Why polymers?

polymeren zijn interessant

omdat er veel bij komt kijken
schalen lopen door elkaar:
• chemie van vorming
(hoofdonderwerp)
 moleculaire struktuur
 microschaal gedrag
(kristallisatie, domeinen)
 macroschaal eigenschappen
(stijfheid, brosheid, elasticiteit)
je kunt niet in alles expert zijn, maar je moet
wel weten dat er meer is dan chemie alleen
om zinvol te kunnen werken in dit gebied.
 What is a polymer?

 [ -monomer- ]n
 A polymer is anything that is hard to get
out of a Schlenk tube
 A polymer is anything that gives broad
NMR spectra
 Plastics, rubbers, superabsorbent materials,
starch, cellulose, peptides, DNA
Atactic polypentene - 1H NMR
Atactic polypentene - 13C NMR
Polymers and oligomers
Typical "polymer properties"
appear at  1000 monomer units

more for small apolar monomers

(polyethene)

less for large polar monomers

(polyester)
"Oligomers" consist of 5-50 units. This is the
region where separation of individual
components is difficult.
Oligomers are mostly used as "performance
chemicals" (synthetic detergents, fuel
additives)
 Questions

If you tear a plastic fiber, do you break

individual polymer chains?
And if you cut it?

What is the strongest polymer?

or
Physical properties
are important

 Crystallinity
 Transparency
 Strength
 Stiffness
 Viscosity
 Tg
 "Melt flow"
 Paintability
 Solid polymers

Amorphous
or
Partially crystalline:
small crystallites, with amorphous regions
between them.
No sharp melting point, but a
melting range of up to 10°C.
Also often a "glass transition temperature"
(Tg) between a brittle glass-like state and a
rubber-like state.
 Chemistry
determines properties

Monomer
solubility, interaction between chains,
surface reactivity
Chain regularity
crystallinity
Crosslinking
rubber-like properties
Molecular weight and distribution
viscosity, melt flow
 Chemical reactions
in polymer synthesis

Polymerization
 chain structure
Stereoselectivity
 chain regularity
Chemoselectivity
 branching
Initiation, termination, chain transfer
 mol wt and distribution
Chemical modification of polymers after their
formation
 Molecular weight
distribution

Mi = mol wt of polymer i
Ni = number of molecules of this polymer
N M i i
Mn 
Number-average:
i

N i
i

N M i i
2

Weight-average: Mw  i

N M
i
i i

Mw
Polydispersity: Q
Mn

Depends on polymerization kinetics,

but is often independent of molecular
weight.
Types of polymerization
Polycondensation

Nylon-66
HOOC + H2N
COOH NH2

- H2O

O H O

N
N N

H O H

Polyester
MeOOC COOMe + HO OH

- MeOH

O
O O
O
O O
Types of polymerization
Ring-opening polymerization

Polyethyleenoxide / Polyethyleenglycol

O O O O O

Polycyclopentene

Nylon-6
O
H O H
NH
N N
N

O H O
Types of polymerization
Addition polymerization

Polyolefins
(polyethene, polypropene, polystyrene, PVC)

R
R R R R R

Poly-dienes
(butadiene, isoprene, chloroprene)
R R R

R
R R

R R R R
 Why would
a polymer form?
Synthetic polymers
energy-rich monomers
 exothermic reaction
polycondensation:
release of small molecule
 entropy gain
ring-opening polymerization:
release of ring strain
addition polymerization
convert  to  bond
(Question: why don't we use polyacetone or
polyacetonitrile?)
 Why would
a polymer form?
Natural polymers
Energy supplied (e.g. via ATP) for each
added monomer
Polymers constructed in a stepwise
manner with precise control over
individual steps
 Peptides
use a "code" to guide step-by-step
synthesis
 Fatty acid synthesis from C2 precursors
stop at exactly the right chain length
(c.f. oligomers: mixtures of
different chain lengths)
 Synthetic polymers
Exothermic reaction, raring to go -
just add the right catalyst

