FuelVol. 75, No. 6, pp.

681 686, 1996

Copyright 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
ELSEVIER 0016-2361(95)00312-6 0016-2361/96 $15.00 + 0.00

Production of stable polypropylene-

modified bitumens

Carlo Giavarini, Paolo De Filippis, M. Laura Santarelli and Marco Scarsella

Dip./ngegneria Chimica, Universit~ di Roma La Sapienza,Via Eudossiana, 18-00184 Roma, /ta/y
(Received 30 July 1995; revised 17 November 1995)

The use of polypropylene polymers and copolymers as modifiers for road bitumens appears promising. The
problem of stability during storage for long periods at high temperatures can be solved by adding
phosphorus compounds, especially polyphosphoric acid, which changes the bitumen structure from sol to
gel. It is demonstrated that the stability of polymer-modified bitumens depends not only on the difference in
density and viscosity between bitumen and polymer but also on bitumen structure. Copyright 1996
Elsevier Science Ltd.
(Keywords: polymer-modified bitumen; polypropylene; stability)

For many years, modified bitumens have been developed
especially for industrial uses, by adding fillers, fibres,
rubber and polymers. Polymer-modified bitumens
(PMBs) became commercial products with the creation
of 'membranes', i.e. reinforced bitumen sheets contain-
ing thermoplastic or elastomeric products, widely used in
Europe for impermeabilization 1-3
Among the first polymeric materials to be used was a
cheap, waxy material obtained as a waste by-product
during polypropylene production: atactic polypropylene
(APP) 4 . APP is no longer produced in many countries,
due to the introduction of new, high-yield units for
propylene polymerization.
In the last 20 years, a wide spectrum of modifying
polymeric materials has been tested with bitumens used
in road construction 5-12. Possible areas of application
are: airports, busy motorways and city roads, special
surfaces such as drain asphalt and thin layers, surface
dressing for high traffic, slurry seals, bridges and tunnels,
crossroads and parking areas for trucks, and renovation
of concrete roads.
For a polymer to be effective, it must blend with the
bitumen and improve resistance at high temperatures
without making the bitumen too viscous at mixing
temperatures or too brittle at low temperatures. If used
in road asphalt, it should be capable of being processed
by conventional equipment. In any case, it must be
available and not expensive, and physically and chemi-
cally stable during storage, application and service.
Major problems are the solubility of polymer in bitumen
and the stability of the modified product.
In actual modified bitumens, thermoplastic rubbers, as
well as some thermoplastic polymers, are mainly used.
The polymer portion ranges from ,-~2 to 10 wt%, mostly
~5 wt%. Processing viscosity and cost play a major role.
Due to the low cost, waste polymeric products, such as
atactic polypropylene, can be used in amounts as high as
25 wt% in waterproofing membranes.
The thermoplastic elastomers used as bitumen modi-
fiers are block copolymers of mono- and diolefins. The
mono-olefin is usually styrene, whereas the diolefin is
butadiene or isoprene. They are synthesized in the SBS
(or SIS) form, where S represents the polystyrene and B
(I) the polybutadiene (polyisoprene).
Polymono-olefin polymers do not contain double
bonds and therefore have good thermal and ageing
resistance, but it is difficult to disperse them in the
bitumen without segregation, unless low molecular
weights and crystallinity are achieved 12-~4. Interesting
products have been described containing a new class of
heterophasic polyolefin copolymers 13'14 which show a
behaviour similar to that of SBS polymers.
Like other PMBs, polyolefin-modified bitumens have
one major drawback: the stability during storage at the
high temperatures required for road application is
usually poor. In fact, polymers have higher viscosity at
high temperature and lower density than bitumen, and
therefore tend to cream. Stability problems are less
important during membrane production, owing to rapid
quenching of the product after mixing of the bitumen
and polymer.
The purpose of this work was to prepare a stable PMB
containing propylene-based polymers (IPP, EPR, het-
erophasic, etc.); stability means that the polymer and the
bitumen should not separate or settle during long storage
periods at temperatures up to 160C. Polyolefinic
polymers have a lower cost and better resistance to
ageing than many other polymers (e.g. SBS), and can be
tailored to confer a wide range of properties on
bitumens 1334.
APPROACH TO THE PROBLEM
As the polyolefinic polymers used in this work are not
reactive materials, chemical interaction with the bitumen
could be considered absent: the bitumen-polymer blend

