International Journal of Biological Macromolecules 256 (2024) 128506

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International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Review

A review on the calculation and application of lignin Hansen

solubility parameters
Qingzhi Ma a, *, Changqing Yu b, Yuran Zhou c, Dinggen Hu c, Jianbin Chen a, c, Xuejin Zhang a, *
a
Key Laboratory of Recycling and Eco-treatment of Waste Biomass of Zhejiang Province, Zhejiang University of Science and Technology, Hangzhou 310023, China
b
Provincial Key Laboratory of New Polyolefin Materials, School of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, China
c
Winbon Schoeller New Materials Co., Ltd., Quzhou 324400, China

A R T I C L E I N F O A B S T R A C T

Keywords: Hansen solubility parameters (HSPs) play a critical role in the majority of processes involving lignin depoly­
Hansen solubility parameters merization, separation, fractionation, and polymer blending, which are directly related to dissolution properties.
Atomic and functional group contribution However, the calculation of lignin HSPs is highly complicated due to the diversity of sources and the complexity
(AFGC) method
of lignin structures. Despite their important role, lignin HSPs have been undervalued, attracting insufficient
Lignin dissolution behavior
attention. This review summarizes the calculation methods for lignin HSPs and proposes a straightforward
method based on lignin subunits. Furthermore, it highlights the crucial applications of lignin HSPs, such as
identifying ideal solvents for lignin dissolution, selecting suitable solvents for lignin depolymerization and
extraction, designing green solvents for lignin fractionation, and guiding the preparation of lignin-based com­
posites. For instance, leveraging HSPs to design a series of solvents could potentially achieve sequential
controllable lignin fractionation, addressing issues of low value-added applications of lignin resulting from poor
homogeneity. Notably, HSPs serve as valuable tools for understanding the dissolution behavior of lignin.
Consequently, we expect this review to be of great interest to researchers specializing in lignin and other
macromolecules.

1. Introduction product upgraded oxygen-rich bio-oils can be obtained via catalysis

Lignin, characterized as a heterogeneous polymer with a phenyl­
propane structure, is the sole polymer capable of naturally supplying a
significant quantity of phenolic compounds [1,2]. Depending on the
number of methoxyl in the benzene ring, the phenylpropane structure is
subdivided into guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H)
units [3]. The side chain of the phenylpropane structure contains
different types and numbers of functional groups, such as hydroxyl,
carboxyl, carbonyl, acyl, and olefin structures [4]. The extraction,
characterization, and utilization of lignin have attracted considerable
attention owing to its renewability and versatility [5,6]. Lignin has
demonstrated rich application value [7]: (1) unmodified or modified
(phosphating, hydroxymethylation, phenolation, sulfonation, carbox­
ylation, epoxidation, esterification, and etherification) lignin can be
directly used as a dispersant, emulsifier, sustained-release agent, sur­
factant, and energy storage material [8,9], (2) lignin can be depoly­
merized, encompassing physical, biological, chemical, and pyrolysis
methods, into smaller molecular platform compounds [10–12], (3)
[13,14], (4) preparation of lignin-based composites, including poly­
urethane, phenolic resin, and aldehyde free adhesive [15–18], and (5)
development of lignin nanoparticles for several applications, such as
adhesives, composites, coatings, and antibacterial agents. [19–21].
However, despite its broad utility, only approximately 5 % of industrial
lignin is utilized in high value applications, with the remaining 95 %
burned to recover heat [22–24].
The complex structure, heterogeneity, and poor solubility of lignin
(except for cases involving alkaline solutions and lignosulfonate) pose
significant challenges, hindering its high value-added applications
[25–27]. Of these, the correlation and compatibility (insolubility,
swelling, dissolution, compatibility, and incompatibility) of lignin with
solvents (or other polymers) profoundly impact its extraction, separa­
tion, purification, modification, fractionation, and other various utili­
zation processes. However, the importance of the correlation and
compatibility behaviors, especially the dissolution behavior of lignin,
has not received adequate attention [28,29]. Dissolution is the process
of mixing multiple substances into a homogeneous phase in a molecular

* Corresponding authors.
E-mail addresses: maqingzhi@zust.edu.cn (Q. Ma), xuejinzhang@126.com (X. Zhang).

