality to CO2
accumulation. By modification, lignin can be used in different applications. The fermentable
sugar yields for biofuel production can be improved by modifying lignin [31].
1.6 Derivatization of lignin
Derivatization of lignin take place by breaking lignin down into component aromatics or repeat
units, using the biopolymer as extracted from the wood, and adding to the lignin biopolymer,
treating it as a starting material to be built on to make constructive materials (Fig.2).
Fig. 2: Derivatives of lignin [25]
4.1

Decomposition of lignin (involves breaking of lignin)

Lignin is decomposed at 300-440C to produce 50 wt % charcoals, 10-15% tar, and lesser

amount of 2-propanone, ethanoic acid (CH3COOH) and methanol. The tar is called wood
creosote and is a complex mixture of substituted phenols and aromatics. This technology leads to
lignin-based surfactants [25, 32].
4.2

Using lignin as extracted from the plant:

Using lignin in the form obtained when it is extracted from the plant does not mean that lignin
exists in the application exactly as it did when withdrawn from the plant. It means that lignin

10

enter the application process as a reagent and is often reacted with other components of the
product as the product is produced [25].
4.3

Functionalization of lignin biopolymer:

4.3.1 Halogenation:
Addition of halide to the alkyl aromatic backbone of lignin is carried out by bubbling chlorine
into spent liquor followed by the additions of bromine (Br) and chlorine (Cl) [25,33]. The wt %
halide in the product is raised to between 20% and 40%.
4.3.2

Grafting by free radical polymerization

Lignin can be grafted after being separated from other plant products. A large number of reports
on the modification of lignin by graft copolymerization are available in literature [34]. Grafted
copolymerization of lignin forms useful products and changes its properties [35]. Lignin has
been grafted with styrene, 4-methyl-2-oxy-3-oxopent-4-ene [25,36,37] (methylmethacrylate), 2propenamide (acrylamide), 2-propene nitrile [25,38] (acrylonitrile), cationic monomers, anionic
monomers, and propanoic acid ethoxylates.
4.3.3

Grafting by anionic chain polymerization:

Grafting of lignin with alkane epoxides forms the polyether products. Attack of base on phenolic
hydroxyl groups initiates the reaction and form phenoxide groups. These phenoxide groups then
attack the polar epoxide ring. A significant side reaction in this process is ring opening
polymerization by nucleophilic attack of OH ion on the ring [25].
Lignin derivatives obtained by these methods have various useful applications which are
summarized in Table 1 [39-59].
Table 1
Types of lignin derivatives and their prospective applications in different fields [39-59]

11

5.

Synthetic polymers functionalized by lignin derivatives

Lignin derivatives are used to functionalize different polymers which have numbers of
applications in a variety of fields such as films and coatings formation, adhesive resin, plastic
and rigid foam formation etc., depicted in Table 2 [60-92].
Table 2
Different techniques for the synthesis and characterization of lignin derivatives based
polymer and their prospective applications in different sectors [60-92].
5.1

Lignosulfonate based polymers:

In lignosulfonate, or sulfonated lignin, the content of phenolic

groups as compared to carboxylic acid (RCOOH) groups is much higher than the native lignin.
In addition, strong sulfonic acid groups are present in sulfonated lignin. It is used as corrosion
control agent in water delivery system. Corrosion resistance of the treated iron was assessed by
EIS method and corrosion rates were measured through Polarization Resistance tests [1]. With
increasing environmental pollution and depletion of fossil fuel, there is an intensive research of
energy storage devices such as fuel cells, Li-ion batteries and super capacitors [93]. Super
capacitors can be divided into pseudo capacitors and electrical double layer capacitors [94].
Super capacitors have special attention due to their vast use in hybrid electric vehicles and
movable electronic devices. The structures and types of electrode materials have great effect on
the performances of super capacitors which in turn affects the electrolyte ion diffusion and the
charge transfer in the electrode during the electrochemical process. Pseudo capacitive materials
(metal oxides, conducting polymers) can achieve high pseudo capacitance through quick and
reversible redox surface process. However, metal oxides suffer from poor ion transport kinetics,
poor electrical conductivity and definite volume variation during chargedischarge process,
cause to poor rate and cycling performance. In the redox process conducting polymers also faced
12

the difficulty of shrinking and swelling. In carbon based material super conductor, due to the
electrical double layer charge storage mechanism is quite different from pseudo capacitive
materials, they can control this problem and express good cycling stability [95]. Graphene, 2-D
nanomaterial, due to excellent physicochemical properties has special attention. However, single
layer graphene tends to agglomerate and restack into graphite structure by van der Waals
interaction and strong pp stacking [96], which highly decreases the specific surface area, thus it
has limiting application as electrode material. Therefore, it has been a hot research area to endow
graphene with unique structures ranging from porous grapheme [97], graphene foams [98], and
grapheme sponges [99] to graphene based gels [100]. When used as electrode materials of super
capacitors, these distinctive porous structures not only inherit the outstanding properties of
graphene, but improved super capacitive performances by facilitating the ion diffusion into the
inside of electrode materials [101]. Zhao et al. [80] prepared porous nitrogen-doped grapheme by
co-pyrolysis of lignosulfonate and graphene oxide in presence of urea, which act as an active
adsorbent to remove Pb+2 from industrial wastewater (Fig 3). Nitrogen-doped graphene has high
capacitance due to the presence of pyridinic N (C5H5N), pyrrolic N and graphitic N [102].
However, certain heat treatment methods in the presence of a N source are used for the
fabrication of nitrogen-doped porous graphene with hard template such as sulfonated polystyrene
(s-PS) [103], SiO2 [104] and poly(methyl methacrylate) (PMMA) [105] . The super capacitive
actions of nitrogen-doped porous graphene have been improved by short diffusion distances of
ions and electrons and faradic reactions of nitrogen hetero-atoms [104].
Fig.3
Schematic illustration of fabrication procedure of nanoporous nitrogen-doped grapheme [80]

