Ullmann S Encyclopedia of Industrial Chemistry - 2014 - Gahleitner - Polypropylene

Polypropylene
MARKUS GAHLEITNER, Borealis Polyolefine GmbH, Linz, Austria

CHRISTIAN PAULIK, Institute of Chemical Technology of Organic Materials, Johannes
Kepler University Linz, Linz, Austria
1. Historical Overview . . . . . . . . . . . . 1 6.1. Additives . . . . . . . . . . . . . . . . . . . 21

2. Polymer Structure . . . . . . . . . . . . . 3 6.2. Compounding and Blending . . . . . . . 23
2.1. Molecular and Chain Structure . . . . 3 6.3. Reactive Modification . . . . . . . . . . 24
2.2. Crystallization and Morphology . . . 5 7. Properties . . . . . . . . . . . . . . . . . . . 24
2.3. Multiphase Copolymers . . . . . . . . . 6 7.1. Homopolymers . . . . . . . . . . . . . . . 24
3. Raw Materials . . . . . . . . . . . . . . . 6 7.2. Random Copolymers . . . . . . . . . . . 25
3.1. Propene and Comonomers. . . . . . . . 6 7.3. Impact Copolymers . . . . . . . . . . . . 27
3.2. Polymerization Diluents . . . . . . . . . 8 7.4. Composites and Blends . . . . . . . . . . 29
3.3. Catalysts . . . . . . . . . . . . . . . . . . . 8 8. Processing and Applications . . . . . . 30
3.3.1. TiCl3-Based Catalysts . . . . . . . . . . 8 8.1. Injection Molding . . . . . . . . . . . . . 30
3.3.2. MgCl2-Supported TiCl4 Catalysts . . 9 8.2. Blow Molding . . . . . . . . . . . . . . . . 32
3.3.3. Single-Site Catalysts . . . . . . . . . . . 10 8.3. Fibers and Flat Yarns . . . . . . . . . . 33
3.3.4. Aluminum Alkyl Cocatalysts and 8.4. Films and Sheets . . . . . . . . . . . . . . 35
Donors . . . . . . . . . . . . . . . . . . . . 10 8.5. Foaming and Coating . . . . . . . . . . . 37
3.4. Hydrogen . . . . . . . . . . . . . . . . . . . 11 8.6. Technical Applications . . . . . . . . . . 37
4. Polymerization Mechanism . . . . . . 11 8.7. Pipes . . . . . . . . . . . . . . . . . . . . . . 39
5. Industrial Polymerization 9. Environmental Aspects . . . . . . . . . . 39
Processes . . . . . . . . . . . . . . . . . . . 13 9.1. Life-Cycle Analysis . . . . . . . . . . . . 40
5.1. Liquid-Phase Processes . . . . . . . . . 15 9.2. Mechanical Recycling. . . . . . . . . . . 41
5.2. Gas-Phase Processes . . . . . . . . . . . 15 9.3. Chemical and Energetic
5.3. Hybrid Processes . . . . . . . . . . . . . . 18 Recycling . . . . . . . . . . . . . ...... 42
6. Product Finishing . . . . . . . . . . . . . 19 References. . . . . . . . . . . . . ...... 42
1. Historical Overview industry. Before that, propene could not be

polymerized to high molecular mass products
The history of polyolefins effectively started with the catalysts then available, namely, free-
with the discovery of high-pressure ethylene radical, anionic, and cationic systems. Even the
polymerization at ICI in the UK in 1933, which most favorable of these yielded only liquids
initiated the development and production of consisting of many isomers and greaselike
low-density polyethylene (LDPE). In the search materials unsuitable for making hard plastic
for a more energy efficient route to poly- products.
ethylene and the development of fully linear ZIEGLER’s group at the Max-Planck-Institut
polymers of this monomer, KARL ZIEGLER dis- f€
ur Kohlenforschung in Germany had for some
covered in 1953 new catalysts based on the years been using aluminum alkyls to convert
combination of transition metal halides (e.g., ethylene to a range of oligomers having an even
titanium chloride) with aluminum alkyls (e.g., number of carbon atoms. Unexpectedly, almost
triethylaluminum) [1]. With these he demon- total conversion to butenes occurred in one
strated that ethylene could be polymerized to a experiment. The cause was eventually traced
high molecular mass, crystalline polymer at to nickel-ion contamination in the autoclave.
moderate pressure and temperature and laid Tests with many other metal compounds
the foundation of a revolution for the plastics revealed that titanium ions were even more
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2 Polypropylene
active in producing polyethylene (PE) with also elucidated around the same time; ANDREW
a high molecular mass, resulting in a first KELLER presented his concept for chain folding
patent [2]. Such combinations of transition in PE crystals in Bristol in 1957 [6].
metal compounds with an aluminum alkyl later The patent dispute over crystalline poly-
became known as Ziegler–Natta (ZN) Cata- propylene in the USA between NATTA and
lysts, thereby acknowledging the immense con- Montecatini on the one side and Phillips Petro-
tribution of GIULIO NATTA to discovering and leum Company on the other was clearly a result
characterizing polypropylene (PP) and other of different legislation between the USA and
(stereoregular) a-olefin polymers in 1954. Europe. The dispute started in 1958 and became
NATTA, Professor and Director of the Milan one of the longest in industrial history, only
Institute of Industrial Chemistry, was a consul- ending 20 years later [7]. Phillips’ polymeriza-
tant to Montecatini, to whom he assigned his tion catalyst, consisting of chromium-ion-pro-
patents. The close collaboration between moted silica–alumina, has not been used in any
ZIEGLER and NATTA was acknowledged in commercial plant to manufacture iPP.
1963 by the joint award of a Nobel Prize in New applications for the polymer with the
Chemistry for their outstanding contributions to impressive combination of a melting point of
polymer science (a fascinating account of these 165 C and a density of 900 kg/m3 were con-
discoveries is provided by MCMILLAN [3]). stantly being found, in 1959 with the produc-
NATTA’s discovery of the stereospecific polym- tion of the PP fiber Meraklon, and in 1962 with
erization of propene to produce isotactic (and first attempts at PP suitcases made by Hoechst.
hence crystalline) polypropylene (iPP) [4] The ZN catalysts also proved to be suitable for
resulted first in products with an isotacticity the production of elastomers based on ethylene
of only around 40%. This regularity was and propene [8]. For a polymer having its glass
increased to 80% within one year through transition around 0 C this turned out to be a
modification of the catalyst, allowing the first decisive factor for evolving into technical appli-
Montecatini production facility for iPP with a cations requiring mechanical stability over a
production volume of 6.103 t/a to go into oper- wide temperature range. Together with the
ation in Ferrara, Italy, in 1957. availability of an initially cheap monomer,
In retrospect, it is clearly recognizable that this resulted in a rapid growth of the production
with the chain branching of PE and the stereo- volume from less than 100103 t/a in 1960 to
structure of PP, two crucial general control 6.1106 t/a in 1980 to more than 53106 t/a in
factors for the crystallinity and mechanics of 2012, making it the most produced single ther-
polymers had been discovered [5]. Finally, the moplastic material (see Fig. 1) [9]. In the same
crystallization structures of the polymers were period, the production volume of new plants
Figure 1. Production-volume development of standard thermoplastics (redrawn after [9])

Polypropylene 3
Figure 2. Regional distribution of global PP production (2012, data from [10])
increased to 200–400103 t/a. A massive HECOs with high impact strength. Modern ZN
regional shift to Asia has occurred in recent catalysts allow the production of reactor-based
years, with Northeast Asia and especially China thermoplastic elastomers with high impact
now having the biggest share in production (see toughness in a temperature range from þ80
Fig. 2) and fewer than ten companies producing to 30 C.
more than 60% [10]. In the field of catalysts, NATTA had already
Technical factors for this massive volume discovered the fundamental suitability of met-
increase are numerous, but mostly related to a allocenes for the homogeneous polymerization
clever combination of catalyst chemistry and of olefins. In 1975 a crucial step forward in the
polymerization technology. A key step in terms practical use was taken with the discovery by
of application range was certainly the develop- KAMINSKY in Hamburg of methylaluminoxane
ment of products long referred to as “block (MAO) as a massively reaction accelerating
copolymers”. These combine a crystalline cocatalyst [12]. This enabled MC-based PE,
PP matrix with embedded particles of and BRINTZINGER in Konstanz extended the con-
ethylene–propene rubber (EPR) and PE, which cept with the use of bridged MCs for iPP in
determine impact resistance and low-tempera- 1984. While the market penetration of metal-
ture resistance [11], and should more correctly locenes and other single-site catalysts has been
be referred to as heterophasic copolymers significantly slower than anticipated, due in
(HECOs) or PP impact copolymers. Important part to the continuous improvement of the
for their development were improved catalysts traditional—and cheaper—ZN systems, the
and the availability of multireactor polymeri- former have enabled unprecedented fine-tuning
zation plants. With the second generation of ZN of chain microstructure by ligand design.
catalysts it became possible from the mid-
1970s to produce “technical” HECOs, but 2. Polymer Structure
with only a moderate EPR content. The intro-
duction of the third generation of ZN catalysts 2.1. Molecular and Chain Structure
at the end of the 1970s together with the break-
through of bulk processes for polymerization Since PP is the largest single thermoplastic
without solvents enabled reliable synthesis of material [9] the structure, morphology, and
4 Polypropylene
Figure 3. Main polypropylene types

A) Isotactic; B) Syndiotactic; C) Atactic
properties of isotactic polypropylene (iPP) have syndiotactic stereoisomers of PP are both semi-
been studied extensively. As the propene crystalline polymers. The melting points are in
monomer is asymmetric, polypropylene can the range of 165 C for iPP and 130 C for sPP.
be produced with different stereochemical con- Isotactic PP dominates the polypropylene mar-
figurations [13]. The different stereoisomers of ket because it is easily produced with hetero-
PP were isolated and characterized by NATTA geneous ZN and metallocene catalysts. In
et al. in 1954–1955. The most common types of addition, it shows easier processing behavior
PP, shown in Figure 3, are isotactic (iPP), and better mechanical properties. Syndiotactic
syndiotactic (sPP), and atactic (aPP). In iPP PP shows a slower crystallization rate and can
all methyl groups are located on the same side only be produced with some metallocene cata-
of the backbone, in sPP on alternating sides, lysts; therefore, it is commercially almost
and in aPP the methyl groups are arranged nonexistent.
randomly along the polymer chain. State-of-the-art ZN catalysts make isotactic
Atactic PP is an amorphous material with PP with only a minor atactic fraction.
much less practical importance than its regular The industrially used ZN systems favor the
counterparts, but it has some niche applications 1,2-insertion and head-to-tail enchainment
like hot-melt adhesives. The isotactic and (Fig. 4). Defects such as a 2,1-insertion
Figure 4. Regioirregularity in polypropylene polymerization

Polypropylene 5
following a 1,2-insertion create irregularities occurs at ca. 110–120 C in a differential scan-

along the PP chain resulting in a lower melting ning calorimeter (DSC) at a cooling rate of
point and lower crystallinity of the material 10 K/min. The observed crystallization rate is
[14]. With metallocene catalysts it is possible dependent on the nucleation rate and the rate of
to produce polypropylene with high isotacticity crystal growth. Crystallization is generally
but lower regioregularity, responsible for their favored by slower cooling from the melt, and
lower melting point compared to PP made with the degree of crystallization can be controlled
a ZN catalyst. With the help of metallocene by the rate of melt quenching and subsequent
catalysts also other stereostructures such as annealing. Very rapid cooling can even sup-
block polymers of isotactic and atactic press crystallization. The degree of crystallinity
sequences can be obtained, but these materials can vary and different types of crystal structures
are not yet in commercial use. depending on the stereochemical structure,
processing conditions, and additives exist
[15]. The observed morphology of PP exhibits
2.2. Crystallization and Morphology a hierarchy of characteristic scales, as shown in
Figure 5. In the cross section of a molded part
Polypropylene molecules associate to form one can see skin–core structures, which on a
supramolecular structures when cooled to tem- finer scale reveal a spherulitic structure on the
peratures below the melting point (crystalliza- order of 1–50 mm. The size of these structures
tion temperature). At the crystallization can be determined by means of optical micros-
temperature, the macromolecules begin to copy, small-angle light scattering (SALS), and
arrange themselves into crystals, and ordered scanning (atomic) force microscopy (SFM).
crystalline regions and disordered amorphous The individual spherulite is composed of lamel-
regions are formed. The growth of the crystals lar-shaped crystals. The lamellar periodicity is
may happen spontaneously (when a highly given by the long spacing and is in the range of
ordered crystal structure is favorable) or may 10–30 nm, depending on processing and
be induced by the presence of a foreign particle thermal history. Typically used protocols are
(e.g., a nucleating agent or the metal mold small-angle X-ray scattering (SAXS), higher-
surface). Typically, the onset of crystallization resolution electron microscopy, and SFM. The
Figure 5. Characteristic hierarchy of morphological scales in PP. The skin–core morphology of an injection-molded specimen
is shown to illustrate the morphology on the visual scale (redrawn after [16])
6 Polypropylene
Table 1. Crystal characteristics of PP [17–19]
Crystal form System r (20 C), g/cm3 Chains per unit cell Tm , C
i-a monoclinic 0.932–0.943 4 171

i-b pseudohexagonal 0.922 9 150
i-g triclinic 0.939 1 131
Smectic 0.916
Amorphous 0.85
sPP orthorhombic 0.93 2 138

