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Tapered Multiblock Copolymers Based on Farnesene and Styrene:

Impact of Biobased Polydiene Architectures on Material Properties
Christian Wahlen, Jan Blankenburg, Philipp von Tiedemann, Johannes Ewald, Paweł Sajkiewicz,
Axel H. E. Müller,* George Floudas,* and Holger Frey*
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ABSTRACT: The reactivity of the biobased monomer β-

farnesene in the statistical anionic copolymerization with styrene
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and the effect of the bottlebrush-like polyfarnesene structure on

the phase separation behavior were investigated. Furthermore,
thermal and material properties of β-farnesene-based thermoplastic
elastomers, based on tri- and pentablock copolymers with styrene,
and their processing behavior were investigated. As shown by 1H
NMR online kinetics, in analogy to both isoprene and β-myrcene,
the direct (i.e., statistical) anionic copolymerization of β-farnesene
and styrene in cyclohexane affords block-like, tapered copolymers
because of the highly diverging reactivity ratios (rFar = 27; rS =
0.037). Algebraic expressions for both the molar and volume composition profiles were derived, which provide a mathematically
accurate picture of the tapered copolymer structure. The one-pot, tapered copolymer approach was used to synthesize series of tri-
(ABA) and pentablock (ABABA) copolymers of styrene (A) and β-farnesene (B), varying the polydiene volume fraction between
0.50 and 0.68, respectively. Depending on the polydiene volume fraction, the tapered multiblock copolymers showed phase
separation in lamellar or hexagonally packed cylindrical structures, as determined by small-angle X-ray scattering. Well-defined
tapered tri- and pentablock copolymers with molecular weights of 120 kg mol−1 and low dispersity (Đ = 1.05−1.16) were obtained.
The order of the tapered poly(farnesene-co-styrene) copolymers bears many similarities (same morphology, practically the same
domain spacing, and a similar degree of segregation) to the corresponding polyisoprene copolymers with the same polydiene volume
fraction. The similar domain spacing is suggestive of looped configurations mainly in the polyisoprene copolymers that are reduced
in the polyterpene copolymers. The influence of the long alkenyl side chains of the polyfarnesene middle blocks on the mechanical
properties of the multiblock copolymers was investigated by tensile testing. For this purpose, the respective tri- and pentablock
copolymers of isoprene (C5 unit) and β-myrcene (C10) with styrene were synthesized as well, containing equal polydiene volume
fractions as their β-farnesene-based (C15) analogs. The mechanical toughness of the polymers increased with decreasing length of the
alkenyl side chains (from β-farnesene to isoprene). Furthermore, tapered polyfarnesene tri- and pentablock copolymers with styrene
exhibit reduced solution viscosity in comparison to, for example, polyisoprene-based tapered PS-b-P(I-co-S) triblock copolymers,
resulting in improved processability by electrospinning. These properties are discussed in terms of the different configurations of the
polyterpene blocks and the pronounced differences of the entanglement molecular weights.

■ INTRODUCTION
Limited fossil feedstocks and the accumulating plastic waste in
using fermentation technology.12 In several approaches
alternative routes to produce thetypically fossil source-
the environment have increased the prominence of research in basedmonomers isoprene and styrene from biomass were
the field of sustainable polymers within the last decade.1−7 also developed in recent works.13−16 However, these approaches
Terpenes such as β-myrcene and β-farnesene are biobased are currently not scalable to an industrially relevant production
alternatives for the petroleum-based 1,3-diene monomers volume. In analogy to isoprene and β-myrcene, the 1,3-diene
butadiene and isoprene, which are commercially used for the moiety of β-farnesene enables its anionic polymerization.
synthesis of thermoplastic elastomers (TPEs) on large scale.8,9
Because of the increasing interest in biobased materials, Received: September 14, 2020
monomers from renewable sources such as β-myrcene are Revised: October 30, 2020
already used on a limited scale as an alternative for Published: November 17, 2020
isoprene.8,10,11 While β-myrcene is industrially produced by
the pyrolysis of β-pinene obtained from turpentine, β-farnesene
is manufactured on large scale from sugar cane (by Amyris, Inc.),

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Obeying the isoprene rule for terpenes, β-myrcene (C10) rubbery polydiene phase. These tapered multiblock copolymers
consists of two isoprene units (C5), while β-farnesene (C15, show outstanding mechanical properties and microphase
sesquiterpene) can be described as an isoprene trimer.17 separation behavior.41−43
Accordingly, the three diene monomers differ in the length of In this work, we aim at presenting a comprehensive picture of
the alkenyl side chain linked to the polymerizable diene unit. β-farnesene/styrene-based copolymers, starting from an inves-
The effect of the long alkenyl side chains on the polymer tigation of the copolymerization kinetics to the synthesis of
properties has been investigated for homopolymers of β- tapered multiblock copolymers. We also studied the resulting
farnesene as well as for copolymers with butadiene in recent materials properties and processing behavior, keeping an eye on
works.18−22 Because of the long C11 or C13 pendant groups, the comparison with the established isoprene and β-myrcene
depending on the respective polydiene-microstructure (1,4- or (multiblock) copolymers with styrene. A series of tri- and
3,4-units), polyfarnesene (PFar) can be described as a pentablock copolymers with constant molecular weights (120 kg
bottlebrush-like polymer. This structure of PFar leads to mol−1), with two different polydiene volume fractions (φPDiene =
reduced melt viscosity in comparison to polyisoprene (PI) 0.5 and 0.68), were prepared. In the series of block copolymers,
and polymyrcene (PMyr), which is explained by the significantly the brush length of the polydiene middle block increases from
higher entanglement molecular weight (Me(PFar) = 50 kg mol−1 isoprene to β-farnesene. Consequently, for a valid comparison of
> Me(PMyr) = 18 kg mol−1 > Me(PI) = 5.4 kg mol−1).19,23 In the multiblock copolymers, the volume fraction of the polydiene
addition, the unique bottlebrush-like structure of PFar results in middle blocks was kept constant for all diene monomers in order
a low glass temperature of 198 K. Furthermore, compared to to study the effect of the bottle-brush architecture of PFar on the
polyisoprene, the PFar Tg exhibits only a weak dependence on phase and the mechanical properties.