13

In the electrode process, nitrogen-doped graphene with porous structure (PNG) shorten the
distance of ion diffusion. As an electrode material of supercapacitor, PNG showed improved
electrochemical behaviors, the capacitance is up to 170 F/g with a high rate action and brilliant
cycling stability.
Gupta et al. [83] synthesized Polyaniline-lignosulfonate/epoxy (PANI-LGS) coatings, used for
corrosion protection of AA2024-T3 (Fig.4 (a). Aluminum alloy AA2024-T3 is used in numerous
components of aircraft [106,107]. The corrosion performance of AA2024 has been well
characterized, pitting corrosion occurs in mildly violent situations [108-110]. Chemical
conversion coatings using chromates is most common method to protect the aluminum alloys,
that are toxic in nature [111]. The conducting polymers (CPs) coatings are used for corrosion
protection of ferrous and non-ferrous alloys [112-117], while PANI CPs is also used for
corrosion protection of aluminum alloys [118,119]. Gupta et al. [83] synthesized polyanilinelignosulfonate/epoxy (PANI-LGS) coatings, used for corrosion protection of AA2024-T3 (Fig.4
(a). Particles show low dispersibility if the PANI-LGS is in less amount content in the epoxy
coating system. Conversely a high content and high mass fraction of particles detracts from the
coating performance due to agglomeration. Galvanic interaction occurs between aluminum and
coatings containing the oxidized and conducting form of PANI, the emeraldine salt (ES), which
is usually formed by doping the non-conducting leucoemeraldine base (EB) with an organic acid.
This galvanic interaction between PANI ES and the aluminum substrate causes to polarization of
the aluminum substrate to more positive potentials with the formation of PANI EB and
subsequent release of the dopant anion [120-129]. Dopants in PANI can play a significant role in
corrosion safety due to the formation of a metal-dopant interface. By uniform distribution of
PANI particles the penetrability of water and oxygen is reduced, thus increasing the corrosion

14

protection efficiency. Corrosion inhibition was increase due to a thickened oxide layer and
assisted by what is posited to be the release of dopant at the defect site by formation of
aluminumsulfonate complex.
Li et al. [70] synthesized the urchin-like polyaniline microspheres by using lignosulfonate as
template. Polyaniline (PANI) has great attention due to its low production cost, ease of synthesis,
brilliant ecological stability and tunable properties [130-132]. PANI has been effectively
fabricated in different forms, like micro-/nano-tubes [133-137], micro-/nanofibers [138] and
micro-/nanospheres [139]. Li et al. [70] synthesized the urchin-like polyaniline microspheres by
using lignosulfonate as template. The ANI/LGS mixture with PANI/LGS ratio (%) at 18/1 and
36/1 designed spheres whereas the PANI nanofibers lied on spherical surface, and only at 9/1 led
the PANI nanofiber to stand on sphere surface in the urchin-like structure.

Urchin-like

PANI/LGS conducting microsphere has improved thermal stability and conductivity as

compared to the pure PANI nanofibers and additional ratios-based conducting microspheres.
Following Fig. 4 (b) shows the formation of microshperes.
Fig.4
(a). Schematic synthesis of lignosulfonate doped polyaniline (pani-LGS) [83]; (b). Mechanism
on formation of urchin-like PANI/LGS conducting microspheres [70]
Zhi et al. [84] developed poly(N-ethylaniline)/lignosulfonate composites (Fig.5). The
introduction of N-ethyl groups in poly(N-ethylaniline) chains and sulfonic groups of LS into the
PNALS chains was increased the solubility of the PNALS composite microspheres and
enabled their applications in various domains, such as corrosion protection, electrically
conductive nanocomposite films and electrochemical devices. PANI is a useful candidate for the
production of nitrogen-containing carbon materials with different morphologies because by

15

adjusting the diameter of polymer spheres the size of carbon spheres can be controlled [140,141].
However, these nitrogen-containing carbon materials have been successfully applied in several
areas, such as catalyst supports [142], super capacitors [143], and Li-ion batteries [144]. Hence,
low-cost and uniform nitrogen-containing carbon materials are prepared from PANIs. By direct
pyrolysis of PNALS composite microspheres at the temperature of 800C low-cost nitrogencontaining carbon nanospheres with an average diameter of 820 were obtained. The combination
of abundant and low cost lingo-sulfonate into PNALS microspheres will definitely decrease the
cost of formulating carbon microspheres and increase their potential uses (Fig 5 (a)). Properties,
structure and morphology of the PNALS composites can be modified by changing the LS:NA
mass ratio. In order to prepare the PNALS composite microspheres the optimal LS:NA mass
ratio 2.5:97.5, has wide range of applications in various fields, including electric double layer
capacitors, , catalyst supports, adsorbents and electrodes for Li-ion batteries.
Ferric ion (Fe+3) is an essential transition metal ion in organisms and plays important
roles in ecological, chemical and biological systems [145,146]. The lack or excess of iron may
cause the several diseases such as Parkinsons disease and anemia [147,148]. The heavy-metal
ions constantly released from industrial and anthropogenic processes caused the serious
environmental and health problems. However, ferric ion is the most dangerous and ubiquitous
pollutants. Fluorescent sensors used for the detection of metal ions have several advantages (high
sensitivity, no sample destruction and fast analysis) over other conventional techniques
[149,150]. Xua et al. [89] prepared lignin-sulfonate/graphene quantum dots (SL/GQDs)
core/shell hybrids for label-free sensitive and selective detection of Fe+3. The GQDs is the new
class of carbon nanomaterials, have great attention due to their novel properties such as,
chemical inertness, easy preparation, stable photoluminescence, low toxicity and tunable surface

16

functionalities [151-154]. Therefore, development of GQDs is a new platform in detection

systems [155-157]. Several examples have been described to determine some ions (Hg+2, PO4-3
and Pb+2) through the fluorescence changes of GQDs [158-160]. Presence of SL at the edge of
GQDs is responsible for the enhancement of fluorescence intensity of GQDs. However, carboxyl
and phenolic groups at the surface of GQDs cause the interaction between SL and metal ion, thus
producing the SL/GQDs composites with both improved determination ability and fluorescent
properties, as shown in Fig. 5 (b).
Fig.5
(a) A possible mechanism for the formation of microspheres and hexagon sheets of the PNA-LS
composites [84]; (b) A low-cost green route to construct a novel sensing platform for Fe+3
detection based on core/shell hybrids by using citric acid and sodium lignosulfonate through onestep treatment [89].
Enzymatic hydrolysis process of lignocelluloses to sugar is gives high selectivity, mild operation
and high yield but cellulosic ethanol difficult to produce commercially because of the high cost
of cellulase enzyme. Furthermore, prior to enzymatic hydrolysis because of the recalcitrance of
lignocelluloses, a pretreatment to alter and/or remove lignin and hemicellulose is necessary.
[161,162]. To reduce the adsorption of cellulase enzyme on cellulose residual lignin would act as
a physical barrier and an attractant to cellulase [163,164]. For nonproductive adsorption of
cellulase on the lignin hydrophobic interaction has identified as the key driving force [165,166].
There is enhanced enzymatic hydrolysis of lignocelluloses in the pretreatment process because
hydrophilicity of lignin is improved by the carboxyl and sulfonation modification [167,168].
During the sulfonation modification, acidic sulfite pretreatment to overcome recalcitrance of
lignocelluloses removed most of hemicellulose and dissolve lignin [169]. Acid sulfite pretreated

