polymers

Review
Brief Overview on Bio-Based Adhesives and Sealants
Solange Magalhães 1, * , Luís Alves 1 , Bruno Medronho 2,3, * , Ana C. Fonseca 4 ,
Anabela Romano 2 , Jorge F.J. Coelho 4 and Magnus Norgren 3
1 CIEPQPF, Department of Chemical Engineering, University of Coimbra, Pólo II—R. Silvio Lima,
3030-790 Coimbra, Portugal; luisalves@ci.uc.pt
2 Faculty of Sciences and Technology (MeditBio), Ed. 8, University of Algarve, Campus de Gambelas,
8005-139 Faro, Portugal; aromano@ualg.pt
3 FSCN, Surface and Colloid Engineering, Mid Sweden University, SE-851 70 Sundsvall, Sweden;
Magnus.Norgren@miun.se
4 CEMMPRE, Department of Chemical Engineering, University of Coimbra, Rua Sílvio Lima-Pólo II,
3030-290 Coimbra, Portugal; ana.clo.fonseca@gmail.com (A.C.F.); jcoelho3@gmail.com (J.F.J.C.)
* Correspondence: solangemagalhaes@eq.uc.pt (S.M.); bfmedronho@ualg.pt (B.M.)




Received: 8 July 2019; Accepted: 8 October 2019; Published: 15 October 2019


Abstract: Adhesives and sealants (AS) are materials with excellent properties, versatility, and simple
curing mechanisms, being widely used in different areas ranging from the construction to the medical
sectors. Due to the fast-growing demand for petroleum-based products and the consequent negative
environmental impact, there is an increasing need to develop novel and more sustainable sources to
obtain raw materials (monomers). This reality is particularly relevant for AS industries, which are
generally dependent on non-sustainable fossil raw materials. In this respect, biopolymers, such as
cellulose, starch, lignin, or proteins, emerge as important alternatives. Nevertheless, substantial
improvements and developments are still required in order to simplify the synthetic routes,
as well as to improve the biopolymer stability and performance of these new bio-based AS
formulations. This environmentally friendly strategy will hopefully lead to the future partial
or even total replacement of non-renewable petroleum-based feedstock. In this brief overview,
the general features of typical AS are reviewed and critically discussed regarding their drawbacks and
advantages. Moreover, the challenges faced by novel and more ecological alternatives, in particular
lignocellulose-based solutions, are highlighted.

Keywords: cellulose; lignin; adhesives; sealants; silicone; adhesion

1. Background
In the construction area different types of adhesives and sealants (AS) are used, such as
polyurethane (PU), epoxies (EP), polyamides (PA), ethylene-vinyl acetate-copolymers (EVA), poly(vinyl
acetate)s (PVAc), silicones, etc. It is estimated that more than 20% of the AS produced worldwide are
applied in the construction field, namely in window and door profiles, pipes and guttering, flooring,
glazing, insulation, building panels, and roofing [1]. In this respect, wood adhesives emerge as a very
important class considering the huge amount consumed worldwide [2–4]. AS also find application in
the electronics, automotive, and energy sectors [5]. Among the different AS those based on silicone
stand out due to their superior features, such as elasticity, versatility, good adhesion, durability, and UV
resistance [5–7].
Globally, the annual amount of manufactured silicone-based AS products is ca. 2,122,000 metric
tons with an estimated revenue of more than €10.6 billion [8]. Despite being clearly a profitable
sector, silicones are quite expensive and non-environmentally friendly, since most of the silicones used

Polymers 2019, 11, 1685; doi:10.3390/polym11101685 www.mdpi.com/journal/polymers

Polymers 2019, 11, 1685 2 of 20

Polymers 2019,are
nowadays 11, obtained
x FOR PEER REVIEW
from non-sustainable and non-renewable fossil-based feedstock and present 2 of 20
a
very limited biodegradability rate [9,10], mainly due to their very low water solubility [11–14].
The fate
The fate ofof silicones
silicones in
in soil
soil is
is largely
largely unknown
unknown butbut some
some studies
studies have
have suggested
suggested that
that in a clay
in a clay
loam, polydimethylsiloxane
loam, polydimethylsiloxane (PDMS) (PDMS) degrades
degrades quite
quite slowly
slowly and
and after
after six
six months
months it
it yields
yields only
only ca.
ca. 3%
3%
of low-molecular-weight water soluble products [11]. This slow degradation rate can be related to
of low-molecular-weight water soluble products [11]. This slow degradation rate can be related to
the high humidity in the soil, since low moisture levels are beneficial for a more efficient and faster
the high humidity in the soil, since low moisture levels are beneficial for a more efficient and faster
degradation [11–14].
degradation [11–14].
Lately there has been an increasing silicone shortage, particularly in the building sector, due to
Lately there has been an increasing silicone shortage, particularly in the building sector, due to
its more recent uses silicone use in the medical area. Strict environmental regulations have also been
its more recent uses silicone use in the medical area. Strict environmental regulations have also
affecting the sector driving a marked growth in consciousness to reduce the fossil dependence and
been affecting the sector driving a marked growth in consciousness to reduce the fossil dependence
mitigate the global pollution [15]. Consequently, the demand for products manufactured from
and mitigate the global pollution [15]. Consequently, the demand for products manufactured from
renewable and sustainable sources, such as biopolymers, has significantly increased, resulting in
renewable and sustainable sources, such as biopolymers, has significantly increased, resulting in
remarkable scientific and industrial advances [16,17]. These advances can lead to a decrease of
remarkable scientific and industrial advances [16,17]. These advances can lead to a decrease of
manufacturing costs while creating new whole “green” businesses opportunities. The more
manufacturing costs while creating new whole “green” businesses opportunities. The more interested
interested reader is guided to the excellent recent review of Heinrich, which discusses the future
reader is guided to the excellent recent review of Heinrich, which discusses the future challenges and
challenges and opportunities of bio-based adhesives [18]. The use of biopolymers in the construction
opportunities of bio-based adhesives [18]. The use of biopolymers in the construction sector is already
sector is already quite significant mainly due to poly(lactic acid) (PLA) and polyhydroxyalkanoates
quite significant mainly due to poly(lactic acid) (PLA) and polyhydroxyalkanoates (PHA), which have
(PHA), which have been driving the fast growth of the bio-based polymer industry in the recent
been driving the fast growth of the bio-based polymer industry in the recent years [19–21]. PHA has
years [19–21]. PHA has also been exploited as bioplastics, fine chemicals, implant biomaterials,
also been exploited as bioplastics, fine chemicals, implant biomaterials, medicines, and biofuels.
medicines, and biofuels. Additionally, PHA have been suggested to improve the robustness of
Additionally, PHA have been suggested to improve the robustness of industrial microorganisms
industrial microorganisms and contribute to the regulation of bacterial metabolism [22]. The
and contribute to the regulation of bacterial metabolism [22]. The applications of PLA are mainly
applications of PLA are mainly as thermoformed products, such as drink cups, take-away food
as thermoformed products, such as drink cups, take-away food trays, containers, and planter
trays, containers, and planter boxes [23]. Despite the significant progress and potential, the
boxes [23]. Despite the significant progress and potential, the biopolymers presently used in AS
biopolymers presently used in AS formulations, such as cellulose derivatives, carrageenans, and
formulations, such as cellulose derivatives, carrageenans, and agarose, are still not fully suitable to
agarose, are still not fully suitable to replace silicone-based ones mainly due to limitations on their
replace silicone-based ones mainly due to limitations on their performance [18].
performance [18].
2. Organosilicon Based Adhesives and Sealants
2. Organosilicon based adhesives and sealants
As mentioned above, silicones are the most commonly used AS [24]. These consist of organosilicon
As mentioned
polymers whose backboneabove, silicones
is mainly are the
composed mostand
of Si–O commonly used(Figure
Si–C linkages AS [24]. These
1) [25]. consist of
Organosilicates
organosilicon
are silicates in polymers
which Si–O whose backbone
is bonded is mainly
to an organic composed
group or evenoftoSi–O andcomplex
a more Si–C linkages
organic(Figure
structure.1)
[25]. Organosilicates are silicates in which Si–O is bonded to an organic group
Such structures are considered to be inorganic because the silicon atom is bonded to carbon throughor even to a more
complex
an oxygen organic structure.
atom unlike Such structures
the organosilicon are considered
structures, whereto besilicon
the inorganic
atom because
bonds the silicon
directly to atom
carbon.is
bonded
The to carbon
organic moietythrough
is typicallyan oxygen
a methylatom
or anunlike the organosilicon
ethyl group [3]. The moststructures, where the
common example silicon
is PDMS,
atom bonds directly to carbon. The organic
a synthetic polymer with a (CH3 )2 SiO repeating unit. moiety is typically a methyl or an ethyl group [3]. The
most common example is PDMS, a synthetic polymer with a (CH3)2SiO repeating unit.
R1 R1 R1

CH3 Si O Si O Si CH3

R2 R2 R2
n

Figure 1. Schematic
Figure 1. Schematic representation
representation of
of aa silicone
silicone molecule.
molecule. R
R11 and
and R
R22 represent
represent different
different substituent
substituent
groups, such as methyl, phenyl, vinyl, hydroxyl, or halogen. Adapted from
groups, such as methyl, phenyl, vinyl, hydroxyl, or halogen. Adapted from [24].[24].

Silicones display the unusual combination of an inorganic chain (similar to silicates and often
Silicones display the unusual combination of an inorganic chain (similar to silicates and often
associated with high surface energy) with organic methyl side groups that are often associated with
associated with high surface energy) with organic methyl side groups that are often associated with
low surface energy [26]. Also, silicones are characterized by high flexibility, a feature that stems from
low surface energy [26]. Also, silicones are characterized by high flexibility, a feature that stems from
the relatively long Si-O and Si-C bond (Si–O ca. 1.64 Å and Si–C ca. 1.88 Å). This allows the silicone
the relatively long Si-O and Si-C bond (Si–O ca. 1.64 Å and Si–C ca. 1.88 Å). This allows the silicone
molecule to adopt many configurations (high configurational entropy) [27]. For instance, while the
molecule to adopt many configurations (high configurational entropy) [27]. For instance, while the
rotational energy of the CH2–CH2 bond in polyethylene is ca. 13.8 kJ/mol, the rotational energy for
the Me2Si–O bond is ca. 3.3 kJ/mol, which can be regarded as “free” rotation [28].
Organosilicon-based polymers containing inorganic structural elements typically display some
remarkable properties, such as excellent resistance to chemicals and adverse weather conditions and
Polymers 2019, 11, 1685 3 of 20
Polymers 2019, 11, x FOR PEER REVIEW 3 of 20