■
the microstructure because the compact branched structure
dominates the effect of the backbone.18 EXPERIMENTAL SECTION
At present, there is little information available regarding
Reagents. Isoprene (99%), sec-butyllithium as a 1.3 M solution in
copolymers of β-farnesene in general and in particular cyclohexane/hexane (92/8), and calcium hydride were purchased from
copolymers with styrene. The resulting materials are promising Acros Organics. β-Myrcene (≥95%) was purchased from Sigma-
with respect to biobased TPEs. Sasaki et al. at Kuraray Co. Aldrich. β-Farnesene, with a purity of 95%, was received from BOC
developed the first ABA triblock copolymers based on styrene Sciences. Cyclohexane was acquired from Fisher Scientific. Cyclo-
and β-farnesene, with a hydrogenated PFar midblock.24 hexane-d12 was received from Deutero GmbH. Cyclohexane was dried
However, to the best of our knowledge, the only work focusing using sec-butyllithium and 1,1-diphenylethylene (DPE) as an indicator
on the copolymerization of this monomer pair was published by (DPE-anion shows red color).
Kirillov et al., who copolymerized styrene and β-farnesene, Instrumentation. SEC measurements were performed in THF as
catalyzed by an ansa-lanthanidocene catalyst, resulting in the mobile phase (flow rate 1 mL/min) on an SDV column set from
PSS (SDV 103, SDV 105, SDV 106) and an RI detector. Calibration was
random copolymers.25 The statistical anionic copolymerization carried out by using PS standards, provided by PSS Polymer Standard
of analogous 1,3-diene monomers, such as isoprene and β- Service GmbH. NMR spectra were recorded on a Bruker AVANCE II
myrcene with styrene (or its derivatives) in apolar solvents such 400 spectrometer with 400 MHz (1H NMR). All spectra are referenced
as cyclohexane affords block-like, tapered copolymers, mirroring internally to the residual proton signals of the deuterated solvent. The
the highly disparate reactivity ratios.26−28 Tapered copolymers thermal properties of the polymers were studied with a Q2000 (TA
of styrene and 1,3-diene monomers such as isoprene or β- Instruments) differential scanning calorimeter (DSC). Two cooling
myrcene are known for their microphase separation behav- and heating cycles were performed with a rate of 10 K min−1 in a
ior,26,27,29 which is mainly driven by the thermodynamic temperature range between 183 and 403 K. The glass temperatures
incompatibility. This is determined by the Flory−Huggins were extracted from the second cycle. Tensile tests were performed
using a material testing machine Z005 (Zwick/Roell, Germany). The
interaction parameter (χ), the molecular weight, and the scanning electron microscopy (SEM) examinations of the fibers were
molecular composition of the polymer, described in terms of conducted on a JEOL JSM-6010PLUS/LV scanning electron micro-
the polymer volume fraction.30−33 Thermal and mechanical scope with an acceleration voltage of 7 kV (secondary electron imaging
properties are mainly governed by the microphase separation mode, working distance: 10 mm, spot size: 50). For the sample
and the resulting bulk morphologies of the copolymers.34−37 preparation, a SEM specimen stub was covered with adhesive carbon
The vast potential of biobased monomers for the synthesis of tape (NEM Tape, Nisshin EM. Co. Ltd.). A small piece of the
TPEs was pointed out in the work of Bolton et al., in which α- nonwoven copolymer was glued onto the tape and coated twice for 2
methyl-p-methyl-styrene based PMyr containing TPEs were min each with a thin layer of gold using a sputter coater (DII-
synthesized by the sequential anionic copolymerization in THF 29030SCTR Smart Coater, JEOL).
X-ray Scattering. Small-angle (SAXS) measurements were made
at low temperatures, capitalizing on dichlorodimethylsilane using CuKα radiation (Rigaku MicroMax 007 X-ray generator, Osmic
coupling.38 However, the respective polymerization of 1,3-diene Confocal Max-Flux curved multilayer optics). Two-dimensional
monomers in THF is known to result in an increased content of diffraction patterns were recorded on an Mar345 image plate detector
side chain vinyl regioisomers (3,4- and 1,2-units) in the polymer at a sample-detector distance of 2076 mm. Intensity distributions as a
backbone.39 The side chain vinyl regioisomers increase the glass function of the modulus of the total scattering vector, q = (4π/λ)
temperature of the rubbery polydiene phase, which is undesired sin(2θ/2), where 2θ is the scattering angle, were obtained by radial
for most applications.40 As an alternative to the polymerization averaging of the two-dimensional datasets. Samples in the form of thick
in THF, the one-step tapered copolymer approach can be used films (∼1 mm) were prepared by slow solvent casting (chloroform).
for the synthesis of styrene-/diene-based tapered multiblock Temperature-dependent measurements of 1 h long were made by
heating the films from 303 to 453 K in 30 K steps and subsequent
copolymers in cyclohexane, relying on sequential monomer cooling to 303 K aiming at obtaining the respective phase.
addition of diene/styrene monomer mixtures, resulting in a Synthesis of Multiblock Copolymers. A mixture of the diene
tapered diblock for each addition step. The multiblock monomer and styrene was dried over CaH2 for 24 h, degassed by three
copolymer synthesis in cyclohexane results in TPE materials freeze−thaw cycles, and distilled into a graduated ampule. In addition,
with a high 1,4-unit content and consequently low Tg of the the required amount of styrene was dried and degassed separately over

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Figure 1. Stacked 1H NMR spectra (400 MHz, C6D12) of the in situ NMR kinetics study of the copolymerization of styrene and β-farnesene at 23 °C
(region from 7.7 to 4.6 ppm).

