Article

Improving the Elastic Response of Tanned Leather by Treatment

with a Carboxylic Elastomer
Daniele Marinai 1 , Cristiana Borchi 1 , Lorenzo Marinai 1 , Gustavo Adrián Defeo 2 , Antonella Manariti 3 ,
Pierpaolo Minei 4 , Valter Castelvetro 3,4, * and Francesco Ciardelli 3,4

1 Kemas s.r.l., Via Sardegna 2, 56029 Santa Croce sull’Arno, Italy; [email protected] (D.M.);
[email protected] (C.B.)
2 CTC Ars Tinctoria s.r.l., Via del Bosco 125, 56029 Santa Croce sull’Arno, Italy; [email protected]
3 Department of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy;
[email protected] (A.M.); [email protected] (F.C.)
4 Spin-PET s.r.l., V.le Rinaldo Piaggio 32, 56025 Pontedera, Italy; [email protected]
* Correspondence: [email protected]

Abstract: The elastic response of chromium-tanned leather was successfully improved by treatment
with XSBR, a carboxylated styrene-butadiene copolymer. The carboxylic groups pending from a
styrene-butadiene rubber (SBR) backbone were found to promote penetration of the aqueous polymer
dispersion into the fibrous tanned leather and participated in pH-reversible physical crosslinking
by H-bonding. The different penetrations of XSBR or SBR were investigated using a micro-FTIR
cross-sectional analysis from the grain (outer) to the flesh (inner) side of 18 wt% elastomer-treated
samples, based on the shaved leather weight. In particular, the profile of the diagnostic out-of-plane
=C-H bending of butadiene and styrene units was consistent with a more effective penetration of
XSBR. The leather with XSBR showed a comparatively lower elastic modulus of 10–15% and roughly
a 10% increase in elongation at the break, indicating better flexibility and shape recovery. Also, the
leather was characterized by a 15% higher burst strength. These results suggest the better swelling of
the ionomeric XSBR in the initial stage of retanning performed at a pH higher than the isoelectric
point of the leather when both the tanned leather and the XSBR ionomer had a negative surface
charge. The high pH favored the penetration of XSBR due to a poor attractive interaction with the
Citation: Marinai, D.; Borchi, C.;
tanned fibrous leather network. Subsequent processing in an acid bath caused further physical
Marinai, L.; Defeo, G.A.; Manariti, A.;
crosslinking through hydrogen bonding between XSBR and the leather.
Minei, P.; Castelvetro, V.; Ciardelli, F.
Improving the Elastic Response of
Tanned Leather by Treatment with a
Keywords: styrene-butadiene rubber; elasticized leather; IR analysis; ionomer; modified tanning
Carboxylic Elastomer. Polymers 2024,
16, 3411. https://doi.org/10.3390/
polym16233411
1. Introduction
Academic Editor: Alexander Malkin
Currently, many carboxylated polymers obtained from post-polymerization modifi-
Received: 31 October 2024 cation reactions are commercially available, such as polystyrene (PS) [1], poly(butyl acry-
Revised: 27 November 2024 late) [2], etc. Such materials are employed in several applications requiring improved adhe-
Accepted: 30 November 2024 sion, compatibility in polymer-based formulations, ion transport capability, etc. Among
Published: 4 December 2024
them, the carboxylated styrene-butadiene copolymer rubber XSBR (Figure 1) has an ex-
panding market [3,4] due to its distinctive characteristics, combining the properties of an
elastomeric material with effectiveness in the formation of strong dipolar and hydrogen
Copyright: © 2024 by the authors.
bonding interactions with other organic polymers, additives, and fillers. Owing to the
Licensee MDPI, Basel, Switzerland. typically highly improved ultimate properties of the resulting multicomponent materials,
This article is an open access article XSBR has several industrial applications in, e.g., paper coatings [5], carpet backing [6],
distributed under the terms and gloves [7], water-based paints [8], membranes [9], and polymer-modified mortars [10].
conditions of the Creative Commons The presence of carboxylic groups in XSBR was found to increase the thickness of
Attribution (CC BY) license (https:// the interphase region between the polymer and a second polymeric phase in blends with
creativecommons.org/licenses/by/ polar polymers, generally resulting in improved compatibility and, therefore, improved
4.0/). mechanical, rheological, and adhesion properties [11,12]. The strong interfacial interaction

Polymers 2024, 16, 3411. https://doi.org/10.3390/polym16233411 https://www.mdpi.com/journal/polymers

Polymers 2024, 16, 3411 2 of 14

of XSBR inorganic fillers and reinforcing components in composites plays a key role in
the effectiveness of the synergistic enhancement of the mechanical properties of these
materials [13]. Various reinforcing and functional fillers such as multi-walled carbon
nanotubes [14], halloysite [15], silica [16], cellulose nanocrystals [17], organically modified
boehmite [18], layered silicates [19], chitosan [20], and chitin [21] have been reported in
combination with XSBR as compatibilizers or as polymer matrixes.