remarkable adhesion
rotational energy of thetoCHsilicate
2 –CH2materials (e.g., ceramics,
bond in polyethylene enamel,
is ca. glass,the
13.8 kJ/mol, concrete, andenergy
rotational others) forand
the
metals
Me2 Si–O (especially
bond is ca.aluminum). Moreover,
3.3 kJ/mol, which can bethese systems
regarded oftenrotation
as “free” present[28].
high heat resistance and
flexibility
Polymers 2019,at
11, low
x FORtemperatures,
Organosilicon-based polymersgood
PEER REVIEW elastic inorganic
containing recovery structural
(resilience), and low
elements shrinkage
typically displayduring
3some
of 20
crosslinking [6].
remarkable properties, such as excellent resistance to chemicals and adverse weather conditions and
remarkable
Typically,
remarkable adhesion
adhesionthe to tosilicate
silicate
crosslinking materials
reaction
materials (e.g.,
(e.g., of ceramics, enamel,
silanesenamel,
ceramics, consists glass,
of
glass, twoconcrete,
concrete,steps, and others)
hydrolysis
and others) and metalsand
and
metals (especially
condensation,
(especially aluminum). aluminum).
as schematically
Moreover, Moreover,
presented these
in Figures
these systems systems
often2 and
presentoften present
3, respectively. high heat
When stored
high heat resistance resistance
under inert
and flexibility andat
flexibility
gas
low(N at low temperatures,
2), the silane good
temperatures, monomers
elasticare good elastic
non-reactive,
recovery recovery
in theand
(resilience), formlow(resilience),
ofshrinkage and
FG–Si–ORduring low shrinkage
wherecrosslinking
–R is the alkyl during
[6].group
crosslinking
and FGTypically,[6].the crosslinking
represents the organic functional
reaction ofgroup.
silanesHowever,
consists ofalkyltriacetoxy silanes can
two steps, hydrolysis andbe hydrolyzed
condensation,
by Typically, the
moisture, originating
as schematically crosslinking
presentedthe reaction
–Si–OH2moiety.
in Figures of silanes
This group When
and 3, respectively. consists of
is alsostored two
knownunder steps,
as “silanol” hydrolysis
inert gasand
(N2can and
), thereadily
silane
condensation,
react to substrates
monomers as schematically presented
or fillers containing
are non-reactive, in the form OH in Figures
groups [29].
of FG–Si–OR 2 and 3, respectively. When stored under
where –R is the alkyl group and FG represents the inert
gas (N 2), the silane monomers are non-reactive, in the form of FG–Si–OR where –R is the alkyl group
organic functional group.OCH However, alkyltriacetoxy silanes can OHbe hydrolyzed by moisture, originating
and FG represents 3
the –Si–OH moiety.the organic
This groupfunctional group.
is also known However,and
as “silanol” alkyltriacetoxy silanes
can readily react can be hydrolyzed
to substrates or fillers
by moisture,
containing OH originating
groups [29]. the –Si–OH moiety. 3 H2OThis group is also known as “silanol” and can readily
R fillers OCH3 OH groups [29].
Si containing R Si OH + 3 CH3OH
react to substrates or
OCH3 OH
OCH3 OH
3 H2O
R=ethyl or methyl R Si OH + 3 CH3OH
R Si OCH3
Figure 2. Representation of the general hydrolysis mechanism of silanes. Adapted from [30].
OCH OH
3
After the hydrolysis of methyl
R=ethyl or alkyltriacetoxy silanes the condensation process may take place. This
results in the adhesion of silanes to the substrates or coupling/dispersing agents to the fillers, as
Figure
Figure 2. Representation
2. Representation ofgeneral
the general hydrolysis mechanism of silanes. Adapted
fromfrom
[30].[30].
schematically illustrated in of the
Figure 3. hydrolysis mechanism of silanes. Adapted

After the hydrolysis

OH of alkyltriacetoxy silanes OH
the condensation
R process
OHmay take place. This
results in the adhesion of silanes to the substrates or coupling/dispersing agents to the fillers, as

n R Si
- H2O
schematically illustrated in Figure 3.
OH R Si O Si ... Si OH

OH OH R OH
OH OH OH R

n R Si OH
- H2O
R Si O + Si ... Si OH
OH OH OH OH OH OH OH
OH OH OH R

Substrate +
OH OH OH OH
Figure 3. Representation of the typical condensation mechanism OH OH
of silanes. OH from [30].
Adapted
Figure 3. Representation of the typical condensation mechanism of silanes. Adapted from [30].

After the hydrolysis of alkyltriacetoxy silanes the condensation process may take place. This results
3. Fundamentals of adhesion Substrate
in the adhesion of silanes to the substrates or coupling/dispersing agents to the fillers, as schematically
The main
illustrated difference
in Figure 3. between sealants and adhesives is that the former typically presents lower
Figure 3. Representation of the typical condensation mechanism of silanes. Adapted from [30].
strength and higher elongation in comparison to adhesives. Sealants are often used to seal joints
3. Fundamentals
between buildingofofcomponents
Adhesion
3. Fundamentals adhesion or materials [29]. Adhesives can be obtained as one-component
products containing
The main all the
difference reactivesealants
between compounds in a unique
and adhesives mixture,
is that and two-component
the former typically presents products
lower
in The main
which and difference
the reactive between
substances in sealants
arecomparison and adhesives
mixed immediately is that the
beforeSealants former
the product typically presents
application. lower
strength higher elongation to adhesives. are often used toJoints often
seal joints
strength
contain aand higher substance
polymeric elongationthat
in comparison
is linked to to adhesives.
the substrate Sealants
via are bonding,
chemical often used to seal joints
physiochemical
between building components or materials [29]. Adhesives can be obtained as one-component products
between
attractions, building
andthe components
physical or materials
interactions. [29]. Adhesivesapplied
can beisobtained as one-component
containing all reactive compoundsThe in away the polymer
unique mixture,isand as important
two-component as its chemical
products in which
products
composition, containing
since itall the reactive
determines the compounds
conditions in a unique
under which mixture,
the and two-component
application must take products
place anda
the reactive substances are mixed immediately before the product application. Joints often contain
in which the
therefore the reactive
possible substances
end-uses. are
It alsomixed immediately
affects other before
factors, such the
as product
the application.
spreading of the Joints often
adhesive on
polymeric substance that is linked to the substrate via chemical bonding, physiochemical attractions,
contain
aandcertaina polymeric
matrix substance
and the area that is
of contact,linked to the
whichisin substrate
turn have via chemical bonding, physiochemical
physical interactions. The way the polymer applied is as aimportant
substantial impact
as its on the
chemical resulting
composition,
attractions,
adhesive and [18].
forces physical interactions. The way the polymer is applied is as important as its chemical
since it determines the conditions under which the application must take place and therefore the
composition,
Adhesives since
oftenit determines
offer a morethe conditions
rigid and durableunder which the application
performance, must
since they are take place
typically usedand
to
therefore the possible end-uses. It also affects other factors, such as the spreading
join two substrates. Despite the differences, AS materials share many features including critical of the adhesive on
a certainrelated
aspects matrixtoandtheirthe area of capacity.
adhesion contact, which
In orderin to
turn have
hold a substantial
surfaces together,impact
fluid ASon are
the preferred
resulting
adhesive forces [18].
Adhesives often offer a more rigid and durable performance, since they are typically used to
join two substrates. Despite the differences, AS materials share many features including critical
aspects related to their adhesion capacity. In order to hold surfaces together, fluid AS are preferred
Polymers 2019, 11, 1685 4 of 20

possible end-uses. It also affects other factors, such as the spreading of the adhesive on a certain matrix
and the area of contact, which in turn have a substantial impact on the resulting adhesive forces [18].
Adhesives often offer a more rigid and durable performance, since they are typically used to join
two substrates.
Polymers Despite
2019, 11, x FOR PEERthe differences, AS materials share many features including critical aspects
REVIEW 4 of 20
related to their adhesion capacity. In order to hold surfaces together, fluid AS are preferred to be
to be applied
applied to a certain
to a certain substrate substrate
in orderin toorder to wet,and
wet, spread, spread, and completely
completely penetrate the penetrate
surfacethe surface
leaving no
leaving no empty
empty voids. Hence,voids. Hence,
AS of low AS of
viscosity arelow viscosity
preferred are
at the preferred
time at the Additionally,
of application. time of application.
in order
Additionally,
to provide strong in order to provide
cohesive strong
strength, the cohesive
AS must strength,
be set or the AS must
solidified by be set or
either solidified
cooling, by either
crosslinking
cooling,
reactions,crosslinking
or via solvent reactions, or viadepending
evaporation, solvent evaporation,
on whether the depending
adhesiveon is whether the adhesive is
hot-melt (thermoplastic),
hot-melt
thermoset, (thermoplastic),
or solvent-based thermoset,
[18,31]. or solvent-based [18,31].
The adhesion
adhesionstrength
strengthis is a measure
a measure of resistance
of the the resistance
of an of an adhesive
adhesive bond tobond to the mechanical
the mechanical removal
removal from a substrate.
from a substrate. It is represented
It is represented as force/area as (MPa
force/area
or N.mm −2
(MPa or ) orN.mm –2 ) or force/length
force/length and commonly and
commonly
named “peel named “peel(N.mm
strength” strength”−1 ) (N.mm ) [24]. A prerequisite
[24]. A–1prerequisite for goodfor good adhesion
adhesion is related is to
related to the
the correct
correct hydrophobic/hydrophilic
hydrophobic/hydrophilic balance balance
betweenbetween the substrate
the substrate and the and the AS [32].
AS [32].
The work of adhesion of a liquid to a solid, WA A,, can
can bebe described
described by by the
the Young–Dupré
Young–Dupré equation
(Equation (1)). It is composed by two measurable parameters; the
(Equation (1)). It is composed by two measurable parameters; the surface tension of the surface tension of the liquid
liquid andand
the
the contact
contact angleangle between
between the liquid
the liquid andand the surface
the surface [33,34].
[33,34].

WA == γγ LG ((1 + cos θ ) . (1)

W A LG 1 + cos θ). (1)
A liquid, such as an AS, cannot wet the surface of a solid substrate unless its surface tension is
A liquid, such as an AS, cannot wet the surface of a solid substrate unless its surface tension is lower
lower than that of the substrate (𝛾 < 𝛾 ). Thus, if a liquid has a higher surface tension than the
than that of the substrate (γLG < γS ). Thus, if a liquid has a higher surface tension than the substrate,
substrate, wetting is not favored [35]. Depending on the substrate different adhesion mechanisms
wetting is not favored [35]. Depending on the substrate different adhesion mechanisms can be observed.
can be observed. For example, metal surfaces can interact by ionic bonds (salt formation), chelate
For example, metal surfaces can interact by ionic bonds (salt formation), chelate complexes on surfaces,
complexes on surfaces, dipole-dipole forces, or hydrogen bonding [24]. On the other hand, plastics
dipole-dipole forces, or hydrogen bonding [24]. On the other hand, plastics (containing oxidized
(containing oxidized surfaces) or wood can react chemically with the AS to form covalent bonds,
surfaces) or wood can react chemically with the AS to form covalent bonds, through the OH groups.
through the OH groups. In this respect, silanes are considered adhesion promoters due to their high
In this respect, silanes are considered adhesion promoters due to their high ability to react with the OH
ability to react with the OH groups of the substrates. Depending on the chemical composition of the
groups of the substrates. Depending on the chemical composition of the substrate different adhesion
substrate different adhesion capacities can be achieved by the silane-based AS, as illustrated in
capacities can be achieved by the silane-based AS, as illustrated in Figure 4.
Figure 4.

Glass
Excellent
Aluminium

Good
Iron/Steel

Moderate
Nickel
Zinc

None
Graphite

Figure 4. Schematic illustration of the effectiveness adhesion of silane-based adhesives and sealants
Figure 4. Schematic illustration of the effectiveness adhesion of silane-based adhesives and sealants
(AS) on different substrates. Adapted from [24].
(AS) on different substrates. Adapted from [24].

4. New generation of adhesives and sealants

The growth of world population and resources consumption, combined with the concerning
challenges of climate change and feedstock scarcity, will rapidly increase the demand for products
Polymers 2019, 11, 1685 5 of 20

4. New Generation of Adhesives and Sealants

The growth of world population and resources consumption, combined with the concerning
challenges of climate change and feedstock scarcity, will rapidly increase the demand for products
manufactured from renewable and sustainable resources. Therefore, it is not surprising that the
development of eco-friendly renewable products in the construction sector, such as in cladding panels,
fiber reinforced polymer composite materials in bridges, and glazing sealants, has considerably
increased in the last years, representing an important driving force for the continued market growth.
For instance, in 2015 the global bio-based construction polymer market was estimated to ca. €10.4
billion [36]. According to the latest Grand View Research Inc. report, this number is expected to
increase to nearly €30 billion in 2024 [37].
Nevertheless, so far, no entirely suitable biopolymer-based alternatives to silicones have
been developed.
In what follows, a brief summary of some of the major achievements is reported mainly focusing
on lignocelluloses, vegetable oils, and proteins.

