Practical Guide To Polypropylene 2 Basic

Practical Guide to Polypropylene
2 Basic Types of PP
PP, a semi-crystalline thermoplastic, is made in its homopolymer form by polymerising
propylene monomer using stereospecific Ziegler-Natta catalysts. The catalyst system is
termed stereospecific because it controls the position of the side (methyl) group in each
propylene unit in the polymeric chain. A typical catalyst system may be prepared by
combining titanium trichloride with tributyl aluminium or its variants. Most commercial
PP is isotactic.
The physical properties and processing characteristics of PP are mainly determined by

the molecular weight (average number of propylene units in a chain), the molecular
weight distribution (variation in average length of chains) and the type and amount of
copolymerising monomer. The selection of the right grade of PP for a specific
application involves
• choosing between homopolymer and copolymer,

• choosing a reactor or controlled rheology grade,
• defining the melt flow rate required and the appropriate additive system.
However, with changes in manufacturing technology, operating conditions and catalyst

systems, the traditional differences between the properties of homopolymers and
copolymers have blurred [4-6]. Hence, an open mind is necessary to select a proper
grade for a particular application.
2.1 Homopolymer
Homopolymer PP is made by polymerising propylene in the presence of a

stereospecific catalyst. Homopolymers are more rigid and have better resistance to high
temperatures than copolymers but their impact strength at temperatures below zero is
Copyright © 2002. iSmithers Rapra Publishing. All rights reserved.
limited (Section 4.3.2).
Typical applications for homopolymer polypropylene include windshield washer tanks,

shrouds for fans and steering columns, housings for domestic appliances such as hair
dryers, sterilisers, irons, coffee makers, toasters, etc., extrusion of fibres and filaments
for carpet backing, upholstery fabrics, clothing, geotextiles, disposable diapers, medical
fabric and automotive interior fabrics.
2.2 Copolymer
The properties of PP depend on the type and amount of comonomer. There are two
basic types: random copolymer and heterophasic or block copolymer. The random
polymers contain 1.5% to 6% by weight of ethylene or higher alkenes (such as butene-
1) in random distribution and in a single chemical phase. The essential difference
between a random and a block copolymer is that the block copolymer contains
9
Tripathi, Devesh. Practical Guide to Polypropylene, iSmithers Rapra Publishing, 2002. ProQuest Ebook Central,
http://ebookcentral.proquest.com/lib/rtulv-ebooks/detail.action?docID=476935.
Created from rtulv-ebooks on 2018-04-04 04:54:05.
comonomer in the form of a dispersed rubber phase [7]. The structure of random and
block copolymerised PP is shown schematically in Figure 4.
—P—P—P—P—E—P—P—P—E—P—P—P—P—P—E—P—P—P—P—P—P—E—P—P—
random copolymer
—P—P—E—E—P—P—P—P—E—E—E—P—P—P—P—P—E—E—E—E—E—P—P—P—
block copolymer
Figure 4 Structure of random and block copolymerised PP molecules. P and E

represent propylene and ethylene monomer units, respectively
Copolymerised PP gives a softer feel to film and fibre products compared to

homopolymers. However, PP copolymers are more expensive than the homopolymers
(see Table 8). Typical applications of copolymerised PP are battery cases, bumper filler
supports, interior trim, glove boxes, package trays and window mouldings, video
cassette boxes, office chairs, disposable containers, boxes and appliance housings.
2.2.1 Random Copolymer
The random copolymer of PP contains chains with a small number (~1.5–6%) of

ethylene or higher olefin units (such as butene or hexane), dispersed randomly among
the propylene units. The presence of ethylene in the polymer chain reduces the
tendency to crystallise and results in improved impact strength, a softer feel, a wider
range of heat sealability, resistance to creasing and improved clarity. Some of the
inherent rigidity of the homopolymer is sacrificed by copolymerisation. Due to the
lower crystallinity, random copolymers have a lower melting point and specific gravity
than the homopolymer. This combination makes copolymers attractive for injection-
moulded houseware, thermoforming, stretch blow mouldings and films [4]. Random
copolymer grade can be used to replace PVC, PS and PET in food packaging and
stationary applications.
2.2.2 Block Copolymer
PP homopolymer is copolymerised with ethylene. In block copolymers, the ethylene