https://doi.org/10.1016/j.ijbiomac.2023.128506
Received 30 August 2023; Received in revised form 24 November 2023; Accepted 28 November 2023
Available online 29 November 2023
0141-8130/© 2023 Elsevier B.V. All rights reserved.
Q. Ma et al.
state. The formation of a solution is a gradual process in which energy is
consumed to overcome the attraction between solute-solute and solvent-
solvent, which is an endothermic process. Conversely, in the solvation
process, where solute-solvent attraction force is established, heat is
released, which is an exothermic process. Following dissolution, an
equilibrium is attained by the intermolecular forces of the solute-solute,
solute-solvent, and solvent-solvent systems. However, the dissolution
behavior of polymers like lignin is notably more complex compared to
small molecules, as it necessitates adequate swelling and dispersion
before the occurrence of dissolution [30].
The overall (total) solubility parameter (δ), defined as the square
root of cohesive energy (E) density, was proposed to aid in under­
standing the compatibility and dissolution behavior of substances
[31–33]. The cohesion energy of the solute and solvent is derived from
the energy of evaporation, which is the total energy required to hold
liquid molecules together. Hansen divided the total energy of vapor­
ization of a substance into three parts: dispersion forces, permanent
dipole–permanent dipole forces, and hydrogen bonding [32,33].
Furthermore, he proposed the concept of Hansen solubility parameters
(HSPs), suggesting that the overall solubility parameter of a substance
comprises three partial solubility parameters: dispersive cohesion (δD),
polar cohesion (δP), and hydrogen bonding cohesion (δH) [34]. Ac­
cording to Hansen’s theory, two substances are more compatible when
their three forces (or parameters) are similar. HSPs have found extensive
application in dissolution-related fields, including but not limited to the
coating industry (for solvent selection), prediction of polymer compat­
ibility and solubility, assessing chemical resistance and permeation
rates, and surface characterization of pigments, fibers, and fillers [35].
However, to the best of our knowledge, no study has systematically
introduced calculation methods for lignin HSPs and their comprehensive
applications. This concise review aims to: 1) summarize polymer
dissolution-related theories, such as the Gibbs free energy of dissolution,
Flory-Huggins interaction parameter, and HSPs, 2) offer an overview of
the essential methods for calculating lignin HSPs and propose a quick
method to compute the partial and overall solubility parameters of
lignin based on its structure; and 3) outline the critical applications of
lignin HSPs, aiming to more effectively guide the selection of solvents
during the lignin extraction and fractionation processes, as well as
predict the compatibility of lignin with other polymers.
2. Critical theories and factors influencing polymer dissolution
behavior
2.1. Gibbs free energy of dissolution
The changes in Gibbs free energy (ΔG) play a fundamental role in
thermodynamics, determining whether the reactions, including disso­
lution, can occur spontaneously. According to Eq. (1) [36], the disso­
lution process can only occur spontaneously when the free energy of
mixing (ΔGM) is either zero or negative.
△GM = △HM − T△SM , (1)
where ΔHM represents the heat of mixing, T is the absolute temperature,
and ΔSM denotes the change in entropy during the mixing process.
Entropy is essentially a description of the degree of chaos, increasing
as the solute dissolves in the solvent, which means that ΔSM is always
positive. Considering the absolute temperature is positive, TΔSM and
–TΔSM are always positive and negative, respectively. When the disso­
lution is exothermic, where both ΔHM and ΔGM are negative, the
dissolution can occur spontaneously. Likewise, in a dissolution process
without heat exchange, wherein ΔHM = 0 and ΔGM is negative, the
dissolution can also occur spontaneously. However, in endothermic
dissolution (ΔHM is positive), determining whether the ΔGM value is
positive or negative becomes uncertain. Therefore, employing ΔG alone
to ascertain lignin solubility in solvents has limitations, particularly
2
International Journal of Biological Macromolecules 256 (2024) 128506
when ΔHM is positive. Furthermore, there is no database available for
lignin mixing heat. Directly measuring mixing heat by combining lignin
and solvent would provide explicit information on whether the lignin is
soluble. Therefore, utilizing ΔG to determine the dissolution behavior of
lignin is more complicated than conducting a direct experiment.
Consequently, alternative tools are required to determine the solubility
of solutes in solvents.
2.2. Flory-Huggins theory and interaction parameter χ
The Flory–Huggins theory plays a vital role in assessing the mutual
miscibility between a polymer and a solvent or another polymer. This
theory was derived from the following three assumptions [37–39]: (1)
each polymer chain is represented as a chain comprising “x” segments,
with each segment having exactly the same volume as a solvent mole­
cule; (2) the polymer chain is completely free, and all conformations
possess the same energy; and (3) the polymer segments in solution
exhibit uniformly distribution, occupying any lattice equally. Therefore,
a polymer solution can be depicted by a lattice divided into cells, with
each cell occupying a segment of the polymer or solvent molecule.
Therefore, the Flory-Huggins interaction parameter (χ12) between the
polymer and the solvent is defined by Eq. (2) [38]:
Z△w12
χ 12 = , (2)
RT
where Z represents the coordination number of the crystalline network
model, Δw12 signifies the mutual interaction energy between polymer
and solvent molecules, R denotes the universal gas constant, and T is the
absolute temperature.
The χ12 is a dimensionless parameter, with χ12kT expressing the
difference in energy of a solvent molecule in pure solvent compared to
its immersion in pure polymer. The osmotic pressure (π) generated when
mixing a pure solvent with a polymer solution can be expressed by Eq.
(3). Accordingly, the following conclusions can be drawn from further
analysis of Eq. (3) (the detailed derivation is summarized in the refer­
ence and omitted here) [33,40,41]: When χ12 = 1/2, the polymer ex­
hibits ideal behavior during mixing with the solvent, referred to as the
θ-point. Under these conditions, the polymer chains in the solution have
no repulsion or attraction, maintaining their original dimensions un­
disturbed. In instances where χ12 < 1/2, the polymer chains unfold in
the solvent, indicating favorable or “good” solvent conditions. In
contrast, when χ12 > 1/2, the polymer chains fold or precipitate in the
solvent, signifying unfavorable or “poor” solvent conditions. The Flory-
Huggins interaction parameter χ12 substantially contributes to under­
standing the dissolution behavior of polymers in various solvents.
[ ( ) ]
(π/C2 ) = RT (1/M2 ) + ϕ2 2 (1/2 − χ 12 )C2 , (3)
where C2 denotes the polymer concentration, M2 represents the molar
mass of the polymer, and ϕ2 signifies the volume fraction.
However, the Flory–Huggins theory does not consider the entropy
caused by polymer chain folding [42]. When a crystalline polymer dis­
solves, its crystal structure undergoes changes. Even for amorphous
polymers, the conformation of the molecular chains transforms, leading
to additional entropy and energy variations. Moreover, the actual dis­
tribution of polymers in the solution is not uniform, further complicating
the scenario.
2.3. HSPs
The concept of solubility parameter was initially proposed by Hil­
debrand and Scott [31,43], defined as the square root of cohesive energy
density, as shown in Eq. (4). The one-component overall solubility
parameter formulated by Hildebrand and Scott is generally applicable to
regular solutions lacking molecular or specific interactions.
Q. Ma et al. International Journal of Biological Macromolecules 256 (2024) 128506

δ = (E/V)1/2 , (4) δ = (ED /V + EP /V + EH /V)1/2 , (6)

where E is the total cohesion energy (or the energy of vaporization) and
can be measured. V denotes the molar volume of both the pure solvent
and polymer. Notably, the numerical value of the solubility parameter in
MPa1/2 is 2.0455 times greater than that in cal1/2⋅cm–3/2.
A shortcoming of the solubility parameter introduced by Hildebrand
and Scott is that the approach is limited to regular solutions and must
consider the influences of polarity and hydrogen-bonding interactions.
Blanks and Prausnitz [44] addressed this by categorizing solubility pa­
rameters into two parts: “nonpolar” and “polar.” Hansen expanded upon
this concept by dividing the total vaporization energy of a liquid into
three constituent parts: dispersion forces, permanent dipole–permanent
dipole forces, and hydrogen bonding. Alternatively, the total cohesive
energy can be considered to comprise three components: dispersion
cohesive (ED), polar cohesive (EP), and hydrogen bonding (EH), as shown
in Eq. (5) [33,43]. Therefore, the overall solubility parameter is the
square root of the sum of these energy densities (that is, dispersion,
polar, and hydrogen bonding), as presented in Eq. (6). Notably, the total
solubility parameter of Hansen and the solubility parameters of Hilde­
brand and Scott are largely the same [45]. Following the definition of
the total solubility parameter, Hansen regarded the energy densities:
dispersion cohesive, polar cohesive, and hydrogen bonding as the pa­
rameters of dispersion cohesion, polar cohesion, and hydrogen bonding
cohesion, respectively. Finally, the HSPs are formulated, wherein the
total solubility parameter δ is composed of three partial solubility pa­
rameters (δD, δP, and δH), satisfying the relationship expressed in Eq. (7).
E = ED + EP + EH , (5)
( )1/2
δ = δD 2 + δP 2 + δH 2 . (7)
The dispersion force, or London force, is a weak intermolecular force
existing between two atoms or molecules when they are in close prox­
imity. It arises due to the transient dipoles present in molecules or atoms.
Every molecule (or atom) has a transient dipole, which induces a similar
transient dipole in a neighboring molecule (or atom), causing an
attractive force between them. Dispersion forces are universal and exist
in all molecules and atoms. Conversely, polar cohesive energy is pri­
marily induced by permanent dipole-permanent dipole interactions.
Similar to permanent dipole-permanent dipole interactions, polar
cohesive energy is present in most molecules. Hydrogen bonding is an
intermolecular interaction that resembles the polar cohesive energy and
is a permanent dipole force. Hydrogen bonding occurs between a
hydrogen atom covalently bonded to other atoms and another atom (X-
H… Y); the atoms (X and Y) on either side of a hydrogen atom are
usually highly electronegative.
In particular, W. Zeng et al. abbreviated Hildebrand solubility
parameter and Hansen total solubility parameter to δ and δT, respec­
tively (Eq. (8)) [45]. They suggested that “the total solubility parameter
of Hansen δT should be equal to the Hildebrand parameter δ, although
the two quantities may differ for materials with specific interactions
when they are determined by different methods [45].” The close or even
identical actual measured data of Hansen’s total solubility parameters
and the Hildebrand parameters (Fig. 1) support the conclusion of Zeng
et al. However, in contrast, M. Belmares et al. [46] and S. Venkatram
et al. [47] abbreviated Hildebrand parameter as δ without introducing

Fig. 1. Representation of the consistency between Hansen total parameter and Hildebrand parameter of the actual measured substance. The substances are
numbered 1–68 based on the Hildebrand parameter and Hansen total parameter in an ascending order. Solvents 1–68 were perfluoroheptane (1), diethyl ether,
trichlorofluoromethane, butyl acetate (iso), benzonitrile, tricresyl phosphate, amyl acetate, butyl acetate (normal), carbon tetrachloride, ethylbenzene (10), mesi­
tylene, xylene, diethyl carbonate, diethyl ketone, toluene, mesityl oxide, ethyl acetate, tetrahydrofuran, isophorone, benzene (20), trichloroethylene, diacetone
alcohol, chloroform, styrene, tetrachloroethylene, dibenzyl ether, benzaldehyde, acetyl chloride, chlorobenzene, tetrahydronaphthalene (30), diethylene glycol
monobutyl ether (normal), methyl acetate, ethyl bromide, tetrachloroethane-1,1,2,2, ethylene dichloride, cyclohexanone, naphthalene, acetone, bromobenzene,
carbon disulfide (40), dichlorobenzene (ortho), diethyl phthalate, nitrobenzene, acetic acid, acetaldehyde, acetic anhydride, aniline, butyronitrile, hexamethyl­
phosphoramide, acetophenone (50), pyridine, quinoline, epichlorhydrin, nitroethane, cyclohexanol, allyl alcohol, acetonitrile, benzyl alcohol, formic acid, ethylene
diamine (60), furfuryl alcohol, nitromethane, methanol, ethylene carbonate, ethylene cyanohydrin, succinic anhydride, formamide, and water (68) [45],
respectively.

