Aramid pulp with physisorbed imidazolium ionic liquids for solvent-casted

enhanced styrene-butadiene rubber composites

 trio da Silva
Vinıcius Deme ,1,2 Marly Maldaner Jacobi,3 Henri Stephan Schrekker,2
Sandro Campos Amico1
1
PPGE3M, School of Engineering, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, Porto Alegre RS
91501-970, Brazil
2
Laboratory of Technological Processes and Catalysis, Institute of Chemistry, Universidade Federal do Rio Grande do Sul, Av.
Bento Gonçalves 9500, Porto Alegre RS 91501-970, Brazil
3
Materials Science Graduate Program, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, Porto Alegre RS
91501-970, Brazil
Correspondence to: V. Deme
 trio da Silva (E - mail: [email protected])

ABSTRACT: Poly-p-phenyleneterephthalamide is a broadly used aramid for the strengthening of materials. Nevertheless, its relatively
inert surface is an obstacle for obtaining composites with enhanced properties. In this work, three ionic liquids (IL) were investigated
as compatibilizers in the preparation of styrene-butadiene rubber (SBR)-aramid pulp composites. The composites were characterized
using hardness and tensile tests, swelling, differential scanning calorimetry, and thermal gravimetric analysis, and also scanning elec-
tron microscopy. Aramid pulp treated with IL showed more fibrillation than the untreated pulp. The best characteristics were found
for the composite with 5 phr of aramid pulp-1 wt % of physisorbed IL, which showed the lowest swelling degree compared to the
IL-free SBR-aramid composite (341% and 410%, respectively) and the highest tensile strength (2.48 MPa), 340% superior to that of
SBR (0.73 MPa), and 25% superior to the IL-free SBR-aramid composite (2.05 MPa). Confirming the potential of imidazolium IL to
be used as compatibilizers in SBR-aramid composites. V C 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46693.

KEYWORDS: composites; fibers; ionic liquids; mechanical properties; rubber

Received 18 January 2018; accepted 7 May 2018

DOI: 10.1002/app.46693

INTRODUCTION Poly-p-phenyleneterephthalamide (PPTA) is the most used ara-

mid due to its high tensile strength-to-weight ratio and excellent
Styrene-butadiene rubber (SBR) is one of the most widely used
thermal stability, which are important properties also for fillers in
rubbers. This versatile material is used in automotive tire and
rubbers. The strength and thermal stability of this aromatic poly-
tire-based products,1 in footwear and engineering products, and
aramid can be attributed to intermolecular hydrogen bonds
in mechanical goods and other applications.2 Elastomers are, in
between carbonyl and NH groups, in combination with aromatic
general, reinforced with conventional fillers such as carbon
p–p stacking interactions between adjacent aramid chains.7
black (CB) and silica3 as in tire tread applications.4,5 Neverthe-
less, due to their particulate morphology, high contents are Fiber reinforced rubber compounds have potential use in a wide
required to achieve the desired properties, which increases the range of more demanding applications, such as tires, transmis-
final density of the composite. In the case of CB, there are other sion and conveyor belts, and high-pressure hoses.8 A variety of
disadvantages related to the high-energy demanding production fibers has been used for that, including PPTA, carbon, glass and
and its polluting potential. As such, the replacement of a signifi- ultrahigh-molecular-weight polyethylene.1 Improvements in wet
cant amount of such a filler by another reinforcing material, in traction and rolling resistance were observed by adding a small
lower content, would be advantageous for the rubber and tire amount of short fiber surface-treated PPTA pulp in CB-filled
industry.6 Also, according to Gopi et al.,6 the reduction in filler tire tread compounds.9–11 For instance, a two-step dipping pro-
would reduce specific gravity and heat generation in the com- cess with (1) epoxy resin (in some cases, replaced by isocyanate)
pound during service, leading to improved performance of the and (2) resorcinol formaldehyde latex (RFL) may be used to
tire tread material. increase reactivity of the fiber surface and, consequently, the

C 2018 Wiley Periodicals, Inc.