5. Cellulose-Based Adhesives and Sealants

Cellulose is the most abundant biopolymer on the planet with an estimated annual production
of ca. 1.5 × 1012 ton [38]. Although cellulose meets most of the requirements needed for an adhesive,
due to its semicrystalline structure and complex network of interactions, such as hydrogen bonding and
hydrophobic interactions, cellulose cannot be melted nor it is easily dissolved in common solvents [39–41].
Nevertheless, once the dissolution problem is overcome using for instance cellulose-derivatives, cellulose
represents a very interesting choice in numerous applications, including as components AS agents, due
to its renewability, availability, low cost, and fascinating physicochemical properties.
The first developed cellulose-based adhesive was trimethylsilylcellulose (TMSC). It is a very
well-known cellulose derivative introduced by Schuyten et al. almost 70 years ago (partial structure
on top of Figure 5) [42]. The TMSC was synthesized through the reaction of cellulose with different
organo-chlorosilanes in the presence of pyridine. The 13 C NMR spectrum in Figure 5 reveals the
typical fingerprint of the synthesized TMSC. Only signals for the substituent (0.0–2.0 ppm) and for the
anhydroglucose unit (103.0–60.8 ppm) were found. The authors have obtained TMSC with different
degrees of substitution in a controlled manner, but with low solubility in some relevant organic solvents,
such as in a toluene/ethanol (80/20) mixture. Later some improvements in the TMSC synthesis led to
products soluble in some organic solvents, such as chloroform, 1,1,1-trichloroethane and o-xylene [43].
Generally, the synthesis of TMSC comprises several steps involving cellulose dissolution in a
non-volatile solvent, such as N,N-dimethylacetamide with LiCl, derivatization in homogenous phase,
and phase separation of the obtained TMSC. The product can be finally dissolved in a common
suitable organic solvent (tetrahydrofuran or toluene) [44]. The obtained silylated cellulose is highly
hydrolysable in the presence of water or another hydroxylated compound. Additionally, polymer
crosslinking can be achieved as a result of either some secondary reactions of the trimethylchlorosilane
itself, or due to the presence of some impurities in the chlorosilane, such as higher chlorinated silanes.
The latter are known to be considerably more reactive than trimethylchlorosilane [43]. The main
challenge is to control the crosslinking process, enabling the reaction of the crosslinker (chlorosilane)
with the OH groups of the substrate.
typical fingerprint of the synthesized TMSC. Only signals for the substituent (0.0–2.0 ppm) and for
the anhydroglucose unit (103.0–60.8 ppm) were found. The authors have obtained TMSC with
different degrees of substitution in a controlled manner, but with low solubility in some relevant
organic solvents, such as in a toluene/ethanol (80/20) mixture. Later some improvements in the
Polymers
TMSC 2019, 11, 1685 led to products soluble in some organic solvents, such as chloroform,
synthesis 6 of 20

1,1,1-trichloroethane and o-xylene [43].

Polymers 2019, 11, x FOR PEER REVIEW 6 of 20

Generally, the synthesis of TMSC comprises several steps involving cellulose dissolution in a
non-volatile solvent, such as N,N-dimethylacetamide with LiCl, derivatization in homogenous
phase, and phase separation of the obtained TMSC. The product can be finally dissolved in a
common suitable organic solvent (tetrahydrofuran or toluene) [44]. The obtained silylated cellulose
is highly hydrolysable in the presence of water or another hydroxylated compound. Additionally,
polymer crosslinking can be achieved as a result of either some secondary reactions of the
trimethylchlorosilane itself, or due to the presence of some impurities in the chlorosilane, such as
higherFigure 5. 1313C NMRsilanes.
chlorinated spectrumTheof trimethylsilylarecellulose (degree of substitution, DS ≈ more
0.43) in reactive
DMSO-d6 ,
Figure 5. C NMR spectrum of latter
trimethylsilylknown to (degree
cellulose be considerably
of substitution, DS ≈ 0.43) in than
R means trimethylsilyl group or H according to DS. Reproduced from [45,46] with permission from
trimethylchlorosilane
DMSO-d6, R means[43]. The main group
trimethylsilyl challenge
or Hisaccording
to control to the
DS. crosslinking
Reproduced process,
from [45,46] enabling
with the
Wiley and Copyright Clearance Center, 2008.
reaction of the crosslinker
permission (chlorosilane)
from Wiley and with the Center,
Copyright Clearance OH groups
2008. of the substrate.
Another interesting route to obtain cellulose-based
Another interesting route to obtain cellulose-based compounds with compounds with potential
potential application
application as as AS
AS
was reported by Stiubianu et al. [47]. The authors have combined a cellulose derivative
was reported by Stiubianu et al. [47]. The authors have combined a cellulose derivative (cellulose acetate, (cellulose
acetate,
DS ≈ 2.5) DS
with≈different
2.5) withmolardifferent
fractionsmolar fractions of poly[dimethyl(methyl-H)siloxane].
of poly[dimethyl(methyl-H)siloxane]. A dehydrocoupling A
dehydrocoupling reaction between the Si–H and the C–OH groups occurred
reaction between the Si–H and the C–OH groups occurred in the presence of the Karstedt’s catalyst, in the presence of the
Karstedt’s
leading catalyst,
to the leading
formation to the formation
of Si–O–C of Si–O–C
bonds (Figure bonds
6). The (Figure
reaction 6). The reaction
proceeded at room proceeded
temperature, at
room temperature, which is quite beneficial for industrial proposes. Nevertheless,
which is quite beneficial for industrial proposes. Nevertheless, an important limitation of this procedure an important
limitation
is related toofthethis procedure
catalyst, whichisshould
relatedbetomaintained
the catalyst,awaywhich
fromshould be acetate
cellulose maintained
or otheraway from
material
cellulose acetate
containing OH groupsor other
duematerial containing
to it enhanced OH groups
reactivity due mixed
after being to it enhanced reactivity
with the other after[47].
reagents being
mixed with the other reagents [47].
OCOCH3 OCOCH3
OCOCH3
O CH OCO OCOCH3 O CH OCO
3 3
O O
CH3OCO O HO O
OH O OCOCH3 O
OCOCH3 OH
+
CH3 CH 3 CH3 CH3
H 3C O O O CH 3
Si Si x Si y Si
CH3 CH 3 H CH3

Karstedt catalyst

OCOCH3 O OCOCH3 O OCOCH3 OCOCH3 O OCOCH3

O CH3OCO O CH3OCO O CH3OCO O CH3OCO
O O O O
O O O O
CH3OCO O CH3OCO O HO O CH3OCO OCOCH3 O
O OH OCOCH3 O OCOCH3 OH O
CH3 CH3 CH3 CH3 CH3 CH3 H 3C CH3 CH3 CH3
O O O O O O O O O O O O O O O
Si Si Si Si Si Si Si Si Si Si Si Si Si
x Si y
CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3
CH3
O OCOCH3 OH OH O OCOCH3 OH
OCOCH3
CH3OCO O CH3OCO O CH3OCO O CH3OCO O
O O O O
O O O O
O CH3OCO O CH3OCO O CH3OCO O CH3OCO
O OCOCH3 O OCOCH3 OCOCH3 O OCOCH3
O

Figure 6. Cellulose silylation and the subsequent regeneration using acid vapor. Reproduced from [47]
Figure
with 6. Cellulose
permission fromsilylation
Springerand
andthe subsequent
Copyright regeneration
Clearance Center, using
2010. acid vapor. Reproduced from
[47] with permission from Springer and Copyright Clearance Center, 2010.

In a related work by Klemm et al., silylated cellulose was prepared in heterogeneous phase
reaction in the presence of ammonia-saturated polar aprotic solvents [48]. Multilayered
supramolecular silylated cellulose structures were formed after applying a Langmuir–Blodgett
technique. These ultrathin films may be also suitable for AS purposes.
Robles et al. have successfully modified the surface of cellulose nanofibrils with aminopropyl
Polymers 2019, 11, 1685 7 of 20

In a related work by Klemm et al., silylated cellulose was prepared in heterogeneous phase reaction
in the presence of ammonia-saturated polar aprotic solvents [48]. Multilayered supramolecular silylated
cellulose structures were formed after applying a Langmuir–Blodgett technique. These ultrathin films
may be also suitable for AS purposes.
Robles et al. have successfully modified the surface of cellulose nanofibrils with aminopropyl
triethoxysilane (ATS) [49]. The process is suggested to occur in four steps, but it basically involves a
chemical grafting on the hydroxyl groups of cellulose chains (Figure 7). The reaction was performed at
105 ◦ C, which is not suitable for AS materials. However, some other works have demonstrated the
possibility of curing of ATS at room temperature [50]. The use of ATS as a curing reagent for cellulosic
raw materials
Polymers appears
2019, 11, as REVIEW
x FOR PEER an interesting approach for bio-based AS, due to the possibility7 of chemical
of 20
crosslinking between ATS and biopolymers (contained in the AS) or surfaces containing OH groups.

EtO
NH 2
Si
EtO
O CH3 O
O CH3
Si OH + Ethanol O OH
Si O CH3 + H2O H2N HO O OH
H2N O OEt
O OH NH 2 EtO OEt
H3C
H3C O O NH 2 Si

3-aminopropyl(triethoxysilane) Activated ATS OH

n
(ATS) EtO EtO
NH 2 + H2O
Si Si Si NH 2
EtO
O O O O O O O

Cellulose Nanofibrils

R1 R2 R3 R4

OH
NH 2 HO OH
NH 2 Si

HO HO
OH NH 2
O CH3 Si Si NH 2
Si OH Si
+ Ethanol HO
Si O CH3 + EtOH H2N O O O O O O O
H2N OH
O
H3C Cellulose Nanofibrils

Figure 7. Schematic illustration of the reactions/interactions between aminopropyl triethoxysilane

Figure 7. Schematic illustration of the reactions/interactions between aminopropyl triethoxysilane
(ATS) and cellulose nanofibrils. Adapted from [49].
(ATS) and cellulose nanofibrils. Adapted from [49].

