P O LY M E R B L E N D S

Application Study. The comparatively low heat resistance of

polyvinyl chloride greatly restricts the use of this cost-effective plastic in fields in which it is

PVC applications
such as building
claddings demand
of the material a
level of heat resistance which it
can fulfil only
in the form of
special mixtures

exposed under mechanical load

to relatively high temperatures.
This property, however, can be
raised at low cost and without

(photo: BASF)

difficulty to technically interesting levels in blends with -methylstyrene-acrylonitrile copolymers (AMSAN). A systematic study shows what the user should pay attention to when doing this.

PVC Becoming Even Hotter

AXEL GOTTSCHALK ET AL.

ue to its ease of processing and

toughness and not least on account
of its competitive price the material polyvinyl chloride (PVC) has captured a secure position in the building
sector. Over half of the Western European
PVC production, running to some 6 million metric tons, is used on building sites
in the form of extruded window and door
profiles, cable sheathing, floor coverings,
pipes and conduits. Accordingly, PVC is
one of the most important materials in
this sector.
The potential of this material in this
field has by far not yet been exhausted.
One of the challenges constraining the
wide use of PVC is the comparatively low
heat resistance of this material. Most PVC
products are recommended for operating
temperatures of 60 to 65C (peak temperatures of up to 80C). At higher temperatures the material begins to soften.
This has negative effects on the dimensional stability of the material, in particular when the part in question is under
mechanical load in use. In some circumstances this is already a problem in

Translated from Kunststoffe 7/2006, pp. 4850

Kunststoffe international 7/2006

pipework carrying hot water or in dark

coloured building panels (title picture)
directly exposed to sunlight.

Increasing Heat Resistance

It is possible to increase the softening temperature of polyvinyl chloride by postproduction chlorination of the main
polymer chain. Chlorinated PVC (CPVC)
having a chlorine content of 66 %, for example (by comparison with 57 % in the
normal material), is suitable for continuous working temperatures of 90C
(peaks of 110C). However, the higher
density (of about 1.6 compared with 1.4
g/cm3 in normal PVC), poor processability and the relatively high price are disadvantages.

Manufacturer

BASF AG
Communication Plastics
Building KS/KC-E100
D-67056 Ludwigshafen / Germany
Phone +49 (0) 6 21/60-46910
Fax +49 (0) 6 21/60-8608248
www.basf.com/kunststoffe

A solution to this problem is found in

blends composed of PVC and polymers
characterised in comparison with
polyvinyl chloride by a relatively high
glass transition temperature. Corresponding mixtures should exhibit higher
heat resistance than pure PVC. A useful
guide value for the heat resistance of a
polymeric material is obtained by measuring its Vicat B50 softening temperature.
It is determined by a practical test
method. In plastics having a low degree
of crystallinity the Vicat temperature is
correlated with the glass transition temperature which can be predicted on the
basis of a simple relationship among the
proportions of the components of a blend
(Gordon-Taylor relationship). In order to
increase the heat resistance of PVC it is
useful to mix this plastic with proportionate amounts of a polymer which is inherently characterised by a high glass
transition temperature.
-Methylstyrene-acrylonitrile copolymers (AMSAN) are polymers which are
highly compatible with PVC and have a
high glass transition temperature. Such a
copolymer (Luran KR 2556) has been employed by BASF since as early as the 1970s
for the production of heat-resistant ABS
plastics (Terluran HH 106 and Terluran

8 PE103616

 P O LY M E R B L E N D S

Fig. 1. The production

of PVC blends in a
planetary extruder
allows optimum
control of the mixing
temperature (company
photo: Entex)

HH 112; the number after the abbreviation HH specifies the Vicat B50 softening
temperature of the High Heat type in
question). Depending on the level of heat
resistance desired, AMSAN here replaces
a proportion of the usual SAN component (Vicat temperature of SAN is approx. 107C, that of AMSAN is approx.
120C).
The idea of using AMSAN or even
SAN or ASA in order to increase the heat
resistance of PVC has already been discussed in the industry for a relatively long
time. New studies conducted by the Sddeutsches Kunststoff-Zentrum (SKZ =
South German Plastics Centre) and BASF
are now helping to adapt the heat resistance of PVC to particularly demanding
applications in cost-effective manner
without the need to take the CPVC route.

Producing Mixtures Under Mild

Conditions
In order to be in a position to evaluate
the effect that the AMSAN component of
the mixture has on the mechanical properties of the polyvinyl chloride, care was
taken to produce the blends under controlled mixing temperatures. In this way
any possible decomposition of the polymer due to local overheating during the
mixing process, which could diminish the
mechanical properties of the blend, is
minimised. This is ensured in optimum
manner by the use of a planetary gear extruder (Entex LWE 50 M2; Fig. 1). The extruded strand is briefly cooled in a water
bath, dried (Rieter SE/100) and pelletised
(Rieter Primo 100). The PVC processed
was an impact-modified, calcium-zinc
stabilised PVC from Solvay whose mean
melt temperature at the tip of the spindle
was approx. 190C. From the blends obtained in this way test specimens were
produced which were subjected, inter alia,
to the following tests: measurement of the
Vicat softening temperature (ISO 306,
method B50), measurement of thermal

