Ziegler-Natta Polymerization:

Synthesis of tacticity specific

polypropylene


S.C.S. Lai (s.lai@chem.LeidenUniv.nl)
Leiden University
April 8th, 2004
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 2
Table of contents
Overview

Mechanism (general)

Structure of catalyst

Stereospecifity\

Role of -TiCl
3


Conclusion


S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 3
Overview, polymerization (1)
Three possible polymer syntheses mechanisms:
Free radicals
ions
metalorganic complexes

Polymers of specific tacticity wanted in industries:


Isotactic Syndiotactic Atactic






S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 4
Overview, polymerization (2)
Linear vs. branched polymers


Ziegler-Natta catalyst generally used to produce linear,
isotactic polypropylene!






S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 5
Overview, history (1)
First report in September 1955 using purple phases of
TiCl
3
(-TiCl
3
and

-TiCl
3
) and AlEt
3
(higher activity) or

AlEt
2
Cl (higher stereoselectivity).



Solvay 1973: Added TiCl
4
, which acted as a catalyst to
convert -TiCl
3
into an active phase of TiCl
3
(higher activity
due to smaller particles).




S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 6
Overview, history (2)
Shell 1980: TiCl
4
supported on MgCl
2
in presence of AlEt
3
or

AlEt
2
Cl. Active species still TiCl
3
.

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


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



S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 7
Mechanism
Two
complications
Why Cl-vacancy?
Why
stereospecific?




Cossee-Arlman postulate (1964)

S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 8
Structure of the catalyst, overview
Three phases of TiCl
3
Color Stucture Activity
-TiCl
3

Purple Hexagonal layered
structure
Isotactic
-TiCl
3


Brown Needle structure Little
stereospecifity
-TiCl
3

Purple Cubic layered
structure
Like -TiCl
3

S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 9
Structure of the catalyst, overview
Schematic view of the structures of -TiCl
2
, -TiCl
3
and

-TiCl
3
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 10
Structure of the catalyst, Cl-
vacancies (1)
Sheet of -TiCl
2
, consisting of 2
layers of Cl with Ti in the
octahedral holes.
Ion count:
(2m
2
2) Cl
-
(m - 1)
2
Ti
2+
-----------------------------
Surplus of 4(m - 1) negative
charges

Offsetting by Cl
-
vacancies
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 11
Structure of the catalyst, Cl-
vacancies (2)
Thus: Surplus of 4 (m 1) Cl
-
on (m 1)
2
Ti
2+
Number of vacancies:



Typical crystal of ~1m has about than 1-2 vacancies per
1000 Ti
2+
-ions.

Analogous calculation for -TiCl3 yields the same result.

|
|
.
|

\
|
~

=
2
2
.
4
1
4
) 1 (
) 1 ( 4
TiCl mole
s equivalent
m m m
m
h
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 12
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

S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 13
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 Ti
3+
1 loosely bound (to 1
Ti
3+
)

Vacancy and L not
equivalent sites

S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 14
Stereospecifity, bonding of
propylene
Two possibilities: 1. Alkalyne moves back to vacancy
2. Alkalyne doesnt move back

Ti
L F
B B
V
B
Ti
B
L B
V
F
B
= = Ti L
V
F
AlEt
3
Ti V
Et
F
CH
2
C H
3
Ti -
Et
F
CH
2
HC
CH
3
Ti CH
2
V
F
CH
Et
C H
3
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 15
Stereospecifity, Polymerization
(1)
Polymer moves back to vacancy isotactic polypropylene
Ti CH
2
V
F
CH
Et
C H
3
Ti
F
V
H
2
C
CH
Et
C H
3
CH
2
C H
3
Ti -
H
2
C
F
CH
Et
C H
3
CH
2
HC
CH
3
Ti CH
2
V
F
CH
2
C H
3
CH
2
CH
Et
C H
3
C H
3
C H
3
R
R
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 16
Stereospecifity, Polymerization
(2)
Polymer doesnt back to vacancy syndiotactic polypropylene
Experimental: Some syndiotactic PP at -70
Ti CH
2
V
F
CH
Et
C H
3
Ti CH
2
|
F
CH
Et
C H
3
CH
3
CH C H
2
CH
2
C H
3
Ti
H
2
C
F
CH
3
HC
CH
2
HC
Et
CH
3
V
C H
3
C H
3
R
R
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 17
-TiCl
3
, Structure (1)
-TiCl
3
has a needle structure:
Cl Cl Cl Cl
Cl Ti
3+
Cl Ti
3+
Cl Ti
3+
Cl
Cl Cl Cl Cl


Actual structure
Cl Cl Cl Cl
Cl Ti
3+
Cl Ti
3+
Cl Ti
3+

Cl Cl

1

2


m

Charges:
3(m+2) +
3(m+9) -
3 vacancies per chain
m

S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 18
-TiCl
3
, Structure (2)

1
site: TiCl
3
F
Cl
2
L
TiCl
3
F
Cl
L
R Charge - 1/2

2
site: TiCl
3
F
Cl
L

TiCl
3
F
R
2
Charge +1/2

S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 19
-TiCl
3
, Reactivity
Reactive sites for
diene-polymerization:


1
site: 1 vacancy, limited
space 1,4 trans-polymers

2
site: 2 vacancies, both
forming pi-bonds with diene
1,4 cis-polymers

Experimental:
butadiene: mixture of trans
and cis
isoprene: only cis



S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 20
Conclusion
Three phases of TiCl
3


Only -TiCl
3
and

-TiCl
3
active in stereospecific Ziegler-
Natta polymerization

Active sites are the Cl
-
-vacancies, located at the edges of
the catalyst.

Stereospecifity are due stereometric interactions, forcing
the same orientation for each propagation step

-TiCl
3
has 2 different active sites, one forcing dienes to
polymerize 1,4-cis, one 1,4-trans, if molecule is flexible.
S.C.S. Lai, April
8th 2003 Ziegler-Natta Polymerization 21
Final remarks

Slides: http://home.wanadoo.nl/scslai
Questions?