Farnaz
FarnazEslah
Eslahetet al.
al. have studiedthe
have studied theformation
formation of adhesives
of adhesives composed
composed of acetylated
of acetylated cellulose
cellulose
nanocrystals (ACNC), soybean flour (SF), and acetylated soybean flour (ASF) [51].
nanocrystals (ACNC), soybean flour (SF), and acetylated soybean flour (ASF) [51]. The acetylation ofThe acetylation of
thethe
cellulose
cellulosenanocrystals
nanocrystals reduces thecrystallinity
reduces the crystallinity of cellulose.
of cellulose. The The SF reaction
SF reaction with anhydride
with acetic acetic anhydride
converts
convertsthethe
amine andand
amine hydroxyl groups
hydroxyl groupsintointo
amides
amidesandand
esters, respectively.
esters, Primary
respectively. andand
Primary secondary
secondary amines in the ASF-based adhesive formulation disappeared, which
amines in the ASF-based adhesive formulation disappeared, which may suggest the reduction of the may suggest the
reduction
amine contentofandtheformation
amine content andInformation
of amides. of amides. In (PEI)/ACNC/NaOH
the SF/polyethylenimine the SF/polyethylenimineformulation
functional groups, such as hydroxyl, carboxyl, and amines can react and createand
(PEI)/ACNC/NaOH formulation functional groups, such as hydroxyl, carboxyl, amines bonds
hydrogen can with
react and create hydrogen bonds with the hydroxyl and carbonyl groups of the ACNC. In the
the hydroxyl and carbonyl groups of the ACNC. In the ASF/PEI/NaOH adhesives, the amines of
ASF/PEI/NaOH adhesives, the amines of the PEI reacted with the esters of the ASF to form amides.
the PEI reacted with the esters of the ASF to form amides. By mixing the ASF formulations with
By mixing the ASF formulations with NaOH and PEI a reduction in water evaporation in the
NaOH and PEI
adhesives a reduction
during hot-pressingin water evaporation
was observed. in bio-based
These the adhesives during
adhesives hot-pressing
were wasthe
found to fulfil observed.
These bio-basedfor
requirements adhesives were found
interior plywood, to fulfil
according to the requirements
the American for interior
National plywood, according to the
Standards.
American National Standards.
Khanjanzadeh et al. have prepared silylated CNC from the reaction of
Khanjanzadeh et al. have prepared
3-aminopropyltriethoxysilane silylated
(APTES) with CNCCNC from the
in aqueous reaction
medium of 3-aminopropyltriethoxysilane
(Figure 8) [52].
(APTES) with CNC in aqueous medium (Figure 8) [52].
ASF/PEI/NaOH adhesives, the amines of the PEI reacted with the esters of the ASF to form amides.
By mixing the ASF formulations with NaOH and PEI a reduction in water evaporation in the
adhesives during hot-pressing was observed. These bio-based adhesives were found to fulfil the
requirements for interior plywood, according to the American National Standards.
Polymers 2019, 11, 1685
Khanjanzadeh et al. have prepared silylated CNC from the reaction8 of of 20
3-aminopropyltriethoxysilane (APTES) with CNC in aqueous medium (Figure 8) [52].

Figure 8. Reaction scheme between 3-aminopropyltriethoxysilane (APTES) and cellulose nanocrystals

(CNC) in the presence of water. Reproduced from [53] with permission from Elsevier and Copyright
Clearance Center, 2018.

The silylation of CNC was carried out through the physical adsorption, chemical grafting,
and condensation reaction between −OH groups of the CNC and the silanol groups of APTES.
The modified CNC were incorporated in urea-formaldehyde adhesives and their performance
investigated. It was observed that the incorporation of modified-CNC improves the mechanical
and other physical properties of the medium density fiberboard panels, while the formaldehyde
emission significantly decreases.
Draman et al. have prepared nanocomposites of cellulose-based adhesive and polypyrrole (PPy)
via a colloidal dispersion method [54]. Cellulose was chemically modified with epoxy to display
adhesion properties. Different ratios of toluenesulfonic acid (TSA)-doped PPy with epoxypropyl
cellulose were tested and their electrical and conductivity properties evaluated as summarized in
Table 1.

Table 1. Thermal conductivity and electrical conductivity of the nanocomposites synthesized [54].

Electrical Conductivity Thermal Conductivity, k

Samples
(Scm−1 ) (Wm−1 K−1 )
PPy 5.422 × 10−6 0.343
TSA-doped PPy, pH 1 8.422 × 10−3 0.432
TSA-doped PPy, pH 3 1.407 × 10−3 0.422
TSA-doped PPy, pH 4 9.955 × 10−4 0.406
TSA-doped PPy:EC (80:20) 1.076 × 10−3 0.399
TSA-doped PPy:EC (70:30) 3.751 × 10−5 0.371
TSA-doped PPy:EC (50:50) 3.350 × 10−8 0.237

Based on the data shown in Table 1, PPy and TSA-doped PPy gave electrical conductivities in the
semiconductive range. The delocalization of π electrons along the polymeric backbone, co-existing
with low ionization potentials and high electron affinities, led to unique electrical properties of the
conjugated nanocomposites including PPy and TSA-doped PPy [55]. The authors have also shown
a decrease in electrical conductivity in the cellulose-based adhesives, since cellulose works as an
insulator. This non-metal material causes interface resistance, which is believed to also be the blockage
for the thermal conductivity [56]. The thermal conductivity displayed suggests that this cellulose-based
material can potentially be used in small electronic devices.
Polymers 2019, 11, 1685 9 of 20

6. Starch Based Adhesives and Sealants

Starch and cellulose are two very similar polysaccharides but with different configurations of the
linkages between the anhydroglucose units. While starch consists of two types of molecules amylase
and amylopectin having the so called α configuration, cellulose has β configuration of the linkages
forming extended ribbon-like conformations. This conformational difference not only makes starch
less crystalline than cellulose but also more easily solubilized.
Biodegradable composites with high robustness and elastic properties based on corn starch and
PDMS have been developed by Ceseracciu et al. [57]. The authors reported a facile method for preparing
a biodegradable elastomer incorporating large amounts of unmodified corn starch (exceeding 80%
by volume) in acetoxy-polyorganosiloxane thermosets. As can be observed in Figure 9, the degree
of transparency of the obtained films change significantly with the amount of starch but overall
the materials are quite mechanically robust. It was also demonstrated that the naturally adsorbed
moisture on the starch surface enables the auto-catalytic rapid hydrolysis of the polyorganosiloxane
forming Si–O–Si networks. Additionally, corn starch granules have also excellent compatibility
with the addition-cure polysiloxane chemistry. Regardless of the starch concentrations used, all the
developed bio-elastomers have hydrophobic surfaces with low friction coefficient and much less water
Polymers 2019, 11, x FOR PEER REVIEW 9 of 20
uptake capacity than thermoplastic starch. The bio-elastomers are biocompatible and estimated to
biodegrade
biocompatible rapidly even in an
and estimated toaquatic environment,
biodegrade thusinavoiding
rapidly even oneenvironment,
an aquatic of the main thus
drawbacks
avoidingof
standard silicones [57].
one of the main drawbacks of standard silicones [57].

Figure 9. Photographs of bio-elastomers containing (a) 50 wt% and (b) 70 wt% of unmodified corn
Figureand
starch 9. Photographs
examples of of bio-elastomers
their transparencycontaining (a) 50 wt% and
in (c,d), respectively. (b) 70from
Adapted wt%[57]
of unmodified corn
with permission
starch and examples of their transparency in (c) and (d), respectively.
from American Chemical Society and Copyright Clearance Center, 2015. Adapted from [57] with
permission from American Chemical Society and Copyright Clearance Center, 2015.
Sugih et al. have studied an alternative method to synthesize poly-(ε-caprolactone) grafted starch
Sugih etanal.interesting
co-polymers, have studied an to
material alternative
be used asmethod to synthesize
compatibilizer poly-(ε-caprolactone)
in starch-polymer grafted
blends [58]. For each
starch co-polymers, an interesting material to be used as compatibilizer in ◦starch-polymer
experiment, pre-dried corn starch and dimethylsulfoxide were stirred at 70 C for about 3 h until blendsa
[58]. solution
clear For eachwas experiment,
formed. Thenpre-dried corn starch and (HMDS)
hexamethyldisilazane dimethylsulfoxide
was added were
to the stirred at 70mixture
gelatinized °C for
about
to 3 h the
initiate until a clear solution
silylation reaction.was
Theformed.
purposeThen hexamethyldisilazane
of silylation (HMDS)
was to make starch morewas added to the
hydrophobic by
partial substitution of the OH groups by trimethylsilyl groups. After 2–4 h reaction time, make
gelatinized mixture to initiate the silylation reaction. The purpose of silylation was to toluenestarch
was
more hydrophobic
added to solubilize bythepartial substitution
precipitated of the OH
and partially groups
silylated by trimethylsilyl
starch. The reaction groups.
scheme is After
shown2–4in
h
reaction
Figure 10. time, toluene was added to solubilize the precipitated and partially silylated starch. The
reaction scheme is shown in Figure 10.

H2C OH H2C OR

H O H H O H
H3C CH3 DMSO
H H H
OH H + H3C Si N Si CH3 OH H + NH3
H3C CH3

H OH H OH

Starch Hexamethyldisilazane
(R=H or Si(CH3)3
Silylated Starch
[58]. For each experiment, pre-dried corn starch and dimethylsulfoxide were stirred at 70 °C for
about 3 h until a clear solution was formed. Then hexamethyldisilazane (HMDS) was added to the
gelatinized mixture to initiate the silylation reaction. The purpose of silylation was to make starch
more hydrophobic by partial substitution of the OH groups by trimethylsilyl groups. After 2–4 h
reaction2019,
Polymers time, toluene was added to solubilize the precipitated and partially silylated starch.
11, 1685 The
10 of 20
reaction scheme is shown in Figure 10.

H2C OH H2C OR

H O H H O H
H3C CH3 DMSO
H H H
OH H + H3C Si N Si CH3 OH H + NH3
H3C CH3

H OH H OH

Starch Hexamethyldisilazane
(R=H or Si(CH3)3
Silylated Starch

Figure 10. Schematic illustration of the reactions involved in the silylation of starch with hexamethyldisilazane
Figure 10.
(HMDS). Schematic
Adapted illustration
from [58], of the from
with permission reactions
Elsevierinvolved in the
and Copyright silylation
Clearance of starch
Center, 2009. with
hexamethyldisilazane (HMDS). Adapted from [58], with permission from Elsevier and Copyright
Clearance
Note thatCenter, 2009. silylated starch is more hydrophobic than pristine starch and thus more
the partially
soluble in organic solvents. This decrease in hydrophilicity allows a more efficient reaction with
Note that the
ε-caprolactone [59].partially silylated starch
The synthesized is more
product hydrophobic
has been suggestedthanas pristine starch
a potential and thus more
compatibilizer in
soluble in organic solvents.
starch-polymer blends [58,59]. This decrease in hydrophilicity allows a more efficient reaction with
ε-caprolactone [59].used
Wei et al. have The hexadecyltrimethoxysilane
synthesized product has been (HDS),suggested
a siloxaneaswith
a potential compatibilizer
a long hydrocarbon in
chain,
starch-polymer blends [58,59].
to prepare hydrophobic modified starch nanocrystals (SNC). The use of long side hydrocarbon chain of
HDS Wei et al. have
was expected used hexadecyltrimethoxysilane
to provide an efficient and simple way(HDS), a siloxane
to improve with a long hydrocarbon
the hydrophobicity of SNC [60].
chain,
The SNCtowere
prepare
preparedhydrophobic modified
by acid hydrolysis starchmaize
of waxy nanocrystals (SNC).toThe
starch according use ofoflong
the method side
Angellier
hydrocarbon chain of HDS was expected to provide an efficient and simple way to
et al [61]. Afterwards, the silane modified SNC was prepared by physical adsorption, chemical grafting,improve the
hydrophobicity of
Polymers 2019, 11, x FOR SNC [60].
PEER REVIEW The SNC were prepared by acid hydrolysis of
and condensation reactions between the hydroxyl and silanol groups, as represented in Figure 11.waxy maize starch
10 of 20
according to the method of Angellier et al [61]. Afterwards, the silane modified SNC was prepared
by physical adsorption, chemical grafting, and condensation reactions between the hydroxyl and
silanol groups, as represented in Figure 11.

HO Si O Si O Si OH
O O O

H2O H H H H H H HO Si O Si O Si OH
O OH H2 O
O O O O O O
Si Si
O HO
O OH
Starch nanocrystal Starch nanocrystal

Figure 11. Reaction scheme between hexadecyltrimethoxysilane (HDS) and starch nanocrystals (SNC).
Figure 11. Reaction scheme between hexadecyltrimethoxysilane (HDS) and starch nanocrystals
Adapted from [60], with permission from Elsevier and Copyright Clearance Center, 2016.
(SNC). Adapted from [60], with permission from Elsevier and Copyright Clearance Center, 2016.
As can be observed in Figure 12, the hydrophobicity and the hydrophobic stability of the modified
SNC As
wascan be to
found observed
increasein Figure
with 12, the
the HDS hydrophobicity and the hydrophobic stability of the
content.
modified SNC was found to increase with the HDS content.