3
Q. Ma et al.
Hansen’s total solubility parameter. Importantly, Hildebrand parameter
δ, as presented in the references of M. Belmares et al. [46] and S. Ven­
katram et al. [47], was calculated by Eq. (7), which has the same right-
hand side as in Eq. (8). In summary, there was no essential difference in
the introduction of Hansen’s total solubility parameter, which is
equivalent to the Hildebrand parameter. For brevity, the Hildebrand
parameter and Hansen’s total solubility parameter are treated as
equivalent in this study.
( )
δT = δD 2 + δP 2 + δH 2 1/2
(8)
Hansen’s approach divided the cohesive energy into three parts,
while Hildebrand and Scott viewed it as a unified whole. This funda­
mental difference lies at the core of two approaches. Notably, other
sources of cohesion energy (such as induced dipoles, metallic bonds, and
electrostatic interactions) are generated in various types of molecules.
Given that organic molecules contain none or limited cohesion energy,
Hansen ignored considering their influence on the cohesive energy.
The HSPs of a polymer can be considered as the length of a vector in a
3-dimensional system with three partial solubility parameters as co­
ordinates [48,49]. The radius of the Hansen sphere, Ro, defines the
extent to which a difference in solubility parameters can be tolerated.
The boundary of the spherical characterization depends on the distance
of good solvents from the center of the sphere (the coordinate of the
polymer) and is calculated using a computerized optimization method
[33]. A solvent, soluble in a polymer, encompasses in the system of
coordinates a volume in which the polymer vector terminates. The
distance between the polymer and the solvent in the sphere (Ra) was
computed in accordance with their respective partial solubility param­
eters in the coordinates, as illustrated in Eq. (9). This equation was
developed from the plots of experimental data where the constant “4”
was determined to be suitable, and accurately represented the solubility
data within a sphere encompassing the good solvents.
[
Ra = 4(δD1 − δD2 )2 + (δP1 − δP2 )2 + (δH1 − δH2 )2
]1/2
, (9)
where δD1, δP1 and δH1 are the partial solubility parameters of solvent,
and δD2, δP2 and δH2 are the partial solubility parameters of solvent.
The relative energy difference (RED) was used to determine the
miscibility of lignin with the solvent, and is defined as the ratio of Ra to
Ro, as shown in Eq. (10):
RED = Ra /R0 (10)
RED numbers <1.0 indicate a high affinity, suggesting that the
polymer is more likely to be soluble, mostly soluble, or partially soluble
in the solvent. In contrast, progressively higher RED values >1 indicate
decreasing affinities, implying that the polymer is more likely to exhibit
swelling or minority swelling in the solvent.
2.4. The relationship between ΔGM and χ 12
In essence, there is a close relationship between the free energy of
mixing (ΔGM in Eq. (1)) and the Flory-Huggins interaction parameter
(χ12 in Eq. (2)). According to the definition of mixed entropy, ΔSM can be
expressed by Eq. (11):
△SM = − R(n1 lnϕ1 + n2 lnϕ2 ), (11)
where n1 and n2 are the mole numbers of solvent and polymer, and ϕ1
and ϕ2 are the volume fractions of solvent and polymer.
The heat of mixing ΔHM can also be expressed by Eq. (12) based on
the Flory–Huggins theory [37–39]:
△HM = − χ 12 RTn1 ϕ2 (12)
Hence, Eq. (12) can be obtained by substituting Eqs. (11) and (12)
into Eq. (1). Importantly, this equation revealed that the free energy of
mixing ΔGM can be calculated according to the Flory-Huggins
4
International Journal of Biological Macromolecules 256 (2024) 128506
interaction parameter χ12 and then used to judge the dissolution
behavior of polymer in the solvent [50–52]:
△GM = RT(n1 lnϕ1 + n2 lnϕ2 + χ 12 n1 ϕ2 ) (13)
2.5. The relationship between χ 12 and HSPs
Both the Flory-Huggins theory and the HSPs concern the law of the
solute dissolution in the solvent, signifying that there should be some
connection between χ12 and HSPs. The Flory-Huggins interaction
parameter χ12 for a system can be estimated where HSPs are known via
Eq. (14) [32,53]. However, the reverse is impossible, that is, estimating
the HSPs when χ12 are known. This is because HSPs comprise three
partial solubility parameters: dispersion forces, permanent dipole-
permanent dipole forces, and hydrogen bonding. However, a single
χ12 cannot be divided into the above three parts.
χ 12 =
v1 [ ]
(δD1 − δD2 )2 + (δP1 − δP2 )2 + (δH1 − δH2 )2 + β, (14)
RT
where v1 represents the molar volume of the solvent. β denotes an
empirical constant that serves as a correction factor for the Flory
combinatorial entropy in polar polymer systems, typically with an
average value of around 0.34. For weak polar polymers, like lignin, the
constant β is negligible and can be set as zero [53].
Notably, accurate χ12 values from numerous solvents (with known
HSPs) and the same polymer can be used to determine the HSPs of the
polymer. Other data such as viscosity, solvency, or swelling from
numerous solvents (with known HSPs) and the same polymer can also be
used to ascertain the HSPs of the polymer [54]. Segarceanu et al. [55]
proposed that the higher the interactions between the solvent and so­
lute, the greater the intrinsic viscosity of the solution. Therefore, the
overall and partial solubility parameters of the polymer can be predicted
from the intrinsic viscosity of the solution and the solubility parameters
of the solvents. Segarceanu et al. [55] then calculated the solubility
parameters of polyesterimide using their method, confirming their ac­
curacy by comparing it with the solubility parameters computed using
Hansen’s dissolution method. However, the main drawback of Segar­
ceanu’s method is that the relationship between the intrinsic viscosity
and solubility of solutes in the solvents is complex and is only set as a
positive correlation. However, this method has not yet been employed to
calculate lignin HSPs.
2.6. Temperature and molecular weight on polymer dissolution
Temperature and molecular weight are also critical factors that affect
polymer solubility. From the perspective of Gibbs free energy, high
temperature is favorable for endothermic dissolution, while low tem­
perature is favorable for exothermic dissolution [33,50].
An increase in the temperature can reduce the energy required for
vaporization, thereby decreasing the solubility parameter of the sub­
stance. However, the change in the solubility parameter of the solute
with increasing or decreasing temperature is usually slightly less than
that of the solute. Therefore, the impact of temperature on solubility
depends on the solubility parameters of the solute and solvent [52]. For
example, when the solubility parameter of the solvent is greater than
that of the solute, an increase in temperature reduces the difference
between the solubility parameters of the solvent and solute, thereby
increasing solubility. Conversely, when the solubility parameter of the
solvent is smaller than that of the solute, an increase in temperature
increases the difference between the solubility parameters of the solvent
and solute, thereby decreasing the solubility.
A higher molecular weight enhances polymer chain entanglement
and thus reduces the tendency for environmental stress cracking when
the solvent is absorbed [56]. A higher molecular weight leads to stronger
entanglements between the polymers, thus reducing the possibility of
environmental stress cracking when the solvent is absorbed and swelled.
Q. Ma et al. International Journal of Biological Macromolecules 256 (2024) 128506