Figure 1. Structure of the XSBR statistic terpolymer (in a typical composition, z is about 3%).

The formation of a 3D network is one of the main requirements for elastomeric materi-
als. However, such a network does not need to be a covalent one, as effective (although
weaker) physical interactions such as in phase-separated rubbery-glassy block copolymers,
ionic interactions in ionomers, and suitably located hydrogen bonding interactions may
perform the work. In the case of the XSBR pH-dependent ionomer, the hydrogen bonding
interactions between carboxyl/carboxylate and hydroxy groups in fillers or other hydrogen
bonding groups in binary polymer blends may result in elastomeric properties due to
the fillers/second polymer acting as discrete (not point-like) physical crosslinking sites.
In XSBR/nano-chitosan (NCS) composites, NCS serves as a multifunctional crosslinker,
building a supramolecular hybrid network as well as reinforcement, providing the XSBR
matrix with both improved mechanical strength and self-healing behavior [22].
In the present study, the potential of XSBR as an elastomeric reinforcement of tanned
leather, characterized by pH-reversible crosslinking behavior through hydrogen bond-
ing [23], was investigated. The pH-dependent physical crosslinking could conveniently
provide a self-vulcanizing rubber for the preparation of TPV-type material (TPV: thermo-
plastic vulcanizate, a type of thermoplastic elastomer that undergoes dynamic vulcaniza-
tion; that is, mild crosslinking during its manufacturing) or for soft crosslinked materials
such as tanned leather. In a reverse-targeted application, collagen-based leather fibers
were used to improve the mechanical performance of rubber [21,22]. However, almost
no example exists for the addition of rubbery polymers to tanned leather to improve its
elastic response. A major obstacle to effective treatments of tanned leather with rubbery
polymers is the poor penetration of such generally hydrophobic macromolecules during the
retanning process, the latter being performed in an aqueous medium. Neither chemical nor
physical crosslinking can easily be achieved once these macromolecules enter the fibrous
proteinaceous network of the leather.
In previous investigations, we found that the elastic response of chromium-tanned
leather could be improved by the addition of an XSBR ionomer (about 3% of the carboxylic
groups) as a latex dispersion in an aqueous bath treatment [24]. Such an improvement in
the mechanical properties was tentatively ascribed to effective penetration and, therefore,
a more uniform dispersion of the carboxyl functional elastomer throughout the protein
fiber structure of the tanned leather, followed by the development of hydrogen bonding
interactions upon decreasing the pH (Figure 2).
Polymers 2024, 16, 3411 3 of 14

Figure 2. Onset of hydrogen bonding interactions (highlighted in red) between XSBR and the collagen
functional groups upon decreasing the pH during the tanning process.

2. Materials and Methods

2.1. Tanned Leather Elastomer Addition
In a typical production process, a load of 100 kg shaved full-grain calf hides with a
thickness of about 1 mm was processed in a drum using conventional chrome tanning.
In subsequent steps, the tanned leather was then fatliquored, dyed with CI Acid Brown 425,
washed with water and then with 0.25% aqueous ammonia to improve wettability, washed
again with water, and drained. Afterwards, it was treated with acetic acid to promote the
subsequent retanning, washed again with water until a pH above 4.5 was obtained, and
retanned (e.g., with the oxazoline-based aldehyde Daplien® W 160 product by Kemas s.r.l.,
Santa Croce sull’Arno, Italy). To further improve the mechanical properties of the retanned
leather, 36 kg of Ambrasan DAS® (commercial name of a ~50% solid water-based car-
boxylated XSBR rubber formulation by Kemas s.r.l.) [24] was added to the same retanning
anionic bath at a pH higher than the isoelectric point of the leather substrate, followed
after 20 min by the addition of an aqueous solution of formic acid, which lowered the
pH down to about 3.5 (lower than the isoelectric point of the leather). The XSBR rubber
was a styrene-butadiene-acrylic-acid terpolymer patented product by Kemas s.r.l.; the
specific polymer of this investigation was characterized by a 3 wt% acrylic acid content.
The obtained rubberized leathers were subsequently drained before performing additional
dyeing with an acid dye, treatment with formic acid, washing with water, fatliquoring with
an emulsion of natural sulphited oil, further treatment with diluted aqueous formic acid,
and washing with water. The obtained leathers were finally extracted from the drum and
dried using a multi-step heat treatment that consisted of heating under a light vacuum at a
temperature between 40 ◦ C and 45 ◦ C until a residual humidity not exceeding 40% of the
leather dry weight was achieved, then they were allowed to dry at room temperature until
about 12% humidity (measured using a hygrometer) was reached. Although the typical
treatment range was between 2.5% and 27.5%, the samples investigated in this work were
treated according to the above procedure and concentrations in which 36 kg of Ambrasan
DAS® was used for 100 kg of initial shaved full-grain hides, resulting in a final sample
identified as 18% XSBR-treated leather. The same treatment range was used to prepare a
reference rubberized leather with conventional (not carboxylated) SBR.