stability in accordance with DIN 53381-1

(test B) as well as measurement of impact
resistance at room temperature (ISO 1791) and elongation at break (ISO 527-2).
Initial trials with proportions of
AMSAN in the blend confirmed that the
Vicat temperature of the blends can be
raised by adding this copolymer. For
every 10 % by weight of AMSAN added
the Vicat temperature increased by approximately 4C (Fig. 2). As expected this
technically significant value is above
those achievable by incorporating equivalent quantities of classic SAN copolymers as well as ASA varieties having correspondingly lower glass transition temperatures.
It is common to all the blends that they
exhibit lower thermal stability than the
starting polymer.While blends composed
of PVC and Terluran HH 106 (ABS) or
112 and Luran S 778 T (ASA) are notable
for slightly, with higher additions sometimes even dramatically, improved levels
of impact resistance, the gain in Vicat
temperature and hence in heat resistance
as a result of AMSAN modification is simultaneously associated with certain
losses in impact resistance.
The impact resistance of (PVC+AMSAN) blends, however, can be raised to

the usual level by resorting to tried and

tested methods of PVC formulation development. Thus, the addition of 5 % by
weight of an acrylate-based impact resistance modifier to a (PVC+AMSAN)
blend (85:15 % by weight) is sufficient to
achieve impact resistance values which
were above those of the unmodified PVC
used for producing the AMSAN blends
(23.8 instead of 16 kJ/m2). As expected
raising the proportion of modifier further increases the impact resistance levels and in all the blends studied the elongation at break values were also at a higher level.

Adapting Thermal Stability by

Means of Stabilisers
On the other hand, the restoration of the
thermal stability of (PVC+AMSAN)
blends requires more detailed consideration of the degradation processes. The
cause of the gradual decomposition of
polyvinyl chloride at relatively high temperatures is the elimination of hydrogen
chloride, which once started proceeds in
accelerated fashion due to autocatalysis.
Initially this gives rise only to local discoloration of the plastic, but later adversely affects the mechanical properties
of the entire product.
A number of routes are available for
stabilising PVC against this degradation
process. Thus, the progress of the reaction can be slowed down by capturing the
hydrogen chloride by means of suitable
basic additives or by converting the first
intermediate of the decomposition
process reactive allyl chloride into
products which pose no threat. To this
end the PVC processor can draw on a
large number of tried and tested additives
having correspondingly varied action
mechanisms.

Heat resistance
Fig. 2. The heat resistance of PVC
blends rises linearly
with the proportions
of the added component a-methylstyrene-acrylonitrile
(AMSAN; type: Luran
KR 2556; graph: BASF)

Kunststoffe

Carl Hanser Verlag, Mnchen

Kunststoffe international 7/2006

P O LY M E R B L E N D S

Thermal stability
Fig. 3. The thermal
stability of (PVC+
AMSAN) blends can
be raised to the level
of the base polymer
PVC by adding only
0.5 % of a suitable
stabiliser (DIN 533811, test B; graph: BASF)

Kunststoffe

In order to test whether established additives are also suitable for retarding the
accelerated degradation reaction in the
presence of nitrite-containing polymers,
trials were carried out on (PVC+ABS)
blends at the Sddeutsches KunststoffZentrum. Not only were the stabilisers
which come into consideration studied,
but also the quantities in which they need
to be added. The stability of each blend
was evaluated in a stream of nitrogen
heated to 200C (DIN 53381-1, test B).
Even small quantities of a suitable stabiliser are capable of effectively retarding
the thermal degradation of (PVC+ABS)
blends. These results are naturally trans-

Kunststoffe international 7/2006

ferable to (PVC+AMSAN) blends. In a direct trial the addition of 0.5 % by weight

of this stabiliser was sufficient to raise the
thermal stability of a mixture of polyvinyl
chloride and an -methylstyrene-acrylonitrile copolymer (90:10 % by weight;
total nitrile content: about 3 %) to the level of the pure PVC (Fig. 3).

Conclusion
This study demonstrates that -methylstyrene-acrylonitrile copolymers such as
Luran KR 2556 from the PlasticsPlus
range of BASFs Styrenic Plastics Division
are suitable for effectively increasing the

heat resistance of polyvinyl chloride. The

possible rates of increase are about 4C
per 10 % by weight of added AMSAN.
Given a corresponding level of addition,
(PVC+AMSAN) blends exhibit levels of
impact resistance and thermal stability
equivalent to those of pure polyvinyl
chloride.
This should have great potential in applications which hitherto could not be
fulfilled at all or could be fulfilled only inadequately because of the low heat resistance of PVC and on grounds of cost.
Specifically in the building sector great
prospects are now opening up for the
blend. In this field there will no doubt be
news in future about some remarkable solutions.
THE AUTHORS
DR. AXEL GOTTSCHALK is Business Manager in
the ABS Specialties/AMSAN Division at BASF AG,
Ludwigshafen/Germany; axel.gottschalk@basf.com
DR. MICHAEL BREULMANN is Market Development Manager for Specialty Copolymers in the same
company.
ERIK FETTER is a student of plastics technology at
the Fachhochschule Aalen/Germany.
DR.-ING. KARSTEN KRETSCHMER is head of the
Compounding Division at SKZ-KFE gGmbH, Wrzburg/
Germany.
DR.-ING. MARTIN BASTIAN has been head of the
institute and managing director of SKZ-KFE gGmbH
since January 2006.