Thermoplastic Rubber

Thermoplastic Rubber
Nonvulcanised or thermoplastic rubber (TR) soles are made of styrene-butadi-
ene-styrene (SBS) block copolymer in which the butadiene domains impart flexibility
and the styrene domains provide the mechanical properties.

From: Adhesive Bonding (Second Edition), 2021

Related terms:

Cross-Link (Molecular Structure), Polyamide, Elastomer, Butanol, Resin, Acrylate,

Polyurethan

View all Topics

Characteristics of Adhesive Materials

Sina Ebnesajjad PhD, Arthur H. Landrock, in Adhesives Technology Handbook (Third
Edition), 2015

5.51 Thermoplastic Rubber (For Use in Adhesives)

Thermoplastic rubber is a relatively new class of polymer. It has the solubility and
thermoplasticity of polystyrene, while at ambient temperatures it has the toughness
and resilience of vulcanized natural rubber or polybutadiene. These rubbers are
actually block copolymers. The simplest form consists of a rubbery mid-block with
two plastic end blocks (A-B-A), as shown in Figure 5.8. Examples of commercial
products are Kraton® and Solprene® [114,115]. These materials are often com-
pounded with plasticizers to decrease hardness and modulus, eliminate drawing,
enhance pressure-sensitive tack, improve low-temperature flexibility, reduce melt
and solution viscosity, decrease cohesive strength or increase plasticity if desired,
and substantially lower material costs. Low levels of thermoplastic rubbers are some-
times added to other rubber adhesives. These materials are used as components in
the following applications: PSAs, hot-melt adhesives, heat-activated assembly adhe-
sives, contact adhesives, reactive contact adhesives, building construction adhesives,
sealants, and binders. Two common varieties of thermoplastic rubber adhesives are
styrene-butadiene-styrene (S-B-S) and styrene-isoprene-styrene (S-I-S) [25].
Figure 5.8. Simplified
Figure
representation
5.8. Simplified
of arepresentation
thermoplastic of
rubber
a thermoplastic
molecule. rubber molecule.

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BondingBonding
in the shoe
in the
industry
shoe industry
José Miguel Martín-Martínez,
José Miguel in
Martín-Martínez,
Adhesive Bonding
in Adhesive
(Second Bonding
Edition), 2021
(Second Edition), 2021

21.4.2.1 Surface
21.4.2.1
preparation
Surfaceofpreparation
nonvulcanised
of nonvulcanised
rubber soles rubber soles
Nonvulcanised or thermoplastic
Nonvulcanisedrubber
or thermoplastic
(TR) soles arerubber
made(TR)
of styrene-butadi-
soles are made of styrene-butadi-
ene-styrene (SBS) block
ene-styrene
copolymer(SBS)inblock
whichcopolymer
the butadiene
in which
domains
the butadiene
impart flexibility
domains impart flexibility
and the styrene domains
and theprovide
styrenethe
domains
mechanical
provide properties.
the mechanical
The styrene
properties.
domains The styrene domains
impart virtual cross-linking
impart virtual
and thermoplastic
cross-linking and behaviour,
thermoplastic
and thebehaviour,
vulcanisation
and the vulcanisation
is not necessary toisprovide
not necessary
dimensional
to provide
stability.
dimensional
TR soles generally
stability. TR
contain
solesSBS
generally contain SBS
copolymer, polystyrene,
copolymer,
plasticisers,
polystyrene,
processing
plasticisers,
oils, fillers
processing
(calciumoils,
carbonate,
fillers (calcium
car- carbonate, car-
bon black), and antioxidants.
bon black),TRandsoles
antioxidants.
have a lowTR surface
soles have
energy,
a low
andsurface
for good
energy, and for good
bonding with polyurethane
bonding adhesives,
with polyurethane
a surfaceadhesives,
treatmentaissurface
mandatory.
treatment
Due is
tomandatory.
their Due to their
softness, TR soles cannot
softness,
be TR
roughened,
soles cannot
andbe they
roughened,
swell by the
and
application
they swellofbythe
themost
application of the most
organic solvents, and
organic
the chemical
solvents,treatments
and the chemical
are the treatments
most commonly
are theused,
mostmainly
commonly used, mainly
halogenation with halogenation
different chemicals
with different
and, lesschemicals
commonly,and,
cyclisation
less commonly,
(treatment
cyclisation (treatment
with sulphuric acid).
with sulphuric acid).

