Polymerization of olefins by

metallocene catalysts

Pasquale Longo
Università di Salerno
plongo@unisa.it
 Molecular Machine
Ziegler – Natta catalysts building some
plastic materials
(Poly-ethylene, Poly-propylene, Poly-styrene, etc. etc.)

This ship is made of only synthetic materials!

 USA production (1960-2000)
(1,000s of metric tons)

year 1960 1970 1980 1990 2000

LDPE 560 1,923 3,307 5,069 7,042

HDPE 70 728 1,998 3,780 6,333
PP - 468 1,655 3,773 7,139
PS 450 1,075 1,597 2,273 3,104
PVC 590 1,413 2,481 4,122 6,551

production went from 1.7 billion tonsm in 1960
to a massive 30.1 billion tonsm in 2000
 PP strength
- very low density
- high stiffness
-  good tensile strength
-  inertness towards acids, alkalis and solvents
-  cost advantage
-  good injection-molding characteristics

very suitable for the large-volume

cost- and weight-conscious markets
(automotive)
 PP automotive applications

Battery cases
Bumpers
Exterior trim
Interior trim
Fuel tanks 1,700 components of 5,000
Instrument panels are made of plastics
Under-the-hood applications 10% of total weight.
Wires and cables 60% of interior weight
 Amminoacids Proteins
Ala Ile Gly Glu
Leu Trp Pro
His
Ile His Leu Phe Arg Gly Trp Ala Ala Glu Gly His Leu Ile Pro Trp Arg Lys
Ser
Glu Ser Arg Pro
Phe Lys Lys

Propylene Poly-propylene
 Input
(brick)
Linus :
Human machine

Output
(building)
Classic machine
(Linus Van Pelt)
 Input
Pro
(amino-acid)
Glu
Rybosom :
Gly
His
Trp Leu Natural Machine
Lys
Ile
Arg
Ser
Phe
Ile

Glu Gly His Gly

Pro
IleLeuPro
Ile
His
Ser
Arg
Phe
Lys
Trp
Leu Trp
His
Ile
Gly
Arg
Ser
Lys
Phe
Leu Arg
Pro
IleIleTrp
Ile
Ser
Gly
Lys
Phe
Leu Arg
Pro
Lys
Trp
Ile
Ser
Gly
IlePro
Phe Ser
Arg
Pro
Ile Ser
Lys
Trp
Gly
Ile Trp
Phe Arg
Lys
Trp
Phe
Gly
Arg Ser
Arg
Ile Lys
Phe
Gly
Lys Ser
Gly
Ile Lys
PheSerSer
Ile Gly
Phe Gly
IlePhe
Phe Gly
Ile Ile Gly
Ile Gly

Output
(protein)
Molecular Machine
(Rybosom)
 Input
(propylene)
Ziegler Natta
Catalysts :
Artificial Machine

Output
(poly-propylene)
Molecular Machine
(Ziegler-Natta catalysts)
 Catalysts for
plastic material
production
1953-1954

Winners of the
Nobel Prize
1963
http://www.nobel.se

Karl Ziegler Giulio Natta

Only italian Nobel prize winner for chemistry !

 The motivations for awarding the
prize to Natta

•  Natural and biological catalysts had

previously dominated the synthesis of
stereoregular polymers.

•  Prof. Natta ended this monopoly.

 Propylene : INPUT

Poly-propylene : OUTPUT

Metallocene : tools
Propylene (CH2=CHCH3)

1
H H
A C

H3C C
2 H

INPUT
 The faces of propene are chiral

A chiral object does not

over-lay its mirror-image
Louis Pasteur - 1848

Mirror

A A* Chirality = asymmetry
Lord Kelvin - 1904
MILESTONES
REACHED
 Overview, history (1)
  First report in September 1955 using “purple phases” of TiCl3 (α-TiCl3
and γ-TiCl3) and AlEt3 (higher activity) or AlEt2Cl (higher
stereoselectivity).

