Chapter 3

3
Polypropylene

Allison Calhoun
Whitman College

Managerial overview
Polypropylene is found in a wide variety of films and
multilayer film structures as a result of its strength,
toughness and high melting point [1]. Additionally, when
formulated with the proper additive packages, poly-
propylene (PP) resins can exhibit excellent process-
ability. The homopolymer chemical structure is rather
simple, a methyl group located on every other methylene
unit (Fig. 3-1).
The placement of this methyl group around the ster-
eocenter during polymerization creates different tactic-
ities (Fig. 3-2).
Methyl groups placed consistently on one side of the
polymer chain generate an isotactic polypropylene.
When these methyl groups alternate from one side to
the other, the polymer is known as syndiotactic.
Fig. 3-2 A schematic of polypropylene tacticities: (a) isotactic with
all methyl groups on the same side of the chain; (b) syndiotactic
with methyl groups alternating above and below the chain;
(c) atactic with methyl groups in a random orientation.

A random ordering of the methyl groups creates an

atactic polymer. The polymer tacticity partially defines
the polymer’s properties. Molecular weight distribution,
degree of crystallinity and the polymerization method
also define the polymer properties. Further chemical
alterations, via copolymerization with monomeric units,
Fig. 3-1 The polypropylene monomer unit. The subscript n such as ethylene and butylenes, create an even more
indicates that this is a repeating unit that is connected to n other comprehensive library of physical properties for specific
monomeric units. applications.
Multilayer Flexible Packaging; ISBN: 9780815520214
Copyright Ó 2009 Elsevier Inc. All rights of reproduction, in any form, reserved.
 CHAPTER 3 Polypropylene

Polymerization the solvent boils off. This monomer is then recycled back
into the monomer stream.
Initial research investigating polypropylene polymeriza-
tion relied on high pressures and radical initiators [2]. Liquid propylene polymerization
This technology produced low molecular weight oligo- of polypropylene
mers with little commercial value. The Ziegler–Natta Another way to achieve polymerization utilizes the liquid
catalyst technology allowed manufacturing of commer- monomer as the polymerization solvent. This process has
cially viable polypropylene. The resulting product was an advantage over the slurry method because the high
predominantly an isotactic polypropylene and could be monomer concentration increases the reaction rate.
manufactured at high molecular weight. Metallocene Runaway reactions, uncontrolled reactions that arise
catalysts were the next generation catalysts and led to from hot spots in the reaction medium, are prevented by
creating both isotactic and syndiotactic high polymer the fact that the monomer itself can absorb excess heat as
with highly controlled molecular weight distributions it vaporizes. The gas phase monomer then can be con-
and tacticities. densed and reintroduced to the reactor. As in the slurry
process, high molecular weight PP and atactic PP form an
insoluble phase in the condensed monomer. This in-
Ziegler–Natta catalyzed polypropylene soluble phase contains both the atactic and isotactic
fractions which are isolated from the liquid propylene at
Ziegler–Natta catalyzed polypropylenes exhibit a rela- the same time. A second separation step removes the
tively broad molecular weight distribution with a weight solvent soluble atactic fraction by using an appropriate
average molecular weight divided by the number average organic solvent resulting in a pure isotactic polypropylene
molecular weight (Mw/Mn) or polydispersity approxi- product.
mately equal to 3.5 [3, 4]. These isotactic polymers
comprise a large majority of the commodity grade resins
used in film manufacture today. Solution polymerization of polypropylene
The Ziegler–Natta catalysts developed for propylene During solution polymerization, the monomer, catalyst
polymerization generally consist of TiCl3 and trialkyl and solvent enter a reactor held at a temperature
aluminum. High weight average molecular weights are between 175 and 250  C. Polymerization in the solvent
achievable with this chemistry, around 4  106 g/mol, creates a viscous polymer solution. A pump removes the
creating a polymeric material that can be processed into solution from the reactor and the solution is filtered to
cohesive films. To improve this catalyst system, specifi- remove any residual catalyst, if necessary. Vacuum drying
cally better to control molecular weight distribution and removes the solvent from the polymer, leaving behind
polymer tacticity as well as to improve the catalyst effi- isotactic and atactic polymer.
ciency, chemists have modified the crystal structure of
the TiCl3, purified the catalysts, introduced transition Gas phase polymerization of polypropylene
metal compounds and/or a Lewis base to act as an elec-
Gas phase polymerization passes gaseous monomer
tron donating species.
through a fluidized bed containing polymer granules and
Ziegler–Natta catalyst chemistry allows polymeriza-
inert-media supported catalyst. Some monomer reacts
tion in four unique polymerization systems: slurry, liquid
within the bed to create polymer and the remainder
propylene, solution and gas phase.
passes through where it is collected and recycled. The
high polymer granules are removed from the bottom of
Slurry process polymerization of polypropylene the fluidized bed along with some of the inert-media
In slurry polymerization, chain growth occurs as mono- supported catalyst. The catalyst is replenished in the
mers dissolved in a hydrocarbon solvent add to growing reactor at the same time.
chains also dissolved in the solvent. Two fractions result
from polymerization: one fraction is soluble in the sol- Metallocene catalyzed polymerization
vent while the other is not. The two fractions are sepa- of polypropylene
rated by centrifugation, thereby creating two product Once manufacturers recognized the benefits of poly-
streams. The insoluble fraction creates the slurry phase propylene in composite film structures, there was an
and is predominantly isotactic material. The soluble increased demand for tightly controlled polypropylene
components are either low molecular weight oligomers materials with low polydispersity and controlled
or highly atactic polypropylene that precipitates from tacticity. The Ziegler–Natta catalysts were unable to
solution when the solvent is boiled off at high tempera- meet these market needs. Additionally, there was a need
tures. Unreacted monomer is also released as a gas when for improved catalyst performance which would reduce

