Coordination Polymerization

Ziegler Natta Polymerization

Similarities and contrasts in ionic polymerization

Similarities between the radical and ionic polymerizations

There are 3 steps: initiation, propagation, and termination.

Differences between the radical and ionic polymerizations In

radical polymerization involves
•radicals
•reactions between two growing chains

In ionic polymerization involves

• carbanions (CΘ) in anionic polymerization and carbonium ions
(C) in cationic polyemerization.
•unimolecular reactions of a chain with its counterion or
a transfer reaction leaving a species too weak to propagate.
 Tacticity
is simply the way pendant groups are arranged along the backbone
chain of a polymer.
when polymers have a regular arrangement of their atoms, like we see in the
isotactic and syndiotactic polystyrene, it is very easy for them to pack together
into crystals and fibers. But if there is no order, as is the case with the atactic
polystyrene, packing can't occur. This is because molecules pack best with other
molecules of the same shape. Try packing a box full of identical objects, and
different objects
Fibers like:
t's important to point out that fibers are always made of polymers which are
arranged into crystals. They have to be able to pack into a regular
arrangement in order to line up as fibers. (In fact, fibers are really a kind of
crystal, a really long kind of crystal.) We can show this by taking a closer
look at the way nylon 6,6 packs into a crystalline fiber.
 Stereoregular Polymerization
Anionic Polymerization of Methyl Methacrylate,

BuLi or H3C OR OR OR OR
CH3
MgBr
O Toluene Isotactic
O -78-0 C
OR
H3C OR OR OR
BuLi
THF -78 C

Syndiotactic
 POLYETHYLENE (LDPE)
R
H2C CH2 H2C CH2
20-40,000 psi
x
150-325° C
Molecular Weights: 20,000-100,000; MWD = 3-20
density = 0.91-0.93 g/cm3 H3C
CH3 H3C
H3C
Highly branched
structure—both long and
H3C
short chain branches C
H2
Tm ~ 105 C, X’linity ~ 40% H3C
CH3

15-30 Methyl groups/1000 C atoms H3C

CH3
Applications: Packaging Film, wire and cable coating, toys,
flexible bottles, housewares, coatings
Coordination polymerization
Coordination polymerization applies a novel class of transition-
metal catalysts, called the Ziegler-Natta catalysts and produced
of polymers with unsual stereospecific structures. The mechanism
and
the kinetics are complicated and the catalysts are usually
solids to form heterogeneous polymerization systems.

History
1939: a high-pressure free-radical polymerization of ethylene
was developed by ICI. PE has some short and long alkane
branches, moderate crystallinity, thermal and mechanical
properties. This product is called LDPE.
1954:
Giulio Natta (Italy) developed a stereochemical process to polymerize
isotactic PP (i-PP). This i-PP had degree of crystallinity comparable to
LDPE and exhibited good mechanical properties in a wide range of
temp. Karl Ziegler (Germany) developed a similar process to
polymerize ethylene at lower temp & pressure to produce HDPE.
This HDPE had fewer branches and a higher degree of crystallinity.
 Ziegler’s Discovery
• 1953 K. Ziegler, E. Holzkamp, H. Breil and H. Martin
• Angew. Chemie 67, 426, 541 (1955); 76, 545 (1964).

Al(Et)3 + NiCl2 CH3CH2CH=CH2 + Ni + AlCl(Et)2

100 atm
110 C
+ Ni(AcAc) Same result
+ Cr(AcAc) White Ppt. (Not reported by Holzkamp)
+ Zr(AcAc) White Ppt. (Eureka! reported by Breil)

Al(Et)3 + TiCl4 CH2CH2

1 atm "linear"
20-70 C Mw = 10,000 - 2,000,000
 Polypropylene (atactic)