17

lignocelluloses was used directly for enzymatic hydrolysis and fermentation without washing
and detoxification ethanol concentration can achieve 42 g/L and its theoretical yield can be 70%
at a low cellulase loading.
The PEG based non-ionic surfactants have proved the most efficient in the enzymatic hydrolysis
of lignocelluloses [170]. Lin et al. [75] developed the lignosulfonate based polyoxyethylene ether
(LS-PEG) on enzymatic hydrolysis of Avicel and corn Stover which established prospective
approaches and strategies for effective application of LS to improve bioconversion of
lignocellulosic biomass.
The lignin based polyoxyethylene ether significantly reduced nonproductive adsorption
of cellulase on lignin and enhanced the enzymatic hydrolysis of lignocelluloses by dispersing
cellulase aggregates. De-zhan et al. [85] developed the eucalyptus lignosulfonate calcium (HLS)
particles as reinforcement in polyvinyl alcohol (PVA) matrix. During the last three decades, for
developing the lignin-based materials two strategies are adopted. One is the modification of
lignin structures by chemical methods due to its abundant groups (methoxyl, aromatic hydrogen
and hydroxyl group) [171-174]. Second one is lignin blends with natural or synthetic polymers
[175178] to change the properties of materials, such as radical capturing ability and high
thermal stability of lignin. They are potential candidates for useful additives, such as flame
retardant, UV stabilizer, antioxidant, and thermal stabilizer in PP, PVC, polyolefin and NBR
[179185]. Mechanical properties decrease with lignin proportion because a very low
compatibility of polar lignin in nonpolar polymer matrix. PVA is a water-soluble and
decomposable polymer which has the good chemical resistance, biocompatibility, optical and gas
barrier properties [186]. The PVA and PVA-based composites are extensively used including
nano fibers [187], packaging materials [188], optical films [189] and coatings [190]. To improve

18

the mechanical strength of PVA used the reinforcing agents such as nanofibril lated celluloses
[191], cellulose nanocrystals [192], CNTs [193] and cellulose nanofibres are used [194].
Eucalyptus has typical hardwood and used as raw materials in pulping and paper industry all
over the world [195]. HLS was used to reinforce PVA film. The tensile strength and Youngs
modulus of 5 wt% HLS/PVA composites were 41% and 384.7% higher than those of pure PVA.
It shows that the pulping waste, lignosulfonate, can be used as reinforcing component for PVA
which is potentially used as biodegradable wrapping film.
Wang et al. [86] synthesized the poly (o-methoxyaniline)lignosulfonate (POMALGS)
composites through oxidative chemical polymerization of o-methoxyaniline by ammonium per
sulfate (APS) in the presence of sodium lignosulfonate (NaLGS). The arrangement of
composites was studied by SEM, FTIR and UVVis spectroscopies.
The mass ratio of NaLGS/POMA had a vital effect on structure and physical properties of the
composites. With increasing the LGS contents AC conductivity increased while the degree of
oxidation decreased. In new mechanism for composite formation proposed, LGS act as adsorbent
and POMA micro/nano spheres embedded or attached as adsorbate. Ammonium persulfate
produced the sulfate groups which acted as the main dopant and were incorporated into the
polymers as proved by elemental analysis and spectral techniques. Rise the NaLGS/POMA
weight ratio shows a higher specific surface area, lower degree of oxidation and lesser POMA
particles, which in turn led to higher free radical scavenging, suggesting a possible antioxidant
application. The radical scavenging of the LGS per se made a further positive contribution to the
antioxidant effect.
5.2

Kraft Lignin based polymers:

19

Kraft lignin (KL), accounting for nearly 85% of total technical lignin, is usually used as fuel for
energy recovery. The structure of lignin is changed by chemical destruction and condensation
during the Kraft pulping processes, and resulting lignin is called kraft lignin or technical lignin.
Lignin with aliphatic thiol groups called Kraft lignin. Technical lignin has low molecular weight,
variable functional group and high polydispersity [60,61].
PEG is used as the most suitable graft-forming polymers due to its distinctive properties such as
low toxicity, good biocompatibility, biodegradability and amphiphilicity [196]. Functionalized
PEG is prepared prior to attaching the PEG to the desired molecule because the terminal
hydroxyl groups are much more reactive than the polyoxyethylene chain. The PEG derivatives
have been proven valuable in a great diversity of chemical and biological endeavors, such as
nonionic surfactant, protein conjugates, phase transfer catalysis (PTC), aqueous two-phase
separation, and pharmaceutical modification [197]. The PEG was modified at one or both
terminal hydroxyl groups preferentially in order to graft onto lignin. Recently, some approaches
had been developed to modify lignin with PEG derivatives in alkaline solution, typically PEGmesylate [198] and PEG-epoxide,[199201] to increase the water solubility of lignin. Modified
lignin (lignin-PEG) with PEG derivatives was soluble in methanol, chloroform, and pyridine in
addition to water [199]. The lignin-PEG copolymer could improve brightness stabilization and
strength properties of high-yield pulps,[198] improve dispersibility and bending strength of
cement and enhance enzymatic hydrolysis of cellulose and lignocelluloses [202,203]. However,
the PEG-mesylate was prepared grindingly from PEG methyl ether (Mw 350) by reacting with
methanesulfonyl chloride in methylene chloride at 0 C using triethylamine as a catalyst,[198]
while the PEG-epoxide was synthesized from PEG by reacting with epichlorohydrin in the
presence of BF3 and then closed loop and de hydrochlorinated in the alkali solution[204].