Anionic polymerization

B- O B O-

RLi + R Li

Insertion polymerization
Cl Cl
Cl R Cl
Ti Ti
Cl Cl
Cl Cl R

R
R
Me2Si Zr Me2Si Zr
Cationic polymerization

R+ + R

R+ + R

Radical polymerization
R + R

Ring-opening metathesis polymerization

M M M
+
 Metal-centered olefin
polymerization
Basic mechanism:
C C
M C
M + C M C C C
C C
2+2 addition is normally "forbidden".
"Allowed" here because of asymmetry in M-C
bond:
Empty acceptor orbitals at M
Polarity M+-C- bond
d-orbitals at M  easier to form small CMC
angles
Insertion also happens at main-group metals;
First non-transition-metal catalyst (Al) reported
recently
(Jordan, JACS 119(1997)8125)
 
*
M
 Requirements for an
active catalyst
 M-C or M-H bond (can be formed in situ)
 Empty site or labile ligand (anion)
 Highly electrophilic metal center
 No easily accessible side reactions
 For stereoregular polymerization:
fairly rigid metal environment
 Insertion is a
2-site mechanism
M
2
C
1
Original Cossee mechanism

C
M M M
C C

"backskip"
Modified mechanism

M M
C C

C C
M M
The carbene mechanism (Green)

H H
M C M C

H
H
M C
M C

Involves change in oxidation state of metal

 unlikely for LnIII, Ti/Zr/HfIV, Ni/PdII
Modified Green mechanism
(agostic assistance)

H H
C
C
M M M H
C

M-H (or M-CH) interaction could facilitate

rotation of the C sp3 orbital.
Agostic interactions occur frequently in
electron-poor transition metal complexes.
- and -agostic interactions are most the
common types. Examples of both have
been found in crystal structures.
The interactions are usually weak (0-6
kcal/mol) and fluxional. -agostic
interactions are strongest.
 Chain transfer
Main chain transfer mechanism:
-elimination

R R
M M R
M R'
H H H

R' R'
M M R'
M
H H H

Balance between M-H and M-C bond

strengths very important for chain lengths.
General trends:
early late
M-C weaker
lower MW
 Other chain transfer
reactions
Alkyl transfer to cocatalyst

M R + Al R'

M R' + Al R

-Me elimination

R R
M M R
M
Me Me Me
 Termination
mechanisms
•Allyl formation

M R + M + RH

•M-C or M-H bond homolysis

(reduction of metal)
M R M +R

Reactions with impurities in monomer

"Burning"
 Fast chain transfer
Isomerization M H + M

M M H +

primary alkyls more stable and more reactive

equilibrium favours internal olefins

Dimerization C4H8

fast
C2H4
M H + C2H4 M Et M Bu
fast but slower
non-productive
Insertion rates:
ethene > -olefin >> internal olefins
 Slow chain transfer
M-H (relatively) unstable
Polymers up to 106-107 D possible
(but often not desirable)
If:
 there is only a single "site"
 kCT is independent of chain length
 kinit is not too small
 tpol >> tchain
then
Q = Mw/Mn  2
Any deviation from the first 3 conditions
increases Q.
Determination of Mn by NMR
(for up to 1000 units)
detectable vinyl and vinylidene end groups
Main MWD analysis method: GPC
 No chain transfer
"living" polymerization

If:
 there is only a single "site"
 kCT "zero" (on time scale of experiment)
 kinit is large relative to kprop
then
Q = Mw/Mn  1
Any deviation increases Q.
Living polymerization can occur if the M-H
bond is very weak.
 Block copolymers

If kterm is "zero" at the laboratory time scale,

one can make block copolymers, e.g.
M M(C2H4)n R M(C3H6)m (C2H4)n R

Not often used for polyolefins, except (Doi):

C3H6 MMA
V M(C3H6)n Me (MMA)m (C3H6)n Me

Also used for SBS rubbers:

Buta diene S tyrene
RLi R(S tyr)n Li R(S tyr)n (But)m Li

BrCH2CH2Br

R(S tyr)n (But)m CH2CH2(But)m (S tyr)n R

S B S
 Controlling the
molecular weight
Very high MW is not always desirable
 add an MW "control agent"
 H2
M R + H2 M H + RH

saturated end groups (NMR)

 other olefin

M R M M H +
R R
MW control agents increase kct and lower the
MW, but do not affect Mw/Mn
 MW distributions

Schulz-Flory distribution
(polymerization with chain transfer)
characterized by
 = kprop/(kprop+kct)
mole fraction of n-mer = n(1‑)

