STEREOCONTROLLED POLYMERIZATION
Asymmetric polymerization
Polymerization via A prochiral monomer is polymerized to
asymmetric synthesis obtain a stereoregular polymer. During the
polymerization process, the coordination of
the incoming monomer on the catalyst takes
place in a selective fashion through only one
enantiotopic face.
Examples:
Polymerization of vinylic monomers, such as propylene,
styrene.
Polymerization of conjugated 1,3-dienes.
R1
R2 asymm.
R1
polym. * *
n
R2
R1 = H, R2 = COOCH3
R1 = H, R2 = CH3
Asymmetric polymerization
Polymerization The chirality of the synthesized polymers is
selective for the helic based on the helic conformation, that is right
sense handed or left handed. The polymers are
optically active.
Only one chain with a preferential
conformation is synthesized.
Examples:
CH3
CH2
O
CH3
o H
n
COOR
Asymmetric polymerization
Stereoelective A chiral racemic monomer is used. Only
polymerization one enantiomer of the chiral racemic
monomer is preferentially polymerized to
yield an optically active polymer.
It is a kinetic optical resolution of a racemic
monomer.
Examples:
* *
*
STEREOCONTROLLED POLYMERIZATION
Asymmetric polymerization
Polymerization via A prochiral monomer is polymerized to
asymmetric synthesis obtain a stereoregular polymer. During the
polymerization process, the coordination of
the incoming monomer on the catalyst takes
place in a selective fashion through only one
enantiotopic face.
Examples:
Polymerization of vinylic monomers, such as propylene,
styrene
Polymerization of conjugated 1,3-dienes.
R1
R2 asymm.
R1
polym. * *
n
R2
R1 = H, R2 = COOCH3
R1 = H, R2 = CH3
Polypropylene synthesis: The CRYPTOCHIRALITY phenomenon
isotactic
syndiotactic
atactic
Polypropylene synthesis
Stereocontrolled polymerization:
Control of stereochemistry via the nature of the
ancillary ligands on the metal centre.
Multiple insertions of the same enantioface:
isotactic polymer
Multiple insertions of the alternating
enantiofaces: syndiotactic polymer
Random enantioface insertions: atactic
polymer
Tacticity
Tacticity
• Isotactic and syndiotactic polymers are crystalline, atactic is
amorphous;
• NMR spectroscopy is a powerful tool for studying polymer
Stereochemistry.
Microtacticity
13C NMR Spectra of polypropylene: methyl pentad region
isotactic
atactic
syndiotactic
Regiochemistry
The possible regiosequences
Tail to tail Head to head Head to tail
are originated by 1,2-Insertion or 2,1-Insertion
ENANTIOSELECTIVE CATALYSIS1
Enantioselective synthesis of small molecules
X
cat*
*
R'
prochiral H R
substrate
chiral product:
the stereochemical events
are not related one to each other
Stereospecific polymerization
cat*
R R R R R
prochiral stereoregular polymer:
monomer the stereochemical events
are related one to each other
cat* = chiral coordination compound
1G. W. Coates et al., Angew. Chem. Int. Ed. 2000, 39, 3626.
STEREOSPECIFIC Ziegler-Natta Catalysts
Synthesis of isotactic polypropylene
ID = internal donor
Catalyst nature: heterogeneous
ED = external donor
The donors
15000 kg PP/mol Ti MPa h di i-PP 97 -98 %
Morphology of catalyst Morphology of catalyst of
support: spherical. PP particles.
STEREOSPECIFIC Ziegler-Natta Catalysts
Synthesis of isotactic polypropylene
MgCl2/TiCl4/AlR3
CH3 CH3 CH3 CH3 CH3 CH3 CH3
H 2C CH CH3
Heterogeneous catalyst.
Stereochemistry of the insertion step: nature of the errors:
A B
Errors of kind A are indicative for the chiral nature of the
catalyst.
