Polyethylene: LDPE

radical
n
initiator

n
ethylene LDPE

• LDPE: Low density polyethylene

• Highly branched material

• Properties and usage:
Stretchable before tearing
Used for flexible plastic bags
Recycled material: trash bags, grocery sacks
 Ziegler/Natta polymerization:
Karl Ziegler
• German chemist, Nobel prize 1963

• 1953/54: Ziegler’s group was studying oligomerization of

ethylene by trialkylaluminum compounds (high pressure and
temp.)

• In the presence of a number of trace transition metals, it was

found that the reaction took place at much lower temperature and
pressure
Transition Metal
R2Al-R +
n
Catalyst
• Polymer had a linear, unbranched structure with high molecular
weight, i.e. HDPE

http://www.nobel.se/chemistry/laureates/1963/
 Ziegler/Natta polymerization:
Giulio Natta
• Italian chemist, Nobel prize 1963
• Learned of Ziegler’s research, and applied findings to other a-
olefins such as propylene and styrene

propylene polypropylene

• Resulting polypropylene was made up of two fractions:

Amorphous: atactic
Crystalline: tactic

• Polypropylene is not produced in radical initiated reactions

http://www.nobel.se/chemistry/laureates/1963/
 Tacticity

isotactic

syndiotactic

atactic

• Isotactic and syndiotactic polymers are crystalline, atactic is

amorphous

• NMR spectroscopy is a powerful tool for studying polymer

stereochemistry

• Ziegler/Natta catalysts allow control of tacticity

 Tacticity
Dyad Tacticity Triad Tacticity
m m m

isotactic (meso, m) isotactic(mm)

r m r

syndiotactic (racemic, r) atactic (mr)

r r

syndiotactic (rr)

• NMR spectroscopy is a powerful tool for studying polymer

stereochemistry

• Tacticity of polymer is determined by % m or r dyads

e.g. Perfectly isotactic polypropylene has 100% m dyads
 Ti-based heterogeneous
Ziegler/Natta catalysts
P CH2
HH
First generation (Solid solution) Cl
• Different crystalline modifications Cl Ti
of Ti(III),(TiCl3)a,b,g,d, + Al(C2H5)2Cl Particle Cl
Core HH
Cl
Al
Second generation (Donor modified)
• TiCl3/AlR3/Lewis Base (e.g. ethers, Et Et
esters, ketones, amines and phosphines)
• Certain Lewis bases increase the stereospecificity of polymerization
and increase the activity of the catalyst

Third generation (Supported)

• TiCl4 + Al/MgCl2/Lewis Base/AlR3
• Increase in catalyst surface area greatly increases polymerization
activity

Broad molecular weight distributions

 Molecular weight distribution
Mn

Weight fraction Mw

Molecular Weight

• In a polydisperse polymer, Mw ≥ Mn
• The polydispersity and breadth of plot, has bearing on the
mechanism of polymerization and the properties of the resulting
polymer
 Metallocene catalysts
• 1955: Natta reported that Cp2TiCl2 activated by AlEt3 could
polymerize ethylene with low activities

• 1981: Sinn and Kaminsky discovered a high activity catalyst:

CH3 ethylene
Zr + AlMe3 + "H2O" Very active catalyst!
CH3

• The key to reactivity was the co-catalyst generated from the

adventitious water, “methylalumoxane(s)” or MAO

Me

x AlMe3 + x H2O Al + 2x CH4

O x
 Role of MAO
• Ziegler/Natta catalysts are water sensitive; excess MAO serves
to dry the solvent and monomers
Me OH

Al + H2O Al + CH4
O x O x

• MAO can alkylate metal halides

Me Cl

Al + [M]-Cl Al + [M]-Me
O x O x

• MAO can abstract alkyl groups from a complex and generate

cations. In this case, MAO is transformed into a weakly-
coordinating anion
Me Me

Al + [M]-Me Al + [M]
O O x
x
Me
 Activation of metallocenes
• The active metallocene catalyst is a cationic alkyl

Me Me
Zr + AgBPh4 Zr [BPh4]
Me

-1/2 CH3CH3
Zr4+ (d0) -Ag0 Zr4+ (d0)
16-electron complex 14-electron complex

• These cationic alkyls polymerize olefins in non-coordinating

solvents, such as toluene, but not in coordinating solvents such as
THF

• A non-coordinating anion is required, i.e. MAO

 Olefin insertion
!
Me Me Me
Zr Zr Zr

Zr Zr Zr
Me Me

Me

• The alkyl resides in one of the equatorial sites and the olefin
binds to the other

• There is a change in the metal coordination site

 α-Olefin insertion
2-position
• a-olefins can insert from two positions: 1-position
R
1,2-addition

Me R Me
!
Me
Zr Zr Zr Zr
R
R
Me
R
2,1-addition

!
Me R Me Me
Zr Zr Zr Zr R

R Me
R

• 1,2-addition is the major mode of insertion, 2,1-insertion usually

leads to chain termination
 Chain termination
• b-Hydrogen elimination

! P
P " P H
(L) M (L) M (L) M +
R R
H R R H R R

• b-Alkyl elimination
!
P " P R P
(L) M (L) M (L) M +

R H R R H R R

• Chain transfer to co-catalyst

R

P
P R' P
(L) M + AlR'3 (L) M Al (L) M + R'2Al
R' R'2
H R R
 Living polymerization: A special case
R
(L) M
R ki = rate of initiation
kp = rate of propagation
activator
activation

R R' R'
R n R
(L) M (L) M (L) M
initiation (ki) R' propagation (kp) n+1
R'

• Initiator and intermediates are stable under reaction conditions

• There is no chain termination
• ki ≥ kp ,
This means that the rate of initiation is greater than rate of
propagation and that all the metal centers are initiated before
propagation takes place
• Polymers with narrow molecular weight distributions are
obtained
 C2 symmetric catalysts
SiMe3
isotactic PP; >99% m diads
m m m
(L) M (L) M-P = Zr P P Zr , Me2Si Y P
P
Me3Si

S R

• C2 symmetric catalysts result in mainly isotactic polymer

• Control is exerted by the ancillary ligands, which direct the
metal-bound polymer, which in turn directs the monomer

‡ ‡
P
+ R + +
• Zr R • Zr R
R • Zr
R
P P
 Cs symmetric catalysts
syndiotactic PP; >99% r diads
r r r
(L) M (L) M-P = Me2C Zr P , Me2Si Zr P
P Me2Si

• Cs symmetric catalysts result in mainly syndiotactic polymer

P
‡ S ‡
P P
S •
Zr+ • • Zr+ • R • Zr+ • R