The enthalpy of melting for 100% crystalline iPP is variously reported, due to different methods, e.g., 16518 J/g [17] and
209 J/g [18].
lamellae are composed of crystallographically Generally multiphase copolymers are

ordered regions [16]. The individual produced in at least two reactors in series.
macromolecule chains form a helical arrange- In the first reactor the isotactic polypropylene
ment packed together in unit cells with matrix is made, and the second produces
specific dimensions. The unit-cell dimensions an ethylene–propene (EP) elastomeric
(0.6–2 nm) are shown in Figure 5 for the a form copolymer. The dispersed copolymer dissi-
of iPP. Commonly wide-angle X-ray scattering pates energy during impact, increasing the
(WAXS), electron diffraction techniques, and toughness of the material. The dispersion of
SFM are used to evaluate the structure on this an elastomeric phase in a PP matrix can also
scale. The a form of isotactic polypropylene is be achieved through melt mixing (compound-
the primary form of PP obtained under normal ing) of rubber materials with polypropylene.
processing conditions. Besides the a form, b, g, An example of the achieved morphology is
and d crystal modifications are known for PP. given in Figure 6.
The basic features of the crystal forms of PP are
given in Table 1 [17–19]. The b form of poly-
propylene exhibits a lower tensile strength at a 3. Raw Materials
given strain rate and higher impact strength
than the a form. The b form can specifically 3.1. Propene and Comonomers
be obtained by the use of nucleating agents
[20]. It converts to the a form only on melting Due to the high sensitivity of ZN catalysts to
and recrystallization. impurities, which lead to a drastic reduction of
the reaction rate and also negatively affect the
product quality (isotacticity) of the polymer,
2.3. Multiphase Copolymers the used propene and comonomers require
high purity [22]. Compounds that will bind
Commercially PP is available in different strongly to the active centers (Ti) of the cata-
forms, dependent on the desired properties. lyst or react with the alumina-based cocata-
Polypropylene homopolymers only consist of lyst, such as polar and highly unsaturated
propene monomer units and provide stiffness, compounds (e.g., acetylenes, dienes, carbon
but their glass transition temperature Tg is about monoxide and dioxide, carbonyl sulfide,
0 C and thus are not usable in subzero environ- water, alcohols, ammonia, and arsine) can
ments. By addition of an elastomeric phase the only be tolerated at parts-per-billion levels
impact resistance of the material is increased [23]. In addition, compounds that do not influ-
[21]. The addition of an elastomeric component ence the chemistry but negatively affect the
leads to a multiphase structure often referred to process by increasing the reactor pressure also
as impact or block copolymer. The achieved must be avoided. These inert substances, such
impact resistance is dependent on the type, as methane, ethane, propane, butane, and
amount, and morphology of the elastomeric nitrogen, also accumulate in the process and
phase, while the polypropylene matrix deter- complicate the monomer recovery section and
mines the stiffness. recycle streams.
Polypropylene 7
Figure 6. TEM image of the morphology of a commercial high-impact EP copolymer with 16.5 wt% elastomer (Borealis
BD310MO). Dark regions correspond to the elastomeric phase with crystalline PE inclusions; contrasted with RuO4 (scale bar
¼ 1 mm)
For the production of polypropylene materi- dehydrogenation of propane from natural

als polymer-grade monomers are used as feed- LPG fields commercially interesting (!
stock, which can be further refined by passing Propene, Section 3.3.1).
the monomers through special purification col-
umns. A typical design consists of four purifi-
cation steps to scavenge and absorb impurities Table 2. Propene quality requirements
[22]. Type of Component Recommended
Table 2 lists the typical specification for component concentration
propene quality. Certain catalyst systems Monomer Propene 99.5 wt% min.
may require the lower levels listed for car- Inert Ethane 500 vol ppm
bonyl sulfide, carbon monoxide, and oxygen Propane 0.5 wt%
Butane 500 vol ppm
(this quality is said to be suitable for N2 þ CH4 300 vol ppm
metallocene catalysts) [24]. Propene propert- Ethylene 50 vol ppm max.
ies relevant to PP production are listed in 1-Butene 50 vol ppm max.
Table 3. Butadienes 10 vol ppm max.
Copolymerizing Isobutene 50 vol ppm max
To broaden the property window of PP monomer (estimated)
certain a-olefins are used in copolymerization Poison Propyne 5 vol ppm max.
with propene. The commercially most impor- Propadiene 5 vol ppm max.
tant comonomer is ethylene, but 1-butene Oxygen 2–5 vol ppm max.
Carbon 0.3–3 vol ppm max.
and higher olefins are reported as well monoxide
[25, 26]. Carbon 5 vol ppm max.
Propene is normally produced outside the dioxide
PP plant by steam cracking of naphtha or gas Carbonyl 0.03–0.5 vol ppm
oil at 700–950 C (! Propene, Section 3.1.) sulfide
Total sulfur
max.
1 wt ppm max.
yielding an ethylene-to-propene weight Water 5 wt ppm max.
ratio of approximately 2:1. The increasing Methanol 5 vol ppm max.
demand for propene derivatives, especially Ammonia 1 vol ppm max.
Hydrogen 10 vol ppm max.
PP, made other routes such as the
8 Polypropylene
Table 3. Propene properties relevant to PP production propene) technologies the used diluents can
Property Value
be removed more easily.
Heat of polymerization 2514 kJ/kg
Boiling point 47.7 C 3.3. Catalysts [27]
Critical temperature 92 C
Critical pressure 4.6 MPa
Vapor pressure at 20 C 0.98 MPa
Heterogeneous ZN catalyst systems still largely
dominate commercial production of highly iso-
tactic PP. The catalyst system consists of a solid
transition metal halide, usually TiCl4, a Lewis
base (referred to as internal electron donor, e.g.,
3.2. Polymerization Diluents
1,3-diethers) on a support (mostly MgCl2), and
an organoaluminum alkylating agent such as
The polymerization of propene can be per-
triethylaluminum (TEA), and a second Lewis
formed under slurry and gas-phase conditions
base (usually called external donor, e.g., alkox-
and combinations thereof. The first commercial
ysilanes) added separately to the polymeriza-
processes used inert hydrocarbons ranging from
tion mixture. An overview on the development
butane to dodecane and refined petroleum frac-
phases of propene polymerization catalysts is
tions as diluents. Typically there is twice as
given in Table 4.
much diluent in the reactor as polymer, and
consequently the demands on the purity of the
diluent are as stringent as for the monomers. 3.3.1. TiCl3-Based Catalysts
The inert diluent helps to transfer the propene to
the solid catalyst and to convey the heat of TiCl3 can form four different crystalline mod-
polymerization to the water-cooled reactor ifications (i.e., a, b, g, and d) dependent on the
jacket. Polar impurities, such as alcohols, car- preparation method used. The a, b, and d
bonyl compounds, water, and sulfur-containing forms are purple, while the fourth is brown
compounds, must be kept below 1–5 ppm. The (b) and not used for PP production due to its
quality of the diluent is monitored regularly by poor stereospecificity. All purple forms have a
means of standard analytical methods, prefera- layer lattice consisting of chlorine atoms with
bly on-line analytics, to prevent accumulation hexagonal (a), cubic (g), or random succes-
of oxidized species and catalyst fragments. sion of hexagonal and cubic close packing (d)
At the end of the polymerization process the (Fig. 7).
used diluent has to be removed completely to The most important process of industrial
guarantee compliance of the PP material with TiCl3 production has been the reduction of
food and drug regulations. Since state-of-the- TiCl4 by means of Al metal or Al alkyls. A
art polymerization plants are based on gas- major refinement in Al alkyl-reduced TiCl3
phase and bulk (polymerization in liquid systems has been made by Solvay [28, 29] in
Table 4. Performance development of ZN catalysts for PP a
Year Catalyst system Productivity, kgPP/gCat. I.I.b, % mmmmc, % Mw/Mn H2 responsed
1954 d-TiCl30.33 AlCl3 þ AlEt2Cl 2–4 90–94 low

1970 d-TiCl3 þ AlEt2Cl 10–15 94–97 low
1968 MgCl2/TiCl4 þ AlR3 15 40 50–60
1971 MgCl2/TiCl4/benzoate þ AlR3/benzoate 15–30 95–97 90–94 8–10 low
1980 MgCl2/TiCl4/phthalate þ AlR3/Silane 40–70 95–99 94–99 6.5–8 medium
1988 MgCl2/TiCl4/diether þ AlR3 100–130 95–98 95–97 5–5.5 very high
1988 MgCl2/TiCl4/diether þ AlR3/silane 70–100 98–99 97–99 4.5–5 high
1999 MgCl2/TiCl4/succinate þ AlR3/silane 40–70 95–99 95–99 10–15 medium
a
Polymerization conditions: liquid propene, 70 C, 2 h.
b
Isotactic index (% insoluble in boiling heptane).
c
Content of isotactic pentads.
d
Melt flow rate change as function of H2 concentration.
Polypropylene 9
Figure 7. Models of chlorine packing in the different TiCl3 modifications: a (left), g (center), d (right) (adapted from [27])
their three-stage process, which gives a four- to titanium catalysts by Montedison (now
fivefold increase in activity: LyondellBasell) in Italy and Mitsui Petro-
chemical Industries (now Mitsui Chemicals)
1. Preparation of a reduced solid by reducing in Japan [30]. Collaboration and cross-licensing
TiCl4 with diethylaluminum chloride between these two companies eased the com-
(DEAC) at 0–2 C, and then heating the mercial success and avoided incipient interfer-
mixture to 65 C. The obtained brown solid ence claims. Starting with finely milled MgCl2,
is a b-TiCl3 (TiCl3x AlCl3y AlEtCl2, where which has a similar structure to violet TiCl3, in
x 0.15 and y 0.20). 1968, routines were identified to create highly
2. The brown b-TiCl3 solid is treated with active and stereoselective catalysts. Though
diisoamyl ether to dissolve out most of other supports with layered structures (e.g.,
the Al compounds. MgBr2, MnCl2, and others) in principle can
3. The above solid is treated with excess TiCl4 also be used to make stereospecific catalysts
diluted in hydrocarbons at 60–70 C to give a for PP, MgCl2 has been used almost exclusively
violet d-TiCl3x (AlEtnCl3–n)y (i-Am2O) because it gives catalysts the highest activity
composition (n ¼ 0–2, x < 0.2, and 0.01 and stereospecificity.
< y < 0.11). After washing with hydro- For the preparation of particle-form sup-
carbons to remove adsorbed TiCl4 and ported catalyst three main procedures have
other byproducts, a catalyst with high been developed:
surface area (150–200 m2/g), high porosity
(> 0.2 cm3/g), and very high activity is 1. Mechanical routes: the different catalyst
obtained. components (usually MgCl2, TiCl4, and a
Lewis base) are milled together in suitable
Similar catalysts have also been described ratios.
by other companies, e.g., the Chisso Corpora- 2. Combined mechanical and chemical routes:
tion, Japan. Adding a Lewis base (benzoic MgCl2 or precursors of MgCl2 are co-milled
esters, alkoxysilanes) is claimed to afford with the Lewis base, followed by one or
high isotacticity and activity. more treatments with excess TiCl4 at tem-
peratures > 80 C and washing with hydro-
3.3.2. MgCl2-Supported TiCl4 Catalysts carbons to remove unconverted TiCl4.
3. Chemical routes: the active MgCl2 is formed
A decisive step in the research on ZN PP simultaneously with the incorporation of the
catalysts was the development of supported Ti compound and the Lewis base.
10 Polypropylene
a. MgCl2 and the Lewis base (e.g., an several groups discovered accidentally that
alcohol) react to form a complex, traces of water improve the catalyst activity
which is subsequently treated with of metallocene-based homogenous catalysts in
the internal donor (Di) and excess the presence of trimethylaluminum (AlMe3).
TiCl4 at temperatures > 80 C, fol- SINN and KAMINSKY first identified the potential
lowed by washing with hydrocarbons. of AlMe3/H2O activators for metallocene-cata-
b. Solid Mg(OR)2 or Mg(OR)Cl is lyzed ethylene polymerization [32]. Since the
treated with Di and excess TiCl4. 1980s the performance of metallocene-based
The MgCl2 is formed by the reaction catalyst systems been improved substantially to
of the Mg compound with TiCl4, and produce isotactic, syndiotactic, and stereoblock
the byproducts (Ti alkoxides) are PP on an industrial scale [33]. Metallocenes
eliminated by subsequent washing. suitable for isotactic PP manufacturing gener-
c. MgR2 or MgRCl (optionally dispersed ally seem to be based on zirconocenes sup-
on SiO2, Al2O3, or other carriers) react ported on inert solids to preserve particle size
with a chlorinating agent to form and shape. This makes them more compatible
active MgCl2, followed by hot treat- with the advanced process technologies of the
ment with Di and excess TiCl4 (as major operators, who refer to them as “drop-in
above). catalysts”. The concept of single-site catalysts
has been expanded to bridged half-sandwich Ti
d. First a solution of MgCl2 or other
amide complexes, which became known as
Mg compounds (e.g., Mg(OR)2,
constrained-geometry catalysts [34]. For
Mg(OCOR)2, MgR2, or Mg silyla-
many years the focus of metallocene catalyst
mide) in suitable solvents such as
development was on group 4 transition metals
ROH, trialkyl phosphate, Ti(OR)4,
such as Ti, Zr, and Hf. Today the potential of
epoxychloropropane, and others is pre-
late transition metal complexes of Ni, Pd, Co,
pared. The solution is then either
and Fe is recognized as well, with heavy patent-
treated with a chlorinating agent to pre-
ing in the field. With the development of single-
cipitate MgCl2, which is then loaded
site catalysts it became possible to specifically
with Ti and Di as described above, or
design polyolefins with narrow molecular mass
directly treated with Di and excess
distribution (polydispersity Mw/Mn ¼ 2), well
TiCl4.
defined regio- and stereoregularity, and molar
e. In a recent development, Borealis mass independent random or sequenced
described a method [31] for in situ comonomer incorporation (see Fig. 8).
formation of the catalyst carrier par- Although isotactic PP remains the poly-
ticle and the actual active species by propylene with the highest commercial interest,
solidifying the catalyst from solution. the opportunities of controlling the micro-
A solution of a complex of a group 2 structure by catalyst design have helped to
metal (Mg compound) and an electron achieve a better understanding of basic struc-
donor in an organic liquid is mixed with ture–property correlations of PP and to expand
a transition metal compound (Ti) to its property range.
produce an emulsion. By changing
temperature and stirring conditions 3.3.4. Aluminum Alkyl Cocatalysts and
solid catalyst particles with regular Donors
spherical shape are obtained.
The cocatalysts used with MgCl2-supported
3.3.3. Single-Site Catalysts catalyst systems are preferably Al trialkyls,
triethylaluminum (TEA), and triisobutylalumi-
Metallocenes have been used for 30 years as num (TIBA). Al alkyl chlorides afford a much
model compounds for ZN reactions. They were poorer performance and can only be used in
quite unsuitable for commercial reactors combination with trialkyls. TEA is made com-
because of their extremely low activity and mercially from aluminum, ethylene, and hydro-
poor stereocontrol. During the mid-1970s gen. Trimethylaluminum is available as methyl
Polypropylene 11
Figure 8. Correlations between metallocene structures and PP architecture (adapted from [32])
aluminoxane (MAO), made through controlled 3.4. Hydrogen

