22.

Polypropylene technology
 General aspects (PP)
 The most recent of the so called commodity plastics
 Broad selection of different grades
 In technically usable form PP has regular molecular structure
…isotactic

Polypropylene is polymerized with coordination or Ziegler-Natta

catalysts using with either slurry or gas-phase process.

Development of polypropylene polymerization technology has

been rapid and it has combined breakthroughs in both
fundamental chemistry and catalysts development for technical
development steps.
 General aspects (PP)

In bulk or mass polymerization of polypropylene liquid propylene

is used as a medium inside the reactor. Thus high polymerization
rate is achieved and simple process engineering is attained. Gas-
phase technology competes with bulk technology. When new
production facilities for PP are built, impact-strength the so called
block copolymers are polymerized exclusively in gas-phase
reactors.

Reasons for the rapid increase in polypropylene utilization have

been highly versatile product in combination with low price, low
weight, low energy content, and good chemical and long-term
properties.
 General aspects (PP)
The following properties are important for PP:

 Adequate impact strength in the whole operating temperature

range
 Preservation of mechanical and visual properties also after
exposure to UV radiation
 No stress-cracking caused by fuels
 Good processing properties for large batches
 Low weight and costs
 Possibility for material recycling
 Low energy content
 Shape stability at elevated temperatures
 Polymerization catalysts
Catalyst technology is in key position…

Typical properties of PP catalysts:

• High stereospecificity
• Very high activity
• Catalyst may remain in the product
• Catalyst must be so stereospecific that extraction of atactic
polymer is not required
• Catalyst activity should last long
• Polymer grows outwards from the active centers on the surface of
catalyst
…
 Polymerization catalysts
…

• The shape of catalyst particles defines the shape of polymer

particles
• Catalyst deactivates
• Various different kinds of active centers
• Desired molecular weight distribution (MWD) must be obtained
for product
• Product should have narrow MWD, high bulk density and good
plastic yield
 Production process
Production process for homopolymer (selection criteria):

 Product properties
 Operating cost
 Safety
 Enviromental issues
 Usability
 Support for research and development
 Investment cost
 Maturity of technology
 Licence issues
 Production process
Three basic process types are used in polypropylene production:
 Bulk process
 Gas-phase process
 Suspension

Solution and slurry processes are already out of date concerning

new investments. However, old slurry-based plants are still in
use.
 Production process
Design parameters of polypropylene process:
 Production process
Structures of polypropylene processes:
 Production process
Comparison of
polypropylene processes:
 Traditional slurry process
Traditional slurry-based production process for PP:
 Bulk process
In bulk process polymerization occurs in liquid propylene. Solid
polymer precipitates further as powdery substance. Bulk process
is usually realized in a stirred tank reactor or by using technology
based on the so called loop reactor.

Usually the extraction of generating heat from the reactor

becomes a problem.

In the case of stirred tank reactors it’s possible to use an external

heat exchanger through which slurry is pumped out and returned
to the reactor. Loop reactors are inexpensive in terms of heat
transfer.
 Gas-phase process
In gas-phase process the production costs are even lower than in
bulk-based production process. However, it should be taken into
account that temperature control inside gas-phase reactor is
probably harder than in a liquid-phase reactor.

Several technical solutions exist for gas-phase polymerization,

e.g., BASF has vertical mixed-bed reactor, Amoco has horizontal
mixed-bed reactor and Union Carbide’s Shell process is based on
the use of a fluidized bed.
 Gas-phase process
BASF’s Novolen PP production process:
 Gas-phase process
Montell’s Spheripol process for the production of homo-PP and
copolymer. Spheripol process is a combined gas-phase and bulk
process (the basic idea was originally developed by Himont):
 Copolymers
Copolymers with ethylene have big importance in PP technique.
Copolymers can be either random copolymers or block
copolymers.

Random copolymers can be produced quite easily either by using

liquid- or gas-phase process with the addition of ethylene.
Copolymers from both processes act as homopolymers. Ethylene
content can be as high as 4 %.

Block copolymers of polypropylene are not random block

copolymers. They are rather referred to as heterophasic
copolymers. They consist of a reactor blend of isotactic
polypropylene and ethylene-propylene rubber.
 Copolymers
Heterophasic copolymer:

Advantage of heterophasic grades is the improved impact strength.