20

Monoexpoxide PEG derivatives and commercial dodecyloxy-PEG-expoxide [201] could

improve the surface activity of lignin further than that of diexpoxide PEG derivatives. The
functionalized PEG derivatives above either were prepared in organic solvents or unusual
commercial products that made lignin modification with PEG derivatives expensive and
complex. Xuliang et al. [60] prepared lignin based polyoxyethylene ether (KL-PEG) from kraft
lignin (KL) and poly(ethylene glycol) (PEG). This KL-PEG copolymer possessing a renewable
lignin support and branched PEGs could be a promising dispersant for similar applications,
including agricultural suspension concentrates. Fifty percent dimethomorph suspension
concentrates (Fig. 6) prepared with the KL-PEG copolymer as dispersant showed higher
suspensibility and lower apparent viscosity compared with lignosulfonate, indicating KL-PEG
had a better dispersing ability for dimethomorph suspension concentrates.
Fig.6
Synthesis Mechanism of KL-PEG Copolymer [60].
Various reports about partial replacement of phenol by lignin in phenol formaldehyde
resins and lignin-based adhesives are available in literature [206-209]. Lignin-derived carbon
fibres have received great attention recently because they serve as low-cost alternatives to PANbased carbon fibres [210215]. Challenges to be overcome include, lignin from black pulping
liquor

needs to be purified, during the carbonization thermal fusing of fibers should be

prevented in post-spinning stabilization of lignin, [214], and finally the realization of target
mechanical properties.
Carbon black is obtained from partial combustion of fossil fuel, about 90% of carbon black is
used in rubber industry for tire reinforcement. Electric conductivity in polymers can be provided
by carbon black [216,217]. Acrylonitrile-butadiene rubber (33% acrylonitrile) filled with carbon

21

black shows electric conductivity which varies with the compression strain applied to the rubber
[218]. By adding the carbon black piezoelectric properties of polymers also increased [219].
Besides low cost, carbon black has better tendency to make conductive networks because of its
chain-like aggregate structure [220]. Oxidation resistance and electrical conductivity are limited
due to this disordered amorphous structure preventing its use in high performance materials
[221]. From phenolformaldehyde resins hollow carbon nanospheres was prepared which
presented a high-performance and low cost applications than to carbon black [222].
Besides fossil fuel, particulate carbon also produced from biogenic precursors [223]. The main
focus in literature is on porous micro particles with high specific surface area [224,225].
Microporous carbon spheres having specific surface areas of up to 530 m2 g-1 are produced by
pyrolysis of Kraft lignin in argon atmosphere [226]. Freeze drying of micro-porous lignin
spheres by thermal stabilization and carbonization produced irregularly shaped carbon [227]. The
production of hollow carbon nanoparticles from lignin is given in two patent applications
[228,229]. Without any pre-treatment other than thermal stabilization carbon micro particles can
be produced from Kraft lignin. Wolfgang et al. [82] developed electrically conductive Kraft
lignin-based carbon filler for polymers. By adding the polycaprolactone, stiffness of the polymer
is improved while strength and strain to failure are degraded. Overall, these results show that
lignin-derived micron-size carbon particles have a potential to replace the fossil-based carbon
black in certain applications.
Conservative poly(arylene ether sulfone)s are ductile and tough thermoplastics with desirable
properties such as hydrolytic and dimensional stability, high temperature stability and durability.
Therefore, they are used to generate many products [230]. These polymers are synthesized by the
base catalyzed stepwise copolymerization of biphenols with 4,4-dichlorodiphenyl sulfone

22

(DCDPS) or 4,4 difluorodi-phenyl sulfone (DFDPS) in an aprotic solvent at high temperatures

by SNAr reactions [231-234]. This reaction has two steps (Fig.7), the first generate the resonance
stable carban ions (iii, iv, v, vi) (Meisenheimer complex13) through the nucleophilic attack of
phenoxide (i) on the halide substituted carbon (ii) next the aromatization of the phenyl ring (vii)
by removal of the halide ion. Different factors affect the resonance stabilization of the
Meisenheimer complex such as the nature of the nucleophile, the activating group, nature of the
leaving group and the solvent used [231,235].
Fig.7
Mechanism of formation of lignin DFDPS Copolymer by the SNAr Reaction [61].
Argyropoulos et al. [61] synthesized and characterized of poly(arylene ether sulfone) Kraft
Lignin heat stable copolymers. The multifunctional nature of lignin, upon copolymerization with
a di-functional monomer, causes it to form a cross-linked and hyper branched polymer, which is
not suitable for further thermoplastic processing. This major problem is removed by properly
reducing the phenolic group of Kraft lignin by masking via methylation with dimethyl sulfate in
alkaline aqueous solution. The characterized copolymers showed the covalent, progressive
incorporation of DFDPS in the lignin structure with relative increases in the molecular weight
averages, their distributions, thermal stability and their glass transition temperatures. Overall,
show that it is possible to control the reactivity of softwood Kraft lignin by the combination of
methylation and fractionation providing a rational means for the formation of modest molecular
weight polyarylene ether sulfone lignin copolymers. It is visualized that the present effort
demonstrates the potential use of technical Kraft lignin as a phenolic precursor for the
construction of heat stable thermoplastic materials with desired properties.

23

Rigid polyurethane (PU) foams are used in engineering applications, i.e., automotive parts,
structural materials and insulation materials [236]. The PU foams are manufactured from the
polyols and isocyanates. Both (isocyanate and polyols) are obtained from petrochemical
resources. There is a growing interest in exploring renewable feedstock to replace petroleum
derived polyols either partially or completely for the production of bio-based PU foams [237],
without losing the thermal, physical and mechanical characteristics of the material. Due to its
high molecular weight and steric hindrance effect, crude lignin has lower reactivity [238], it can
only replace 30% of the polyols used in the formation of PU foams. Hydrolytic depolymerization
of KL, using water as a solvent under alkaline conditions, to convert high molecular weight KL
into low molecular weight depolymerized KL (DKL) was found to be a favorable approach
[239]. The resulting DKLs have lower molecular weights and high hydroxyl numbers. Therefore
DKLs can be substitute for petroleum-based polyols as reactive bio-polyols at a larger
replacement ratio than KL for the production of rigid PU foams as insulating material, the
polymeric foam materials particularly used in the construction industry. Nubla et al. [91]
prepared rigid PU foam by hydrolytically depolymerization of Kraft lignin. Superior
combination of thermal, mechanical and physical properties were shown by the oxypropylated
DKL-based BRPU foam. All BRPU foams are thermally stable up to approximately 200 C.
5.3

Lignocellulose based polymers:

Cellulosic fiber is renewable raw material having properties such as easy availability,
biodegradability and remarkable physio-mechanical properties [240,241]. Recently, electrospinning process is used to create nano/ultrathin PET fibers, for use in bio medical fields [242244]. Electro-spun mats prepared from PET having a high hydrophobicity due to their rough
surface and low surface energy [245] and lower mechanical properties which limits their