V

46693 (1 of 7) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46693

ARTICLE WILEYONLINELIBRARY.COM/APP

methylimidazolium chloride (C4MImCl), 95%, was used as pur-

chased from Sigma-Aldrich (St. Louis, Missouri, USA). A procedure
reported in the literature17 was followed for the synthesis of 1-n-
butyl-3-methylimidazolium methanesulfonate (C4MImMeS) IL and
1-triethylene glycol monomethyl ether-3-methylimidazolium metha-
Figure 1. Chemical structures of the ionic liquids tested as nesulfonate (C7O3MImMeS) IL, and the resulting spectral data were
compatibilizers. in accordance with those reported.17 Their chemical structures are
shown in Figure 1.
rubber–fiber interaction. Fiber fibrillation is another approach Before IL-treatment of the AP, Soxhlet extraction with acetone
for improving the rubber-aramid adhesion.8,10 as solvent was performed for 24 h to remove its finish. Subse-
Ionic liquids (IL), in special the imidazolium cation-based ones, quently, the finish-free AP was treated with ethanolic IL solu-
have the potential to be used as compatibilizers in the prepara- tions (Table I), containing IL amounts that corresponded to 0.5,
tion of polymeric nanocomposites, which is due to the involve- 1.0, and 2.0 wt % of IL in relation to the mass of AP. The AP,
ment of their p-cloud in p–p stacking and their hydrogen atoms immersed in the IL solution, was placed in an ultrasonic bath
(C2AH, C4AH, and C5AH) in hydrogen bonds with fillers. For at 60 8C for 1 h. Then the AP with adsorbed IL was dried in an
instance, carbon nanotubes form strong physical interactions oven at 110 8C for 12 h. AP that underwent Soxhlet extraction
with the aromatic imidazolium cation through p–p stacking, but was not treated with IL was used as reference.
enabling compatibilization with a polymer matrix through its N- The SBR–AP composites were prepared by solvent casting, keep-
substituent.12 In the case of silica fillers, hydrogen bonds form ing the AP-content constant at 5 phr (parts per hundred of rub-
between imidazolium IL and the silica surface, which has been ber), and the corresponding samples were codified, using SBR/
exploited in the preparation of polymer–silica composites.13–15 A.IL. content (i.e., SBR/A.Cl.05 stands for SBR with AP, which
Herein, the potential of three imidazolium IL to compatibilize was treated with 0.5 wt % of C4MImCl). Solvent casting was
aramid pulp-SBR composites was investigated in this work. The chosen considering the reported better mixing and the use of
imidazolium cation and the IL anion could favor interaction lower temperatures compared to other methods.16 The tempera-
with the polar aramid through hydrogen bonds and the less polar ture control at this stage is very relevant, as rapid evaporation
imidazolium N-substituent could enhance interaction with the of the solvent would leave bubbles on the surface of the film
apolar SBR matrix. The new modified SBR-aramid composites and inner defects or voids at the fiber–matrix interface.
were prepared by solvent casting,16 and characterized to study In previous studies,18,19 incorporation of 10 phr of AP in poly-
rubber–filler interaction, using aramid- and IL-free SBR and the mer composites significantly decreased strain at break. There-
IL-free aramid-SBR composite for comparison. fore, in this work, the fiber content was kept at 5 phr in an
attempt to allow high strains, avoiding weak regions due to
EXPERIMENTAL macrophase separation. Also, if added in great amount, the
SBR (trade name 1502) provided by Petroflex S.A. (now Arlanxeo pulp tends to aggregate, preventing dispersion of bundles to the
Brasil S.A. Duque de Caxias, Rio de Janeiro, Brazil) and p-Aramid filament level.20 SBR (2.0 g) was dissolved in THF (40 mL)
PPTA pulp (AP) donated by DuPont were used in this study. Ace- using magnetic stirring at room temperature. After that,
tone and tetrahydrofuran (THF) were purchased from VETEC Quı- dicumyl peroxide (0.25 phr) was added to the mixture as a cur-
mica Fina Ltda (Duque de Caxias, Rio de Janeiro, Brazil) and used ing agent. Subsequently, the IL-treated AP (5 phr) was added to
without further purification. Ethanol 95% was used as purchased the solution, mechanically stirred for 1 h, placed in an ultra-
from FMAIA (S~ao Paulo, Brazil). Dicumyl peroxide was recrystal- sonic bath for 1 h, and stirred again for 1 h. Finally, the mix-
lized from a commercial product. The IL 1-n-butyl-3- ture was left at room temperature for 48 h to volatilize the
solvent and to produce the composite film, which was cured at
Table I. Weight Percentage of IL Based on the AP Mass, and the Corre- 160 8C, in a hot press, at 30 kN for 10 min (Figure 2). The ara-
sponding Concentration of the Ethanolic Solution mid- and IL-free SBR and the IL-free SBR-aramid composite
(using finish-free AP) were prepared under the same conditions
IL wt % M (mmol/L) for comparison purposes.

