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The fundamentals of catalytic olefin polymerization

Basics of initiation, propagation and termination.

Olefin polymerization versus olefin oligomerization.

Chain transfer agents.

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Why would polyolefins form?

σ π
σ+π

σ+π 2σ
ΔH∅ = -21.2 kcal/mol
Energy-rich monomer

σ
σ σ
σ
2
Ways to prepare polyolefins
Free radical polymerization
Cationic/anionic polymerization
Ring opening metathesis polymerization
Ziegler-Natta type coordination polymerization

LDPE

a-PS

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Free radical polymerization

Initiation and propagation

Initiation propagation

1000-2000 atm., 200oC


Disadvantages:
Difficult to control.
High temperatures and pressures required.
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Free radical polymerization

termination by coupling

1000-2000 atm., 200oC


Disadvantages:
Difficult to control.
High temperatures and pressures required.
5
Free radical polymerization

termination by H-transfer

1000-2000 atm., 200oC


Disadvantages:
Difficult to control.
High temperatures and pressures required.
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Free radical polymerization
termination by radical transfer
(gives branches)

1000-2000 atm., 200oC


Disadvantages:
Difficult to control.
High temperatures and pressures required.
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Ways to prepare polyolefins
Free radical polymerization
Cationic/anionic polymerization
Ring opening metathesis polymerization
Ziegler-Natta type coordination polymerization

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Cationic/anionic polymerization

Cationic polymerization

Anionic polymerization

Disadvantages:
Little control.
Very low temperatures required.
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Ways to prepare polyolefins
Free radical polymerization
Cationic/anionic polymerization
Olefin metathesis polymerization
Ziegler-Natta type coordination polymerization

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Ring opening metathesis polymerization

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Ways to prepare polyolefins
Free radical polymerization
Cationic/anionic polymerization
Ring opening metathesis polymerization
Ziegler-Natta type coordination polymerization

a-PP, i-PP, s-PP

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Ziegler-Natta coordination polymerization
How to activate an olefin:
First the olefin has to coordinate to the metal.

High valent, electron poor transition metal center that interacts


with the  orbital of the olefin.

Low valent, electron rich transition metal center that interacts


with the * orbital of the olefin.

xz yz xy x2-y2 Z2

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Ziegler-Natta polymerization – catalyst
High valent catalyst systems -
Cocat.
general requirements
d+ d- Electrophilic metal center (can be cationic)
CH3
Metal Vacant coordination site
Polarized metal-polymer bond
Ancillary ligand Robust ancillary ligand system
Sometimes a cocatalyst is required
H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br K

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

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Ziegler-Natta polymerization – catalyst
Polymer
- Molecular weight
- Tacticity
Cocatalyst/counterion - Comonomer content
- Coordinative tendency - Block structure
- Electronics - Cross linking
- Stereodirecting characteristics - Polar function groups
Cocat.

d+ d CH2
-

Metal

Ancillary ligand Monomer


- Electronics - Electronics
- Sterics - Sterics
- Stereodirecting characteristics - Polar functional groups

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Ziegler-Natta polymerization – catalyst

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Ziegler-Natta polymerization – catalyst

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Ziegler-Natta polymerization – mechanism

General reaction mechanism

Initiation
Activation of the catalyst precursor

Propagation
Chain growth

Termination
Chain transfer, catalyst decomposition

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Mechanism – poisoning

Problem: sensitivity of the catalysts to


oxygen, moisture and other heteroatom
containing impurities.

For most catalysts, the solvent and


feed should be extremely pure…

…Why is that?

Ziegler's original reactor.

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Mechanism – poisoning
Problem: sensitivity of the catalysts to oxygen, moisture
and other heteroatom containing impurities.

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Mechanism – initiation
Initiation
Generation of an electrophilic metal site that contains a
metal-carbon or metal-hydrogen bond.

Catalyst precursors are generally metal halide species.

In most cases the alkylation is done with aluminum alkyls.

Ziegler-Natta precatalyst (MgCl2 / TiCl4 / ester) is treated


with AlEt2Cl for activation.

Homogeneous catalyst precursors are generally treated


with methylalumoxane.