Good impact strength is achieved only when the properties of the

rubber phase, such as particle size, their distribution and adhesion,
are at the right level.
 Copolymers

Quality of a copolymer is dependent on, e.g., the following factors:

 Type of homopolymer matrix, isotacticity, melt index etc.

 Ethylene/propylene ratio
 Homopolymer/copolymer ratio
 Distribution and size of phases
 Copolymers
AMOCO/Chisso gas-phase process for PP block copolymers:
 Copolymers

BASF-Norchem production process for E-P copolymer:

 Polymerization processes of
homopolymer PP:
Process Bulk ( liquid pool ) Dilute slurry Gas phase
Corporation Himont / Dart / El Paso AMOCO Sumitomo BASF / ICI / USI AMOCO
Mitsui Montedison Montedison Union Carbide
Sumitomo
Reactor Loop CSTR CSTR Fluidized- vertical horizontal
bed mixed-bed mixed-bed
Solvent - - n-hexane - - -
n-heptane
Catalyst Ti support Ti support or Ti support or Ti support Ti support or Ti support of
supportless supportless supportless supportless
Yield ( kg / g kat. ) 20-40 20-30 20-40 3-15 3-10 3-10
Tacticity max. 99 % max. 98 % max. 98 % max 98 % max. 98 % max. 98 %
Temperature ( °C ) 60-80 60-75 60-80 60-80 70-90 70-90
Pressure ( atm ) 30-40 30-40 15-20 20 20 20
Residence time ( h ) 1-2 2 3-4 3-5 4 4
Grade change- 4% 6% 10 % 12 % 12 % 3-4 %
loss per week
Molec. weight ( MI ) 0,1-800 0,1-800 0,1-100 0,1-750 0,1-100 0,1-100
MWD narrow-wide
-
 Polymerization processes of
homopolymer PP:
Process Bulk ( liquid pool ) + second phase "Suspension" Solution Multistep gas
Corporation Himont / Sumitomo Dart / Montedison / Dupont Sumitomo BASF / ICI / AMOCO /
Mitsui El Paso Dutral Exxon Union USI Chisso
Goodrich Carbide
Uniroyal
Reactor Loop- CSTR- CSTR- CSTR CSTR Fluidized-
- Mixed-bed Mixed-bed
fluidized- CSTR mixed-bed
- bed x 2 (vertical) - (vertical) x 2
bed (horizontal) Mixed bed
Solvent - - - Monomers and different - - -
diluents solvents
Catalyst Ti Ti Ti Ti/V Ti/V Ti Ti support or Ti support
support support or support or support unsupported
without without
T ( °C ) 60-80 60-75 40-75 0-20 30-60 60-80 70-90 70-90
Paressure (atm)
Phase 1 30-40 30-40 30-40 5-20 10-20 20 20 20
Phase 2 20 30-40 20 - - 20 20 20
Residence time (h) 1-2 2 2-5 1 0,1-1 3-5 4 4
Comonomers ethylene + ethylene ethylene Ethylene, Ethylene, Ethylene + Ethylene + Ethylene +
others butylene, dienes others others others

dienes
 Objectives for PP process:

 Wider selection of copolymers and terpolymer products

 New catalysts and processes for polar monomers and dienes
 Improved control over copolymer composition, composition
distribution and crystallinity
 More efficient adjustment of MWD
 Improved control over catalyst activity profiles
 Improved control over the shape of polymer particles
 Shorter residence times inside reactor, which leads to higher
productivity and shorter grade change times
 Modern on-line process control systems for evaluation of polymer
properties
 Borstar (PP)

• Borstar PP is based on the earlier-developed Borealis Borstar PE

process that was originally developed to produce bimodal MWD.
• Borstar is a modular process. Production facility consists of a
loop reactor and a large gas-phase reactor.
• It can be used to produce both homo- and copolymers.
• Significant advantages in comparison to traditional production
methods of polypropylene:
– Fast start-up and grade change
– High monomer concentration
– High catalyst activity
– More efficient use of propylene
– The basic properties of a product are generated already in the
reactor  lower production costs
 Borstar (PP)

• Significantly higher temperature range (80 - 92 °C) can be used

than with traditional production methods for PP (70 °C).
• Higher operating temperature enables also the production of
polypropylene grades with very high melt index and very wide
molecular weight distribution
• In Borstar PP processes ethylene can be used as a comonomer as
high as 10 % concentrations, when producing random
copolymers.
Borealis Borstar production
process for PP