CaH2 for 24 h and was directly distilled into the reaction flask. Dried
cyclohexane was distilled into the reaction flask, followed by flushing
the flask with argon and the initiation of the polymerization of the first
■ RESULTS AND DISCUSSION
In Situ 1H NMR Copolymerization Kinetics. The kinetics
styrene block with a 1.3 M sec-BuLi solution. After 2 h, a mixture of the of the statistical anionic copolymerization of styrene with
diene monomer and styrene was added through addition from an isoprene and β-myrcene has been investigated in depth in the
ampule. For pentablock copolymers a second addition of the monomer past and in recent years.26,27,45,46 In the current work, we expand
mixture was carried out. The living polymerization was terminated by the understanding of the copolymerization kinetics of styrene
the addition of degassed 2-propanol. Afterward, the polymer was with 1,3-diene derivatives to the copolymerization of styrene
precipitated in 2-propanol and dried under vacuum. The equipment with β-farnesene. 1H NMR kinetic experiments enable to
employed and the synthesis scheme are shown in Figure S12.
In Situ 1H NMR Kinetics Experiments. The monomers and the
determine the reactivity ratios, based on the nonterminal
solvent were dried by the same procedure as for the multiblock copolymerization model, which produces reliable results for
copolymer synthesis. The monomer/solvent mixtures were prepared in modeling the anionic copolymerization in various sys-
an argon-filled glove box (MBRAUN UNILAB, <0.1 ppm of O2 and tems.27,47,48 The sec-butyllithium ([Ini]0 = 0.017 mol L−1)
<0.1 ppm of H2O). For the copolymerization at 23 °C a mixture of initiated copolymerization of β-farnesene ([Far]0 = 0.56 mol L−1
0.1 mL of β-farnesene (0.42 mmol, [Far]0 = 0.56 mol L−1) and 0.05 mL ) and styrene ([S]0 = 0.56 mol L−1) at 23 °C in deuterated
of styrene (0.42 mmol, [S]0 = 0.56 mol L−1) in (0.6 mL of cyclohexane- cyclohexane was monitored by 1H NMR spectroscopy,
d12) was filled into NMR tubes and sealed with rubber septa. After following the decrease of the methylene protons of styrene at
initiation with 0.01 mL of sec-butyllithium ([Ini]0 = 0.017 mol L−1) via
syringe, the solution was vigorously homogenized by shaking several
5.78−5.54 ppm (blue color) and β-farnesene at 6.41−6.28 ppm
times. Subsequently, the NMR tube was immediately inserted in the (green color) (stacked 1H NMR spectra are shown in Figure 1,
1
H NMR spectrometer (AVANCE III HD 400 from Bruker; equipped every 10th spectrum is shown, spectra were recorded every 30 s).
with a 5 mm BBFO-SmartProbe (Z-gradient probe), ATM, and The normalized concentrations of both monomers, deter-
SampleXPress 60). A spectrum was recorded every 30 s with one scan mined by integration of the monomer signals in the 1H NMR
until complete disappearance of the monomer signals. In addition to the spectra, are plotted as a function of time and function of total
kinetics studies at 23 °C, similar NMR kinetic studies were carried out monomer conversion Figure 2a,b. This shows the strongly
at 30 and 40 °C. preferred incorporation of β-farnesene at the early stage of the
Electrospinning. The copolymer nanofiber preparation by electro-
copolymerization, resulting in a PFar block with a small amount
spinning was adapted and modified from one of our previous works.44
The copolymer was dissolved in a mixture of THF and DMF of incorporated styrene units, followed by a steep gradient. After
(80:20 v/v) to a concentration of 25−35 wt % (depending on the complete conversion of β-farnesene, the remaining styrene
copolymer) by stirring at room temperature overnight. The spinning forms a pure polystyrene block, resulting in a tapered copolymer.
process was conducted using a rotating drum as the collector (diameter: For the determination of the reactivity ratios the integrated
2 cm, length: 13 cm, rotation speed of 292 rpm), covered with equation47 for the nonterminal (ideal) model according to
aluminum foil. A distance between the needle tip (type Braun Sterican Wall48 was fitted to the experimental data, as shown in Figure S1.
23G, with filed-down tip) and the collector drum of 10 cm was adjusted, The value of the explanatory power (R2) very close to unity
and the spinning was conducted horizontally at a voltage of 17 kV and verifies the accuracy of the fit and the adequate description of the
with a flow rate of 1.75 mL h−1. The temperature inside the spinning
chamber was 27−29 °C at a humidity of 45−50%. SEM was used for the
copolymerization by the nonterminal model. Highly diverging
characterization of the resulting fibers (as reported in Instrumentation). reactivity ratios were determined for the copolymerization of β-
The diameters from 50 fibers were used in the calculation of the fiber farnesene and styrene (rFar = 27, rS = 0.037). In addition to the
diameter distribution using software ImageJ. For evaluation, OriginPro integrated ideal method, both the Jaacks49 and the Meyer−
9.0 (OriginLab Corporation) was used. Lowry50 formalism were used to determine the reactivity ratios,
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In addition, the homopolymerization 1H NMR kinetics of β-

