Olefin polymerization

In an attempted distillation of ethyl lithium, Ziegler observed α-olefins. He reasoned that

the following process was occurring involving partial decomposition of C2H5Li and
formation of ethylene :

insertion β-H elimination

Li + LiH
Li

Organoaluminum compounds such as Et2AlH displayed even higher activities towards

ethylene resulting in higher aluminum alkyls that could be readily hydrolyzed to produce
higher alcohols.

excess
H
Al Al Al
n
m

1
 Ziegler-Natta polymerization
Ziegler wondered what other metals may do. An exploration of this curiosity led to the
TiCl3/Et2AlCl catalyzed Zeigler-Natta polymerization (Nobel Prize, 1963) which is currently
used commercially to produce ~15 million tons of polyethylene and polypropylene
annually. Ziegler's original process for ethylene polymerization:

TiCl4 / AlR3

ethylene polyethylene

Natta extended this to propylene polymerization. He found that a greater stereospecificity

could be achieved by using crystalline TiCl3, with the amount of the desired isotactic
polypropylene increased to 90%.

TiCl3 / AlR3

propylene polypropylene

Ziegler, Angew. Chem. 1955, 67, 541.

Natta, Angew. Chem. 1956, 68, 393.
2
 General features of TM-catalyzed polymerization
Oligomer, n = 3 – 100
Polymer, n > 1000

R LnM R
n
Termination R = H, alkyl
via β-H elimination
R
Ln M R
H
n insertion
LnM

Propagation
via insertion
R
R LnM

LnM

R
R
LnM
LnM
insertion

3
 Isotactic polypropylene
Polymerization of alkenes is of great industrial importance, and one key issue is the
production of stereoregular polymers. The most important isotactic polypropylene has a
higher melting point, density and tensile strength than the soft and elastic atactic form.
Also of commercial importance is syndiotactic polypropylene.

isotactic: stereoregular material, long syndiotactic: long sequences having

sequences having the same the opposite stereochemistry at
stereochemistry at adjacent carbons. adjacent carbons. Physical
Physical properties: crystalline with a properties: semi-crystalline with a
melting temperature ~165°C. melting temperature ~100°C.

atactic: stereo-random polymer that

behaves as an amorphous gum
elastomer.

4
 Cossee mechanism for polypropylene
According to the Cossee mechanism, propagation of the polymer occurs at the Ti centers.
The role of the alkyl aluminum species is that of an initiator, by alkylating TiCl3. The δ-form
of TiCl3 is stereoselective below 100°C. In the more recent form of the catalyst (used since
the 1980s), TiCl4 is supported on MgCl2, and AlEt3 may be used for alkylation.

Me H Me HMe H
Cl Cl Cl
Polymer Polymer Polymer
Ti Cl Ti Cl Ti Cl
Cl Ti Cl Cl Ti Cl Cl Ti Cl

Cl Ti Cl Ti Cl Ti

disfavored favored

Representation of a Ti center on the edge of a TiCl3 crystal. The

growing polymer occupies one open site. Propene preferentially
binds with the methyl substituent anti to the polymer chain.

Cossee TL 1960 (17) 17. 5

Brintzinger Angewandte 1995 (34) 1143.
 Metallocene polymerization catalysts
The development of Ziegler-Natta catalysts has, since the 1980’s, included the use of
metallocenes – complexes of early transition metals with Cp ligands or ligands derived
from cyclopentadiene.
Cl
Ti
Cl

n Natta JACS 1957 (79) 2975.

ethylene Et2AlCl polyethylene Breslow JACS 1957 (79) 5072.

