polymers

Article
Recycling and Reprocessing of Thermoplastic
Polyurethane Materials towards
Nonwoven Processing
Bastian Wölfel 1, *, Andreas Seefried 2 , Vincent Allen 1 , Joachim Kaschta 1 , Christopher Holmes 2
and Dirk W. Schubert 1, *
1 Institute of Polymer Materials, Friedrich-Alexander University, Erlangen-Nürnberg (FAU), Martensstraße 7,
91058 Erlangen, Germany
2 Adidas AG, Adi-Dassler-Straße 1, 91074 Herzogenaurach, Germany
* Correspondence: bastian.woelfel@fau.de (B.W.); dirk.schubert@fau.de (D.W.S.)




Received: 28 June 2020; Accepted: 21 August 2020; Published: 25 August 2020


Abstract: Thermoplastic Polyurethane (TPU) is a unique tailorable material due to the interactions
of hard and soft segments within the block-copolymer chain. Therefore, various products can be
created out of this material. A general trend towards a circular economy with regards to sustainability
in combination with TPU being comparably expensive is of high interest to recycle production as
well as post-consumer wastes. A systematic study investigating the property changes of TPU is
provided, focusing on two major aspects. The first aspect focuses on characterizing the change
of basic raw material properties through recycling. Gel permeation chromatography (GPC) and
processing load during extrusion indicate a decrease in molar mass and consequently viscosity with
an increasing number of recycling cycles. This leads to a change in morphology at lower molar mass,
characterized by differential scanning calorimetry (DSC) and visualized by atomic force microscope
(AFM). The change in molar mass and morphology with increasing number of recycling cycles has an
impact on the material performance under tensile stress. The second aspect describes processing of
the recycled TPU to nonwoven fabrics utilizing melt blowing, which are evaluated with respect to
relevant mechanical properties and related to molecular characteristics. The molar mass turns out
to be the governing factor regarding mechanical performance and processing conditions for melt
blown products.

Keywords: recycling; reprocessing; TPU; thermoplastic elastomers; TPE; thermoplastic;

polyurethane; elastomers; nonwoven; processing; melt blown; molar mass; mechanical properties;
methylendiphenylisocyanate; MDI; polytetramethylene glycol; PTMG; morphology; structure; phase
separation; sustainability; circular economy

1. Introduction
Thermoplastic Polyurethane (TPU) belongs to the class of thermoplastic elastomers, combining
desirable elastomeric properties at application temperatures and thermoplastic processability.
Their characteristics are based on the intra- and intermolecular interactions in the block-copolymer
chain consisting of hard and soft segments. The possibility of creating different soft-to-hard-block-ratios
makes it a unique tailorable material and implies the main advantage over classic homo-polymers.
Consequently, the application range comprises e.g., biomedical products, filtration, furniture,
construction materials, insulation, and footwear amongst others, making polyurethane products
the fifth-biggest polymer market globally [1–7]. With TPUs being comparably expensive, it is of high
interest to recycle production wastes like trim-cuts or gating systems as well as post-consumer waste.

Polymers 2020, 12, 1917; doi:10.3390/polym12091917 www.mdpi.com/journal/polymers

 Polymers
Polymers 2020,
2020, 12,12, x FOR PEER REVIEW
1917 2 of2 13
of 13

The block-copolymer chain of TPU typically consist of an isocyanate hard segment and ester or
Thebased
ether block-copolymer
soft segments. chain of TPUfortypically
Examples commerciallyconsistapplied
of an isocyanate
hard segment hardbase
segment and ester
constituents are or
ether based soft segmentsHad.
hexamethylene diisocyanate Examples(HDI)for commercially
[8], tolueneapplied hard segment
diisocyanate base constituents
(TDI) [9–11] andare
methylendiphenylisocyanate
hexamethylene diisocyanate (HDI) (MDI) [12–19],diisocyanate
[8], toluene combined with (TDI)soft segments
[9–11] like polyethylene glycol
and methylendiphenylisocyanate
(PEG)
(MDI) [20,21]combined
[12–19], as an examplewithfor ester
soft based orlike
segments thepolyethylene
ether based polytetrahydrofurans
glycol (PEG) [20,21](PTMEG/PTMG)
as an example for
[8,18,19,22].
ester based or Astheaether
resultbased
of thepolytetrahydrofurans
stronger affinity of the(PTMEG/PTMG)
hard segments to[8,18,19,22].
the ester groupsAs athan
result to of
thethe
ether groups in the soft segment, the solubility of the hard segments in the ester
stronger affinity of the hard segments to the ester groups than to the ether groups in the soft segment, elastomer is higher
theand their segregation
solubility of the hard lower
segments thaninin thethe ether
ester elastomer
elastomer [11,23,24].
is higher Accordingly,
and their segregationthe lower
properties
than in forthe
ester-
ether and ether-based
elastomer [11,23,24].materials exhibit
Accordingly, thedifferent
properties peculiarities, with
for ester- and the latter named
ether-based type
materials comprising
exhibit different
advantageous performances in terms of flexibility, especially at low temperatures,
peculiarities, with the latter named type comprising advantageous performances in terms of flexibility, hydrolysis, and
resistance to microbes. The last two factors are of particular importance regarding filtration
especially at low temperatures, hydrolysis, and resistance to microbes. The last two factors are of particular
applications, where melt blowing is state of the art [25]. Commercially applied materials in industry,
importance regarding filtration applications, where melt blowing is state of the art [25]. Commercially
as well as in sports engineering, are ether-based TPUs consisting of a MDI+BD (butane diol) hard and
applied materials in industry, as well as in sports engineering, are ether-based TPUs consisting of a
PTMG (polytetramethylene glycol) soft segment (SS) [7,22].
MDI+BD (butane diol) hard and PTMG (polytetramethylene glycol) soft segment (SS) [7,22].
To form hard segment (HS) domains, the hard and soft segments (SS) in the chains must separate
To form hard segment (HS) domains, the hard and soft segments (SS) in the chains must separate
into different phases on the micro level. The arrangement into hard segment domains can only be
into differentabove
successful phasesa on the micro
critical level. The
hard segment arrangement
length into hard
as displayed segment
in Figure domains
1. Below this, can
the only
hardbe
successful
segmentsaboveare adissolved
critical hard segment
in the length and
soft phase as displayed in Figure
can therefore not 1.function
Below this,
as athe hardsegment
hard segments
are[13,17,18,26].
dissolved in the soft phase and can therefore not function as a hard segment [13,17,18,26].

