Experiment 5th

Gel Permeation Chromatography (GPC)

Group 4
1. Deni Alek Sandy A10706009 (Main Writer’s)
2. Lely Ayu Ningsih A10706002
3. Matthew Christian Haryanto B10706207
4. Sintia Bela B10706214
Experiment 3
Gel Permeation Chromatography (GPC)
Purpose:

1. Understand the gel permeation chromatography (GPC) of the basic principle.

2. Learn the basic components GPC instrument.
3. Training students to use GPC measuring polymer molecular weight and molecular weight
distribution.
4. Learn to control important variables polymer molecular weight distribution of the reaction.

Foreword:

The average molecular weight and molecular weight distribution of the polymer on the mechanical
and thermal properties of polymer materials are playing an extremely important role, J.C. Morre
proposed to use gel permeation assay (GPC) in 1964 measuring polymer molecular weight
distribution, it has now been in R & D and quality control work has been widely adopted. Gel
permeation chromatography (GPC) is a type of size exclusion chromatography (SEC), that
separates analytes on the basis of size. GPC was due to the principle of separation of small
molecules can easily penetrate through the pore diffusion into the interior of the gel particles, and
therefore more time-consuming fractions; on the contrary a large molecular weight molecules
readily diffuse into the interior of the gel particles, so the eluting time is shorter. Eluting polymer
concentration detection instruments include the UV detector (UV detector) and the RI detector
(refractive index detector), and so on.

Principle:

When the polymer solution sample through the separation column, be separated depending on the
size of the sample component solute molecules. Chromatography under appropriate operating
conditions, each component separated by column will produce a slight speed difference, so that
the components can be successively separated from the column.

1. Introduction
Gel permeation chromatography (GPC), more correctly termed size exclusion
chromatography, is a separation method, which is widely used for estimating the molecular-weight
distributions of polymers. The separation takes place in a chromatographic column filled with gel
beads that are rigid, highly porous and non-ionic. Highly cross-linked porous polystyrene and
porous glass are preferred column-packing materials.1
In a typical GPC experiment, a dilute polymer solution is introduced into the GPC column
in which an appropriate solvent is flowing. A GPC column does not separate according to mass,
but rather via other mechanisms. As the dissolved polymer molecules flow through the porous
beads, they can diffuse into the internal pore structure of the gel to an extent depending on their
size and the pore size distribution of the gel. The largest polymer molecules of the solute cannot
penetrate the pores within the cross-linked gel beads, and thus elute first (their retention volume is
smaller). Smaller polymer molecules of the solute are retained within the gel beads. The larger
the molecule, therefore, the less time it spends inside the gel, and the sooner it flows through
the column. The different molecular species are eluted (hence called elution time) from the
column in order of their molecular size as distinguished from their molecular weight, the largest
emerging first (Figure 2.1).2
Once the polymer molecules are separated and come out from column, at least one
detector is needed to tell what and how many polymer molecules are at a certain time (elution
time). The typical detectors are RI (Differential Refractive Index), UV (ultraviolet) and LS (light
scattering detector). Some not-so-common detectors can also be found in the GPC systems, such
as capillary viscometer detector
The most common 1) RI detector in use today is based on the deflection of a beam of light
as it passes through a dual compartment flow cell. One side of the compartment contains the
reference solvent of refractive index no, which is static during the measurement process. The other
side contains the sample solution, i.e., the column eluent, having refractive index n. The
differential signal will give the concentration of eluent. In order to use the RI detector
quantitatively, the calibration constant must be determined. 2) UV detector is similar to a UV
spectrometer, but only detects the UV absorption at the certain wavelength. The absorption is
proportional to the concentration of eluent. 3) Light scattering detector is based on the fact that
intensity of light scattered by a polymer molecule is proportional to the square of its mass. LS can