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Mechanism – initiation

If the competing electrophile


is Lewis acidic enough, it can
even abstract a chloride ion.

Strong Lewis acid competes


for the electrons of the
chloride ion.

Alkyl - chloride ion exchange


finally affords the active
catalyst consisting of a cationic
zirconium alkyl species.

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Mechanism – initiation

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Mechanism – initiation

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Mechanism – initiation

C* < [Zr]
TOF > 103 s-1

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Mechanism – propagation
Propagation
Modified Cossee-Arlman mechanism – migratory insertion

Important for stereospecific polymerization


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Mechanism – propagation

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Mechanism – propagation
Propagation
Green-Rooney carbene mechanism

This mechanism requires a base to scavenge the proton.

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Mechanism – propagation
Propagation
Green-Rooney carbene mechanism

This mechanism involves a change in the oxidation state


of the metal, which is unlikely for LnIII, TiIV/ZrIV/HfIV, NiII/PdII…

…but it did result in another modification


of the Cossee-Arlman mechanism.

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Mechanism – propagation
Propagation
Modified Cossee-Arlman mechanism – agostic interaction

α α β

The agostic interaction


increases the interaction of
α the C sp3 with the olefin.

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Mechanism – termination
Termination

β-hydrogen elimination

The extreme of agostic interaction is hydrogen transfer to the metal


Depends on relative bond strength of M-C and M-H whether or not this occurs

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Mechanism – termination
Termination

β-hydrogen transfer to monomer

Generally most accepted termination mechanism

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Mechanism – Choice of metal

Early transition metals Late transition metals


Fast insertion Slow insertion
Slow b-H elimination Fast b-H elimination
kins >> kb-H kins << kb-H
EM-C ≈ EM-H EM-C < EM-H

Highly oxophilic Poorly oxophilic


Low tolerance to polar groups High tolerance to polar groups
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Mechanism – termination
Termination

β-alkyl elimination/transfer to monomer

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Mechanism – termination
Propagation versus termination

Termination requires more room than propagation

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Mechanism – chain transfer processes

Besides spontaneous chain transfer processes, chain transfer


can be induced by adding chain transfer agents (CTA’s).

Chain transfer agents are used to:


Control the polymer molecular weight
Control polydispersity
Introduce functional groups
Reactivate dormant sites

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Chain transfer – hydrogenolysis
Dihydrogen is the most commonly used chain
transfer agent (CTA) to control the molecular weight.

d+ d-
d+ d+
d- d-
d- d+

Dihydrogen is a weak Lewis base (like olefins) that can easily be polarized
formally producing an acidic proton that can protonate off the polymer chain.

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Chain transfer – CTA’s
Substrates of the type H-X where X is more electropositive
than H can also be used as chain transfer agents.

d+ d-
d+ d+
d- d-
d- d+
d- d+

X = H, BR2, SiR3, … H-X is already polarized, which facilitates the reaction.

HX

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Chain transfer – CTA’s
Substrates of the type H-X where X is more electronegative
than H can also be used as chain transfer agent.

d+ d-
d+ d+
d- d-
d- d+
d- d+

This process only works when M-X is not too strong.

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Chain transfer – CTA’s
Main group metal alkyls can also function as chain transfer agents.

d+ d-
d+ d+ d+
d- d- d-
d- d+
d- d+

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Reactivating dormant sites
Dormant sites and ways-out

primary alkyl
ZnEt2 Chain transfer to zinc
dormant site
1,2-insertion (fast)

H2
primary alkyl 2,1-insertion

secondary alkyl

hydrogenolysis
D (very fast)

1,2-insertion Isomerization
(very slow) (slow) ethylene insertion
(fast) 41
Reactivating dormant sites
Enforced β-H elimination

Dormant site

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Chain transfer – CTA’s

Chain transfer to main group metal alkyl CTA's is a


relative new way to:

Control the molecular weight


PDI
Produce end-functionalized polyolefins
Multi-block copolymers.

For this mechanism to be effective, a living catalyst is required.

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Chain transfer – multi-block copolymers

What else can be done with chain transfer agents?

Could it transfer chains between different catalysts?

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Chain transfer – multi-block copolymers

CTA

Both catalysts (M1 and M2) should be living catalysts.