addition of water to the trialkyl.
The external donor (De) that can be used is Hydrogen is used as molar mass regulator in the
dependent on the type of internal donor (Di). In reactor and its concentration must be accurately
the early 1980s alkyl phthalates were intro- controlled.
duced as Di together with alkoxysilanes as
De, affording improved productivity and iso-
tacticity (see Table 4). These catalysts are still 4. Polymerization Mechanism [35]
in use in many industrial PP manufacturing
processes. Later 1,3-diethers were introduced For the catalytic polymerization of a-olefins
as internal donors providing even better activi- different models and reaction mechanisms were
ties and isotacticities without the need for any developed. COSSEE [36–38] developed a model
external donor. The most recent developments to explain the catalytic polymerization process
use succinates as Di; as in the case of phthalates, of ethylene or 1-alkenes at a titanium center.
also here alkoxysilanes are used as De. The The catalytic cycle is shown in Figure 9. It starts
performance of these catalyst systems is com- with the side-on complexation of the a-olefin,
parable to that of the phthalate systems, but which activates the C–C double bond. This is
they lead to much broader molecular weight followed by insertion into the Ti–C bond
distributions. through a cyclic transition state, by which the
12 Polypropylene
Figure 9. Catalytic cycle for propene polymerization at a heterogeneous TiCl3 catalyst according to COSSEE and ARLMAN
(adapted from [35])
polymer chain grows by one monomer unit. replaced by an alkyl group. In this way, a
Simultaneously, the vacant site becomes free Ti–C bond is generated at the surface of the
again for complexation of a monomer TiCl3 particle. The propene (olefin) can insert
molecule. into this Ti<C->C bond provided there is a
Together with ARLMAN, COSSEE explained vacant site for olefin complexation. This
how the active sites are formed at the surface incoming propene molecule approaches the
of TiCl3. The chloride anions form a closely active site, whose immediate crystal geometry
packed array with gaps where the much smaller controls both the initial coordination and the
Ti cations are located. Each Ti cation is then configuration as the monomer inserts into the
surrounded octahedrally by six chloride anions. titanium–alkyl s bond. Accordingly, this is a
At the surface, the titanium centers and the template-type polymerization controlled by the
chloride anions are exposed (Fig. 10), and surface shape, and not by the previously
thus accessible to other components. In the inserted monomer unit. Atactic polymer is
proposed mechanism one chloride ion reacts formed at more open surface sites having two
with the alkyl aluminum compound and is vacancies or two weakly bonded chlorine
atoms. On complexation of one propene mole-
cule to the Ti center, the complex shown in
Figure 10 (the figure shows ethene complex-
ation) is formed. In Figure 10, the three chlorine
ions at the surface of the TiCl3 particle are
shown together with the CH2 group of the
growing chain; the nearest-neighbor chlorine
ion inside the crystal cannot be seen. A propene
molecule occupies the sixth Ti coordination
site. Starting from this transition state, propene
is inserted into the Ti–C bond. One catalytic
cycle, as shown in Figure 9, is thus completed.
In addition to the main reaction, chain
propagation (with the monomer as the reaction
partner), there are further reactions at the
active site, such as b-hydride elimination,
which leads to removal of the polymer
Figure 10. Structure of the active center with a complexed chain from the active center along with the
ethylene molecule formation of a vinyl group at the chain end,
Polypropylene 13
or chain-transfer reactions with hydrogen and Table 5. Some typical PP processes (homopolymer reactor)
alkyl aluminum compounds. Regime Process (technology supplier)
It is very unlikely that the active sites on the
TiCl3 crystal are all uniform, so a distribution of Gas phase Unipol (Dow)
Innovene PP (Ineos)
imperfections results. This is why ZN catalysts Horizone (JPP)
are referred to as multisite catalysts to empha- Spherizone (LyondellBasell)
size the observed wide distribution of polymer Novolen (Novolen)
chain lengths and stereoregularities. In MgCl2- Bulk Spheripol (LyondellBasell)
Borstar (Borealis)
supported titanium chloride systems, it is Hypol II (Mitsui)
assumed that about 10–20% of the Ti is in ExxonMobil
the form of active sites. Surface geometry still Slurry Several
controls stereoregularity, but Lewis bases are
much involved in this regulation [39] (see also
Chap. 3).
Metallocene and other single-site catalysts Historically the suspension processes are
have well-defined structures, which in turn lead the oldest ones; three facts are decisive for
to narrow molecular mass distributions and the design:
better control of chain irregularities, including
new types of chain defects obtained with 1. The limited polymerization yield of the
selected combinations of metallocenes and alu- catalyst, which on the one hand resulted
minoxanes. Metallocenes can be used in solu- in the necessity to remove the catalyst resi-
tion, but for better control of particle size and dues. On the other hand, it implied the use of
shape, heterogenized systems are preferred. serial reactors for improving productivity.
Supported single-site catalysts can be used as 2. The necessity to remove amorphous frac-
so-called drop-in catalysts to emphasize the tions (atactic PP, which is found at ZN
ease of using these systems in existing plants catalysts in low molecular masses and
without spoiling catalyst or plant performance. waxy form) because of the limited stereo-
control in the polymerization.
3. The fact that complex copolymers with
5. Industrial Polymerization multiphase structure and various solubility
Processes [40] were soon considered as important products
to expand the application range of PP.
Since the start of industrial PP production in
1957 the advances in catalyst technology and In Figure 11 the block design for an early PP
the demand for improved product performance process is compared with a fourth-generation
have been the main drivers for the development ZN catalyst setup. Especially the advances in
of propylene polymerization processes [41]. catalyst technology led to the design of more
The processes can be grouped into three efficient processes, and thus the elimination of
main categories: gas-phase, bulk, and improved some process steps.
slurry. All state-of-the-art process technologies For slurry- and gas-phase reactors the poly-
employ a gas-phase or bulk reactor system for mer is formed around heterogeneous catalyst
the production of homopolymers and random particles. Slurry technologies can be divided
copolymers. For the polymerization of impact into diluent and bulk processes. In diluent
copolymers (heterophasic copolymers) an addi- technologies, an inert diluent (typically a
tional gas-phase reactor is connected in series. C4–C6 alkane) is used to disperse the growing
The typical current PP processes are listed in polymer particles, while the monomer (propene
Table 5. and ethylene as comonomer) is introduced as a
Polyolefin production lines have been gas and other comonomers (higher a-olefins)
developed to extremely efficient and large are fed as liquids. In bulk technology the
machines, starting with annual capacities of polymerization takes place in the liquid propyl-
about 5 103 t in 1963 to more than 400 ene monomer. Slurry technology can be used
103 t for the newest plants being built now. for the production of PE and PP, while bulk
14 Polypropylene
Figure 11. Polyolefin plant designs

A) Early PP process; B) State-of-the-art PP process
technology is restricted to polypropylene and polymerized in gas-phase reactors. They can

its copolymers. In slurry polymerizations auto- be classified into fluidized-bed reactors (FBRs)
claves and loop reactors are used. Ethylene, and stirred-bed reactors (SBRs). In FBRs a
propene, and higher a-olefins can also be gaseous stream of monomer and an inert gas
Polypropylene 15
(nitrogen) fluidizes the polymer particles, while (or other comonomers). Higher concentrations
mechanical stirring is responsible for suspend- of the comonomer or the production of rubber
ing the polymer particles in gas-phase SBRs. phases (ethylene–propylene rubber) in hetero-
This reactor type can be subdivided into hori- phasic copolymers are not feasible due to the
zontal and vertical reactors. solubility of the rubber in the liquid monomer.
For the production of these materials hybrid
processes (see Section 5.3 or multistage gas-
5.1. Liquid-Phase Processes phase reactors) are used.
Loop reactors account for production of
The first commercial PP production processes about 50% of all commercial polyolefins (PE
were based on slurry technology. The main and PP) and many different reactor configura-
advantage of using slurries rather than the tions are used in industrial processes. The loop
gas phase is the far better heat-transfer capacity reactor can be placed in the vertical (Phillips,
when the polymer particles are suspended in a Spheripol, Borstar processes) or horizontal
liquid. However, slurry processes require a position (USI process). The loops can have
workup section for the diluent, leading to extra up to 12 legs (the loop shown in Fig. 12 has
costs in the investment and operation of the four legs), and each leg can be up to 60 m tall.
plant. The volume of a typical loop reactor is on the
Most first-generation PP processes used order of 100 m3, which corresponds to a capac-
slurry conditions (Hercules and Montecatini) ity of roughly 250 103 t/a. The solid content is
with hexane as diluent. Two to four stirred tank in the range of 40–50 vol%, mainly limited by
reactors (autoclaves operated at 60–80 C and the viscosity of the slurry. A pump provides for
5–15 bar) not only allowed good monomer circulation of the slurry at the bottom of one of
conversion, but also the production of copoly- the legs. High fluid velocities (10–30 m/s)
mers with multiphase structure. The limits are create a turbulent flow, which helps to prevent
defined here by the copolymer solubility but particle settling and also improves the heat-
also the available heat-transfer surface per unit transfer coefficient.
volume compared with loop reactors.
The workup of the reaction mixture in these
early processes was rather tedious. Both the 5.2. Gas-Phase Processes
atactic fractions and the catalyst, which is still
used today for producing PP grades with very Gas-phase processes are an economical and
high purity, which are, for example, required energy-efficient alternative to liquid-phase
for producing capacitor films, had to be polymerization. Separation of polymer from
removed. The catalyst is decomposed with a the unconverted monomer is easy, since the
mixture of alcohol and NaOH/H2O, followed monomer is in the gas phase. There is no
by separation of the organic and aqueous need to flash off large amounts of liquids, which
phases. The aqueous stream is distilled, leaving means a significant cost reduction compared to
the catalyst residue in the wastewater. The slurry processes. Another advantage of gas-
organic stream is then sent to a centrifuge for phase processes is their potentially broader
removing the iPP part. From the diluent stream product window, as there are no solubility
the aPP is recovered in a thin-film evaporator, limits for hydrogen and monomers in the
while the iPP is purified with steam and dried. reaction medium. Polypropylenes with very
Polymerization in liquid propene as polym- high melt flows (low viscosities) and high
erization medium (bulk process) can be per- comonomer contents can be produced. How-
formed in continuous stirred-tank reactors or ever, the actual flexibility of the process
loop reactors. In both cases the use of liquid depends on the reactor size and the residence-
monomer as polymerization medium maxi- time distribution (RTD). A drawback of gas-
mizes the polymerization rate due to the high phase reactors is their limited heat-transfer
monomer concentration. Bulk processes are capability. To enhance the thermal character-
used to produce homopolymers and random istics of these reactor types special actions must
copolymers with less than 5 wt% of ethylene be taken. One possibility is to inject small
16 Polypropylene
Figure 12. Spheripol process

a) Loop reactors; b) Primary cyclone; c) Copolymer fluidized bed; d) Secondary and copolymer cyclone; e) Deactivation;
f) Purging
amounts of liquid components below their dew on a horizontal stirred gas-phase reactor. The
points or the use of inert gas-phase compounds reaction conditions are 65–85 C for the homo-
with a higher heat capacity than nitrogen. polymer reactor and a pressure in the range of
From a process design perspective gas-phase 25–30 bar. The residence time per reactor is
reactors are available as FBRs and SBRs in typically 1 h. The spacing of the injection
vertical and horizontal configuration, as well as points for the catalyst and cocatalyst appear
the multizone-circulating reactor (MZCR) to be critical for this type of reactor. If they are
introduced by LyondellBasell. to close one encounters lump formation in the
The Unipol process by Dow was initially feed zone; if they are too far apart the catalyst is
developed for PE production in the late 1970s not properly activated. Adding the ethylene–
and later adapted for the polymerization of PP propene rubber in a second gas-phase reactor
by introducing Shell high-activity catalysts can make heterophasic copolymers.
(SHAC) [23]. The process is based on a large Vertical stirred gas-phase reactors were
FBR for the production of homopolymers and developed first by BASF, Novolen technology,
random copolymers and can be extended by a and put into operation in 1967. Originally the
second, smaller, gas-phase reactor for the pro- design was that of a stirred autoclave with a
duction of heterophasic copolymers. The basic bottom-mounted helical stirrer. This stirrer is
design of the process is shown in Figure 13. The designed to convey the particles up the reactor
expanded upper section in the reactor is wall and let them fall down through the center
designed to reduce gas velocity and powder of the bed. The special design of the agitation
entrainment. Reaction conditions are reported system is considered to be responsible for
as 60–70 C for the homopolymer reactor and a forming subsegments in the reactor. Thus, it
pressure in the range of 25–30 bar. The resi- is claimed that the reactor behaves like a
dence time per reactor is typically 1 h. Thus, the cascade of a large number of CSTRs. The
grade transition times are comparable with heat is removed by circulating monomer gas
those of loop reactors. The Unipol process through an external heat exchanger. For impact-
has a unique product discharge system, using modified PP, a rubber phase is polymerized in
a cyclone separator. the second gas-phase reactor connected in
The Innovene and the Japan Polypropylene series. Figure 14 shows the design of the Novo-
(JPP) Horizone process technology are based len process.
a) Primary reactor; b) Copolymerizer; c) Compressors; d) Condensers; e) Liquid pump; f) Filters; g) Primary cyclone;
17
a) Primary fluidized bed; b) Copolymer fluidized bed; c) Compressors; d) Coolers; e), f) Discharge cyclones; g) Purge
Polypropylene
Figure 14. BASF gas-phase Novolen process