The cyclisation surface

The cyclisation
treatment of surface
TR soletreatment
has beenofproposed
TR sole hasat laboratory
been proposedscale at laboratory scale
and is carried out by
andimmersion
is carried out
in concentrated
by immersion (95 wt%)
in concentrated
sulphuric(95 wt%)
acid for less
sulphuric acid for less
than 1 min, followed
thanby1 min,
neutralisation
followedwithby neutralisation
ammonium hydroxide
with ammonium
and extensive
hydroxide and extensive
water washing, andwater
the drying
washing,of the
andtreated
the drying
TR sole
of the
is necessary.
treated TRThesolecyclisation
is necessary. The cyclisation
treatment creates atreatment
brittle layer
creates
on TRasole
brittle
surface
layer which
on TR sole
uponsurface
flexingwhich
and stretching
upon flexing and stretching
develops microcracks
develops
in which
microcracks
the mechanical
in whichinterlocking
the mechanical
of theinterlocking
polyurethaneof the polyurethane
adhesive is favoured
adhesive
[76]. Furthermore,
is favoured [76].
the treatment
Furthermore,withthe
sulphuric
treatmentacidwith
produces
sulphuric acid produces
sulphonation and oxidation
sulphonation
of some
and CC
oxidation
bonds of some
the butadiene
CC bonds units
of the
of butadiene
SBS. On the units of SBS. On the
other hand, the styrene
othercontent
hand, the in styrene
TR sole content
determines
in TRthesole
extent
determines
but not the nature
extent but not the nature
of the surface modifications
of the surface
causedmodifications
by treatment caused
with sulphuric
by treatmentacid;with
thesulphuric
lower theacid; the lower the
styrene content, the
styrene
more content,
noticeable thethe
more
modifications
noticeable ontheTRmodifications
surface. on TR surface.
Chlorination is the most common industrial surface treatment for TR sole be-
cause it is effective for several formulations, is cheap, and is easy to apply, and
the treated TR sole surfaces remain reactive with many polyurethane adhesives
for at least 3 months after surface preparation. Several chlorination surface treat-
ments for TR soles have been proposed, but the most commonly used chlorinat-
ing agent is an organic solvent (ketone or ester) solution of trichloroisocyanuric
acid (TCI)—1,3,5-trichloro-1,3,5-triazine-2,4,6-trione (Fig. 21.3), a common prod-
uct used as disinfectant in swimming pools. The organic solvent in TCI solutions
determines the degree of TR sole surface wetting, and the actual chlorinating species
are produced by the reaction of the TCI with the organic solvent. TCI solutions
should be applied with a soft brush on TR sole surface and left to dry to avoid
degradation of TR sole by the solvent [77]. For avoiding the deleterious effect of the
organic solvent in TR soles with low styrene content, acidified sodium hypochlorite
aqueous solutions containing small amounts of 1-octyl-2-pyrrolidone wetting agent
have been proposed [78]. The chlorination treatment is restricted to about 1 μm
surface depth of TR sole, and the enhanced adhesion is due to improved wettability
and the creation of chlorine moieties on the surface. Aqueous solutions of sodium
dichloroisocyanurate (DCI) (Fig. 21.3) have also been used to increase the adhesion
of TR soles [79]. The chemical structure of DCI is somewhat similar to that of
TCI, and relatively concentrated DCI water solutions are necessary to obtain good
bonding. On the other hand, successful surface chlorination treatment of TR sole
with aqueous N-chloro-p-toluenesulphonamide solutions (obtained by acidifying
chloramine T solutions) at 20–80°C for about 1 min has been proposed at laboratory
scale [78], and the actual chlorinating species is SO2-C6H4-NCl-Cl.
 Chlorination is the most common industrial surface treatment for TR sole be-
cause it is effective for several formulations, is cheap, and is easy to apply, and
the treated TR sole surfaces remain reactive with many polyurethane adhesives
for at least 3 months after surface preparation. Several chlorination surface treat-
ments for TR soles have been proposed, but the most commonly used chlorinat-
ing agent is an organic solvent (ketone or ester) solution of trichloroisocyanuric
acid (TCI)—1,3,5-trichloro-1,3,5-triazine-2,4,6-trione (Fig. 21.3), a common prod-
uct used as disinfectant in swimming pools. The organic solvent in TCI solutions
determines the degree of TR sole surface wetting, and the actual chlorinating species
are produced by the reaction of the TCI with the organic solvent. TCI solutions
should be applied with a soft brush on TR sole surface and left to dry to avoid
degradation of TR sole by the solvent [77]. For avoiding the deleterious effect of the
organic solvent in TR soles with low styrene content, acidified sodium hypochlorite
aqueous solutions containing small amounts of 1-octyl-2-pyrrolidone wetting agent
have been proposed [78]. The chlorination treatment is restricted to about 1 μm
surface depth of TR sole, and the enhanced adhesion is due to improved wettability
and the creation of chlorine moieties on the surface. Aqueous solutions of sodium
dichloroisocyanurate (DCI) (Fig. 21.3) have also been used to increase the adhesion
of TR soles [79]. The chemical structure of DCI is somewhat similar to that of
TCI, and relatively concentrated DCI water solutions are necessary to obtain good
bonding. On the other hand, successful surface chlorination treatment of TR sole
with aqueous N-chloro-p-toluenesulphonamide solutions (obtained by acidifying
chloramine T solutions) at 20–80°C for about 1 min has been proposed at laboratory
scale [78], and the actual chlorinating species is SO2-C6H4-NCl-Cl.

Fig. 21.3. ChemicalFig.

structures
21.3. Chemical
of DCI (sodium
structures
dichloroisocyanurate)
of DCI (sodium dichloroisocyanurate)
and TCI and TCI
(trichloroisocyanuric
(trichloroisocyanuric
acid). acid).