Figure
Figure 1. 1. Schematicexample
Schematic exampleof
ofthe
thearrangement
arrangement of
of ether
etherbased
basedthermoplastic
thermoplasticpolyurethane
polyurethane consisting
consisting
of methylendiphenylisocyanate(MDI)/BD
of methylendiphenylisocyanate (MDI)/BDhard
hard and
and PTMG
PTMG soft
soft segments
segmentsafter
after[13,17,18,26].
[13,17,18,26].

2. Motivation
2. Motivation
Recycling
RecyclingTPUs
TPUshas hasbeen
beennamed
named inin several
several patents describingaasupplemental
patents describing supplementaloptionoption forfor
a a
nonwoven
nonwoven fabrication
fabrication process,
process,but butwas
wasneither
neither specified further,
further, nor
norpublished.
published.AllAll scientific
scientific relevant
relevant
studies
studies concerning
concerning the the recycling
recycling of TPUs
of TPUs targettarget injection
injection molded molded specimens
specimens in comparison
in comparison to
to extrusion.
extrusion. Degradation occurs in all kinds of thermoplastic processes and can
Degradation occurs in all kinds of thermoplastic processes and can interfere with the crystallizationinterfere with the
crystallization
processes. This is processes. This is during
especially distinct especially distinct
injection duringwhere
molding, injection molding,
varying whereand
orientation varying
cooling
orientation
conditions and cooling
influence conditions
the resulting influencemechanical
measured the resultingproperties.
measured mechanical properties.
AA systematic
systematic studyinvestigating
study investigatingthe the property
property changes
changesof ofreprocessed
reprocessedTPUTPUfrom
from a raw
a raw material
material
perspective is provided. It is well known that during (multiple) processing the molar
perspective is provided. It is well known that during (multiple) processing the molar mass decreases; mass decreases;
thisthis
waswas quantified
quantified by permeation
by gel gel permeation chromatography
chromatography (GPC).(GPC). The mechanical
The mechanical properties
properties of
of polymers
polymers depend on their molecular structure as Flory has already shown in 1945 [27]. Therefore,
depend on their molecular structure as Flory has already shown in 1945 [27]. Therefore, mechanical
mechanical tests on plates of controlled equal pressing conditions have been conducted with regard
tests on plates of controlled equal pressing conditions have been conducted with regard to tensile stress
to tensile stress and elongation at break. The change in molar mass with an increasing number of
and elongation at break. The change in molar mass with an increasing number of cycles additionally
cycles additionally has an influence on the crystallization behavior of the TPU [12,26,28], but has,
has an influence on the crystallization behavior of the TPU [12,26,28], but has, until now, never been
until now, never been related to an actual recycling study.
related Subsequent
to an actualprocessing
recycling study.
of the recycled TPUs to nonwoven fabrics using melt blowing is also
Subsequent
evaluated processing
and the of the recycled
fabric properties TPUs
are related to to nonwoven
molecular fabrics using
characteristics. Themelt
molarblowing
mass isisthealso
evaluated
governing factor regarding mechanical performance and processing conditions for melt blowing.the
and the fabric properties are related to molecular characteristics. The molar mass is
governing factor
This has been regarding mechanical
characterized through the performance
examination ofand processing
the obtained conditions
nonwovens viafor meltand
tensile blowing.
tear
This has been
strength, characterized
as well as GPC. through the examination of the obtained nonwovens via tensile and tear
strength, as well as GPC.
Polymers 2020, 12, 1917 3 of 13

Polymers 2020, 12, x FOR PEER REVIEW 3 of 13

A major characteristic of TPUs is that the onset of degradation mechanisms is already within the
A major characteristic of TPUs is that the onset of degradation mechanisms is already within the
recommended processing window provided by manufacturers of commercial products [8,15,18,19,21,26,29,30].
recommended processing window provided by manufacturers of commercial products
Therefore, it is of enormous importance to identify the correlation between (multiple) processing, the
[8,15,18,19,21,26,29,30]. Therefore, it is of enormous importance to identify the correlation between
changed molar
(multiple) mass and
processing, theresulting
changedstructures.
molar mass and resulting structures.
3. Materials and Methods
3. Materials and Methods
The
Theexperimental
experimentalsetup
setup displayed
displayed in
in Figure
Figure 22 is
is comprised
comprised ofof three
threemajor
majorsteps:
steps:material
material
compounding,
compounding, raw material analysis
raw material analysis in
in the
the context of recycling, and applying these materials in in
context of recycling, and applying these materials
nonwoven
nonwoven production.
production.

Figure
Figure 2.2.Schematic
Schematicof
ofthe
the experimental
experimental setup:
setup:Reprocessing
Reprocessingofofthe Thermoplastic
the ThermoplasticPolyurethane
Polyurethane(TPU)
(TPU)
andand characterizationofofthe
characterization theimpact
impact of
of recycling
recycling on
on the
the bulk
bulkmaterial
materialandandapplication
applicationof of
thethe
recycled
recycled
materials
materials as nonwoven
as nonwoven through
through melt blowing.
melt blowing. Relevant
Relevant processing
processing and preparation
and sample sample preparation
parameters
areparameters
indicated.are indicated.

AA polyether-based
polyether-based thermoplastic
thermoplastic polyurethane
polyurethane resinresin of Shore
of 80A 80A Shore hardness,
hardness, consisting
consisting of MDI+BDof
MDI+BD hard and PTMG soft segments and featuring a hard segment content
hard and PTMG soft segments and featuring a hard segment content of roughly 30 wt% was used of roughly 30 wt%
in was used inPrior
the study. the study. Prior to compounding
to compounding the TPU the TPU material
material was driedwasfor
dried
twofor two hours
hours at 80 ◦atC80
in°C in a
a Motan
Motan (Motan Holding GmbH, Konstanz, Germany) Luxor dehumidifier before
(Motan Holding GmbH, Konstanz, Germany) Luxor dehumidifier before every processing step and every processing
is step and isconsidered
therefore therefore considered
the standardthe drying
standard drying procedure.
procedure. Compounding
Compounding was performed
was performed in a
in a Leistritz
Leistritz (Leistritz Extrusionstechnik GmbH, Nürnberg, Germany) twin screw extruder with
(Leistritz Extrusionstechnik GmbH, Nürnberg, Germany) twin screw extruder with kneading elements
kneading elements at 205 °C and 33 rpm, followed by a two-step cooling procedure using water and
at 205 ◦ C and 33 rpm, followed by a two-step cooling procedure using water and liquid nitrogen to
liquid nitrogen to allow for granulation. The granulated material was then reprocessed using the
allow for granulation. The granulated material was then reprocessed using the same steps a total
same steps a total of 8 times. Material was retained at completed processing of runs 1, 2, 4, and 8 to
of 8 times. Material was retained at completed processing of runs 1, 2, 4, and 8 to perform both
perform both the raw material analysis, part one, and nonwoven production, part two. Included in
thethe
raw material
results analysis, part
is a comparison one,
to the and raw
virgin nonwoven
material,production,
which did not part two. Included
undergo in theprocess,
the extrusion results is
a comparison to the virgin raw material, which did not undergo the extrusion
i.e., Run 0. The chosen processing temperature is based on the recommended processing windows process, i.e., Run 0.
Theprovided by manufacturers of comparable grades and hardness. It ensures that all existent crystalline by
chosen processing temperature is based on the recommended processing windows provided
manufacturers
structures areoftransformed
comparableintogrades andstate
molten hardness. It ensures
according that all existent crystalline structures are
to [17,26].
transformed into molten state according to [17,26].
Polymers 2020, 12, 1917 4 of 13