content is much higher than the random copolymers. The copolymerised part of the
material is rubbery and forms a separate dispersed phase within the PP matrix. As a
result, block copolymerised PP is much tougher than homopolymerised PP and can
withstand higher impact even at low temperatures but at the expense of transparency
and softening point. The main applications of the block copolymerised PP are similar to
those of elastomer-modified PP but where the impact property requirement is not that
critical.
10
2.3 Elastomer-Modified Polypropylene
Extremely high toughness at low temperatures can be achieved by modifying PP with

elastomers, mainly ethylene propylene rubber (EPR), ethylene propylene diene rubber
(EPDM) or plastomers. Plastomers are very low density (<0.88 g/cm3) copolymers of
ethylene and an olefin produced using metallocene technology. Plastomers can have
narrow molecular weight distribution and more long chain branching than EPR and
EPDM.
Modification of PP with elastomers causes loss of hardness and stiffness. If elastomer-

modified PP is considered for food-related applications, relevant national and
international regulations should be checked for compliance. Shrinkage of elastomer-
modified grades is lower than the copolymer grades due to reduced crystallinity and
increased free volume. Further, elastomer-modified grades allow good paint adhesion
since the rubber phase provides sites for etching or surface treatment. For outdoor
applications, black-coloured or light-stabilised materials are required. Low melt flow
rate grades are used for extrusion and blow moulding where there are higher impact
requirements than can be met with PP homopolymers. However, higher melt flow rate
grades are more suitable for injection moulding, once again where better impact
strength is justified in terms of application suitability. Elastomer blends are commonly
used in the automotive industry for bumpers, bumper covers, protective side strips,
spoilers, steering wheel covers, mudguards for tractors and lorries, and other parts
which are likely to encounter high impact stresses.
2.4 Controlled Rheology
The polymerisation techniques for PP lead to a wide range of molecular weight. The
molecular weight distribution can be controlled by splitting the PP chains using
hydrogen peroxide into smaller units in the post-reaction stage. This reduces molecular
weight and narrows its distribution and, consequently, increases melt flow rate. Most of
such controlled rheology (CR) grades have melt flow rate (MFR) values higher than 20
g/10 min at 230 °C at 2.16 kg load. It can be as high as 120–150 g/10 min or more.
Moulding cycles for the CR grades can be up to 15% faster, and warpage and shrinkage
is reduced because of reduced orientation of polymer chains in the flow direction and
the reduction in injection pressure due to easy flow of the material. Reactor grades of
PP have a broad molecular weight distribution (Mw to Mn ratio of 5–12), but CR grades
offer a substantially lower ratio (~3–5). However, the breakdown of polymeric chains
might lead to formation of low molecular weight polymers or oligomers that can cause
odour problems (organoleptic problems) in PP (Section 4.8.1). The other problem with
the CR grades is the reduction in impact strength due to the reduction in molecular
weight. The impact properties of the CR grades should be carefully monitored,
particularly at low temperatures.
CR grades are available both as homopolymers and copolymers. Copolymer-based CR

grades for injection moulding flow well and are highly resistant to warpage and internal
stresses. These grades find application in thin-walled packaging for food and
11
pharmaceuticals, video cassettes, automotive parts, machine housing parts, suitcases,

crates and freezer containers and other warpage prone parts. However, the arrival of
metallocene-catalysed PP (which offers advantages such as better organoleptic
properties and narrow molecular distribution) is set to challenge the use of CR grades in
traditional applications.
2.5 Metallocene Polymers
Metallocenes are a new generation of olefin polymerisation catalyst. They have

attracted widespread attention because of their high activity and versatile performance
with different monomers. The principal obstacles to their use in PP production have
been that their melting point and molecular weight are too low. These problems are now
solved with newly designed stereo-specific zircocenes making isotactic and syndiotactic
PP of high molecular weight and varying stereoactivity. Metallocene catalysts provide
enhanced control over the molecular make up of PP [8]. Reactor grades with extremely
high isotacticity (~1% atacticity in comparison to a minimum 3–4% atacticity of
conventionally polymerised PP) and narrow molecular weight distribution are possible.
The narrow molecular weight distribution results in lower shear sensitivity of the PP
resin and provides low melt elasticity and elongation viscosity in extrusion (Section
6.1.2).
Metallocene-polymerised copolymers offer the same mechanical properties as the