1
Fred W. Billmeyer, JR. “Textbook of Polymer Science”, Third edition, A willey-Interscience
Publication.
2
Jan F. Rabek, “Experimental Methods in Polymer Chemistry”, Physical Principles and
Applications, A Wiley-Interscience Publication.
be used to give the 'true' molecular weight data for polymer samples, additionally, the
information on differences in structure (or composition) between samples. Light scattering
detector works with at least one IR detector, which will give the concentration information that
LSD needed.
GPC is extremely valuable for both analytic and preparative work with a wide variety of
systems ranging from low to very high molecular weights. The method can be applied to a wide
variety of solvents and polymers depending on the types of gel used. With polystyrene gels,
relatively non-polar polymers can be measured in solvents such as tetrahydrofuran, toluene, or (at
high temperature) dichlorobenzene. With porous glass gels, more polar systems, including aqueous
solvents, can be used. A few milligram of sample is sufficient for analytical work, which could be
completed in as short as a few minutes using modern high-pressure, high-speed equipment.

Porous Gel
Bead

Polymer
Molecule

Figure 2.1. Principle of the separation of molecules according to size by gel permeation
chromatography3

Earlier, it was said that GPC is used to estimate the molecular weight distribution of
polymers, including: weight average molecular weight (Mw), number average molecular weight
calculation (Mn), polydispersity index (PDI) and average degree of polymerization ( DP ).
Theoretically, this information could be obtained using the formulae listed below as Equation 2.1
through Equation 2.4. In these equations, N refers to the number of polymer chains having
molecular weight M and for DP calculation, a molecular weight of 104 Daltons for polystyrene
will be used. These values are essential in polymer characterization. Molecular weight (calculated
as Mn or Mw) of a polymer, for example, is related directly to a polymer’s physical properties.

3
ERS Department, Trent University, http://whale.wheelock.edu/bwcontaminants/analysis.htmL.
While Mn represents the number average molecular weight, Mw represents the weight average
molecular weight. The ratio of the two gives information about the distribution of the chain lengths
within a polymer, a term known as polydispersity index (PDI). The average degree of
polymerization ( DP ), which is not as important as the other three parameters, represents the
average number of monomers that make up the polymer chains.

N M i i
2
w M i i
Mw = i
= i
(Equation 2.1)
N M i
i i w i
i

N M i i
Mn = i
(Equation 2.2)
N i
i

Mw
PDI = (Equation 2.3)
Mn

Polymer molecular weight (M n )

DP = (Equation 2.4)
Monomer molecular weight
The figure below shows a generic GPC setup.

Filter (ca 0.5 um)

Pump GPC
Columns
Injector
Loop
To Waste
Concentration
Detector

Optional
Optional Detector #1
To Waste
Waste Detector #2 e.g. Viscosity
e.g Light
Flow Scattering

Voids: Uniform
Diameter D helps Pore: Size is 
minimize voids given by the
correlation length
 D = 1 - 50 m
How it works: Large molecules can’t permeate the pores. They travel rapidly through the void
volume. Small molecules travel partly through the porous packing materiales & go slower due to
hydrodynamic shielding from the flow field (if you climb a pine tree on a windy day, it will be less
windy once you’re up in the tree a bit).
Materials and Instruments
1. High-performance gel permeation chromatograph (GPC, Model: Millennium32,
Waters)
2. LC level tetrahydrofuran (THF)
3. The standard sample: polystyrene (430000, 43000, 9600 g / mol)

Experimental Procedure
1. Remove the clip from the venting tube then insert the tube into the waste
bottle.
2. Press “shift” “1” to delete the purge function and remove the cap on the
injection port.
3. Rinse the syringe with THF then take 200 µL THF. Remove the bubble inside
the syringe by sucking more liquid and slowly pushing out the liquid.
4. Turn the knob to “load” then insert the syringe and inject the sample.
5. Open the software “Empower 3” then press “Login new user”.
6. Type in the the username : system and password : manager then press OK.

7. Choose “E2-302” file then press OK.

8. Type in the sample name in the window below then choose “Inject Broad
Samples”. After that, press “Prepare”.

9. Turn the knob to “Inject” and press “Injection” at the same time.

10. Wait until the data analysis is done.

11. After the data analysis is done, open the window below then press “Browse
projects”.

12. Choose “E2-302” file, press “Channel”, then “Update”.

13. Choose your data, then open the data by clicking “File” “Open”
“Processing Method” then choose either “PS-1081023” or “PS-10810231”.