Several alternate chlorination

Several alternate
surfacechlorination
treatmentssurface
for TR soles
treatments
have been
for TR
proposed
soles have been proposed
at laboratory scale.atElectrochemical
laboratory scale. treatment
Electrochemical
consiststreatment
of the immersion
consists of
of TR
the immersion of TR
sole in an electrochemical
sole in an cellelectrochemical
of silver nitratecell
in 3.25 M
of silvernitric
nitrate
acid
in followed
3.25 M nitric
by acid followed by
treatment with nitric
treatment
acid andwithwater
nitric
washing
acid and
untilwater
neutral
washing
pH has until
beenneutral
proposed
pH has been proposed
but its effectivenessbutin its
improving
effectiveness
the adhesive
in improving
strength
the is
adhesive
limitedstrength
[80]. Different
is limited [80]. Different
environmentally friendly
environmentally
surface preparations
friendly surface
with radiations
preparations of TR
withsoles
radiations
have also
of TR soles have also
been proposed. Thesebeentreatments
proposed.are These
clean
treatments
(no chemicals
are clean
or reactions
(no chemicals
by-products
or reactions by-products
are generated) andarefast,generated)
and furthermore,
and fast,online
and furthermore,
bonding canonline
be produced,
bondingso canthese
be produced, so these
surface preparationsurface
methods preparation
are promising
methodsin shoe
are promising
industry. Corona
in shoedischarge,
industry. Corona discharge,
low-pressure radio-frequency (RF) gas plasma, and ultraviolet (UV) coupled to ozone
(UV-ozone) treatments have been successfully used at laboratory scale to improve
the adhesion of several TR soles.
 low-pressure radio-frequency (RF) gas plasma, and ultraviolet (UV) coupled to ozone
(UV-ozone) treatments have been successfully used at laboratory scale to improve
the adhesion of several TR soles.

The treatment withThecorona

treatment
discharge
withimproved
corona discharge
the wettability
improved
of TR
thesole
wettability
due to the
of TR sole due to the
formation of polarformation
moieties on of the
polarsurface;
moieties
surface
on the
cleaning
surface;and
surface
removal
cleaning
of con-
and removal of con-
taminants (mainly taminants
demoulding (mainly
silicone
demoulding
moieties) were
silicone
produced
moieties)
too,were
but produced
the peel too, but the peel
strength values of strength
joints madevalues
withofpolyurethane
joints made with
adhesive
polyurethane
moderately adhesive
increased
moderately increased
[81]. [81].

Low-pressure RF gas
Low-pressure
plasma surfaceRF gas
treatment
plasma enhanced
surface treatment
the adhesion
enhanced
of TRthesoles
adhesion of TR soles
to different polyurethane
to different
adhesives
polyurethane
[82]. Different
adhesives
gases
[82].
(oxygen,
Different
nitrogen,
gases (oxygen,
and nitrogen, and
oxygen-nitrogen mixtures)
oxygen-nitrogen
can be used
mixtures)
to generate
can beRFused
plasma
to generate
and theRFtreatment
plasma and the treatment
partially removed hydrocarbon
partially removed
moieties
hydrocarbon
from TR sole
moieties
surface;fromtheTRformation
sole surface;
of the formation of
oxygen moieties and
oxygen
surface
moieties
roughness
and surface
was alsoroughness
produced.was Onalso
the other
produced.
hand,On thethe other hand, the
treatment of TR with
treatment
low-pressure
of TR with
RF plasma
low-pressure
in CCl4 RF
for plasma
a few seconds
in CCl4 has
for aalso
few seconds has also
been proposed for been
improving
proposedadhesion
for improving
to polyurethane
adhesionadhesive,
to polyurethane
a drastic adhesive,
increase a drastic increase
in peel strength was
in observed,
peel strength
and was
the improved
observed, adhesive
and the improved
strength was
adhesive
ascribed
strength
to was ascribed to
the chemical bonding
the chemical
between the bonding
carbon-oxygen
between the
moieties
carbon-oxygen
species onmoieties
the surfacespecies on the surface
and the isocyanateand
groups
the isocyanate
of the adhesive
groups[83].
of the adhesive [83].

The surface treatment

The with
surface
UV-ozone
treatmentusing
withlow-pressure
UV-ozone usingmercury
low-pressure
vapour lamp
mercury vapour lamp
enriched in 175 nmenriched
wavelength
in 175 nm
has been
wavelength
shown tohas
be successful
been shown to to
increase
be successful
TR soleto increase TR sole
adhesion to polyurethane
adhesion adhesive
to polyurethane
[84]. UV-ozone
adhesive
treatment
[84]. UV-ozone
improved treatment
wettability
improved wettability
and created roughness
and created
and oxygen
roughness
and nitrogen
and oxygen
moieties
and nitrogen
on TR solemoieties
surface,on TR sole surface,
to a greater extent to
byaincreasing
greater extent
the treatment
by increasing
time.the
Thetreatment
nature andtime.
content
The nature
of and content of
fillers in TR sole determine
fillers in TR
thesole
extent
determine
of surface
themodification
extent of surface
and adhesion
modification
whenand adhesion when
treated with UV-ozone.
treatedSeveral
with UV-ozone.
TR soles containing
Several TRdifferent
soles containing
amounts different
of calcium amounts of calcium
carbonate and/or silica
carbonate
fillers and/or
were surface-treated
silica fillers were
with
surface-treated
UV-ozone, and with
improved
UV-ozone, and improved
wettability, and chemical
wettability,
(oxidation)
and chemical
and morphological
(oxidation) and
modifications
morphological
(roughness,
modifications (roughness,
ablation, and surface
ablation,
melting)
andwere
surface
foundmelting)
[85]. Aswere
a consequence
found [85]. of
As these
a consequence
surface of these surface
modifications, UV-ozone
modifications,
treatment UV-ozone
increased treatment
the adhesive
increased
strength
the in
adhesive
all joints
strength in all joints
made with polyurethane
made with
adhesive,
polyurethane
more noticeably
adhesive,inmore
the joints
noticeably
made inwith
theTRjoints
sole made with TR sole
containing silica filler
containing
than in the
silicaone
filler
containing
than in thecalcium
one containing
carbonate calcium
filler. carbonate filler.