conventional Ziegler-Natta catalysed polymers, similar deflection temperature under
load but with lower melting point (147–158 °C). Metallocene-catalysed PP significantly
improves the property window of conventionally polymerised PP. Significant
improvements in modulus and hot tack strength are observed while water vapour
transmission rate, haze and heat seal initiation temperature is reduced [9]. High melt
flow properties without the use of organic peroxides (as required by CR grades) means
that the metallocene polymers offer superior organoleptic properties. The properties of
metallocene-polymerised PP are compared with Ziegler-Natta homopolymer and
copolymer PP in Table 10 [10]. It can be seen that the mechanical properties (tensile
modulus and tensile yield strength) of metallocene-catalysed PP are similar to that of
homopolymer PP while the optical properties (gloss and haze) are similar to random
polymer. This unique combination of mechanical and optical properties is associated
with ease of flow resulting from a higher MFR value and narrower molecular
distribution. Because of the lower molecular weight distribution, the metallocene-based
PP offers low warpage and is particularly suitable for thin-walled packaging products
for dairy products such as yoghurts and cheese. Other targeted markets for metallocene
polymers are medical products such as petri dishes and syringe bodies.
Europe’s first commercial metallocene-catalysed PP was launched by Targor, the joint

venture between BASF and Hoechst (now Basell), with the trade name of Metocene.
Exxon Mobil (Achieve) and BP have also produced grades of metallocene-catalysed
PP.
12
Table 10 Comparison of the properties of metallocene-polymerised PP with PP

homopolymer and copolymer manufactured using Ziegler-Natta catalyst [10]
Ziegler-Natta Ziegler-Natta
Metallocene
Property homopolymer random
PP
PP copolymer PP
MFR (230 °C/2.16 kg) 60 48 48
Tensile yield strength (MPa) 35 35 29
Tensile modulus (GPa) 1.7 1.55 1.15
Charpy impact strength at 23
2 90 103 180
°C (kJ/m )
Haze (%) 7 60 7
Specular gloss at 20° (%) 77 57 65
2.6 Syndiotactic and Atactic PP
Syndiotactic PP is available from, e.g., Fina Oils and Chemicals, and Mitsui Toatsu
Chemicals, polymerised using metallocene catalysts. It is claimed that the syndiotactic
structure provides better impact strength, greater flexibility, lower haze, lower heat
deflection temperature and lower residual monomer content. However, the full
properties of these polymers are still to be evaluated and it remains to be seen whether
syndiotactic PP can offer properties which are unique enough to market it as superior to
isotactic PP and which can provide justification for the higher cost of material [8, 11,
12].
Atactic PP is an amorphous material and has little strength. The main application of
atactic PP is in coatings in conjunction with bitumen or asphalt.
2.7 Filled Grades of PP
While most of the PP produced is used without mineral filler, the use of such materials
is more common in PP than with PE. PE has very low modulus and stiffness.
Consequently, the improvement in mechanical properties achieved by addition of fillers
is not significant. By choosing the appropriate filler, PP type and compounding
technology, it is possible to design products with properties approaching those of some
engineering polymers. For these reasons, fillers are used not only to reduce the polymer
content and cost but also to enhance its performance. As a result, a significant number
of filled and reinforced PP grades has been developed and are successfully used in
different applications. The improved stiffness and heat deformation resistance has led to
the use of such compounds for the manufacture of heater housings, car mounting
components and several domestic appliances. The main fillers and reinforcements for
PP are discussed in this section. Their impact on its mechanical properties is discussed
in Section 4.3.6.
13
It is reported that products made from PP have no effect on the biosphere after landfill
disposal. However, mineral fillers may remain on the disposal site for a very long time
or build up in incinerators.
2.7.1 Talc Filled PP
Control of the average particle size, the particle size distribution, the purity and the
aspect ratio of the filler is necessary to achieve consistent product quality in talc filled
PP. In some grades of talc filled PP, water absorption may be an important factor. This
will affect the surface appearance of the moulded product and the adhesion of the resin
to the filler.
Grades filled with 10% to 40% talc by weight have been produced. Both homopolymer
and copolymer grades of PP are used. Talc filled grades offer higher stiffness, better
surface aesthetics, lower coefficient of thermal expansion, lower shrinkage, and
improved scratch and mar resistance than non-filled grades. Heat deflection temperature
and mould shrinkage are also improved by the addition of talc. Flexural modulus
increases dramatically with added talc at the expense of tensile strength. In some cases,
impact modifiers are added to maintain the impact strength, but at the expense of
stiffness. Filled copolymer grades offer higher yield elongation at the expense of tensile
yield strength.
The main applications for talc filled PP grades are in car heater casing, motor housing,
dryer drums, textile bobbins, industrial and agriculture plant components. Talc filled PP
sheet is used as an alternative to carton board.
2.7.2 Calcium Carbonate Filled PP
Calcium carbonate is also commonly used as a filler for PP. In comparison to the talc
filled grades, the calcium carbonate filled grades are claimed to have higher impact
strength, brighter colour, higher thermal stability and improved fatigue strength, but
lower stiffness and tensile strength. Calcium carbonate is added to PP at the same
loading as talc, from 10–40% by weight. However, in a highly filled system, non-
uniformity of mechanical properties can result from poor dispersion during the
compounding process.
The main applications of calcium carbonate filled PP are in instrument panels, motor
vehicle grills, heater boxes and garden furniture.
2.7.3 Glass Fibre Reinforced PP
Glass fibres are used to confer enhanced strength and rigidity. These fibres are usually
coated with silanes, lubricants, film formers and, sometimes, antioxidants and antistatic
agents. These coatings provide better fibre-matrix adhesion, consequently enhancing
the mechanical properties of the product. These coatings are also intended to reduce
14
breakage of the glass fibre during manufacturing and processing. Substantial