Poisson distribution
(living polymerization)
characterized by
 = ratio monomer:"catalyst"
mole fraction of n-mer = ne-/n!
Schulz- Flory distribution
 max of MWD mol frac at max wt frac at max Mn/M Mw/M Mw/Mn
0.70 0.80 0.22523 0.14573 4.33 4.13 0.95
0.90 7.49 0.04542 0.03919 11.00 17.18 1.56
0.95 17.50 0.02038 0.01892 21.00 37.10 1.77
0.99 97.50 0.00375 0.00370 101.00 197.02 1.95

Poisson distribution
 max of MWD mol frac at max wt frac at max Mn/M Mw/M Mw/Mn
1.00 1.00 0.36788 0.36788 3.00 3.33 1.11
3.00 3.00 0.22404 0.22404 5.00 5.60 1.12
5.00 5.00 0.17547 0.17547 7.00 7.71 1.10
10.00 10.00 0.12511 0.12511 12.00 12.83 1.07
30.00 30.00 0.07263 0.07263 32.00 32.94 1.03
100.0 100.00 0.03986 0.03986 102.00 102.98 1.01
0
 Typical polymerization
conditions
(Pre)catalyst on a support
Active species generated in situ (e.g., by
addition of "cocatalyst")
Al alkyls or similar added as "scavengers"
Very pure monomer used
70 - 150°C
 Gas phase (ethene, ethene/propene)
 Liquid olefin (propene, higher olefins)
 Classical Ethene
Polymerization Catalysts
Ziegler catalysts
MCln + Et2AlCl "ClxMEt"
Role of Al alkyl
 alkylation
 reduction of M (via M-C or M-H bond
homolysis?)
 scavenger
 weakly coordination anion?

P P
M Cl M + alCl
al

"Almost any metal can polymerize ethene"

 Commercial
Ziegler catalysts
are always heterogeneous

 High-surface TiCl3
formed in situ from TiCl4 and Al alkyl
 TiCl3 on support (e.g. MgCl2), prepared in
a complicated process starting e.g. from
TiCl4 and Mg(OAr)2.
Nature of active site not very clear.
Chain transfer is slow  high MW
H2 or temperature used to control MW.
Distribution of different sites on surface
 broad MWD (Q = 5-30)
Catalyst productivity > 106 g/g Ti/hr
 catalyst residue removal not needed.
 Types of polyethylene
different application areas

High-density (HDPE)
produced by Z-N or metallocene catalysis
Low-density (LDPE)
produced by high-temperature radical
polymerization
Linear low-density (LLDPE)
produced by Z-N or metallocene catalysis
with some -olefin comonomer
Long-chain-branched
produced by Brookhart-type catalysts or by
metallocene catalysis with long-chain -
olefin comonomer
 Other classical PE
catalysts (1)
VCl4/EtAlCl2 and related systems
"Possibly the most active ethene
polymerization catalysts" (Shell, 1972).
But: V catalyzes PE autoxidation and most
be removed
Homogeneous? VIII?
Halogenated compounds added to improve
catalyst stability (reoxidation of VII to
VIII?)
Fairly narrow MWD (Q = 2-4)
VIII is paramagnetic
 this is a difficult system to study!
 Other classical PE
catalysts (2)
CrO3 or Cp2Cr on silica (Phillips)
Cr oxides need to be "activated" with a
reductant (H2, ethylene)
Metallocenes are currently replacing Z-N
catalysts for commercial production of
specific types of PE.
 Generalization

In simple, hard-donor ligand environments,

early first-row metals are the best catalysts.

 M-H vs M-C
 easier to form "naked" ions
 accessibility of different oxidation states
 cost
 Polypropene

Propene polymerization is more difficult than

ethene polymerization:
 Insertion of -olefins is slower than of
ethene
 Termination by -elimination is easier
 Generally, some degree of stereocontrol is
necessary to make an interesting product
But (isotactic) PP is attractive because it has a
higher melting point than PE.
PP stereoregularity
atactic
(Post-It)

isotactic
(Most common PP)

syndiotactic
(Not a commercial
product yet)

hemi-isotactic
Laboratory
curiosities
block-isotactic

PP is not chiral!!!
 Commercial PP
production
Ziegler-Natta technology

The process to make an iso-specific catalyst is

complex. An example:
 Pre-treatment of support with an organic
"donor" (ether or ester)
 Absorption of TiCl4 on surface
 Addition of Al alkyl mixed with a second
"donor" (ester or di-ester)
Some surface sites are better for
isospecificity than others
Aspecific sites can be converted into
isospecific ones
Fair syndiotacticity is also possible, but much
more difficult.
 The active site
of Z-N catalysts?
There have been many proposals for the
active site in Z-N catalysts and the reason
for its isospecificity.