Both catalysts (M1 and M2) should have a good response for the CTA.
Chain transfer should be slower than insertion but not too much slower.

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Chain transfer – multi-block copolymers
Ethylene / 1-alkene copolymers - Shuttle chemistry

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Chain transfer – multi-block copolymers
Ethylene / 1-alkene copolymers - Shuttle chemistry

High Tm
High modulus A copolymer is obtained with the soft-characteristics of
Low solubility an amorphous random copolymer and the hard-
High clarity characteristics of a crystalline homopolymer.
Low PDI
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Summary
How does the reaction of the active catalyst with the olefin take place?

• The electron rich olefin is attracted to the electron poor metal center
• The olefin binds to the empty metal orbital
• The polar M-C bond introduces an induced dipole on the olefin
• The opposite charges attract each other which leads to -bond formation
• Metal-alkyl with b-agostic interaction as resting state
• The alkyl group rotates away making space for the new olefin to approach

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Summary
How does termination takes place?

b-H transfer/elimination Hydrogenation by H2


(spontaneous) (chain transfer agent)

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Polyolefins: Catalysis and dedicated analysis

-Market

-Homogeneous olefin polymerization catalysts


Metallocenes

Post-metallocenes

Middle and late transition metal catalysts

Cocatalysts

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Coordination polymerization – market
Polyolefins in the global thermoplastic
resins market

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Coordination polymerization – market
Polyolefins in the global thermoplastic
resins market

PET
LDPE
5%
13%
PVC LLDPE
20% 10%

ABS HDPE
4% 18%
PS
8%
PP
22%

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Coordination polymerization – market

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Coordination polymerization – market

Quite some plastic per year!

24 km 4 mm

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Coordination polymerization – market

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Coordination polymerization – market

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Coordination polymerization – market

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Coordination polymerization – catalyst types

Ziegler-Natta
heterogeneous

Phillips
heterogeneous

Single-site
homogeneous

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Heterogeneous Ziegler-Natta catalysts
Applied for i-PP, HDPE, LLDPE

Mostly titanium based (TiCl4, Ti(OBu)4)


Supported on TiCl3 (1st gen.), MgCl2 and/or SiO2
Co-catalysts: Al(CH2CH3)3, Al(CH2CH3)2Cl, ….
Non-uniform active species, leading to
Broad molecular weight distribution
Heterogeneous melting behavior
Reactor blend

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Heterogeneous Ziegler-Natta catalysts
MgCl2

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Heterogeneous Ziegler-Natta catalysts
MgCl2 + TiCl4

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Heterogeneous Ziegler-Natta catalysts
MgCl2 + TiCl4

These chlorides are displaced by


one alkyl and the metal is being
reduced, which forms the active
site.

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Heterogeneous Ziegler-Natta catalysts
MgCl2 + TiCl4

C2

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Heterogeneous Phillips catalysts
Applied for mainly HDPE.

Chromium based e.g. CrO3/SiO2


High temperature activation required
Co-catalyst: none, B(CH2CH3)3, AlR3
Non-uniform active species, leading to
Broad molecular weight distribution (typical >10)
Heterogeneous melting behavior
Reactor blend

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Heterogeneous Phillips catalysts

Over 30 % of the HDPE is currently


synthesized using the Phillips catalyst.

No hydrogen response,
Mw can only be altered
by temperature.

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Homogeneous single-site catalysts
Applied for i-PP, s-PP, HDPE, LLDPE, VLDPE, ….

Group 4 metal (Ti, Zr, Hf) based


Co-catalysts: MAO, boranes, borates, ….
Uniform active species yielding narrow molecular weight distribution
In general improved product quality
In principle easier product/catalyst tailoring
Depending on the process the catalysts are supported on SiO2 or MgCl2

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Catalyst costs
Ziegler-Natta Phillips Single-site
Catalyst price €50-€400/kg €20-€80/kg €100-€750/kg
Catalyst activity 20-50 kgpp/gcat 2-10 kgPE/gcat 2-20 kgpp/gcat
Catalyst costs 1-20 €/T 2-40 €/T 5-375 €/T

Quick and dirty calculation


1 ton of polymer €1.000,-
1 ton of monomer €650,-
Business costs* €250,-
Profit €100,-

* of which €20 for cat costs.