2.2. Analytical Techniques

Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra were
recorded using a Thermo-Fischer Nicolet iS50 FTIR spectrometer (Waltham, MA, USA)
interfaced with an ATR ITX accessory equipped with a diamond crystal. Spectra were
recorded in the spectral range between 4000 and 650 cm−1 using 64 scans and a spectral
resolution of 4 cm−1 . The ATR spectra of XSBR and SBR polymers were recorded on cast
films obtained by casting and thoroughly drying the commercial aqueous dispersions
at reduced pressure. A micro-ATR analysis on cross-sections of raw and rubber-treated
tanned leather was performed with a Thermo Scientific Nicolet iN10 MX integrated FTIR
Polymers 2024, 16, 3411 4 of 14

microscope using a slide-on ATR objective equipped with a germanium crystal probe and
operated at a 35% pressure strength (maximum pressure 1.5 kg). Samples were cut into
40 µm thick slices at room temperature using a Leica LN22 microtome (Wetzlar, Germany)
with a steel blade, and the cross-sectional profile of the tanned leather was analyzed by
recording 20–25 spectra along a scan line from the grain to the flesh side. Micro-ATR
spectral maps were recorded using a step size of 50 µm for a total of 100 spectra over the
selected 500 × 500 µm area. The ATR spectra were recorded using an MCT detector cooled
with liquid nitrogen, collecting 64 transients at 4 cm−1 resolution in the spectral range
between 675 and 4000 cm−1 . All spectra were normalized using the peak at 1237 cm−1 from
the C-N stretching and H-N-C bending vibration modes (amide III) [25]. Scanning electron
microscopy (SEM) images were recorded at Pontlab s.r.l., Pontedera (Italy) using a Zeiss
EVO MA 15 instrument (Carl Zeiss Pvt. Ltd., Cambourne, Cambridge CB23 6DW, UK).

2.3. Mechanical Properties

For this research, one bovine leather was divided into enough pieces to obtain samples
for the individual application of the different polymers (SBR and XSBR) as well as samples
for reference tests. Sampling was conducted using zones of the leather symmetrically
positioned at opposite sides with respect to the animal backbone for the two different poly-
mers and along the backbone line for the reference samples to achieve comparative results
regardless of the typical fiber structure differences within different areas. Four leather test
samples were cut from each specimen, two parallel and two perpendicular to the backbone,
and conditioned for 24 h following ISO 2419 recommendations [26]. After measuring the
thickness of each sample at three points with a caliper, the mechanical properties were
assessed using the following four test methods: ISO 3379:2015 “Determination of distension
and strength of surface” (ball burst method) [27]; ISO 3377-1 “Determination of tear load
Part 1: Single edge tear” [28]; ISO 3377-2 “Determination of tear load Part 2: Double edge
tear” [29]; and ISO 3376 “Determination of the tensile strength, elongation at a specified
load and elongation at maximum force of leather” [30]. The distension and the strength
of the grain layer (the thin papillary layer of the dermis underneath the epidermis) were
evaluated according to ISO 3379:2015 by considering the end point to be the appearance
of the first crack as detected with the aid of a magnifying lens. This method emulated
mechanical stress during lasting (the stage of fitting the assembled shoe onto a foot-shaped
mold or last) in shoe production. Both single-edge and double-edged tear strength tests are
performed to verify if leather articles and production processes meet the requirements for
given applications (shoes, garments, leather goods, upholstery, etc.); these were performed
on samples obtained by cutting two specimens aligned parallel and two additional ones
aligned perpendicular, respectively, to the animal backbone. In the ISO 3377-2 method, an
elongated hexagonal lozenge is cut off inside the specimen and a dynamometer pulls the
two opposite edges, causing the leather to tear. The highest force exerted upon tearing
is recorded as the maximum strength. In the more conventional ISO 3376 method [30],
a rectangular or dog-bone-shaped leather specimen is clamped to a dynamometer and
stretched to measure the elongation at the break, and the corresponding load or tensile
strength are expressed in N.