farnesene has been investigated, showing that the homopolyme-
rization rate of β-farnesene (kFarFar = 3.2 × 10−3 (L/mol)1/4 s−1,
at 23 °C in cyclohexane) is significantly higher than the rate of
isoprene (kII = 0.61 × 10−3 (L/mol)1/4 s−1, at 23 °C),28 resulting
in a faster copolymerization with styrene, as shown and
discussed in detail in the Supporting Information (Tables S3−
S5 and Figure S10). We tentatively suggest that the higher
homopolymerization rate of β-farnesene is caused by its steric
bulk, which most likely impedes aggregation of the PFar-Li chain
ends. The shorter reaction times of the copolymerization of β-
farnesene and styrene are demonstrated at some Monte Carlo
simulation examples in Table S6.
The resulting bulk morphologies of (block) copolymers,
discussed in an ensuing section of this work, mainly depend on
the volume fraction of the polymer blocks and their
thermodynamic incompatibility.54 Because the degree of phase
separation can influence the related key material properties of
(block) copolymers, understanding of the volume based
monomer gradient profile is crucial.30−34 Thus, it is necessary
to convert the molar composition profile into the volume
composition profile. To the best of our knowledge, the molar
and volume composition profiles have not been accessible by
algebraic expressions to date. In the Supporting Information, we
show the analytical derivation of the explicit expressions both for
the molar and volume composition profiles. These expressions
can be directly implemented in simple spreadsheet software (a
Microsoft Excel spreadsheet is given as Supporting Information)
and in this way render the depiction of the copolymer
composition profile easily accessible. Furthermore, this
approach eliminates the risk of introducing numerical errors
compared to previous approaches that use numerical integration
to depict the composition profiles.29,55 The results of applying
the related equations for the copolymerization of styrene with
1,3-dienes are shown in Figure 3. The difference in the molar
and volume composition profile depends on the molecular
Figure 2. (a) Time-conversion plots of the copolymerization of β- weight and the corresponding volume of the 1,3-diene
farnesene (green) and styrene (blue). Monomer concentrations were monomer. Obviously, the shift from the molar to volume
determined by in situ 1H NMR spectroscopy in C6D12 at 23 °C. (b) composition profile strongly depends on the 1,3-diene
Comonomer concentrations as a function of total conversion. (c) monomer employed. While the shift for the isoprene-based
Calculated molar composition profile of the corresponding tapered copolymers is low, it increases with increasing volume of the
copolymer. diene monomer units from β-myrcene (C10, isoprene dimer) to
β-farnesene (C15, isoprene trimer). The steepness of the
gradient and the disparity of the reactivity ratios increases in
as shown and discussed in the Supporting Information (Table the order I/S < Far/S < Myr/S.
S1 and Figures S1,S2). The reactivity ratios were used for the Tapered Multiblock Copolymer Synthesis and Molec-
calculation of the molar composition profile, shown in Figure 2c. ular Characterization. The synthesis of tapered multiblock
Additional kinetic studies were performed at 30 and 40 °C, copolymers by the sequential addition of monomer mixtures was
resulting in no significant changes in the reactivity ratios reported by our group for the monomer pairs isoprene/styrene
(Figures S3−S8). However, the fits for the terminal model by and isoprene/4-methyl-styrene.41,42 In the concept of TPEs, the
Mayo−Lewis51 (in the form of the Meyer−Lowry equation) polydiene blocks determine the elastic behavior of the material.
resulted in a deviation of the reactivity ratios in comparison to To generate a TPE material, an ABA triblock polymer structure
the ideal/nonterminal model and in a clear temperature is required, which translates to long polydiene B blocks that have
dependence of the reactivity ratios, without any tendency. For to be fixated by two terminal styrenic A-blocks that form the
copolymerization following the nonterminal model, the Meyer− noncovalent crosslinking domains.56 Thus, in contrast to our
Lowry treatment can be numerically instable. These results previous works on tapered multiblock copolymers, in the current
illustrate the problem of overfitting, which results from using an work we prepared a pure polystyrene block before adding the
overly complex model to describe experimental data, as is diene/styrene mixture to generate the tapered blocks, as shown
discussed in detail in the Supporting Information (Table S2 and in Figure 4a. The concept of tapered triblock copolymers, based
Figure S9).52,53 Therefore, the resulting values from the ideal on styrene and isoprene (or butadiene), was developed by
model of Wall in the form of the integrated ideal equation were Geoffrey and Milkovich at Shell Co.57 This concept for the
regarded to be more reliable and used for the depiction of the polymer architecture was recently used for the synthesis of
composition profiles. tapered multiblock star copolymers based on I/S to achieve
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enables a direct comparison of the mechanical and processing

behavior of the tapered block copolymers.
The synthesis of the tri- and pentablock copolymers was
performed with the three 1,3-diene monomers, resulting in
molecular weights in a range of 107−140 kg mol−1 and low
dispersities between 1.05 and 1.16 (Figures S13−S15; Table 1).
The deviation of the SEC-data from the theoretical molecular
weight can be explained by the overestimated molecular weight
of polyisoprene when using a polystyrene standard. In addition,
the increasing length of the side chain of the polydiene-units on
going from isoprene to β-farnesene results in a bottlebrush-like
structure of the PFar middle blocks, which alters the
hydrodynamic volume and results in underestimated molecular
weights of the tapered PFar copolymers in comparison to their
polyisoprene analogs.59 The polydiene microstructure of the
tapered copolymers was determined by 1H NMR spectroscopy
(spectra are shown in Figures S16−S18). For the polyisoprene
based polymers a 3,4-regioisomer content around 5.2% was
found, which is in accordance with the literature.60 In the series
of polyisoprene, PMyr and PFar-based tapered copolymers the
content of 3,4-units remains almost constant in a range of 5.2−
6.6%.
Thermal Properties. The influence of the polydiene
Figure 3. Shift from the molar composition profile of the tapered architecture on the thermal behavior was investigated by DSC
copolymers to the volume composition profile (orange) for equal total measurements (DSC curves are shown in Figure S19). The
volume fractions (φPDiene) and the corresponding reactivity ratios. occurrence of two glass temperatures for all tri- and pentablock
copolymers (with φPDiene = 0.5) is an indication for the phase
optimized mechanical properties.58 The procedure used in the separation of the polydiene- and the polystyrene domains, which
current work results in two polystyrene end blocks, which in is a precondition for the TPE behavior. More insight into the
effect results in physical cross-linking of the polymer chains phase behavior requires structural investigation (SAXS measure-
because of vitrification of the PS domains. A second addition of ments below). The glass temperature of the flexible polydiene
the respective diene/styrene monomer mixture enables the block (Tg,PDiene) decreases for all series of tri- and pentablock
synthesis of tapered pentablock copolymers. copolymers in the order polyisoprene > PMyr > PFar (Figure
In this work, for each tapered tri- and pentablock copolymer S20). The effect of the slightly increasing amount of 3,4-units in
composition, the analogous PFar, PMyr, and polyisoprene- the series from polyisoprene to PFar, which is known to increase
based copolymer was synthesized, keeping the total polydiene Tg,40,61 is overcompensated by the bottlebrush-like structure of
volume fraction (φPDiene) constant, as shown with respect to the the PFar blocks.18 In the latter, the lower glass temperature
different volume requirement of the 1,3-diene monomers, results mainly from the longer side groups with the free ends that
according to Figure 3. The three copolymer systems have the effectively plasticize the backbone. Because the glass temper-
same polydiene volume fraction but very different chain length ature is mainly (but not solely)62 a property of the backbone
of the diene midblock. As demonstrated below in the SAXS (associated with the freezing of the backbone motions) a lower
measurements, this is a key feature of the copolymers that temperature is necessary for PFar to vitrify.