Fuel 1996 Volume 75 Number 6 681

Production of stable polypropvlene-modified bitumens: C. Giavarini et al.
Table 1 Density* (gcm -3) of some olefinic polymers at different temperatures
Temperature Heterophasic
(C) copolymer
25 0.86
160 0.78
170 0.78
200 - 0.75
* ASTM D-1505
t Isotactic polypropylene
:~Low-density polyethylene
High-density polyethylene
can therefore be studied as a binary system of two
immiscible phases.
The polyolefinic polymer used in this work was
previously 'tailored' in terms of molecular weight
(MW), propylene/ethylene ratio and crystallinity, for
bitumen modification 13'14. In spite of this, notable
differences exist between the densities and viscosities of
the bitumen and the polymer.
Generally, the bitumen has a density of ~1 gcm -3 at
25C and ~0.9gcm -3 at 160C; the density of the
heterophasic copolymers is lower than that of the
bitumen, both at room and at higher temperatures (see
Table 1). The viscosity of a heterophasic copolymer at
160C is in the range 500-10 000 Pa s, while the viscosity
of a bitumen ranges from 100 to 200 mPa s; therefore, at
the storage temperature (160C) the viscosity of the
polymer is much higher than that of bitumen. Such large
differences in density and viscosity probably do not assist
the formation of a stable and homogeneous mixture.
A modification to increase the density of the copoly-
mer was carried out by the addition of various inorganic
compounds (mica powder, kaolin, SiO2, M~g(OH)2)
having densities in the range of 2.0-2.8gcm-'. These
substances were added to the polymer by a twin-screw
extruder, and sometimes they were linked to the
polymeric structure (e.g. SiO2 was linked by silaniza-
tion). The average density of the modified polymers
ranged from 0.85 to 0.95gcm- 3 at 160C. The results
were not successful; therefore, modification of the
viscosity of the bitumen was considered instead.
A first attempt was made by adding petroleum heavy
ends and other organic compounds (polyphenyl wax)
generally used during the production of SBS-modified
bitumen. Such additions (2-5 wt%) were not successful.
Better results were obtained by the addition of low
percentages of phosphoric or, still better, polyphos-
phoric acid (HPO3)n to the bitumen.
The addition of the acid was suggested by the
Table 2 Properties of the heterophasic copolymers
Total intrinsic
MFR* viscosityt
Polymer (g (10 min) -1 ) (mlg -1 )
A 0.6 270
B 4.0 175
C 8.0 152
*Melt flow rate, ASTM D-1238 L
t ASTM D-2857
:~(1) Xylene-soluble fraction at 23C, (2) xylene-insoluble fraction at
23C
682 Fuel 1996 Volume 75 Number 6
IPPI IPP
homopolymer random LDPE~: HDPE
0.90 0.90 0.92 0.94
0.81 0.77 0.77 0.75
0.81 - - -
- - 0.75
observation that the acid-treated bitumens gave products
having better physical and rheological properties and a
much better ageing resistance 15. In the case of thermal
(e.g. visbreaker) bitumens, the result of such reaction was
the formation of insoluble material which could be
separated 16. Formation of insoluble material was not
detected when adding (HPOa)n or other phosphorus
compounds to straight-run (SR) bitumens; nevertheless,
a reaction took place and an upgraded SR bitumen was
obtained 16.
EXPERIMENTAL
Heterophasic ethylene-propylene copolymers were used
for the preparation of the PMBs. The properties of the
polymers are reported in Table 2.
The copolymers were analysed by determining melt
flow rate (ASTM D-1238 L) and intrinsic viscosity
(ASTM D-2857). To measure the intrinsic viscosity, the
polymer was treated with o-xylene at 23C; the insoluble
fraction (IPP) was separated from the soluble EPR
fraction. Such fractions plus the original copolymer were
dissolved in tetralin and the intrinsic viscosity was
measured at 135C.
The straight-run (SR) bitumens were produced in a
number of refineries by vacuum distillation of various
crude mixes (Table 3). To confirm the effect of the acid,
two blown bitumens were also mixed with the copolymer
(Table 3).
Polyphosphoric acid from Carlo Erba was used
without further purification.
The reaction apparatus consisted of a glass reactor
designed to contain 600 g of sample, equipped with a
mechanical stirrer with a homogenizing head and a
thermostatic heater. The bitumen (400-500g) was
heated to ~180C in the stirred reactor and the acid
was then added (1-5wt%). After stirring for 1 h, the
copolymer (2-10wt%) was added to the acid-treated
bitumen and the temperature was maintained at 180C
for a further 1 h.
The bitumens and the PMBs were characterized
according to the standard ASTM or IP procedures.
Intrinsic Viscosity and rheological curves were measured with a
viscosityt :~ Rheometrics RAA rheometer in controlled strain,
(ml g - 1)
frequency 10 rad s-1 with a temperature ramp. Asphal-
(1) (2) tenes were determined according to the IP 143/81
standard method. The average molecular weight of the
320 150
198 133 bitumens was measured by cryoscopy in benzene. The
166 121 effect of the acid on the bitumen was observed by optical
microscopy, while the dispersion of the polymer was
controlled by fluorescence microscopy (200 ).
The stability of the mixtures was determined by the
'toothpaste tube test'iT: a sample of PMB was placed
 Production of stable polypropylene-modified bitumens. C. Giavarini et al.