24

applications in biological system due to membrane fouling [245-247]. Silva et al. [248] prepared
mats with high hydrophilic character from PET/chitosan hybrid nanofibers via electro-spinning
process (Fig.8). Li et al. [245] and Silva et al. [248] also established the better mechanical
properties for composites than PET mats. Santosa et al. [72] synthesized ultrathin and nanoscale
fibers by room temperature electro spinning of lignocellulosic sisal fibers (S) and recycled PET
trifluoroacetic acid solutions, used as a reinforcing agent in composites. The properties of the
resulting mats (S/PET ratios from 0.1 to 0.4) were examined by infrared spectroscopy, scanning
electronic microscopy (SEM), contact angle measurements (CA), thermogravimetry analysis
(TGA) and dynamic mechanical analysis (DMA). The DMA not only described the Tg and
storage modulus of materials but also clarified the interactions between the PET chains and the
components of the sisal fibers. The wet-ability of the mats was dependent on the sisal/PET ratio
and ranged from highly hydrophobic (neat PET, advancing angle of 134 by contact angle
measurements) to super hydrophilic 0, immediate absorption of the water droplet). This
investigation open the door for a number of possibilities where lignocellulosic biomass can be
combined with polymer matrices to improve and control their properties like hydrophilicity and
stiffness.
Fig.8
Schematic representation of a lignocellulosic fiber and its main components, as well as possible
interaction with PET [72].
Liu et al. [79] prepared lignin-graft-poly (-caprolactone) copolymer (BBL-g-PCL) using bio
butanol lignin (BBL), and PCL-grafted BBL for use in the field of UV-protective coating film
such as agricultural bags and food packaging. Graft copolymerization is a simple approach to
modify lignin and alter its physical and chemical characteristics [249-251]. By forming the free-

25

radical sites on the backbone of lignin and copolymerization of lignin free-radical sites with
vinyl monomers copolymers were produced, limited the biodegradability of copolymers was
ascribed to the non-degradable vinyl polymer chains in copolymers [252].
Butanol has higher energy content and is less hygroscopic so it is used as a liquid fuel [253].
During the butanol production a large amount of bio butanol lignin is obtained as a co product.
Due to self-aggregation of lignin blending of unmodified BBL with commercial polymer
materials gives composites with poor mechanical properties [254]. For the synthesis of lignin
graft PLA and PCL copolymers, ring-opening polymerization (ROP) technique is widely used.
For the ROP several hydroxyl groups on the surface of lignin act as reactive sites [250,255].
Oliveira et al. [255] described the ring opening polymerization of -caprolactone with softwood
Kraft lignin. Matsushita et al. [256] successfully produced lignin-graft-poly (-caprolactone)
polyesters from sulfuric acid lignin that was recovered from the production of bioethanol, and
catalyzed by zinc chloride. By ROP of -caprolactone an array of lignin-graft-poly( caprolactone) were obtained which initiated by soda lignin in the presence of stannous octanoate
[250]. However, to increase the potential applications of BBL in polymeric materials, some
further chemical modifications should be carried out [250,255-257]. A series of BBL-g-PCL
copolymers with different molecular weights, ranging from 367 to8163 g mol-1, were obtained
(Fig.9) by adjusting the mass ratios of the CL monomer to BBL. By increasing amount of PCL
the values of Tm and Xc of BBL-g-PCL were enhanced. The thermal stability of BBL-g-PCL
copolymers was higher than that of neat BBL. Moreover, the increase of residue char occurred
with increase of the BBL segments in the copolymer. An AFM study shows that the BBL-g-PCL
copolymer had good dispersion characteristic than BBL.
Fig.9

26

Synthesis of BBL grafted copolymer (BBL-PCL) ring opening polymerization [79].

Lignocellulosic ethanol is manufactured from energy crops, straw, wood and different
agricultural and wood processing waste products [258]. For the production of bioethanol from
lingo-cellulosic materials the basic processing steps are pretreatment (steam explosion, acid or
alkali treatment), enzymatic hydrolysis, fermentation and distillation. The ethanol residue (ER),
as the by-product of enzymatic hydrolysis, is rich in highly activated lignin. Zhang et al [92]
prepared ligninphenolformaldehyde (LPF) adhesive by using lingo-cellulosic ethanol residue,
for use in water resistant applications. The ER was condensed with phenol and formaldehyde
under alkaline condition to produce the ethanol residue- modified phenolformaldehyde (ERPF)
adhesive used for exterior plywood [259]. By decreasing the bonding strength higher levels of
substitutions with ER were limited. In the ERPF adhesives with increase of substitution rate, the
content of aliphatic OH group increased and phenolic OH group decreased. In the initial stage
ER combined into the ERPF adhesives that will make better thermal stability for ERPF
adhesives, but the substitution rate should not be too high.
5.4

Lignophenol based polymers:

Lignophenol prepared by the phase separation method, have highly phenolic function, high
stability and less heterogeneous as compared to native lignin. Zhang et al. [71] synthesized the
bio-phenol-hydroxymethyl furfural (BPHMF) resin, by using a hydrolysis lignin (HL) and
glucose as a precursor for HMF (Fig.10).
Fig.10
Reaction mechanism of the BPHMF resin formation from bio-phenols and in-situ generated
HMF [71].

27

The BPHMF resins are used as polymeric matrix reinforced by fibers. In 1907 phenolformaldehyde (PF) resins were first designed, they still stand at an in dispensable place among
fire retarding materials, composite matrixes, binders and adhesives [260,261]. Phenol and its
vapors are dangerous to heart, skin, respiratory tract, human eye and central nervous system
[262,263]. The hydrolysis lignin (HL) refers to residues obtained from the biomass enzymatic
hydrolysis process [264]. HL is not a pure lignin. Furfural [265] and glyoxal [266] have been
reported to substitute the formaldehyde in preparing phenolic resins [267]. Substituting
formaldehyde with glucose-derived HMF for phenolic type phenol-hydroxymethyl furfural
(PHMF) resin is useful with respect to both cost and sustainability [268]. Due to its rigid
structure and the presence of additional cross-linkages created by DHL the thermal stability was
improved by adding PDHL as partial phenol substation. Curing of the BPHMF resin requires
higher curing temperature (157C) and a longer time as compared with PHMF resin. The
BPHMF-fiberglass thermoset composite demonstrated a high Tg (272C), and tensile strength
(89 MPa) comparable to other phenolic composites.
5.5