3. Results
The retanning of leather using a rubber-based component in the formulation aimed to
improve the elasticity and tear strength of the tanned leather. However, a lack of uniform
penetration of the rubber, applied as an aqueous emulsion, throughout the leather could
result in poor reinforcement of the final leather product. To assess the effectiveness of the
penetration and the distribution of the rubber into the tanned leather, a retanning process
of chrome-tanned leather was performed in this comparative study with the addition of
either one of two rubbery polymers, namely, a carboxylic XSBR ionomer or a conventional
SBR. Although a broader range of compositions was prepared and characterized (see the
Supplementary Materials, where additional µ-ATR-FTIR spectra taken across the section of
Polymers 2024, 16, 3411 5 of 14

leather samples treated with 30 and 55 wt% of either SBR or XSBR are shown in Figures S1
and S2, respectively), the results of the spectroscopic investigation and of the mechanical
tests reported hereafter focused on a representative treatment with 18 wt% of the polymer,
and the loading referred to the original shaved full-grain leather weight.

3.1. FTIR Analysis

The introduction of carboxylic side groups into the hydrophobic polymer structure
was expected to promote its emulsification, its penetration within the tight fibrous network
of the tanned leather, and interaction with the proteinaceous collagen fibers, resulting in
improved effectiveness compared with the non-carboxylated parent polymer. For this
purpose, a simple and sensitive technique was required to assess the effectiveness of the
penetration that was capable of discriminating the rubbery polymer from the bulk proteina-
ceous material along with the acrylic polymer(s) used in the tanning steps. Attenuated
total reflectance Fourier-transformed infrared (ATR-FTIR) spectroscopy is a powerful and
sensitive tool to assess the presence of specific functional groups on the surface layer of
a material. The micro-ATR probe allows mapping of their distribution on a surface or a
cross-sectional area, if a cross-section of a sample can be produced. However, monitoring
the penetration of carboxylated rubber into the fibrous structure of the tanned leather
using the carboxylic group as a marker was quite challenging, even for the FTIR sensitivity,
given the low 3% content of carboxylic side groups in the XSBR rubber applied as a leather
modifier in this study and also the presence of carboxylic groups in the tanned leather. The
ATR-FTIR spectra of the untreated tanned leather and of the two SBR and XSBR rubbers
are compared in Figure 3.

Figure 3. ATR-FTIR spectra of (a) untreated tanned leather; (b) styrene-butadiene rubber (SBR);
(c) carboxylated styrene-butadiene rubber (XSBR).
Polymers 2024, 16, 3411 6 of 14

The ATR spectrum of untreated tanned leather (Figure 3a) presented characteristic
absorptions at 1649 and 1546 cm− 1 from the -HN-C=O stretching (Amide I) and the N-H
deformation (Amide II). The weak carbonyl stretching absorption at 1734 cm− 1 could be
ascribed to ester groups from lipids (both endogen and added in the fatliquoring step) and
to the acrylic copolymer added in the tanning step. In the spectral range below 1000 cm− 1 ,
the weak absorptions due to out-of-plane =C-H deformations at 972, 920, 837, and 697 cm− 1
have been ascribed to vegetable tannins used in the tanning process [31]. In the ATR
spectra of SBR and XSBR (Figure 3, profiles b and c), the C-H stretching absorptions of
the butadiene and styrene repeat units occurred at 3025 and 3069 cm− 1 (=C-H) and at
2844 and 2915 cm− 1 (main chain methylene). The carbonyl absorption at 1730 cm− 1 from
the XSBR rubber (weak carboxylic absorption due to the low concentration) overlapped
with the absorptions from the leather matrix (including acrylic copolymers introduced
in the tanning step), thus preventing the unambiguous distinction of the two rubbers
once applied to the leather (e.g., to assess the possible preferential absorption of one of
them). The two rubbers presented additional weaker absorptions at 1638 cm− 1 (vinyl
C=C stretching in 1,2-butadiene units), 1601 and 1493 cm− 1 (aromatic ring stretching), and
the characteristic peaks for the butadiene units at 966, 910, and 758 cm− 1 from the =C-H
deformations of the 1,4-trans, 1,2-vinyl, and 1,4-cis structures, respectively [5]; the peak at
697 cm− 1 could finally be ascribed to the out-of-plane =C-H deformation of styrene units,
although it may have also received a contribution from butadiene ones [32,33]. The peaks
at 966 and 910 cm− 1 were of diagnostic interest because they could easily be distinguished
from the absorptions of the tanned leather matrix. Therefore, they were selected to evaluate
the extent of penetration and the distribution of the rubber within the leather. For this
purpose, two sampling methods were employed, as described in the next two sections.
The first method consisted of slicing the 1 mm thick leather parallel to the sample surface,
resulting in three slices; then, the new surfaces, generated at different depths from the
original grain and flesh external leather surfaces, were analyzed using ATR-FTIR (or by
micro-ATR-FTIR for a more detailed mapping). The second method consisted of cutting
the leather perpendicular to the sample surface and then recording an FTIR cross-sectional
profile using a micro-ATR probe.