C4MImCl 0.5 0.65 Swelling measurements of the cured composites were performed
C4MImCl 1.0 1.30 by immersing samples of known weight in toluene at 30 8C for
72 h, long enough to reach equilibrium. Samples were removed
C4MImCl 2.0 2.60
from the solvent, the surface was rapidly dried, and the samples
C4MImMeS 0.5 0.50
were weighed again. From the mass of the sample before and after
C4MImMeS 1.0 1.00
swelling, the mass of the solvent absorbed per gram of sample
C4MImMeS 2.0 2.00 was determined. The swelling degree was expressed as the weight
C7O3MImMeS 0.5 0.35 of solvent (in g)/weight of dry composite (in g) 3100%.
C7O3MImMeS 1.0 0.70
Shore A hardness of the composites films with a minimum
C7O3MImMeS 2.0 1.40
thickness of 3.7 mm was measured using a Bareiss model GS-

46693 (2 of 7) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46693

ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 2. Schematic representation of the AP-treatment and preparation of the rubber composites. *RT 5room temperature.

709 equipment. Seven points were evaluated in each sample, each sample. These tests provided the average values of tensile
and measurements were taken after 3, 15, and 30 s of penetra- strength and strain at break. The tensile strength was calculated
tion of the durometer tip in the sample. by dividing the maximum force per unit of the cross-sectional
Differential scanning calorimetry (DSC) was performed to area of the unstrained specimen (T 5 Fmax/Ao). The strain at
determine glass transition temperature (Tg) of the composites, break was calculated by dividing the increase in length (at
using DSC Q20 from TA Instruments. The DSC instrument was break) by the initial gauge length (E 5 100 3 [L 2 L0]/L0).
calibrated using indium. The sample (average weight: 5.7 mg) The surfaces of the commercial AP, AP washed with acetone,
was sealed in an aluminum pan and then heated and cooled AP treated with IL and composites were analyzed by scanning
between 290 and 150 8C at a rate of 10 8C/min. The Tg was electron microscopy (SEM), using a Phenom ProX microscope.
determined in the first heating run. The samples were readily covered with a thin layer of gold, and
Thermal gravimetric analysis (TGA) was performed on a TA the SBR composites were fractured in liquid nitrogen before
Instruments Q50 thermogravimetric analyzer to determine the metallization of the fractured surface.
IL-content adsorbed on the AP surface, and to evaluate thermal
RESULTS AND DISCUSSION
stability of the composites. The extrapolated Tonset refers to the
temperature at which the weight loss began and was specified IL Surface Treatment of AP
by ASTM E473 and ASTM E2550. The reproducible Tonset value Treatment of AP with IL was performed after removal of the
of the independent parameter was found by extrapolating the finish from the commercial AP, which was done to favor direct
dependent parameter baseline prior to the event and a tangent
constructed at the inflection point on the leading edge to their
intersection. The sample (average weight: 10 mg) was placed in
a platinum pan, and heated at 20 8C/min from 35 to 940 8C.
To analyze the functional groups present on the surface of the ara-
mid pulp (untreated and treated), Fourier-transform infrared
spectroscopy (FTIR) in the mid infrared range (4000–500 cm21)
was performed in an ALPHA-P, compact Bruker FTIR
spectrometer.
Tensile properties of the composites were evaluated in a DL
5000/10000 EMIC equipment, equipped with a 50 N load cell
and determined according to ASTM D412. The samples were Figure 3. SEM micrographs of (a) commercial AP after washing with ace-
cut in a rectangular format (length 5 50 mm; width 5 10 mm; tone and (b) AP after washing with acetone and subsequently treating
average thickness 5 0.4 mm). The tests were performed at room with C4MImCl (1.0 wt %) (scale bar: 10 lm). [Color figure can be viewed
temperature at a rate of 50 mm/min using three specimens for at wileyonlinelibrary.com]

