BASIC PRINCIPLES OF POLYMER MOLECULAR

WEIGHTS
Polymers are mixtures of molecules of different
molecular weight. Why?
A typical polymer sample contains a multitude of
individual molecular chains, many of which may
have widely differing molecular weights.

To distinguish between different samples of the

same polymer, need an average MW.

Mechanical properties and processing behaviour

depend on the average size and the distribution of
sizes of macromolecules in the sample. The
influence depends on both the property and on the
nature of the polymer (e.g. effect of MW on
viscosity and modulus of amorphous polymers).

Average MW and breadth of the MWD are

determined by the polymerization process. The
control of MW is essential for the practical
application of a polymerization process.
Successful market competition of a plastic
depends on the ability to control MW during the
reaction (Reaction Engineering) and the
understanding of how MW influences final
application properties (Polymer Science and
Polymer Processing).

MWD AND MW AVERAGES

Peebles (1971); Billingham (1977)

Basic concepts from small particle statistics

Ni indicates the number of molecules with a MW
equal to Mi

Definitions
Number average MW (

MN

Ni M i
=
Ni

Weight average MW

MW

MN

MW

Ci M i
=
Ci

Arithmetic means of the number and weight

distributions of molecular weights
and M W may be measured directly but it is
usually necessary to measure the detailed
distribution to estimate higher averages
MN

MW averages of a discrete distribution of

molecular weights can be defined by the
generalized expression:

Ni M i
M =
-1
Ni M i

where the parameter '' is a weighting factor

=1

===>

MN

=2

===>

MW

=3

===>

MZ

=4

===>

MZ+1

Example:
Consider a polymer sample for which 99% of the
weight is composed of material with MW=20,000 and
the remaining 1% of MW = 109
Then:
MN = 20,200
MW = 107
MZ = 109
Obviously, MW and MZ must be used with care in
such an instance
High MW portion ===> microgel
MW and MZ emphasize the high MW portion of the
distribution to a greater extent than does MN

A more useful definition is in terms of the moments

of the distribution:

j = qi M i

where
j

j-th moment of the MWD

Mi =

molecular weight of i-th species

qi

quantity of polymer with mol.

weight Mi per unit volume of
the sample (e.g. Ni, xi, Ci, wi)

Generalization beyond two averages; facilitate the

estimation of parameters related to the breadth
and the symmetry of the distribution

Breadth Of The MWD

M N MW M Z
The equality occurs only if all the species have
the same MW (monodisperse polymer)
Polydispersity index :

PDI = M W
MN
PDI = M W - 1
MN
Not a sound statistical measure of the distribution
breadth

Correct measure of distribution breadth:

2

MN

= MW - 1
MN

w = MZ - 1
2

MW

MW

If distribution is monodisperse, then:

= w2 = 0

and

M N = MW = M Z
and

PDI = 1

Highly branched polymers have a PDI of 20 or

more
Most polymers have a PDI in the range 2-20
Condensation polymers:
PDI = 2

Most probable distribution

Anionic polystyrenes:
PDI = 1.04
assumed monodisperse; calibration standards