Ziegler-Natta Catalysis of

Alkene Polymerization

The catalysts used in coordination

polymerization are transition-metal organic
compounds.
 Ethylene oligomerization

n H2C CH2

Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2

Triethylaluminum catalyzes the formation of

alkenes from ethylene.
These compounds are called ethylene
oligomers and the process is called
oligomerization.
 Karl Ziegler (1950)

n H2C CH2

Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2

Ziegler found that oligomerization was

affected differently by different transition
metals. Some gave oligomers with 6-18
carbons, others gave polyethylene.
 Karl Ziegler (1950)

n H2C CH2

Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2

The ethylene oligomers formed under

Ziegler's conditions are called linear a-olefins
and have become important industrial
chemicals.
 Karl Ziegler (1950)

n H2C CH2

Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2

The polyethylene formed under Ziegler's

conditions is called high-density polyethylene
and has, in many ways, more desirable
properties than the polyethylene formed by
free-radical polymerization.
 Giulio Natta

n H2C CHCH3

Al(CH2CH3)3

polypropylene

Natta found that polymerization of propene

under Ziegler's conditions gave mainly
isotactic polypropylene. This discovery made
it possible to produce polypropylene having
useful properties.
 Ziegler-Natta Catalysts

A typical Ziegler-Natta catalyst is a

combination of TiCl4 and (CH3CH2)2AlCl, or
TiCl3 and (CH3CH2)3Al.
Many Ziegler-Natta catalyst combinations
include a metallocene.
 Ziegler Natta Catalysts
• Too numerous to describe all variants
• Two Components
– Transition metal compound Group IV to VIII metals
“catalyst”
– Organometallic compound Group I to III metals
“co-catalyst”

I II III IV V VI VII VIII I II III

 Ziegler Natta Catalysts
• Prepared by mixing in a dry, inert solvent in
absence of oxygen, usually at low temperatures
• Usually heterogeneous
 Ziegler Natta Catalyst
• Example: Titanium catalyst
AlR3 + TiCl4 AlR2Cl + TiRCl3

AlR2Cl + TiCl4 AlRCl2 + TiRCl3

AlR3 + TiRCl3 AlR2Cl + TiR2Cl2

TiRCl3 TiCl3 + R .
TiRCl3 TiCl2 + RCl

TiCl4 + TiCL2 2 TiCl3

 Mechanism of Coordination Polymerization

Al(CH2CH3)3 + TiCl4 ClAl(CH2CH3)2

+
CH3CH2TiCl3
 Mechanism of Coordination Polymerization

Al(CH2CH3)3 + TiCl4 ClAl(CH2CH3)2

+
CH3CH2TiCl3

CH3CH2TiCl3 + H2C CH2

CH3CH2TiCl3

H2C CH2
Mechanism of Coordination Polymerization

CH3CH2TiCl3

H2C CH2
Mechanism of Coordination Polymerization

TiCl3

CH3CH2CH2CH2

CH3CH2TiCl3

H2C CH2
 Mechanism of Coordination Polymerization

TiCl3

CH3CH2CH2CH2

H2C CH2 H2C CH2

TiCl3

CH3CH2CH2CH2
 Mechanism of Coordination Polymerization

CH3CH2CH2CH2CH2CH2

TiCl3

H2C CH2

TiCl3

CH3CH2CH2CH2
Mechanism of Coordination Polymerization

CH3CH2CH2CH2CH2CH2

TiCl3

H2C CH2

etc.
 A

B
E

D C
 General Composition of Catalyst
System
Group I – Transition Metals Additives
III
Metals
AlEt3 TiCl4 H2
R C CH
Et2AlCl a,g, d TiCl3 O2, H2O
EtAlCl2 MgCl2 Support
i-Bu3Al VCl3, VoCL3, R-OH
V(AcAc)3 Phenols
Et2Mg Titanocene R3N, R2O, R3P
Et2Zn dichloride Aryl esters