Figure 4. (a) Synthetic strategy for tapered multiblock copolymers of styrene and 1,3-diene monomers (isoprene, myrcene, or farnesene), (b) volume
composition profile (incorporation volume of styrene [FStyrene(V)] vs volume-based chain position) of tri- and pentablock copolymers with constant
polydiene volume fraction (φPDiene = 0.5) and constant molecular weight (120 kg mol−1).

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Table 1. Characterization Data of Synthesized Series of Tapered Tri- and Pentablock Copolymers of Styrene and Different 1,3-
Diene Monomers and with Constant Polydiene Volume Fractions (φPDiene = 0.5 or 0.68)a
Mnth Mnb Tg,PDiened Tg,PSd microstructurec 1,4-units dnorme
sample (kg/mol) (kg/mol) Đb xDienec φPDienec (K) (K) (%) (nm)
PS0.25-b-P(I0.5-co-S0.25) 120 122.7 1.09 0.57 0.5 220 355 94.8 35.6
PS0.25-b-P(Myr0.5-co-S0.25) 120 106.8 1.12 0.40 0.5 214 366 93.9 36.0
PS0.25-b-P(Far0.5-co-S0.25) 120 107.6 1.14 0.31 0.5 205 366 93.6 36.0
PS0.17-b-P(I0.25-co-S0.17)2 120 140.1 1.12 0.57 0.5 224 358 94.8 24.7
PS0.17-b-P(Myr0.25-co-S0.17)2 120 136.5 1.15 0.40 0.5 214 356 93.5 25.2
PS0.17-b-P(Far0.25-co-S0.17)2 120 123.3 1.16 0.31 0.5 209 361 93.4 25.5
PS0.16-b-P(I0.68-co-S0.16) 115 127.1 1.05 0.74 0.68 218 94.8 36.7
PS0.16-b-P(Myr0.68-co-S0.16) 115 119.3 1.08 0.59 0.68 212 94.1 37.7
PS0.16-b-P(Far0.68-co-S0.16) 115 108.7 1.09 0.49 0.68 203 93.6 36.5
a
Volume fractions are given in form of subscript values in the sample names. bDetermined by SEC measurements in THF at 25 °C using PS
standards (Figures S13−S15). cDetermined from 1H NMR spectra (400 MHz, CDCl3, Figures S13−S15). dDetermined by DSC measurements
(Figure S19). eDetermined by SAXS measurements.

For the triblock copolymers with a polydiene volume fraction the first maximum) of 35.6, 33.6, and 33.7 nm, respectively, for
of φPDiene = 0.68 merely the Tg of the polydiene phase was the polyisoprene, PMyr, and PFar blocks. To account for the
observable, which is even lower than for the corresponding difference in the block molecular weights (Table 1, and further
triblocks with φPDiene = 0.5. The lack of a detectable Tg of the assuming Gaussian statistics for simplicity) we can obtain a
polystyrene domains is caused by the sensitivity limitation of the normalized spacing as dnorm = (do/M1/2)/(do/M1/2)isoprene that
DSC measurement (the heat capacity step ΔcP at Tg, is inversely amounts to 36 nm for the PMyr and PFar blocks.
proportional to temperature). In this case, SAXS provides The similarity in the domain spacing of the PFar triblock
unambiguously the nanodomain morphology. copolymers with the corresponding polyisoprene and PMyr
Morphology. The morphology of the tapered tri- and copolymers has some important implications for the conforma-
pentablock copolymers can be discussed with respect to the tional properties of the diene blocks. In an SIS triblock
SAXS curves depicted in Figures 5−7. The temperature- copolymer the mid-block has a large fraction of looped
configurations (in the range of 0.4−0.6 according to experiment,
theory, and simulation).63 However, loops in PMyr, and even
more so in PFar, blocks are increasingly more difficult because of
the bottlebrush-like structure of the polydiene blocks that
restricts such configurations. Hence, the similar d-spacing is the
result of the similar interaction parameters, χS/Myr and χS/Far with
the respective χS/I and of the different configurations (loops vs
bridges) of the polydiene blocks.
The reduced intensity for the even numbered reflections in
the polyisoprene and PMyr copolymers reveals that the
polydiene and PS domains have equal volumes (positions
where the form factor has a minimum). Note that this is not case
in the PFar copolymers (PFar and PS domains have slightly
different volumes) where all reflections appear in similar
intensities.
The corresponding SAXS results for the asymmetric triblock
Figure 5. SAXS patterns of the triblock copolymers with polydiene
copolymers (polydiene volume fraction of φPDiene = 0.68) are
volume fraction of φPDiene = 0.5 shown at different temperatures shown in Figure 6. SAXS patterns of the triblock copolymers
obtained on heating. Arrows indicate the positions of the Bragg with polydiene volume fraction of φPDiene = 0.68 shown at
reflections corresponding to a lamellar morphology. different temperatures obtained on heating and cooling (cooling
curves are indicated by c). Arrows indicate the positions of the
dependent SAXS patterns of all triblock copolymers share Bragg reflections corresponding to a cylindrical morphology. All
some features (Figure 5). All patterns exhibit a strong peak at triblock copolymers exhibit Bragg reflections with relative q
low q followed by higher order reflections. The number and values of 1:31/2:41/2:71/2:91/2 revealing a hexagonally packed
intensity of the higher order reflections depends on temperature. cylindrical structure (HPC) composed of PS cylinders in a diene
In general, all triblock copolymers show increased tendency for matrix. The periodicity (d = do(4/3)1/2; do = 2π/q*), normalized
phase separation at temperatures above the polystyrene Tg. This for the difference in molecular weights, is now at 36.7, 37.7, and
might sound paradoxical as increasing temperature brings the 36.5 nm, respectively, for the polyisoprene, PMyr and PFar
copolymers closer to the disordered state. The increased blocks. Again, this is suggestive of a similar degree of segregation
nanophase separation here reflects the enhanced mobility of but different diene configurations in the asymmetric triblock
chains (e.g., annealing above the polystyrene Tg). Bragg copolymers.
reflections appear with relative q values of 1:2:3:4, correspond- All patterns of the pentablock copolymers translate to a LAM
ing to a lamellar structure (LAM) with periodicity (as do = 2π/ morphology of reduced periodicity as compared to the triblock
q*, q* is the modulus of the scattering vector corresponding to copolymers. Domain-spacings normalized for the different
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Figure 6. SAXS patterns of the triblock copolymers with polydiene volume fraction of φPDiene = 0.68 shown at different temperatures obtained on
heating and cooling (cooling curves are indicated by c). Arrows indicate the positions of the Bragg reflections corresponding to a cylindrical
morphology.