Sodium-lignosulfonate based polymers:

Ligno-sulfonates (sulfonated lignin), are obtained from the sulfite pulping process as byproducts. There are different types of lignosulfonates such as those of, like sodium, ammonium,
calcium and magnesium. They are water soluble due to the presence of sulfonate groups [269272]. Oliveira et al. [76] developed Ligno-polyurethanic materials based on oxypropylated
sodium lignosulfonate and castor oil blends, for use in formation of rigid foams. Castor oil (CO)
consists of triglycerides of ricin oleic acid that contains hydroxyl groups. To prepare the
polyurethane, CO is used as a raw material [273]. Brazil is one of the largest world producers of
this oil [274]. In production of polyurethane, the use of lignin after chemical modification

28

(etherification or esterification reactions) is gaining attention these days because specific groups
in lignin become more readily available causing an increase in reactivity [275]. Laurichesse et al.
[276] prepared polyurethane with different NCO: OH molar ratio and different soft segment
length by producing polyols from modified lignin by esterification with chlorinated fatty acid
(oleoyl chloride) in solvent-free system. Cateto et al. [277] used four different kinds of
oxypropylated lignins (Alcell, Indulin AT, Curan 27-11P and Sarkanda) related with a
commercial polyol (Fig.11) for preparing rigid polyurethane foams. In oxypropylation, phenolic
hydroxyl groups are sterically less accessible and less reactive as a nucleophile, participate in the
ether linkages in which another linked carbon is inserted into a hydroxyalkyl group (Fig. 11a).
Therefore, instead of a phenolic hydroxyl group, an alcoholic hydroxyl group is also present,
which is more reactive as a nucleophile. In addition, the length of the introduced hydroxyalkyl
chain provides more accessibility to the reactive sites than the phenolic and alcoholic hydroxyl
ones present in the lignin structure. In fact, the solid lignin develops a liquid polyol by adding the
ether moieties [278-280].
Fig.11
Schematic representation of (a) oxypropylation reaction of the sodium lignosulfonate and (b)
polymerization reaction of the propylene oxide initiated by hydroxyl group [76].
Xiao et al. [78] synthesized Nitrilebutadiene rubber (NBR) based layered double hydroxide
(LDHs) composites by using sodium lignosulfonate modified LDH (SLSLDH) as a filler.
During the past decade, layered silicate/rubber composites were prepared by numerous
processing techniques, like melt compounding [281-283], solution blending [284,285], and latex
compounding [286,287]. These systems showed improved thermal, barrier and mechanical
properties [288-290]. The use of LDH in the rubber matrix has invited a great interest from

29

academic research and industry. For making rubber composites LDH can be treated similarly as
layered silicates. In addition, LDH shows different advantages compared to layered silicates e.g.
flame retardancy of the polymer matrix is improved because its endothermic decomposition is
below the decomposition temperature of many polymeric materials. Organic modification is
required to increase the compatibility between LDH and polymer because good dispersion of
LDH in rubber is difficult due to organicinorganic incompatibility. The LDH has positively
charged layers so it could be modified with negatively charged organic species via both the
surface adsorption and anion-exchange [291-293]. There are some electrostatic interactions
between positively charged LDH layers and anionic lignosulfonate [294]. To form SLSLDH
complex, LDH will be produced in the presence of sodium lignosulfonate (SLS). Both LDH and
SLSLDH can improve the mechanical properties of NBR composites. However, SLSLDH has
shown more superior reinforcing effect compared with pristine LDH.
5.6

Organosolv lignin based polymers:

Organosolv lignin, with low inorganic impurities such as sulfur and ash, is an important
precursor for the conversion to CFs [295-298]. Baker [299] reported that the tensile strength of
CFs melt spun from a purified organosolv lignin is as high as 0.71 GPa. Electro-spinning is a
technique that allows fabrication of robust, multi-functional fibrous materials [300,301]. By
applying external electric field during the process ultrathin fibers having submicron to nanometer
(from 10-2 to 1 mm) diameters can be formed by continuously stretching of a visco-elastic jet.
Nanofibers have higher modulus, toughness, and strength as compared to micro-scale fibers
[302,303]. The smaller diameter size not only affects mechanical properties but the higher
specific surface area shows a favorable way to improving poor interfacial bonding between the
microfibers and matrix in the composites. Neat epoxy matrices are also reinforced by electro-

30

spun nonwoven membranes [304,305]. They also increased the fracture toughness of a highperformance composite laminates [306,307]. Blending lignin with high-molecular-weight
polymer additives such as polyethylene oxide (PEO) [295,308-310], polyvinyl alcohol (PVA)
[311,312], or PAN [313-316] is a direct approach for tuning electro spin ability. By using PAN
as an additive in electro spinning would theoretically improves the mechanical performance of
lignin-based CFs. Fiber fusion is a detrimental process in the production of conventional ligninbased carbon fibers [317]. Organosolv lignin (Alcell) blended with 10 wt.% PEO as plasticizer
formed fused fibrous carbon mats having superior charge capacity as compared to non-fused
carbon fibers, an effect that was enhanced by nitrogen-doping [308]. Kadla et al. [317] reported
that after thermo stabilization electrospun fibers based on a mixture of Kraft lignin fractions with
different molecular weight (Mw), the Tg showed inter fiber fusion (Fig.12) [318,319]. Ding et al.
[90] prepared the carbon fibers from organosolv lignin/polyacrylonitrile blends.
Fig.12
Reaction scheme of lignin butyration to convert hydroxyl groups to esters [90].
The weakened intermolecular interaction butyrated lignin reduced the viscosity of lignin/PAN
blends and led to the reduction of spun fiber diameter. Precursor fibers derived from lignin/PAN exhibited lower carbon yield than after thermal treatment; however, the yield was
comparable to that of PAN-based fibers. Inter-fiber bonding occurred with -lignin/PAN 50-50
fibers during the oxidative thermo stabilization at 200 C (0.2 C/min) because of enhanced
thermal mobility of the modified lignin molecules. After carbonization at 1000C, the resultant
fused CF mats showed significant improvement in mechanical properties compared to nonbonded lignin/PAN 50-50 carbonized fibers. The reinforcing mechanism was attributed to the
change of the fabric network features. This study demonstrated a new approach to manipulating