Figure 12. Photographs of a water drop on the surface of SNC and silylated SNC. Adapted from [60],
 Figure 11. Reaction scheme between hexadecyltrimethoxysilane (HDS) and starch nanocrystals
(SNC). Adapted from [60], with permission from Elsevier and Copyright Clearance Center, 2016.

As2019,
Polymers can11,be1685
observed
in Figure 12, the hydrophobicity and the hydrophobic stability of the
11 of 20
modified SNC was found to increase with the HDS content.

Figure 12. Photographs of a water drop on the surface of SNC and silylated SNC. Adapted from [60],
Figure 12. Photographs of a water drop on the surface of SNC and silylated SNC. Adapted from [60],
with permission from Elsevier and Copyright Clearance Center, 2016.
with permission from Elsevier and Copyright Clearance Center, 2016.
The dispersion of modified SNC was significantly improved due to the introduction of the long
chainThe dispersion of
hydrocarbon. modifiedthe
Moreover, SNC was significantly
hydrophobically improved
modified SNCdue showto the introduction
great compatibility of the
withlong
the
chain hydrocarbon.
non-polar solvents. Moreover, the hydrophobically modified SNC show great compatibility with the
non-polar solvents.
7. Lignin Based Adhesives and Sealants
7. Lignin based adhesives and sealants
Lignin is one of the most abundant biopolymers on earth and makes up 15% to 30% of the cell
Lignin is one plants.
walls of terrestrial of the most abundant
It is an inexpensivebiopolymers
renewableon earth and
resource makes
which up 15%
possesses to 30% ofattractive
numerous the cell
walls of terrestrial plants. It is an inexpensive renewable resource which possesses
properties, such as high thermal stability, biodegradability, high carbon content, antioxidant activity, numerous
attractive
and favorable properties,
stiffness. such
The use as ofhigh
ligninthermal stability,
in different biodegradability,
applications has been a topichigh carbon for
of interest content,
many
antioxidant activity,
researchers [4,62]. and favorable stiffness. The use of lignin in different applications has been a
topicNowadays,
of interest for many researchers [4,62].
most of the aromatic feed chemicals originate from non-renewable fossil sources.
Nowadays,
It is believed thatmost of could
lignin the aromatic
be a very feed chemicals
appealing originate
future sourcefrom non-renewable
of natural polyphenolsfossilto
sources.
compete It
is believed that lignin could be a very appealing future source of natural polyphenols
and eventually substitute petroleum-based precursors. Despite its great potential to be used in the to compete
and eventually
preparation substitute
of novel petroleum-based
materials, lignin finds precursors. Despite itsIn
limited applications. great potential
the case of thetopulp
be used
and in the
paper
preparation of novel materials, lignin finds limited applications. In the case of
industry less than 2% of the overall produced lignin is employed as concrete additives, stabilizing or the pulp and paper
industry
dispersant less than 2%
agents. Theofmajority
the overall produced
of what lignin
remains is employed
is simply disposedas concrete
or burnt additives, stabilizing
as a low-grade fuel. or
dispersant agents.
Stiubianu The
et al. majority
have of what
used lignin toremains
produceisan simply disposed
elastomer with or burnt asproperties
improved a low-grade forfuel.
energy
harvesting and actuation [63]. In their work, lignin additions that ranged from 0% to 50% by weight
relative to siloxane do not act as stiffener for the siloxane but rather act as a bulk filler material.
The systems were prepared using well-known and simple methods applied in silicone chemistry,
preserving the softness and low value of Young’s modulus, characteristic of silicones. The developed
elastomers have low water sorption due to their hydrophobic features and low dielectric constant.
These properties were enhanced with the lignin content added to the formulation. Despite the presence
of lignin, which could facilitate the conduction of electrical currents, all the samples were observed to
present low conductivity, thus behaving as very interesting insulators.
Feldman et al. have developed PU materials modified with lignin [64]. The results obtained
suggest that lignin acts as a reinforcing agent adding rigidity to the polymeric matrix. This was further
confirmed by the increase in toughness and shore of the blended sealants. The curing mode of PU was
also observed to change with the addition of lignin. Moreover, the initial setting time was reduced with
the addition of lignin, but the rate of curing was found to remain constant. This suggests that the matrix
is hardened in direct proportion to the amount of lignin present in the blend. It was hypothesized
that the incorporation of lignin may contribute to an increase in the degree of crosslinking of the PU
sealant [64].
Another interesting study was reported by Scarica et al., where a novel lignin-based thermosetting
polyester (PE) coating system was developed. The material was synthesized via the functionalization
of softwood lignin with succinic anhydride (SAn) (Figure 13) [65]. Materials containing different ratios
of SAn/lignin were prepared and subsequently employed as macromolecular building blocks for the
fully cross-linked lignin-based PE coatings (Figure 14).
 functionalization of softwood lignin with succinic anhydride (SAn) (Figure 13) [65]. Materials
degree of crosslinking of the PU sealant [64].
containing different ratios of SAn/lignin were prepared and subsequently employed as
Another interesting study was reported by Scarica et al., where a novel lignin-based
macromolecular building blocks for the fully cross-linked lignin-based PE coatings (Figure 14).
thermosetting polyester (PE) coating system was developed. The material was synthesized via the
functionalization of softwood ligninO withOsuccinicO anhydride (SAn)lignin
(Figure 13)O [65]. Materials
lignin
containing
Polymers different
2019, 11, 1685 MeO
ratios of SAn/lignin were prepared and subsequently employed 12 OH
of as
20
MeO O
macromolecular building blocks forOH the fully cross-linked lignin-based PE coatings (Figure 14).
lignin O
lignin O O lignin O lignin O
O
lignin O lignin
MeO OH OH
MeO OH O
OH
lignin O
lignin
Figure 13. Schematic representation of the functionalization
lignin O reaction between lignin and succinic
lignin O (SAn) to produce succinylated lignin. Adapted from [65],
anhydride OH with permission from American
OH and Copyright Clearance Center, 2018.
Chemical Society
Figure 13. Schematic representation of the functionalization reaction between lignin and succinic
Figure 13. (SAn)
This work
anhydride Schematic representation
introduces
to produce of the
asuccinylated functionalization
straightforward
lignin. toreaction
strategyfrom
Adapted develop
[65], between
with new lignin andAmerican
succinic
high-lignin-content
permission from PE
anhydride
thermosetting (SAn) to
systems
Chemical Society produce
andthat succinylated
may be
Copyright lignin.
suitableCenter,
Clearance Adapted from
for bio-derived
2018. [65], with permission from American
coatings and adhesive alternatives [66].
Chemical Society and Copyright Clearance Center, 2018.

This work introduces a straightforward strategy to develop new high-lignin-content PE

thermosetting systems that may be suitable for bio-derived coatings and adhesive alternatives [66].

Figure 14. Process of curing the succinylated lignin in a substrate. Adapted from [65], with permission
from American Chemical Society and Copyright Clearance Center, 2018.
Figure 14. Process of curing the succinylated lignin in a substrate. Adapted from [65], with
permission
This work from American
introduces a Chemical Society and
straightforward Copyright
strategy to Clearance
develop Center, 2018.
new high-lignin-content PE
thermosetting systems that may be suitable for bio-derived coatings and adhesive alternatives [66].
In another interesting report, lignin-based anticorrosive coatings have been developed after
In another
Figure interesting
14. Process report, succinylated
of curing lignin-basedlignin
anticorrosive coatings have been
[65],developed
lignin fractionalization (LF) the
and silanization in a substrate.
(LF-S) [67]. ForAdapted from
the silanization with
reaction,
after lignin
Polymers 2019, fractionalization
11, x FOR PEER REVIEW (LF) and silanization (LF-S) [67]. For the
permission from American Chemical Society and Copyright Clearance Center, 2018. silanization reaction,
12 of 20
1-isocyanate-3-trimethoxysilylpropane (ITMSP) and dibutyltin dilaurate (DBTDL) have been used,
1-isocyanate-3-trimethoxysilylpropane
as schematically presented inreport,
In another interesting 15.(ITMSP) and
Figurelignin-based dibutyltincoatings
anticorrosive dilauratehave
(DBTDL)
been have been used,
developed after
as schematically presented in Figure 15.
lignin fractionalization (LF) and silanization (LF-S) [67]. For the silanization reaction,
lignin OH
O
OMe
Δ, t
+ lignin O C N Si OMe
MeO DBTDL
OMe
H
MeO Si NCO
MeO

Figure 15. Schematic representation of the silanization of lignin. Adapted from [67], with permission
Figure
from 15. Schematic
American representation
Chemical Society andofCopyright
the silanization of lignin.
Clearance Adapted
Center, 2019. from [67], with permission
from American Chemical Society and Copyright Clearance Center, 2019.
The authors report four different methods to obtain lignin-based coatings. The first two methods
The authors
comprise report deposition
solution-based four different methods
of LF to obtain
and LF-S, followedlignin-based coatings.
by appropriate The treatment.
thermal first two
methods comprise solution-based deposition of LF and LF-S, followed by appropriate
The third coating was obtained from a formulation containing LF-S and acetic acid, which worked thermal
treatment. The third coating was obtained from a formulation containing LF-S and acetic
as a co-crosslinking agent. Acetic acid was selected in order to determine the viability of using acid, H+
which
worked
as as to
catalyst a promote
co-crosslinking agent. Acetic
the hydrolysis acid was selected
and condensation in order
reactions of the to determine
methoxy the in
groups viability of
silanized
using H + as catalyst to promote the hydrolysis and condensation reactions of the methoxy groups in
lignin, thereby envisaging improved adhesion to the target metallic substrates (Figure 16). In the last
silanized lignin,
formulation, the thereby envisaging
cross-linking improved orthosilicate
agent tetraethyl adhesion to the target
(TEOS) wasmetallic substrates (Figure
also incorporated in order16).
to
In the lastitsformulation,
evaluate ability to actthe cross-linking agenthybrid
as organic-inorganic tetraethyl orthosilicate
crosslinker in the (TEOS) was also
lignin-based incorporated
coating system.
in order to evaluate its ability to act as organic-inorganic hybrid crosslinker in the lignin-based
coating system.
lignin

lignin lignin
C O

H N
worked as a co-crosslinking agent. Acetic acid was selected in order to determine the viability of
using H+ as catalyst to promote the hydrolysis and condensation reactions of the methoxy groups in
silanized lignin, thereby envisaging improved adhesion to the target metallic substrates (Figure 16).
In the last formulation, the cross-linking agent tetraethyl orthosilicate (TEOS) was also incorporated
Polymers
in order to 11,
2019, 1685
evaluate 13 of 20
its ability to act as organic-inorganic hybrid crosslinker in the lignin-based
coating system.
lignin