Figure 13. Unipol fluidized-bed process
h) Deactivation/purge
18 Polypropylene
separating the composition of two reaction

zones with the help of a barrier fluid introduced
at the top of the downer. The fast circulation of
the growing polymer particles between the
different reaction zones makes the residence
time per pass in each zone one order of magni-
tude smaller than the overall residence time.
This leads to a very good homogeneity of the
final product even for bimodal compositions.
The multizone circulating reactor can be
connected with an additional gas-phase reactor
(FBR) for producing heterophasic copolymers.
5.3. Hybrid Processes
Hybrid processes combine the production of a

homopolymer or random copolymer with low
ethylene content in liquid propene with the
production of a rubber phase (ethylene-propene
rubber) in a sequential gas-phase reactor.
The dominant hybrid process is the Spher-
ipol process by LyondellBasell. Figure 12
shows a two-loop and single-FBR Spheripol
design. Roughly one-third of today’s world PP
Figure 15. LyondellBasell Spherizone multizone circulat- production is based on this technology. In this
ing gas-phase process (adapted from [42]) process monomer and catalyst components are
a) Riser: upward pneumatic transport; b) Downer: packed fed into the first loop reactor for homo- and
bed moving downward; c) Product discharge; d) Gas fan; random copolymerization. Due to the large
e) Heat exchanger; f) Internal gas/solid separator;
g) Condenser
surface-to-volume ratio of loop reactors, the
heat-removal capacity is high and enables
high specific outputs exceeding 400 kg h1
The Spherizone multizone circulating m3 of PP. The shape of the spherical catalyst
reactor (MZCR), presented in Figure 15, was particles, consisting of many microscopic
developed by Basell and first commercialized MgCl2 single crystals with active surface, is
in the early 2000s. This reactor concept builds replicated to give spherical polymer particles
on the riser-tube design known from fluid cata- with a narrow particle size distribution.
lytic cracking. The Spherizone technology con- Coupled with the high liquid velocities in the
sists of two interconnected reaction zones—a loop reactor, reactor fouling can be avoided.
riser and a downer—separated by a cyclone. In Operating conditions are in the range of
the riser (the first reaction zone) the gas velocity 60–80 C and 35–50 bar.
is high and thus this zone acts like a fast- For impact (heterophasic) copolymers, a
fluidized bed. In the connected cyclone the gas-phase reactor is required. Upon exiting
polymer particles are separated from the gas the loop reactors, the propene–PP slurry is
and then enter the second reaction zone depressurized and flashed. The pressure must
(downer). The downer can be characterized be adjusted to allow recycling of the vaporized
as a moving packed bed [42]. The two different monomer by condensation and to be sufficient
sections of the reactor can be operated at dif- for gas-phase copolymerization. The ethylene–
ferent concentrations of hydrogen and propene rubber needed for impact copolymer is
comonomer, leading to bimodal polymer qual- produced in an FBR at temperatures up to
ities (with respect to molecular mass and/or 100 C and a pressure of 15 bar. A second (or
comonomer concentration). This is achieved by even third) FBR can be added to the process
Polypropylene 19
for tailoring the rubber phase with respect described process design PP manufacturers
to molecular weight and comonomer can produce a wide range of product qualities,
concentration. but this must be balanced with the capital
The Mitsui Hypol bulk polypropylene pro- investments needed for full-fledged reactor
cess was originally based on two stirred auto- train.
clave reactors in place of the loop reactors
shown for the Spheripol process in Figure 12,
followed by two stirred FBRs. In the Hypol II 6. Product Finishing
process loop reactors replace the stirred auto-
claves. The gas-phase reactors are also used to The so-called dry end of a polymerization
produce homopolymers, enabling a broader plant starts at the discharge point from the
polymer-property window. last polymerization reactor and involves
The design and operation of the ExxonMobil deactivation, powder purification, and in most
PP process technology was originally based on cases melt compounding. Even if the polymer is
the Hypol design but has been modified with planned to be sold as powder, it must be stabi-
respect to gas-phase reactor operation. lized, as PP is far more susceptible to radical
Borealis has developed the Borstar poly- attack and degradation than PE. In any case, the
olefin process technology for the production transport and sale of PP can be handled both in
of PE and PP. A basic design of the Borstar PP bulk form (silo trucks or railway cars) and in
technology is given in Figure 16. The platform packages of various sizes, ranging from 25 kg
for making homopolymers and random copoly- bags to big-bags and octabins (corrugated card-
mers is based on a loop reactor followed by an board containers with PE-film inlays) contain-
FBR. The loop reactor allows polymerization ing up to 1000 kg.
under sub- or supercritical conditions. For PE Melt homogenization can provide several
this is done in propane and PP is polymerized in functions for the final product, ranging from
liquid propene. The advantage of running the homogenization (especially relevant for poly-
loop reactor under supercritical conditions is mers with a bimodal or generally broad molec-
the possibility of increased hydrogen and ular mass distribution (MWD) and heterophasic
comonomer concentration without the forma- copolymers [43]) through the dispersion of
tion of gas bubbles. In the next section an stabilizers and other functional additives to
ethylene–propene rubber is made in an FBR generating a product with homogeneous parti-
for producing impact copolymers. Powder cle (pellet) size. With increasing plant size,
transfer from the homopolymer FBR to the the respective equipment has also increased
rubber gas-phase reactor allows complete gas in throughput from 15–20 t/h in 1990 to
separation for better design of the rubber. An 50–75 t/h in 2010. In addition to cost, extruders
additional rubber FBR can be added to the are selected according to the following factors:
reactor train if high elastomer contents are powder morphology, product melt flow rate
required. (MFR) range, melt filtration needs, devolatal-
The hybrid processes are the workhorses of ization options, throughput flexibility, temper-
the polypropylene industry. Loop reactors dom- ature control, mixing needs, and additive feeds.
inate the bulk polymerization processes due to Single-screw machines are hardly used any
the better heat-transfer capacity and thus higher more, while twin-screw extruders with co-rotat-
production rates. Hybrid processes contain up ing and segmented screws dominate the market
to six reactors split between a sector dedicated because of their high flexibility and good mix-
to homopolymers and random copolymers and ing efficiency. A balance between mixing
a second sector used for the production of a quality and polymer degradation must always
rubbery phase (ethylene–propylene rubber) to be kept, with temperature (220–260 C) and
increase the toughness of the polymers. This specific energy input (SEI) as decisive
second block contains only FBRs. The two factors. A gear pump between the die plate
blocks are almost always separated by a kind and the discharge end of the screw can
of gas lock/flash in order to better control the be used both to reduce the SEI and to increase
properties of the different phases. With the the throughput.
j) Purge bin
a) Prepolymerizer; b) Loop reactor; c) First gas-phase reactor; d) Second gas-phase reactor; e) Third gas-phase reactor; f) Coolers; g) Separators; h) Low-pressure degasser; i) Dryer;
Figure 16. Borstar PP process scheme (four-reactor setup)
Polypropylene
20
Polypropylene 21
Pelletization is possible in strand form or in An approximate distinction is drawn between

underwater systems. Modern polymerization additives (up to 1 wt% addition, typically ca.
plants are, however, too big for the former in 0.05–0.3 wt%) and fillers or reinforcements (5–
which several melt strands from the die plate 40 wt% addition). The most important additives
are quenched in water for solidification and [44] are antioxidants and UV stabilizers.
then chopped by high-speed cutters into 2–5 More than PE, PP must be protected against
mm long cylinders. In underwater systems, oxidation, particularly above 100 C. The dom-
high-speed knives rotate against the extruder inant reaction is chain scission by free-radical
die plate to cut off short lengths of the molten attack at the tertiary carbon atoms of the back-
extrudate. The insulated die plate is immersed bone. The different types of antioxidants can be
in water, which solidifies the lens-shaped pel- divided into:
lets and also transports them to a sieving and
drying device. While nitrogen must be used for
H donors/primary antioxidants (e.g., steri-
powder conveying up to the extruder, air can be
cally hindered phenols; active mostly at
used for pneumatic pellet transport afterwards.
application temperatures)
The direct sale of nonstabilized or (mostly)
spray-stabilized PP powder is very limited. Hydroperoxide decomposers/secondary
While in the 1990s Himont (presently antioxidants (e.g., phosphites; active
LyondellBasell) still assumed that the spherical mostly at processing temperatures)
powders resulting from fourth-generation cata- Radical scavengers [hindered amine light
lysts and the Spheripol process would be suit- stabilizers (HALS); specific against UV-
able in nonpelletized form for large parts of the induced radicals)
market, applications are largely limited to roto-
molding, melt-blown fiber spinning, and use as In Figure 17 the autooxidation process and
supports for liquid additives like peroxides. the principle of antioxidants in polymers is
While energy-intensive extrusion and pelletiza- illustrated. The reaction starts on the left-
tion operations could be saved, the limited hand side of the scheme, where scission of
choice of additives and the homogenization the chain (R) initiated by, e.g., heat and shear
problems more than compensate these advan- to give the alkyl radical (R ) is shown. The alkyl
tages in most areas. radical can be directly deactivated with a radi-
cal scavenger or forms the peroxy radical
6.1. Additives (ROO ) in the presence of oxygen. Both the
H donor (primary antioxidant) and the radical
Nonpolymeric additives generally allow further scavenger can work as antioxidant here. Other-
modification of the properties of polyolefins. wise, ROO will react with other chains by
Figure 17. General scheme of inhibition of thermo-oxidative degradation of PP

22 Polypropylene
hydrogen abstraction (cleavage of the weakest but also simple glyceryl monostearate, reduce
C–H bond). This leads to the formation of the surface resistivity from >1013 to ca. 107 V.
hydroperoxide (ROOH), which is relatively The mechanism involves slow diffusion of the
unstable and decomposes into the reactive alk- additive to the surface, where it picks up atmo-
oxy radical (RO ) and the hydroxy radical spheric moisture. Time and humidity are impor-
( OH). ROO reacts with the H donor to tant, and while at 50% RH most of the
form stable ROOH. Hydroperoxide decompos- recommended additives are satisfactory, dryer
ers (secondary antioxidants) are used to induce environments require the use of fatty amine
(from ROOH) the formation of inert alkoxy derivatives.
(RO ) and hydroxy radicals ( OH) to avoid Slip and antiblocking agents are mainly used
chain fracture, which otherwise results in dis- in film production where high-speed handling
coloration and brittleness. requires a controlled reduction in frictional
A further contribution to long-term stabil- forces; 0.1–0.5 wt% of oleamide, erucamide,
ity is the use of acid scavengers for neutraliz- or mixtures thereof is usually sufficient. Fine,
ing decomposition products of ZN catalysts, spherical particles of silica or other minerals
especially HCl. The most common is Ca stea- prevent layers of film adhering to each other
rate (0.05–0.1 wt%), which also prevents during storage.
equipment corrosion. It behaves as a mild Nucleating agents for PP crystallization [45]
slip agent and suppresses attack of HCl on are applied both for improving processability
certain antioxidants. Stearates or oxides of and final performance. The combination of
zinc and magnesium are also in use, and moderately slow crystal growth at large under-
synthetic hydrotalcite (a hydrated magnesium coolings together with the practical absence of
aluminum hydroxycarbonate) is the latest sporadic nucleation makes iPP, which melts at
addition to this class. 160–170 C but crystallizes at 100–130 C, an
Besides the thermomechanical loading to be ideal material for controlled nucleation. In
expected for a specific application, additive addition, the different crystal modifications of
packages are also defined by critical environ- iPP (a, b, and g) can be controlled in their
mental interactions, e.g., NOx with fibers or respective expression, and thus affect the
detergent solutions with appliance components. mechanical and optical profile of the material.
The choice of stabilizer is further influenced by A wide range of chemically very different
regulatory constraints such as global or specific substances (see Fig. 18) can be used; decisive
migration limits. is the crystalline and not the molecular struc-
Continuous outdoor exposure also requires ture, because nucleation happens by epitaxy
protection from the damaging effects of UV and “lattice matching”. These additives must
radiation, for which UV absorbers (in the sim- be distributed very well. Different routes can be
plest case carbon black or TiO2) or radical applied here, and the Borealis nucleation tech-
scavengers are used. Polymer photooxidation nology (BNT) has a special position: Because
results from the combined action of light and the dispersion occurs already during the polym-
oxygen. First, the polymer chain is excited by erization step, a very low concentration of a
the absorption of light (hn), and UV absorbers polymeric nucleating agent is sufficient for
act in this stage of degradation. In the presence optimum performance [46]. Improvements of
of oxygen and further light, an alkyl radical stiffness (modulus) and the related heat deflec-
(R ) is formed, and radical scavengers (HALS) tion temperature by selectively nucleating the a
are used to scavenge radicals. In contrast to UV modification is one of the key targets. Another
light, the effect of high-energy radiation like target of a nucleation is improved transparency
electrons or g rays cannot be prevented by and clarity; here nucleation will even help to
additives alone; polymer design measures prevent haze increase during steam sterilization
must be considered here. (normally caused by postcrystallization at the
Antistatic agents act against static charges elevated temperature used). As crystallization
and resulting dust deposits on many plastics; is also accelerated, nucleation also helps to
0.2–1.0 wt% of polar additives such as poly- reduce cycle times in injection molding and
ether fatty amide and fatty amine condensates, to allow higher speed in extrusion processes.
Polypropylene 23
Figure 18. Classification of nucleating agents for PP
Specific b nucleation is a useful tool for most important filler, while calcium carbonate,
improving impact strength and reducing crack kaolin, wollastonite, and mica are used to a
growth in pipe materials, where it has already lesser extent.
been used for many years [20]. Careful balanc- When using glass fibers (GF), which give
ing of the overall additives recipe is essential in the highest strength, further improvements are
any case, because both adverse and beneficial possible by modifying the fiber surface (siz-
interactions occur between some of the ing) and using compatibilizers (adhesives).
components. Both short (S) GF having an initial fiber length
of 3–5 mm and long (L) GF are applied. While
SGF compounds are produced in normal melt
6.2. Compounding and Blending mixing, LGF–PP is produced by impregnating
continuous GF rovings with a high-MFR
For PP, modification after the polymerization matrix and cutting the resulting strand after
process plays a major role in expanding the solidification to 10–15 mm length. Special
property range. Besides the already mentioned processing operations are required in the latter
co-rotating twin-screw extruders with special case to avoid excessive fiber breakage [48],
mixing elements for improving the quality of but the resulting material is well suited for
dispersion and resulting phase structure, other metal replacement, especially in the automo-
kneaders and mixers are used for special tive area.
requirements. The Farrel kneader, for example, Organic reinforcing fibers are obtained
has a large blending chamber for adding EPR, from natural (regenerative) sources such as
EPDM, and other elastomers in form of a bale, hemp, flax, sisal, and wood, including high-
while the Buss co-kneader allows more gentle crystallinity man-made cellulose fibers [49].
dispersion of glass fibers by combining rotating The strength of glass fiber reinforced materials
and pulsating melt movement. is not achieved with such additives and the lot-
Modifications of mechanical properties as to-lot variations of natural fibers are a problem;
well as shrinkage and thermal expansion are the full combustibility and improved sustain-
possible through the addition of fillers and ability of such composites are, however, seen as
reinforcements of mostly mineral nature. The an advantage.
respective effects are determined by the prop- Modification or blending with elastomeric
erties of the base polymer as well as by the or polymeric components for further expand-
quantity and nature of the filler [47]. Talc with ing the property range of PP is discussed in
an average particle size of 0.6–10 mm is the Section 7.4.
24 Polypropylene
6.3. Reactive Modification The chain structure, i.e., the presence of