14. After that, choose “Processing method wizard”, press “ok”, then choose
“next” until “Finish” button appear, then choose “copy curve”. The data
analysis will be shown on the table below the curve.

15. To save the data, press “File”, then choose “save” “all and preview results”.
16. Repeat step 3-15 by injecting sample 1 on the first week and sample 2 on the
second week. For THF, step 11-15 is unneccesary.
17. After the experiment is finished, press “shift” “1” again to purge the system.
Turn the knob to “inject” and apply the clip on the venting tube again.
 Result and Explanation
Questions
1. Include other measurement method of polymer molecular weight and give simple
instructions!
A. Static Light Scattering (SLS)
Static light scattering (SLS) is a technique to measure absolute molecular weight using the
relationship between the intensity of light scattered by a molecule and its molecular weight and
size, as described by the Rayleigh theory. In the simplest terms, Rayleigh theory says that larger
molecules scatter more light than smaller molecules from a given light source and that the
intensity of the scattered light is proportional to the molecule’s molecular weight.

Figure. Modes of scattering solution

There are two ways to measure absolute molecular weight by static light scattering:
a. Batch measurement using a cuvette
b. In combination with a chromatography instrument.
Batch measurement with cuvette-based instruments is an ensemble technique. Therefore, the
result calculated is the weight average molecular weight of the entire sample measured.
However, the most common way of measuring absolute molecular weight is to add an SLS
detector e.g. Low Angle Light Scattering LALS, Right Angle Light Scattering RALS or Multi
Angle Light Scattering MALS to a GPC/SEC system.
The three approaches to SLS have been developed:
• Right angle light scattering (RALS) - Scattering intensity is determined at 90° to the
incident beam. It offers a very good signal to noise ratio, however, does not take into
account anisotropic scattering. The assumption is that the scattering intensity at 0° is just
 as that at 90°. This is a suitable approach for small molecules but not for anisotropic
scatterers.
• Low angle light scattering (LALS) - In LALS, scattering intensity is determined at an
angle very close to 0° in order to eliminate the error related to anisotropic scattering.
This is fine for all molecules, however, the signal-to-noise ratio becomes challenging
for smaller molecules. A combination of RALS/LALS technology is a good prospect.
• Multi-angle light scattering (MALS) – The approach adopted with MALS is measuring
at several angles and extrapolating the same to determine a value for scattering intensity
at 0°C. MALS is suitable for all molecule sizes but the method is more complicated than
LALS or RAls.
It is possible to use all the three light scattering techniques in batch mode, but they are more
frequently applied in flow mode, with the light scattering detector constituting a gel
permeation/size exclusion chromatography (GPC/SEC) detector array.

Figure. Scheme of light scattering.

B. Viscometry
Viscosity is an internal property of a fluid that offers resistance to flow. It is due to the internal
friction of molecules and mainly depends on the nature & temperature of the liquid. Many
methods are available for measuring viscosity of polymer solution. The Ostwald method is a
simple method for the measurement of viscosity, in which viscosity of liquid is measured by
comparing the viscosity of an unknown liquid with that of liquid whose viscosity is known. In
this method viscosity of liquid is measured by comparing the flow times of two liquids of equal
volumes using same viscometer.
Consider two liquids are passing through a capillary of same viscometer. Then the coefficient
of viscosity of liquid (η2) is given by equation

Here t1 and t2 are the time of flow of the liquids and ρ1 and ρ2 are the respective densities.
And η1 is the coefficient of viscosity of water.
For a given liquid η has a specific value at the same temperature.
Various mixtures of two non-interacting liquids viscosities will lie among the viscosities of
those pure components. The time of flow of liquid depends on the viscosity and composition.
In this method the flow times are measured for different known compositions and a graph is
plot for time of flow and compositions. The unknown composition can be determined by
plotting a graph for the time of flow and compositions.
The molecular weight of the polymer is measured by using viscometer and the molecular weight
obtained by this technique is called viscosity average molecular weight. The molecular weight
of the polymer solution is very high so the viscosity of polymer solution is very high compared
to that of pure solvent.
From the Mark-Houwink equation the relationship among the molecular weight and viscosity
are given below.