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TribologyTribology
of Polymeric
of Polymeric
Nanocompos-
Nanocompos-
ites ites
József Karger-Kocsis,
József
Dávid
Karger-Kocsis,
Felhás, in Tribology
Dávid Felhás,
and Interface
in Tribology
Engineering
and Interface
Series,Engineering Series,
2008 2008
13.2.3.1 Thermoplastics
 13.2.3.1 Thermoplastics
Rubber/thermoplasticRubber/thermoplastic
hybrids can be produced hybridsbycan melt
be mixing
produced of rubbers
by melt mixing
with of rubbers with
thermoplastics priorthermoplastics
to curing theprior
former.to curing
A furthertheoption
former.is Atofurther
combine option
withis to combine with
the curable rubberthemonomers
curable rubber
and oligomers,
monomers which
andcanoligomers,
be polymerized
which can under
be polymerized under
the same conditions thewhere
samethe conditions
rubber vulcanization
where the rubber is performed.
vulcanizationExactly,
is performed.
this Exactly, this
concept is followedconcept
when using
is followed
cyclic butylene
when using terephthalate
cyclic butylene(CBT)terephthalate
oligomers, as(CBT) oligomers, as
disclosed in a recent
disclosed
patent [52].
in a recent
CBT oligomers
patent [52].melt
CBTat ca.
oligomers
140°C above
melt at which
ca. 140°C above which
they polymerize intothey
poly(butylene
polymerize intoterephthalate)
poly(butylene(PBT)terephthalate)
([53]–[54] and(PBT)references
([53]–[54] and references
therein). The beautytherein).
of this material
The beauty is that
of this
it polymerizes
material is thatand italso
polymerizes
crystallizesand below
also crystallizes below
the melting temperature
the melting
of thetemperature
resulting PBT of (melting
the resulting
temperature
PBT (melting 225°C).
temperature
For 225°C). For
that purpose, isothermal
that purpose,
treatment isothermal
betweentreatment
170 and 190°Cbetween is usually
170 and preferred.
190°C is usually preferred.
Recall that this temperature
Recall thatagrees
this temperature
fairly with that
agrees
of the
fairly
rubber
with vulcanization.
that of the rubber In vulcanization. In
addition, the polymerization
addition, thetime polymerization
of CBT can also timebeofadjusted
CBT cantoalsothatbeof adjusted
the rubber to that of the rubber
curing by selectingcuring
suitable
by catalysts.
selectingTo suitable
check catalysts.
the potentialTo check
of thisthe
hybridization,
potential of this hybridization,
HNBR mixes with HNBRCBT® 160 mixes
(Cyclics,
with CBT
Schwarzheide,
® 160 (Cyclics,
Germany)
Schwarzheide,
were produced
Germany) by were produced by
mixing on a two-rollmixing
mill. on
In aa subsequent
two-roll mill. step
In athe
subsequent
mixes were step
hotthe
pressed
mixesatwere hot pressed at
T=190°C for 25 min. T=190°C
This wasforenough
25 min.toThis polymerize
was enoughthe CBTto polymerize
and cure thethe HNBR,
CBT and cure the HNBR,
respectively. Differential
respectively.
scanning Differential
calorimetricscanning
(DSC) calorimetric
traces confirmed (DSC)thattraces
theconfirmed
CBT that the CBT
was polymerized towas PBTpolymerized
but not welltocrystallized.
PBT but notHampered
well crystallized.
crystallization
Hampered is a crystallization is a
peculiar feature of peculiar
the polymerized
feature ofCBT the[55].
polymerized
The COFCBT and [55].
specific
Thewear
COFdata and ofspecific
the wear data of the
HNBR/PBT hybridHNBR/PBT
and the reference
hybrid HNBR
and thearereference
displayed HNBRin Fig.
are13.9.
displayed in Fig. 13.9.

Fig. 13.9. COFs (a) Fig.

and 13.9.
specific
COFs
wear(a)rates
and (b)
specific
of thewear
HNBRrates
and(b)HNBR
of the HNBR
+ 100 phr
andCBT
HNBR + 100 phr CBT
(=45 wt%) as assessed
(=45inwt%)
different
as assessed
tribotests.
in different
Note: The
tribotests.
testing conditions
Note: The testing
agree with
conditions agree with
those indicated in those
Fig. 13.1.
indicated in Fig. 13.1.