31

inter-fiber bonding using an inexpensive lignin/PAN blend precursor system to produce fibrous
nano-carbon materials with promising characteristics for fiber-reinforced composite applications.
Jacob et al. [81] developed the reactivity enhancement of organosolv lignin by phenolation.
Phenol formaldehyde (PF), polybenzoxazines (PB) and epoxy resins have huge potentials
application due to the excellent performance expressions in dimensional stability, mechanical
properties, flame resistance and chemical durability [320-322]. In the first stages of lignin
biosynthesis (i.e. shikimate and monolignols) all para-positions and some ortho-positions in the
phenolic ring are occupied (relevant for PF and PB). On the other hand, subsequently the
majority of phenolic hydroxyl groups are etherified the reactivity of lignin in all three resins is
largely reduced [323]. For PF and PB resins hydroxyl methylation process is used, which does
not directly increase the number of reactive sites, but lowers competing reactions [324].
Demethylation of lignin is another approach representing high potential since the 2 and 6 ring
position are free in all lignins. The catalytic paths do not yet occur and the reagents applied
(halide or sulfur compounds in at least equimolar quantities) are undesirable for large scale and
environmental benign production [325,326]. By combining oxidation and reduction of the
aromatic ring demethylated lignin can also be prepared. However, this method still lacks reaction
control and suitable reagents [327]. Alternative of the above methods, the reactivity in the side
chain of lignin could be utilized, which focus on the functionalization of the aromatic moiety.
The reaction of phenol with the lignin model compound guaiacylglycerol--guaiacyl ether was
studied by Lin et al. [328,329]. Products obtained from the etherification of phenol with lignin
side chain carbons were also detected. Practically phenolation was studied by Funaoka et al.
[330] phenolated lignin obtained by directly applying phenols in the pulping of wood. They
established a two phase system to instantaneously separate the wood components, phenolate

32

lignin and perform carbohydrate hydrolysis. The process runs in several plants, however,
massive amounts of acid and phenol derivative were used (23 and 10 times the weight of the dry
wood meal, respectively). The lignophenol contained up to 0.9 mol phenol per C9 unit
exclusively linked to the C [331]. The way to increase lignin reactivity by phenolation was also
investigated for ammonium lignosulfonate [332]. The authors discovered that low lignosulfonate
concentration (30%), high temperature (160C) and long reaction time (160 min) are optimal
conditions. Beech organosolv lignin highly soluble in phenol, thus phenol/lignin feed ratios as
0.5 might be realized. From the carbon content of activated lignin a simple and fast method to
deduce the degree of phenolation was presented. Dispersity and Mw were reduced during the
phenolation further increasing the suitability for application in the three resin systems.
6.

Conclusion and future trends:

Lignin and lignin derivatives biopolymers have prospective array of commercial applications and
thus they can be widely used in different areas such as industrial applications, pulp industry,
plastic, agriculture and other industrial areas. Biopolymer based lignin blends including protein
lignin blends and starchlignin blends also shown promising application in the various fields.
Extraction, derivatization and functionalization of lignin biopolymer give a brief insight in the
development of various products for common use. Lignosulfonate, Kraft Lignin, lignocellulose,
lignophenol, sodium-lignosulfonate and organosolv lignin based polymers has knocked new
doors for the researchers for the development of well-designed biomaterials, biodegradable
films, composites and for potential industrial applications. Lignin is expected to be next
generation precursor for biofuels and other applications. Owing to these developments, industries
such as aerospace, petrochemicals, construction, and automobiles will witness dynamic growth.
Development of biobased derivatives of lignin will change the future circumstances.
33

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Figure Captions
Fig.1 (a) Monolignols in lignin; (b) Representative structure of lignin
Fig. 2 Derivatives of lignin
Fig.3 Schematic illustration of fabrication procedure of nanoporous nitrogen-doped grapheme
Fig.4 (a). Schematic synthesis of lignosulfonate doped polyaniline (pani-LGS);

(b).

Mechanism on formation of urchin-like PANI/LGS conducting microspheres

Fig.5 (a) A possible mechanism for the formation of microspheres and hexagon sheets of the
PNA-LS composites; (b) A low-cost green route to construct a novel sensing platform for
Fe+3 detection based on core/shell hybrids by using citric acid and sodium lignosulfonate
through one-step treatment.
Fig.6 Synthesis Mechanism of KL-PEG Copolymer
Fig.7 Mechanism of formation of lignin DFDPS Copolymer by the SNAr Reaction
Fig.8 Schematic representation of a lignocellulosic fiber and its main components, as well as
possible interaction with PET
Fig.9 Synthesis of BBL grafted copolymer (BBL-PCL) ring opening polymerization
Fig.10 Reaction mechanism of the BPHMF resin formation from bio-phenols and in-situ
generated HMF
Fig.11 Schematic representation of (a) oxypropylation reaction of the sodium lignosulfonate and
(b) polymerization reaction of the propylene oxide initiated by hydroxyl group
Fig.12 Reaction scheme of lignin butyration to convert hydroxyl groups to esters

61

Table 1
Types of lignin derivatives and their prospective applications in different fields [39-59]
Sr.
#

Material Composition Techniques

for
Characteri
zation
Grafted sulfonated
1H-NMR,
alkali lignin polymer
FT-IR

Properties/Applications

References

Dispersant in coal-water slurry

[39]

Rice husk extracted

lignin-TEOS(Tetra
Ethyl Oxysilane)
Biocomposites
Poly (methyl
methacrylate) / ligninbased fillers

FT-IR,
SEM,
DSC,PSD,
AAS
NMR, DLS,
DSC,TEM

Nickel removal from sol-gel

process
[40]
Engineering polymers and give
extraordinary toughness and
strength in polymer
nanocomposites
[41]

Modification of lignin
by phosphorus
molecules

TGA,
PCFC,
STEM,
cone-FTIR
FTIR,
pycnometry

Used for bio based flame

retardant component.