32
 Polypropylene CHAPTER 3

residual catalyst levels in the final polymer, thereby In general, isotactic homopolymer polypropylene has
enhancing the polymer’s stability. The most effective way a high degree of crystallinity thereby creating a material
to achieve these goals found to date is to use metallocene that is strong, with low permeability to vapor or solvents
catalysts. Metallocene catalysts control the polymeriza- and high chemical resistance. Isotactic polypropylene –
tion by permitting only those monomers that approach with the exception of the mesomorphic crystalline form –
with a specific orientation to attach to the growing chain. is typically opaque, due to the high concentrations of
This results in increased tacticity control in the final crystalline regions.
polymer. In addition, the metallocene catalysts have Isotactic polypropylene exhibits four crystalline
only one active polymerization site, which results in structures: alpha, beta, gamma and mesomorphic [3, 5].
a narrower molecular weight distribution than achieved Each of these structures forms under specific processing
by Ziegler–Natta catalysts (Mw/Mn z2.0). These cata- conditions and defines the properties of the poly-
lysts introduce their own special defects which actually propylene. In polypropylene containing the alpha, beta
result in a slightly lower melting temperature than can be and gamma structures, the final material is typically
achieved with the best Ziegler–Natta catalysts. opaque due to the light scattering by spherulites with
Metallocenes are homogeneous catalysts that are often sizes similar to the wavelength of visible light.
soluble in organic solvents. Therefore, polymerization
can occur via a solution process with a non-polar diluent Alpha crystallinity
dissolving the propylene gas, the catalyst and the co- Alpha crystallinity arises from a helical conformation
catalyst system. They can also be adsorbed onto an inert of the polymer chains described by a monoclinic unit
substrate which acts as part of the fluidized bed for gas cell. This structure represents the most thermody-
phase polymerization processes. namically stable structure and forms readily as the
polypropylene cools below its crystallization tempera-
ture. The helices align to form crystallites which then
General classes of polypropylene associate to form sheet-like lamellae. Cross-hatching
resins microstructure arises as secondary lamellae grow per-
pendicularly off the primary lamellae. These secondary
Atactic polypropylene lamellae create a supermolecular structure by
connecting the neighboring primary lamellae. The
Atactic polypropylene, though the first manufactured secondary lamellae can further associate to create
polypropylene, finds little commercial use in the film spherulites (Fig. 3-3).
industry. The random methyl group placement creates Another way to look at the spherulites and the
a polymer with low crystallinity. It is a soft and tacky lamella arrangement in the spherulite is shown in
material with low strength. It has high vapor and gas Fig. 3-4.
permeability and little solvent resistance. Commercial Fig. 3-5 [6] is a picture of a PP spherulite grown be-
applications are very limited, however, it can be found as tween glass slides on a microscope hot stage.
a component in adhesives and roofing systems. Polypropylene crystallites can be the size of the
wavelength of light and therefore tend to refract light
and be translucent with high haze and low trans-
Isotactic polypropylene parency. There are several additives that can promote
nucleation, reduce the spherulite size below the
Isotactic polypropylene produced through current wavelength of light and make the quenched PP more
catalyst technology can be more than 95% isotactic as transparent. Fig. 3-6 [7] is an optical micrograph that
defined by the percent isotactic pentads in the polymer shows the effect of a nucleating agent on spherulite
chain. This method, typically accomplished through size.
nuclear magnetic resonance (NMR) spectrometry de-
termines the fraction of five adjacent units with methyl
groups all on the same side of the polymer chain rel- Beta crystallinity
ative to the total number of pentads in the polymer. Beta crystallinity is observed when the polymer is cooled
The advantages isotactic polymer has relative to the quickly below its melting point. The polymer chains do
syndio- and atactic polypropylene arise from its high not have the time required to form the thermodynami-
crystallinity. Typical isotactic polypropylenes range cally stable alpha crystallinity. Beta crystalline polymer
from 40 to 70% crystallinity. The resulting polymer has has a lower density and lower melting point than alpha
a higher melting point (160–180  C), higher density crystals. Once the polymer is heated or placed under
and higher strength relative to the syndiotactic and strain, the beta crystallinity will revert to the alpha
atactic forms. structure.