Note that the COFNote

is practically
that the not
COFinfluenced
is practically
by the
not PBT,
influenced
except by thethe
fretting,
PBT, except the fretting,
where some increasewhere
wassome
found. increase
Combination
was found.
with Combination
PBT reduced the withspecific
PBT reduced
wear the specific wear
rate under both POPrateand
under
ROPbothbut POP
slightly
andincreased
ROP but forslightly
fretting.
increased
It has to
forbefretting. It has to be
added that this modification
added thatdoubled
this modification
the tensiledoubled
strengththeand
tensile
even strength
the ultimate
and even the ultimate
tensile strain, whereas,
tensilein strain,
the tearwhereas,
strengthinantheeightfold
tear strength
increase
an eightfold
was achieved.increase was achieved.
The related hybrid The
should
related
possess
hybrid
an should
interpenetrating
possess annetwork
interpenetrating
(IPN, morenetwork
correctly
(IPN, more correctly
a semi-IPN) structure,
a semi-IPN)
i.e. bothstructure,
vulcanizedi.e.
rubber
both vulcanized
and thermoplastic
rubber andPBTthermoplastic
phases PBT phases
are continuous. This
arewas
continuous.
supportedThis apartwas
from
supported
the failure
apart
mode
fromofthetensile
failure
loaded
mode of tensile loaded
specimens (showing “trellis” effect) and also by the appearance of the worn surface
(cf. Fig. 13.10).
 specimens (showing “trellis” effect) and also by the appearance of the worn surface
(cf. Fig. 13.10).

Fig. 13.10. SEM picture

Fig. 13.10.
taken SEM
from picture
the worntaken
surface
from ofthe
theworn
HNBR surface
containing
of the 100
HNBRphrcontaining 100 phr
(=45 wt%) polymerized
(=45 CBT
wt%)after
polymerized
the POP CBT
test. after
Note:theSliding
POP test.
direction
Note:isSliding
downward.
direction is downward.

Apart from the ring-opening

Apart frompolymerization,
the ring-opening other
polymerization,
polymerizationother
techniques
polymerization techniques
can also be adopted cantoalso
produce
be adopted
rubber/thermoplastic
to produce rubber/thermoplastic
hybrids. For example,hybrids.
the For example, the
crosslinked rubbercrosslinked
can be swollenrubberin suitable
can be swollen
liquid monomers
in suitable and
liquid
polymerized
monomers and polymerized
into the corresponding
into the
thermoplastic
corresponding further
thermoplastic
on. The structure
furtherof on.
the
The
resulting
structure of the resulting
hybrid is a semi-IPN.hybrid
The is
most
a semi-IPN.
promising The
candidates
most promising
for hybridization
candidatesare,forhowever,
hybridization are, however,
polyurethanes (PUs). polyurethanes
This note is based
(PUs).onThis
thenote
factisthat
based
PUson
exhibit
the fact
outstanding
that PUs exhibit
wear outstanding wear
resistance (e.g. [56]).
resistance
Moreover, (e.g.
their
[56]).
polyaddition
Moreover, reactions
their polyaddition
are less affected
reactions
by are
those
less affected by those
of rubber curing. Theof rubber
potential
curing.
of rubber/PU
The potential
hybridization
of rubber/PU
will be
hybridization
shown in the will
next
be shown in the next
section (13.2.3.2.) in
section
the example
(13.2.3.2.)of reactive
in the example
(crosslinkable)
of reactive
PU versions.
(crosslinkable) PU versions.

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Sliding friction
Slidingand
friction
wearand
of “nanomod-
wear of “nanomod-
ified” andified”
coated
andrubbers
coated rubbers
József Karger-Kocsis,
József
Dávid
Karger-Kocsis,
Felhős, in Tribology
Dávid Felhős,
of Polymeric
in Tribology
Nanocomposites
of Polymeric(Sec-
Nanocomposites (Sec-
ond Edition), 2013ond Edition), 2013

