Molar mass distribution

Molar mass distribution

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 (Ni) and the molar mass (Mi) of that species. [1] 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 Mn
• Weight average molar mass or Mw
• Viscosity average molar mass or Mv
• Z average molar mass or Mz

$M_n=\frac{\sum M_i N_i} {\sum N_i}, M_w=\frac{\sum M_i^2 N_i} {\sum M_i N_i}, M_z=\frac{\sum M_i^3 N_i} {\sum M_i^2 N_i}, M_v=\left[\frac{\sum M_i^{1+a} N_i} {\sum M_i N_i}\right]^\frac{1} {a}$ [2]

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 weight average molar mass. Mv is obtained from viscosimetry and Mz 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: Mn < Mv < Mw < Mz. Polydispersity of a sample is defined as Mw divided by Mn and gives an indication just how narrow a distribution is.[2]

The most common technique for measuring molecular weight 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 thousand psi. The limited accessibility of stationary phase pore volume for the polymer molecules results in shorter elution times for high-molecular-weight species. The use of low polydispersity standards allows the user to correlate retention time with molecular weight, 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-weight-insensitive, so it is ideal for a single-detector GPC system, as it allows the generation of mass v's molecular weight curves. Less common but more accurate and reliable is a molecular-weight-sensitive detector using multi-angle laser-light scattering - see Static Light Scattering. These detectors directly measure the molecular weight 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 Mw and a small reduction in Mn thus reducing polydispersity.

Number average molecular weight

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

$\bar{M}_n=\frac{\sum_i N_iM_i}{\sum_i N_i}$

The number average molecular weight 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 [3].

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

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

Weight average molecular weight

The weight average molecular weight is a way of describing the molecular weight 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 weight average molecular weight, this is calculated by

$\bar{M}_w=\frac{\sum_i N_iM_i^2}{\sum_i N_iM_i}$

where Ni is the number of molecules of molecular weight Mi.

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

The weight average molecular weight can be determined by light scattering, small angle neutron scattering (SANS), X-ray scattering, and sedimentation velocity.

An alternative measure of molecular weight for a polymer is the number average molecular weight; the ratio of the weight average to the number average is called the polydispersity index.

The weight-average molecular weight, Mw, 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 Mo is the molecular weight of the repeating unit.

References

1. ^ I. Katime "Química Física Macromolecular". Servicio Editorial de la Universidad del País Vasco. Bilbao
2. ^ a b R.J. Young and P.A. Lovell, Introduction to Polymers, 1991
3. ^ Polymer Molecular Weight Analysis by 1H NMR Spectroscopy Josephat U. Izunobi and Clement L. Higginbotham J. Chem. Educ., 2011, 88 (8), pp 1098–1104 doi:10.1021/ed100461v

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