3.2. ATR-FTIR Mapping of Internal Layers of Rubber-Treated Tanned Leather

ATR-FTIR intensity profiles were obtained by analyzing six surfaces of three slices
from each of the two samples treated with XSBR and SBR, respectively. The slices were
prepared by cutting the leather parallel to the outer grain surface. The depth profiles at 966
and 910 cm− 1 , reported in Figure 4, showed similar trends for each treating polymer, as one
would expect because both absorptions were characteristic of the treating polymer with
negligible contributions from the leather matrix. On the contrary, clear differences could be
observed when comparing the profiles of samples treated with either SBR or XSBR. In the
case of the SBR-treated leather, the concentration of the rubber appeared to be higher in
the grain and flesh external surfaces (layers a and e in Figure 4) than in the internal layers
(layers b and c). In contrast, the intensity profiles of XSBR-treated samples presented a
moderate variation, indicating a more uniform distribution of the rubber from the grain
surface throughout the bulk and down to the flesh side.
The rubber distribution within each of the above surfaces was also evaluated by
recording µ-ATR-FTIR maps of 500 × 500 µm areas. These were processed as correlation
maps of the recorded µ-ATR-FTIR spectra in the range between 1000 cm− 1 and 675 cm− 1
using the ATR spectrum of pure SBR (Figure 5) as the reference for the correlation, as
performed by the software of the FTIR instrument. The selected spectral range comprised
absorptions from the =C-H deformation modes of the styrene and butadiene units of
both rubbers with negligible contributions from the leather matrix. The correlation maps
obtained from slices at different depths, shown in Figures 6 and 7, were in good agreement
with the intensity profiles of Figure 4. In the SBR-treated leather, the rubber concentration
appeared to be quite high and uniformly distributed on the outer surfaces (Figure 6a,f)
Polymers 2024, 16, 3411 7 of 14

with predominant red-green regions showing a good correlation with the SBR spectrum,
but were nearly absent in the inner layers across the thickness of the leather (extended blue
regions, indicating a poor correlation with the SBR spectrum). This was clearly indicative
of poor SBR penetration into the tanned leather. On the contrary, a similar concentration
and relatively uniform distribution of the rubber throughout the tested areas and across
the leather profile was apparent from the correlation maps of the XSBR-treated leather,
confirming the better penetration of the carboxylated rubber.

(a) (b)
Figure 4. Intensity profile at 966 cm−1 (a) and at 910 cm−1 (b) based on the ATR-FTIR analyses of
three slices of tanned leather treated with either SBR (black line) or XSBR (red line). The scan line
zero-point (length axis) is set on the grain (outer) side. The letters refer to surface maps recorded
from layers at the given depth, obtained by slicing the sample parallel to the leather surface (see also
the maps in Figures 6 and 7).

Figure 5. Spectral range comprising absorptions from =C-H deformation modes of styrene and
butadiene units, selected to assess the correlation between the reference spectra of the two rubbers
(representative spectrum recorded from SBR-treated leather, outer surface, and flesh side).
Polymers 2024, 16, 3411 8 of 14

Figure 6. False-color µ-ATR-FTIR correlation maps with SBR as the reference for 1 mm thick SBR-
treated leather sliced parallel to the grain surface: (a) grain side; (b) inner layer at about 70 µm from
grain; (c) layer at about 470 µm from grain; (d) layer at about 530 µm from grain; (e) layer at about
70 µm from flesh; (f) flesh side. The color range from blue to red indicates increasingly better matches
between the µ-ATR-FTIR spectra and that of SBR. A poor correlation indicates that SBR was nearly
absent. Map area 500 × 500 µm, scale bar in frame (d); spectral range 675–1000 cm−1 .