The fact that cross-linked and crystalline polymers are almost insoluble (∑ )1/2
is suitable evidence [33,52,57]. Notably, when the solubility parameters δH =
△
∑ ei-H , (18)
are the same, small-molecule solvents are more likely to dissolve the △Vi
polymers than larger solvent molecules. This is because small-molecule
solvents are more likely to approach polymers, especially large-molecule where Δei-D, Δei-P, and Δei-H are the evaporation energies required to
polymers, with significant steric hindrance. overcome the dispersion cohesion, polar cohesion, and hydrogen
bonding cohesion of atoms or functional groups, respectively, and Δvi
represents the molar volume of an atom or functional group.
3. The calculation of polymer HSPs

4. The calculation of lignin HSPs

The cohesive energy, which holds the molecules together, can be
directly measured by vaporizing the substance, particularly the solvent,
4.1. Hansen dissolution method
from liquid to gas. The vaporization method has proven to be reliable for
measuring the total cohesive energy of solvent molecules. However, the
Hansen first measured the HSPs in lignin using the dissolution
cohesive energy of high-molecular-weight polymers, such as lignin,
method [33,49]. Eighty-two solvents with known HSPs were used to
cannot be measured using the evaporation method. As the heating
dissolve milled wood lignin (MWL), with the results divided into five
temperature increased, the high-molecular-weight polymers underwent
categories based on visual observations: soluble, majority-soluble,
pyrolysis and were depolymerized into more minor molecular com­
partially soluble, swelling, and minority-swelling. Then, the cate­
pounds before reaching the boiling point. In addition, the three partial
gories: soluble, majority soluble, and partially soluble were coded as
cohesive energies (ED, EP, and EH) cannot be determined depending on
soluble, while swelling and minor swelling were labeled as insoluble
the evaporation method because the contributions of these three types of
[33,49,66]. The soluble or insoluble fractions and the solubility pa­
partial cohesive energies to vaporization cannot be clearly
rameters of the solvents were processed by the Hansen computer pro­
distinguished.
gram [67]. Finally, the solubility parameters δD, δP, δH, and δ (10.7,
The polar and dispersion cohesive energies are usually measured
6.89, 8.26, and 15.2 cal1/2⋅cm–3/2 respectively), as well as Ro (6.70 cal1/
through complex experiments and calculations rooted in the theory of 2
⋅cm–3/2), for MWL were obtained (Table 1). Depending on the lignin
statistical thermodynamics [33]. These experiments and calculations are
solubility parameters, we can quantitatively (rather than qualitatively)
so refined that the ED and EP values of most monomolecular solvents and
analyze the dissolution behavior of lignin [33,49].
polymers can be obtained by referring to a handbook. The δD parameter
Numerous researchers have improved Hansen’s dissolution method
was calculated according to the procedure outlined by Blanks and
[64,66,68–71]. Vebber et al. [66] optimized the HSPs calculation pro­
Prausnitz [44]. Standard figures can be used to determine this param­
cess for polymers using a genetic algorithm. The partial and overall
eter, depending on the aliphatic, cycloaliphatic, or aromatic type. The
solubility parameters of MWL calculated by Vebber et al. [66] based on
ED of straight-chain hydrocarbons was shown to be a function of the
the improved genetic algorithms method were 10.6, 6.93, 8.28, and
molar volume and reduced temperature (Tr). If the molar volume and Tr
15.1 cal1/2⋅cm–3/2, which is highly consistent with the results of the
of a molecule are known, the ED can be found in the standard figure, and
Hansen dissolution method 10.7, 6.89, 8.26, and 15.2 cal1/2⋅cm–3/2
the δD parameter can be confirmed. The dispersion cohesive energy
[33,49]. Díaz de los Ríos et al. [71] determined the HSPs and Hansen
density (ED/V) for cycloalkanes and aromatic hydrocarbons was shown
sphere radii using the Solver add-in in Microsoft Excel. The result for
to be a function of molar volume and Tr. If the molar volume and Tr of a
lignin HSPs is an optimal region rather than a point [71,72]. The Hansen
molecule are known, ED/V can be found in the standard figure, and then
dissolution method provides an important basis for the calculation of
the δD parameter can be obtained by taking the square root of ED/V.
lignin HSPs and the exploration of lignin dissolution behavior. However,
Hansen and Beerbower [58] proposed Eq. (15) to calculate the δP. An
the Hansen dissolution method has two shortcomings: (1) its reliance on
advantage of this equation is that δP can be calculated using the dipole
qualitative rather than quantitative measurement can lead to theoretical
moment, which can be obtained from the McClellan standard table [59].
inaccuracies, although the use of a large number of solvents compen­
Notably, the results calculated using this equation are reliable. The EH
sates for this inaccuracy; and (2) the method is complex, owing to the
can be computed by subtracting the polar and dispersion energies of
necessity of employing large amounts of solvents [64].
vaporization from the total vaporization energy.
/
δP = 18.3(DM) V1/2 , (15) 4.2. Inverse gas chromatography (IGC) method
1/2
where the constant 18.3 yields this parameter in units of cal ⋅cm –3/2
, Ren et al. [69] calculated lignin solubility parameters using the IGC
and DM represents the dipole moment of the molecule. method rooted in the Flory-Huggins interaction parameter [57]. First,
The atomic and functional group contribution (AFGC) method is a the retention volumes of the six solutes were determined by gas chro­
valuable and widely-used tool for calculating the HSPs of polymers matography employing alkali lignin as the stationary phase. The ther­
[58,60–63]. When the structure of the repeating unit of the polymer is modynamics parameters of the probe solvents (primarily including
known, and the reliable latent heat and dipole moment data are absent, weight fraction activity coefficient, molar absorption enthalpy, and
the HSPs of the polymer can be computed using AFGC. The partial sol­ molar evaporation enthalpy) and the interaction parameters between
ubility parameters were calculated employing Eqs. (16)–(18). The alkali lignin and solvents were calculated in turn. Finally, the average
overall solubility parameter can then be obtained utilizing Eq. (11). The overall solubility parameter of 11.9 cal1/2⋅cm–3/2 for alkali lignin be­
related molar volume, dispersion cohesive energy, polar cohesive en­ tween the temperatures of 25–100 ◦ C was calculated (Table 1). More
ergy, and hydrogen bonding of atoms and functional groups comprising details regarding the use of the IGC method to measure overall lignin
the polymer can be obtained from the references [33, 43, 64, 65]. solubility parameters can be found in a previous study [69]. The overall
(∑
△ei-D
)1/2 solubility parameter of alkali lignin measured by IGC displayed the
δD = ∑ , (16) result of 11.9 cal1/2⋅cm–3/2. This is nearly identical to that measured by
△Vi
the Hansen dissolution method (12.0 cal1/2⋅cm–3/2), proving the accu­
(∑ )1/2 racy of the IGC method. Additionally, when the temperature increased
△
δP = ∑ ei-P , (17) from 25 to 100 ◦ C, the overall solubility parameter of the alkali lignin
△Vi
decreased slowly from 12.0 to 11.8 cal1/2⋅cm–3/2 (Table 1), indicating
that the investigated condition temperature showed limited influence on

5
Q. Ma et al. International Journal of Biological Macromolecules 256 (2024) 128506

Table 1 the overall solubility parameter. Ren et al. [69] presented a new method
Lignin solubility parameters calculated via different methods. for determining the overall lignin solubility parameters depending on
Calculation methods and lignin samples Solubility parameters (cal1/2⋅cm–3/ the IGC. However, the three partial solubility parameters, and the radius
2
) of the Hansen sphere of alkali lignin, were not (or cannot be) determined
δD δP δH δ by the IGC method [69,79].