  Solvay 1973: Added TiCl4, which acted as a catalyst to convert β-

TiCl3 into an active phase of TiCl3 (higher activity due to smaller
particles).
 Overview, history (2)
  Shell 1980: TiCl4 supported on MgCl2 in presence of AlEt3 or AlEt2Cl.
Active species still TiCl3 .

  Other remarks:
  Awarded Nobel price in 1963.
  1980’s: Process attributed to Robert Banks and J. Paul Hogan

Cerutti, L; International Journal for Philosophy of Chemistry, 1999 (5), 3-41

 Mechanism

  Two complications
  Why Cl-vacancy?
  Why stereospecific?

Cossee-Arlman postulate (1964)

 Structure of the catalyst, overview
•  Three phases of TiCl3
Color Stucture Activity

α-TiCl3 Purple Hexagonal layered Isotactic

structure

β-TiCl3 Brown Needle structure Little

stereospecifity

γ-TiCl3 Purple Cubic layered Like α-TiCl3

structure
 Structure of the catalyst, overview

•  Schematic view of the structures of α-TiCl2, α-TiCl3 and ß-TiCl3

 Structure of the catalyst, active site (1)

•  Cl-vacancies on the edges of the crystal.

•  Electron Microscopy: active sites are on the edges

•  Ti at the active sites in a square of Cl

Structure of the catalyst, active site (2)

•  Square makes an angle of

55° with the base plane.

-
•  Cl ’s not equivalent:
–  3 stuck in crystal
–  1 bound by 2 Ti3+
–  1 loosely bound (to 1 Ti3+)

•  Vacancy and L not

equivalent sites
Stereospecifity, bonding of propylene
V
V V Et
L F B AlEt3
Ti = B Ti L = Ti L Ti V
B B F F F
B B

H3C
H3C Et
Et CH3 V CH
CH2 HC
Ti - Ti CH2
F CH2 F

Two possibilities: 1. Alkalyne moves back to vacancy

2. Alkalyne doesn’t move back
Stereospecifity, Polymerization (1)
H3C H3C
Et Et
CH CH
H3C
V Et H3C
CH H2C H2C CH3
CH2 HC
Ti CH2 Ti V Ti -
F F F CH2

H3C
Et
CH H3C H3C
H3C
V CH2 CH2 R R

Ti CH2
F

Polymer moves back to vacancy  isotactic polypropylene

Stereospecifity, Polymerization (2)
CH3 CH3 CH3
H3C Et H3C Et
H3C H2C CH HC HC
V CH | CH2 Et
CH H2C
CH2
Ti CH2 Ti CH2 Ti V
F F F

H3C H3C

R R

Polymer doesn’t back to vacancy  syndiotactic polypropylene

Experimental: Some syndiotactic PP at -70°
 Cossee s mechanism
R R

X X C3H6 X X

X X

X X

insertion

X X X
R C3H6 X
R
X
X
X
X
 The Polymerization reaction

C C Polymer
Polymer Polymer
+ CH2=CH2 C C
Zr Zr Zr
C5 C5 C5 C5 C5 C5

C Polymer
C Polymer C
Zr C Zr
Piet Cossee
1964
C5 C5 C5 C5
Allegra said that …
CH 3

C*
CH 2 P
 Zambelli found that ….
Steric control

C C C C C C

C C C C C C C C C C C C C C a

C C C

C C b
C C C C C C C C C C C C

C C C
 Hydrocarbons monomers

Ethylene

Propylene Styrene
 Conseguence of Chirality
The right foot can only wear right shoes.

A Better
(more reactive)

A*

Catalyst
Poly-propylene :

OUTPUT
 Poly-propylene
Isotactic Polypropylene
* * * * * * * *

Syndiotactic polypropylene
* * * *

*
Atactic Polypropylene
* * *
* * * *

* * * *
 Poly-propylene
If only one face of propylene gives co-ordination
to the catalyst…
A A A A A A

* * * * * * * *

Isotactic Polypropylene
 Poly-propylene
If propylene gives co-ordination to the catalyst alternatively
with one and the other face …
A A A

A* A* A*

* * * *

* * * *
Syndiotactic Polypropylene
 Poly-propylene
If propylene can give co-ordination to the
catalyst with both the faces …
A A A

A* A* A*

* * * *

*Atactic
* poly-propylene
* *
Metallocenes :
Molecular Tools
 How is a Z/N metallocene
catalyst made?