The first part deals with the material’s inherent change due to the recycling procedure. Hence the
material was dried, pressed into plates using a Vogt (VOGT Labormaschinen GmbH, Berlin, Germany)
vacuum press and analyzed regarding change of molar mass, mechanical behavior, and material
structure. The samples for mechanical analysis were punched out from the bulk material plates in
dimensions comparable to DIN ISO 527-2 1BB mini dog-bones. For determining material structure,
differential scanning calorimetry (DSC) Q2000 from TA Instruments Inc. (New Castle, DE, USA) was
used with a heating rate of 10 ◦ C/min in a range of 20 to 240 ◦ C and sample size of 6–8 mg was performed.
The second part compromises the processing of the before characterized recycled materials into
nonwovens. Therefore, a melt blowing line from FET (Fibre Extrusion Technology Ltd., Leeds, UK) with
a 14 cm wide die-head, comprising 41 holes with a diameter of 250 µm, was used. The melt temperature
was 215 ◦ C. A throughput of 0.007 cm3 /s per hole was achieved by the melt pump at 20 rpm. Hot air (ot
air225 ◦ C, 1830 L/min) was blowing the melt onto the 0.4 m/min travelling belt. The resulting roughly
15 cm wide nonwoven was analyzed in terms of resulting molar mass and its mechanical behavior
regarding tensile strength in machine direction (MD) and cross direction (CD) and tear strength in MD.
The specimens for tensile testing, sized as a rectangle of 10 mm × 90 mm, were punched out of the
nonwoven. The tear strength samples are adapted to DIN ISO 34-1 and rescaled to 35 mm × 70 mm
with a 35 mm incision in MD justified by the nonwoven sizing. A Zwick-Roell Z050 tensile testing
machine (ZwickRoell GmbH & Co. KG, Ulm, Germany), with a 1 kN load cell and pneumatic clamps
under 7 bar pressure, performed the mechanical analysis.
All Differences in molar mass were characterized by gel permeation chromatography (GPC 1260
Infinity II, Agilent Technologies, Santa Clara, CA, USA) with N,N–Dimethylacetamid (DMAc) and
Lithium-Bromide (LiBr) as a solvent. The used columns (set to 60 ◦ C) are supplied by PSS (PSS Polymer
Standards Service GmbH, Mainz, Germany) and combined with a dRI detector Shodex 101, LS detector
Wyatt Minidawn (Wyatt Technology Corporation, Santa Barbara, CA, USA). The flow rate of the mobile
phase was 1 mL/min. The samples were measured and evaluated using the software “PSS SECurity2
GPC System” (Build 8251, PSS Polymer Standards Service GmbH, Mainz, Germany).

4. Results and Discussion

Figure 3 displays the change of chain length expressed by the weight average molar mass Mw as a
function of the number of recycling runs. It is observed that the raw material reveals an asymptotic
decrease in molar mass when reprocessed in an extruder. The molar mass is not dropping under
roughly 40 kg/mol when reaching an equilibrium state, which may be due to concurrent degradation
and build up processes in the TPU which have been described in literature [18].
As the degradation mechanisms are of mechanical and thermal nature resulting in a decay of molar
mass (Mw ) over recycling steps (n), this context can be described by an exponential decay function:

Mw (n) = (Mw,0 − Mw,∞ ) ∗ exp(−n/ñ) + Mw,∞

with : Mw,0 = (92.7 ± 2.3) kg/mol
(1a)
Mw,∞ = (41.1 ± 3.8) kg/mol
n = 3.0 ± 0.5

In this relation Mw,0 describes the initial molar mass of the virgin product, Mw,∞ is the asymptotic
molar mass after an infinite number recycling steps and ñ describes the degree of decay per recycling
run in molar mass degradation. Equation (1a) is attributed to the solution of the first order differential
equation:
dMw /dn = −(Mw − Mw,∞ )/ñ (1b)

Beside the temperature, the degradation is furthermore depending on the mechanical forces
transmitted onto the polymer chain. As the shear forces are dependent on viscosity and thus on
chain length it is obvious that the forces applied to individual chains have to decrease with increasing
number of recycling runs.
 4. Results and Discussion
Figure 3 displays the change of chain length expressed by the weight average molar mass Mw as
Polymers 2020, 12, x FOR PEER REVIEW 5 of 13
a function of the number of recycling runs. It is observed that the raw material reveals an asymptotic
decrease in molar mass when reprocessed in an extruder. The molar mass is not dropping under
Figure 3. Decrease of Mw as a function of recycling runs for fixed temperature (T = 205 °C) and fixed
roughly
Polymers 40 12,
2020,
extruder
kg/mol
1917 when
rotational
reaching an equilibrium state, which may be due to concurrent degradation
speed (33 rpm). The dashed line shows the best fit of Equation (1). 5 of 13
and build up processes in the TPU which have been described in literature [18].
As the degradation mechanisms are of mechanical and thermal nature resulting in a decay of
molar mass (Mw) over recycling steps (n), this context can be described by an exponential decay
function:
Mw(n) = (Mw,0 – Mw,∞) * exp(−n/ñ) + Mw,∞