Hansen dissolution method

MWL [33] 10.7 6.89 8.26 15.2 4.3. AFGC method
MWL on genetic algorithm optimized Hansen 10.6 6.93 8.28 15.1
dissolution method [66]
Sugar cane bagasse lignin [68] 10.5 4.17 10.7 15.5
Ni et al. [65] computed the overall solubility parameter of lignin
Alkali lignin1 [69] 8.42 6.04 6.03 12.0 employing the AFGC method based on the empirical C9 formula devel­
oped by Hoy et al. [60]. First, the C9 molecular formula of the hardwood
IGC method ALCELL lignin was determined by elemental analysis. Secondly, the G/
Alkali lignin1 at 25, 40, 60, 80, and 100 ◦ C S/H ratio of the hardwood ALCELL lignin (76/20/4) was reasonably
12.0, 11.9, 11.9, 11.9, and 11.8
(Overall solubility parameters) [69] inferred according to the C9 molecular formula and hardwood charac­
Average of Alkali lignin1 at 25 ◦ C–100 ◦ C [69] N/A N/A N/A 11.9 teristics. Third, the atomic and functional groups or the empirical C9
Alkali lignin2 [73] N/A N/A N/A 9.82
formulas of the G, S, and H units were further clarified (Fig. 2). For
example, the numbers of methylene (>CH2), methine (>CH–), and
AFGC method based on the lignin empirical C9 formula
olefin (>C=) structures, methoxyl and hydroxyl groups, and atomic
AlCELL lignin (G: S: H = 74: 20:6) [65] N/A N/A N/A 13.7
Almond shell lignin (G: S = 1: 1.25) [74] N/A N/A N/A 14.6
oxygen were 1, 1, 1, 1 and 1, and 1 for the G unit; 1, 2, 0, 2 and 2, and 1
Cornstalk lignin (G: S: H = 40: 50: 10) [75] N/A N/A N/A 13.7 for the S units; and 1, 1, 1, 0 and 1, and 2 for the H units (Fig. 2). At last,
Bagasse enzymatic hydrolysis/mild acidolysis
N/A N/A N/A 14.0
the overall solubility parameter of G, S, and H units was calculated as
lignin (EMAL) (G: S: H = 2.65: 1: 5.07) [76] 13.5, 14.2, and 14.1 cal1/2⋅cm–3/2, respectively, according to Eqs. (16)–
(18) and (7), respectively. Then, the δ of hardwood ALCELL lignin was
AFGC method based on the lignin structure (the lignin structure was not clearly calculated as 13.7 cal1/2⋅cm–3/2 depending on its G/S/H ratio (Table 1).
revealed in the reference) [77] Ni et al. [65] provided a more straightforward method without
Pine kraft lignin 8.17 6.70 5.72 12.0
Acetylated pine kraft lignin 7.87 5.87 4.99 11.0
complicated experimental measurements and tedious calculations to
Propionated pine kraft lignin 7.97 5.62 4.74 10.8 determine the overall solubility parameter of lignin compared to the
Butyrated pine kraft lignin 8.02 5.43 4.55 10.7 Hansen dissolution [33,49] and the IGC methods [69]. However, Ni
Maleated pine kraft lignin 7.63 6.45 5.23 11.2 et al. [65] did not consider the differences between lignin atoms and
Methacrylated pine kraft lignin 7.78 5.72 4.50 10.7
functional groups caused by different raw materials and separation
Hardwood kraft lignin 8.17 6.60 5.53 11.9
Acetylated hardwood kraft lignin 7.87 5.92 5.04 11.1 methods. In addition, the lignin partial solubility parameters and the
Propionated hardwood kraft lignin 7.97 5.62 4.74 10.9 radius of the Hansen sphere were not determined in their study.
Butyrated hardwood kraft lignin 8.02 5.43 4.55 10.7 Wool et al. [77] calculated the partial and overall solubility param­
Maleated hardwood kraft lignin 7.63 6.41 5.23 11.3 eters of several lignin samples, including that of pine kraft, hardwood
Methacrylated hardwood kraft lignin 7.78 5.72 4.50 10.7
kraft, and esterified, using the AFGC model. The result revealed that the
partial and overall solubility parameters were 8.17, 6.70, 5.53, and 12.0
Molecular dynamics simulations based on the lignin model polymeric structure [56]
cal1/2⋅cm–3/2 for pine kraft lignin and 8.17, 6.60, 5.53, and 11.9 cal1/
9.33 (δe = 2
Lignin (DP = 8) 9.14
δP + δH)
13.1 ⋅cm–3/2 for hardwood kraft lignin (Table 1). Regrettably, a detailed
9.04 (δe = lignin structure and calculation process have not yet been reported [77].
Lignin (DP = 11) 8.82 12.6
δP + δH) This may explain why the calculation of partial solubility parameters
7.83 (δe = using the AFGC method has not been widely adopted.
Lignin (DP = 26) 8.09 11.3
δP + δH)
Mohan et al. [56] calculated the HSPs of empirical model lignin,
composed of all possible linkages, such as β-1, β-5, 5–5, β-O-4, α-O-4, and
AFGC method based on the lignin expanded C9 formula [78]
4-O-5, depending on the molecular dynamics simulations (MDS).
12.87;
Bioethanol residual lignin (L1); acetylated L1 N/A N/A N/A
10.97
However, the explicit separation of the contributions of polar and
13.09; hydrogen bonds from electrostatic terms (δe) cannot be achieved
Hardwood kraft lignin (L2); acetylated L2 N/A N/A N/A
11.32 through the MDS method [80]. The empirical model of lignin having a
13.42; degree of polymerization (DP) of 8, 11, and 26 exhibited δD of 9.14,
Softwood kraft lignin (L3); acetylated L3 N/A N/A N/A
11.03
9.33, and 13.1 cal1/2⋅cm–3/2; δe of 8.82, 9.04, and 12.6 cal1/2⋅cm–3/2; and
12.92;
Non-wood soda lignin (L4); acetylated L4 N/A N/A N/A
11.04

AFGC method based on the lignin expanded C9 formula [64]

wheat straw organic acid lignin (WSOAL) 10.8 4.15 6.30 13.2
eucalyptus kraft lignin (EKL) 10.9 4.27 6.47 13.4
bamboo kraft lignin (BKL) 10.9 4.28 6.51 13.4
softwood kraft lignin (SKL) 11.1 4.31 7.38 14.0

AFGC method based on the lignin empirical C9 formula (quick method to calculate
HSPs proposed in this review)
WSOAL (G: S: H = 51: 42: 7) [64] 10.5 4.58 7.72 13.8
EKL (G: S = 19.3: 80.7) [64] 10.4 4.81 8.23 14.1
BKL (G: S: H = 22.2: 63.1: 14.7) [64] 10.5 4.74 8.05 14.0
SKL (G: H = 95.8: 4.2) [64] 10.7 4.30 7.11 13.5

Fig. 2. The empirical structure of lignin units.