For a producer of 1000 kton polymer/year, decreasing


catalyst costs by €1/T can save €1.000.000/year.
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Homogeneous single-site catalysts

Advantages of well-defined single-site catalysts.

Tunability of the catalyst performance through designed


ligand modification

Enhanced stereo control

Uniform, random and tunable comonomer incorporation

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Early metallocene catalysis

Ferrocene (18 VE) Titanocene dichloride (16 VE)

Breslow, 1955

+ AlEt2Cl HDPE
very low yield

Limited activity
Propene; only dimerization
Active species unclear
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Early metallocene catalysis

Catalyst precursor Active species


Inactive in ethylene polymerization unless a small amount of water is added.

Careful hydrolysis of AlMe3 yields methylaluminoxane (MAO)


with unprecedented cocatalyst abilities.

polyethylene

+ [MeAlO]n
atactic polypropylene

high activity

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Metallocene catalysts – C2v symmetric

C2v

Dh symmetric – no stereo control

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Metallocene catalysts – C2v symmetric

No preference
for the position
of the polymer
chain.

atactic PP

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Metallocene catalysts – C2 symmetric

C2

C2-symmetric – stereo control

Ziegler-Natta catalyst 73
Metallocene catalysts – C2 symmetric
Growing chain preferentially
points away from the steric
bulk of the ligand system.

Growing chain is responsible


for "indirect stereo control".
Without growing chain, there
is no stereo control.

isotactic PP

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Metallocene catalysts – C2 symmetric

isospecific isospecific isospecific

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Metallocene catalysts – Cs symmetric

Cs

Cs-symmetric – stereo control

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Metallocene catalysts – Cs symmetric
Growing chain preferentially
points away from the steric
bulk of the ligand system.

Growing chain is responsible


for "indirect stereo control".
Without growing chain, there
is no stereo control.
syndiotactic PP

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Metallocene catalysts – Cs symmetric

syndiospecific syndiospecific syndiospecific

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Metallocene catalystsand their effect on tacticity.
Different ligand symmetries
By designing the catalyst's ligand system, various including
some unprecedented types of polypropylene are available.

C2v (atactic) C2 (isotactic) Cs (syndiotactic)

What if we remove the symmetry?

C1 (???)
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Metallocene catalysts – C1 symmetric
The effective steric hindrance of the methyl
group is comparable to that of the fused aryl
group.

hemi-isotactic PP

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Metallocene catalysts – C1 symmetric

aspecific isospecific aspecific

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Metallocene catalysts – C1 symmetric
One side is sterically too crowded for the polymer chain.
As a result, directly after insertion of a propylene
molecule the polymer chain skips back to the less
crowded side.

isotactic PP
isotactic PP

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Metallocene catalysts – C1 symmetric

insertion

isospecific back skipping

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Development of metallocene catalysts
Different ligand structures lead to different types of polypropylene.

stereoblock i-PP (83% mmmm) i-PP (92% mmmm) i-PP (93% mmmm)
i-PP (30% mmmm) High Mw

> 0oC a-PP


-45oC i-PP (83% m)

i-PP (90% mmmm) i-PP (89% mmmm)


High Mw

i-PP (99% mmmm)


High Mw
s-PP (80% rrrr)
s-PP (90% rrrr)

hemi-i-PP

i-PP (95% mmmm)


UHMW a-PP 84
s-PP (90% rrrr)
Synthesis of metallocene catalysts
Ligand synthesis
– the carbon skeleton is the most difficult part

Metal halide complexes


– there is no standard synthetic route for metallocenes
– problem with formation of meso species.

