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Coordination Polymerization

Ziegler Natta Processes

Stereoregular Polymerization
Cationic Initiation of Vinyl Ethers Schildknecht et al. Ind. Eng. Chem. 39, 180, (1947)
BF3.Et2O Propane - 80-60 C
OR OR OR OR

O CH2 H3C CH3

Isotactic vinyl ether

Stereoregular Polymerization
Anionic Polymerization of Methyl Methacrylate, H. Yuki, K. Hatada, K.Ohta, and Y. Okamoto, J. Macromol. Sci. A9, 983 (1975)
CH3 O O BuLi or MgBr Toluene -78-0 C BuLi THF -78 C
H3C OR
OR OR OR

Isotactic
H3C OR OR
OR OR

Syndiotactic

POLYETHYLENE (LDPE)
R H2C CH2 20-40,000 psi 150-325 C H2C CH2 x

Molecular Weights: 20,000-100,000; MWD = 3-20 density = 0.91-0.93 g/cm3 H3C

Highly branched structureboth long and short chain branches


Tm ~ 105 C, Xlinity ~ 40%

H3C

CH3

H3C

H3C C H2 H3C H3C CH3 CH3

15-30 Methyl groups/1000 C atoms Applications: Packaging Film, wire and cable coating, toys, flexible bottles, housewares, coatings

Zieglers 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


Same result
White Ppt. (Not reported by Holzkamp) White Ppt. (Eureka! reported by Breil)

+ Ni(AcAc)
+ Cr(AcAc) + Zr(AcAc)

Al(Et)3 + TiCl4

CH2CH2 1 atm "linear" 20-70 C Mw = 10,000 - 2,000,000

Polypropylene (atactic)
CH3 R * CH2 CH3 n Low molecular weight oils

Formation of allyl radicals via chain transfer limits achievable molecular weights for all a-olefins

Nattas 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

TiCl3 Al(Et)2Cl

CH3

CH3

CH3

CH3

Isotactic
VCl4 - 78 C Al(iBu)2Cl
O in CH3 CH3 CH3 CH3

CH3

CH3

Syndiotactic

Ziegler and Natta awarded Nobel Prize in 1963

Polypropylene (isotactic)
CH3 TiCl3 Al(Et)2Cl
Density ~ 0.9-0.91 g/cm3very high strength to weight ratio Tm = 165-175C: Use temperature up to 120 C Copolymers with 2-5% ethyleneincreases clarity and toughness of films Applications: dishwasher safe plastic ware, carpet yarn, fibers and ropes, webbing, auto parts
CH3 CH3 CH3 CH3

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 resistancemedical implants MWD = 3-20 density = 0.94-0.96 g/cm3 Tm ~ 133-138 C, Xlinity ~ 80% Generally opaque Applications: Bottles, drums, pipe, conduit, sheet, film

Polyethylene (LLDPE)
Copolymer of ethylene with a-olefin
CH3 CH3 CH3 CH3 CH3

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 ~ 70-105C, 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 III Metals AlEt3 Et2AlCl EtAlCl2 i-Bu3Al Et2Mg Et2Zn Et4Pb Transition Metals TiCl4 a,g, d TiCl3 MgCl2 Support VCl3, VoCL3, V(AcAc)3 Titanocene dichloride Ti(OiBu)4 (Mo, Cr, Zr, W, Mn, Ni) Additives H2 O2, H2O
R C CH

R-OH Phenols R3N, R2O, R3P Aryl esters HMPA, DMF

Adjuvants used to control Stereochemistry

O O CH2CH3 N H

Si O

O O

Ethyl benzoate 2,2,6,6-tetramethylpiperidine

Phenyl trimethoxy silane

Hindered amine (also antioxidant)

Nature of Active Sites


R Al R Cl Cl Ti Cl Cl
Monometallic site

H3C

Cl d Ti Cl Cl

d CH2

Al

R R

Bimetallic site

Active sites at the surface of a TiClx crystal on catalyst surface.

Monometallic Mechanism for Propagation


Monomer forms -complex with vacant d-orbital

CH2 Cl Ti Cl Cl Cl

CH3

CH2 Cl Ti Cl Cl Cl

CH3

Alkyl chain end migrates to -complex to form new -bond to metal

H2C CH3 Cl Ti Cl Cl Cl CH2

CH2 Cl Ti Cl Cl Cl

CH3

Monometallic Mechanism for Propagation


Chain must migrate to original site to assure formation of isotactic structure

H2C CH3 Cl Ti Cl Cl Cl CH2

H3C 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. -hydride shift
C H CH2 Ti R Al Ti CH2 CH2 H Al R Ti CH2 R Al

2. Reaction with H2 (Molecular weight control!)


C H H H CH2 Al Ti R CH2 CH3 H Ti Al R Ti CH2 R Al

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 VOCl3 Et AlCl V(AcAc)3 2

Catalyst soluble in hydrocarbons Continuous catalyst addition required to maintain activity

.4-.8 .5-.1 0.05

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
Z-N multisited catalyst, multiple site reactivities depending upon specific electronic and steric environments

Me

Single site catalyst every site has same chemical environment

Kaminsky Catalyst System


W. Kaminsky et.al. Angew. Chem. Eng. Ed. 19, 390, (1980); Angew. Chem. 97, 507 (1985)
Me X + X CH3 * Al O * n

Al:Zr = 1000

Linear HD PE 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 Al(CH3)3 + H2O
CH3 Al O O Al Al O O Al CH3 CH3

CH3 * Al O * n

0C

n = 10-20

MAO
Proposed structure

Al O O Al Al

Nature of active catalyst


X Cp2Me X CH3 + * Al O * n

MAO
CH3 X CH3 + Al O X Al m

Transition metal alkylation

Cp2Me

CH3 Cp2Me CH2 +

X X Al O Al O m

Ionization to form active sites

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: -H elimination, etc. Limited control of molecular weight distribution

Evolution of single site catalysts


Date Metallocene Stereo control Performance

1950s

None

Moderate Mw PE
Some comonomer incorporation

Me

Early 1980s
Me

None

High MW PE Better comonomer incorporation

Synthesis of Syndiotactic Polystyrene


N. Ishihara et.al. Macromolecules 21, 3356 (1988); 19, 2462 (1986)
Cl Cl * Al O * + n

Styrene
44.1%

Ti

CH3

Ti Cl Cl Cl

99.2%

Ti

Cl Cl 1.0%

syndiotactic polystyrene

m.p. = 265C

Evolution of single site catalysts


Date Metallocene Late 1980s
N Me R

Stereo control Slight Highly Syndiotactic

Performance Very High Mw PE, excellent comonomer incorporation Used commercially for PP

Late 1980s

R R Me

Early 1990s
Me

Highly Used commercially Isotactic for PP

Technology S-curves for polyolefin production