3.3.

Polypropylene
BASIC POLYMERIZATION REACTION

• Propylene is catalytically polymerized to form a linear,

flexible-chain polymer according to the following equation:

• The reaction is exothermic. Its heat of reaction is in the

order of 20.0 kcal/mol or 83.6 kJ/mol:
• There are three types of monomer insertions with respect to the
pendent methyl groups: the meso, racemic.
• Meso insertion produces a polymer with the methyl groups in the
same spatial position, which is referred to as isotactic polymer;
• Racemic insertion produces a polymer with the methyl groups in
alternating locations, referred to as the syndiotactic polymer.
• When the monomer insertion is random and nonstereospecific, a
noncrystalline atactic polymer is produced.
• These three forms of polypropylene are schematically represented in
the following chain configurations:
1. Isotactic polypropylene

2. Syndiotactic polypropylene

3. Atactic polypropylene

•The relative amount of these three types of polymers depends greatly

on the catalyst type and its activity.
Reaction Mechanism
• The mechanism for the catalytic polymerization of
propylene is represented by the following equations:

1. Initiation

2. Chain growth

3. Chain transfer and termination

• A growing chain generally proceeds through the
following reactions to its termination:
(a) Elimination of b-H group

(b) Elimination of b-CH3 group

(c) Transfer to monomer

(d) Transfer to activated hydrogen compound

(e) Transfer to alkyl-metal site

where [cat] denotes catalyst, Mt the transition metal, and P

the polymer chain.
Polymerization Temperature and Time
• The rate of polymerization increases with increasing temperature
within a given temperature range.
• At the maximum temperature limit, the catalyst gradually
deactivates and the reaction rate declines.
• Some catalysts may hold the reaction rate steady for a long period
of time after a short acceleration; others may allow the reaction
rate to decline with time after the induction period
Catalyst Systems
• The growth of polypropylene has largely depended on
the development of its polymerization catalysts.
• Invention of Ziegler–Natta catalysts and the
subsequent introduction of metallocene catalysts
brought about significant improvement in catalyst
efficiency and polymer quality.
Ziegler–Natta Catalysts
• Ziegler catalyst with aluminum trialkyl–titanium trichloride (R3Al–
TiCl3) catalyst and successfully prepared highly stereoregular
polypropylene.
Metallocene Catalysts
• The metallocene compounds have finite, single, active sites that
exhibit strong selectivity for the steric conformation of the
monomer.
• Thus, the compounds of transition metals such as titanium (Ti),
zirconium (Zr), and hafnium (Hf) have been extensively
investigated as the activated catalyst site.
Polymerization Processes
Basic Polymerization Processes

• Dozens of polymerization methods have been developed

since the commercialization of polypropylene.

• These methods can be grouped into four classes: slurry,

solution, bulk, and gas-phase processes.
Chain growth polymerizationPolyacrylonitrile (PAN),

• Polyacrylonitrile (PAN), linear polyethylene (PE) and

isotactic polypropylene (PP) are significant polymers
for fiber industry.
• Their monomers have a vinyl structure represented by
a general formula

Where X is CN, H and CH3, respectively, for the three polymers

• A monomer called acrylonitrile, which forms polymers that
can be used to make plastics, rubbers, synthetic fibers and
carbon fibers.
• Acrylonitrile is made up of a vinyl group and a nitrile group.
• Acrylonitrile is made up of a vinyl group, which is a carbon
double bonded to another carbon, as well a nitrile, which is a
carbon triple bonded to a nitrogen
Mechanism of Chain Growth Polymerization
• The general mechanism of free radical polymerization is shown in below.
• Initiation proceeds in two steps: decomposition of initiator to yield initiator
radicals, R•, followed by addition of R• to monomer, M, to give a new
radical, M1•.
• The rate constants for these two reactions are kd (rate constant for
dissociation) and ki (rate constant for initiation).
• In the propagation step, the monomer radical, M1• adds to another
monomer molecule to form a new radical, M2• , which in turn, adds to M to
form M3•.
• This continues at a rate constant kp (rate constant for propagation).
Initiation Rate constant
(Kd)
(ki)
Propagation
(kp)
.
.
.
(kp)
Termination
(ktc)
(ktd)
Acrylonitrile Polymerization
• The homopolymer, PAN, is rarely used in fiber
manufacturing with the exception of industrial
applications where resistance to chemical attack is
of prime importance.
• PAN is a homopolymer that is difficult to spin and
dye, and therefore virtually all commercial acrylic
fibers are made from acrylonitrile combined with at
least one other monomer.
• Acrylonitrile and its comonomers can be polymerized by any of the well-
known free radical methods.

• Bulk polymerization is the most fundamental of these, but its commercial

use is limited by its autocatalytic nature.

• Aqueous dispersion polymerization is the most common commercial

method, while solution polymerization is used in cases where the spinning
dope can be prepared directly from the polymerization reaction product.

• Emulsion polymerization is used primarily for modacrylic compositions

where a high level of a water insoluble monomer is used or where the
monomer mixture is relatively slow-reacting.