13.2.3.1 Thermoplastics
13.2.3.1 Thermoplastics
Rubber/thermoplastic
Rubber/thermoplastic
hybrids can be produced
hybridsbycan
melt
be mixing
produced of rubbers
by melt mixing
with of rubbers with
thermoplastics prior
thermoplastics
to curing theprior
former.
to curing
A further
theoption
former.is Atofurther
combine option
withis to combine with
the curable rubberthe
monomers
curable rubber
and oligomers
monomers thatand
canoligomers
be polymerized
that can
under
be polymerized
the under the
same conditions in which the rubber vulcanization is performed. Exactly, this con-
cept is followed when using cyclic butylene terephthalate (CBT) oligomers. CBT
oligomers melt at about 140 °C above which they polymerize into poly(butylene
terephthalate) (PBT) ([56–59] and references therein). The beauty of this material
is that it polymerizes and also crystallizes below the melting of the resulting PBT
(melting temperature ≈ 225 °C). For that purpose isothermal treatment between 170
and 190 °C is usually preferred [57]. Recall that this temperature agrees fairly with
that of rubber vulcanization. In addition, the polymerization time of CBT can also
be adjusted to that of rubber curing by selecting suitable catalysts. To check the
potential of this hybridization, HNBR mixes with CBT® 160 (Cyclics, Schwarzheide,
Germany) were produced by mixing on a two-roll mill. In a subsequent step the
mixes were hot pressed at T = 190 °C for 25 min. This was enough to polymerize
the CBT and cure the HNBR, respectively. Differential scanning calorimetric traces
confirmed that the CBT was polymerized to PBT but not well crystallized. Hampered
crystallization is a peculiar feature of the polymerized CBT [58]. The COF and specific
wear data of the HNBR/PBT hybrid and the reference HNBR are displayed in Fig.
13.9.
same conditions in which the rubber vulcanization is performed. Exactly, this con-
cept is followed when using cyclic butylene terephthalate (CBT) oligomers. CBT
oligomers melt at about 140 °C above which they polymerize into poly(butylene
terephthalate) (PBT) ([56–59] and references therein). The beauty of this material
is that it polymerizes and also crystallizes below the melting of the resulting PBT
(melting temperature ≈ 225 °C). For that purpose isothermal treatment between 170
and 190 °C is usually preferred [57]. Recall that this temperature agrees fairly with
that of rubber vulcanization. In addition, the polymerization time of CBT can also
be adjusted to that of rubber curing by selecting suitable catalysts. To check the
potential of this hybridization, HNBR mixes with CBT® 160 (Cyclics, Schwarzheide,
Germany) were produced by mixing on a two-roll mill. In a subsequent step the
mixes were hot pressed at T = 190 °C for 25 min. This was enough to polymerize
the CBT and cure the HNBR, respectively. Differential scanning calorimetric traces
confirmed that the CBT was polymerized to PBT but not well crystallized. Hampered
crystallization is a peculiar feature of the polymerized CBT [58]. The COF and specific
wear data of the HNBR/PBT hybrid and the reference HNBR are displayed in Fig.
13.9.
FIGURE 13.9. COFs (a) and specific wear rates (b) of the HNBR and HNBR + 100 phr
CBT (=45 wt%) as assessed in different tribotests. The testing conditions agree with
those indicated in Fig. 13.1.
 FIGURE 13.9. COFs (a) and specific wear rates (b) of the HNBR and HNBR + 100 phr
CBT (=45 wt%) as assessed in different tribotests. The testing conditions agree with
those indicated in Fig. 13.1.

Note that the COF Note

is practically
that thenotCOF influenced
is practically
by the
notPBT,
influenced
except by
thethe
fretting,
PBT, except
where the fretting, where
some increase wassomefound. increase
Combination
was found.
with Combination
PBT reduced the withspecific
PBT reduced
wear ratethe specific wear rate
under both POP and under
ROPboth
but POP
slightly
andincreased
ROP but forslightly
fretting.
increased
It has to
forbe fretting.
added It that
has to be added that
this modification doubled
this modification
the tensiledoubled
strengththe
andtensile
even strength
the ultimate
and tensile
even the strain,
ultimate tensile strain,
whereas in the tearwhereas
strengthinan theeightfold
tear strength
increase
an eightfold
was achieved increase
[60]. The
was achieved
related [60]. The related
hybrid should possess
hybrid
an interpenetrating
should possess annetwork
interpenetrating
(IPN, morenetwork
correctly (IPN,
a semi-IPN)
more correctly a semi-IPN)
structure, i.e. bothstructure,
vulcanizedi.e.rubber
both and
vulcanized
thermoplastic
rubber and PBTthermoplastic
phases are continuous
PBT phases are continuous
[61]. This was supported
[61]. This
apartwasfrom
supported
the failure
apart
mode
fromofthe thefailure
tensilemode
loaded ofspecimens
the tensile loaded specimens
(showing “trellis” effect)
(showingalso“trellis”
by the appearance
effect) also byof the appearance
worn surfaceof(cf. theFig.
worn13.10).
surface (cf. Fig. 13.10).
It has to be emphasized
It has that
to beinemphasized
an IPN the that
size of
in the
an IPNconstituent
the size of“bands”
the constituent
is in the “bands” is in the
range of some hundreds
range of of some
nanometers.
hundreds of nanometers.

FIGURE 13.10. SEMFIGURE

picture13.10.
of theSEM
wornpicture
surfaceofofthetheworn
HNBRsurface
containing
of the HNBR
100 phrcontaining 100 phr
(=45 wt%) polymerized
(=45 wt%)
CBT after
polymerized
the POPCBT
test. after
Sliding
thedirection
POP test.isSliding
downward.
direction is downward.

In a follow-up workInthe
a follow-up
effects of work
CBT amount
the effects
andofits
CBT
polymerization
amount and degree
its polymerization
on the degree on the
sliding wear performance
sliding wear
of HNBR-based
performance systems
of HNBR-based
were addressed
systems [62].
were
It was
addressed
es- [62]. It was es-
tablished that the recrystallized,
tablished that unpolymerized
the recrystallized,
CBT unpolymerized
acts as efficient CBTreinforcement
acts as efficient reinforcement
whereby reducing the
whereby
specific
reducing
wear rate,
theas
specific
well. Romhány
wear rate,et al.
as well.
[59]Romhány
emphasized et al.
that
[59] emphasized that
the solid-phase high-energy
the solid-phase
ball milling
high-energy
of CBTball
withmilling
graphitic
of CBT
nanofillers
with graphitic
(graphene,
nanofillers (graphene,
CNT, etc.) is the most
CNT, straightforward
etc.) is the mostmethod
straightforward
for the disintegration
method for the of thedisintegration
filler of the filler
agglomerates. Theagglomerates.
related CBT/nanofiller
The related
powder
CBT/nanofiller
is well suited
powder
for the
is incorporation
well suited for the incorporation
in rubber mixes. in rubber mixes.