46693 (3 of 7) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46693

ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 4. FTIR transmittance spectra of (a) A (AP washed with acetone), A.Cl.20 (AP washed with acetone and treated with 2 wt % of C4MImCl),
A.MeS.20 (AP washed with acetone and treated with 2 wt % of C4MImMeS), and A.C7O3.20 (AP washed with acetone and treated with 2 wt % of
C7O3MImMeS), (b) A, A.Cl.20, and C4MImCl, (c) A, A.MeS.20, and C4MImMeS, and (d) A, A.C7O3.20, and C7O3MImMeS. [Color figure can be viewed
at wileyonlinelibrary.com]

interfacial interaction between AP and IL. Figure 3 shows treatments are shown in Figure 4, and they show the three char-
micrographs of AP after removal of the finish [Figure 3(a)] and acteristic aramid peaks at 3300 (NAH stretching vibrations in a
after the subsequent treatment with 1.0 wt % of C4MImCl [Fig- secondary amide in trans form with a bonded hydrogen), 1640
ure 3(b)]. AP is a fibrillated form of short aramid fibers, which (amide C@O stretching for hydrogen-bonded amide groups),
is clearly visible in both samples. Interestingly, degree of fibrilla- and 1540 cm21 (NAH group).22,23 FTIR analyzes of the IL
tion as well as roughness of the bundles in the AP treated with showed spectral bands in the 3200–3000 cm21 region attributed
1.0 wt % of C4MImCl was higher, and this could improve the to the coupled aromatic CAH stretching vibrations of the imi-
SBR–AP interaction mainly due to increased mechanical inter- dazolium ring, while those within 3000–2850 cm21 can be
locking,21 resulting in better load transfer from matrix to fibers assigned to the aliphatic CAH stretches of the CH2 and CH3
through shear forces on the interface.20 In Figure 3(a,b), quali- groups of the butyl chains. Noticeably, imidazolium ring
tative evaluation shows several smaller fibrils and a large bundle stretching modes within 1564–1164 cm21 are seen for all three
in the center (in the red circles). In Figure 3(a), this bundle has IL and SO–3 stretching at 1097 cm21 for C7O3MImMeS. And
a relatively smoother surface compared to the rough and fibril- the absorption of water produced a broad OAH peak at about
lated surface of the material treated with the IL solution [central 3400 cm21.17,24,25
bundle in Figure 3(b)].
The absence of IL-related peaks and wavenumber shifts in the
Other tests were also performed to evaluate the surface treat- AP-related peaks can suggest that (1) a minor part of the IL
ment of AP, however, TGA traces did not confirm the theoreti- was adsorbed on the outer surface and most of it was located in
cal IL-contents of 0.5, 1.0, and 2.0 wt %. The FTIR the interior of the AP bundles, (2) there may be overlaps of the
transmittance spectra of the AP before and after the IL IL and AP characteristic peaks, since the latter was present in

46693 (4 of 7) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46693

ARTICLE WILEYONLINELIBRARY.COM/APP

number of holes (in red circles) present mostly in SBR/A due to

the pull-out of the AP filler. Since pull-out is a sign of a weak
matrix–filler interaction, the SBR/A.Cl.10 micrographs show
preliminary indications that the IL C4MImCl acted as
compatibilizer.
Interfacial Interaction of the SBR–AP Composites
Equilibrium swelling tests can be used to evaluate interaction
between filler and matrix, in this case, the bonding between AP
fibers and SBR. The polymer chain segments bonded to fibers
will swell less than the others, which will reflect as lower swell-
ing degree of the composite. This way, if adhesion improves,
swelling is restricted in the region around the fiber.26
Incorporation of AP into the SBR matrix resulted in a strong
reduction in swelling, as shown in Table II. As a strong interfa-
cial chemical interaction between the incompatible SBR matrix
and the AP filler is unlikely, the increase in adhesion was proba-
bly due to mechanical anchoring of the fibrils in the matrix.8
Application of AP with adsorbed IL resulted in minor fluctua-
tions in swelling. The lowest swelling value, 340%, was achieved
with the SBR/A.Cl.10 composite, indicating a stronger SBR/AP
adhesion with 1.0 wt % of the IL C4MImCl. This could be
Figure 5. SEM micrographs of (a-,b) SBR/A (scale bar: 20 and 10 lm), ascribed to the effective role of this IL as compatibilizer. The
(c,d) SBR/A.Cl.10 (scale bar: 20 and 10 lm). [Color figure can be viewed nonpolar N-butyl side chain of the imidazolium cation could
at wileyonlinelibrary.com] interact with the nonpolar SBR rubber chains through van der
Waals forces. Furthermore, disruption of the hydrogen bonding
much greater amount. Although the amount and location of IL network of the aramid chains as a consequence of the IL chlo-
in the AP are inconclusive, the previous SEM micrographs (Fig- ride anion [see the increased fibrillation in Figure 3(b),7 the
ure 3) showed morphological features that are expected to pro- AP-IL chloride anion hydrogen bond and the IL chloride anion-
mote its effectiveness as filler. IL imidazolium cation Coulomb/hydrogen bond interactions
Solvent Casted SBR–AP Composites could further favor the role of this IL as compatibilizer.
The SBR–AP composites were prepared by solvent casting vary- Mechanical Properties of the SBR/AP Composites
ing the type and content of ionic liquid. SEM micrographs of The tensile properties of the SBR/AP composites are summa-
the SBR-AP composites (Figure 5) show two distinct phases: (1) rized in Table II. Although Nillawong et al.10 reported a
the continuous SBR phase, and (2) the discontinuous AP phase. decrease in tensile strength with the addition (2–10 phr) of
In general, the AP fibers were randomly distributed. Although either untreated or treated AP to SBR, the solvent-casted com-
both fiber bundles and smaller fibrils were dispersed in the SBR posite SBR/A showed an almost threefold increase in tensile
matrix, no significant variations in dispersion degree were strength (Figure 6). Aramid fibers possess a unique morphology
observed between SBR/A and SBR/A.Cl.10. An important differ- and may contain several levels of overlapping microscopic and
ence between the fractured surfaces of both composites is the macroscopic structures.20,27 The characteristic fibrillation of the