Mechanism:

Al Cl Al Cl Al Cl
Cl Et2AlCl Cl Cl Cl Cl Cl Cl
Ti Ti Ti Ti
Cl
alkylation migratory
insertion
Unlike the heterogeneous Ziegler-Natta
polymerization catalysts, the Ti catalysts are n
ineffective for propylene polymerization.
propagation

Al Cl Al Cl Al Cl
Cl Cl Cl Cl Cl Cl
H H
Ti H Ti Ti
n n
β-H elimination
n
6
Breslow JACS 1959 (81) 81.
 Metallocene polymerization catalysts
Trace amounts of water cause a significant increase in the rates of ethylene polymerization
by Cp2TiEtCl / AlEt2Cl system. It was later found that water also activated analogous Zr
complexes (which are unreactive in the pure form) to highly active catalysts for both
ethylene and propylene polymerization.

X n
Zr
ethylene X = Cl or Me polyethylene

AlR3
n
propylene atactic polypropylene

Hydrolysis of AlMe3 results in the formation of a mixture of oligomeric methylaluminoxanes.

Preformed MAO is equally effective as an activator of Cp2ZrMe2 and Cp2ZrCl2 catalysts
towards olefin polymerization.
Me
H2O O Al
Al Me Me Me Al O
Me
Me Al O or O Al
n Al O Me
Me
MAO n

Barron JACS 1995 (117) 6465. 7

 Activation by MAO
It is postulated that the highly Lewis acidic Al centers in MAO "abstract" CH3 resulting in a
cationic Zr complex and a [CH3-MAO]− counterion that may be weakly associated with the
metal.
Cl
Zr
Cl

MAO
polymer
β-H elimination Me
Zr MAO
Me
H3
C H3
Al(MAO) C
Zr Al(MAO)
Zr
Me

CH3
propagation H3 Al(MAO)
C
Al(MAO)
Zr Zr
Me

insertion

Kaminsky ACIEE 1976 (15) 630.

Kaminsky ACIEE 1980 (19) 390.
Brintzinger ACIEE 1995 (34) 1143.
8
 Cationic metallocene catalysts
[Cp2ZrMe(THF)]+ was one of the first cationic complexes used for ethylene polymerization.
The low polymerization activity was attributed to the coordinated THF which competes with
ethylene for binding.

AgBPh4 (1 eq)
Cl O
Zr Zr BPh4
Me Me
THF

Jordan JACS 1986 (108) 7410.

First well-characterized cationic zirconocene catalyst

capable of propylene polymerization at high rates:
Zr-C 2.25, 2.56 Å

H3
B(C6F5)3 (1 eq) C B(C6F5)3
Me
Zr Zr
Me Me
C6H6

Marks JACS 1991 (113) 3623.

9
 C2-symmetrical metallocene catalysts
Brintzinger's C2-symmetric catalysts:
1-Naphthyl

Me
Zr Zr Me2Si Zr
Cl Cl Cl Cl Cl
Me Cl

Naphthyl-1
Ethylene-bis-(indenyl) Ethylene-bis-
zirconium dichloride (tetrahydroindenyl)
zirconium dichloride

MAO MAO MAO

50 ºC 60 ºC 50 ºC

78% isotacticity,188 activity 91% isotacticity, 7700 activity >99% isotacticity, 875 activity
(kg pol/mol Zr·h), (kg pol/mol Zr·h), Mw = 12,000. (kg pol/mol Zr·h), Mw = 920,000.
Mw=24,000. Brintzinger ACIEE 1985 (6) 507. Paulus OM 1994 (13) 954.
Paulus OM 1994 (13) 954.

10
 C2-symmetrical metallocene catalysts
Proposed model for isospecific polymerization: The C2-symmetrical ligand controls the
stereochemistry of monomer addition. Olefin binds with the Me-substituent anti to the growing
polymer chain. Stabilizing C-H agostic interaction is thought to rigidify the TS thereby
increasing the stereospecificity of insertion.
polymer is in
open quadrant

Polym Polym
H ∗
H
Zr H Zr∗ H
H Zr
H
H
n
Me is down in
open quadrant C-H agostic TS

The meso form of the catalyst gives Zr

atactic polypropylene Cl Cl

Ewan JACS 1984 (106) 6355.