CH3 R CH3
* n
CH2
Low molecular weight oils

Formation of allyl radicals via chain transfer limits achievable

molecular weights for all a-olefins
 Natta’s Discovery
• 1954 Guilio Natta, P. Pino, P. Corradini, and F. Danusso
• J. Am. Chem. Soc. 77, 1708 (1955) Crystallographic Data on PP
• J. Polym. Sci. 16, 143 (1955) Polymerization described in French
CH3 CH3 CH3 CH3
TiCl3
CH3
Al(Et)2Cl
Isotactic
CH3
CH3 CH3 CH3
VCl4 - 78 C
CH3
Al(iBu)2Cl
CH3
O in Syndiotactic

Ziegler and Natta awarded Nobel Prize in 1963

 - Before Z-N Catalyst invention, PP composites were only atactic form
- After that, isotactic PP composites of extraordinary MW(>106) is synthesized

Characteristic conditions for PP

PP and solid catalysts are put together at 50℃ to 90℃ below 5atm.
After stopping of reaction, it is washed with H2O or ROH to remove the catalysts.
MW is on the control of chain transfer agent
E.g.) CO2, O2, H2, H2O, …
Dr. Ziegler and Dr. Natta
A Ziegler-Natta catalyst is usually a metal-organic complex of a
metal cation from groups I – III {Al2(C2H5)3} and a metal
compound from groups IV – VIII {TiCl.}4
Ziegler-Natta catalyst: TiCl’4

The Ti has been reduced from Ti(IV)

to Ti(III) and the chlorine bridge is
called three-center bond.
 Polypropylene (isotactic)
CH3 CH3 CH3 CH3
TiCl3
CH3
Al(Et)2Cl

Density ~ 0.9-0.91 g/cm3—very high strength to weight ratio

Tm = 165-175C: Use temperature up to 120 C

Copolymers with 2-5% ethylene—increases clarity and

toughness of films

Applications: dishwasher safe plastic ware, carpet yarn,

fibers and ropes, webbing, auto parts
The different stereoisomers may have very different physical
properties. For example, atactic polypropylene is a useless,
gummy solid, while the isotactic version is a highly crystalline,
tough plastic that can even be made into fibers.
 Polyethylene (HDPE)
CH3
Essentially linear
structure
Few long chain branches, 0.5-3
methyl groups/ 1000 C atoms

Molecular Weights: 50,000-250,000 for molding compounds

250,000-1,500,000 for pipe compounds
>1,500,000 super abrasion resistance—medical implants
MWD = 3-20
density = 0.94-0.96 g/cm3
Tm ~ 133-138 C, X’linity ~ 80% Generally opaque
Applications: Bottles, drums, pipe, conduit, sheet, film
 Polyethylene (LLDPE)
• Copolymer of ethylene with a-olefin
CH3
CH3
CH3 CH3

CH3

x y

Density controlled by co-monomer concentration; 1-butene (ethyl), or

1-hexene (butyl), or 1-octene (hexyl) (branch structure)

Applications: Shirt bags, high strength films

 CATALYST PREPARATION

Ball mill MgCl2 (support) with TiCl4 to produce maximum

surface area and incorporate Ti atoms in MgCl2 crystals

Add Al(Et)3 along with Lewis base like ethyl benzoate

Al(Et)3 reduces TiCl4 to form active complex
Ethyl Benzoate modifies active sites to enhance
stereoselectivity

Catalyst activity 50-2000 kg polypropylene/g Ti with

isospecificity of > 90%
 Nature of Active Sites
R R H 3C
Al 
R Cl Cl  CH2 R
Ti Al
Cl Ti Cl R
Cl
Cl Cl
Monometallic site Bimetallic site

Active sites at the surface of a TiClx crystal on catalyst

surface.
Monometallic Mechanism for Propagation
Monomer forms π -complex with vacant d-orbital

CH3
CH2 CH2
Cl Ti Cl Cl Ti Cl CH3
Cl Cl Cl Cl

Alkyl chain end migrates to π -complex to

form new σ-bond to metal

H2C CH2
Cl Ti Cl CH3 Cl Ti Cl CH3
Cl Cl Cl Cl
CH2
Monometallic Mechanism for Propagation