lignin lignin
C O

H N

O O

C O C O

H N H N
Si
O O

Si Si
O
O O
OH OH OH OH OH O OH O
Δ

H+ lignin-coated metal surface

metal substrate

Figure 16. Schematic representation of the covalent bonding between lignin fractionalization and
Figure 16. Schematic
silanization (LF-S) andrepresentation of promoted
metal substrate the covalent bonding
by the between
presence lignin
of acetic acidfractionalization and
and heat. Adapted
silanization (LF-S) and metal substrate promoted by the presence of acetic acid and heat. Adapted
from [67], with permission from American Chemical Society and Copyright Clearance Center, 2019.
from [67], with permission from American Chemical Society and Copyright Clearance Center, 2019.
The latter method, where TEOS was used as a cross-linker, was found to be the most promising
due toThe latter
the more method, where TEOS
rigid structure was used
originated as athe
from cross-linker,
presence of was
thefound to be phase
inorganic the mostthatpromising
partially
due to the more rigid structure originated from the
hinders macromolecular movement in the cross-linker system [67].presence of the inorganic phase that partially
hinders macromolecular movement in the cross-linker system [67].
8. Other Systems: Vegetable Oils and Protein Based Silanes
8. Other systems: vegetable oils and protein based silanes
Vegetable oils present versatile chemical options for different applications since they host reactive
sites,Vegetable
such as esteroilsgroups,
present versatile
double chemical
bonds, options
and allylic for different
hydrogens [68–70]. applications
On the other since
hand, they host
the use of
reactive sites,
vegetable such
oils as a rawas ester groups,
material double
has many bonds, andsuch
advantages, allylic hydrogens price
as availability, [68–70]. On thesustainability,
stability, other hand,
the use of vegetable
physico-chemical oils as aand
properties, rawecological
material reasons
has many advantages,
(e.g., such
sequestration ofas availability,
carbon dioxide price stability,
by plants) [21].
Rapeseed is the most important oilseed in Europe and largely used in the production of biodiesel [71].
From a chemical point of view, the long aliphatic chains present in a typical vegetable oil can be used
for the synthesis of for example, new silanes and polysiloxanes. These novel systems with hydrophobic
features could find applications as coatings for the protection of different surfaces, such as wood, metal,
or even concrete [69].
Several plants that produce unsaturated oils are claimed to be important in a healthy human
diet. Their reactive unsaturated bonds also make them suitable candidates for other applications.
For instance, these unsaturated oils have been used as coatings, such as the case of catalyzed oxidative
curing of linseed oil finishes [72]. Another pursued application is the conversion of the unsaturated
carbon bonds into polyols, which can be further transformed into PU [73]. As mentioned before,
PUs have been widely used as adhesives since they only require mild curing temperature conditions,
using the existing moisture of wood. Moreover, PU is more capable of bonding wood matrixes with
higher moisture contents than are phenolic and amino-based resins and adhesives. Fatty oils for non-PU
routes are also being investigated for making adhesives and coatings [74]. For example, vegetable oil
alternatives to silanes have been developed by attaching the siloxane groups to the carboxylic groups
of fatty acids from rapeseed oil [69]. Due to the problems related to glycerine removal formed during
vegetable oil saponification, the process was preceded by the reaction of oil transesterification leading
to methyl ester of fatty acids. The purified methyl esters were subjected to a posterior saponification
and then the resultant sodium salts of fatty acids were subjected to nucleophilic substitution with
3-chloropropyltrimethoxysilane in the presence of potassium iodide as the catalyst (Figure 17).
vegetable oil alternatives to silanes have been developed by attaching the siloxane groups to the
carboxylic groups of fatty acids from rapeseed oil [69]. Due to the problems related to glycerine
removal formed during vegetable oil saponification, the process was preceded by the reaction of oil
transesterification leading to methyl ester of fatty acids. The purified methyl esters were subjected to
a posterior saponification and then the resultant sodium salts of fatty acids were subjected to
Polymers 2019, 11, 1685 14 of 20
nucleophilic substitution with 3-chloropropyltrimethoxysilane in the presence of potassium iodide
as the catalyst (Figure 17).

O Na O

+ Cl Si O
O O

Kl,
DMF

O
O Si O
O
O

Figure 17. Scheme reaction of the synthesis of rapeseed-based silane. Adapted from [69], with permission
Figure 17. Scheme reaction of the synthesis of rapeseed-based silane. Adapted from [69], with
from Springer Nature and Copyright Clearance Center, 2018.
permission from Springer Nature and Copyright Clearance Center, 2018.
In fact, the obtained silane following the procedure described in Figure 17 has been employed in
In fact, the obtained silane following the procedure described in Figure 17 has been employed
the creation of a coating capable to protect wood against water. As introduced before, due to water
in the creation of a coating capable to protect wood against water. As introduced before, due to
exposition hydrolysis and condensation reactions may occur, leading to the formation of Si–OH groups.
water exposition hydrolysis and condensation reactions may occur, leading to the formation of
The subsequent two types of condensation reactions between Si–OH and Si–OH–CH3 moieties create a
Si–OH groups. The subsequent two types of condensation reactions between Si–OH and Si–OH–CH3
well-developed cross-linked network consisting of Si–O–Si covalent bonds. Wood-O–Si covalent bonds
moieties create a well-developed cross-linked network consisting of Si–O–Si covalent bonds.
are then formed as a result of reactions occurring between –OH groups present in wood, and Si–OH
Wood-O–Si covalent
Polymers 2019, 11, bonds
x FOR PEER are then formed as a result of reactions occurring between –OH groups
REVIEW 14 of 20
and Si–O–CH3 groups present in the solution (Figure 18).
present in wood, and Si–OH and Si–O–CH3 groups present in the solution (Figure 18).

O
O
OH
O
O
Si O O
O
O Si O
O
O Si O
O
O
Si O
OH
O

WOOD

Figure 18. Schematic illustration of the covalent bonds formed between the silane groups of the
vegetable
Figure 18.oil-based coating
Schematic and OH of
illustration groups of wood. bonds
the covalent Adapted from [69],
formed with permission
between from Springer
the silane groups of the
Nature and Copyright Clearance Center, 2018.
vegetable oil-based coating and OH groups of wood. Adapted from [69], with permission from
Springer Nature and Copyright Clearance Center, 2018.
The coating is found to be attached to the surface of the modified element following the essential
principle of the adhesive formulations. Furthermore, the aliphatic chain bonded to the silicon atom
The coating is found to be attached to the surface of the modified element following the
makes the surface of wood substrate more hydrophobic in comparison to the unmodified sample,
essential principle of the adhesive formulations. Furthermore, the aliphatic chain bonded to the
thus forming a real protection against moisture-rich environments.
silicon atom makes the surface of wood substrate more hydrophobic in comparison to the
Protein-based AS have been explored particularly for biomedical applications, such as cardiac,
unmodified sample, thus forming a real protection against moisture-rich environments.
vascular, oral, and reconstructive surgery [75]. These protein-based systems are typically used directly
Protein-based AS have been explored particularly for biomedical applications, such as cardiac,
or in combination with a crosslinking agent that forms covalent bonds with the tissue surface [76,77].
vascular, oral, and reconstructive surgery [75]. These protein-based systems are typically used
Proteins can be directly extracted from human or other animal sources, offering many advantages over
directly or in combination with a crosslinking agent that forms covalent bonds with the tissue
other common glues regarding biocompatibility and mechanical properties. Strausberg et al. have
surface [76,77]. Proteins can be directly extracted from human or other animal sources, offering
many advantages over other common glues regarding biocompatibility and mechanical properties.
Strausberg et al. have studied different marine organisms regarding their potential use as adhesives
in classical medical and dental applications [78]. Some mussels and barnacles can produce
remarkable moisture-resistant adhesives. For instance, the blue mussel Mytilus edulis synthesizes a
specific polyphenolic adhesive protein, which plays a key role in the attachment to surfaces. The
Polymers 2019, 11, 1685 15 of 20

studied different marine organisms regarding their potential use as adhesives in classical medical
and dental applications [78]. Some mussels and barnacles can produce remarkable moisture-resistant
adhesives. For instance, the blue mussel Mytilus edulis synthesizes a specific polyphenolic adhesive
protein, which plays a key role in the attachment to surfaces. The protein is located in a thread-like
structure known as byssus, which also contains several other proteins including collagen. When secreted
and applied, the byssal adhesive is highly cross-linked and cannot be readily analyzed. The adherence
of the engineered mussel adhesive protein in an aqueous environment to various surfaces including
polystyrene, glass, hydrogel, and collagen has been tested. In each case, the activation to the quinone
form of the protein was required for good surface adhesion. The nature of the chemical bond involved
in cross-linking has not yet been determined. However, the authors have suggested that quinone
residues could bond to the c-amino group of lysine through a Michael addition reaction.
Kumar et al. have developed adhesives and plastics from soy protein. An initial protein acylation
(Figure
Polymers 19)
2019,was
11, xperformed to improve functional properties, such as solubility and surface hydrophobicity.
FOR PEER REVIEW
Polymers 2019, 11, x FOR PEER REVIEW
15 of 20
15 of 20

O O
O O

SOYPROTEIN-NH + H C C SOYPROTEIN-NH C CH
SOYPROTEIN-NH22 + H33C C SOYPROTEIN-NH C CH33
O
O
H C C
H33C C

O
O
Figure 19.
Figure Acylation of
19. Acylation of an
an amino
amino group
group of
of soy
soy protein. Adapted from
protein. Adapted from [79],
[79], with
with permission
permission from
from
Figure 19. Acylation of an amino group of soy protein. Adapted from [79], with permission from
Elsevier and Copyright Clearance Center, 2002.
Elsevier and Copyright Clearance Center, 2002.
Elsevier and Copyright Clearance Center, 2002.
It has
It has been
been shown
shown that
that the
the silanization
silanizationusing
using3-(2-aminoethyl)-aminopropyltrimethoxy
3-(2-aminoethyl)-aminopropyltrimethoxysilane
silaneasasa
It hasagent
coupling beenenhances
shown thatthethe silanization
interfacial usingbetween
adhesion 3-(2-aminoethyl)-aminopropyltrimethoxy
the soy matrix and, for instance, silane
glass as
fiber
a coupling agent enhances the interfacial adhesion between the soy matrix and, for instance, glass
atocoupling
produce agent enhances composites
fiber-reinforced the interfacial adhesion
(Figure 20). between the soy matrix and, for instance, glass
fiber to produce fiber-reinforced composites (Figure 20).
fiber to produce fiber-reinforced composites (Figure 20).
O CH3
O CH3
H H2 H2 H2
2HC H
C H
C2 O H
C2 H
C2 CH2Si O CH3
SOYPROTEIN-NH2 + 2HC C C O C C CH2Si O CH3
SOYPROTEIN-NH2 +
O O CH3
O O CH3

O CH3
O CH3
H2 H H2 H2 H2
SOYPROTEIN-NH H2
C H
C H
C2 O H
C2 H
C2 CH Si O CH
SOYPROTEIN-NH C C C O C C CH22Si O CH33

OH O CH3
OH O CH3

HO
HO
HO
HO
HO
HO

O
H2 H2 H2 H2 O
H2 H
SOYPROTEIN-NH C H
C H
C2 O H
C2 H
C2 CH Si O
SOYPROTEIN-NH C C C O C C CH22Si O
O
OH O
OH

Figure Silanation of
Silanation of soy
of soy protein
soy protein for
protein for improving
for improving interfacial
improving interfacial adhesion
interfacial adhesion in glass fiber reinforced
adhesion in
Figure 20.
20. Silanation glass fiber reinforced
composites. Adapted
Adapted from
from[79],
[79],with
with permission
permission from
from Elsevier
Elsevier and and Copyright
Copyright Clearance
Clearance Center,
Center, 2002.
composites. Adapted from [79], with permission from Elsevier and Copyright Clearance Center,
2002.
2002.

