6 Polymerization

1 Introduction
1.1 Polyethylene
1.2 Polypropylene
2 Catalysts for Polyethylene
3 Catalysts for Polypropylene
4 Catalytic Cycle for Alkene Polymerization
4.1 Cossee–Arlman Mechanism
4.2 Mechanism of Alkene Insertion
4.3 Mechanistic Evidence
5 Metallocene Catalysts
5.1 Structures of Metallocene Catalysts and the
Co-catalysts
5.2 Special Features and Advantages of Metallocene
Catalysts
5.3 Mechanism of Polymerization and Stereocontrol
by Metallocene Catalysts
6 Chromocene and Heterogeneous Catalysts
 6.7 Polymers of Other Alkenes
6.8 Engineering Aspects

The two largest production:

1. Polyethylene
2. Polypropylene
Mainly by heterogeneous process until the early 1990
(use of homogeneous metallocene catalysts).

1.1 Polyethylene (discovered in 1933 by ICI lab)

1. HDPE:
From low temp and pressure (0.96 g/cm3)
2. LDPE:
From with high temp and pressure (0.92 g/cm3)
3. LLDPE
Small amount of butane/octene as co-monomers

Structural features  physical properties

e.g. elasticity, crystallinity……..

1.2 Polypropylene
Determination of iso- or syndiotacticity by 13C NMR
50 MHz: pentad
150 MHz: Nonad
Relative intensity  Degree of tacticity

Because of its ordered structure, an isotactic polymer

has higher m.p. and tensile strength (拉 力 ) than the
atactic polymer.
Typically, the m.p.:
isotactic polymers = 165 - 171°C
atactic polymers = < 0 °C.

2 CATALYSTS FOR POLYETHYLENE

Heterogeneous catalysts
1. Phillips Catalyst (CrO3 on silica)
2. Union Carbide Catalyst
Silica + chromocene  silica supported catalyst
3. Ziegler Catalyst
A. TiCl4 + trialkylaluminum compound in organic
solvent
(colloidal (膠體的 )  heterogeneous)
B. TiCl3 on solid support

For both chromium- and titanium-based

catalysts, choice and pretreatment of
the supported catalyst as well as other
process parameters determine the
molecular weights, distribution of the
molecular weights, and the extent of
branching of the polymer chains.
 Physical properties
3 CATALYSTS FOR POLYPROPYLENE
Discovered by Natta (TiCl3 + organoaluminum
reagent) to produce isotactic polypropylene with
high crystallinity
Three generations of catalysts
1. TiCl4/organoaluminum compound
TiCl3 from the reduction of TiCl4 by the
organoaluminum compound)
TiCl3 exists in 4 crystalline forms: α, β, γ, δ (
polymorphs)
β form (purple) has a chain structure, the others
(brown) are layers.
 α, β, γ, δ give high tacticity, β does not.

Reduction of TiCl4 by organoaluminum compound

2. TiCl4/organoaluminum/promoter
Monoethyl reagent poisons the catalyst by blocking
the coordination site.

Addition of promoters (ether/esters) to destroy

AlEtCl2
3. TiCl3 supported on
MgCl2/organoaluminum/promoter
 highly effective: 30,000 g of
polypropylene per gram of catalyst
per hour could be achieved with an
isotacticity index of 96–99%.

4 CATALYTIC CYCLE FOR ALKENE

POLYMERIZATION
1. Cossee–Arlman mechanism
2. Green–Rooney mechanism.

4.1 Cossee–Arlman Mechanism

 direct insertion of alkene into the
metal–alkyl bond without the
formation of any intermediate.

6.6  three routes

1. with hydrogen gas
2. β-elimination
3. The last route is non-catalytic; living
polymerization
Cossee–Arlman Mechanism
Direct insertion: transition state 6.8

Green-Rooney Mechanism
Agostic interaction of α hydrogen: intermediates

α hydrogen γ hydrogen

Which mechanisms (Cossee–Arlman

Mechanism/Green-Rooney Mechanism) is the true
mechanism???
Difficult to tell because it is difficult to determine the
transition state or intermediates in heterogeneous
Ziegler-Natta catalyst!!

Indirect evidence from homogeneous metallocene

catalyst
Does not totally support Green-Rooney Mechanism!!
But agostic interaction should present!

Transition state 6.12!!

Similar to 6.8; only difference is agostic interaction
or not!!!

Agostic interaction is important for stereoregular

polymerization of metallocene catalysts!!! (no
consequence in ethylene polymerization)

4.3 Mechanistic Evidence

4f14

A model of metallocene compound for mechanistic

studies.
5. Metallocene Catalyst
Background
Homogeneous catalysts discovered in 1980s
A milestone in polymer chemistry
$5 billions investment + 1500 patent
0.5 tones of polypropylene in 2003
5.1 Structures of Metallocene Catalysts and the Co-
Catalysts

a: part of indenyl ligand possible

b: M is Ti(IV) or Zr(IV)
c: A is an optional bridging atom eg. Si, C.
d: X = Cl, alkyl
e.g.
 Metallocene Catalyst/H2O/AlMe3
H2O/AlMe3  MAO (methyl aluminoxanes; actual co-
catalyst)
MAO to generate coordinatively unsaturated
intermediates 6.27

Abstraction of CH3 from 6.26 because of high Lewis

acidity of MAO
MAO
The general formula of MAO is given by Me2Al-O-
[AlMe]n-OAlMe2, where n is between 5 and 20.
27
Structural information from Al NMR and X-ray
crystallography

Advantages of Metallocene catalysts over Zieglar-

Natta catalysts
1. polymerize a very wide variety of vinyl
 monomers irrespective of their molecular weights
and steric features.
2. the advantage of single site  produce extremely
uniform homopolymers and co-polymers
(Ziegler–Natta catalyst, with nonidentical
coordination environments around the
catalytically active metal centers, give polymers
with broad molecular-weight distributions.)
3. The predominant mechanism for chain
termination is by β-hydride elimination. This
produces a vinyl double bond at the end of each
polymer chain.
4. The most important feature of the metallocene
catalysts is their ability to produce highly
stereoregular polymers  choices of ligands

5.3 Mechanism of Polymerization and

Stereocontrol by Metallocene Catalysts
Cs symmetry C2 symmetry
Which catalyst is chiral?

Chiral catalyst  isotactic polymer

Achiral catalyst  syndiotactic polymer
Temperature dependence

Predict the tacticity of the polymer with

temperature!

A variety of monomers possible

Mechanisms

6 CHROMOCENE AND HETEROGENEOUS

CATALYSTS
 The oxidation state of chromocene on silica = +2
or +3? (see page 4)
 Well defined chromocene complexes for HDPE
production
Practice the electron counts and oxidation states??
 6.39 is inactive in the production of HDPE.
 The oxidation state should be _______
7 Polymers of other alkenes
8 Engineering Aspects
See the textbook