mers) are expected to influence the mechanical properties

discussed below (in opposite ways), yet it is unknown which
effect will prevail.
Mechanical Properties. The mechanical properties of the
tapered tri- and pentablock copolymers were investigated by
uniaxial tensile measurements. The representative stress−strain
plots for the tapered copolymers with a polydiene volume
fraction of 0.5 and 0.68 are shown in Figures 8 and 11. The

Figure 7. SAXS patterns of the triblock (top, blue) and pentablock

copolymers (bottom, green) with polydiene volume fraction of φPDiene
= 0.5, shown at 423 K. Arrows indicate the positions of the Bragg
reflections corresponding to a lamellar morphology.

molecular weights amount to 24.7, 25.2, and 25.5 nm,

respectively, for the polyisoprene, PMyr, and PFar blocks
(Figure 7, Table 1). The reduced domain spacing relative to the Figure 8. Representative stress−strain curves of the three series of
triblock copolymers is a composite effect. In the case of the tapered tri- (continuous lines) and pentablock (dashed lines)
polyisoprene blocks, it reflects the increased number of blocks at copolymers with different polydiene blocks: polyisoprene (black),
a fixed overall molecular weight and the configuration of the PMyr (red), and PFar (blue). The volume fraction of the polydiene
mid-blocks (e.g., further formation of loops), whereas in the case phase is identical for all copolymers (φPDiene = 0.5).
of PMyr and PFar blocks it mainly reflects the increase in block
number. investigation of the mechanical properties reveals striking
In summary, the phase behavior of the PMyr and PFar differences between the different polydiene architectures of
copolymers bears many similarities (same morphology, practi- the tapered block copolymers, both regarding their yield point
cally the same domain spacing and a similar degree of characteristics and the properties at the point of mechanical
segregation) to the corresponding polyisoprene copolymers. failure. Focusing on the point of mechanical failure, the stress at
The same domain spacing further suggests that specific chain break (σb), strain at break (εb), and ultimate toughness decrease
configurations (loops) that are present in the polyisoperene in the order polyisoprene > PMyr > PFar (values are shown in
copolymers are minimized in PMyr and PFar copolymers. The Table S7). We recall here that all copolymers exhibit the same
two effects (reduced entanglement molecular weight and morphology (LAM), have similar degree of segregation but
increased bridging configurations in PMyr and PFar copoly- differ considerably in the configurations of the polydiene blocks.
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Based on the increasing bridging configurations of the

polyterpene blocks one would expect increasing stress and
strain at break, and ultimate toughness, whereas the opposite is
observed. As discussed in the Morphology section, polyterpenes
have an increasing tendency to be less entangled (PMyr) or even
to be unentangled (PFar). Comparing these two parameters,
that is, increasing bridging configurations and increasing
propensity for unentangled chains it is the latter that prevails
and eventually controls the mechanical response. This trend also
occurs in the yield point characteristics. While the Ey modulus
does not change significantly from the isoprene- to the β-
myrcene-based triblocks, there is a slight decrease in the yield
stress (σy). In contrast, all β-farnesene-based triblocks show Figure 10. Toughness of the tapered tri- and pentablock copolymers
clearly lower values for Ey and for the yield stress (see Table S7 (φPDiene = 0.5) in dependence of number of blocks and polydiene block
and Figures 9 and S23). (same color codes used as for the stress−strain curves). Values are
determined as the average of 5 independent measurements. Errors are
given in the 1σ interval.

polymer blocks. For the PMyr-based series the molecular

weights of the PMyr blocks approach the entanglement
molecular weight of PMyr, whereas for the PFar blocks the
molecular weight is below Me for the pentablock copolymer,
resulting in no significant decrease in toughness. Accordingly,
the decrease in toughness is attributed mainly to the absence of
entanglements of the polydiene blocks between the terminal
styrene blocks, which are known to contribute to the mechanical
properties of TPEs.67,68 Furthermore, the values of Ey decrease
with increasing number of blocks, as shown in Figure 9.
The series of tapered triblock copolymers with a higher
Figure 9. Young’s modulus of the tapered tri- and pentablock polydiene volume fraction (φPDiene = 0.68), showing hexagonally
copolymers (φPDiene = 0.5) in dependence of number of blocks and packed cylindrical morphologies, was also investigated by tensile
polydiene block (same color codes as used for the stress−strain curves). measurements. The stress−strain plots (Figure 11) show
Values are determined as the average of 5 independent measurements.
Errors are given in the 1σ interval.

