Analysis of Molecular Weight Using Gel Permeation

Chromatography and the Effect of Chain Transfer

Agents
Roman Drake
Department of Chemical and Biological Engineering, Northwestern University, Evanston,
Illinois 60201, United States

ABSTRACT
Gel Permeation Chromatography is a type of size exclusion chromatography that
separates polymers by size, or molecular weight. Using the polystyrene synthesized
in Lab 1, this type of chromatography was used to determine the number-average,
weight-average, and z-average molecular weights of different samples to determine
the effect of initiator concentration on molecular weight. This allowed verification
that the number-molecular weight is proportional to the inverse of the square root
of initiator concentration. In addition to this, dispersity (M n/Mw) of a polymer made
by free-radical polymerization was verified to be approximately 1.5-2.0. Finally, it
was verified that the addition of chain transfer agents decreases the molecular
weight of a polymer.
INTRODUCTION
The number-average degree of polymerization of a polymer synthesized by freeradical polymerization can be found to be

DP n=

k apparent [ M ]
1 /2

[I]

(Equation 1)

where kapparent is a combination of rate parameters, [M] is the monomer

concentration, and [I] is the initiator concentration. The number-average molecular
weight of a polymer is proportional to the degree of polymerization, so for samples
in which monomer concentration is held equal, it should be true that
1/ 2

M n [ I ]

(Equation 2)

The dispersity of a polymer, or ratio of the weight-average to number-average

molecular weight (Mw/Mn) synthesized by free-radical polymerization is
approximately 1.5-2.0. This lab will use Gel Permeation Chromatography, a type of
size exclusion chromatography, to determine the molecular weights of different
polymer samples to verify that they follow these proportionalities. The numberaverage (as well as weight-average and z-average) molecular weight can be
calculated by

ci
i

M n=

ci
Mi

ci M i
M w=

ci

c i M 2i
M z=

ci M i

(Equations 3-5)

It will also analyze the effects of a chain transfer agent on the molecular weight of
polymers.
EXPERIMENTAL SECTION
8.0 mL of styrene was added to 10 mL test tubes. Varying amounts of benzoyl
peroxide initiator was then added to the test tubes The tubes were placed in an oil
bath at 70C and allowed to react. A chain transfer agent was added one of the test
tubes. After reacting, the polystyrene was precipitated into methanol. The
precipitated polymer was then recovered and dried in a vacuum oven. The
experiment was conducted a second time.
After the polystyrene was precipitated, gel permeation chromatography was
performed on it. The polystyrene was dissolved in a reservoir of tetrahydrofuran
solvent in the ratio 1 mg polymer/1 mL THF. It was then injected into a column of
gel. This gel has pores of different sizes. Smaller polymer molecules enter the pores
and are thus delayed in their passage through the column, while larger molecules
cannot enter the pores and will experience no such delay. Therefore, larger
molecules will elute through the column faster than smaller molecules. After exiting
the column, the eluant passes through a differential refractometer, which measures
the difference in refractive index between the eluant and pure tetrahydrofuran.
Using this difference and the derivative of refractive index as a function of polymer
concentration dn/dc can be used to determine the weight concentration of polymer
at a given elution time. Using the distribution of concentration and the
establishment of a baseline, the number-average, weight-average, and z-average
molecular weights for a polystyrene sample were determined.
RESULTS AND DISCUSSION
Because the reported values of concentration hovered around zero, with some of
them actually being negative, the baseline can be set at zero. To analyze the data, a
polymer peak region, in which there were no negative values, was identified. The
number-average, weight-average, and z-average molecular weights were
determined using Equations 3, 4, and 5, respectively. Table 1 shows the numberaverage, weight-average, and z-average molecular weights, as well as the
dispersity, for polymer samples given different initiator concentrations.
Table 1: Initiator Concentration, Mn, Mw, Mz, and Dispersity
[I]
Mn
Mw
Mz

0.0094
4
129000
200000
288000

0.0119

0.0150

0.0189

113000
151000
208000

95800
152000
214000

92900
137000
193000

0.021
7*
62200
86500
27200

0.0219

0.0258

73200
120000
185000

68200
111000
159000

0.025
9*
50800
77000
18200

0
0
Mw/Mn
1.55
1.34
1.59
1.47
1.39
1.64
1.63
1.52
* Chain transfer agents were added to these samples. They are thus not included in
Figure 1
To verify Equation 2, Mn was plotted as a function of [I] -1/2. Figure 1 shows this
relationship.

Mn vs. [I]-1/2
140000
120000
100000
80000

Mn

60000
40000
20000
0

6.5

7.5

8.5

9.5

10

10.5

11

[I]-1/2

Figure 1: Plot of Mn vs. [I]-1/2

According to Figure 1, Mn is proportional to [I]-1/2, as the data are linear with an R2
value of 0.967, verifying Equation 2. The average value of dispersity for the samples
in which a chain-transfer agent was not added is 1.53. Table 1 indicates that M n
significantly decreases with the addition of chain-transfer agents. This is because
the chain transfer agent increases the rate of termination. The dispersity is also
slightly smaller for the cases where chain-transfer agent was added.

The Raw data for initiator concentration was taken from Lab 1. Sample calculations
are not appropriate as displaying them would either be exhausting, as with M n, or
trivial, as with dispersity.