with: Mw,0 = (92.7 ± 2.3) kg/mol

(1)
Mw,∞ = (41.1 ± 3.8) kg/mol
ñ = 3.0 ± 0.5
In this relation Mw,0 describes the initial molar mass of the virgin product, Mw,∞ is the asymptotic
molar mass after an infinite number recycling steps and ñ describes the degree of decay per recycling
run in molar mass degradation. Equation (1) is attributed to the solution of the first order differential
equation:
dMw/dn = − (Mw – Mw,∞)/ñ (1b)
Beside the temperature, the degradation is furthermore depending on the mechanical forces
transmitted
Figure 3. onto the polymer
Decrease of Mw as chain. As the
a function shear forces
of recycling runs are dependent
for fixed on viscosity
temperature (T = 205and
◦ C)thus on chain
and fixed
length it is obvious that the forces applied to individual chains have
extruder rotational speed (33 rpm). The dashed line shows the best fit of Equation (1).to decrease with increasing
number of recycling runs.
AArather
rathersurprising
surprisingbehavior
behavior of of the
the bulk
bulk material can be observed
observed in in the
the tensile
tensiletests,
tests,displayed
displayed
ininFigure
Figure 4. While
Whilethe
the stress
stress at break
at break decreases
decreases withwith reprocessing
reprocessing (decreasing
(decreasing Mw ) according
Mw) according to Flory’sto
Flory’s [27] suggestion,
[27] suggestion, the elongation
the elongation at break
at break increases.
increases. It isItworth
is worth
to to note
note thatmost
that mostcommonly
commonlyused used
materials
materialsbecome
becomebrittle
brittle as
as aa result
result of
of the
the decreasing
decreasing chain
chain length due to recycling.
recycling. This
Thisinevitably
inevitably
leadstotothe
leads thefinding
findingthat
thatthe
thematerial
material becomes
becomes lessless strong
strong and more ductile. The The dependence
dependenceof ofthe
the
stressatatbreak
stress breakononMMww can
can bebe described
described by Flory’s [27] equation
equation as:
as:
σBreak(Mw) = A – B/Mw
σBreak (Mw ) = A − B/Mw
with : A = (60.0 ± 1.6) N/mm 2
with: A = (60.0 ± 1.6) N/mm
 2  (2)(2)
B = (1400 ± 100) N/mm2 × kg/mol
B = (1400± 100) (N/mm2 × kg/mol)

Figure 4. Stress and elongation at break of recycled TPU as a function of weight average molar mass
Mw . The top axis indicates the recycling step Rx (x = 0, 1, 2, 4, and 8). The red dashed line is a guide to
the eye whilst the grey line displays the best fit of Equation (2).
Polymers 2020, 12, x FOR PEER REVIEW 6 of 13

Figure 4. Stress and elongation at break of recycled TPU as a function of weight average molar mass
Mw2020,
Polymers . The12,
top axis indicates the recycling step Rx (x = 0, 1, 2, 4, and 8). The red dashed line is a guide to 6 of 13
1917
the eye whilst the grey line displays the best fit of Equation (2).

The
The values suggest that the
suggest that the stress
stress at
at break
break could
couldnot
notexceed
exceed60 N/mm2 2even
60N/mm evenforforinfinitely
infinitelyhigh
high
molar masses.
molar masses. However, it is very unlikely to obtain TPU products of this composition
is very unlikely to obtain TPU products of this composition exceeding theexceeding the
framework
framework of of the investigated molar masses.
masses. The
Thevirgin
virginproduct
productandandthe
theeight
eighttimes
timesrecycled
recycled material
material
state
state the
the entire possible molar mass mass values,
values,making
makingititananinterpolative
interpolativeviewviewand
andawarding
awardingadditional
additional
interpretive
interpretive strength to this relation.
relation. The
Theelongation
elongationbehavior
behaviorisisnot
notfurther
furtherdescribed
describedbased
basedononthis
this
plot,
plot, as
as itit does
does not follow common rules and and requires
requires aa separate
separatefollow
followup updiscussion.
discussion.
Considering the
Considering the display
display of of the
the stress
stress at
at different
different elongations
elongationsininFigure
Figure5a5aand andthetheslope
slopeofof
corresponding stress-strain-curves
corresponding stress-strain-curves in Figure 5b, the the presumption
presumptionof ofaagain
gainininductility
ductilitycancanbebeassumed
assumed
confirmed. However,
confirmed. However,this thiseffect
effectisisonly
onlyevident
evidentforfordeformations
deformationslarger
largerthan
than100%
100% and
and hence
hence raises
raises the
the question
question if there
if there is a modification
is a modification of hard
of the the hard segments
segments taking
taking place place during
during recycling
recycling and and
whichwhich
parts
parts
of the of
TPU thedegrade.
TPU degrade.

(a) (b)
Figure 5. (a) Tensile
Figure 5. (a) stress
Tensileof recycled
stress ofTPU material
recycled TPUfor material
different elongations
for differentaselongations
a function of as
weight averageof
a function
molarweight
mass M w. The top
average axismass
molar indicates
Mw .the recycling
The top axisstep Rx (x =the
indicates 0, 1, 2, 4, andstep
recycling 8); (b) (x = 0, 1, 2, 4, mean
RxCorresponding and 8);
stress–strain–curves
(b) Corresponding of the measured
mean values from recycling
stress–strain–curves step Rx values
of the measured (x = 0, 1, 2, 4,recycling
from and 8) shown
step Rx (a).= 0, 1, 2,
in (x
4, and 8) shown in (a).
To get to the reasons for the peculiar behavior, DSC measurements were performed and the
enthalpyget
To of to the reasons during
crystallization for the cooling
peculiarafter
behavior,
the firstDSC
heatmeasurements
up are compared wereandperformed
benchmarked and to the
enthalpy of crystallization during cooling after the first heat up are compared
their melting enthalpy in the following heating run number two (Figure 6). An exemplary DSC and benchmarked to their
melting enthalpy
measurement canin be
the understood
following heating run number
in Figure A1 in the twoAppendix
(Figure 6). A.An The
exemplary
melting DSC measurement
enthalpies are
can
effectively identical to their enthalpies of crystallization, which assures we are not measuring anto
be understood in Figure A1 in the Appendix A. The melting enthalpies are effectively identical
their enthalpies
artefact. From of crystallization,
Figure 6 it can which assures that
be observed we are not measuring
crystallinity, an artefact.
represented byFrom
the Figure
enthalpy 6 it of
can
be observed that
crystallization, is crystallinity,
decreasing fromrepresented bymaterial
the virgin the enthalpy of crystallization,
towards the two times is decreasing
recycled fromby
material the
virgin material towards the two times recycled material by about 60%. From
about 60%. From the highly amorphous material obtained in run two, crystallinity rises again with the highly amorphous
material obtained
the following in run two,
recycling steps,crystallinity risesinitial
almost to the againvalue
with the following
of the virgin recycling
material. steps, almost
This leads totothethe
initial valuethat
hypothesis of the virgin
there arematerial. Thisdegradation
two separate leads to the hypothesis
regimes forthatsoftthere are two
and hard separate
segments ofdegradation
which the
TPU consists.
regimes for softAsandTGAhardanalysis of comparably
segments of whichchemically structured
the TPU consists. AsTPUs
TGAhave shown
analysis of [14,15],
comparablythe
hard segments
chemically start to
structured TPUsdegrade at around
have shown 200the
[14,15], °C,hard
whereas the start
segments soft segments
to degradeonly degrade
at around 200at ◦ C,

temperatures
whereas the softabove 300 °C.
segments Therefore,
only degradethe HS will degrade
at temperatures above ◦
at processing temperature
300 C. Therefore, the HSwhile the SS
will degrade
at processing temperature while the SS remain stable [14,15]. Hence after the degradation of thesoft
remain stable [14,15]. Hence after the degradation of the hard segments, it is assumed that the hard
segments that
segments, constitutethat
it is assumed the the
governing resistance
soft segments thatto melt flowthe
constitute and are, therefore,
governing degraded
resistance to meltfrom
flowrun and
twotherefore,
are, onwards. degraded from run two onwards.
This is backed by the corresponding peak temperature of the melt peak in the second heating
run. It can be observed that after the second recycling step the values are constant. The behavior of
the peak temperature in correspondence to the present hard domain structure was analyzed in detail
by Hu and Koberstein et al. and Martin et al. and published in 1994 and 1997, respectively [17,26].
Polymers 2020, 12, x FOR PEER REVIEW 7 of 13