Table II. Swelling, Tensile Strength, and Strain at Break of the SBR/AP Composites

Sample Swelling (%) Tensile strength (MPa) Strain at break (%)

SBR 716 6 42 0.73 6 0.03 549.2 6 18.7
SBR/A 410 6 5 2.05 6 0.03 84.2 6 7.1
SBR/A.Cl.05 441 6 12 1.84 6 0.09 83.6 6 7.9
SBR/A.Cl.10 341 6 12 2.48 6 0.07 64.8 6 5.4
SBR/A.Cl.20 413 6 20 1.92 6 0.12 102.5 6 2.5
SBR/A.MeS.05 535 6 24 1.71 6 0.12 166.4 6 51.1
SBR/A.MeS.10 376 6 29 2.04 6 0.21 73.7 6 5.1
SBR/A.MeS.20 429 6 15 1.79 6 0.09 97.9 6 10.9
SBR/A.C7O3.05 351 6 16 1.34 6 0.04 108.0 6 10.3
SBR/A.C7O3.10 473 6 4 1.68 6 0.05 112.9 6 5.3
SBR/A.C7O3.20 385 6 18 2.02 6 0.06 85.6 6 5.7

46693 (5 of 7) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46693

ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 6. Tensile curves of SBR, SBR/A, and SBR/A.Cl.10 up to 100%

strain (SBR failed at 549%). [Color figure can be viewed at wileyonlineli-
brary.com]

