Tacticity, Geometric Isomerism

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For an isolated polymer molecule it is not possible to assign a unique value of r because the
chain conformations and hence r changes continuously due o rotation of backbone bonds.Since
the single polymer chain can take any of an infinite number of conformations an average
magnitude of r over all possible conformations is therefore computed from the mean of the
squares of end to end distance and is called the root mean square (RMS) end to end distance and
r 2 >1 /2
it is represented by
> means that the quantity is averaged over time.
It is given by a rather simple equation
r 2 >1 /2
Average chain end to end distance r = = d N
Where d is the C-C bond distance and N is the total no of bonds.
N = total no of bonds.
No of mers = N/2
Distance covered by one mer = 2x = 2 d sin /2
L = no of mers x distance covered by one mer
N
Or L = 2 x ( 2 d sin /2) = N d sin /2
L = N d sin /2 and r = d N
Tacticity
Tacticity is a term used to describe the way pendent groups on a polymer chain are arranged on
a polymer backbone. The tacticity of a polymer is determined by what side of the polymer chain
the pendant groups are on. This relative position can have dramatic effects on the physical
properties of the polymer. Tacticity only arises when there is an asymmetric carbon in the
polymer chain backbone.
If there is no order to the way the pendant group adds, (completely random) the polymer is said
to be atactic.
What does this have to do with anything, you ask? A lot! You see, 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.
Figure 1. Isotactic vs. Syndiotactic

This figure represents the structure of isotactic and syndiotactic polymers.
Isotactic poly(propene)
A bit of the isotactic poly(propene) chain looks like this:

Note: Dotted lines show bonds going back into the screen or paper, and wedge shapes show
them coming out towards you.
Atactic poly(propene)
In atactic poly(propene) the CH3 groups are orientated randomly along the chain.
This lack of regularity makes it impossible for the chains to lie closely together and so the van
der Waals attractions between them are weaker. Atactic poly(propene) is much softer with a
lower melting point.
It is formed as a waste product during the manufacture of isotactic poly(propene) and its uses
are limited. It is used, for example, in road paint, in making roofing materials like "roofing felt",
and in some sealants and adhesives.
Syndiotactic poly(propene)
Syndiotactic poly(propene) is a relatively new material and is another regularly arranged

version of poly(propene). In this case, every alternate CH3 group is orientated in the same way.
This regularity means that the chains can pack closely, and van der Waals attractions will be
fairly strong. However, the attractions aren't as strong as in isotactic poly(propene). This makes
syndiotactic poly(propene) softer and gives it a lower melting point.
Because syndiotactic poly(propene) is relatively new, at the time of writing uses were still being
developed. It has uses in packaging - for example, in plastic film for shrink wrapping food.
There are also medical uses - for example, in medical tubing and for medical bags and pouches.
There are a wide range of other potential uses - either on its own, or in mixtures with isotactic
poly(propene).
Many common and useful polymers, such as polystyrene, polyacrylonitrile and poly(vinyl
chloride) are atactic as normally prepared. Customized catalysts that effect stereoregular
polymerization of polypropylene and some other monomers have been developed, and the
improved properties associated with the increased crystallinity of these products has made this
an important field of investigation. The following values of Tg have been reported.
The properties of a given polymer will vary considerably with its tacticity. Thus, atactic
polypropylene is useless as a solid construction material, and is employed mainly as a
component of adhesives or as a soft matrix for composite materials. In contrast, isotactic
polypropylene is a high-melting solid (ca. 170 C) which can be molded or machined into
structural components.

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Figure 1. Isotactic vs. Syndiotactic

A bit of the isotactic poly(propene) chain looks like this:

Syndiotactic poly(propene) is a relatively new material and is another regularly arranged

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