Grubbs Acc. Chem. Res. 1996 (29) 85. 11
Coates Chem. Rev. 2000 (100) 1223.
 Torsional isomers
Removal of the bridge between the indenyl ligands allows rotation about the metal ligand
bond and formation of C2- and meso- isomers, which have similar energies. The phenyl
substituents were incorporated to slow down the ligand rotation. The result of this was
production of an isotactic-atactic stereoblock copolymer.

Zr Zr
R R

C2 -isomer meso-isomer

isotactic block, < 28 % atactic block

Waymouth Science 1995 267 217. 12

 Shell higher olefin process - SHOP
SHOP process is operated on a 1 million ton capacity and constitutes one of the largest
applications of homogeneous catalysis.
Ph Ph
P Ph
Ni
Ph O PPh3
99% linear
ethylene, activity: 6,000 mol ethylene/ mol Ni 98% α-olefins
40 atm n up to C30
50 ºC, toluene

Mechanism: Ph Ph Ph Ph Ph Ph
P Ph P Ph
insertion P H
Ni Ni Ni
Ph O PPh3 Ph O Ph O Ph
-PPh3
β-H elimination Ph

Ph Ph
Ph Ph P
P H Ni H
Ni Ph O
Ph O
associative
displacement

Ph Ph Ph Ph
P H P
Ni Ni
Ph O Ph O
n
Ph Ph
β-H elimination P H propagation
Ni
Ph O 13
Keim and Kruger Angewandte 1978 (17) 466.
n
Keim Angewandte 1990 (29) 235.
 Brookhart’s cationic Ni(II) catalyst
The rate of associative displacement leading to chain termination is retarded in these systems
by the steric bulk of the ligand which blocks the axial positions above and below the plane of
the Ni complex, and thus hinders addition of C2H4 and formation of 5-coordinate species.

N Br
Ni
N Br 71 methyl branches per
1000 carbon atoms

MAO
n m
ethylene, 25 ºC, toluene
1 atm
branched polyethylene
Mw = 410,000

Catalyst activation:
Ar MAO Ar Ar +
N Br N N
Ni Ni Ni
N Br N Me N Me
Ar Ar Ar

Brookhart JACS 1995 (117) 6414.

Brookhart Chem. Rev. 2000 (100) 1169. 14
 Mechanism of branching

catalyst activation

MAO
N Br N N
Ni Ni Ni
N Br N CH3 N CH3

insertion
propagation

Linear high N H N N
Mw polymer Ni Ni Ni
N N N

branched high
n Mw polymer
branching

β-H elimination re-insertion propagation

N N N H
H
Ni Ni Ni
N N n N
n n m

15
 Grubbs’ neutral Ni(II) catalyst
Unlike heterogeneous Ziegler-Natta and homogeneous cationic metallocene polymerization
catalysts (poisoned by O, N, and S heteroatom functionality), the neutral Ni(II) catalyst is
highly tolerant of oxygenated functionality. Olefin polymerizations can be run in the presence
of ether, ketone, and ester additives without significantly inhibiting catalyst activity.

O Ph
Ni
N PPh 3
Pri
Pri
linear PE
ethylene, Mw > 250,000
7 atm 10 ºC, toluene n

activity: 3,700 kg PE/h⋅mol Ni

Grubbs Science 2000 (287) 460.

16
 Proposed catalytic cycle
The rate of associative displacement of the polymer leading to chain
termination is retarded in these systems (as in the Brookhart system)
by the steric bulk of the ligand, which blocks the axial positions above
and below the plane of the Ni complex.
O Ph
Ni
N PPh 3
Pri
Pri N Ph N Ph N H
Ni Ni Ni
O PPh3 O O Ph
-PPh3
insertion Ph

N
N H Ni H
Ni O
O
associative
displacement

N H N
Ni Ni
O O
n

β-H elimination propagation

N H
Ni
O
n
17