6
Q. Ma et al. International Journal of Biological Macromolecules 256 (2024) 128506

δ of 8.09, 7.83, and 11.3 cal1/2⋅cm–3/2, as shown in Table 1. The Table 2

advantage of the MDS approach is evident: it helps to understand the The calculation process partial and overall solubility parameters of G, S, and H
solubility parameters from the perspective of the lignin structure, units based on the AFGC method.
especially the DP and linkages. However, the inability to distinguish The calculation process partial and overall solubility parameters (G unit as an
between polar and hydrogen-bonding cohesion parameters introduces example)
certain limitations. Atom or group Number Δei-D Δei-P Δei-H Δei cal/ Δvi
Lignin structures determine the lignin solubility parameters; how­ in C9 cal/mol cal/ cal/ mol cm3/
ever, none of the above methods establish a relationship between the mol mol mol
exact lignin structure and solubility parameters. Samend et al. [78,81] Tri-
analyzed the element content through elemental analysis. Furthermore, substituted 1 7530 50 50 7630 33.4
they examined the functional group content (aliphatic hydroxyl (OHal), phenyl (G)
-OHal 1 1370 1100 4650 7120 10
phenolic hydroxyl (OHph), carboxyl) and G/S/H ratio via 31P nuclear >CH2 1 1180 0 0 1180 16.1
magnetic resonance (NMR), investigated the methoxyl groups, the >C= 1 800 60 180 1040 − 5.5
number of aliphatic hydrogens (Hal), and aromatic hydrogens (Hph) by -O- 1 0 425 375 800 3.8
1 -CH< 1 820 0 0 820 − 1
H NMR. Subsequently, they measured the expanded C9 formula
-OCH3 1 1125 425 375 1925 37.3
(C9Hal ph al ph
y1Hy2 Oz(OH)m1(OH)m2 (OCH3)n), calculating the overall solubility
2×9
parameters of lignin employing the AFGC method. The overall solubility Δv[a]
o
= 18.0
parameters of bioethanol residual lignin, hardwood kraft lignin, soft­ Sum – 12,825 2060 5630 20,515 112.1
wood kraft lignin, and non-wood soda lignin were 12.9, 13.1, 13.4, and Solubility parameter of G δD δP δH δ
–
12.9 cal1/2⋅cm–3/2, respectively (Table 1). The overall solubility pa­ (cal1/2⋅cm–3/2) 10.7 4.29 7.09 13.5

rameters calculated using the expanded C9 formula were considered to

be more accurate than those calculated using the empirical C9 formula.
However, partial solubility parameters were ignored. Partial and overall solubility parameters (cal1/2⋅cm–3/2) of G, S, and H units

In our previous study [64], we utilized reliable analytical methods to δD δP δH δ

determine the exact structure of lignin. We subsequently conducted (1)
elemental analysis to determine the C, H, N, S, and O contents, (2) 1H
NMR spectroscopy analysis to determine the methoxyl content, (3) 31P
NMR spectroscopy analysis to determine the phenolic hydroxyl (OHal),
aliphatic hydroxyl (OHph), carboxyl, and acetoxyl group contents, (4)
two-dimensional (2D) heteronuclear single-quantum coherence (HSQC)
NMR spectroscopy analysis to determine the ratios of G, S, and H units
[64]. We derived a more detailed expanded C9 formula
(C9HyOz(OH)al ph
m1(OH)m2(OCH3)n1(COOH)n2(CH3COO)n3) for lignin and
calculated the HSPs of the four lignin samples using the AFGC method
[64]. The result revealed the δD, δP, δH, and δ of wheat straw organic acid
lignin (WSOAL), eucalyptus kraft lignin (EKL), bamboo kraft lignin
(BKL), and softwood kraft lignin (SKL) as (10.8, 4.15, 6.30, and 13.2
cal1/2⋅cm–3/2), (10.9, 4.27, 6.47, and 13.4 cal1/2⋅cm–3/2), (10.9, 4.28,
6.51, and 13.4 cal1/2⋅cm–3/2), and (11.1, 4.31, 7.38, and 14.0 cal1/
2
⋅cm–3/2), respectively (Table 1). Thus, we established a universal and
accurate method for determining the solubility parameters of lignin
according to its structure. However, the analysis and calculation of the
solubility parameters rooted in the expanded C9 formula are compli­
cated and tedious.
4.4. A quick method to calculate lignin HSPs
Existing methods for determining the solubility parameters of lignin
face limitations. Some are tedious, such as the Hansen dissolution
method [33,49] and the AFGC method derived from the accurate
expanded C9 formula outlined in our previous study [64]. Others are
unable to determine all the partial solubility parameters, including the
IGC method [69] and the AFGC method based on the empirical by Ni
et al. [65].
In this review, we propose a more accessible and quick approach for
measuring the HSPs of lignin using the AFGC method derived from the
empirical C9 formula of lignin. First, the HSPs of the G, S, and H subunits
of the empirical C9 formula (Fig. 2) were calculated using the AFGC
method. The calculation process was shown in Table 2, and the partial
and overall solubility parameters (δD, δP, δH, and δ) were (10.7, 4.29,
7.09, and 13.5 cal1/2⋅cm–3/2) for G subunit, (10.3, 4.93, 8.50, and 14.2
cal1/2⋅cm–3/2) for S subunit, and (10.9, 4.59, 7.60, and 14.1 cal1/2⋅cm–3/
2
) for H subunit (Table 2). The HSPs of lignin can then be easily calcu­
lated using Eqs. (19)–(22) since the HSPs are proportional to the con­
tents of the G, S, and H subunits. This method is largely based on the
findings of Ni et al. [65,77].
G 10.7 4.29 7.09 13.5
S 10.3 4.93 8.50 14.2
H 10.9 4.59 7.60 14.1
δD-L = 10.7 × G% + 10.3 × S% + 10.9 × H%, (19)
δP-L = 4.29 × G% + 4.93 × S% + 4.59 × H%, (20)
δH-L = 7.09 × G% + 8.50 × S% + 7.60 × H%, (21)
( )
δL = δD-L 2 + δP-L 2 + δH-L 2 1/2
, (22)
where δD-L, δP-L, δH-L, and δL were the HSPs of lignin, and G%, S%, and H
% were the ratio of G, S and H subunits, respectively.
The HSPs of lignin were based on the calculation methods. Different
testing methods may yield different levels of response (or error) to lignin
impurities (such as polysaccharides, sugars, and inorganic components).
At present, there is a lack of research on the influence of impurities on
the HSP results using various test methods. However, if the G/S/H ratio
of lignin can be accurately determined using the quick AFGC method,
the HSPs of lignin can also be precisely computed to eliminate the in­
fluence of impurities.
We further recalculated the HSPs of WOSAL, EKL, BKL, and SKL
employing an established rapid method. As the ratio of the G, S, and H
subunits of these lignin samples was calculated utilizing the 2D NMR
semi-quantitative method (Table 1) [64], their HSPs were calculated
through Eqs. (19)–(22). The result revealed that the (δD, δP, δH, and δ) of
WOSAL, EKL, BKL, and SKL were (10.5, 4.85, 7.72, and 13.8 cal1/2⋅cm–3/
2
), (10.4, 4.81, 8.23, and 14.1 cal1/2⋅cm–3/2), (10.5, 4.74, 8.05, and 14.0
cal1/2⋅cm–3/2), and (10.7, 4.30, 7.11, and 13.5 cal1/2⋅cm–3/2) respec­
tively (Table 1). When compared to the HSPs of WOSAL, EKL, BKL, and
SKL, calculated based on expanded C9 structure (Table 1), the values
calculated via the quick method displayed a small absolute error of
0.30–0.50 cal1/2⋅cm–3/2 for δD, 0–0.54 cal1/2⋅cm–3/2 for δP, 0.27–1.76
cal1/2⋅cm–3/2 for δH, and 0.50–0.70 cal1/2⋅cm–3/2 for δ. In summary, this
is a straightforward and effective method for measuring lignin HSPs
using the AFGC method according to the empirical C9 formula proposed
in this review. This particularly when the accuracy requirements are not
exceptionally high. For further accuracy, the lignin HSPs were calcu­
lated using the AFGC method and the expanded C9 formula of lignin,
which was measured using a set of detailed analyses of the lignin