Table 3 Characteristics of the bitumens and acid-treated bitumens

R&B Penetration, Viscosity,

(HPO3) n softening point* T = 25Ct Asphaltenes++ 120C
Bitumen (wt%) (C) (10-1 m m ) (wt%) MW (Pa s)

SR2 0 44 170 8.9 851 0.48

1 53 90 12.5 1060 0.98
3 75 65 - 1315 18.15
SR4 0 47 135 11.8 888 0.53
1 56 87 - 1102 1.78
3 76 50 1455 24.48
5 90 44 - 1918 20.35
SR6 0 43 160 9.7 799 0.70
1 54 71 14.1 918 1.30
3 76 51 1187 15.00
SR8 0 43 160 9.7 911 0.36
1 50 82 13.7 1130 0.76
2 72 73 - 1394 5.83
3 80 66 24.0 1565 13.76
B1 0 117 13 29.0 1298
B2 0 107 26 33.8 1193

* ASTM D36. t ASTM D5. ~:IP 143

inside a toothpaste tube and held for 3 d at 160C. After
this time, the sample was cut into three parts. The
bottom and the upper parts were tested by the ring-and-
ball (R&B) test: a difference of a few degrees between top
and bottom was considered a good result.
RESULTS AND DISCUSSION
Table 3 shows a comparison between the properties of
the original SR samples and those of the products
obtained after the addition of polyphosphoric acid.
Table 4 reports the characteristics of the mixtures
obtained by adding heterophasic copolymers A, B and
C to the acid-treated bitumens.
The polyphosphoric acid treatment was responsible
for higher softening points and lower penetration values,
with an increase in the penetration index of all bitumen
samples; the asphaltene content was increased, as well as
the average molecular weight and viscosity of the
bitumens ~5.
When the acid-treated bitumens were treated with
polymers (2-10 wt%), the segregation decreased, pro-
vided that at least 3 wt% of the acid was added to the
bitumen. The acid addition greatly reduced the difference
between the R&B temperatures of the upper and lower
part of the 'toothpaste tube' specimen. It should be noted
that this stability test is very severe.
Under the microscope, the samples of the bitumens
treated with /> 3 wt% of acid showed the presence of
particles dispersed in a yellow-brown 'oil' (clear grey in
Figure 1). Figure 2 shows the difference between a
bitumen modified by a heterophasic copolymer (left) and
one treated with polyphosphoric acid and then modified
with the same heterophasic copolymer (right). The

Table 4 Characteristics of the PMBs obtained from acid-treated and blown bitumens

Copolymer R&B Stability,

(HPO3) n softening point* Penetration? AT
Bitumen (wt%) (wt%) Type (C) (10 -l m m ) PI:~ (K)
SR 2 0 5 B 68 43 2.0 50
1 3 B 70 43 2.4 50
3 2 B 80 43 4.0 3
SR 4 0 5 B 58 42 0.2 48
3 2 B 81 48 4.3 2
3 3 A 100 34 5.7 3
3 3 C 94 37 5.3 3
3 5 C 99 32 5.4 4
3 7 C 108 26 5.8 2
SR 6 0 5 B 60 62 1.6 44
3 2 B 91 45 5.4 2
SR 8 0 5 B 60 52 1.2 47
2 3 B 83 52 1.7 2
3 2 B 90 53 3.0 2
B 1 - 5 B 130 13 6.2 0
B2 - 5 B 105 26 5.5 0
* A S T M D36
"["A S T M D5
:~Penetration index (ref. 18)
Difference between R&B temperatures of upper and lower sections in the toothpaste tube test
See Table 2