These are probably all incorrect or very

incomplete. Our basic understanding of the
system is still poor, and this is the reason
metallocenes have had such a dramatic
impact recently.
 The active site
of Z-N catalysts?
There is consensus about the direct Ti
environment on the surface; and it is
probably TiIII. Cl
Cl P
Cl Ti
Cl
Insertion occurs primarily in a 1,2-fashion
(determined from end-group analysis).
P P
Ti Ti
+ Me
Me
Steric bulk near the Ti center must be
responsible for the isospecificity (site
control).
The Cossee mechanism was originally proposed to explain the
isospecificity. If the site has approximate C 2 symmetry, the
modified Cossee mechanism would also explain the results.
 Errors in Z-N PP

 Stereo-errors

 Regio-errors

 "1,3-insertion"
 Mechanism of
1,3-insertion

H
Ti P Ti Ti +
P
P

Ti
Ti
H +
P P

(has been demonstrated by labelling)

 Effect of addition of H2

 Reduction of MW
 Increase in activity
 Increase in iso-specificity
Explanation:
"Dormant sites", formed by an insertion
error, have lower propagation rate but still
react rapidly with H2.

The H2 effect allows a better determination of

the number of active sites. From this, we
can conclude that in the best Z-N catalysts,
high isospecificity is obtained not just by
blocking aspecific insertion, but by
"optimizing" for isospecific insertion!
 PP tacticity
Analysis of errors by 13C NMR.
Stereochemistry usually expressed in
"linkages":

m ("meso") linkage r ("racemic") linkage

NMR can be used to distinguish different
linkages, e.g. mmrm vs mrrm "pentads".
Formal view: site vs chain-end control
Assume stereochemistry of next insertion is
determined completely by:
Geometry of metal site ("site control")
Stereochemistry of last inserted unit ("chain-
end control")
These extremes can be distinguished by the
insertion errors.
site control:

m m m r r m
chain-end control:

m m m r m m
Always observe a distribution of different
linkages.
Statistics can be used to analyze the results in
terms of site control, chain-end control,
mixed control, or mixture of different sites
with different specificities.
 The Doi system for
propene polymerization
V(acac)3 + EtAlCl2
 Mainly syndiotactic
 Living (Q = 1.0‑1.2) at low temperature
(up to ‑40 °C)
 Activity in the order of kg/g V/hr
 Homogeneous
 Large ligand effects:

O
V ca 6% of V active
O
3

O
V ca 95% of V active
O
3
 Doi system

Possible explanation:
 active site relatively open:
O P
V X
O

 2,1-insertion (at least for the syndiotactic

blocks)
 chain-end control

P P
P
Me Me
Me
H
V V
H Me
Me Me V
r linkage
 Metallocenes
the wave of the future?

M R X

M = TiIV, ZrIV, HfIV

X = weakly coordinating anion
(MAO, borate, carborate)

Kaminsky, Ewen, Marks

 Cp2TiR+ polymerizes propene with slight and
temperature-dependent isospecificity
 mainly 1,2-insertion
 chain-end control
P P
H P H jkk
H
Me Me
Me
Ti Ti
Me Me
Me m linkage
Ti
vs P
Me
H Me H
H Me
P
Ti
P Ti r linkage
Me Me
Me
Ti

Stereopreference depends on difference in

steric interaction with Cp of P and Me
groups.
 The "trick" of
metallocenes
Discriminating between chain positions
("site control")

P
M vs M
P

Preferred chain position independent of

previous insertion stereochemistry
After every insertion, the chain moves to the
other site at Zr.
 Chain preferences the same
(i.e. related by 2-fold axis)
 isospecific polymerization
 Chain preferences opposite
(i.e. related by mirror plane)
 syndiospecific polymerization
 One site with a strong preference,
the other without preference
 hemi-isotactic polymerization
Double stereodifferentiation: the absolute
configuration of the last inserted monomer
affects the preference, so the tacticity of a
unit after an insertion error is atypical. This
complicates interpretation of NMR data.
In an extreme case, one could
(theoretically)make a new polymer:
Typical metallocenes