AP used and the selected method of preparation by solvent cast-

ing enhanced SBR/A tensile strength, most likely due to
mechanical anchoring of the fibrils.8 In general, the SBR/AP
composites showed superior tensile strength compared to neat
SBR, which was accompanied by a reduction in strain at break.
This can be seen in Figure 6, where the SBR/A and SBR/A.Cl.10
composites ruptured before 100% strain but the rubber (SBR)
failed at 549.2% 6 18.7% (Table II). Within the tested IL addi-
tives and IL contents, the highest tensile strength was achieved
by the SBR/A.Cl.10 composite, outperforming the IL-free SBR/A
composite. That is, an increase in tensile strength of approxi-
mately 25%, for SBR/A.Cl.10 compared to SBR/A, was achieved,
which is significant, especially taking into account that this is a
RFL- and CB-free system.
As for hardness results, the IL-free SBR/A composite showed
two times higher hardness in comparison to the neat SBR sam-
ple (Table III). In contrast, the use of IL caused only minor var- Figure 7. (a) DSC curves, (b) TGA curves, and (c) DTGA curves of SBR,
iations. Here again, the SBR/A.Cl.10 composite presented the SBR/A, and SBR/A.Cl.10. [Color figure can be viewed at wileyonlineli-
greatest increment among the studied materials, reaching an brary.com]
average value of 63 (T3). Interestingly, this value (with only 5
phr of AP and no CB) is at the same level (63–63.5) of those
Table III. Hardness of the SBR/AP Composites reported for SBR composites with AP (10 phr) and CB (60
phr).10
Hardness (shore A)
Thermal Properties of the SBR/AP Composites
Sample T3a T15a T30a Natural rubber contains naturally occurring antioxidants. In
SBR 30 6 1 27 6 2 26 6 2 contrast, SBR is a synthetic rubber that is susceptible to oxida-
SBR/A 60 6 3 57 6 4 55 6 5 tive degradation unless special precautions are taken to stabilize
the polymers. Standard practice in the industry includes incor-
SBR/A.Cl.05 58 6 4 54 6 4 53 6 5
porating a stabilizing agent in the polymer during manufacture.
SBR/A.Cl.10 63 6 2 60 6 3 58 6 4
Although the presence of an effective stabilizing agent is a prime
SBR/A.Cl.20 62 6 5 60 6 5 59 6 5
factor in preventing heat degradation of SBR, other factors also
SBR/A.MeS.05 50 6 4 46 6 4 44 6 4 influence thermal stability of the polymer.28
SBR/A.MeS.10 59 6 4 56 6 3 55 6 3
In order to evaluate the thermal properties, as a consequence of
SBR/A.MeS.20 53 6 2 51 6 3 49 6 4
the incorporation of AP, the composites were submitted to DSC
SBR/A.C7O3.05 49 6 3 43 6 3 40 6 3
and TGA analyses, whose results are shown in Figure 7(a,b) and
SBR/A.C7O3.10 53 6 3 49 6 3 48 6 4 Table IV. Incorporation of the AP filler and the use of IL com-
SBR/A.C7O3.20 56 6 4 54 6 4 53 6 4 patibilizers did not affect the glass transition temperature of
T3, T15, and T30 are the hardness values measured after 3, 15, and SBR (Table IV). This can be considered an advantage because
30 s, respectively. even though there was an improvement in mechanical

