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Mechanisms of Operation: Isotactic Polymerisation

Mechanisms of operation for producing polymers using Ziegler-Natta catalysts are discussed. Two mechanisms are described: isotactic and syndiotactic polymerization. For isotactic polymerization, a TiCl3 catalyst reacts with propylene to add monomers to the growing chain in the same orientation. For syndiotactic polymerization, a VCl4 catalyst is used, which adds monomers alternately to opposite sides of the growing chain, resulting in a syndiotactic structure. Both mechanisms involve the monomer attacking the metal atom after a co-catalyst donates a group and removes a chlorine, forming a transition state before polymerization continues.

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100 views4 pages

Mechanisms of Operation: Isotactic Polymerisation

Mechanisms of operation for producing polymers using Ziegler-Natta catalysts are discussed. Two mechanisms are described: isotactic and syndiotactic polymerization. For isotactic polymerization, a TiCl3 catalyst reacts with propylene to add monomers to the growing chain in the same orientation. For syndiotactic polymerization, a VCl4 catalyst is used, which adds monomers alternately to opposite sides of the growing chain, resulting in a syndiotactic structure. Both mechanisms involve the monomer attacking the metal atom after a co-catalyst donates a group and removes a chlorine, forming a transition state before polymerization continues.

Uploaded by

Dwi Utami
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© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Mechanisms of operation

To produce the polymer, catalysis needs to take place, while the catalyst is suspended the monomer
(either ethylene or propylene) is bubbled through. The phase of the catalyst is important, a solid catalyst makes
catalysis faster since the liquid reactant finds it easier to bind with a solid catalyst.
There are many different mechanisms that could occur, however only two mechanims will be discussed here,
these are;
 Isotactic polymerisation
 Syndiotactic polymerisation
They are both monometallic mechanisms but their mechanisms of attack are different. By using different
Ziegler-Natta catalysts two polymers can be made which vary in their structure. Here is a description of the two
mechanisms;

Isotactic polymerisation
In order to produce an isotactic polymer a TiCl3in conjuction with AlEt3 catalyst needs to used to react
with propylene. In the TiCl3 cocatalyst all interior Ti3+ atoms have 6 Cl- atoms attached to them but at the
surfaces each Ti3+ atom is only surrounded by 5 Cl- atoms. Therefore the Ti3+ atoms have an empty space with
which to react.

As shown above the diethylaluminium chloride co-catalyst donates an ethyl group to the TiCl3, and a chlorine
atom is removed. This leaves just four Chlorine atoms left bonded to the Titanium atom, which is now ready to
accept the monomer, propylene. The monomer, which is normally non-polar uses the two electrons in the -
system of the carbon-carbon double bond to attack the Titanium atom. The monomer has then taken the place of
the Chlorine atom, and since it is approximately the same size can be placed close to the Titanium atom so that
further reaction can take place. The mechanism that takes place is shown below.

The product above is made when the -bond overlaps with a Titanium orbital, simultaneously the -orbital
overlaps with another Titanium orbital. This means that electrons can move around the complex, in the way
shown below;
This step is known as the Transition stage, and is assisted by the alkene group's ability to overlap in this way.
Following this Transition stage the complex undergoes migration where the molecules rearrange themselves to
form a more reactive species.

The Titanium atom is then in the correct position to carry on polymerisation using the mechanism described
above.

Syndiotactic polymerisation

This type of polymerisation involves using the VCl4 and Al(C2H5)2Cl Ziegler-Natta catalyst. The
mechanism of reaction is similar to isotactic polymerisation, however the Al(C2H5)2Cl co-catalyst is
complictaed to draw and so has been shortened as shown below;
The propylene monomer will attack the Vanadium atom in the same way as it attacks Titanium, forming a -
complex at the Vanadium orbital which was emptied of Chlorine. The Transition state is reached as before with
the Vanadium orbital overlapping with the  and -orbitals.

There is one important difference in the two mechanisms, that is that the Polymer chain does not move position
in the syndiotactic polymerisation.

When the next monomer attacks the Vanadium atom and joins the chain, the polymer chain moves position
back to where it started. The blue methyl groups in the first monomer, and the red methyl groups of the second
monomer have arranged themselves so that the next monomer has only one place to attach, so that its methyl
group is on the other side. This is how this unique mechanism forms a syndiotactic polymer as oppose to an
isotactic one.

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