Apart from the ring-opening

Apart frompolymerization,
the ring-opening other
polymerization,
polymerization
other
techniques
polymerization techniques
can also be adopted
cantoalso
produce
be adopted
rubber/thermoplastic
to produce rubber/thermoplastic
hybrids. For example,
hybrids.
the For example, the
cross-linked rubbercross-linked
can be swollen
rubber
in suitable
can be swollen
liquid monomers
in suitable and
liquid
polymerized
monomers and polymerized
into the corresponding
into the
thermoplastic
corresponding
further
thermoplastic
on. The structure
furtherof
on.the
The
resulting
structure of the resulting
hybrid is a semi-IPN. The most promising candidates for hybridization are, however,
polyurethanes (PUs). This note is based on the fact that PUs exhibit outstanding wear
resistance (e.g. [63]). Moreover, their polyaddition reactions are less affected by those
of rubber curing. The potential of rubber/PU hybridization will be shown in the next
Section 13.2.3.2 on the example of reactive (i.e. cross-linkable) PU versions.
 hybrid is a semi-IPN. The most promising candidates for hybridization are, however,
polyurethanes (PUs). This note is based on the fact that PUs exhibit outstanding wear
resistance (e.g. [63]). Moreover, their polyaddition reactions are less affected by those
of rubber curing. The potential of rubber/PU hybridization will be shown in the next
Section 13.2.3.2 on the example of reactive (i.e. cross-linkable) PU versions.

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Phthalonitrile-Based
Phthalonitrile-Based
Blends and
Blends and
Copolymers
Copolymers
Mehdi Derradji, ...Mehdi
WenbinDerradji,
Liu, in Phthalonitrile
... Wenbin Liu,Resins
in Phthalonitrile
and Composites,
Resins2018
and Composites, 2018

4.2.9 Phthalonitrile/Carboxyl-Terminated
4.2.9 Phthalonitrile/Carboxyl-Terminated
Butadiene Acryloni-
Butadiene Acryloni-
trile Rubber trile Rubber
Similarly to the thermoplastics,
Similarly to the rubbers
thermoplastics,
can also berubbers
used ascantoughening
also be usedagents
as toughening
for agents for
the PN resins. Thethe
objective
PN resins.
is also
The
to objective
prepare an is also
interpenetrating
to prepare annetwork
interpenetrating
with a network with a
high resistance to the
highcrack
resistance
growthtoandthepropagation.
crack growthThe andonly
propagation.
report aboutThe the
onlyuse
report about the use
of rubber as curingofcatalyzed
rubber asascuring
well ascatalyzed
tougheningas well
agent
as toughening
was reportedagentby Pan
waset reported
al. by Pan et al.
The authors studiedThetheauthors
effect ofstudied
varioustheamounts
effect ofofvarious
carboxyl-terminated
amounts of carboxyl-terminated
butadiene butadiene
acrylonitrile (CTBN)
acrylonitrile
rubber (Fig.(CTBN)
4.24) on
rubber
the curing
(Fig. 4.24)
behavior
on theandcuring
processability
behavior and processability
of a BAPh resin [61].
of The
a BAPh
investigations
resin [61]. The
alsoinvestigations
included the use alsoofincluded
the BAPh/CTBN
the use of the BAPh/CTBN
blends as advancedblends
matricesas advanced
for glass fiber-reinforced
matrices for glass composites.
fiber-reinforced
The blends
composites.
were The blends were
formulated as follows:
formulated
to a meltasoffollows:
BAPh monomers
to a melt ofwasBAPh
consecutively
monomersadded
was consecutively
2 wt.% added 2 wt.%
DDS curing agent DDS
and 10,
curing
20, 30,
agent
andand
40 wt.%
10, 20,
weight
30, andratios
40 wt.%
of CTBN.
weight
Theratios
mixtures
of CTBN. The mixtures
were then mechanically
were then
stirred
mechanically
for 30 min at stirred
200°Cforto30 min
finally afford
at 200°C
thetoBAPh/CTBN
finally afford the BAPh/CTBN
prepolymers. prepolymers.

Figure 4.24. Chemical

Figure
structure
4.24. Chemical
of the CTBN
structure
rubber.
of the
CTBN,
CTBN
carboxyl-terminated
rubber. CTBN, carboxyl-terminated
butadiene acrylonitrile.
butadiene acrylonitrile.