Where η is the intrinsic viscosity, M is Molecular weight, K and α are constants for a particular
polymer solvent system.
If we know the K and α values for a given polymer solution the intrinsic viscosity and molecular
weight can be calculate using the above equation.
C. Osmometry
Osmometry is applied to determine number average of molecular weight (Mn). There are two
types of osmometer:
1. Vapor pressure osmometry (VPO).
2. Membrane osmometry.
Vapor pressure osmometry measures vapor pressure indirectly by measuring the change in
temperature of a polymer solution on dilution by solvent vapor and is generally useful for
polymers with Mn below 10,000–40,000 g/mol. When molecular weight is more than that limit,
the quantity being measured becomes very small to detect. A typical vapor osmometry shows
in the Figure 2.2.172.2.17. Vapor pressure is very sensitive because of this reason it is measured
indirectly by using thermistors to measure voltage changes caused by changes in temperature.

Figure Schematic vapor pressure osmometry.

Membrane osmometry is absolute technique to determine Mn. The solvent is separated from the
polymer solution with semipermeable membrane that is strongly held between the two
chambers. One chamber is sealed by a valve with a transducer attached to a thin stainless-steel
diaphragm which permits the measurement of pressure in the chamber continuously. Membrane
osmometry is useful to determine Mn about 20,000-30,000 g/mol and less than 500,000 g/mol.
When Mn of polymer sample more than 500,000 g/mol, the osmotic pressure of polymer
solution becomes very small to measure absolute number average of molecular weight. In this
technique, there are problems with membrane leakage and symmetry. The advantages of this
technique is that it doesn’t require calibration and it gives an absolute value of Mn for polymer
samples.

Figure. Schematic of membrane osmometry.

Molecular Weight Analysis of Sample 1
After we do experiment, we got the data of styrene calibration curve to determine the
molecular weight of sample, as follows:
GPC Calibration Plot

5.50

5.00

4.50
Log Mol Wt

4.00

3.50

3.00

16.00 18.00 20.00 22.00 24.00 26.00 28.00

Retention Time

Figure 1. GPC calibration curve plot for Sample 1

Then, from fig.1 we got the data of molecules weight, retention time, calculated weight,
and % residual, as follows:

Mol Wt RT Calculated Weight

(Daltons) % Residual
(Daltons) (min)
1 387000 16.001 387629 -0.162
2 43700 19.014 43507 0.444
3 6520 23.762 6579 -0.904
4 580 28.827 590 -1.753
5 9970 22.541 9953 0.167
6 890 28.251 870 2.254
Then we made a table which it contain molecular weight, log molecular weight and its
retention time to make a graph of calibration curve as follows:
Mol Wt Log Mol Wt Retention Time,
(Daltons) min
1 387000 5.58771 16.001
2 43700 4.64048 19.014
3 9970 3.99870 22.541
4 6520 3.81425 23.762
5 9970 3.99870 28.251
6 580 2.76343 28.827
Futhermore, we make a figure from table 2, then plot it into graph and we get a calibration curve
equation as a standard equation to determine the molecular weight of sample 1.
GPC Distribution Table
Retention Mol Wt Log Mol Area Cumulative dWt/d Vt - Vo
Time Wt % (log m)
1 16.001 387000 5.58771 660 91.053 69259.13 No
2 19.014 43700 4.64048 539 93.374 9417.13 No
3 22.541 9970 3.99870 429 95.258 2493.31 No
4 23.762 6520 3.81425 326 96.723 1709.38 No
5 28.251 9970 3.99870 239 97.815 2493.31 No
6 28.827 580 2.76343 178 96.619 209.88 No

4
Log Mol wt

y = -0.1657x + 7.956
1 R² = 0.7959

0
10 12 14 16 18 20 22 24 26 28 30
Retention Time, Min

Figure 2. GPC Curve Plot Analysis for Sample 1

Calibration Curve Equation:
Y = -0.1657x + 7.956
Sample 1: Analysis Result
From experiment done before, we got a figure of GPC analysis graph of sample 1
and a data of Mw, Mn, MP, Mz, Mz+1, and Polydispersity as follows:
 Auto-Scaled Chromatogram