7
Q. Ma et al.
structure proposed in our previous study [64].
5. Application of lignin HSPs
5.1. Searching for ideal solvents to dissolve lignin
According to HSPs theory, substances with similar solubility pa­
rameters show high compatibility and are more likely to dissolve in each
other [33]. Therefore, HSPs are crucial tools in the search for solvents to
dissolve lignin [82]. S. Venkatram et al. proposed that when the dif­
ference between the solvent and polymer δ value is <0.978 cal1/2⋅cm–3/2
(2 MPa1/2), the solvent is considered as a good solvent for the polymer.
Conversely, when the difference between the solvent and polymer δ
value is >0.978 cal1/2⋅cm–3/2 (2 MPa1/2), the solvent is classified as a
non-solvent for the polymer [47]. Furthermore, a radius Ro of 3.91 (8
MPa1/2) is the boundary of the Hansen sphere. Solvents that fall inside
the sphere of the polymer are deemed good solvents, and those that fall
outside the sphere are considered non-solvents [47].
The dissolution behavior of ALCELL lignin with a total solubility
parameter of 13.7 cal1/2⋅cm–3/2 in an ethanol/water system was inves­
tigated when the total solubility parameter of solvents decreased
continuously from 22.3 to 12.1 cal1/2⋅cm–3/2, as the ethanol ratio
increased from 0 to 100 % [65]. ALCELL lignin exhibited higher solu­
bility of 17.8 to 18.0 g/L in ethanol/water system with total solubility
parameters ranging from 13.2 to 14.1 cal1/2⋅cm–3/2， which is quite
close to the solubility parameter of lignin (13.7 cal1/2⋅cm–3/2). The
relationship between the solubility of bagasse EMAL solubility in 1, 4-
butanediol/water mixture and the total solubility parameter has been
established [76]. EMAL, with a total solubility parameter of 14.0 cal1/
2
⋅cm–3/2, showed the highest solubility at 1, 4-butanediol/water (80/20,
v/v) solvent, with the total solubility parameter of 14.6 cal1/2⋅cm–3/2.
This further demonstrates that the search for good solvents to dissolve
lignin is possible based on the overall solubility parameters.
In our previous study, we established a dissolution model of WSOAL,
EKL, BKL, and SKL in formic acid/water and acetic acid/water systems.
Furthermore, the relationship between lignin solubility and HSPs had
conformed to a Gaussian curve with a correlation of 0.954 [64].
Significantly, the established dissolution model accurately predicted
lignin solubility in a formic acid/acetic acid/water system. The model
adhered to the solubility parameter theory, overcoming the limitations
of the “like dissolves like” principle in organic acid/water systems, and
provided a concise method for selecting solvent systems, as well as their
ratios, to dissolve or precipitate lignin.
Organosolv lignin, with a solubility parameter of 12.5 cal1/2⋅cm–3/2,
exhibited its maximum solubility in γ-valerolactone (GVL)/water sol­
vents (92–96/8–4, wt%), with similar solubility parameters ranging
from 11.8 to 12.4 cal1/2⋅cm–3/2 [83]. The selected GVL/water systems
with solubility parameters close to those of lignin can be used for lignin
extraction [83]. HSPs reveal a significant correlation with the solubility
of lignin and guaiacol in different tetrahydrofuran(THF)/water systems
[84]. In conclusion, the solubility parameters can determine the THF/
water ratio during the depolymerization of lignin for guaiacol produc­
tion [84].
Lignin exhibited higher solubility in five deep eutectic solvents
(DESs: choline chloride/glycerol, choline chloride/oxalic acid, choline
chloride/malic acid, choline chloride/lactic acid, and choline chloride/
glacial acetic acid) than in common solvents, such as water, ether,
ethanol, chloroform, dimethyl sulfoxide, dioxane, tetrahydrofuran,
acetone, carbon tetrachloride, n-hexane, and ethyl acetate [85]. This is
because the hydrogen-bonding cohesion parameter of DESs is closer to
that of lignin than that of common solvents, and the hydrogen-bonding
force is the most dominant force in determining lignin solubility.
In addition to searching for good solvents to dissolve lignin
depending on the solubility parameters, it is also feasible to enhance its
solubility by modifying the lignin solubility parameters. Hardwood and
softwood lignins are esterified (acetylated, propionated, butyrated,
8
International Journal of Biological Macromolecules 256 (2024) 128506
meleated, and methacrylated) to decrease their HSPs and, therefore,
reduce their difference from that of solvents [77]. As expected, the
solubility of esterified lignin samples (such as styrene-containing ther­
moset resins) in nonpolar solvents was improved [77]. Phloretic acid-
esterified wheat straw soda lignin also displayed lower HSPs and
higher solubility than unesterified lignin [86]. Esterified lignin also
demonstrates a higher onset temperature of thermal degradation and
glass transition temperature, rendering it suitable for unsaturated
thermosetting composites.
5.2. Selecting solvents for lignin depolymerization and extraction
HSPs have been proven helpful in selecting solvents for lignin
depolymerization and extraction from lignocellulosic raw materials
[87,88]. The lignin in hydrolyzed almond shells, with a total solubility
parameter of 14.6 cal1/2⋅cm–3/2, was extracted under acetone/water,
ethanol/water, and dioxane/water systems [74]. The lignin extraction
yield reached its maximum value when the total solubility parameters of
acetone/water, ethanol/water, and dioxane/water were 14.4, 15.6, and
14.0 cal1/2⋅cm–3/2 respectively, which was close to that of lignin. The
degree of lignin removal from enzymatically hydrolyzed cornstalks
tends to increase when the total solubility parameters of lignin and
ethanol/water, 1, 4-dioxane/water, and tetrahydrofuran/water solvents
become more closely matched [75]. The relationship between RED
(calculated based on the HSPs of lignin and various solvents) and the
degree of delignification of acid-hydrolyzed sugarcane bagasse was
established [68]. A linear relationship with a correlation of 0.93856 was
observed between RED and the extent of delignification. The smaller the
difference in the partial solubility parameters between lignin and the
solvents, the higher the degree of delignification [68]. The degree of
lignin removal from biomass and RED demonstrated a correlation of
0.8432 [89]. Similar results were achieved for the depolymerization of
coir and poplar using an alcohol/water/acidic ionic liquid solvent sys­
tem [90]. These results prove that solubility parameters can be used for
solvent screening in biomass depolymerization.
Ionic liquids (IL) have proven efficient for the pretreatment of
biomass, such as carbohydrate dissolution and lignin extraction, under
mild conditions [91]. However, the difficulty in ionic liquid recovery
hinders the broad application of this approach. The solubility and
Kamlet-Taft parameters play an essential role as reference criteria when
selecting suitable organic solvents for extracting IL from the IL-lignin
system [92]. [BMIM]OAc/water solvents (60/40, wt%), with an over­
all solubility parameter of 12.8 cal1/2⋅cm–3/2, reached the maximum
lignin (with an overall solubility parameter of 12.9 cal1/2⋅cm–3/2)
extraction degree for water hyacinth [54]. The theoretical interpreta­
tion, which is based on the solubility parameter concept, agrees with the
experimental results when solvents containing IL are selected for lignin
delignification [93].
In summary, HSPs can be used to select solvents and determine their
ratio for lignin depolymerization and extraction from lignocellulosic and
acid- or enzyme-pretreated raw materials. Notably, during lignin
delignification and extraction, the following processes also occurred:
impregnation of solvents into the raw material cell wall, cleavage of
covalent bonds between lignin and carbohydrates, cleavage of ether
bonds between lignin molecules, and formation of a lignin condensed
structure. Therefore, these complex reactions should be considered
when HSPs are used to select solvents for lignin extraction.
5.3. Designing green solvents for lignin fractionation
The instability in performance caused by polydispersity is a bottle­
neck that restricts high-value applications of lignin. Lignin fractionation,
especially via sequential solvent extraction rooted in lignin solubility,