The ability of the active

The ability
hydroxyl
of the
groups
activeofhydroxyl
CTBN togroups
catalyzeofthe
CTBNcuretoreaction
catalyze the cure reaction
of the PN units wasofevidenced
the PN units
by DSC.
was evidenced
In fact, allby
theDSC.
blends
In fact,
showed
all the
a promi-
blends showed a promi-
nent curing exothermnentpeaking
curing exotherm
at around peaking
360°C. Moreover,
at around increasing
360°C. Moreover,
the CTBN increasing the CTBN
amount resulted inamount
increases
resulted
in the in
heat
increases
of polymerizations.
in the heat ofMeanwhile,
polymerizations.
the curing
Meanwhile, the curing
exotherms slightly exotherms
shifted to lower
slightly
temperatures.
shifted to lower
Thustemperatures.
it was provenThusthat the
it was
CTBN
proven that the CTBN
could effectively catalyze the cyano addition reaction of PN monomers and since
the hydroxyl groups were also attached to the CTBN units, the resulting copolymers
were mainly composed of interpenetrating polymers chains.
they liquefied and the seals failed. It allowed oil to condense on insulation, causing
a real fire. The sealants should have been tested before use. New sealants have been
developed using polybutene, a low molecular weight oligomer, but problems have
been experienced when it was used as a sealant for glazed roofs in buildings. The
problem is probably caused by premature oxidation and can be inhibited by using a
nitrogen blanket during manufacture at high temperatures.
 they liquefied and the seals failed. It allowed oil to condense on insulation, causing
a real fire. The sealants should have been tested before use. New sealants have been
developed using polybutene, a low molecular weight oligomer, but problems have
been experienced when it was used as a sealant for glazed roofs in buildings. The
problem is probably caused by premature oxidation and can be inhibited by using a
nitrogen blanket during manufacture at high temperatures.

New ways of usingNew bothways

conventional
of using both
and newconventional
materials andshould
newalways
materials
be tested
should byalways be tested by
exposing those materials
exposing to the
thoseconditions
materialsexpected
to the conditions
in service.expected
And those in conditions
service. And those conditions
should be the worst should
expected,
be the anworst
objective
expected,
whichan is not
objective
alwayswhich
easy to
is not
achieve
always
in easy to achieve in
practice, as the ozone
practice,
problem
as thein the
ozonesemi-conductor
problem in the factory
semi-conductor
demonstrated. factory
Butdemonstrated. But
there is a wealth ofthere
information
is a wealthavailable
of information
in the literature,
availableincreasingly
in the literature,
provided
increasingly
by provided by
sources on the Worldsources
Wideon Web.the Similar
World Wide
problems
Web.maySimilar
haveproblems
been found maybefore
have been
in found before in
another applicationanother
of the same
application
materialof and
the same
can give
material
guidance
and to
can
prospective
give guidance future
to prospective future
uses. Some generaluses.principles
Some general
can alsoprinciples
give cluescanas toalso
possible
give clues
potential
as to pitfalls,
possible potential pitfalls,
such as the high reactivity
such as ofthedouble
high reactivity
bonds inof chain
double
molecules,
bonds inespecially
chain molecules,
to oxidative
especially to oxidative
processes. Productprocesses.
failures, however,
Product arefailures,
not widely
however,
disseminated
are not widely
unless disseminated
already in unless already in
the public domain thethrough
publicrecalls,
domain court
through
casesrecalls,
or alertscourt
published
cases or
inalerts
the technical
published in the technical
press. In the absence
press.
of any
In the
suchabsence
warnings,
of anythere
suchis warnings,
no better way
there
of isresearching
no better way of researching
product integrity than
product
by carefully
integritydesigned
than by carefully
direct testing.
designed direct testing.

But even when cases Butreach

even court,
when bias
casesfrequently
reach court,
occurs
biasamong
frequently
some occurs
experts,
among
whosome experts, who
provide clients withprovide
the opinions
clients they
with would
the opinions
like to hear
they would
rather than
like tothe
hear
truth
rather than the truth
of the matter. It certainly
of the matter.
happened It certainly
with thehappened
Hytrel washers,
with the
andHytrel
lengthened
washers,theand lengthened the
case as a result andcase
the as
costs
a result
of consulting
and the costs
otherofexperts.
consulting
Investigations
other experts.should
Investigations
be should be
independent because independent
no one gains because
fromnoa poor
one gains
and misleading
from a poor report,
and misleading
least of all report, least of all
those who instructthose
such experts.
who instruct
If there
suchis experts.
a fundamental
If thereproblem,
is a fundamental
it shouldproblem,
be it should be
exposed, analysed exposed,
and publicized
analysed
so that
and yet
publicized
more problems
so that yet
of more
the same
problems
kind do
of the same kind do
not recur. not recur.

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TYPICALTYPICAL
METHODSMETHODS
OF QUALITY
OF QUALITY
CONTROLCONTROL
OF PLASTICIZERS
OF PLASTICIZERS
GEORGE WYPYCH,
GEORGE
in Handbook
WYPYCH,
of Plasticizers
in Handbook(Third
of Edition),
Plasticizers
2017
(Third Edition), 2017

3.3 AGING STUDIES

3.3 AGING STUDIES
Accelerated heat aging
Accelerated
tests ofheat
vulcanized
aging tests
and thermoplastic
of vulcanized and
rubber
thermoplastic
are conducted
rubber are conducted
according to ISO standard.
according123to
InISO
respect
standard.
to plasticized
123 In respect
samples
to plasticized
it is important
samples
to test
it is important to test
materials in separate ovens to prevent cross-contamination of samples which may
contain, in addition to plasticizer, other additives which may be transferred such as
accelerators and antioxidants.
Tensile
strength (MPa)