Copolymers of soy protein isolate (SPI) have also been prepared by heating an alkaline
Copolymers of soy protein isolate (SPI) have also been prepared by heating an alkaline
dispersion of SPI with cationic epoxide or an acrylate monomer to originate modified protein
dispersion of SPI with cationic epoxide or an acrylate monomer to originate modified protein
materials. The modified protein can be used alone or in combination with styrene-butadiene rubber
materials. The modified protein can be used alone or in combination with styrene-butadiene rubber
latex for paper coating [79]. The performance of this protein-based adhesive has been shown to be
Polymers 2019, 11, 1685 16 of 20

Copolymers of soy protein isolate (SPI) have also been prepared by heating an alkaline dispersion of
SPI with cationic epoxide or an acrylate monomer to originate modified protein materials. The modified
protein can be used alone or in combination with styrene-butadiene rubber latex for paper coating [79].
The performance of this protein-based adhesive has been shown to be dependent on the particle size,
nature of the surface, protein structure, viscosity, and pH.
Liu et al. have demonstrated that although soy protein-based adhesives have relatively low
strength, low water resistance, and sensitivity to biological degradation, this can be significantly
improved by combining them with a functional group typically found in marine adhesive proteins.
The authors have observed that this modification converts the soy protein into a robust and
water-resistant adhesive with superior performance in wood applications [80]. The adhesive strengths
and water resistance of plywood samples bonded with the developed bio-adhesive are competitive
with commercial PF and UF resins. The modification of soy protein using marine adhesive proteins
as a model, could also lead to the development of superior and water-resistant adhesives for other
applications and materials than wood.

9. Concluding Remarks
Silicones have a major role on the adhesives and sealants market due to their superior
physicochemical and mechanical properties and simple curing mechanisms. However, the poor
biodegradability and recent scarce availability of silicone-based materials has been triggering the
development of novel bio-based alternatives. This brief overview clearly demonstrates the opportunities
introduced by renewable resources, such as cellulose, lignin, starch, vegetable oils, or proteins, in the
formation of novel bio-based materials to substitute traditional adhesives and sealants with reduced
human and environmental toxicity, competitive performance, and improved biodegradability.
One important factor that differentiates bio-based adhesives from traditional adhesives based
on petroleum-derived materials is their varied “molecular architecture”, which can confer new
functionalities to the final product. Additionally, the connections and hierarchical structures provided
by nature (striking in the case of lignin and proteins) may also offer novel complex and not easily
accessible features found in traditional polymerization chemistry. This versatility of many bio-based
molecules may also enable their use addressing more than one function in a formulation. The use
of biopolymers may also avoid the need of extensive polymerization processes, since biopolymers
are already large macromolecules with a high density of functional groups. Such a high number of
functional groups is expected to lead to higher crosslinking densities, which might confer superior
properties in many applications.
It is also clear that several monomers derived from renewable sources often contain combinations
of functional groups that would not be easily synthesized or economically viable if produced through
petrochemical pathways.
The advantages of bio-based materials, and the strategies briefly highlighted in this work, pave the
way and contribute for a future society less dependent on non-renewable and polluting fossil feedstock.
The available examples in the literature are still scarce, partially because it is important for industries
to maintain trade secrets on formulations. Nevertheless, the potential is obvious and therefore it is
expected that the combination of the adhesion power of siloxane groups with the beneficial properties of
bio-based raw materials will reinforce the development of novel innovative and competitive materials,
in comparison to the rather non-sustainable adhesives and sealants used nowadays.

Author Contributions: Conceptualization: S.M., L.A. and B.M.; writing—original draft preparation: S.M., L.A.,
B.M. and A.C.F.; writing—review and editing: S.M., L.A., B.M., A.C.F., A.R., J.F.J.C. and M.N.
Acknowledgments: The authors are thankful to Pecol, Sistemas de Fixação for sharing the market and
environmental information. This work was financially supported by the Portuguese Foundation for Science and
Technology, FCT, via the projects PTDC/AGR-TEC/4814/2014 and PTDC/ASP-SIL/30619/2017, and researcher grant
IF/01005/2014 (B.M.).
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2019, 11, 1685 17 of 20

References
1. Segura, D.M.; Nurse, A.D.; McCourt, A.; Phelps, R.; Segura, A. Chapter 3 Chemistry of polyurethane
adhesives and sealants. In Handbook of Adhesives and Sealants; Cognard, P., Ed.; Elsevier Science Ltd.:
New York, NY, USA, 2005; Volume 1, pp. 101–162.
2. He, Z. (Ed.) Bio-based Wood Adhesives: Preparation, Characterization, and Testing; CRC Press: Boca Raton, FL,
USA, 2017; pp. 1–356.
3. Petric, M. Influence of Silicon-Containing Compounds on Adhesives for and Adhesion to Wood and
Lignocellulosic Materials: A Critical Review. Rev. Adhes. Adhes. 2018, 6, 26–81. [CrossRef]
4. Pizzi, A.; Mittal, K.L. (Eds.) Wood Adhesives; CRC Press: Boca Raton, FL, USA, 2011; pp. 1–451.
5. Ogliani, E.; Yu, L.; Mazurek, P.; Skov, A.L. Designing reliable silicone elastomers for high-temperature
applications. Polym. Degrad. Stab. 2018, 157, 175–180. [CrossRef]
6. Kim, H.J.; Lim, D.H.; Hwang, H.D.; Lee, B.H. Composition of Adhesives. In Handbook of Adhesion Technology;
da Silva, L.F.M., Öchsner, A., Adams, R.D., Eds.; Springer Berlin Heidelberg: Berlin/Heidelberg, Germany,
2011; pp. 291–314.
7. Guillaume, S.M. Advances in the synthesis of silyl-modified polymers (SMPs). Polym. Chem. 2018, 9, 1911–1926.
[CrossRef]
8. Research, Z.M. Global Silane Modified Polymer Market 2019—Henkel Ltd., The Dow Chemical
Company, Evonik, Kaneka Americas Holding, Inc. Available online: https://economicsaffairs.com/global-
silane-modified-polymer-market-2019-henkel-ltd-the-dow-chemical-company-evonik-kaneka-americas-
holding-inc/6176/ (accessed on 2 February 2019).
9. Darracq, G.; Couvert, A.; Couriol, C.; Amrane, A.; Thomas, D.; Dumont, E.; Andres, Y.; Le Cloirec, P. Silicone
oil: An effective absorbent for the removal of hydrophobic volatile organic compounds. J. Chem. Technol.
Biotechnol. 2010, 85, 309–313. [CrossRef]
10. Lukasiak, J.; Dorosz, A.; Prokopowicz, M.; Rosciszewski, P.; Falkiewicz, B. Biodegradation of Silicones
(Organosiloxanes). Biopolym. Online: Biol. Chem. Biotechnol. Appl. 2002, 9, 539–568.
11. Lehmann, R.G.; Varaprath, S.; Frye, C.L. Degradation of silicone polymers in soil. Environ. Toxicol. Chem.
1994, 13, 1061–1064. [CrossRef]
12. Lehmann, R.G.; Miller, J.R.; Xu, S.; Singh, U.B.; Reece, C.F. Degradation of Silicone Polymer at Different Soil
Moistures. Environ. Sci. Technol. 1998, 32, 1260–1264. [CrossRef]
13. Xu, S.; Lehmann, R.G.; Miller, J.R.; Chandra, G. Degradation of Polydimethylsiloxanes (Silicones) as
Influenced by Clay Minerals. Environ. Sci. Technol. 1998, 32, 1199–1206. [CrossRef]
14. Lehmann, R.G.; Miller, J.R.; Kozerski, G.E. Degradation of silicone polymer in a field soil under natural
conditions. Chemosphere 2000, 41, 743–749. [CrossRef]
15. Bhisey, M.R. Transparency Market Reseach. Available online: https://www.transparencymarketresearch.com
(accessed on 20 February 2019).
16. Salleh, K.M.; Hashim, R.; Sulaiman, O.; Hiziroglu, S.; Nadhari, W.N.A.W.; Abd Karim, N.; Jumhuri, N.;
Ang, L.Z.P. Evaluation of properties of starch-based adhesives and particleboard manufactured from them.
J. Adhes. Sci. Technol. 2015, 29, 319–336. [CrossRef]
17. Vnucec, D.; Kutnar, A.; Gorsek, A. Soy-based adhesives for wood-bonding—A review. J. Adhes. Sci. Technol.
2017, 31, 910–931. [CrossRef]
18. Heinrich, L.A. Future opportunities for bio-based adhesives—Advantages beyond renewability. Green Chem.
2019, 21, 1866–1888. [CrossRef]
19. Plank, J. Applications of Biopolymers in Construction Engineering. Biopolym. Online: Biol. Chem. Biotechnol.
Appl. 2005, 10, 29–93. [CrossRef]
20. Shen, L.; Worrell, E.; Patel, M. Present and future development in plastics from biomass. Biofuels Bioprod.
Bioref. 2010, 4, 25–40. [CrossRef]
21. Kumar, S.; Samal, S.K.; Mohanty, S.; Nayak, S.K. Recent Development of Biobased Epoxy Resins: A Review.
Polym.-Plast. Technol. 2018, 57, 133–155. [CrossRef]
22. Chen, G.-Q. (Ed.) Plastics from Bacteria: Natural Functions and Applications; Springer: New York, NY, USA,
2010; Volume 14.
23. Chen, G.-Q. (Ed.) Introduction of Bacterial Plastics PHA, PLA, PBS, PE, PTT, and PPP; Springer:
Berlin/Heidelberg, Germany, 2010; Volume 14.
Polymers 2019, 11, 1685 18 of 20