33
 CHAPTER 3 Polypropylene

large crystalline domains from forming. Therefore, the

crystalline regions are small with poor alignment between
the individual crystallites. The properties of a smectic
crystalline polypropylene lie between those of alpha
crystalline and atactic polypropylene. The polymer will
be transparent and will revert to an alpha crystalline
structure upon heating.

Syndiotactic polypropylene
With the introduction of single-site catalysts, syndio-
tactic polypropylene became commercially available,
however, its use is not widespread in multilayer film
manufacture. Until this time, syndiotactic polypropylene
was not a viable commercial product as its manufacture
was not feasible with the prior catalyst technologies [3, 5].
The syndiotacticity of the single site catalyst produced
polymer rarely exceeds 75%, based on pentad se-
quences. The polymer, relative to isotactic poly-
propylene, has a lower melting point (approximately
138 C relative to approximately 155–160 C) and
a lower density (0.89 g/cm3 relative to 0.93 g/cm3).
The crystallites that form in syndiotactic polypropylene
are more complex than those formed in the isotactic
polymer. This complexity reduces the rate at which the
crystallites can form, meaning that the polymer crys-
tallizes very slowly. [8, 9]

Processing
Polypropylene’s excellent strength, low surface energy,
low gas and liquid permeability and relative ease of
processing make it an attractive option for use in
Fig. 3-3 Semicrystalline structure of polypropylene. (a) crystallite
formed from polymer chains associating; (b) secondary
crystallization associating crystallites to form lamellae; (c) formation
of spherulites from long range structuring of lamellae.

Gamma crystallinity
Isotactic polypropylene also can exhibit gamma crystal-
linity, though this form rarely arises from processing
under standard conditions. The gamma crystallites form
a cross-hatched structure just as seen in alpha crystal-
linity. However, the crystallites grow in two directions at
the same time, resulting in a highly crystalline, high
density material. The mechanism for the formation of
gamma crystallinity is believed to rely on shearing an
alpha crystalline polymer, which creates a more uniform
crystal structure.

Smectic or mesomorphic crystallinity

Rapidly quenched isotactic polypropylene exhibits an Fig. 3-4 Spherulite crystal morphology showing the lamella, tie
additional form of crystallinity. Rapid cooling prevents molecules and amorphous domain.

34
 Polypropylene CHAPTER 3

Fig. 3-6 Two optical micrographs show the effect of a nucleating

agent on spherulite size. In nucleated polypropylene, right,
Fig. 3-5 A Maltese cross pattern of birefringence obtained using spherulites are smaller and more numerous than in unnucleated
optical microscopy under crossed polarizers. Polypropylene was polypropylene, left.
isothermally crystallized at a pressure of 100 MPa.