Zr Me 2S i Zr isospecific

Zr syndiospecific

Zr Zr

block-isotactic

see e.g. Brintzinger,

Angew. Chem. IE 34(1995)1143
 Characteristics of
metallocene
polymerization
 Difficult to get MW as high as Z-N
catalysts
 H2 has same effects as in Z-N catalysis
(dormant sites)
 Narrow MWD (Q  2)
 Rates can be extremely high
(> 107 g/g Zr/hr)
 Chain transfer by -H and -Me
elimination
Errors same as in Z-N catalysis, plus:
stereo-errors after insertion
(demonstrated by labelling studies and by
dependence of isospecificity on
[monomer])
 Mechanism of
epimerization
Zr

Zr
H

H
Zr

Zr

vinylene end-groups

Zr
H

H
Zr

Zr

Zr
 Back-skip
Inversion at the metal

M R M R

Does not affect isospecific polymerization but

results in a stereo-error in syndiospecific
polymerization
Back-skip more difficult in highly bent
systems (short bridges between the rings)
Back-skip after each insertion will usually
result in isospecific polymerization
(cf Z-N systems)
 Non-metallocene ETM
polymerisation catalysts
(just a selection)
Ar
N
Ti R Me 2S i Ti
N R Cr
N R
R THF
Ar

McConville "Constrained-Geometry" Theopold

SiMe 3
O
N
Me 2S i X Zr
R
Ti Zr R
R O
N Me 2S i
R N
R
SiMe 3
"LovaCat"
Horton Schaverien

Mostly non-stereoregular. Differences in

rate of termination (MW) and incorporation
of higher olefins.
 General conclusion

An M-C bond, an "empty site" and

electrophilicity are enough for
polymerization. Most unsaturated ETM
compounds can in principle polymerize
olefins.

The ligand environment is needed for

suppressing side reactions
and for "tuning" MW, chemospecificity
and stereospecificity
 Polymerisation
at LTM centers
Mostly low MW, but with "hard" donors MW
can be higher.
Isomerization ("chain running").
Lower sensitivity to functionalized olefins.
R2 R
P
R2
Ni N
P R N
N
Ni O
Rh
O
X R
O
SHOP (Keim) Flood

S iMe 3

Me 3S i N
N P + Ni(COD)2
Co
Me 3S i N
(Me O)3P R
S iMe 3
Brookhart
Fink
Exercise: Look up the Fink reference
(Angew Chem IE 24(1985)1001)
and explain his results.
 The SHOP process (1)

Basic reaction:
" "
O P
Ni

Main byproducts:

Special properties of SHOP catalyst:

isomerization rate low
very little insertion of -olefin
 The SHOP process (2)

Depending on market,
desired products are:
 Hexene and Octene,
as comonomers for polyethene and
polypropene
 C10-C18 olefins
for detergents
(hydroformylation or sulphonation)
Butene is "waste"
Schulz-Flory distribution is broad
 relatively large amount of undesired
products
 The SHOP process (3)

"Ni" separation
C6, C8 useful
C10-C18 products

isomerization C4
Na/K/Al2O 3 C20 and up
metathesis
"Co/Mo"

broad range of separation

internal olefins

C6-C18 internal olefins

Oligomerisation carried out in polar solvent

(diol) in which products are insoluble.
 LTM oligomerization
and polymerization
Problem:
easy chain transfer by -elimination
because M-H bond stable (relative to
M-C bond).

H H
M
M

 Low MW (dimers or oligomers instead of

polymers)
 Isomerization
But there are exceptions ! Why ?
 Chain transfer
via -elimination?

