Coordination Polymerization

Ziegler Natta Processes

 Stereoregular Polymerization
Cationic Initiation of Vinyl Ethers
Schildknecht et al. Ind. Eng. Chem. 39, 180, (1947)

OR OR OR OR
BF3.Et2O
O
Propane
CH2 - 80-60 C
H3C Isotactic vinyl ether
CH3
 Stereoregular Polymerization
Anionic Polymerization of Methyl Methacrylate,
H. Yuki, K. Hatada, K.Ohta, and Y. Okamoto, J.
Macromol. Sci. A9, 983 (1975)

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
 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

 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
 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

 UNIPOL Process
N. F. Brockman and J. B. Rogan, Ind. Eng. Chem. Prod. Res. Dev.
24, 278 (1985)

Temp ~ 70-105°C, Pressure ~ 2-3 MPa

 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%
 Catalyst Formation

AlEt3 + TiCl4 → EtTiCl3 + Et2AlCl

Et2AlCl + TiCl4 → EtTiCl3 + EtAlCl2

EtTiCl3 + AlEt3 → Et2TiCl2 + EtAlCl2

EtTiCl3 → TiCl3 + Et. (source of radical products)

Et. + TiCl4 → EtCl + TiCl3

TiCl3 + AlEt3 → EtTiCl2 + Et2AlCl

 General Composition of Catalyst System
Group I – Transition Metals Additives
III Metals
AlEt3 TiCl4 H2
Et2AlCl a,g, d TiCl3 O2, H2O
EtAlCl2 MgCl2 Support R C CH
i-Bu3Al VCl3, VoCL3, R-OH
V(AcAc)3 Phenols
Et2Mg Titanocene dichloride R3N, R2O, R3P
Et2Zn Ti(OiBu)4 Aryl esters
Et4Pb (Mo, Cr, Zr, W, Mn, HMPA, DMF
Ni)
 Adjuvants used to control Stereochemistry

O O
Si
CH2CH3 O
O O
N
H Phenyl
Ethyl benzoate trimethoxy
2,2,6,6-tetramethylpiperidine silane
Hindered amine (also
antioxidant)
 Nature of Active Sites
R R H3C
Al d
R Cl Cl d 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.
 Enantiomorphic Site Control Model for
Isospecific Polymerization
Stereocontrol is imposed by initiator active site alone with
no influence from the propagating chain end, i.e. no
penultimate effect
Demonstrated by: 13C analysis of isotactic structures

not

Stereochemistry can be controlled by catalyst enantiomers

 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

 Ethylene-Propylene Diene Rubber (EPDM)
S. Cesca, Macromolecular Reviews, 10, 1-231 (1975)

+ +
CH3 Catalyst
VOCl3 soluble in
Et AlCl
V(AcAc)3 2 hydrocarbons

Continuous
.4-.8 catalyst addition
.5-.1 required to
0.05
maintain activity

Rigid control of monomer feed ratio required to assure

incorporation of propylene and diene monomers
 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
Methylalumoxane: the Key Cocatalyst
toluene CH3
Al(CH3)3 + H2O * Al O *
0C n
CH3 n = 10-20

Al MAO
O O CH3
Al O Al
AlAl CH3 Proposed structure
O O O
Al Al
 Nature of active catalyst

X CH3
Cp2Me + * Al O *
n Transition metal
X
alkylation
MAO

CH3 CH3 X
Cp2Me + Al O Al
X m O

CH3 X X Ionization to
form active sites
CH2 Al O Al O
Cp2Me + m

Noncoordinating Anion, NCA

 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
Technology S-curves for polyolefin
production