[10, 11]. Manufacturers of these resins recognize this issue

multilayer films. However, its opacity may be a detri- so they generally stabilize them well before sending them to
ment for packaging applications. their customers. However, stability may be a considerable
To overcome the issues of opacity, orientation breaks issue if the stabilizer is ineffective for the processing con-
up the spherulitic structure thereby resulting in a trans- ditions or is used up during processing or use.
parent film. Additionally, orientation improves tensile The most common degradation during manufacturing
properties, impact strength and reduces gas permeability. is that of thermo-oxidative degradation. In this process,
Polypropylene may be used to manufacture single layer oxygen and high temperatures create an autocatalytic
films or as a component in multilayer films via both cast and reaction which promotes the formation of double bonds
blown film processing. In multilayer films, polypropylene in the polymer chain, creates chain scissions and generates
can serve as the major layer to provide structural integrity low molecular weight volatile products. The double bonds
to the film or it may be used as a minor layer for specific end up conjugated on the chains which leads to off color
functionality. In either blown or cast film processing of resin with a yellow tint. The low molecular weight volatile
multilayer films, coextrusion generates the individual materials can lead to holes in the film (under very extreme
layers. Processors accomplish adhesion between the layers conditions) or thin spots where the volatiles flashed off at
by using pressure to create intimate contact between the the die. Another issue associated with degradation is
layers when they are still hot. In blown and cast film pro- molecular weight reduction induced by the chain scission
cesses the layer joining is usually done inside the die. events which reduces the polymer melt viscosity. This can
However, in some blown film processes a hot nip can in- lead to ineffective mixing and pumping of the polymer
tentionally block the collapsing bubble together and thereby changing the final film properties.
double the number of layers minus one. To prevent this degradation from occurring, pro-
One functional application of polypropylene as a non- cessors need to confirm that the stabilizer works under
structural layer is found when a polypropylene the processing conditions including residence time, shear
copolymer, including ethylene- and ethylene, butylene- conditions and temperature regime that the polymer will
propylene copolymers, is used as the skin layer of experience. This becomes especially critical when recy-
a multilayer film. These copolymers exhibit lower cled material is introduced to the process. The stabilizer
melting points thereby promoting a good heat seal will already be depleted in this recycled material which
during conversion of the film into functional packaging. can lead to additional problems during its reprocessing.
Another processing concern is that polypropylene’s melt
strength may be inadequate to sustain a stable bubble during
Challenges of using blown film processing. This means that the bubble may sag
polypropylene or dance under its own weight resulting in uneven film
thicknesses across the bubble. A recent improvement to this
The challenges associated with using polypropylene in film resin family includes a polypropylene which contains long-
applications are mostly centred on the fact that it is an in- chain branching. This branching increases entanglements
trinsically unstable polymer that degrades via oxidative, among the polymer chains promoting greater cohesion of the
thermo-oxidative and ultraviolet degradation processes polymer. This, therefore, increases the melt strength.

35
 CHAPTER 3 Polypropylene

Summary
Polypropylene provides the film manufacturer with range of applications in many different arenas. Con-
strength, toughness, high melt temperature and ease of sumable and medical packaging, labels, stickers, personal
processing that makes it a star among the polyolefin hygiene and construction films all have been made with
resins. Films produced with this polymer find a wide this versatile resin.

References
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2. E.P. Moore, The rebirth of polypropylene: supported catalysts, Hanser/Gardner Publications, Cincinnati, 1998.
3. N. Pasquini (Ed.), Polypropylene handbook, products, technologies and markets, Hanser/Gardner Publications, Cincinnati, 2005.
4. G. Odian, Principles of polymerization, 3rd edn, Wiley Interscience Publications, New York, 1991.
5. E.P. Moore Jr. (Ed.), Polypropylene handbook, Hanser-Gardner Publications, Cincinnati, 1996.
6. C. Maier, Polypropylene – the definitive user’s guide and databook, p 11. Plastics Design Library, William Andrew Inc, 1998.
7. C. Maier, Polypropylene – The definitive user’s guide and databook, p 12. Plastics Design Library, William Andrew Inc, 1998.
8. P.C. Painter, M.M. Coleman, Fundamentals of polymer science, Technomic Publications, Lancaster, PA, 1997.
9. G.W. Ehrenstein, Polymeric materials: structure – properties – applications, Hanser/Gardner Publications, Cincinnati, 2001.
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11. K. Pielichowski, J. Njugana, Thermal degradation of polymeric materials, Rapra Technology, Shrewsbury, UK, 2005.

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