Polymers 2020, 12, 1917 7 of 13

They found that a decrease in average hard segment length directly leads to a lower melting peak
temperature. This results from the higher order of hard segments that can be achieved upon a
higher number of H-bonds inside the hard phase. This makes the structure more resistant to phase
transformation. Based on this it can be concluded that the hard segment structure remains constant
for recycling runs greater than two and therefore any changes in crystallinity after recycle run 2 are
based on changes in the soft segments. The general molecular structure of this MDI/BD TPU is not
changing during processing as it is subject to “transurethanisation” [17,18,29,31]. The dissociation of
the urethane bond to free isocyanate and hydroxyl end-groups is the primary degradation mechanism:
From a temperature between 200 until 330 ◦ C isocyanates and alcohols are the exclusively appearing
degradation
Polymers products
2020, 12, [15,29,30].
x FOR PEER REVIEW 7 of 13

Figure 6. Left axis: Enthalpy of crystallization as a function of weight average molar mass Mw. Right
axis: Corresponding melting peak temperature in dependence of the average molar mass. The top
axis indicates the recycling step Rx (x = 0, 1, 2, 4, and 8). The dashed lines are a guide to the eye.

This is backed by the corresponding peak temperature of the melt peak in the second heating
run. It can be observed that after the second recycling step the values are constant. The behavior of
the peak temperature in correspondence to the present hard domain structure was analyzed in detail
by Hu and Koberstein et al. and Martin et al. and published in 1994 and 1997, respectively [17,26].
They found that a decrease in average hard segment length directly leads to a lower melting peak
temperature. This results from the higher order of hard segments that can be achieved upon a higher
number of H-bonds inside the hard phase. This makes the structure more resistant to phase
transformation. Based on this it can be concluded that the hard segment structure remains constant
for recycling runs greater than two and therefore any changes in crystallinity after recycle run 2 are
based on changes in the soft segments. The general molecular structure of this MDI/BD TPU is not
changing
Figureduring
6. Left processing
axis: Enthalpyas of
it is subject to “transurethanisation”
crystallization [17,18,29,31].
weight average
as a function of weight average The
massdissociation
molar mass
molar MMww. Right of
the urethane bond tomelting
axis: Corresponding
Corresponding free isocyanate
melting peak and in
peaktemperature
temperature hydroxyl
in end-groups
dependence
dependence of the
of the is molar
average
average themolar
primary
mass. Thedegradation
mass. The top
top axis
indicates the recycling step Rx (x = 0, 1, 2, 4, and 8). The dashed lines are a guide to the eye.
mechanism:
axis From
indicates thea temperature
recycling step Rx between
(x = 0, 1, 2,200
4, until
and 8). 330
The °C
dashed isocyanates
lines are a and
guide toalcohols
the eye. are the
exclusively appearing degradation products [15,29,30].
Attempting
This is backed
Attempting to obtain
to obtain further evidence
by the further evidence
corresponding for temperature
peak
for the hypothesis
the hypothesis of two
of of
the two regimes,
meltregimes, AFM
peak inAFM imagesheating
the second
images of the
of the
samples
run. were
It can
samples recorded
recorded and
be observed
were that the
and phase
after
the images
the second
phase are
are displayed
imagesrecycling step in
displayed in Figure
the values7.
Figure 7.are constant. The behavior of
the peak temperature in correspondence to the present hard domain structure was analyzed in detail
by Hu and Koberstein et al. and Martin et al. and published in 1994 and 1997, respectively [17,26].
They found that a decrease in average hard segment length directly leads to a lower melting peak
temperature. This results from the higher order of hard segments that can be achieved upon a higher
number of H-bonds inside the hard phase. This makes the structure more resistant to phase
transformation. Based on this it can be concluded that the hard segment structure remains constant
for recycling runs greater than two and therefore any changes in crystallinity after recycle run 2 are
based on changes in the soft segments. The general molecular structure of this MDI/BD TPU is not
changing during processing as it is subject to “transurethanisation” [17,18,29,31]. The dissociation of
the urethane bond to free isocyanate and hydroxyl end-groups is the primary degradation
mechanism: From a temperature between 200 until 330 °C isocyanates and alcohols are the
exclusively appearing degradation products [15,29,30].
Attempting to obtain further evidence for the hypothesis of two regimes, AFM images of the
samples were recorded and the phase images are displayed in Figure 7.

Figure 7. AFM
AFM pictures
pictures of
of the
the morphology
morphology of
of virgin
virgin (R0),
(R0), two
two times
times recycled
recycled (R2) and 8 times
times recycled
(R8) TPU together with possible hard segment (HS)- and soft soft segment
segment (SS)-structures.
(SS)-structures. The sides of
each image have a length of 5 µm.
Polymers 2020, 12, 1917
x FOR PEER REVIEW 8 of 13