stereo- and regiodefects
An even broader variety of structural modifi- Nucleating additives (see Section 6.1) [53]
cation is possible by reactive post-reactor
processes. The earliest version was targeted As for all semicrystalline polymers, process-
at modifying the molecular mass distribution, ing history and component geometry will play a
whereby the preferential splitting of PP chains further role in affecting the final properties, and
in radical reactions allows tailored production the evolution of performance over time will
of narrow molecular mass distributions [50]. depend on a proper stabilization.
This process, known as visbreaking or (con- While a proper parameter for the average
trolled rheology) CR process, is best applied chain length is the weight average of the molec-
to PP homopolymers or random copolymers, ular mass distribution Mw in industrial practice
leading to products with higher MFR and polymers are normally defined by their melt
broader Newtonian region of the viscosity flow rate (MFR), which in the case of PP is
curve. Often liquid peroxides are in use, which determined at 230 C and 2.16 kg load. The two
are sprayed under nitrogen onto the warm parameters are related via the melt viscosity,
reactor powder before it is fed to the pelleti- where the zero-shear viscosity h0 is propor-
zation extruder. In large-scale plants, vis- tional to the 3.4-th power of Mw [43]. At higher
breaking also allows the production of a shear rates normally encountered in processing
multiplicity of grades from one reactor setting. and more characteristic for MFR determina-
While for reactor grades of PP (with broad tion, the dependence is still greater than a power
MWD), stiffness increases with increasing of two because much chain entanglement still
MFR, it remains constant or is reduced for exists. The exact correlation, however, also
visbroken (narrow-MWD) grades. At the same depends on the broadness (polydispersity,
time, transparency and surface gloss are rather defined as ratio between Mw and the number
improved, and these grades have significant average of the molecular mass distribution Mn)
advantages in fiber spinning and cast-film and shape of the molecular mass distribution.
processes. PP-H grades are commercially available in an
Other reactive modification steps for PP are MFR range of 0.3–1000, corresponding to an
also mostly based on radical-initiated grafting Mw of 500–20 kg/mol and covering applica-
reactions [51]. The potential applications of tions from sheet and pipe extrusion to high-
this technology range from the production of speed fiber spinning.
long-chain branched PP with high melt With modern ZN catalysts a single-step
strength (strain hardening) offering advan- reaction gives a polydispersity Mw/Mn of 4–
tages in foaming [52] and other processes 6, while with older catalyst types (TiCl3, used in
with strong extensional flowlike extrusion diluent-based slurry processes) Mw/Mn can be
coating, via the stabilization or partial cross- up to 8. Broad or bimodal molecular mass
linking of phase structures (to the point of distributions are achieved by multistage polym-
thermoplastic vulcanizates, TPVs) up to polar erization with varying hydrogen feed and/or
modifiers (e.g., by grafting with maleic temperature, while narrow molecular mass dis-
anhydride). tributions with Mw/Mn down to ca. 2 are mostly
achieved by visbreaking (see Section 6.3). Both
versions have specific advantages: High poly-
7. Properties dispersities deliver higher crystal orientation
through flow-induced crystallization [54, 55],
7.1. Homopolymers especially in injection molding, which results in
higher stiffness and heat resistance and is con-
For PP homopolymers (PP-H), the mechanical sequently of interest for technical applications.
and optical performance is determined by: Narrow-MWD grades crystallize more slowly
[53] and have advantages in film casting and
The average molecular mass and molecu- fiber spinning, but also for special molding
lar mass distribution applications like film hinges.
Polypropylene 25
The chain structure of PP homopolymers is much more randomly distributed along the
affected by stereo- and regiodefects, the latter chain. At the same time, higher a-olefins
only being relevant for single-site catalysts like 1-butene and 1-hexene can be copoly-
(SSC). An absolute quantification of stereo- merized more easily.
regularity is only possible by 13C NMR spec-
troscopy in solution, with isotactic triads (mm) A very special case of PP-H is syndiotactic
or pentads (mmmm) being used for quantifica- polypropylene (sPP), which is characterized
tion. Commercial PP has a pentad regularity of by significantly lower crystallinity and
>92%, and very high stereoregularity of >97% stiffness [58]. It can be polymerized with
is achievable with modern ZN catalysts and specific SSCs, both MC and constrained-
suitable external donors, even without remov- geometry types, and varied over a wide
ing any soluble (atactic) byproduct. Besides a range by controlling the relative content of
broad MWD, high isotacticity is a further tool isotactic, syndiotactic, and atactic sequences.
for reaching highest stiffness [54]. Alternative Its commercial relevance is, however, so
measures for isotacticity are FTIR spectroscopy far rather limited, largely as a consequence
(in the solid state, where sample preparation of the high solubility in various organic
must be considered) and the content of hep- solvents.
tanes-soluble fraction. For some applications An overview of the most relevant properties
like nonwovens with thermobonded fibers or of different PP product families can be found in
biaxially oriented PP (BOPP) film, processing Table 6.
can be facilitated by reduced isotacticity or
chain regularity in general. This is readily
achieved by lowering the donor feed in polym- 7.2. Random Copolymers
erization, or by introducing small amounts of
copolymerized ethylene. Similar to the variation of density and mechan-
When isotactic PP is produced by SSC or, ical properties when moving from high density
more specifically, metallocene catalysts (MC), polyethylene (HDPE) to linear low density
three major product-related differences over polyethylene (LLDPE) by copolymerization
ZN catalysts are evident [56, 57]: with higher a-olefins like 1-butene (C4) and
1-hexene (C6), the properties of PP can be
1. The polymers have a much lower poly- modified already in one-step polymerizations.
dispersity, with Mw/Mn in the range of Incorporating ca. 2–5 wt% of ethylene (C2) into
1.8–3. Also, the amount of solubles, meas- the chain lowers the overall crystallinity, gives a
ured both in cold xylene (XCS) and in broader softening range with reduced melting
boiling hexane (C6) is reduced significantly, points (see Figure 19), lowers the glass transi-
as is the level of hydrocarbon emissions. All tion temperature, increases the fraction of sol-
of these advantages can be explained by the uble polymer, and improves transparency and
reduced amount of oligomers generated in surface gloss [59]. Ethylene–propene random
SSC-based polymerization. copolymers (EP-RACOs) are somewhat
2. Besides the stereoregularity, the presence of tougher than homopolymers, and do not exhibit
regiodefects (misinsertions of monomers) the familiar stress-whitening behavior of the
must be considered. Most relevant are the tougher copolymer impact grades. These
2,1 regiodefects commonly defined as the changes for EP-RACOs are determined by
sum of 2,1-erythro and 2,1-threo regiode- the amount of comonomer and its distribution
fects, which can be present up to 2 mol% along the chain, with significant differences
depending on the MC type. While MC- resulting from catalyst and donor type. The
based PP-H types can have a high isotactic- randomness or rather the probability for iso-
ity, these defects cause a significant reduc- lated C2 units in the chain decreases with
tion of the melting point and limit both heat increasing amount, leading to phase-separation
resistance and stiffness [57]. phenomena in case of ZN catalysts at contents
3. All chain defects, but also the insertions of >5 wt%; higher values can be achieved with
comonomers—and specially ethylene—are metallocene catalysts.
26
Table 6. Overview of most relevant PP properties for various grade families
Unmodified PP grades Compounds
Soft (1) Standard (2) Random (3) Impact (4) HCPP (5) Talc Glass fiber Filler & elastomer
Polypropylene
Filler content, wt% 0 0 0 0 0 20–40 20–50 10–25

MFR (230 C/2.16 kg). g/10 min 0.5–15 0.3–1000 0.3–100 0.5–100 2–50 0.5–15 1–10 0.5–50
Density, g/cm3 ISO 1183 0.900 0.905 0.900 0.900 0.905 1.05–1.25 1.04–1.22 0.95–1.15
Melting point, C ISO 3146 135–150 160–167 135–150 160–167 165–169 164–168 164–168 164–168
Glass transition, C ISO 6721-7 –10 to 0 0–4 –10 to 0 0–4 0–4 0–4 0–4 0–4
60 to 35 60 to 35 60 to 35(5) 65 to 45
Flexural modulus, MPa ISO 178 300–700 700–1500 1200–1900 >1900 2500–5000 5000–9000 1000–2000
Yield stress, MPa ISO 527 15–25 25–40 20–30 25–40 40–50 25–35 70–140 15–30
Extension at yield, % ISO 527 15–25 5–15 15–25 5–15 4–10 2–4 2–4 5–15
Extension at break, % ISO 527 >300 20–800 30–1000 20–200 5–40 15–30 3–5 6–10
Charpy IS, kJ/m2 ISO 179 1eU
þ23 C n.b. 10–n.b. 15–n.b. 50–n.b. 30–n.b. 10–n.b. 25–50 n.b.
20 C 30–n.b. 3–80 5–n.b. 10–n.b. 3–40 2–20 20–40 20–n.b.
Charpy NIS, kJ/m2 ISO 179 1eA
þ23 C 10–n.b. 2–25 5–50 10–n.b. 2–4 2–12 7–20 15–35
20 C 5–50 1–10 2–15 5–60 1–3 1–5 4–15 5–25
Vicat softening temperature, C ISO 306
Vicat A 80–120 100–140 85–110 140–150 150–160 150–160 140–160 100–130
Vicat B 30–60 50–90 35–65 70–100 100–120 80–100 100–130 40–60
Heat deflection temperature, C ISO 75
HDT-A 35–45 40–60 40–55 50–70 60–80 60–90 130–150 40–60
HDT-B 50–70 70–100 55–75 100–120 110–130 120–140 150–160 70–100
Gloss 20 , % ISO 2813 30–60 60–80 60–80 70–80 70–80 5–30 20–40 20–40
Ball indentation hardness, N/mm2 ISO 2039-1 20–40 30–80 30–50 80–90 >90 80–90 100–120 40–60

1: High-EPR heterophasic and random-heterophasic copolymers; 2: Homopolymers; 3: Random co- and terpolymers; 4: Heterophasic copolymers; 5: Homopolymers and low-EPR HECOs.

IS: impact strength; NIS: notched impact strength; n.b.: not broken.
Polypropylene 27
Figure 19. Effect of comonomer effect in EP random copolymers on melting point (^) and crystallinity (&) (data from [60])
All changes in mechanical properties and lattice. While for the g phase some advantages
optics are related to a reduced crystallization regarding transparency and ductility can be
speed and a lower lamellar thickness caused by found and promotion by a-nucleating agents
the comonomer-related chain defects [60]. This is possible [45], no specific technical benefits of
also results in a better quenchability of EP- the d phase have been identified so far.
RACOs to the mesomorphic state, making them
ideal materials for highly transparent cast films,
where also the broader melting or sealing range 7.3. Impact Copolymers
is an advantage.
The increased amount of XCS- and C6- Sections 5.2 and 5.3 describe multistage
soluble material in EP-RACOs is, however, copolymerization systems for producing high-
limiting their applicability in this and other impact copolymers of PP. These combine a
areas, especially when packaging of food or crystalline PP matrix (produced in the first
pharmaceutical products is the intended use. A 1–2 reactors) with embedded particles of
better balance between softness and solubles EPR and PE (produced in one or more follow-
content is possible with C4 copolymers, per- ing reactors) giving impact and low-tempera-
haps because the solubles are produced at semi- ture resistance [63]. While often still referred to
exposed catalyst sites more easily accessible to as block copolymers, the correct term for
ethylene [59]. The higher Tg and lower tough- such products is heterophasic copolymers
ness of C3/C4 copolymers can be compensated (EP-HECOs) or PP impact copolymers.
by producing terpolymers with C3, C4, and C2, In-reactor production of EP-HECOs has
for which also other advantages like improved been found to be more effective than com-
processability are found [61]. Typical applica- pounding (see Section 6.2) for producing
tions for these specialty grades are sealing impact-modified PP. On the one hand, cost
layers in coextruded films. and energy are saved by eliminating the exter-
Common to all random copolymers is a shift nal elastomer components and the compound-
in crystalline structure from the predominant ing step, and on the other hand morphology and
monoclinic a modification to the orthorhombic performance advantages are achieved. The
g phase. A new crystal modification was iden- structure of these reactor blends has been
tified in MC-based copolymers with higher shown to be rather complex: Besides the PP
a-olefins [62]. The trigonal d modification matrix and the amorphous ethylene–propene
allows better incorporation of side chains rubber (EPR), they can also comprise crystal-
resulting from these comonomers in the crystal line copolymers having both PP and PE
28 Polypropylene
crystallizable segments, and even neat high- matrix–dispersed phase compatibility, and the
density PE (HDPE). The elucidation of processing conditions.
this complex structure has been progressing One critical factor is already the catalyst
by combining cross-fractionation with morphology. In the production of EP-HECOs,
various thermal, spectroscopic, and chromato- the morphology of the produced polymer
graphic techniques correlating the molecular particles replicates the morphology of the
structure to the performance of these materials employed catalyst particles. Spherical
[64, 65]. aggregates of microcrystalline MgCl2 are con-
Since their development in the 1970s [11], ventionally used as support material for
these materials have conquered a wide range of the TiCl4 in ZN catalysts [63], offering a
applications from seemingly trivial packaging porous structure with large surface area.
uses to technically complex parts. The matrix The maximum amount of EPR/PE which
consisting of a PP homopolymer or, in the can be accommodated in the polymer granule
case of random heterophasic copolymers, an without causing stickiness appears to primar-
EP-RACO is responsible for retaining good ily depend on the porosity of the catalyst
high-temperature performance and adequate particle. Figure 20 shows the difference in
stiffness, while the particulate EPR/PE phase distribution of the EPR phase between the
contributes good toughness. Depending on original reactor “powder” (defined by the
the composition of the EPR component the catalyst structure) and the pelletized or proc-
respective Tg can be as low as 60 C, resulting essed polymer [66].
especially in improved impact performance at While details of the EPR composition and its
subzero temperatures. While such low glass viscosity ratio relative to the matrix are highly
transitions can be achieved by a high ethylene relevant for product design in detail, a key
content in the EPR phase, high propene content factor for increasing the energy absorption
in the same will enhance the compatibility to capacity is to increase the EPR weight fraction
the matrix, allowing better transparency [21]. in EP-HECOs. Here, the toughness is improved
Overall, the size, shape, internal structure, and by reducing the interparticle distance, resulting
spatial packing of the dispersed EPR domains in a stepwise brittle-to-tough transition as a
(which generally range from 0.2 to 4 mm in function of EPR concentration, combined
average diameter under equilibrium conditions) with linear reduction of tensile modulus (see
are critical parameters affecting not only the Fig. 21). The blend concentration at which this
mechanical performance but also properties transition occurs is determined by the chemical
like surface appearance and migration. The composition of matrix and dispersed phase as
morphology is a complex result of the rheolog- well as their viscosity ratio, but also on the
ical parameters of the single components, the geometry and test conditions. For PP/EPR
Figure 20. Relation between powder morphology (left) and granule morphology (right), revealed by RuO4-contrasted
transmission electron microscopy (TEM); high-impact EP copolymer type with 26 wt% ethylene and 22 wt% elastomer (EPR;
xylene-soluble fraction); EPR is dark because of lower crystallinity; PP matrix and PE inclusions in particles are light; scale
bars 2 mm
Polypropylene 29
Figure 21. Effect of EPR concentration on stiffness (flexural modulus, ISO 178) and toughness (Charpy notched impact
strength, ISO 179 1eA) at 23 C for a series of random-heterophasic copolymers with constant matrix and EPR composition
(data from [21])
blends the phase transition and the respective For the still-used external EPRs or ethyl-
development of the mechanical performance ene–propene–diene elastomers (EPDM) based
has been comprehensively discussed [67]. on vanadium catalysts, a two-stage process in
which the elastomer is first compounded with
PP to give a 50–70 wt% masterbatch of the
7.4. Composites and Blends rubber as free-flowing granules is commonly
used. Only rather C2-rich EPR types are suf-
An extension or even an alternative to multi- ficiently crystalline to be pelletized in pure
stage polymerization with the production of form [69]. Also different PE types can be
EPR can be the addition of external elastomers. added in minor amounts for property design.
This was historically the first approach to In the presence of an EPR phase, preferably
impact modification of PP, for example, blend- reactor-made, the PE will be located inside
ing of PP-H with 10–20 wt% of polyisobuty- and towards the center of these rubber droplets
lene (PIB) elastomer. Nowadays this route is [70], and mostly enhances the room-tempera-
instead used for fine-tuning the property pro- ture impact strength and limits shrinkage.
file. High impact strengths can be achieved with Addition of HDPE is especially suitable for
ethylene-co-octene or -butene plastomers and the reduction of stress whitening or scratch
elastomers based on polymerization with sin- sensitivity.
gle-site catalysts in solution [68]. The Blends of PP with other polymers were
comonomer content and the molecular mass studied intensely in the 1990s and were even
of these homogeneous copolymers can be var- commercialized in some cases. Three blend
ied over a wide range, allowing applicability in partners were most studied (in order of increas-
a wide range of stiffness and MFR. For special ing polarity): polystyrene (PS), poly(methyl
purposes, styrene-based elastomers of the di- or methacrylate) (PMMA), and polyamide-6
triblock type have found uses despite their (PA-6). In all cases, besides viscosity matching
higher price. Mostly hydrogenated styrene– as with other multiphase PP systems, also the
butadiene triblock systems (SEBS) are used, use of an appropriate block or graft copolymer
which can be designed in a wide range of as compatibilizer is required for delivering
compatibility and viscosity by varying the good property combinations [71, 72].
molecular mass and individual block lengths. While PS can add stiffness, surface gloss,
30 Polypropylene
and print- as well as paintability, PA-6 was 7 kg, with a wide span between developing
shown to deliver a good combination of modu- countries, the BRIC-countries (e.g., India at 2.1
lus and temperature resistance, especially when kg), and highly industrialized countries (West-
combined with glass-fiber reinforcement. The ern Europe 18.4 kg) [73].
most relevant example of blend commerciali- The wide range of PP applications [74]
zation was the Hivalloy product line of Himont clearly results from the possibility to adapt
(now LyondellBasell), based on a reactive mod- the polymer structure, its processability, and
ification concept with PS and PMMA as blend final performance to many conversion routes
partners. Introduced on the market in 1994 and and requirement profiles. A general trend
produced as pure blends but also reinforced towards material substitution has allowed PP
with glass fibers, the product line was stopped to grow by replacing more costly polymers like
in 2001 and finally considered a commercial polycarbonate (PC) and acrylonitrile–butadi-
failure. ene–styrene terpolymers (ABS), but also
“traditional” materials like glass and metal.
This process, often involving a redesign of
8. Processing and Applications the respective application (e.g., going from
metal cans to stand-up pouches for food
In the global application distribution for PP (see packaging) and can result in a significant over-
Fig. 22) the extrusion segments (films and all reduction of raw material and energy con-
fibers, but also coating and pipe extrusion) sumption (see Chap. 9).
used slightly more than 50%, while injection
and blow molding made up less than 50% of the
consumption. In 2010, the global PP market 8.1. Injection Molding
was about 50 106 t/a, with more than 50% of
this being used in the Asian-Pacific region. Injection molding is used for a wide range of
Further perspectives for volume growth can packaging material and general purpose items
be illustrated best with the annual per-capita with limited requirements, as well as for most
consumption: The global average in 2010 was of the technical uses of PP. As these two
Figure 22. Global application distribution for PP in 2010 (CMAI data, after [73])
Polypropylene 31
segments require quite different materials and