46693 (6 of 7) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46693

ARTICLE WILEYONLINELIBRARY.COM/APP

Table IV. Thermal Properties of the SBR/AP Composites 5. Choi, S.-S.; Kwon, H.-M.; Kim, Y.; Ko, E.; Lee, K.-S. Polym.
Int. 2018, 67, 340.
Sample Tg (8C)a T5 (8C)2 T10 (8C)2 Tonset (8C)3 6. Gopi, J. A.; Patel, S. K.; Tripathy, D. K.; Chandra, A. K. Int.
SBR 256 253 365 421 J. Plast. Technol. 2016, 20, 345.
SBR/A 256 257 369 420 7. Dewilde, S.; Dehaen, W.; Binnemans, K. Green Chem. 2016,
18, 1639.
SBR/A.Cl.10 256 251 365 420
SBR/A.MeS.10 256 249 366 419 8. Wennekes, W. B.; Datta, R. N.; Noordermeer, J. W. M.;
Elkink, F. Rubber Chem. Technol. 2008, 81, 523.
a
Determined by DSC.
9. Datta, R. N. Rubber Chem. Technol. 2006, 79, 26.
T5 and T10 are the temperatures at 5% and 10% mass loss, respec-
tively, determined by TGA. 10. Nillawong, M.; Sae-oui, P.; Suchiva, K.; Sirisinha, C. Rubber
Extrapolated onset temperature as determined by TGA. Chem. Technol. 2016, 89, 640.
11. Kashani, M. R. J. Appl. Polym. Sci. 2009, 113, 1355.
properties, the material did not present an increase in Tg, which
12. Kleinschmidt, A. C.; Almeida, J. H. S.; Donato, R. K.;
could restrict applicability of the final composite. Similarly, only
Schrekker, H. S.; Marques, V. C.; Corat, E. J.; Amico, S. C. J.
minor variations were observed in resistance to thermal degra- Nanosci. Nanotechnol. 2016, 16, 9132.
dation [Figure 7(b,c)], with mostly overlapped curves. This also
13. Donato, R. K.; Perchacz, M.; Ponyrko, S.; Donato, K. Z.;
means that stability of the elastomeric phase is not affected by
Schrekker, H. S.; Benes, H.; Matejka, L. RSC Adv. 2015, 5,
the presence of aramid or the ionic liquid treated aramid. SBR
91330.
can easily undergo oxidation due to the instability of unsatu-
14. Donato, K. Z.; Lavorgna, M.; Donato, R. K.; Raucci, M. G.;
rated double bonds and the presence of active allylic hydrogens
Buonocore, G. G.; Ambrosio, L.; Schrekker, H. S.; Mauler,
of the butadiene units when exposed to thermal, oxidative or
R. S. ACS Sustain. Chem. Eng. 2017, 5, 1094.
radiant conditions, which leads to scission of polymer chains.
These reactions may lead to significant reduction in mechanical 15. Donato, K. Z.; Donato, R. K.; Lavorgna, M.; Ambrosio, L.;
Matejka, L.; Mauler, R. S.; Schrekker, H. S. J. Sol-Gel Sci.
properties of the SBR, and eventually shorten service life of the
Technol. 2015, 76, 414.
composites.29
16. Schruben, D. L.; Gonzalez, P. Polym. Eng. Sci. 2000, 40, 139.
CONCLUSIONS 17. Schrekker, H. S.; Silva, D. O.; Gelesky, M. A.; Stracke, M. P.;
Among the tested IL, C4MImCl was identified as a potential Schrekker, C. M. L.; Gonçalves, R. S.; Dupont, J. J. Braz.
compatibilizer for the preparation of SBR/AP composites with Chem. Soc. 2008, 19, 426.
enhanced properties. The application of 1.0 wt % of C4MImCl 18. Uchiyama, Y.; Wada, N.; Iwai, T.; Ueda, S.; Sado, S. J. Appl.
resulted in superior tensile strength and hardness values, which Polym. Sci. 2005, 95, 82.
was not associated with an increase in glass transition tempera- 19. L
opez Manchado, M. A.; Arroyo, M. Polym. Compos. 2002,
ture. In all, the presented results substantiate the potential of 23, 666.
the use of ionic liquid as compatibilizer between SBR and AP, 20. Hintze, C.; Shirazi, M.; Wiessner, S.; Talma, a. G.; Heinrich,
considering that there is currently no efficient, simple treatment G.; Noordermeer, J. W. M. Rubber Chem. Technol. 2013, 86,
with a substance of low toxicity to the environment. As such, 579.
this IL-based approach holds promise for the development of 21. Gonzalez-Chi, P. I.; Rodrıguez-Uicab, O.; Martin-Barrera,
reinforced elastomeric matrix composites with aramid pulp, C.; Uribe-Calderon, J.; Canche-Escamilla, G.; Yazdani-
allowing the use of less aggressive substances thorough a RFL- Pedram, M.; May-Pat, A.; Aviles, F. Compos. Part B: Eng.
free and CB-free route. 2017, 122, 16.
22. Villar-Rodil, S.; Paredes, J. I.; Martınez-Alonso, A.; Tasc
on,
ACKNOWLEDGMENTS
J. M. D. Chem. Mater. 2001, 13, 4297.
The authors would like to thank CAPES and CNPq for the financial 23. Wu, J.; Cheng, X. H. Tribol. Lett. 2006, 24, 195.
support. DuPont is kindly acknowledged for the donation of AP.
24. Brandt, A.; Ray, M. J.; To, T. Q.; Leak, D. J.; Murphy, R. J.;
Welton, T. Green Chem. 2011, 13, 2489.
25. Macmillan, A. C.; McIntire, T. M.; Epstein, S. A.;
REFERENCES Nizkorodov, S. A. J. Phys. Chem. C 2014, 118, 29458.
1. Chilan, C.; Wenxia, W.; Jianguo, Z. J. Thermoplast. Compos. 26. Kraus, G. J. Appl. Polym. Sci. 1963, 7, 861.
Mater. 2016, 29, 1167. 27. Chatzi, E. G.; Koenig, J. L. Polym. Plast. Technol. Eng. 1987,
2. Zhang, Y.; Zhang, Q.; Liu, Q.; Cheng, H.; Frost, R. L. J. 26, 229.
Therm. Anal. Calorim. 2014, 115, 1013. 28. Hunter, B. A.; Nawakowski, A. C.; Barnhart, R. R.;
3. Subramaniam, K.; Das, A.; St€ockelhuber, K. W.; Heinrich, Campbell, E. M.; Hansen, E. B. Rubber Chem. Technol. 1960,
G. Rubber Chem. Technol. 2013, 86, 367. 33, 510.
4. Mao, Y.; Li, S.; Fang, R. L.; Ploehn, H. J. J. Appl. Polym. Sci. 29. Zhou, J.; Wei, L.; Wei, H.; Zheng, J.; Huang, G. RSC Adv.
2017, 134, 45025. 2017, 7, 53596.

46693 (7 of 7) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.46693