Ancillary
Ligands + Group 4
Metal = Metallocene
How is a Z/N metallocene
catalyst made?

The metal is of
group 4.
How is a Z/N metallocene catalyst
made?

Which are the

ligands ?
How is a Z/N metallocene catalyst made?

? ?
? ?

? ?
? ?

More than 10,000 ligands !

How is a Z/N metallocene catalyst
made?
?
?

Which are the

other ligands?
How is a Z/N metallocene catalyst
made?
x
x

Which are the

other ligands?
 Activators
Al(CH3)3 + H2O Al O
CH3 n
REPRESENTS A BREAKTHROUGH
B(C 6F5)3

(C 6H5)3C + B(C 6F5)4 -

(C6H5)2NH + B(C 6F5)4 -

 Cation
Cp2MX2 + MAO [Cp2M(CH3)] + + [MAOX]-

CH3

+


Zr
C5 C5
How is a Z/N metallocene catalyst
made?

Polimerochain
Polymer
Monomero
Monomer
Which are the
other ligands?
Zr
C5 C5
 How is a Z/N metallocene
catalyst made?

Polyethylene
Ethylene
Which are the
other ligands?
Zr
C5 C5
How is a Z/N metallocene catalyst
made?

Polypropylene
Propylene
Which
are
the

other
ligands?

Zr
C5 C5
 The Tools at work:

Fundamental reaction
The Fundamental reaction

A chain of Snoopy kennels

The Catalytic Cycle
 Polymerization reaction

One monomer insertion is going on every

millionth of a second.

A metallocene has a very high reactivity: it

can give 10,000-20,000 monomers insertion
for macromolecules

A metallocene has a very high activity: 1 g of

metallocene can produce more than 1,000 kg
of polymer before it becomes inactive.
 The Tools at work:

Formation of stereoregular
polymers.
Stereoregular polymers.
The Symmetry of the King of diamonds
(isospecific symmetry)
The Symmetry of the King of diamonds
(isospecific symmetry)

Better situation !

Growing chain Growing chain

The Symmetry of the King of diamonds
(isospecific symmetry)
A* A

Growing chain
 Consequence of the Chirality
The right foot can wear only right shoes !

A*

Catalyst
The Symmetry of the King of diamonds
(isospecific symmetry)
A* A A* A
Better
? or ? ? situation!
or ?

Growing chain Growing chain

The Symmetry of the King of diamonds
(isospecific symmetry)

A A
Growing chain

Growing chain ?
The Symmetry of the King of diamonds
(isospecific symmetry)

+
=
Isotactic Poly-propylene
A metallocene having the same symmetry of the
King of diamonds produces an isotactic polymer.
Polymerization reaction as a
catalytic cycle.
C2 symmetric metallocene

chain
Mt Mt
chain

m m m m m m m
 Allegra
By utilizing C2 symmetric stereorigid metallocene Allegra’s
conclusion was verified and an isotactic polypropylene
was obtained. The two sites of cationic catalyst with the
C2-symmetry are homotopics, and perform isotactic
polymerization of propene. An eventual back-skip reaction
of the chain, before a following monomer insertion, does
not influence the polymerization stereochemistry .

chain
Mt Mt
chain
How is a Z/N metallocene catalyst made?

? ?
? ?

? ?
? ?

More than 10,000 ligands

have been synthesized
 Symmetry of Chess
(syndiospecific symmetry)
 Symmetry of Chess
(syndiospecific symmetry)

Better situation

Growing chain Growing chain

 Symmetry of Chess
(syndiospecific symmetry)
A* A A* A
Better
? or ? ?situationor ! ?