processing considerations, the simpler segment
is discussed here, and the technical segment in
Section 8.6.
Two main groups of factors define the selec-
tion of PP grades for injection molding appli-
cations: part geometry, especially the flow ratio
(i.e., the ratio of longest path to the section
thickness) and the complexity of the part, and
the thermomechanical requirements in the
respective application. A simple increase of
the MFR, for which a range between 1 and
100 g/10 min (230 C/2.16 kg) is presently
available for injection molding, will allow
thin and narrow cavities to be filled even
over longer distances, but the impact strength Figure 23. Integral hinge (Courtesy of the “Propathene”
of such materials will be greatly reduced. Com- Business, ICI Chemicals & Polymers)
pensating this by moving from PP homopoly-
mers to random or heterophasic copolymers warpage in molded products results from aniso-
will in turn compromise stiffness, heat resist- tropic shrinkage and reflects both internal
ance, and transparency. stresses and crystal orientation. PP grades
In addition, the formation of crystalline with high MFR and/or narrow MWD (low
superstructures like shear-induced skin layers polydispersity) can help to reduce this problem
[75] is decisive both for the solidification speed [60].
and the mechanical strength of the molded An important practical aspect of PP con-
parts. The presence of a high molecular mass cerns its ability to form strong integral hinges,
fraction is decisive here, which makes highly such as in a lidded box, where the lid is
polydisperse grades more prone to skin-layer permanently attached to the base by a thin
formation. Further polymer-related factors are web of polymer along the whole of one edge
anisotropic fillers and nucleating agents [76], (Fig. 23). This web, about 0.25–0.6 mm thick,
but melt temperature and flow speed are also can be produced directly in the molding pro-
relevant. Thus, like in all semicrystalline poly- cess. An initial flexing of the hinge while
mers, the processing parameters become a part slightly warm induces the correct molecular
of the final property design. Standard process- orientation to permit repeated opening, even
ing conditions used for PP are [77]: at subzero temperatures. In the laboratory, such
hinges have withstood 23106 flexes without
Melt temperature Tm: 200–265 C failure [74].
Apart from this extreme case, injection-
Injection pressure pinj: 50–150 MPa
molded parts of PP range in wall thickness
Injection speed vinj: 100–400 mm/s from 0.3 mm (e.g., for thin-wall dairy cups)
Mold (wall) temperature Tw: 30–60 C to 10 mm (e.g. for pressurized ion-exchanger
cartridges in coffee vending machines). Mostly,
As a rule of thumb, lower Tm values are used however, wall thicknesses above 4 mm are
for higher MFRs, and lower Tw values for avoided by partial foaming (see Section 8.6)
thinner parts. This may even lead to partial or by gas- or water-assisted injection molding.
quenching, a phenomenon which is discussed These seemingly complex processes have been
in Section 8.4. Besides mechanics and optics, developed to a degree of practical simplicity,
the resulting crystalline structure also deter- making them useful even for mass production
mines the extent and anisotropy of in- and of articles like beer crates and toys.
post-molding shrinkage. Linear post-molding General purpose items injection molded
shrinkage of PP is 1.0–1.5%, of which 85% from PP can largely be categorized into three
occurs within the first 24 h. Distortion or groups [74]:
32 Polypropylene
1. Household articles and general consumer 0.4–1.0 MPa [79]. High molecular mass poly-
products, covering such diverse uses as mers having an MFR of ca. 1.0–2.5 g/10 min,
kitchenware, garden furniture, toys, and combined with low melt temperatures at the die
luggage. Kitchen bowls and storage contain- of 200–210 C, provide a suitably stiff melt. If the
ers were among the first articles produced melt stress in a heavy PP parison exceeds ca.
from PP, and outdoor furniture such as 20 kPa, then the resulting tension thinning will
stadium seats also already has a long be troublesome as regards parison stability and
application history. Nevertheless, the devel- uniform wall thickness. EBM is cheaper and
opment of highly transparent molding simpler to operate, but the produced articles
grades and improved UV stabilization con- will always show a certain degree of surface
cepts have improved the possibilities roughness limiting the transparency and gloss. In
significantly. modern processing equipment, control of the
2. Packaging systems, ranging from thin- final container wall thickness by modifying
walled cups and beakers through buckets the parison thickness along its extrusion direc-
and pails to folding boxes and crates for tion can significantly improve appearance and
transport packaging. The requirements vary performance [80]. A variation of the EBM pro-
broadly, but weight reduction and materials cess is the blow, fill, and seal (BFS) process,
savings have been the main factor in recent mostly used in the medical area for ampoules and
years. High-crystallinity PP grades, very infusion bottles. While LDPE is mostly used in
often as heterophasic copolymers with a this process, special PP grades are also gradually
good subzero impact performance, domi- becoming available.
nate the transport packaging segment, while Injection blow molding (IBM) and the more
nucleated random copolymers give the best common injection stretch blow molding
product visibility. (ISBM) are two-stage processes in which first
3. Medical articles and pharmaceutical a preform is produced by injection molding.
packaging systems have special require- Blowing (in IBM) or a sequence of stretching
ments in terms of allowed additives and and blowing (in ISBM) takes place in a second
required purity. Disposable syringes were mold which maintains the high-definition
the first PP application here, and already neck and thread of the preform. In both cases,
required sterilizability as a further parame- the produced bottles or wide-mouth containers
ter. The entrance barriers for polymer pro- are characterized by better optical and
ducers are higher here, mostly due to the mechanical performance, but also by
long approval processes [78]. improved dimensional accuracy. Significantly
different polymers are required here [81]
which have an MFR of 10–25 g/10 min and
8.2. Blow Molding are preferably nucleated random copolymer
types in order to facilitate processing. While
For producing bottles, canisters, and other con- PP is used in much smaller volumes than
tainers, blow molding processes have been poly(ethylene terephthalate) (PET) for ISBM
employed mostly for PE for a long time already. bottles, it has a number of clear advantages in
While PP has been slower in the initial market water-vapor permeability and heat resistance,
development, advantages of this polymer, such which enable hot filling and/or steam
as better heat resistance and transparency, have sterilization.
enabled the gradual development of a signifi- Products from these processes are mostly
cant application volume. Two different pro- used for packaging in the food area (dairy
cesses with different degrees of complexity products, fresh juices, still water), the nonfood
and different requirements for the material area (household cleaners, dishwashing liquids,
used are distinguished here: cosmetics, body-care products), and also the
In extrusion blow molding (EBM) medical/pharmaceutical area. EBM processes
an extruded molten parison (tube) is transferred can also be used for technical applications like
to a mold in which the end is clamped and fluid containers for cars, dishwashers, and
it is inflated with low-pressure air at other household equipment. A special use for
Polypropylene 33
PP-based ISBM bottles are sterilizable baby and melt pumps before the 8–20 spinnerets
bottles, as well as reusable sports bottles. having 50–250 holes each. For the CF process,
Like in films or injection molding, multi- a long spinline is preferred which can combine
layer constructions resulting from coextruded spinning and finishing stages as well as out-of-
parisons (EBM) or two-component preforms line drawing options. An air-cooling gap of 2–5
can be used as precursors for the bottles m is needed between the die plate and the wind-
when special barrier properties are required. up roll. Line speeds up to 1000 m/min at the
Most commonly, a central layer of ethylene– spinning stage, increasing to 3000 m/min dur-
vinyl alcohol copolymer (EVOH) to reduce ing solid drawing over hot rolls, require com-
oxygen diffusion is combined with moisture- plex and expensive haul-off, drawing, and
protective outer layers of propene–ethylene windup sections. The product is preferably
random copolymer to give containers suitable sold as continuous yarn or tow.
for storing oxygen-sensitive food products. The BCF process is mostly used for carpet
face and upholstery yarns and characterized by
the addition of a “bulking” step after spinning
8.3. Fibers and Flat Yarns or spinning and orientation. The bulking or
texturizing at 140–160 C in a jet with com-
One of the biggest application areas of PP pressed air has a similar effect to the crimping
homopolymers are fibers and tapes as well as process used for other textile fibers, causing
their derivatives. The respective applications fibers to have a wavy to curly structure for
cover a wide range of physical forms, including higher volume. While the MFR range is the
increasing amounts of versatile nonwoven fab- same as for CF, broader molecular mass distri-
rics [82, 83]. Monoaxial orientation in the solid bution and higher crystallinity can give advan-
or semisolid state can be applied to conven- tages here.
tional spinneret yarns, as with polyamides and In spunbonding, filament spinning and web
polyesters, and to flat tapes made from extruded formation are integrated into one process,
film. These application forms differ in various yielding a continuous bonded mat of partially
respects listed in Table 7. oriented yarn as a consequence of some draw in
The three conventional PP fiber operations the venturi-type haul-off operating at up to
are continuous filament (CF), bulked continu- 5000 m/min. There is no further drawing as
ous filament (BCF), and staple fiber (SF). In the fiber is collected as a mat on the take-off
any case the formation of the primary molten belt for conversion into nonwoven fabrics.
fiber by extrusion through a die plate perforated These are used, for example, in geotextiles,
by many small holes is crucial. High melt furnishings, and carpet backing [85]. The bal-
temperatures (230–280 C) and melt flow rates ance between drawdown rate and orientation in
(MFR 10–30 g/10 min; preferably combined this process is influenced by the polymer
with narrow molecular mass distribution for molecular mass distribution.
high extensibility [84]) are applied on short Figure 24 depicts a compact shortspin pro-
extruders, mostly combined with manifolds cess for staple fiber production using a die
Table 7. Polypropylene fiber processes
Process Filament count, tex Product
Long spin 0.2–3.0 high-tenacity monofilament; drawing integral or separate; high output
BCF yarn 0.2–2.0 special case of long spin making only bulked continuous fiber
Spunbonded 0.2–2.0 venturi haul off; no 2nd stage draw; bonded mat output
Shortspin 0.2–40 compact unit; tow stretched and cut in line for staple
Melt blown 0.002–0.02 low orientation, very fine fiber; only bonded mat output
Fibrillated yarn 110–500 oriented slit film; fibrillated for baler twine, rope, etc.
Weaving tape ca. 110 nonfibrillated slit film for carpet backing, sacks, etc.
Strapping tape 500–1000 thick, oriented tape as a steel alternative

pffiffiffiffiffiffi
tex ¼ weight in grams of 1000 m of yarn; equivalent cylindrical fiber diameter in mm ¼ 37 tex.
34 Polypropylene
Figure 25. Melt blowing process