It can be observed that finely structured and clearly separated, discrete phases of different
It cantobethe
resistance observed
cantilever thatare finely
presentstructured
in the Run and 8clearlymaterial.separated, discrete
Constituted phases
of short of different
chains, which
feature an increased mobility, the shortened HS are likely to separate and form crystals. In the which
resistance to the cantilever are present in the Run 8 material. Constituted of short chains, Run 2
feature anthe
material, increased mobility,
SS are still intact andthe shortened
likely to hinderHS arethe likely to separate
arrangement ofand formshortened
already crystals. In HS,theleading
Run 2
material, the SS are still intact and likely to hinder the arrangement
to a low crystallinity. This can be seen in the AFM image with a high amount of bright SS phase with of already shortened HS, leading to
a low crystallinity. This can be seen in the AFM image with a
isolated darker HS phase. In the virgin R0 material both phases are assumed to be intact and wellhigh amount of bright SS phase with
isolated darker
intermixed, HS phase.
wherefore In the
no clear virgin R0within
separation material scaleboth phases areLong
is detectable. assumed
chains to need
be intact
moreand time well
to
intermixed, wherefore no clear separation within scale is detectable.
diffuse and phase separate, thus for the virgin material potentially higher crystallinity could be Long chains need more time
to diffuseby
achieved and phase separate,
applying an additional thus annealing
for the virgin material
procedure potentially higher crystallinity could be
[26].
achieved by applying an additional annealing procedure [26].
The conclusion from the first part targeting the raw material properties is that the present TPU
The conclusion
degrades in two steps. fromAs the
the first part targeting
recommended the raw temperatures
processing material properties
of the isTPUsthatare
theabove
present 200TPU°C
degrades
and in two
therefore steps.inside
already As thethe recommended
degradation regime processing of thetemperatures
hard segments, of the TPUs
these areare
theabove 200 ◦to
first ones C
and therefore already inside the degradation regime of the hard
degrade. After two steps of recycling in the extruder the hard segments are already degraded to a segments, these are the first ones to
degrade.
large After
extent. Thetwo steps of
shortage of recycling
hard segments in the is extruder
reflectedthe byhard segments
a decrease in Tare already
m during degraded
DSC. This is to thea
large extent.
reason why they The cannot
shortage of hardto
assemble segments
a properishard reflected
phaseby a decrease
anymore in Tm
as they areduring DSC.
sterically This is the
hindered by
reason why they cannot assemble to a proper hard phase anymore
the intact soft segments. This is the reason why the AFM shows a large amount of bright soft phase. as they are sterically hindered by
the intact
The soft segments.
soft segments are then This is the reason
degraded why the
afterwards, as AFM
they are showsnowa the
large amount
main of brighttosoft
contribution phase.
viscosity
The soft segments
through their molar are thenItdegraded
mass. can only afterwards, as they are
be the soft segments now the main
shortening contribution
to achieve further to viscosity
decrease in
through their molar mass. It can only be the soft segments shortening
molar mass as the melting peak temperature reflecting hard segment length does not change after to achieve further decrease in
molar
the massrecycling
second as the melting
step. peak
Aftertemperature
both parts ofreflecting
the TPU,hard soft segment
and hardlength does are
segments, not degraded,
change after the
there
second recycling step. After both parts of the TPU, soft and hard
is also a low molar mass. This leads to increasingly mobile chains being able to assemble more segments, are degraded, there is also
a low molar
efficiently, mass.reflects
which This leads to increasingly
in a higher mobile chains
melting enthalpy and thebeingclearly able to assemble
structured hardmore
phaseefficiently,
observed
which
for “Run reflects in a higher
8” material via melting
AFM. All enthalpy and the are
these findings clearly structuredreflected
additionally hard phasein theobserved for “Run
presented results8”
material via AFM. All
obtained from tensile tests. these findings are additionally reflected in the presented results obtained from
tensileThetests.
above described and analyzed recycled TPUs were processed to nonwoven fabrics using
melt The aboveFigure
blowing. described and analyzed
8 compares recycled
the Mw-values of TPUs wereto
the fabrics processed
the values toofnonwoven
the materials fabrics using
not being
melt blowing. Figure 8 compares
processed into nonwoven. Due to the higher the M w -values
temperatures in the melt blowing process togetherbeing
of the fabrics to the values of the materials not with
processed
an order ofinto nonwoven.
magnitude Due shear
higher to the stress
higherdue temperatures
to the small in the melt blowing
capillaries in the process
spinneret,together with an
the recorded
order of
molar magnitude
masses of thehigher
nonwovensshear are stress due tocompared
smaller the small to capillaries in thethey
the materials spinneret,
were made the recorded
of. However,molar
masses
the molarof the nonwovens
mass still doesare notsmaller
drop compared
under thetoasymptote
the materials they werethrough
discovered made of.multiple
However,extrusions
the molar
mass still does
described above.notThis
dropleads
undertothe theasymptote
suggestion discovered
that this through
asymptote multiple extrusions
is a material described
specific above.
parameter
This leads to the suggestion that this asymptote is a material specific
rather than dependent on processing conditions and is described in Figure 8. Processing TPU via melt parameter rather than dependent
on processing
blowing providesconditions and is described
an inherently in Figure 8.and
higher degradation Processing TPU viaadds
hence roughly melt three
blowing provides
recycling an
steps
inherently to
compared higher degradation and hence roughly adds three recycling steps compared to extrusion.
extrusion.

Figure 8. Decrease
Decrease of
of M
Mwwas
asaafunction
functionofofrecycling
recyclingruns
runsfor
forthe
thematerial
materialof
ofthe
therecycling
recyclingstudy
study(crosses)
(crosses)
and the nonwoven
nonwovenmademadeout
outofofitit(rectangles).
(rectangles).The
Thedashed
dashed lines
lines areare
thethe best
best adjustment
adjustment of Equation
of Equation (1).
(1).
Polymers 2020, 12, 1917 9 of 13

Polymers
Due2020, 12, xfact
to the FORthat
PEERtwo
REVIEW
different processes, melt blowing and extrusion, with different9 typical of 13