improvements in tensile strength and modulus are only realised after a coupling
reaction takes place between organofunctional silanes on the glass fibre and reactive
groups introduced into the PP molecule. There are many commercial glass fibre grades
that impart enhanced performance in PP.
The higher aspect ratio of glass fibre imparts higher reinforcing efficiency than talc,
calcium carbonate or mica. Glass fibre reinforced PP has been successfully used to
replace engineering thermoplastics in various applications. It has replaced PC, ABS,
polyesters and PA in hand-held tools, automotive grill opening reinforcing panels and
pump housings. Glass fibre reinforced grades are used for car and truck fan shrouds, car
rear light housing, radiation expansion tank, grills, headlamp housing, furniture frames
and washing machine components.
2.7.4 Mica Reinforced PP
Mica is a generic term encompassing a family of minerals, mainly hydrated potassium

aluminosilicates. Due to its high aspect ratio (about 50–100) mica gives higher flexural
modulus than talc or calcium carbonate at the same loading. More significant
improvement in tensile strength is obtained upon the use of appropriate coupling agents.
Due to overall mechanical property profile and high temperature resistance, mica
reinforced PP is used in several automotive applications, e.g., crash pad retainers,
battery and fan shrouds. As mica is dark in colour, it is not suitable for light-coloured
articles.
2.8 Additives for PP
Many other additives can be added to PP to provide or improve different functionality.

Commonly used functional additives are given in Table 11 and further discussed in
Section 4. However, it should be noted that the improvement in a certain property (or
properties) on addition of additives is generally at the expense of some other useful

properties. Hence, any change in material should be considered thoroughly to
understand its full impact on the product quality, specification and suitability for the
intended application.
The presence of additives in PP can significantly increase the toxicity of the resin.
These substances can migrate into food or water through plastic packaging or to the
body through medical devices. The handling of the additives might require special
handling instructions and they can produce toxic degradation products during
processing. Detailed information about the toxicity and hazard of special additive or
material may be obtained from the Material Safety Data Sheets from the manufacturer.
Some ingredients known to cause health and safety problems used in PP are blowing
agents, peroxides, fillers (such as glass fibre), pigments (particularly lead- and
cadmium-based pigments) and flame retardants.
15
As a rule of thumb, if any additive is added to the formulation of the PP, it should be
tested for its likely impact on food and medical applications. Resin should conform to
the regulations for health and safety.
Table 11 Commonly used functional additives for PP