a) Extruder; b) Gear pump; c) Heated die; d) Hot air
manifold; e) Collector; f) Take-off roll
short, low-orientation fibers of very low diam-

eter onto a moving steel-web belt, where they
are bonded together and wound onto a roll. This
process produces nonwoven fabrics which are
of increasing importance for industrial wipes
and surgical wrap, and for a variety of filtration
Figure 24. Shortspin process applications, such as face masks made from
a) Spinneret; b) Quenched fibers; c) Air-jet cooling; bonded mats of very fine fibers. MB fiber
Courtesy of the “Propathene” Business, ICI Chemicals & webs have only limited mechanical strength
Polymers
and can be combined with spunbonded webs
in a so-called SMS structure.
containing ca. 40 000 holes. Cooling air jets For producing flat yarns, extruded film is
freeze the melt within about 20 mm so that used as the basis. Melt from a conventional slot
godet haul-off rolls can be placed only 1 m die is rapidly quenched with cold water or
away from the die. Orientation is achieved by water-cooled steel rolls to give low-crystallinity
the in-line stretching of this tow in an air oven, film, 50–250 mm thick (see Fig. 26). Razor-
followed by chopping in line to produce staple blade-type knives then slit this broad film into
[82]. Broad-molecular mass distribution poly- strips 5–20 mm wide, which are oriented in a
mers again give the necessary melt strength, hot air oven at 120–180 C by drawing between
while MFR requirements increase from 7 to 20 godet rolls at ratios in the range 5 : 1 to 10 : 1.
g/10 min as the filaments become finer. These Both film thickness and width diminish in this
find use in carpet face fiber, and diaper cover operation by approximately the square root of
stock applications. A useful feature of PP fab- the draw ratio. These yarns are preferably
rics made from fine fibers is the ability of woven into cheap textile structures used for
underwear garments to reduce clamminess by bigbags or food transportation like rice or grain
transferring moisture away from the skin to an bags.
outer absorbent layer. Polypropylene-based Fibrillated tape is another variety in the
fabrics are also used for sports clothing and “low-performance” area. While flat yarns are
socks, but the low melting point of PP calls for quite strong in the direction of draw, they are
special attention to the heat setting of the very weak in the transverse direction. With
average domestic iron. normal PP homopolymer, simply twisting
For the most recent production process high-draw-ratio tape induces spontaneous
(Fig. 25), melt-blown (MB) fibers, air is blown fibrillation. A web of irregular fine fibers is
through a very fluid polymer melt maintained at formed as the film splits down its length. The
high temperature to assist chain scission in the resulting product resembles a coarse sisal
spinning process itself [74]. Polymer MFR at twine, for which it is a good substitute. Such
the nozzle can range from 200 to 800 g/10 min fibrillated yarns can be tailored to specific
or higher, achieved by visbreaking with some applications by controlling draw ratios, thick-
residual peroxide in the polymer before extru- ness, and polymer. Nowadays, pin fibrillation,
sion. The specially designed die, having a row in which a co-rotating spiked roll contacts the
of nozzles along its width, sprays a stream of film just after slitting, offers more precise
Polypropylene 35
Figure 26. Flat tape/yarn production unit

a) Windup frame; b) Third godet stand; c) Hot-air annealing oven; d) Second godet stand; e) Hot-air orientation oven; f) First
godet stand; g) Simple film costing unit; h) Extruder; i) Film die; j) Water-cooled chromium-plated rolls or water bath; k)
Slitting unit; l) Starting drum; m) Individual precision flangeless bobbin wind up; Courtesy of the “Propathene” Business, ICI
Chemicals & Polymers
control over this step. The products are familiar The more common processing step is film
as baler twine, string, and some ropes. casting with extrusion from a slit die onto a
Highly oriented fibers or tapes are also the (relatively) cold roll. The so-called chill roll is
starting point for the production of self- kept at temperatures between 15 and 80 C by
reinforced PP parts [86, 87]. The ability to liquid cooling or heating, depending on the
reach very high specific strength in fiber spin- polymer processed and its final destination. If
ning processes by post-drawing in the solid or the film is applied directly after solidification in
semi-solid state is used in combination with this step, in which only a limited degree of
weaving and sintering of such high-strength PP orientation in machine direction is achieved, it
fibers to plates for later thermoforming. These is known as cast film, which covers a thickness
products are marketed under the trade name range of ca. 30–300 mm. The rapid cooling
Curv and can reach modulus values of up to leads to films of low crystallinity and good
5000 MPa. The geometrical design is however optics, which can be influenced in performance
limited to thermoformed parts. both by a choice of polymer and additives and
Thick, 0.3–0.9 mm, oriented tapes are estab- by variation of the processing conditions [89].
lished alternatives to steel bands in many strap- If the film runs from the chill/take-up roll
ping applications. They are generally made by further through a calendar-like arrangement of
the water-quench process operating at draw rolls for solidifying and annealing, it is known
ratios of 9–10. Thicker tapes are made from as roll-stack film with a primary thickness
foil or individually extruded film tapes. High range of 300–2000 mm (see Fig. 27). These
molecular mass, MFR 0.4–2.0 g/10 min, PP films or sheets are primarily used for subse-
homopolymers and EP impact copolymers with quent thermoforming applications. For this pro-
added chalk and polyethylene largely suppress cess a variety of methods can be used
fibrillation. A further precaution here is to depending on the desired shape and dimension.
emboss the finished tape with a diamond pat- Both in-line and off-line processes are applied
tern. A useful aspect of PP strapping tapes is with two essential steps, heating and shaping,
their higher elongation and elastic recovery the former mostly by infrared irradiation and
which helps them to remain tight on packages the latter by mechanical force, air pressure, or
prone to shrink or settle. vacuum. Thermoforming is the only film
8.4. Films and Sheets
Depending on the processing technology

employed, PP can be processed into films
and sheets ranging in thickness from 5 to Figure 27. Three-roll stack extrusion
2000 mm and converted further to a wide a) Extruder; b) Slot die; c) Polishing stack; d) Nip rolls;
variety of products [88]. e) Wind up
36 Polypropylene
processing segment in which nucleation is

applied to a significant extent [90].
In the thinner part of this thickness range,
special high-efficiency cooling setups can be
used to produce the lowest crystallinity and
highest transparency. With water-bath or
steel-belt technology, the ideal materials for
pharmaceutical tablet blisters or transparent
folding boxes are produced. The application
of non-nucleated PP homopolymers is advisa-
ble in these special cases.
The thinnest films (5–30 mm) are produced
by postdrawing (postorientation) of a thicker
cast film, whereby monoaxial orientation
(MOPP) and biaxial orientation (BOPP) is pos-
sible [91]. The BOPP films are characterized by
a much higher orientation, stiffness, gloss, and
transparency in comparison to cast film. While
in the packaging area, the low water-vapor
permeability and the excellent optical appear-
ance are especially appreciated, the high
mechanical and thermal resistance make
BOPP also suitable for electrical capacitors.
A similar thickness range to cast films can
also be reached by film blowing, which for PP
is still of much lower importance than PE. Air-
cooled blown films are only possible with
specific grades combining a certain amount
of melt strength (at a general MFR range of
1.5–3 g/10 min) with fast crystallization, and on
modern processing lines. Water-quenched
blown film, originally the only processing
method suitable for PP, has been making a
comeback recently, especially for applications
with increased optical performance require-
ments [92, 93]. Air-cooled blown film is also
Figure 28. BOPP bubble process
the first step of an alternative BOPP process, the a) Cast tube; b), c) Stretching heaters; d) Bubble guides;
so-called double-bubble technology with f) Air ring; g) Wind up, slitting, etc
sequential longitudinal and transverse stretch-
ing of the film tube (see Fig. 28).
In general, materials with MFR values of ethylene, but for sealing layers also terpolymers
1.5–4 are used for BOPP, thermoforming, and with ethylene and butene are used. Impact
blown film applications, while for cast films copolymers are limited mostly to nontranspar-
polymers with an MFR of 7–20 are preferred ent applications with low-temperature tough-
(always 230 C/2.16 kg). While the low-MFR ness requirements, unless special polymer
grades should have a rather broad molecular designs are applied which allow a combination
mass distribution to have sufficient melt of transparency and toughness (e.g.,
strength, the higher MFR cast film grades pref- “interpolymer” concept with high propene con-
erably have a narrow molecular mass distribu- tent in the EPR phase [74]).
tion, for example, visbroken or SSC-PP types. In any case multilayer constructions are
The film area is largely dominated by PP possible and even necessary in case of packag-
homopolymers and random copolymers with ing applications requiring the combination of
Polypropylene 37
different requirements, such as sealability, ster- These particles are then foamed and fused
ilizability, and integration of barrier layers (for under elevated temperatures into the desired
this, polar polymers like EVOH or oriented PA shape. Normal pipe or even thermoforming
are used) or peel-layers for a more easy opening grades can be used here, but an addition of
of a packaging (here multiphase systems like some long-chain branched PP (high melt
PE–PP blends are applied). Through metalliza- strength PP, HMS-PP [51, 52] allows for a
tion (e.g., by chemical vapor deposition, CVD) lower final foam density.
and lamination even more complex structures In contrast, HMS-PP is absolutely required
can be designed. Preferably multilayer co- for extrusion foaming processes and especially
extrusion with specially design film extrusion solvent-free processes applying carbon dioxide
heads ahead of the die is used for producing [97]. Extruded PP foam has excellent mechani-
such constructions. Lamination with hot-melt cal properties including high temperature
or reactive adhesives is applied whenever non- resistance and can be tailored in its toughness
polymeric (e.g., paper or metal), specially ori- by blending HMS-PP homopolymers with EP
ented (e.g., oriented PA) or already printed impact copolymers. The final application
(e.g., PET) layers are required. In this case, ranges from extruded sheets thermoformed
and also whenever printing or gluing of the film into food trays or packaging components to
is intended, the film surface is activated by pipe insulation layers.
corona, plasma, or flame treatment. Corona Other processes facilitated or even enabled
treatment is the most common process here, by HMS-PP are thermoforming at high draw
but the fact that surface polarity generated with ratios (deep shapes) and especially extrusion
this method will decay over time must be coating [98], which is otherwise a clear domain
considered when planning production pro- of long-chain branched LDPE. The Recart pro-
cesses [94]. cess of Tetra-Pak, in which sterilizable coated
In summary PP films cover an extremely cardboard packages are produced for food
broad area that reaches from textile packaging packaging, is based on such materials
through medical applications up to electronic which have a higher MFR than for foaming
components like capacitors. Special require- (8–15 g/10 min as compared to 2–4 g/10 min)
ments can be achieved partly by specific proc- and must be free of crosslinked fractions which
essing or material combinations, but in other would form gels in the coating process.
areas like sterilizability [95], low-temperature
toughness, or resistance to aggressive media,
special polymer design is required. 8.6. Technical Applications
As a rule, technical parts from PP and its

8.5. Foaming and Coating composites are produced by injection molding
or its process variations like inlay, gas-injec-
The foamability of normal PP with linear chain tion, and two-component molding. Elaborate
structure is limited and even in specially part and mold design are required both to fulfill
designed foam injection technologies like the the requirements to surface quality and to pro-
MuCell process only rather high foam densities cess special materials like short and long glass-
can be achieved [96]. Good foam cell nuclea- fiber-reinforced PP (SGF- and LGF-PP) [99].
tion, which is always given in fiber or mineral LGF-PP can be further diluted to vary the final
reinforced materials, can improve the situation fiber concentration and the related mechanics in
sufficiently here, in combination with a broad the actual processing step, in which special
MWD and especially the presence of a high mold and machine design is required.
molecular weight component. Especially in the development of modern
A low MFR (0.5–1.5 g/10 min) is also cars PP plays an important role due to its
sufficient for particle foaming processes in combination of density (part weight) and
which, as in the case of polystyrene, massive mechanics (strength) [100]; out of the ca.
PP particles are impregnated with a solvent 17% mass fraction of thermoplastics in passen-
(hydrocarbon or halogenated hydrocarbon). ger cars, 70% is polypropylene (see Fig. 29).
38 Polypropylene
performance is further balanced by external

elastomers and mineral reinforcements. Surface
quality is important both for painted and the
minority of nonpainted applications and it is
clearly related to phase structure [102]. Another
critical aspect for gap-free combination with
metal parts is the thermal expansion of the
material, which is normally closely related to
shrinkage [103].
For automotive interior applications, slightly
lower impact resistance and especially no
toughness below 20 C is acceptable, leading
to modified recipes for composite design. Here,
however, scratch resistance [104] and low lev-
els of emissions and odor are important factors.
A variety of techniques ranging from back
Figure 29. Composition change of a European passenger injection molding onto foam/textile combina-
car from 1990 to 2005 (internal data of Borealis AG)
tions over metal or modified wood inlays to the
application of soft varnishes are used for
An overall important contribution of the poly- design; the contribution of these components
mer fraction is the weight reduction compared to overall stability must be considered.
to metals, which is essential for reducing the One of the oldest areas of PP application in
fuel consumption. As about 90% of lifespan car design is the under-the-hood segment,
energy demand of a car occurs in the usage where air ducts, battery cases, and fluid con-
phase; replacing 350–500 kg of other materials tainers were already produced from PP homo-
in a car with about 200 kg of polymers results in polymers in the 1960s. The most recent
about 750 L of fuel saved in a car’s lifespan. innovation in this segment are air-intake mani-
SGF-PP and LGF-PP, targeted at metal folds made of GF-reinforced PP, replacing GF
replacement and often also component integra- reinforced PA-6 with advantages in water
tion, find numerous uses in modern car design, adsorption and sound damping.
generally supported by modeling [101]. From Due to its good chemical and electrical
front-end modules, integrating headlight and resistance PP is inherently suitable also for
bumper support as well as the cooling system, applications in the electrical and electronics
through dashboard carriers and underbody pro- sector. In practice, uses range from housing
tection elements, the range extends to complete and internal components in household equip-
door and hatch modules, in which LGF-PP ment via connector systems for low voltage up
frames can be combined with injection-molded to BOPP capacitor films. For the last-named PP
cover elements to achieve largely metal free homopolymers with extremely high purity are
constructions. For the latter, as generally for applied. A common key requirement for hous-
automotive exterior and interior elements, com- ings is the surface quality. As the “reference
posites based on high-impact EP copolymers material” is mostly ABS, a combination of
are applied. gloss and surface hardness or scratch resistance
Automotive exterior applications started at is required here, which can only be achieved
side trims and door steps, progressed into bum- with high-crystallinity PP grades.
pers, and now include fenders and other parts of The white-goods industry with washing
the car body. Basically the only part of a machines and dishwashers as main products
passenger car’s body which has not yet been is an especially important application area of
designed and produced from a PP-based mate- PP-based composites with mineral fillers and
rial is the roof. Base materials for the compo- glass fibers [105]. SGF-PP and LGF-PP are
sites used here are EP impact copolymers with used in areas with high dynamic loads, like
an EPR content of 20–30 wt% and frequently a the tubs of washing machines, and special lye-
high-crystallinity matrix, and the mechanical resistant stabilization systems must be used.
Polypropylene 39
8.7. Pipes Ring seals with rubber inserts allow some