With an increase of the block number from 3 to 5, keeping the

overall molecular weight (120 kg mol−1) and the polydiene
volume fraction (φPDiene = 0.5) constant, there are several factors
that affect the mechanical properties: (i) the increasing bridging
fraction of the polydiene middle blocks,64 (ii) the decreasing
molecular weights of the individual blocks, effectively reducing
the number of entanglements, and (iii) additional bridges in the
glassy domains by the polystyrene midblock in the pentablock
structures.65,66 In the pentablock series (dashed lines in Figure
8), the same trends regarding the ultimate mechanical properties
and the yield point can be observed. Comparing the tapered tri- Figure 11. Representative stress−strain curves of the of tapered triblock
and pentablock copolymer series, for the isoprene-based copolymers (φ PDiene = 0.68) with varying polydiene blocks:
samples, both the toughness, σb, and εb increase with increasing polyisoprene (black), PMyr (red), and PFar (blue).
block number, as reported in the literature.42 However, this
trend is not followed by the terpene-based tapered block
copolymer samples. The correlation of the ultimate toughness significantly different behavior in comparison to the samples
with the number of blocks of the tapered block copolymers with with φPDiene = 0.5. The copolymers now exhibit the stress−strain
φPDiene = 0.5 and varying polydiene structures is presented in behavior of conventional TPEs (φPDiene ≈ 0.65−0.8), which do
Figure 10. In contrast to the isoprene-based copolymers, the not show any yield point.34,35,69 In general, similar trends
toughness in the β-myrcene-based samples slightly decreases regarding toughness, stress at break (σb), and strain at break (εb)
with increasing number of blocks, while the toughness of the β- can be observed for the triblock series with φPDiene = 0.68, as
farnesene sample remains nearly constant (U ≈ 40 MJ m−3). given in Table S8 and Figure 11. The copolymer PS0.16-b-P(I0.68-
Given the similar phase and degree of segregation, this trend can co-S0.16) shows different behavior in comparison to the
be correlated to the molecular weights of the single polydiene corresponding β-myrcene and β-farnesene-based samples. The
blocks in relation to the corresponding entanglement molecular point of mechanical failure of PS0.16-b-P(I0.68-co-S0.16) was not
weights (Me) of the polydienes, listed in Tables S9 and S10. An reached because of the limitation of the testing machine. In
increasing block number at constant overall molecular weight contrast to PS0.16-b-P(Myr0.68-co-S0.16) and PS0.16-b-P(Far0.68-co-
results in a decrease of the molecular weight of the single S0.16) that exhibit an elastomeric behavior, the copolymer PS0.16-
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b-P(I0.68-co-S0.16) undergoes strain hardening, starting at range. In all cases, well-defined fibers in a range of 1.82−1.99 μm
εb ≈ 700%. In analogy to the stress−strain behavior of the diameter were obtained. As an example, the SEM image, as well
samples with φPDiene = 0.5, the difference in the mechanical as the fiber thickness distribution of the PS0.25-b-P(Far0.5-co-
properties can be explained by the decreasing number of S0.25) sample are shown in Figure 12.
entanglements in the order PI > PMyr > PFar, as a consequence
of the bottlebrush-like structure of PFar.
Processing. Linear ABA type tri- or A(BA)n multiblock
copolymers show excellent mechanical properties, but there are
limitations in the processing of the materials, due to their high
melt and solution viscosity.70 Branched structures are well-
known for their reduced melt viscosities in comparison to their
linear analogs. In comparison to the linear polyisoprene
segments of the tapered copolymers, the PFar segments can
be described as bottlebrush-like structures because of their long
C11/C13 side chains. As a consequence they possess very high
entanglement molecular weight (50 kg mol−1) that results in a
reduced melt viscosity.19 To demonstrate the impact of this
unique architectural feature of PFar on the processing behavior
of thermoplastic elastomeric materials, electrospinning was
selected as exemplary processing technique to generate
nanofibers of the tapered block copolymers. The Experimental
Section of the electrospinning experiments can be found in the
Supporting Information. Electrospinning is a versatile and viable
processing method, which is attracting increased attention in
academic research as well as in commercial applications.71−74
The solution viscosity is one of the most important parameters
in electrospinning for the production of well-defined nano-
fibers.75 There is a limited viscosity range, where electrospinning
of a polymer solution is possible. While too low viscosity results
in the formation of droplets (so-called electrospraying) or
“beads” on fibers (concentration dependency of the morphology
is shown in Figure S24), too high concentration of the polymer
solution results in the formation of extremely thick fibers leading
in a boundary case to prohibition of fiber formation (see Figure
S25a).76 The solution viscosities of the tapered tri- and Figure 12. SEM image of electrospun PS0.25-b-P(Far0.5-co-S0.25) tapered
pentablock copolymers dissolved in THF/DMF (80/20 v/v) triblock copolymer nanofibers and distribution of the fiber diameters.
were measured with a viscometer (Brookfield DV-III Ultra).
The deviation of the diameter distribution is given by the
The same trend in solution viscosity could be observed for the
standard deviation of the Gauss fit. The solution viscosity of the pentablock copolymers. Because of the smaller polydiene
triblock copolymers dissolved in THF/DMF (80/20 v/v) domains of the pentablock copolymers, the solution viscosity
decreased from polyisoprene to PFar-based samples, of the same decreases with increasing number of blocks (see Table S11,
molecular weight and total polydiene volume fraction, Supporting Information). The complete results of the viscosity
corresponding to the decreasing side chain length of the measurements of all sample and all SEM images as well as fiber
polydiene-units (viscosities and resulting fiber diameter are distributions and diameters are available in the Supporting
presented in Table 2) and the reduced number of entangle- Information (Figures S25−S27). The results show the potential
ments. of β-farnesene (and even β-myrcene)-based TPEs for simplified
While the ABA triblocks containing PMyr and PFar segments processing, exemplified by the processing method “electro-
were spinnable at high solution concentrations of 30 wt %, the spinning”. The reduced viscosity of PFar-based block copoly-
polymer solution of the polyisoprene triblock had to be diluted mers enable to produce microfibers from concentrated polymer
to a concentration of 25 wt % to reach a processable viscosity solutions, which offers an economical benefit over established
isoprene/styrene-based TPEs. Furthermore, the reduced melt
Table 2. Solution Viscosity of Tapered Triblock Copolymers viscosity of the β-farnesene-based TPEs is of importance for
(φPDiene = 0.5) Dissolved in THF/DMF (80/20 v/v) with processing methods such as melt extrusion.19 Electrospinning
Different Concentrations (30 and 25 wt %) and the enables direct access to various microfiber assemblies, that are
Diameters of the Resulting Nanofibers potentially suitable for membrane applications.71 Further work
in this area is currently under way.