Figure 7. False-color µ-ATR-FTIR correlation maps of XSBR-treated leather slices, recorded as

described in Figure 6 (SBR-treated leather): (a) grain side; (b) inner layer at about 70 µm from grain;
(c) layer at about 470 µm from grain; (d) layer at about 530 µm from grain; (e) layer at about 70 µm
from flesh; (f) flesh side.
Polymers 2024, 16, 3411 9 of 14

3.3. Distribution of Rubber Within the Tanned Leather Using Micro-ATR-FTIR Depth Profiling
The penetration effectiveness of the two rubbers was also assessed by recording a
micro-ATR (µ-ATR) scan line across sections of SBR and XSBR tanned leather, respectively
(Figure 8a). The ATR spectra shown in Figure 8b are representative of the central region
of the cross-section, where the largest differences were observed by mapping the layers
(Figures 6 and 7). The presence of the characteristic peaks at 966, 910, 758, and 697 cm− 1
from the styrene and butadiene units of the rubbers, clearly observed only in the spec-
trum of the XSBR-treated leather (red profile in Figure 8b), was consistent with its more
effective penetration into the tanned fibrous network. The better penetration of XSBR was
highlighted by the µ-ATR intensity profiles along the cross-section of the carboxylated
SBR- and XSBR-treated leather samples for absorptions at 966 cm− 1 and 910 cm− 1 from
the butadiene units (Figure 9). The intensity of both peaks for the XSBR-treated leather
was about three times larger than in the case of the SBR-treated leather, confirming the
better penetration of the carboxylated rubber with respect to the not-functionalized one.
The large fluctuation in absorbance recorded across the XSBR-treated leather was due
to the point-like µ-ATR analysis of the fibrous and highly heterogeneous tanned leather
matrix; such fluctuations could also be the result of poor contact between the leather and
the ATR probe (Ge crystal) at some points of the cross-sectional surface due to the complex
morphology of the analyzed samples.

(a) (b)

Figure 8. (a) Optical micrograph of rubber-treated leather cross-section showing the scan line used
for the micro-ATR analyses; (b) spectra of SBR-treated (black line) and XSBR-treated (red line) leather
samples taken at a position about 650 µm from the grain layer surface, with the magnification of the
diagnostic region between 1000 and 670 cm−1 shown in the inset.

Scanning electron microscopy (SEM) images were also recorded from the grain surfaces
of XSBR-treated and untreated tanned leather. The good penetration of XSBR, applied
along with the retanning agents at a pH higher than the isoelectric point of the leather, was
confirmed by the improved fullness of the cross-sectional morphology of the treated leather
(Figure 10b). It is worth pointing out that the alkaline pH during retanning causes some
Polymers 2024, 16, 3411 10 of 14

swelling of the leather and likely facilitated the diffusion of the ionomeric XSBR within
the fibrous leather matrix, but it prevented an effective H-bonding interaction between
the carboxylate groups of XSBR and the collagen protein of the leather; on the other hand,
the soft rubber domains within the fibrous leather structure were expected to turn into
elastomeric ones at a final retanning pH ≈ 5 (lower than the isoelectric point of the tanned
leather), converting the carboxylate into effective H-bonding carboxylic groups.

(a) (b)
Figure 9. Intensity profile at (a) 966 cm−1 and (b) 910 cm−1 , for XSBR-treated (red line) and SBR-
treated (black line) leather (reported as the ratio of the intensity of the absorption from the tanned
leather matrix at 1235 cm−1 ). The scan line zero-point (length axis) is set at the grain (outer) side. The
arrows indicate the depth at which the spectra in Figure 3 were recorded.

(a) (b)

(c) (d)
Figure 10. SEM micrographs (left) and photograph of the cross-section (right) of the leather without
an elastomer (a,b) and treated with XSBR (c,d).
Polymers 2024, 16, 3411 11 of 14

3.4. Mechanical Response of Rubber-Treated Leathers

The improved mechanical properties of the leather upon application of the carboxy-
lated XSBR within the retanning process were apparent from the results of the mechanical
tests, as listed in Tables 1–3.
The results of the ball burst test for the determination of the distension and strength of
the leather surface (ISO 3379:2015), as shown in Table 1, indicated that treatment with XSBR
resulted in about a 25% increase in the elongation at the break compared with the untreated
leather. This translated into improved flexibility and higher lastability (i.e., durability in
use) of the rubberized leather.