H H
M H M
M M M H +

Propagation Chain transfer

According to theoretical studies,

termination could never compete with propagation!
 Explanation
Chain transfer does not involve a free hydride
Associative displacement:
R'

M H

H R' R R'
R
M
M + +
R R' H

M H

"chain transfer to monomer"

Anion or solvent assistance:
H X X R

M +X M H M +
R
H
R

Monomer, anion and solvent can occur in

chain transfer rate equations.
 The "famous”
Brookhart system
Ar M = Ni or Pd
Ar = hindered aryl
N R
M
N

Ar

Enough space for insertion

but not for associative displacement
 high MW.
Enough space for (reversible) -elimination
and olefin rotation
 chain running
 Chain running

1,2-insn
M
M
P
P

2,1-insn
M M
P P
P P

Product more linear than expected

 2,1- vs 1,2-insertion

1,2-insertion is the most common reaction

2,1-insertion can be favoured if:
 The metal is relatively open
 Insertion is in a M-H bond (as opposed to
M-C)
 The olefin has a functional group in
-position
Me O
O
 LTM systems are more
compatible with
functionalized olefins
COOMe COOMe

N R
M
N
O
Me O COOMe

Low incorporation of acrylate because M-

acrylate coordination weaker than M-
ethene coordination (why?).
But after coordination, acrylate is more
reactive.
 Acrylate inserts
in a 2,1-fashion
P P
O
M M
M OMe

O OMe
OMe P
O

chain running
OMe
O
M

The 5-membered chelate ring is relatively

stable.
Copolymerisation is much slower than ethene
polymerisation (factor 30-300).
Characteristics of LTM
polymerization catalysis
 Rates can be comparable to ETM catalysts
 Anion coordination is not a major problem
 Can be compatible with protic solvents
and functionalized monomers
 MW tends to be (much) lower, unless
associative displacement is blocked
 Chain running gives rise to unusual
branching
 No convenient general "ligand skeleton"
for easy tuning

+   +
M (n) H M (n-2) H
Hard ligands destabilize hydride
 higher MW.
 Comparison of ETM and
LTM catalysts
H
H
M M
M M
H

can be a significant
barrier for ETM
barrier significant H
systems (Ziegler)
for LTM systems M
but much lower for
ETM systems.
faster for
-agostic assistance
LTM systems
mainly for ETM systems. H
M

Anion displacement may be chain

a significant factor in running
the rate of polymerization. chain
H
transfer
M
 Challenges in olefin
polymerization
 Comonomer incorporation
 Stereocontrol
 Control over branching (long chain
branching)
 Morphology (reactor fouling, space-time
yield)
 "True gas-phase" processes
 New monomers

 New block copolymers

 Diene polymerisation

Butadiene is "waste" from crackers

 any application is welcome

BuLi or
TiI3 / AlR3

VCl3 /
(iBu)3Al

BuLi /
chelating ether

Rubbers, often hydrogenated to saturated

polymers
 Ligand influence on
diene polymerization
O CF3COO O
CF3 Ni Ni
CF3 Ni
O O
cis

CF3COO CF3COO
CF3COO
Ni Ni
Ni
L L
L

trans
Diene polymerization -
general C1
attack

always C3
terminal attack
attack P
on diene

C1
attack

syn trans-1,4 P
P

C1
attack

P
P anti cis-1,4

P
P
C3
attack

1,2

P anti syn
P
 RLi catalyzed diene
polymerization
Without added ligand: P
cis/trans

P
Li
Li
Li
Li 1,4
P
P

insertion within
coordination sphere
butadiene: 35% cis, 54% trans, 11% 1,2
isoprene: > 90% cis
With added chelating ligand:

attack on
mainly 1,2 P
"free" diene

Li
L L
 Lanthanide-catalyzed
diene polymerization
With Ln(allyl)3 or LiLn(allyl)4:
P
P

LnX2 LnX2

P LnX2
syn
trans-1,4 polymer

With a weakly coordinating counterion:

Ln(allyl)3 + EtAlCl2
P

LnX
LnX LnX
anti
P cis-1,4 polymer
 Ni-catalyzed diene
polymerization
Mainly 1,4. More cis with hard counterions,
bulky added ligands, or "ligand-free”
trans polymer

Ni Ni Ni
P P P
syn less reactive

Ni
Ni Ni
anti
P not reactive
P P

cis polymer
Rate of syn-anti equilibrium depends on
ligands at Ni
 Co-catalyzed diene
polymerization
Co(allyl)2I: nearly pure cis-1,4, via
4-coordination
Co(methylheptadienyl)(butadiene):
syndiotactic 1,2
Me L

L Co
Co P

P
P
-L
L Co
Co
+ C4H6

Switches to cis-1,4 on addition of Lewis acids.