shear rates yield the same asymptotic molar mass value within the experimental error, it is evident
Due to the fact that two different processes, melt blowing and extrusion, with different typical
that local stresses acting on the polymer chains are identical. When the chains are initially longer,
shear rates yield the same asymptotic molar mass value within the experimental error, it is evident
the process with a higher shear rate (or elongation rate) yields the higher stress on the chain. This results
that local stresses acting on the polymer chains are identical. When the chains are initially longer, the
in a faster chain scission, therefore lowering the viscosity due to the molar mass reduction and finally
process with a higher shear rate (or elongation rate) yields the higher stress on the chain. This results
reducing
in a fasterthe stress
chain on thetherefore
scission, chain. This means
lowering the an equilibrium
viscosity is reached
due to the molar massindependent
reduction andof the initial
finally
shear rate (or elongation rate). The only constraint, which must be fulfilled
reducing the stress on the chain. This means an equilibrium is reached independent of the initial shearthat different processes
yield
ratethe
(or same asymptotic
elongation rate). Themolar
only mass, is that which
constraint, the initial
muststress on the that
be fulfilled chain is larger
different than theyield
processes critical
stress
the same asymptotic molar mass, is that the initial stress on the chain is larger than the critical stress of
needed for chain scission. If only thermal degradation would be relevant, the right side
Equation
needed (1b), the differential
for chain scission. If equation
only thermal would only consist
degradation wouldof a be
constant andthe
relevant, Mw dependence
noright side of Equationwould
result. For differential
(1b), the TPUs the initial
equationMw would
itself isonly
alsoconsist
dependent on the applied
of a constant and no temperature
Mw dependence as discussed in [18].
would result.
Therefore,
For TPUsone thecan assume
initial that aisthermal
Mw itself driven equilibrium
also dependent on the appliedmolartemperature
mass is reached very fastinfollowed
as discussed [18].
byTherefore,
a subsequent one mechanically
can assume that driven a thermal driven
degradation as equilibrium
described above.molar mass is reached very fast
followed by a subsequent
As observed for the raw mechanically
material, the driven degradation
mechanical as described
performance of theabove.
nonwoven is dependent on
the molarAs observed
mass andfor the raw in
displayed material,
Figure the mechanical
9. Tensile performance
strength in machine of direction
the nonwoven(MD),iscross
dependent
direction
on the molar mass and displayed in Figure 9. Tensile strength in machine
(CD) and tear strength (TS) follow a qualitatively comparable linear trend. This behavior is due direction (MD), cross
to the
direction (CD) and tear strength (TS) follow a qualitatively comparable
formation of the nonwoven from single fibers. Generally, a higher number of fibers is orientatedlinear trend. This behavior is in
due to the formation of the nonwoven from single fibers. Generally, a higher
MD, wherefore the tensile strength in this direction is expected to be higher. In this study the tensile number of fibers is
orientated in
performance in MD,
CD iswherefore the tensile of
roughly two-thirds strength
MD. The in this
fiberdirection is expected
orientation to beashigher.
distribution, well asInthethis
base
study the tensile performance in CD is roughly two-thirds of MD. The fiber orientation distribution,
weight of the fabric, play a significant role in the resulting mechanical properties. In nonwovens,
as well as the base weight of the fabric, play a significant role in the resulting mechanical properties.
the base weight corresponds to the sample thickness, in this study it is 305 g/m2 ± 5% for all 2samples.
In nonwovens, the base weight corresponds to the sample thickness, in this study it is 305 g/m ± 5%
By keeping the processing conditions identical for all considered materials, the named above factors
for all samples. By keeping the processing conditions identical for all considered materials, the named
can be neglected for interpretation and resulting forces can be regarded as strengths. If tensile strength
above factors can be neglected for interpretation and resulting forces can be regarded as strengths. If
in MD and CD would not follow the same qualitative trend the learnings would be based on artefacts,
tensile strength in MD and CD would not follow the same qualitative trend the learnings would be
e.g., incomparable
based on artefacts, fiber orientation
e.g., distribution,
incomparable and therefore
fiber orientation representsand
distribution, a plausibility
therefore check. The only
represents a
exception
plausibility check. The only exception is the nonwoven material NW-R1. During its production die- for
is the nonwoven material NW-R1. During its production die-hole blockages occurred
which
hole reason
blockages these pointsfor
occurred shall be interpreted
which reason thesewith caution.
points shall be interpreted with caution.

Figure
Figure 9.9.Tensile
Tensileand
andtear
tearstrength
strength ofof various
various nonwoven
nonwoven materials
materialsasasaafunction
functionofofMM w. The toptop
w . The axisaxis
indicates the starting material (NW-Rx) for the nonwoven (x = 0, 1, 2, 4, and 8). In addition
indicates the starting material (NW-Rx) for the nonwoven (x = 0, 1, 2, 4, and 8). In addition a mixture of a mixture
R0of+R0
R8+(50%)
R8 (50%) is shown
is shown (its(its results
results areare close
close to to R1).The
R1). Thedashed
dashedlines
linesare
areaaguide
guide toto the
the eye.
eye.

Comparingthe
Comparing themaximum
maximum elongation
elongation at
at break
breaktotothe
therespective
respectiveforce (Figure
force 10),
(Figure it can
10), be be
it can seen
seen
that
that it it increasestowards
increases towardsthe
thefabric
fabric produced
produced from
from twice
twicerecycled
recycledmaterial.
material.This can
This bebe
can explained by by
explained
Polymers 2020, 12, 1917 10 of 13
Polymers 2020, 12, x FOR PEER REVIEW 10 of 13

the already described properties of this material with regard to strongly pronounced soft phases and
consequently lower crystallization and is visualized
visualized in
in Figure
Figure 10.
10.

Figure 10.
10. Force at break
break (F
(Fmax
max)) and elongation at break
break (ε@F
(ε@Fmax
max)) as
as aa function of Mw
w for various

nonwovens (NW0-NW8, closed symbols) and a nonwoven made of 50/50 wt % mixture of R0 and R8
(open symbol). The dashed lines are a guide to the eye.

This observation
observationisisfurther indication
further towards
indication the hypothesis
towards of twoof
the hypothesis separate degradation
two separate regimes
degradation
for soft and
regimes for hard segments.
soft and ProducingProducing
hard segments. nonwovens from 50/50from
nonwovens mixtures
50/50out of virgin
mixtures outand
of eight
virgintimes
and
recycled material, which is close to
eight times recycled material, which w,∞ M , the resulting nonwoven properties are also mean.
is close to Mw,∞, the resulting nonwoven properties are also In the
present
mean. Incase
the this equals
present a molar
case massaand
this equals molarthemass
respective mechanical
and the respectiveperformance close to the fabric
mechanical performance close
produced from once recycled material. This is a remarkable finding which holds
to the fabric produced from once recycled material. This is a remarkable finding which holds thethe possibility to
tailor the aspired material performance by mixing and opens the potential for products
possibility to tailor the aspired material performance by mixing and opens the potential for products made from
recycled
made TPU.
from recycled TPU.