SEM,XRD,

Used in pharmaceutical industry

Corrosion inhibitor for iron-based
materials
Used to produce the
saccharification and fermentation
of unbleached softwood pulp
for bioethanol production
Modified urethane lignin act as a
filler

Ligninphenol
formaldehyde aerogels
and cryogels
Aspen lignin

Sulfonated Kraft lignin

EIS

Amphipathic lignin

GC

Urethane modified
Lignin

FTIR, GPC,
SEM,X-ray,
TGA
NMR,FTIR,
XPS,TGA,
FTIR,
1HNMR,
TGA,
HPAEC,

[42]
For better insulating
performances
[43]
[44]

10

Aminated lignin

11

Cationic softwood
kraft lignin

12

Organosolv lignin

[45]

[46]

[47]
Used in epoxy resins as a biobased reactive additive
[48]
Used as a flocculant for dye
removal from model wastewater
[49]
Improve the water resistance of
62

13

Kraft lignin and

esterified lignin

14

Lignin-derived
lignophenols

UV/Visible,
FT-IR,
AFM,
FTIR,TGA

SEM

films
[50]
Presence of both
lignins(KL,EL) reduced the water
absorption of TPS
Used to decreased the plasma
triglyceride levels

[51]

[52]
15

Starchsodium
lignosulfonate

SEC,HPLC

Used for antioxidant activity in

food and cosmetics

16

-O-4 phenolic dimer

lignin
lignincarbohydrate

FTIR,NMR

Production of fuel

ATRFTIR,GCMS
FTIR

Enhanced the hydrophobic

properties of renewable fibers

[53]

17

18

lignin-aminophenol

[54]

[55]
Used as protease adsorbents
[56]

19

20

21

acylation of lignin

Alkali-O2 oxidized
lignin-bio based
concrete plastisizer
Ethanol organosolv
lignin

FT-IR,
GPC,
31PNMR,
TGA/DSC,
NMR
SEC ,UV

Show good compatibility with the

polymeric matrix
[57]

Used to the Formation of biobased concrete plasticizer

[58]

FT-IR,DSC,
NMR,TGA

Mild steel corrosion inhibitor in

corrosive media

[59]

63

Table 2
Different techniques for the synthesis and characterization of lignin derivatives based
polymer and their prospective applications in different sectors [60-92].
Sr.
#
22

Material
Composition
Polyoxyethylene
Ether - Kraft Lignin

Techniques for
Characterization
FT-IR,UV,GPC,

Properties/Applications
Used for dispersant in
dimethomorph
&agriculture suspension
concentrates
Used in formation of heat
stable compounds

23

Poly(arylene ether
sulfone) - Kraft
Lignin

NMR,TGA

24

Ester epoxy resin lignosulfonate

glycerol

FTIR,DSC,
TGA

Resins formation

25

Alkylated lignin polypropylene

FTIR,

Used as additives

References

[60]

[61]

[62]

[63]
26

Organosolv lignin acrylamide based

hydrogels

FTIR,SEM,

Used for reactive filler in

hydrogels
[64]

27

28

Lignosulfonate Poly(Nmethylaniline)
Lignosulfonate-based
acidic resin with 2methylfuran and
furfural

TEM,X-ray

FTIR,XRD,TEM,N
MR

Used as antimicrobial
material

[65]

Preparation of fuel and jet

oil

[66]
29

30

Sodium
lignosulfonate
grafted poly(acrylic
acid-co-acryl amide)
composite
Ligninsulphonate polystyrene plastics

FTIR,TG/DSC,SEM

Formation of super
absorbent polymer

DSC

Plastic formation

Lignosulphonate

TEM, FTIR,

Corrosion Protection of

[67]

[68]
31

64

based PolyanilinePoly(Acrylamide CoAcrylic Acid)

TGA,SEM

aluminium alloy

Polyaniline
microspheres lignosulfonate
Phenolic lignin phenolhydroxymethylfurfura
l resin
Lignocellulosic nano
cellulosic fibers

TEM,XRD,UV

SEM,TGA,DMA,

Formation of fibers

35

Lignosulfonates
/laccase-coatings and
films

UV

Formation of films

36

Polyols- organosolv
lignin and fatty acids

1H NMR, FT-IR,
DSC, TGA, DMTA

Production of
polyurethane

[69]
32

33

34

Used for enhanced

conductivity and Thermal
stability.
GCExcellent thermal stability
MS,DSC,GPC,TGA, in bio composites
DMA,NMR

[70]

[71]

[72]

[73]

[74]
37

38

Lignosulfonatepolyoxyethylene ether

Lignopolyurethanic sodium
lignosulfonate

UV spectroscopy

IR,TGA,DMA,SEM

Increased the
hydrophobicity of
Lignosulfonatepolyoxyethylene ether
Flexural moduli
that are significantly
higher

[75]

[76]
39

Polypropylene
lignocellulose

SEM

Used for tensile and high

impact strength

40

Nitrilebutadiene
rubber Lignosulfonate
Poly(-caprolactone) lignocellulosic

XRD,FTIR,SEM,TE
M,TGA

Dispersant for rubber

composite

AFM,XPS,NMR,FT
IR,GPC,DSC,TGA

Used for UV-blocking

coatings,

Lignosulfonate graphene oxide based

on nitrogen-doped
graphene
Organosolv lignin
phenolation -biobased thermosets

FTIR,GCD,EIS

Act as dispersant

1H, 31P and 13C

NMR, Pyrolysis
GC/MS,GPC,

Used in thermosetting
resins

[77]

41

[78]

[79]
42

43

[80]

65

UV
[81]
44

kraft lignin-based
carbon nanoparticals
filler

SEM,X ray,DSC

Electrically conductive

45

Polyanilinelignosulfonate/epoxy
poly(Nethylaniline)/lignosulf
onate

EIS,FTIR,X
ray,SEM
TGA,XRD,FTIR,SE
M

Used for corrosion

protection
Used to make the films,
which act as corrosion
protection

46

[82]
[83]

[84]
47

lignosulfonate SEM,DSC,DMA
polyvinyl alcohol film
lignosulfonate
FTIR,UV-vis,SEM,
composites - poly(omethoxyaniline)

Used as reinforcement

49

pyrite-xanthatelignosulfonate-based
biopolymer

FTIR-ATR

Act as depressant

50

Ligninsulfonate/graph
ene-carbon material

FTIR,UV,TEM

Excellent fluorescent
sensing

51

Carbon fibers based

on organosolv
lignin/polyacrylonitril
e blends

FTIR,NMR,GPC,FE
-SEM,TGA

Carbon fiber used as a

reinforcement in
composite application

52

Phenolformaldehyde
resol - organosolv
pine lignin
Bio-based rigid
polyurethane -Kraft
lignin
Lignocellulosic
ethanol based on
ligninphenol
formaldehyde

NMR,FTIR,DSC,U
V,HPLC

Lignin thermal stability

increased

48

[85]
Used in potential
antioxidant application.
[86]

[87]

[88]

[89]

53

54

[90]
NMR,DSC,SEM

Formation of rigid foam

[91]

FTIR,NMR,GPC,TG Used in resin adhesive

A
[92]

66