24. Bodo Müller, W.R. Formulating Adhesives and Sealants. Chemistry, Physics and Applications; Vincentz Network:
Hanover, Germany, 2010.
25. Mittal, K.L. Silanes and Other Coupling Agents; Taylor & Francis: Boca Raton, FL, USA, 2009.
26. Owen, M.J. Why Silicones Behave Funny. Dow Corning Corp. 1981, 11, 288.
27. Mojsiewicz-Pieńkowska, K.; Jamrógiewicz, M.; Szymkowska, K.; Krenczkowska, D. Direct Human Contact
with Siloxanes (Silicones)—Safety or Risk Part 1. Characteristics of Siloxanes (Silicones). Front. Pharmacol.
2016, 7, 132. [CrossRef]
28. Stoiljkovic, D.; Jovanović, S. Compression, supramolecular organization and free radical polymerization of
ethylene gas. Polyolefins J. 2019, 6, 23–41. [CrossRef]
29. De Buyl, F. Silicone sealants and structural adhesives. Int. J. Adhes. Adhes. 2001, 21, 411–422. [CrossRef]
30. Müller, B.A.R.; Walter. Formulating Adhesives and Sealants; Vincentz Network GmbH & Co KG: Hanover,
Germany, 2010.
31. Ferdosian, F.; Pan, Z.; Gao, G.; Zhao, B. Bio-Based Adhesives and Evaluation for Wood Composites
Application. Polymers 2017, 9, 70. [CrossRef]
32. Jiménez-Pardo, I.; Van der Ven, L.G.J.; Van Benthem, R.A.T.M.; De With, G.; Esteves, A.C.C. Hydrophilic
Self-Replenishing Coatings with Long-Term Water Stability for Anti-Fouling Applications. Coatings 2018, 8, 184.
[CrossRef]
33. Ayyad, A.H. Thermodynamic derivation of the Young–Dupré form equations for the case of two immiscible
liquid drops resting on a solid substrate. J. Colloid Interface Sci. 2010, 346, 483–485. [CrossRef]
34. Rajendran, M.B.A.P. A Review on Electroactive Polymers Development for Aerospace Applications. J. Intell.
Mater. Syst. Struct. 2018, 29, 3681–3695. [CrossRef]
35. Kronberg, B.; Holmberg, K.; Lindman, B. Surface Chemistry of Surfactants and Polymers; Wiley: Hoboken, NJ,
USA, 2014.
36. Bio Based Construction Polymers Market Analysis By Product (Cellulose Acetate, Epoxies, Polyethylene
Terephthalate (PET), Polyurethane), By Application (Pipe, Profile, Insulation) And Segment Forecasts To
2024. Available online: http://news.bio-based.eu/grand-view-research-bio-based-construction-polymers-
market-analysis-and-segment-forecasts-to-2024/ (accessed on 28 January 2019).
37. Market Research Report. Available online: https://www.grandviewresearch.com/press-release/global-bio-
based-construction-polymers-market (accessed on 8 May 2019).
38. Ahuja, D.; Kaushik, A.; Singh, M. Simultaneous extraction of lignin and cellulose nanofibrils from waste jute
bags using one pot pre-treatment. Int. J. Biol. Macromol. 2018, 107, 1294–1301. [CrossRef]
39. Lindman, B.; Medronho, B.; Alves, L.; Costa, C.; Edlund, H.; Norgren, M. The relevance of structural
features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena.
Phys. Chem. Chem. Phys. 2017, 19, 23704–23718. [CrossRef]
40. Medronho, B.; Lindman, B. Competing forces during cellulose dissolution: From solvents to mechanisms.
Curr. Opin. Colloid Interface Sci. 2014, 19, 32–40. [CrossRef]
41. Medronho, B.; Romano, A.; Miguel, M.G.; Stigsson, L.; Lindman, B. Rationalizing cellulose (in)solubility:
reviewing basic physicochemical aspects and role of hydrophobic interactions. Cellulose 2012, 19, 581–587.
[CrossRef]
42. Schuyten, H.A.; Weaver, J.W.; Reid, J.D.; Jurgens, J.F. Trimethylsilylcellulose. J. Am. Chem. Soc.
1948, 70, 1919–1920. [CrossRef]
43. Bontea, D.; Ioan, C. Synthesis and Characterization of Trimethylsilylcellulose in Solution AU-Aelenei, Nicolae.
J. Macromol. Sci. Part A 1998, 35, 1667–1680. [CrossRef]
44. Carapeto, A.P.; Ferraria, A.M.; Botelho do Rego, A.M. Trimethylsilylcellulose synthesis revisited. Polym. Test.
2017, 58, 236–240. [CrossRef]
45. Heinze, S.K.T.L.T. Interactions of ionic liquids with polysaccharides. VI. Pure cellulose nanoparticles from
trimethylsilyl cellulose synthesized in ionic liquids. J. Polym. Sci. 2008, 46, 4070–4080. [CrossRef]
46. Kostag, M.; Köhler, S.; Liebert, T.; Heinze, T. Pure Cellulose Nanoparticles from Trimethylsilyl Cellulose.
Macromol. Symp. 2010, 294, 96–106. [CrossRef]
47. Stiubianu, G.; Racles, C.; Cazacu, M.; Simionescu, B.C. Silicone-modified cellulose. Crosslinking of cellulose
acetate with poly[dimethyl(methyl-H)siloxane] by Pt-catalyzed dehydrogenative coupling. J. Mater. Sci.
2010, 45, 4141–4150. [CrossRef]
Polymers 2019, 11, 1685 19 of 20

48. Klemm, D.; Stein, A. Silylated Cellulose Materials in Design of Supramolecular Structures of Ultrathin
Cellulose Films. J. Macromol. Sci. Pure 1995, A32, 899–904. [CrossRef]
49. Robles, E.; Csóka, L.; Labidi, J. Effect of Reaction Conditions on the Surface Modification of Cellulose
Nanofibrils with Aminopropyl Triethoxysilane. Coatings 2018, 8, 139. [CrossRef]
50. Vandenberg, E.T.; Bertilsson, L.; Liedberg, B.; Uvdal, K.; Erlandsson, R.; Elwing, H.; Lundström, I. Structure
of 3-aminopropyl triethoxy silane on silicon oxide. J. Colloid Interface Sci. 1991, 147, 103–118. [CrossRef]
51. Eslah, F.; Jonoobi, M.; Faezipour, M.; Ashori, A. Chemical modification of soybean flour-based adhesives
using acetylated cellulose nanocrystals. Polym. Compos. 2018, 39, 3618–3625. [CrossRef]
52. Khanjanzadeh, H.; Behrooz, R.; Bahramifar, N.; Gindl-Altmutter, W.; Bacher, M.; Edler, M.; Griesser, T.
Surface chemical functionalization of cellulose nanocrystals by 3-aminopropyltriethoxysilane. Int. J. Biol.
Macromol. 2018, 106, 1288–1296. [CrossRef]
53. Khanjanzadeh, H.; Behrooz, R.; Bahramifar, N.; Pinkl, S.; Gindl-Altmutter, W. Application of surface chemical
functionalized cellulose nanocrystals to improve the performance of UF adhesives used in wood based
composites—MDF type. Carbohydr. Polym. 2019, 206, 11–20. [CrossRef]
54. Syed draman, S.F.; Daik, R.; El-Sheikh, S.; Abdul latif, F. Nanocomposites of cellulose-based adhesive
and toluenesulfonic acid-doped polypyrrole prepared via colloidal dispersion. J. Reinf. Plast. Comp.
2013, 32, 1553–1560. [CrossRef]
55. Ghalib, H.; Abdullah, I.; Daik, R. Synthesis of Polypyrrole Nanoparticles in Natural Rubber-Polystyrene
Blend via Emulsion Polymerization. J. Appl. Polym. Sci. 2012, 123, 2115–2121. [CrossRef]
56. Ates, M.; Karazehira, T.; Sarac, A. Conducting Polymers and their Applications. Curr. Phys. Chem.
2012, 2, 224–240. [CrossRef]
57. Ceseracciu, L.; Heredia-Guerrero, J.A.; Dante, S.; Athanassiou, A.; Bayer, I.S. Robust and Biodegradable
Elastomers Based on Corn Starch and Polydimethylsiloxane (PDMS). Acs Appl. Mater. Interfaces
2015, 7, 3742–3753. [CrossRef]
58. Sugih, A.K.; Picchioni, F.; Janssen, L.P.B.M.; Heeres, H.J. Synthesis of poly-(epsilon)-caprolactone grafted
starch co-polymers by ring-opening polymerisation using silylated starch precursors. Carbohydr. Polym.
2009, 77, 267–275. [CrossRef]
59. Sugih, A.K.; Picchioni, F.; Janssen, L.P.B.M.; Heeres, H.J. Synthesis of poly-(ε)-caprolactone grafted
starch co-polymers by ring-opening polymerisation using silylated starch precursors. Carbohydr. Polym.
2009, 77, 267–275. [CrossRef]
60. Wei, B.; Sun, B.; Zhang, B.; Long, J.; Chen, L.; Tian, Y. Synthesis, characterization and hydrophobicity of
silylated starch nanocrystal. Carbohydr. Polym. 2016, 136, 1203–1208. [CrossRef]
61. Angellier, H.; Choisnard, L.; Molina-Boisseau, S.; Ozil, P.; Dufresne, A. Optimization of the preparation
of aqueous suspensions of waxy maize starch nanocrystals using a response surface methodology.
Biomacromolecules 2004, 5, 1545–1551. [CrossRef]
62. Norgren, M.; Edlund, H. Lignin: Recent advances and emerging applications. Curr. Opin. Colloid Interface
Sci. 2014, 19, 409–416. [CrossRef]
63. Stiubianu, G.; Bele, A.; Tugui, C.; Musteata, V. New dielectric elastomers with improved properties for energy
harvesting and actuation. In Advanced Topics in Optoelectronics, Microelectronics, and Nanotechnologies VII;
International Society for Optics and Photonics: Bellingham, WA, USA, 2016; Volume 9258, p. 925808.
64. Feldman, D.; Lacasse, M.; St. J. Manley, R. Polyurethane-based sealants modified by blending with Kraft
lignin. J. Appl. Polym. Sci. 1988, 35, 247–257. [CrossRef]
65. Scarica, C.; Suriano, R.; Levi, M.; Turri, S.; Griffini, G. Lignin Functionalized with Succinic Anhydride as
Building Block for Biobased Thermosetting Polyester Coatings. Acs Sustain. Chem. Eng. 2018, 6, 3392–3401.
[CrossRef]
66. Robert, T.; Friebel, S. Itaconic acid—A versatile building block for renewable polyesters with enhanced
functionality. Green Chem. 2016, 18, 2922–2934. [CrossRef]
67. Carlos de Haro, J.; Magagnin, L.; Turri, S.; Griffini, G. Lignin-Based Anticorrosion Coatings for the Protection
of Aluminum Surfaces. Acs Sustain. Chem. Eng. 2019, 7, 6213–6222. [CrossRef]
68. De Haro, J.C.; Allegretti, C.; Smit, A.T.; Turri, S.; D’Arrigo, P.; Griffini, G. Bio-based polyurethane coatings
with high biomass content: Tailored properties by lignin selection. ACS Sustain. Chem. Eng. 2019. [CrossRef]
69. Szubert, K. Synthesis of organofunctional silane from rapeseed oil and its application as a coating material.
Cellulose 2018, 25, 6269–6278. [CrossRef]
Polymers 2019, 11, 1685 20 of 20

70. Mohd Salleh, K.; Hashim, R.; Sulaiman, O.; Hiziroglu, S.; Wan Nadhari, W.N.A.; Abd Karim, N.; Jumhuri, N.;
Zuin Ping Ang, L. Evaluation of properties of starch-based adhesives and particleboard manufactured from
them. J. Adhes. Sci. Technol. 2015, 29. [CrossRef]
71. Britz, W.; Hertel, T.W. Impacts of EU biofuels directives on global markets and EU environmental quality:
An integrated PE, global CGE analysis. Agric. Ecosyst. Environ. 2011, 142, 102–109. [CrossRef]
72. Mallégol, J.; Lemaire, J.; Gardette, J.-L. Drier influence on the curing of linseed oil. Prog. Org. Coat.
2000, 39, 107–113. [CrossRef]
73. Li, Y.; Luo, X.; Hu, S. (Eds.) Polyols and Polyurethanes from Vegetable Oils and Their Derivatives. In
Handbook of Bio-based Polyols and Polyurethanes; Springer International Publishing: Cham, Switzerland, 2015;
Volume 1, pp. 15–43.
74. Pizzi, A. Bioadhesives for Wood and Fibres. Rev. Adhes. Adhes. 2013, 1, 88–113. [CrossRef]
75. Zhang, W.S.; Yu, X.Q.; Li, Y.; Su, Z.Q.; Jandt, K.D.; Wei, G. Protein-mimetic peptide nanofibers: Motif design,
self-assembly synthesis, and sequence-specific biomedical applications. Prog. Polym. Sci. 2018, 80, 94–124.
[CrossRef]
76. Rathi, S.; Saka, R.; Domb, A.J.; Khan, W. Protein-based bioadhesives and bioglues. Polym. Adv. Technol.
2019, 30, 217–234. [CrossRef]
77. Clark, R. Fibrin sealant in wound repair: A systematic survey of the literature. Expert Opin. Investig. Drugs.
2000, 9, 2371–2392. [CrossRef]
78. Strausberg, R.L.; Link, R.P. Protein-based medical adhesives. Trends Biotechnol. 1990, 8, 53–57. [CrossRef]
79. Kumar, R.; Choudhary, V.; Mishra, S.; Varma, I.K.; Mattiason, B. Adhesives and plastics based on soy protein
products. Ind. Crop. Prod. 2002, 16, 155–172. [CrossRef]
80. Liu, Y.; Li, K. Chemical Modification of Soy Protein for Wood Adhesives. Macromol. Rapid Commun.
2002, 23, 739–742. [CrossRef]

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