Growing chain Growing chain

 Symmetry of Chess
(syndiospecific symmetry)

Growing chain

Growing chain
 Symmetry of Chess
(syndiospecific symmetry)
A A*

Growing
Growing
Growing chain
chain
chain

?
Growing chain
 symmetry of Chess
(syndiospecific symmetry)

+
=

Syndiotactic Poly-propylene
A metallocene having chess symmetry produces a
syndiotactic polymer
Cs Symmetric Metallocene

chain chain
Mt Mt

r r r r r r r
The comparison of the symmetries

King of diamonds Chess

Growing chain Growing chain
 Mechanism….

The syndiospecificity of catalysts having

Cs - symmetry was the first experimental
evidence that Cossee’s chain migratory
insertion was operative.

chain chain
Mt Mt
 Mechanism …
Occasional meso (m) diads defects provide
evidence for back-skip reactions of the chain,
according to the hypothesis of Cossee and
Arlman which suggested that “the growing
alkyl group moves back to its original position
after each incorporation of a new monomeric
unit”.

r r m m r r r
Mechanism of Cossee and Arlman
R R

X X C3H6 X X

X X

X X

insertion

R
X X back -sk ip
X X
R
X
X
X
X
 Cossee and Arlman
The presence of tert-butyl group forbids the growing chain to
be located in the inward position , close to tert-butyl group,
thus, after each monomer insertion, the growing chain skips
back to the less crowded outward position. Hence, insertion
always takes place with the same face, because it occurs each
time on the same site of the catalyst that becomes isospecific.

chain
Mt
m m m m m m m
 Summary….
Metallocenes are molecular tools that change input
molecules (alkenes) into output molecules (polymers).

Monomer Polymer
Ethylene Polyethylene

Propylene Polypropylene
 Summary….
Metallocenes are intelligent and change pro-
chyral monomers (propylene) into stereoregular
polymers (polypropylene iso- or syndiotactic)
Monomer Symmetry Polymer
King of Diamonds isotactic polypropylene

propylene
Chess
syndiotactic polypropylene
Possible polypropylene from metallocenes:

ZrX 2
atactic polypropylene ZrX 2
hemisotactic polypropylene

ZrX 2
isotactic polypropylene
TiPh 2
isotactic block polypropylene

ZrX 2 ZrX 2
syndiotactic polypropylene atactic - isotactic
block polypropylene
 C1 Symmetric Metallocene

chain chain
Mt Mt

R or S R R or S R R or S R R or S R
Elastomeric polypropylene

+ +
Zr P Zr P
 2-(1-cyclopentadienyl)2-(1-phenyl)propano titanium
trichloride

(CH
(CH3))22C(Cp)(Ph)TiCl
C(Cp)(Ph)TiCl3 3 + MAO

atattico
atactic aatTT==50°C
50°C

Propylene

Isotactic at T = - 60°C

(CH3)2C(Cp)(Ph)TiCl3 [m]=0.76

Cp2TiCl2 [m]=0.85

CpTiCl3 [m]=0.51

Longo, P.; Amendola, A.G.; Fortunato, E.; Boccia, A.C.; Zambelli, A.; Macromol. Rapid
Commun. 2001, 22, 339.
 Active specie

+ +

Ti P Ti P

high temperature low temperature

Longo, P.; Amendola, A.G.; Fortunato, E.; Boccia, A.C.; Zambelli, A.; Macromol. Rapid
Commun. 2001, 22, 339.
2-(1-indenyl)2-(1-naphtyl)propano
zirconium trichloride

CH3
C
CH3 ZrCl 3 + MAO
 Hapto-flexible catalysts

C. De Rosa, F. Auriemma, G. Circielli, A. C. Boccia, P. Longo Macromolecules, 36, 3465, 2003

 Ethylene-Propylene Rubber
Common uses:

Automotive applications 44%

Roofing membrane 18%
Oil additives 10%
Wires and cables 8%
(Gaskets, seals,
Other coated fabric,
footwear, rug underlay) 20%.
THE END