Introduction to Polymer Science (by Yuqi Cai, PH.D. of Chem. Eng.

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Polymer
Chemistry
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Classification of Polymers
Common Addition Polymers
Common Condensation Polymers
Macromolecular Weight
Polymer materials do not exhibit a single definite molar mass, unlike
small-molecular-weight substances. They consist of mixtures of
macromolecular chains with different numbers of repeating units, with
each chain having its own molar mass.
A single molecular weight of PE=28*n, wherein 28 is the monomers
molecular weight, n is the polymerization degree.
In commercial PE resins molecular weights range from several
thousands to millions. A average molecular weight and weight
distribution are calculated to characterize macromolecular structure
and properties.
Macromolecular Weight Distribution
- Polymer resin from even the same polymerization conditions
may have different molecular chain length and sometimes
branching structures.
- Assuming n
i
is the number of macromolecules with
molecular weight M
i
(a is a constant that depends on the polymer/solvent pair used in viscosity measurement)
Mn < Mv < Mw < Mz < Mz+1
Implications of Macromolecular Weight Distribution
Mn
Is not a continuous function of M, or discrete function instead
Most sensitive to lower end tail fraction of molecules
General indication of average macromolecular chain length and relevant
mechanical properties such as tensile strength and elongation
Any property which is only sensitive to the number of molecules present
or a property that is not influenced by the size of any particle in the
mixture, e.g., the colligative properties of solutions such as boiling point
elevation, freezing point depression, and osmotic pressure can be used
for measuring Mn
End group titration is also used to measure Mn
Mw
Greater emphasis on higher molecular weight fractions
Stronger effect on melt rheology, crystallinity and dynamic mechanical
properties
Light scattering and SEC/GPC are used to determine Mw
Mz
Greatest emphasis on higher molecular tail fraction on a distribution
curve
A Z-average molecular weight is obtained from centrifugation data
Method of MW Measurement for Polymers
10
7
Light Scattering Mw
10
7
GPC or SEC
10
7
Ultracentrifugation Mz
10
7
Intrinsic Viscosity Mv
10
5
Osmotic Pressure
10
4
Vapour Pressure
Lowering
10
4
Freeing Point
Depression
10
4
Boiling Point Elevation
2.5 x 10
4
Eng group determination Mn
Upper limit of MW Measurement Method Type of MW Average
Width of Molecular Weight Distribution ( MWD)
Polydisperse Index or PDI = Mw/Mn
If PDI=1, called Monodisperse, i.e. all molecular weights are identical in a
polymer sample, only achievable in special living polymerization reactions
PDI>1, called Polydisperse
True for almost all synthetic polymers
Varying on polymerization methods, and catalyst selections
having strong effect on melt viscoelasticity, melt processability and mechanical
properties of polymer materials
The closer the PDI approaches a value of 1, the narrower is the polymer's
molecular weight distribution.
Comparison of the MWDs of Z-N and metallocene
polyolefin (Foster and Wasserman, 1997)
Molar mass distribution for a narrow and
broad Poly(styrene)
PDI of different Types of Polymers
>50 Step reaction of tri- or
tetra-functional
monomers
Network Polymers
2-50 Free radical addition Branched polymers
2-30 Coordination
complexes
2-10 Free radical addition Addition Polymers
~2 Step reaction of
bifunctional monomers
Condensation
Polymers
1.0-1.05 Anionic group transfer Living Polymers
Polydisperse Index
(PDI)
Polymerization
mechanism
Type of Polymer