Enantiomorphic site control
P
P = growing polymer chain
CH3
open site
CH3
Cl Cl Exposed
Ti CH2
Cl site
hindered site
Cl CH2
Blocked site
STEREOSPECIFIC Ziegler-Natta Catalysts
Synthesis of syndiotactic polypropylene
CH3 CH3 CH3 CH3 CH3 CH3 CH3
VCl4/C6H5OCH3/Al(C2H5)2Cl
H 2C CH CH3
Catalyst nature: homogeneous
General aspects of stereospecific polymerization of propylene
Catalyst MgCl2/TiCl4/AlR3 VCl4/C6H5OCH3/Al(C2H5)2Cl
Stereoregularity isotactic syndiotactic
Regioselectivity primary secondary
Control of enantiomorfic site chain end
stereochemistry
LnM-CH2-CH-P LnM-CH-CH2-P
CH3 CH3
Soluble catalysts
Low activity towards ethylene
Ti Cl + Al(C H )
2 5 3
Cl
Inactivity towards propylene
Very high activity towards ethylene
Zr Cl + MAO
Cl Good activity towards propylene
Metallocene catalysts
A + MAO leads to isotactic polypropylene
B + MAO leads to atactic polyproylene
ansa-zirconocenes catalysts:
stereorigid of C2 symmetry
The isotactic PP synthesized with X ZrCl2
metallocene catalysts differs from
that obtained with catalysts based on
Ti for:
lower molecular weight;
narrower molecular weight distribution;
the tacticity: from almost atactic to perfectly isotactic PP can
be obtained;
not fully regioregular: insertions with secondary
regiochemistry are also observed;
random distribution of stereo- and regio-errors.
The evolution of metallocene catalysts1: the root
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
The evolution of metallocene catalysts: the tree
Ewen’s Symmetry
Rules
CS
SYNDIOSPECIFIC Catalyst1
ZrCl2
ISOSPECIFIC Catalysts1
C2 pseudo-C2 C1
ZrCl2
ZrCl2 ZrCl2
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
ansa-zirconocenes catalysts of C2 symmetry
4 3 4
3
3
2 2
1
X ZrCl2 X ZrCl2 X ZrCl2
C ZrCl2
Si ZrCl2 Si ZrCl2
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
DIFFERENT INSERTION WAYS FOR PROPYLENE1
Primary insertion
Secondary insertion
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
The key-in-the-lock model: one lock, one key
The key-in-the-lock model: two locks, one key
THE ELEMENTS OF CHIRALITY1
propylene enantioface growing chain
CH3
H CH3
CH2 CH
M P M
* P
HH
enantiomorphic site
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
CHIRAL INDUCTION FOR THE PRIMARY INSERTION1
Site control
H CH3
M
* P
HH
Chain-end
control
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
CHIRAL INDUCTION FOR THE PRIMARY INSERTION1
stereoerrors
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
THE CATALYTIC CYCLE
CS
SYNDIOSPECIFIC Catalyst 1
ZrCl2
CH3
CH2 CH-P CH3
Zr CH3 Zr
CH3
CH2 CH- CH2 CH-P
CH3 CH3
CH3 CH2 CH- CH2 CH- CH2 CH-P
Zr CH3 CH3 CH3
CH3
[Link] et al.,
Chem. Rev. 2000,
100, 1253.
ISOSPECIFIC Catalyst1 C1
ZrCl2
Catalyst for the synthesis of
polypropylene with stereoblocks
Catalyst in Catalyst in
chiral conformation meso conformation
Cl ki
Zr Cl
Cl Zr
k-i Cl
kpi
kpa
Isotactic block Atactic block
Catalyst for the synthesis of
polypropylene with stereoblocks
Trend of productivity:
MeB(C6F5)3¯ << B(C6F5)4¯ ⋍ MAO
STEREOSPECIFIC Catalysts 1:
a summary
TiCl3 The Ti isospecific sites are featured by C2 symmetry
(Allegra, 1971)
TiCl2 Brintzinger, 1982 Isotactic PP (Ewen, 1984)
racemic complex isotactic PP
meso complex atactic PP
Kaminsky and
ZrCl2
Brintzinger,
1985
1L. Resconi et al., Chem. Rev. 2000, 100, 1253.
Propylene polymerization catalyzed by NON
metallocene complexes
+
N CH3
Pd B(ArF)4- amorfous PP
N OEt2 Mw = 15 000
N
= (2,6-i-PrPh)2DABH2
N
R N R isotactic PP
N N (insertion with
R' R' secondary
Fe
regiochemistry)
Cl Cl
1S. D. Ittel et al., Chem. Rev. 2000, 100, 1169.
Propylene polymerization with catalysts based
on Pd(II):
microstructure of synthesized polypropylene
(CH2)x CH3
CH3CH=CH2 (CH2)y (CH)z
n
Polymer microstructure might be related to the following
features of the catalyst:
• alkene insertion might occur with both primary and
secondary regiochemistry;
• the catalyst can move along the polymer chain in both
directions.