Metal alkyl complexes


– relatively unstable
– several improved routes are available

Well-defined metal alkyl cations


– unstable
– boranes or borates are the standard cation generators
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Synthesis of metallocene catalysts
Ligand synthesis is often a multi-step process giving low overall yields.

major – rac minor – meso


A problem with C2 symmetric catalysts is that is Cs product is also formed.
Whereas the C2 symmetric catalysts yields i-PP, the Cs symmetric one affords a-PP.
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Characteristics of metallocene catalysts

Single-site catalyst afford low PDI


Homogeneous comonomer incorporation
Polymerization rates can be extremely high (> 107 g·g(Zr)-1·h-1)

Difficult to get high molecular weight polypropylene


Metallocenes are somewhat less sensitive to H2 for Mw control

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Early transition metal post-metallocenes

more electron deficient – more 'open'

Activated with MAO gave an excellent


copolymerization catalyst.
Copolymerizes α-olefins (short chain branching)
and re-inserts macromonomers (long chain
branching).
Living 1-hexene polymerization.

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Development of metallocene catalysts

89
Characteristics of post-metallocene catalysts
Easy to synthesize – allows parallel synthesis and
high throughput screening

No isomer separation needed

Robust – can be used at high temperature

Open ligand system comonomer incorporation

Generally less suitable for the synthesis of highly isotactic PP,


exception forms the new generation of octahedral complexes

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Middle and late transition metal catalysts

Keim, Starzewski, Ittel Brookhart catalyst, HDPE


Brookhart catalyst, HDPE
oligomers, HDPE

Grubbs catalyst,
moderately branched PE
Brookhart Gibson catalyst, Brookhart catalyst, highly
α-olefins → HDPE branched PE

91
Early versus late transition metal catalysts
Very active catalysts (easily 107 – 108 gpol∙molcat-1∙h-1∙bar-1)
Very reactive catalyst - difficult to investigate
[M]-P (with agostic interaction) is the resting state
Coordination is rate limiting?

LTM ETM
resting state resting state

Much slower catalyst (easily 102 – 103 gpol∙molcat-1∙h-1∙bar-1)


Easy to study by NMR
[M](C2H4)-P is the resting state
Insertion is rate limiting

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Early versus late transition metal catalysts
Polymerization rate is dependent on [C2H4]
Linear polyethylene
Also excellent for a-olefins
Poorly tolerant to polar groups

Polymerization rate is zero-order with respect to


[C2H4]
Branched polyethylene
Poor activity for a-olefins
Tolerant to polar groups
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Processes and catalysts

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Processes and catalysts

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Processes and catalysts

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Processes and catalysts

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Processes and catalysts

Reactor type CSTR Loop Fluidized bed


Operation Solution Slurry Gas
conditions High Temp Medium Temp Medium Temp
Short residence time Longer residence time Long residence time
Low conversion High conversion Medium-high conversion
Polymer specs preferably Preferably highly Medium to highly
amorphous or low crystalline crystalline
melting
Catalyst specs Thermally robust Good morphology Excellent morphology
High Mw capability Mechanically resistant Mechanically resistant
Good comonomer Stable kinetic profile Stable kinetic profile
incorporation Good H2 response

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Immobilization of homogeneous catalysts
Advantages of immobilization:
Can be applied in existing processes
Polymer particle morphology control by replication
High bulk density
No reactor fouling
Less cocatalyst required

Homogeneous Heterogeneous
solution process slurry process

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Immobilization of homogeneous catalysts
Advantages of immobilization:
Can be applied in existing processes
Polymer particle morphology control by replication
High bulk density
No reactor fouling
Less cocatalyst required

100
Immobilization techniques
Amorphous silica is most commonly used support.
- High (and tunable) degree of surface functionalities (silanols) to anchor catalyst
- High surface area and pore volume
- Fragments evenly

Grafting Electrostatic interaction with grafted cocatalyst Tethering


Advantage: Advantage: Advantage:
- easy to prepare - easy to prepare - well-defined
- well-defined single sites single sites
- no leaching
Disadvantage: Disadvantage: Disadvantage:
- leaching - leaching (?) - difficult to prepare
- low activity - varying activity
- ill-defined 101
Importance of catalyst immobilization

When do we need catalyst immobilization ?


When we want to use a homogeneous catalyst
in a gas-phase or slurry/suspension process.

When can we use homogeneous catalysts ?


When the polymer is soluble in the polymerization medium:
amorphous (non-crystalline) elastomers (EPDM) or
plastomers containing high comonomer content (VLDPE)

When the polymer is crystalline but the polymerization


temperature is higher than the melting point of the polymer
produced (solution process for LLDPE: 150 – 250 oC)

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