movement in domestic waste pipes. Also
The highest molecular masses of PP are used in used are flanged joints, hot-plate butt welding,
the pipe area where, compared to PE, the and socket-fusion welding, the last-named
application volume is rather small [106]. A being optionally supplemented with hot-gas
normal MFR range (230 C/2.16 kg) for PP bead welding. Compression joints involving
used in pipe extrusion is 0.3–0.8 g/10 min, copper alloys should not be used at tempera-
while still higher levels of processability are tures exceeding 60 C because of reduced life
used for injection-molded fittings complement- expectancy resulting from Cu ions; the use of
ing pipe installation systems. The applied proc- metal deactivators in stabilization can only
essing temperatures range from 220 to 280 C, partly remedy this hazard.
the latter mostly occurring in multilayer extru-
sion heads, and must be controlled rather well
both to avoid degradation and to ensure proper 9. Environmental Aspects
crystallization, whereby PP is generally far
more sensitive than PE. After some decades of success, polymers have
For pressure pipes, two polymer modifica- been going through a hard time recently. For the
tions play an important role: Random copoly- first time since the oil crisis of the early 1970s,
mers with ethylene are used for hot-water and global production decreased in 2008 as a result
underfloor heating installation, while b-nucle- of the economic crisis. At the same time, public
ated PP homopolymers find use in industrial perception of “plastics” deteriorated, with crit-
piping applications and are especially suitable ical views on issues like the release of endo-
for contact with aggressive chemicals like con- crine disruptors, littering, and waste. While
centrated acids. Pressure, creep, and crack- some of these arguments may be justified,
propagation resistance of these materials is many remain superficial like the quarrel about
specified in relation to pipe dimensions in single-use plastic shopping bags. Being less
ASTM and ISO standards [107]. Here, also visible as a packaging material, PP has not
the new material class for hot- and cold-water been affected as much as PE by this discussion,
pipes, known as PP-RCT (RCT stands for but the widespread idea that all petro-based
random, crystalline, temperature-resistant), is polymers can and will be quickly replaced by
specified. The combination of EP random “bio-based” or even biodegradable materials of
copolymers with b nucleation allows pipes to course affects customers’ choices when looking
be used at higher pressures or wall thickness to for materials for new applications.
be reduced. In reality, bio-based polymers account for
Another application area which has experi- less than 0.5% of the global polymer produc-
enced significant volume growth in recent years tion, and besides the widely discussed question
is nonpressurized sewage pipes for domestic of resources for their production and the related
and infrastructure areas [108]. Especially in the competition with nutritional usage there are
case of large diameters the external load on a also technical issues [109]. While bio-based
pipe in the ground is bigger than the internal PE (or even PP which may become available
load, a problem that can be solved, for example, as well) will of course not exhibit different
by multilayer, rib, or corrugated pipe construc- properties than its petro-based counterpart,
tions. High-modulus impact copolymers are most biodegradable polymers suffer from sig-
nearly exclusively used here, as the toughness nificant shortcomings in terms of processing
requirements are rather high. The development stability, mechanical and optical performance
presently continues in the direction of even but mostly long-term stability. Life-cycle
larger parts like shafts and manholes to achieve assessments [110] need to include these factors,
full mono-material solutions for sewage sys- which frequently lead to heavier and more
tems. For large cross-sectional dimensions complex solutions being taken into considera-
fiber-glass-reinforced types are in use here. tion in order to be realistic.
Pipe jointing uses all the common tech- Even apart from the discussion of bio-
niques, with the exception of solvent welding. versus petro-based materials, the question of
40 Polypropylene
long-term monomer supply is clearly an issue Manufactures in Europe) publishes LCAs or

for the polymer industry as a whole [111], even “environmental product declarations” at regular
though presently only ca. 6% of total crude oil intervals. For PP, this was last updated in 2008
consumption is employed for polymer produc- [114] and provides an overview of all relevant
tion. Natural-gas-based production, including input and output parameters in PP production, a
olefin conversion steps such as olefin metathe- key figure of which is the average amount of
sis, will therefore become more important. 1.565 kg fossil fuel equivalents needed for
Feedstock recycling can also contribute, as producing 1 kg of PP. From an alternative angle
can improved polymer and component design the energy demand can be broken down into
to reduce the amount of material necessary for 52.6 MJ/kg for feedstock and 20.4 MJ/kg for
fulfilling a certain function. Overall, however, process energy.
the numerous advantages of polymers over Because LCAs should rather be done on an
traditional materials must be kept in mind application level, both processing and usage
[112]. aspects must be considered there. Conversion
energy demand is generally lower for poly-
mers than for metals or glass due to their lower
9.1. Life-Cycle Analysis melting point and processing temperature, and
emissions from conversion are generally not
When comparing the environmental impact of critical for PP, like for other polyolefins [115].
different materials, numerous factors must be The possibility for saving energy by using PP
considered. Life-cycle analysis (LCA) is a in automotive applications is discussed in
common and widely used approach for quanti- Section 8.6, but also in the packaging area
fying energy and resource usage as well as there are numerous positive examples. Real-
gaseous, liquid, and solid waste streams asso- istic LCAs in this area [113, 116] actually
ciated with producing a specific material or conclude that, depending on the boundary
article, assuming identical boundary conditions conditions, even biopolymers may only
[113]. In contrast to a complete LCA, other offer marginal (if any) advantages over
measures like carbon footprint (essentially spe- polyolefins.
cific CO2 number per unit weight or applica- While the PP base polymer will normally
tion; see Fig. 30 for a comparison of standard define the major part of energy demand, fillers
thermoplastics) or water footprint can only or reinforcements as well as additives also
cover some aspects of the situation. contribute. For standard additives like the nec-
For most standard thermoplastics, essary antioxidants this is considered in
PlasticsEurope (the Association of Plastics the PlasticsEurope evaluation [114]. For
Figure 30. Comparison of the carbon footprint (CO2 equivalents) of different standard and advanced thermoplastics (data
collected from www.plasticseurope.org in July 2013)
Polypropylene 41
reinforcing fibers, although glass fibers still The Mg, Ti, and Al residues are
dominate the market, the use of organic fibers mostly oxides or hydroxides from the
from renewable sources is increasing in recent deactivation step with water vapor (free
years [49]. Whether this improves the LCA and HCl or other residual chlorides
the sustainability in general depends, however, are handled by acid scavengers, see
on the achieved thermomechanical perform- Section 6.1)
ance of the thus-produced composites [117]. The amount is very low (<400 ppm) due
Normal LCAs will find their limits of to the high productivity of modern
comparability whenever toxic waste streams catalysts.
are involved in the production process. Pro-
pene and ethylene monomers themselves are
nontoxic asphyxiant gases whose flammable 9.2. Mechanical Recycling
nature calls for the usual extensive fire pre-
cautions, as ignition by static electricity is The chemical structure and inherent properties
possible with high-pressure leaks and acciden- of PP make it well suited to recycling opera-
tal discharges. Monomer recycling is a stan- tions [118]. There is no fear about cross-
dard element in industrial production linking, nor of complications with plasticizers
processes, but some waste gas will still end or chlorine-rich species. Re-extruding PP usu-
up in traditional flare stacks or modern ground ally lowers its molecular mass and narrows the
flares. In the latter, the visual impact of flares molecular mass distribution, particularly in
as well as the noise level is reduced signifi- aged feedstock. This can be helpful in some
cantly. Since emission certificates for CO2 are applications requiring enhanced flowability, but
a relevant cost factor in many countries world- it negatively affects the mechanical perform-
wide, producers are working continuously on ance and especially the impact strength. Other
reducing flaring volumes. factors to be considered in reprocessing and
Although catalyst components constitute aging are loss of oxidation stability,
only a very small proportion of plant materials, discoloration, contamination, and odor
both their manufacture and disposal involve development.
noxious substances. Titanium tetrachloride is As a rule, increasing heterogeneity (even
used for all catalysts, sometimes in considera- within the same polymer class), contamination,
ble excess for high-activity systems. Whereas and age of the starting material for mechanical
expensive recycle and recovery stages may be recycling will reduce the possibilities for pro-
installed as capacities increase, some remaining ducing high-value secondary grades. Even
complex residues will require disposal. Often, elaborate cleaning and sorting operations
this involves hydrolysis with water to generate have been generally found to be unable to really
corrosive HCl and titanium dioxide suspen- purify and upgrade highly mixed waste streams
sions. After neutralization with alkali, these [119].
slurries are either discharged as aqueous efflu- In PP production, off-specification materials
ent or settled out and used in landfill. Lower will result from grade transitions, production
aluminum alkyls are pyrophoric, react violently faults, technical flaws, and test runs for the
with water, and are intensely aggressive introduction of new grades. Resulting devia-
towards exposed skin. Safe handling usually tions in MFR, copolymer characteristics, and
calls for full protective clothing. Disposal can the like will determine whether the respective
be by burning in special facilities to generate material can be added to prime products in
alumina, or quite often, by controlled hydroly- minor amounts in a process normally called
sis with water after deactivation with alcohols. trimming. Otherwise, these are pelletized sep-
Some alkyl manufacturing plants will accept arately and re-classified as low-requirement
returned waste alkyls for disposal in their own products to be sold to processors or independent
dedicated facilities. compounders.
In contrast to those toxic ingredients the Recycling in the conversion industry is
catalyst residues in the final polymer are not based on the fact that turning PP into moldings,
critical as: pipes, film, etc. invariably involves some scrap
42 Polypropylene
production. Apart from substandard articles, least a reduction of the nonthermoplastic con-
there are sprues from moldings, edge trim tent will facilitate recycling [121]. Closed-loop
from film and sheet, parison waste, and recycling systems are another option for large-
stamped sheet from thermoforming. These volume applications and especially helpful in
are recovered for recycling by the converter recycling high-performance materials in tech-
himself if the application allows, or sometimes nical applications.
by an external compounder. Problems may
arise here due to stabilizer consumption in
multiple melting processes as well as by the 9.3. Chemical and Energetic Recycling
presence of foreign polymers like in multilayer
co-extrusion. PP can be cracked to liquid hydrocarbons by
A quite different situation arises when trying thermal pyrolysis at 400–550 C or even lower
to recycle PP after its service life, as in recy- temperatures in the presence of suitable cata-
cling of post-consumer plastic waste [118, lysts. Other thermoplastics, such as PE and PS,
119]. Unless collected separately, thermoplas- can also be pyrolyzed to liquid products, allow-
tic materials make up 8–12 wt% of the munici- ing mixed feedstock recycling for MSW frac-
pal solid waste (MSW) stream in industrialized tions not suitable for mechanical recycling
countries and will only contribute positively to processes [122].
the calorific value of MSW if incinerated (see Modern MSW incineration technology, with
below). Recovery of a useable plastic fraction energy recovery in the form of electricity gen-
from MSW after undifferentiated disposal is a eration, can take advantage of the high calorific
hopeless task, but even the recovery and reuse value of thermoplastics. Municipal waste calo-
of mixed plastics is quite difficult. The devel- rific values average 10 kJ/g, compared with 30–
opment of specific low-profile applications and 35 kJ/g for coal. At 44 kJ/g, PP and other
fabrication processes for such comingled poly- polyolefins have the same calorific value as
mers, which are largely incompatible and con- fuel oil. Moreover, PP has an exceptionally
taminated, has natural limits. Using mixed low sulfur content, which makes it a very clean
thermoplastic waste for massive products, fuel with no apprehensions about toxic flue-gas
such as posts, construction boards, and other emissions.
bulky structures for which resistance to water
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Polypropylene

MARKUS GAHLEITNER, Borealis Polyolefine GmbH, Linz, Austria

1. Historical Overview . . . . . . . . . . . . 1 6.1. Additives . . . . . . . . . . . . . . . . . . . 21

1. Historical Overview industry. Before that, propene could not be

# 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 1. Production-volume development of standard thermoplastics (redrawn after [9])

Figure 2. Regional distribution of global PP production (2012, data from [10])

Figure 3. Main polypropylene types

Figure 4. Regioirregularity in polypropylene polymerization

following a 1,2-insertion create irregularities occurs at ca. 110–120 C in a differential scan-

Table 1. Crystal characteristics of PP [17–19]

i-a monoclinic 0.932–0.943 4 171

lamellae are composed of crystallographically Generally multiphase copolymers are

For the production of polypropylene materi- dehydrogenation of propane from natural

Table 4. Performance development of ZN catalysts for PP a

Year Catalyst system Productivity, kgPP/gCat. I.I.b, % mmmmc, % Mw/Mn H2 responsed

1954 d-TiCl30.33 AlCl3 þ AlEt2Cl 2–4 90–94 low

aluminoxane (MAO), made through controlled 3.4. Hydrogen

Figure 11. Polyolefin plant designs

technology is restricted to polypropylene and polymerized in gas-phase reactors. They can

Figure 12. Spheripol process

Figure 14. BASF gas-phase Novolen process

separating the composition of two reaction

5.3. Hybrid Processes

Hybrid processes combine the production of a

Pelletization is possible in strand form or in An approximate distinction is drawn between

Figure 17. General scheme of inhibition of thermo-oxidative degradation of PP

Figure 18. Classification of nucleating agents for PP

6.3. Reactive Modification The chain structure, i.e., the presence of

Table 6. Overview of most relevant PP properties for various grade families

Unmodified PP grades Compounds

Filler content, wt% 0 0 0 0 0 20–40 20–50 10–25

segments require quite different materials and

Table 7. Polypropylene fiber processes

Process Filament count, tex Product

Figure 25. Melt blowing process

short, low-orientation fibers of very low diam-

Figure 26. Flat tape/yarn production unit

8.4. Films and Sheets

Depending on the processing technology

processing segment in which nucleation is

As a rule, technical parts from PP and its

performance is further balanced by external

8.7. Pipes Ring seals with rubber inserts allow some

long-term monomer supply is clearly an issue Manufactures in Europe) publishes LCAs or

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1954 d-TiCl30.33 AlCl3 þ AlEt2Cl 2–4 90–94 low

Unmodified PP grades Compounds

Process Filament count, tex Product