■
η/mPa s η/mPa s
sample (30 wt %) (25 wt %) d/μm
PS0.25-b-P(I0.5-co-S0.25) 5500 850 1.99 ± 0.39a
CONCLUSIONS
PS0.25-b-P(Myr0.5-co-S0.25) 760 170 1.82 ± 0.50b We have studied the direct, that is, statistical anionic
PS0.25-b-P(Far0.5-co-S0.25) 420 140 1.88 ± 0.44b copolymerization of β-farnesene and styrene in cyclohexane
and the resulting monomer gradient in the polymer chains
a
Spun from 25 wt % solution. bSpun from 30 wt % solution. formed. Furthermore, we have investigated the consequences of
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the gradient composition on the morphology and mechanical Evaluation of 1H NMR homo- and copolymerization
properties of the resulting, partially biobased TPEs. A detailed experiments (determination of rate constants an reactivity
kinetics study of the sec-butyllithium initiated statistical ratios), comparison of integrated ideal and Meyer−Lowry
copolymerization in cyclohexane as well as the homopolyme- fit, determination of reaction times of copolymers,
rization of β-farnesene was performed by in situ 1H NMR synthesis scheme and characterization of tri- and
measurements. The considerably faster homopolymerization pentablock copolymers, SAXS measurements, tensile
kinetics of β-farnesene (kFarFar = 3.2 × 10−3 (L/mol)1/4 s−1, at 23 tests, electrospinning, and algebraic derivation of the
°C), in comparison to the established isoprene systems (kII = molar and volume composition profile of copolymers for
0.61 × 10−3 (L/mol)1/4 s−1, at 23 °C),28 can be used to create the nonterminal and terminal model (PDF)
strongly tapered and block copolymers at reduced reaction Visualization of molar and volume composition profile of
times. Similar to the isoprene- and β-myrcene-based styrene copolymers (Excel spreadsheet) (XLSX)

■
copolymerization, the copolymerization kinetics of β-farnesene
and styrene showed highly disparate reactivity ratios (rFar = 27; AUTHOR INFORMATION
rS = 0.037, determined by the integrated ideal method), leading Corresponding Authors
to block-like, tapered copolymers for the copolymerization in Axel H. E. Müller − Department of Chemistry, Johannes
cyclohexane. For the design of tailor-made copolymers with Gutenberg University Mainz, 55128 Mainz, Germany;
adjustable material properties, the volume composition profile Email: [email protected]
of the resulting tapered copolymers is essential. For this purpose, George Floudas − Max Planck Institute for Polymer Research,
we introduced analytically derived algebraic expressions for the D-55125 Mainz, Germany; Department of Physics, University
molar and volume composition profiles, which were directly of Ioannina, 45110 Ioannina, Greece; orcid.org/0000-
implemented in a simple Microsoft Excel spreadsheet (included 0003-4629-3817; Email: gfl[email protected]
in the Supporting Information), making the depiction of the Holger Frey − Department of Chemistry, Johannes Gutenberg
copolymer composition profile directly accessible. University Mainz, 55128 Mainz, Germany; orcid.org/
The tapered building blocks were used for the synthesis of 0000-0002-9916-3103; Email: [email protected]
both tri- (ABA) and pentablock (ABABA) copolymers of β-
farnesene (B block) and styrene (A block) with total polydiene Authors
volume fractions of 0.50 and 0.68. In addition, the Christian Wahlen − Department of Chemistry, Johannes
corresponding tri- and pentablock copolymers with isoprene Gutenberg University Mainz, 55128 Mainz, Germany
(C5) and β-myrcene (C10) were synthesized, containing the Jan Blankenburg − Department of Chemistry, Johannes
same polydiene volume fractions as their β-farnesene-based Gutenberg University Mainz, 55128 Mainz, Germany
(C15) analogs. This approach resulted in well-defined tapered Philipp von Tiedemann − Department of Chemistry, Johannes
tri- and pentablock copolymers with molecular weights of 120 kg Gutenberg University Mainz, 55128 Mainz, Germany
mol−1 for all samples and low dispersities in the range of 1.05− Johannes Ewald − Department of Chemistry, Johannes
1.16. This series of multiblock copolymers enabled a Gutenberg University Mainz, 55128 Mainz, Germany
comprehensive study of the influence of the polydiene Paweł Sajkiewicz − Institute of Fundamental Technological
architecture on the thermal and mechanical properties of the Research, Polish Academy of Sciences, 02-106 Warsaw, Poland
TPEs as well as their processability. The copolymers exhibit the Complete contact information is available at:
same morphology, as shown by SAXS. Depending on the https://pubs.acs.org/10.1021/acs.macromol.0c02118
polydiene volume fraction, multiblock copolymers show phase
separation in lamellar or hexagonally packed cylindrical Author Contributions
morphologies, almost the same domain spacing and a similar The manuscript was written through contributions of all
degree of segregation. The similarity in domain spacing reveals authors. All authors have given approval to the final version of
that specific chain configurations (loops) that are present in the the manuscript.
polyisoprene copolymers are minimized in PMyr and practically Notes
absent in the PFar tri- and pentablock copolymers. The tensile The authors declare no competing financial interest.

■
properties of the tri- and pentablock copolymers depend
strongly on the polydiene structure. The toughness of both tri- ACKNOWLEDGMENTS
and pentablock copolymers decreases in the order PI > PMyr >
Andreas Hanewald and Dr. Kaloian Koynov are acknowledged
PFar-based block copolymers, which is ascribed to reduced
for their valuable help with the mechanical characterization. The
number of entanglements of the polydiene midblocks
authors thank Monika Schmelzer for the valuable support with
[(Me(PFar) > Me(PMyr) > Me(PI)].
the SEC measurements, Ramona Barent for the support with the
Furthermore, the reduced solution viscosity of the tapered
data evaluation and Marcel Fickenscher for his support
PFar tri- and pentablock copolymers in comparison to their
regarding graphics design.

■
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