Renewal theory

In linear polymers the individual polymer chains rarely have exactly the same degree of polymerization and molar mass, and there is always a distribution around an average value. The molar mass distribution (or molecular weight distribution) in a polymer describes the relationship between the number of moles of each polymer species (N_i) and the molar mass (M_i) of that species. The molar mass distribution of a polymer may be modified by polymer fractionation.

Definition of molar mass averages

Different average values can be defined depending on the statistical method that is applied. The weighted mean can be taken with the weight fraction, the mole fraction or the volume fraction:

• Number average molar mass or M_n
• Mass average molar mass or M_w
• Viscosity average molar mass or M_v
• Z average molar mass or M_z

$M_{n}={\frac {\sum M_{i}N_{i}}{\sum N_{i}}},\quad M_{w}={\frac {\sum M_{i}^{2}N_{i}}{\sum M_{i}N_{i}}},\quad M_{z}={\frac {\sum M_{i}^{3}N_{i}}{\sum M_{i}^{2}N_{i}}},\quad M_{v}=\left[{\frac {\sum M_{i}^{1+a}N_{i}}{\sum M_{i}N_{i}}}\right]^{\frac {1}{a}}$

Here a is the exponent in the Mark-Houwink equation that relates the intrinsic viscosity to molar mass.

Measurement

These different definitions have true physical meaning because different techniques in physical polymer chemistry often measure just one of them. For instance, osmometry measures number average molar mass and small-angle laser light scattering measures mass average molar mass. M_v is obtained from viscosimetry and M_z by sedimentation in an analytical ultracentrifuge. The quantity a in the expression for the viscosity average molar mass varies from 0.5 to 0.8 and depends on the interaction between solvent and polymer in a dilute solution. In a typical distribution curve, the average values are related to each other as follows: M_n < M_v < M_w < M_z. Polydispersity of a sample is defined as M_w divided by M_n and gives an indication just how narrow a distribution is.

The most common technique for measuring molecular mass used in modern times is a variant of high-pressure liquid chromatography (HPLC) known by the interchangeable terms of size exclusion chromatography (SEC) and gel permeation chromatography (GPC). These techniques involve forcing a polymer solution through a matrix of cross-linked polymer particles at a pressure of up to several hundred Bar. The limited accessibility of stationary phase pore volume for the polymer molecules results in shorter elution times for high-molecular-mass species. The use of low polydispersity standards allows the user to correlate retention time with molecular mass, although the actual correlation is with the Hydrodynamic volume. If the relationship between molar mass and the hydrodynamic volume changes (i.e., the polymer is not exactly the same shape as the standard) then the calibration for mass is in error.

The most common detectors used for size exclusion chromatography include online methods similar to the bench methods used above. By far the most common is the differential refractive index detector that measures the change in refractive index of the solvent. This detector is concentration-sensitive and very molecular-mass-insensitive, so it is ideal for a single-detector GPC system, as it allows the generation of mass v's molecular mass curves. Less common but more accurate and reliable is a molecular-mass-sensitive detector using multi-angle laser-light scattering - see Static Light Scattering. These detectors directly measure the molecular mass of the polymer and are most often used in conjunction with differental refractive index detectors. A further alternative is either low-angle light scattering, which uses a single low angle to determine the molar mass, or Right-Angle-Light Laser scattering in combination with a viscometer, although this latter technique does not give an absolute measure of molar mass but one relative to the structural model used.

The molar mass distribution of a polymer sample depends on factors such as chemical kinetics and work-up procedure. Ideal step-growth polymerization gives a polymer with polydispersity of 2. Ideal living polymerization results in a polydispersity of 1. By dissolving a polymer an insoluble high molar mass fraction may be filtered off resulting in a large reduction in M_m and a small reduction in M_n thus reducing polydispersity.

Number average molecular mass

The number average molecular mass is a way of determining the molecular mass of a polymer. Polymer molecules, even ones of the same type, come in different sizes (chain lengths, for linear polymers), so the average molecular mass will depend on the method of averaging. The number average molecular mass is the ordinary arithmetic mean or average of the molecular masses of the individual macromolecules. It is determined by measuring the molecular mass of n polymer molecules, summing the masses, and dividing by n.

${\bar {M}}_{n}={\frac {\sum _{i}N_{i}M_{i}}{\sum _{i}N_{i}}}$

The number average molecular mass of a polymer can be determined by gel permeation chromatography, viscometry via the (Mark-Houwink equation), colligative methods such as vapor pressure osmometry, end-group determination or proton NMR.

An alternative measure of the molecular mass of a polymer is the mass average molecular mass. The ratio of the mass average to the number average is called the polydispersity index.

High Number-Average Molecular Mass Polymers may be obtained only with a high fractional monomer conversion in the case of step-growth polymerization, as per the Carothers' equation.

Mass average molecular mass

The mass average molecular mass is a way of describing the molecular mass of a polymer. Polymer molecules, even if of the same type, come in different sizes (chain lengths, for linear polymers), so we have to take an average of some kind. For the mass average molecular mass, this is calculated by

${\bar {M}}_{w}={\frac {\sum _{i}N_{i}M_{i}^{2}}{\sum _{i}N_{i}M_{i}}}$

where $N_{i}$ is the number of molecules of molecular mass $M_{i}$.

If the mass average molecular mass is m, and one chooses a random monomer, then the polymer it belongs to will have a mass of m on average (for a homopolymer).

The mass average molecular mass can be determined by static light scattering, small angle neutron scattering, X-ray scattering, and sedimentation velocity.

The ratio of the mass average to the number average is called the polydispersity index.

The mass-average molecular mass, M_w, is also related to the fractional monomer conversion, p, in step-growth polymerization as per Carothers' equation:

${\bar {X}}_{w}={\frac {1+p}{1-p}}\quad {\bar {M}}_{w}={\frac {M_{o}\left(1+p\right)}{1-p}}$, where M_o is the molecular mass of the repeating unit.

See also

• Distribution function
• Chemical equilibrium
• Mass distribution
• Sedimentation

References

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