Additive Functionality
To reduce accumulation of dust and associated possible fire
Antistatic agents
hazard
To decrease the friction between the film and the machinery
Slipping agents
during processing
Antiblocking agents To avoid films sticking together
Metal deactivators To reduce degradation due to the presence of metals
Blowing agents To reduce density
Nucleating agents To improve transparency and clarity
Antifogging agents To prevent condensation forming
Biocides To control the growth of micro-organisms and bacteria
Flame retardants To reduce flammability of the material or to suppress smoke
To prevent thermal oxidative degradation during processing and
Antioxidants
service
Lubricants To lower melt viscosity and prevent sticking to metal surface
UV stabilisers To protect against harmful UV radiation
Light stabiliser To provide stability against visible light
2.9 Identification of PP Type
Identification of a plastic component may be required for various reasons, e.g., the
identification of the material of a competitive product or defective products returned
from the field. The simplest technique to identify PP is by burning a small specimen. PP
burns with a blue flame with a yellow tip and smells of burning candle when the flame
is extinguished. PP floats on water and can be easily cut providing smooth surfaces. PP
is soluble in hot toluene. Most of the above observations for identification of PP are
similar to those of PE. Hence, further tests are invariably required for confirmation of
polymer type. The results from flame testing are further complicated by the presence of
comonomers, fillers and additives such as flame retardants, blowing agents, lubricants
and stabilisers. Hence, chemical and thermal analysis is required for positive
identification of the polymer. Infrared (IR) spectroscopy is the most widely used
technique for the positive identification of PP. Typical IR spectra (transmittance (T)
plotted against wavenumber) for different types of PP are shown in Figure 5. IR
spectroscopy can provide limited information about the fillers as well. Differential
scanning calorimeter (DSC) thermograms may be required to confirm the presence of
ethylene comonomer in the case of copolymerised PP or to measure the degree of
crystallinity in the PP artefacts (Section 3.3).
Further information about the fillers can be obtained from thermogravimetric analysis
(TGA) and X-ray fluoroscence spectroscopy (XRF). In TGA, the weight loss and
16
derivative weight loss of the polymer are measured as a function of temperature while
XRF provides the elemental analysis of the polymer compound.
Figure 5a Typical IR spectrum for homopolymer PP [13]

Figure 5b Typical IR spectrum for copolymer PP [13]
17
18

Practical Guide To Polypropylene 2 Basic

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Practical Guide To Polypropylene 2 Basic

Uploaded by

Copyright:

Available Formats

Practical Guide to Polypropylene

The physical properties and processing characteristics of PP are mainly determined by

• choosing between homopolymer and copolymer,

However, with changes in manufacturing technology, operating conditions and catalyst

Homopolymer PP is made by polymerising propylene in the presence of a

limited (Section 4.3.2).

Typical applications for homopolymer polypropylene include windshield washer tanks,

Figure 4 Structure of random and block copolymerised PP molecules. P and E

Copolymerised PP gives a softer feel to film and fibre products compared to

2.2.1 Random Copolymer

The random copolymer of PP contains chains with a small number (~1.5–6%) of

2.2.2 Block Copolymer

PP homopolymer is copolymerised with ethylene. In block copolymers, the ethylene

2.3 Elastomer-Modified Polypropylene

Extremely high toughness at low temperatures can be achieved by modifying PP with

Modification of PP with elastomers causes loss of hardness and stiffness. If elastomer-

2.4 Controlled Rheology

CR grades are available both as homopolymers and copolymers. Copolymer-based CR

pharmaceuticals, video cassettes, automotive parts, machine housing parts, suitcases,

2.5 Metallocene Polymers

Metallocenes are a new generation of olefin polymerisation catalyst. They have

Metallocene-polymerised copolymers offer the same mechanical properties as the

Europe’s first commercial metallocene-catalysed PP was launched by Targor, the joint

Table 10 Comparison of the properties of metallocene-polymerised PP with PP

2.6 Syndiotactic and Atactic PP

2.7 Filled Grades of PP

2.7.1 Talc Filled PP

2.7.2 Calcium Carbonate Filled PP

2.7.3 Glass Fibre Reinforced PP

breakage of the glass fibre during manufacturing and processing. Substantial

2.7.4 Mica Reinforced PP

Mica is a generic term encompassing a family of minerals, mainly hydrated potassium

2.8 Additives for PP

Many other additives can be added to PP to provide or improve different functionality.

properties) on addition of additives is generally at the expense of some other useful

Table 11 Commonly used functional additives for PP

2.9 Identification of PP Type

Figure 5a Typical IR spectrum for homopolymer PP [13]

Figure 5b Typical IR spectrum for copolymer PP [13]

You might also like