 Styrene polymerization
very reactive:

 cationic
 acid
 radical (e.g. air)
 anionic
 metal
Product is usually atactic. Clear, somewhat
brittle, soluble in several organic solvents.
Used for glue, food packaging, EPS.
Syndiotactic polystyrene has a higher melting
point.
Can only be prepared via metal-catalyzed
polymerization.
Best catalyst:

Ti(III) + Al a lkyls
RO OR

Mechanism unknown. Probably 2,1-insertion

and chain-end control.

Ti
P
Ti P
 Syntheses of
(well-defined)
polymerization catalysts

 Ligand synthesis
The carbon skeleton is the most difficult part.

 Metal complexes
 Metal alkyls
 Metal alkyl cations
 Alternative routes
 Ligands for
metallocenes
Substituted cyclopentadienyls
SiMe3

CpNa + Me3SiCl

O R OH R

RLi H+

NR2

R2NLi
-

Ansa-metallocene ligand construction

Me2SiCl2 + CpLi Me2SiCp2

Br CH2 CH2 Br + CpNa CpNa



CpNa
 Metallocenes
"Cp2"Li2 + ZrCl4(THF)2 "Cp2"ZrCl2
Frequently fails:
Reduction, attack on THF, ...
Low yields, complicated mixtures
"Cp2"(SiMe3)2 + TiCl4 "Cp2"TiCl2 + Me3SiCl
Also Sn
"Cp2"H2 + Zr(NMe2)4 "Cp2"Zr(NMe2)2

HCl

"Cp2"ZrCl2
 (Ligand)ZrCl2 often binds ethers and/or metal
halides. Complexes often poorly soluble and
difficult to purify.
 Synthesis of pure (CpA)(CpB)ZrCl2 is difficult.
Cp exchange is catalyzed by e.g. Mg halides.
For more acidic ligands also:
OH O O O
+ Zr(benzyl)4 Zr(benzyl)2 + Zr
OH O O O
 Alkylation
 In situ with MAO
 Alkylating agents
RLi
 Non-selective (ligand displacement)
 Reduction
 Incompatible with many solvents
 Usually ineffective with lanthanides (need RNa
or RK)
 Convenient if commercially available
RMgX, R2Mg
 Easily prepared
 Little affinity for N-donor ligands
 Use R2Mg for reactions in less polar
solvents
R2Zn
 Very mild
 Can be prepared in situ from RMgX and ZnCl2
 Generation of cations

Alkyl abstraction
MR2 + "MAO" MR+ "(R-MAO)-
MR2 + BAr3 MR+ RBAr3-
MR2 + Ph3C+BAr4- MR+ BAr4- + Ph3CR

Protonation
MR2 + PhNMe2H+BAr4- MR+ BAr4- + PhNMe2 +RH

Oxidation
+ - + - .
(0)
MR2 + Ag Carb MR Carb + Ag +R
.
MR2 + Fc+BAr4- MR+ BAr4- + Fc +R
. + - .
MR2 + B11CMe12 MR (B11CMe12) +R
-Diimine complexes

ArNH2
-H2O
O O ArN NAr

NiBr2(DME) (TMEDA)NiMe2

ArN NAr
ArN NAr
Ni
Ni
Br Br
Me Me
 Alternative routes

Hydride instead of alkyl

P X P H
Ni NaBH4 Ni
O S O S

"Oxidative" protonation

P H+ P
Ni Ni
P P

H+
L4Ni L4NiH+
 Problems in generation
of "active species"
 Usually insoluble in apolar solvents
(alkanes, arenes)
 Often separate oily phase with arenes
(-stacking?)
 Complexation or reaction with polar
solvents
ZrMe+ + CH2Cl2 + C6H6
ZrCl+ + CH4 + C6H5CH2Cl + (C6H5)2CH2

 Most common solvents: toluene,

bromobenzene, o-dichlorobenzene
 Purification difficult or impossible
• Solubility changes during polymerization
N
Ti Me
N
N
Ti (C2H4)10 Me
N
N
Ti (C2H4)100 Me
N

• Generation in absence of olefin: often

rapid decomposition
• Generation in presence of olefin:
precursors may react with solvent and/or
olefin +
Ph3C + olefin
BAr3 + trace H2O + olefin
Br
I III
Rh + C6H5Br Rh
C6H5