Fuel 1996 Volume 75 Number 6 683

 Production of stable polypropylene-modified bitumens: C. Giavarini et al.
5 i~m
i i
Figure 1 Photomicrograph of sample SR-8 treated with 3wt%
(HPO3)n
dispersion of the acid-treated sample is definitely better
than that of the other, which shows coarse polymer
particles.
It was demonstrated in a previous paper 15 that the
reaction of (HPO3) n with SR bitumens can be considered
as a chemical oxidation, in which the increases in
asphaltenes and viscosity are similar to those for blown
bitumens. This involves a change towards a gel structure
of the colloidal system19-23; however, it seems reasonable
to exclude an increase in polarity typical of air-blown
bitumens. In fact, 31p n.m.r, spectroscopy 15 did not show
any formation of ester compounds, while it showed the
presence of charge-transfer complexes between phos-
phorus and the aromatic structures of the asphaltenes.
Such complexes increase the average molecular weight of
the asphaltenes and could be considered similar to
charge-transfer complexes with halogens, especially
iodine 24.
It is reasonable to consider the particles shown by
microscopy (Figure 1) as the result of condensation of the
complexes previously described; these condensed pro-
ducts are comparable with the micelles described by Yen
in his colloidal model for the sol-gel structure of a
5 p,m
Figure 2 Photomicrographs of bitumen SR-8 modified with 5 wt% of copolymer B (left) and bitumen SR_8 treated with 3 wt% (HPO3). and then
modified with 2 wt% of copolymer B (right)
684 Fuel 1996 Volume 75 Number 6
i~
5 p,m
Figure 3 Photomicrograph of blown bitumen B-I modified with
5 wt% of copolymer B
bitumen25; it may be supposed that their MW is very
high, approaching the polymer M W 14'26.
To support the explanations given for the effect of
acid, two PMBs were prepared using hard blown
bitumens (Table 4). The stability tests were satisfactory,
confirming the good homogenization of blown bitumens
and polymers; the dispersion of the copolymer was better
than in the unblown bitumen, but coarser than in the
acid-treated bitumen (Figure 3). It seems reasonable to
ascribe this difference to the higher polarity of a blown
bitumen, which does not allow perfect dispersion of an
apolar olefinic polymer.
The change towards a gel structure of the acid-treated
bitumen is confirmed by the rheological curves of the air-
blown and acid-treated bitumens (Figure 4). In fact, the
trend of tan6 vs. T for air-blown and acid-treated
bitumens was similar and relatively constant with
increasing T, while the untreated samples showed
increasing values of tan 6 with increasing T, typical of
sol-type bitumens, where the interactions among asphal-
tenes are less than in blown and acid-treated
products 27,28.
From the practical point of view however, hard blown
, , 5 I~m
 Production of stable polypropylene-modified bitumens." C. Giavarini et al.

10 4

m
N
103
x
I

W le
lC
Ic
u
102 N
Illl~ I I le
mllm
W I N

(/D
V
c-
o
101
B)

100

C)

10-1 I I I I I I I I I I
O. 0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 110.0
Temp [*C]
Figure 4 Rheometriccurves:A, sampleSR-8; B, sampleSR-8treatedwith 3wt% (HPO3)n;C, sampleB-1

bitumens cannot be used to prepare road bitumens, REFERENCES

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CONCLUSIONS
The stability ofa PMB is not only linked to the difference
in density and viscosity between bitumen and copolymer:
the structure of the bitumen is also important, and stable
mixtures are obtained when a gel structure is produced in
a bitumen.
A stable modified bitumen containing heterophasic
copolymers is obtained by a pretreatment with a small
proportion (3 wt%) of polyphosphoric acid. In fact, the
acid improves homogenization of the polymer by shifting
to a gel structure; the PMBs thus produced have good
characteristics and optimum stability. By adding 2-
3 wt% of polymer to an acid-treated bitumen, a stable
PMB is obtained with the same characteristics as an
'untreated' PMB containing 5-6wt% polymer. There-
fore the cost of the treatment is more than counter-
balanced by the polymer saving; moreover, the product
obtained is stable during storage at high temperatures for
long periods.
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686 Fuel 1996 Volume 75 Number 6