Table 1. Elongation at the break 1 of retanned leather in the crust 2 : influence of XSBR addition.

Retanned Leather, Retanned Leather + XSBR,

Sample
mm mm
1 6.32 9.93
2 8.25 10.11
3 7.25 10.08
Average ± St. Dev. 7.27 ± 0.97 10.04 ± 0.11
1 ISO 3379:2015 “Determination of distension and strength of leather surface”. 2 In tannery terminology, crust
leather is an intermediate dry stage after the wet process (beamhouse, tanning, and retanning) and before finishing.

The improved mechanical properties of the leather rubberized with XSBR were further
confirmed by the tear strength tests performed according to UNI EN ISO 3377-1 (single-
edge tear, also known as “trouser tear” test) and ISO 3377-2 (double-edged tear test).
The linear load resistance response to elongation and the tear resistance results, as listed
in Table 2, were in good agreement with the results expected for a uniform dispersion
of the carboxylated elastomer in the leather matrix, as previously highlighted by the
spectroscopic analyses.

Table 2. Tear resistance of tanned leather: influence of XSBR addition.

Tear Load: Single-Edge Tear 1 Tear Load: Double-Edge Tear 2

(N) (N)
Sample
Retanned Retanned Retanned Retanned
Leather Leather + XSBR Leather Leather + XSBR
Parallel 29.8 36.7 68.3 116.2
Parallel 36.4 55.3 60.2 104.0
Perpendicular 31.2 37.2 62.2 112.3
Perpendicular 34.3 43.5 61.8 110.8
Average ± St. Dev. 32.9 ± 3.0 43.2 ± 8.7 63.1 ± 3.6 110.8 ± 5.1
1 ISO 3377-1. 2 ISO 3377-2.

To comparatively evaluate the effectiveness of the two rubbers, tensile stress-strain

tests were performed according to ISO 3376 on retanned leather samples rubberized with
either SBR or XSBR. The results, as reported in Table 3, indicated a slightly lower (about
5%) tensile strength and higher (20%) extensibility, with full deformation recovery upon
release of the applied stress, of the XSBR-treated leather compared with the leather treated
with SBR. This was a significant and highly desired result when compared with the typical
mechanical properties not only of untreated (not rubberized) tanned leather, but also of
SBR-treated leather. The highly hydrophobic SBR rubber hardly penetrated the bulk of the
leather, as previously shown in the FTIR microscopy analysis of the leather layers, and it
could only develop weak hydrophobic interactions, insufficient to convert the SBR rubber
into a true elastomer or to achieve the desired physical strengthening of the treated leather.
Polymers 2024, 16, 3411 12 of 14

Table 3. Tensile strength and elongation tests according to ISO 3376 1 .

Thickness Tensile Strength ± St. Dev. Elongation at Break ± St. Dev.

Sample
(mm) (N/mm2 ) (%)
Retanned leather (RL) 1.38 13.4 ± 2.5 47.4 ± 7.4
RL with XSBR 1.42 17.0 ± 1.8 65.7 ± 6.7
RL with SBR 1.35 17.9 ± 2.7 55.7 ± 10.2
1 Average and standard deviation of the results from four replicate measurements. Each set of measurements was
performed using four leather samples cut from the same leather piece, two parallel and two perpendicular to
the backbone.

The enhancement in the mechanical properties of the retanned leather achieved by

a relatively small fraction (here, 18 wt%) of elastomer-like XSBR domains and, in partic-
ular, the improved elastic response were in agreement with the already-discussed more
effective penetration of the carboxylic rubber into the fibrous network structure, along
with the excellent adhesive interaction between the elastomeric domains and the tanned
leather fibers, further enhanced by the onset of intra- and inter-polymeric pH-reversible
H-bonding interactions.
In particular, the improved stretchability of the retanned leather treated with XSBR, as
determined by elongation-at-break measurements using different test methods (Tables 1
and 3), could be ascribed to the combination of a more uniform dispersion of elastomeric
XSBR domains in the bulk of the leather than in the case of SBR as well as the effective
generation of an H-bonded network involving the carboxylic acid groups of XSBR upon
switching the pH to below the isoelectric point of both the leather and ionomer in the last
processing stage. Such H-bonding can turn a soft rubber into an elastomeric and highly
adhesive material, while the ionomeric nature of the same polymer at a pH higher than
the isoelectric point of both the leather and XSBR promoted its dispersion in water and its
penetration within the network structure during the leather retanning process.