Chain must migrate to original site to assure

formation of isotactic structure

H2C
CH3 H3C
Cl Ti Cl
Cl Cl CH2
CH2 Cl Ti Cl
Cl Cl

If no migration occurs, syndiotactic placements

will form.
 Modes of Termination
1. β-hydride shift

C H CH2
CH2 H CH2
CH2
Al Al Ti Al
Ti Ti
R R R

2. Reaction with H2 (Molecular weight control!)

C H CH2
H H CH3 H
CH2 CH2
Al Al Ti Al
Ti Ti
R R R
Types Of Monomers Accessible for ZN Processes
1. a-Olefins
H2C CH2
CH3 CH2CH3 R
2. Dienes, (Butadiene, Isoprene, CH2=C=CH2)

trans-1,4 cis-1,4 iso- and syndio-1,2

1.2 Disubstituted double bonds do not polymerize

 Development of Single Site Catalysts

R Cl
Cl Ti
Cl Cl Me

Z-N multisited catalyst, multiple

site reactivities depending upon Single site catalyst—
specific electronic and steric every site has same
environments chemical environment
 Kaminsky Catalyst System
W. Kaminsky et.al. Angew. Chem. Eng. Ed. 19, 390,
(1980); Angew. Chem. 97, 507 (1985)
CH3
X +
Me * Al O *
n
X Linear HD PE
Al:Zr = 1000
Activity = 107 g/mol Zr
Me = Tl, Zr, Hf

CH3

Atactic polypropylene, Mw/Mn = 1.5-2.5

Activity = 106 g/mol Zr
 Homogeneous Z-N Polymerization
Advantages:
High Catalytic Activity
Impressive control of stereochemistry
Well defined catalyst precursors
Design of Polymer microstructures, including chiral
polymers
Disadvantages:
Requires large excess of Aluminoxane (counter-ion)
Higher tendency for chain termination: β-H elimination, etc.
Limited control of molecular weight distribution
 Evolution of single site catalysts
Date Metallocene Stereo Performance
control

1950’s None Moderate Mw PE

Some comonomer
incorporation
Me

Early None High MW PE

1980’s Better comonomer
Me incorporation
 Synthesis of Syndiotactic Polystyrene
N. Ishihara et.al. Macromolecules 21, 3356 (1988); 19, 2462 (1986)

Cl Styrene
Ti
Cl 44.1%

* O
Al +
n* Ti Cl
CH3 Cl Cl 99.2%

Ti Cl syndiotactic polystyrene
Cl 1.0%
m.p. = 265C
 Evolution of single site catalysts

Date Metallocene Stereo Performance

Late control Very High Mw PE,
1980’s Slight excellent comonomer
N Me
incorporation
R
Late R Highly Used commercially
1980’s R Syndio- for PP
Me
tactic

Early Highly Used commercially

1990’s Isotactic for PP
Me
 Conclusion
 Three phases of TiCl3

 Only α-TiCl3 and γ-TiCl3 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

 ß-TiCl3 has 2 different active sites, one forcing dienes to polymerize

1,4-cis, one 1,4-trans, if molecule is flexible.
Ziegler-Natta Polymerization 35
 ZN spesifications

• Limited to ethylene and other a-olefins like propylene.

(Actually, it is the only good way to polymerize these
monomers.)
• Produces linear polymer, with very few branches (e.g., high
density polyethylene, HDPE).
• Capable of producing homo-tactic polymers.
• Most commercial initiators are insoluble complexes or
supported on insoluble carriers.
• Very complex mechanism, still poorly understood for the
heterogeneous systems.
• Termination is almost exclusively by chain transfer.
• Modern "high mileage" initiators produce up to 1000's of kg
per g initiator.
• Initiators are often called "catalysts" even though they are
consumed by the process. Many chains are started per
molecule of initiator.