5. Summary
5. Summary and
and Conclusions
Conclusions
This study
This study hashasrevealed
revealednew newinsights
insightsinto
intomolar
molarmass mass dependent
dependent TPUTPU raw raw material
material behavior,
behavior, as
as well as nonwoven attributes on an application relevant level. When
well as nonwoven attributes on an application relevant level. When reprocessed and therefore reprocessed and therefore
recycled, the
recycled, therawrawmaterial
material reveals
revealsan exponential
an exponential decrease in molar
decrease mass with
in molar mass thewith
number
the of recycling
number of
runs, but limited by an asymptote. It is not dropping under roughly
recycling runs, but limited by an asymptote. It is not dropping under roughly 40 kg/mol when 40 kg/mol when reaching an
equilibrium
reaching state. A rather
an equilibrium surprising
state. A rather behavior
surprising can be observed
behavior can beunder tensile
observed stress.
under While
tensile the
stress.
stress at break is lower for smaller chain length and, therefore, follows Flory’s
While the stress at break is lower for smaller chain length and, therefore, follows Flory’s suggestion suggestion for molar
mass
for dependence,
molar the elongation
mass dependence, at break meanwhile
the elongation increases. increases.
at break meanwhile The most The commonly used materials
most commonly used
become brittle as a result of recycling, this TPU gets weaker for deformations
materials become brittle as a result of recycling, this TPU gets weaker for deformations larger larger than 100%thanand
stays identical
100% and stayswithin the errors
identical withinfor thelower
errorsdeformation. DSC measurements
for lower deformation. indicate thatindicate
DSC measurements crystallinity
that
of virgin and eight times recycled material (R8) is comparable. Whereas
crystallinity of virgin and eight times recycled material (R8) is comparable. Whereas for two times for two times recycled
material, crystallization
recycled enthalpy decreases
material, crystallization enthalpyby about 60%
decreases byapproaching
about 60% aapproaching
minimum. This twice recycled
a minimum. This
material is highly amorphous in comparison due to hard segment (crystallinity
twice recycled material is highly amorphous in comparison due to hard segment (crystallinity creator) degradation.
AFM images
creator) reveal different
degradation. AFM imagescrystallization patternscrystallization
reveal different for the variouspatterns
recycledfor materials. Thisrecycled
the various leads to
the hypothesis that there are two separate degradation regimes for soft and hard
materials. This leads to the hypothesis that there are two separate degradation regimes for soft and segments of which the
TPU ◦
hard consists.
segmentsHard segments
of which the TPUstartconsists.
to degrade at around
Hard segments 200start
C, which is inside
to degrade the processing
at around window
200 °C, which is
of the material. Therefore, the HS degrades prior to the SS, whose thermal
inside the processing window of the material. Therefore, the HS degrades prior to the SS, whose degradation does not start
◦ C. Hence, after the degradation of the hard segments, it is assumed that the soft segments
until 300degradation
thermal does not start until 300 °C. Hence, after the degradation of the hard segments,
are responsible for resistance
it is assumed that the soft segments to melt flow and are, therefore,
are responsible degraded
for resistance to from run two
melt flow andonwards.
are, therefore,
degraded from run two onwards.
Nonwoven fabrics using melt blowing were produced from the various recycled grades at
constant extrusion conditions. Even though processing temperatures and shear rates have been one
Polymers 2020, 12, 1917 11 of 13

Nonwoven fabrics using melt blowing were produced from the various recycled grades at constant
extrusion conditions. Even though processing temperatures and shear rates have been one order
of magnitude higher during melt blowing compared to the preceding extruder recycling, the molar
Polymers 2020, 12, x FOR PEER REVIEW 11 of 13
mass still does not drop under the asymptote of 40 kg/mol discovered through multiple extrusion.
This obvious
order of magnitude higher during melt blowing compared to the preceding extruder recycling, the leads
independence of the asymptotic molar mass from temperature and shear conditions
to the suggestion
molar mass that still this
doesvalue describes
not drop under thea material
asymptote specific parameter.
of 40 kg/mol The melt
discovered blowing
through multipleprocess is
roughlyextrusion.
equivalent This toobvious
3 recycling steps which
independence extends
of the the study
asymptotic molar to effectively
mass 11 recycling
from temperature and steps
shear in total.
As wellconditions
as observed leadsontorawthe suggestion that this
material level, thevalue describesperformance
mechanical a material specific
of theparameter.
nonwoven Theismelt
dependent
on the molar mass. Looking at the maximum elongation at break during tensile testing,11it can be
blowing process is roughly equivalent to 3 recycling steps which extends the study to effectively
recycling steps in total. As well as observed on raw material level, the mechanical performance of the
seen that it increases towards the fabric produced from material recycled twice and drops afterwards.
nonwoven is dependent on the molar mass. Looking at the maximum elongation at break during
This observation further
tensile testing, it cansupports theit hypothesis
be seen that of two
increases towards theseparate degradation
fabric produced regimes
from material for soft and
recycled
hard segments.
twice and Producing
drops afterwards.nonwovens from 50/50
This observation mixtures
further outthe
supports of hypothesis
virgin andofeight times recycled
two separate
degradation
(close to regimes molar
the asymptotic for soft mass)
and hard segments.
material Producing
results nonwovens from
in nonwovens 50/50 mixtures
roughly featuring outproperties
of
virgin and eight times recycled (close to the asymptotic molar mass) material
following a linear mixing rule with respect to molar mass dependence of properties. In the present results in nonwovens
roughly featuring properties following a linear mixing rule with respect to molar mass dependence
case, this equals a molar mass and the respective mechanical performance close to the fabric produced
of properties. In the present case, this equals a molar mass and the respective mechanical performance
from once recycled material. This is remarkable and holds the possibility to tailor the aspired material
close to the fabric produced from once recycled material. This is remarkable and holds the possibility
performance
to tailorby mixing
the aspiredand opens
material up potential
performance for tailoring
by mixing products
and opens madeforfrom
up potential recycled
tailoring materials.
products
made from recycled materials.
Author Contributions: Conceptualization, B.W.; Data curation, B.W. and V.A.; Formal analysis, B.W.; Investigation,
B.W. andAuthor
V.A.; Methodology,
Contributions: B.W.; Project administration,
Conceptualization, B.W.; Data B.W.; Resources,
curation, B.W. andD.W.S.,
V.A.; A.S. andanalysis,
Formal C.H.; Software,
B.W.; B.W.;
Supervision, B.W., A.S.,
Investigation, B.W.J.K.
and and
V.A.;D.W.S.; Validation,
Methodology, B.W.,administration,
B.W.; Project A.S., J.K. andB.W.;
D.W.S.; Visualization,
Resources, B.W.,
D.W.S., A.S. V.A. and J.K.;
and C.H.;
Writing—original draft,
Software, B.W.; B.W.; Writing—review
Supervision, & editing,
B.W., A.S., J.K. and A.S., J.K. and
D.W.S.; Validation, B.W.,D.W.S. Alland
A.S., J.K. authors
D.W.S.;have read and agreed
Visualization,
to the published
B.W., V.A.version
and J.K.;of the manuscript.
Writing – original draft, B.W.; Writing – review & editing, A.S., J.K. and D.W.S. All authors
have
Funding: read
This and agreed
research to the published
received version
no external of the manuscript.
funding.
Funding: This The
Acknowledgments: research received
authors no external
want to thankfunding
the support of Baolin Zhao concerning AFM measurements and
Inge Herzer
Acknowledgments: The authors wantthe
concerning GPC, both from Institute
to thank of Polymer
the support Materials.
of Baolin Zhao concerning AFM measurements and
ConflictsInge Herzer concerning GPC, both from the Institute of Polymer Materials.
of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
Appendix A
Appendix A

Figure A1. Exemplary differential scanning calorimetry (DSC)-curve of the first cooling and second
heating run of the virgin (R0) material under 10 K/min temperature ramp. The corresponding
crystallization and melting peaks are highlighted.
Polymers 2020, 12, 1917 12 of 13

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