4. Conclusions
The primary objective of this study originated from a successful experimental attempt
performed in a technical environment to render elastic the flexible domains present in
soft chromium-tanned leather. The approach was simply based on the addition of an
aqueous suspension of the carboxylated XSBR elastomer in the tanning reactor during
the retanning process, a product innovation subsequently recognized by the release of
an international patent. The present study provides scientific support for the molecular
interpretation of the observed improvements in the leather properties at a macroscopic
level. In particular, the supramolecular structure of the tanned leather, consisting of a
crosslinked network of collagen protein fibers, was effectively modified by treatment with
XSBR, a styrene-butadiene-acrylic-acid terpolymer characterized by elastic behavior similar
to conventional SBR, that was expected to ensure a better interaction with the collagen
protein of leather due to the presence of a small (2–3%) amount of carboxylic groups along
the macromolecular chain.
Under alkaline conditions, the anionic carboxylate groups of XSBR were found to be
critical in promoting the penetration of the ionomer within the fibrous network of tanned
leather. The improved penetration of XSBR (vs. the electroneutral SBR) could be ascribed
to its improved dispersibility in water and lower tendency to stick to the outer surface
of the leather substrate due to the repulsive electrostatic interaction at a pH above the
isoelectric point of the collagen fibers. In the subsequent processing step, the lower pH
allowed the carboxylate groups to turn into H-bonding carboxylic acid groups. This step
was of critical importance; to ensure significant elastic recovery of the deformation, the
domains of the XSBR polymer interdispersed within the fibrous material must not only be
soft (rubbery, i.e., amorphous and with a low glass transition temperature), but also mildly
crosslinked, either physically or chemically, and have a good adhesive interaction with the
fibrous leather network. This objective was achieved with the XSBR rubber, which could be
Polymers 2024, 16, 3411 13 of 14

turned into a slightly crosslinked elastomeric material through intermolecular H-bonding

at an acidic pH.
The presence in the bulk of the leather of soft elastomeric domains, also capable of
hydrogen bonding at the interface with the collagen fibers and tanning agents, provided the
treated leather with improved stress recovery after deformation, thus limiting the defects
produced by fatigue during use.

5. Patent
The present work originates from an issued patent to D. Marinai: “Tanning process
for producing leather with high elastic properties and leather obtained”, European patent
EP3041962.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/polym16233411/s1. Figure S1: Optical micrograph and line scan
recorded by µ-ATR-FTIR on the leather treated with 55% and 30% SBR; Figure S2: Optical micrograph
and line scan recorded by µ-ATR-FTIR on the leather treated with 55% and 30% XSBR.
Author Contributions: Conceptualization: F.C.; Methodology: D.M., C.B., L.M. and A.M.; Investiga-
tion: A.M., G.A.D., C.B. and P.M.; Resources: G.A.D., D.M., F.C. and V.C.; Writing—Original Draft
Preparation: A.M., F.C., G.A.D. and D.M.; Writing—Review and Editing: A.M., V.C., F.C., G.A.D. and
D.M.; Supervision: V.C., F.C. and D.M. All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: The original contributions presented in this study are included in the
article/Supplementary Material. Further inquiries can be directed to the corresponding author.
Conflicts of Interest: Daniele Marinai is the owner of Kemas s.r.l. and holds the patent on the product
application, from which the research reported in the paper originated. Lorenzo Marinai and Cristiana
Borchi are permanent employees of Kemas s.r.l.; Gustavo Adrián Defeo is the vice-president of the
company CTC Ars Tinctoria, contracted by Kemas s.r.l. to support the development of the product
from which the research of this work originated. Francesco Ciardelli is the President and research
associate of Spin-PET s.r.l., the company contracted by Kemas s.r.l. to support the further studies of
the product from which the research of this work originated, and to succesfully defend the existing
patent against a lawsuit from competitors. Pierpaolo Minei is a permanent research staff of Spin-PET
s.r.l. Valter Castelvetro and Antonella Manariti are personnel from the University of Pisa, initially
contracted to run some of the analyses, then involved without any additional financial committment
in the further investigations leading to the research paper. The authors declare no conflict of interest.

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