can potentially obtain lignin fractions with excellent homogeneity and
stable performance [25,94–96]. Two to five solvent systems with
different solubility parameters comprising water [65,97,98] and organic
Q. Ma et al.
solvents, such as hexane, acetone [97–102], ether, dichloromethane,
[103], ethyl acetate [97,99,100,104], methanol [99,100,102–104],
ethanol [65,99,101,104], dioxane [102,104], 2− /n-butanol, n-butanol,
1, 4-butanediol [76], formic acid [105], acetic acid and methyl ethyl
ketone [99], are often used for lignin fractionation. Ajao et al. [99]
fractionated lignin using methanol, ethanol, acetone, methyl ethyl ke­
tone, and ethyl acetate. The result suggested that the molecular weight
of the dissolved fraction is below that of the insoluble fraction. Jiang
et al. [100] dissolved lignin using a mixture of methanol/acetone and
successively added ethyl caproate, ethyl acetate/petroleum ether, and
petroleum ether to reduce the solvent solubility parameters for contin­
uous fractionation. The molecular weight and glass transition temper­
ature of the insoluble lignin fractions decreased successively, whereas
those of the phenolic hydroxyl and carboxyl groups increased. Sun et al.
conducted sequential extraction of kraft-AQ lignin using hexane, diethyl
ether, methylene chloride, methanol, and dioxane (with total solubility
parameters of 7.3, 7.4, 9.7, 14.5, and 10.0 cal1/2⋅cm–3/2, respectively)
[90]. The five resulting fractions exhibited lower polydispersity and
better thermal stability.
Sequential fractionation is essential for obtaining homogeneous and
stable lignin fractions [106]. However, the relationship between the
difference in solubility parameters (between lignin and solvents) and the
characteristics of the fractions has yet to be established. The following
two issues need to be studied to reveal the mechanisms underlying the
solubility parameters of lignin fractionation. The HSPS of the lignin
benzene ring and the side-chain propane structure were different. For
example, the HSPs (δD, δP, δH, and δ) of the benzene ring structure and
side chain propane structure of bamboo kraft lignin are (15.1, 1.23,
1.23, and 15.2 cal1/2⋅cm–3/2) and (8.75, 5.78, 9.85 and 14.4 cal1/2⋅cm–3/
2
), respectively. Although their total solubility parameter is close to each
other, their partial solubility parameters are significantly different.
Thus, the difference between the lignin benzene ring and the side-chain
propane structure during fractionation should be further studied. In
contrast, the three partial solubility parameters are fundamentally
derived from different intramolecular or intermolecular interactions of
dispersion, polar, and hydrogen bond forces. However, differences in
fractionation have not yet been revealed.
5.4. Guiding the preparation of lignin-based composites
Lignin is a renewable and biodegradable aromatic polymer that can
be used to produce high-value thermosetting plastics, thermoplastic
plastics, and other composites or blends [107]. Compared with the
original lignin and polymers, the synergistic effects in lignin polymer
blends can result in superior curing time, durability, and mechanical
performance [108,109]. Importantly, lignin-based polymers cause
minimal or no environmental pollution associated with existing poly­
mers produced by petroleum refining platform products [110]. The
HSPs are practical tools for predicting the compatibility of lignin with
other polymers. The more significant the difference in solubility pa­
rameters between lignin and other polymers, the more difficult it is to
become miscible because more electron-donor/electron-acceptor in­
teractions are needed to bridge the energy gap than in a less miscible
system [107,110].
The total solubility parameter of acetylated pristine lignin (10.2 cal1/
2
⋅cm–3/2) was closer to that of poly lactic acid (PLA) 9.88 cal1/2⋅cm–3/2
when compared to unacetylated pristine lignin (12.9 cal1/2⋅cm–3/2)
[111]. As expected, the acetylated lignin demonstrated enhanced
compatibility with PLA, and the resulting acetylated lignin/PLA film
exhibited well-balanced optical and mechanical properties [111,112].
Alkaline lignin and polyvinyl alcohol (PVA) with total solubility pa­
rameters of 9.82 and 13.5 cal1/2⋅cm–3/2 were mixed to form new blends
[73]. The total solubility parameter of lignin/PVA membranes were
8.56, 9.14, 8.14, and 8.00 cal1/2⋅cm–3/2 when the proportions of incor­
porated lignin were 10, 15, 20, and 25 %, respectively. Interestingly, the
composite membrane with 15 % lignin, which had the highest total
9
International Journal of Biological Macromolecules 256 (2024) 128506
solubility parameter of 9.14 cal1/2⋅cm–3/2, exhibited the highest tensile
strength of 18.86 MPa and a hydrophilic contact angle of 89o [73]. The
blends of alkaline lignin/ acrylonitrile− butadiene− styrene (ABS) pre­
pared by mixing showed the total solubility parameters of 8.51, 9.39,
9.28, and 8.49 cal1/2⋅cm–3/2 when the proportions of incorporated lignin
were 0, 10, 20, and 30 %, respectively [113]. The total solubility pa­
rameters of the alkaline lignin/ABS blends initially increased and then
decreased as the tensile strength and thermal weight loss temperature
increased. These results provide vital support for the preparation of
high-performance alkaline lignin blends containing PVA, ABS, or other
polymers. Haridevan et al. observed that solubility parameters, molec­
ular weight, dielectric constants, and structure determine the dispersion
and solubility of lignin in polyols [114]. Therefore, selecting polyols
depending on their solubility enables the preparation of sustainable,
compatible, and high-performance polyurethanes [114,115]. HSPs have
helped predict and rationalize the behavior of lignin-based rubber
composites [116]. The results highlighted that the affinity between
lignin and rubber could be quantified according to the HSP theory.
6. Conclusions
This review summarizes dissolution-related theories, such as the
Gibbs free energy of dissolution, Flory-Huggins interaction parameters,
and HSPs. HSPs reflect intermolecular or intramolecular interaction
forces and can be useful for a deeper understanding of the lignin
dissolution behavior.
The HSPs of lignin can be calculated using the Hansen dissolution,
IGC, and AFGC methods depending on the lignin solubility in various
solutions, interaction parameters between lignin and solvents, and the
empirical model or the accurate expanded structure of lignin, respec­
tively. However, owing to the complexity of the lignin structure, these
methods are not sufficiently concise or cannot calculate the three partial
solubility parameters. Therefore, we propose a quick method for
measuring the partial and overall solubility parameters of lignin using
the AFGC method based on empirical C9 subunits. The partial and
overall solubility parameters (δD, δP, δH, and δ) of G, S, and H subunits
were calculated as (10.7, 4.29, 7.09, and 13.5 cal1/2⋅cm–3/2), (10.3, 4.93,
8.50, and 14.2 cal1/2⋅cm–3/2), and (10.9, 4.59, 7.60, and 14.1 cal1/
2
⋅cm–3/2), respectively. The HSPs of the lignin were calculated using Eqs.
(19)–(22), once the ratios of the G, S, and H subunits are determined.
HSPs are crucial for guiding most processes related to lignin swelling
and dissolution. At present, HSPs primarily aid in the search for ideal
solvents to dissolve lignin, selection of solvents for lignin depolymer­
ization and extraction, design of green solvents for lignin fractionation,
and preparation of lignin-based composites. Therefore, it is necessary to
focus more attention on lignin HSPs to better guide scientific and
applied research on lignin.
CRediT authorship contribution statement
Qingzhi Ma: Investigation, Methodology, Writing – original draft,
Writing – review & editing. Changqing Yu: Conceptualization, Formal
analysis. Yuran Zhou: Funding acquisition, Supervision, Writing – re­
view & editing. Dinggen Hu: Funding acquisition, Investigation. Jian­
bin Chen: Conceptualization, Formal analysis, Funding acquisition.
Xuejin Zhang: Funding acquisition, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors are grateful for the supporting of Research Start-up
Q. Ma et al. International Journal of Biological Macromolecules 256 (2024) 128506

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