200.00

6530
150.00

100.00
MV

50.00

0.00

-50.00

0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00

Minutes
Figure 3. Data Analysis of Sample 1 by GPC
Retention Mw Mn MP Mz Mz+1 Polydispersity
Time (PDI)
1 6531 6347 6530 6703 6870 1.028988

From experiment, we get the data of retention time of sample 1, then input the value to
calibration curve equation, we can get
y = -0.1657x + 7.956
y = -0.1657 (X) + 7.956
we get log mol wt of sample 2 value of y, after that, substitute the value to anti log value, and
we get
log y =y
molecular weight = 10^y
molecular weight (at peak) = MP = 6530
So, the molecular weight of sample 1 is 6530
Number average molecular weight: Mn
From the data, we also got analysis data of Mn is the number average molecular weight is the
statistical average molecular weight of all the polymer chains in the sample, and is defined by:
where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular
weight. Mn can be predicted by polymerization mechanisms and is measured by methods that
determine the number of molecules in a sample of a given weight; for example, colligative
methods such as end-group assay. If Mn is quoted for a molecular weight distribution, there are
equal numbers of molecules on either side of Mn in the distribution. From the data analysis of
sample 1, we got Mn value of 6347.
Weight average molecular weight: Mw
The weight average molecular weight is defined by:

Compared to Mn, Mw takes into account the molecular weight of a chain in determining
contributions to the molecular weight average. The more massive the chain, the more the chain
contributes to Mw. Mw is determined by methods that are sensitive to the molecular size rather
than just their number, such as light scattering techniques. If Mw is quoted for a molecular
weight distribution, there is an equal weight of molecules on either side of Mw in the
distribution. From the data analysis of sample 1, we got Mw value of 6531.
Higher average molecular weights: Mz, Mz+1
In general, a series of average molecular weights can be defined by the equation:

where: n = 1 gives M = Mw
n = 2 gives M = Mz
n = 3 gives M = Mz+1
The higher averages are increasingly more sensitive to high molecular weight polymers and
accordingly are increasingly more difficult to measure with precision. They tend to be
associated with methods that measure the motion of polymer molecules, such as diffusion or
sedimentation techniques. Although the z-averages are not commonly quoted for polymers,
several important methods for measuring the dimensions of chains that yield z-average
molecular weights.
For all synthetic polydisperse polymers:
Mn < Mw < Mz < Mz+1
From data analysis also we can get the polydispersity index (PDI) value of sample 1 of
1.028988, Which the value is comes from
𝑀𝑤
PDI =
𝑀𝑛
 6531
PDI =
6347

PDI = 1.028988
Because the value of PDI is 1.028988 or have Mw/Mn of 1.02 to 1.10 thus it be the best
controlled synthetic polymers (narrow polymers used for calibrations)
Molecular Weight Analysis of Sample 2
After we do experiment, we got the data of styrene calibration curve to determine the
molecular weight of sample, as follows:
GPC Calibration Plot

4.60

4.40

4.20

4.00
Log Mol Wt

3.80

3.60

3.40

3.20

3.00

2.80

19.00 20.00 21.00 22.00 23.00 24.00 25.00 26.00 27.00 28.00
Retention Time

Figure 4. GPC Curve Plot Analysis for Sample 2

Then, from fig.4 we got the data of molecules weight, retention time, calculated weight,
and % residual, as follows:

Mol Wt RT Calculated Weight

(Daltons) % Residual
(Daltons) (min)
1 43700 18.716 43581 0.274
2 19500 20.518 19753 -1.281
3 13300 21.479 13317 -0.131
4 9970 22.207 9940 0.303
5 6520 23.371 6229 4.670
6 2780 25.140 2971 -6.416
7 1390 26.786 1384 0.453
8 890 27.796 819 8.631
9 580 28.310 615 -5.653
 Then we made a table which it contains molecular weight, log molecular weight and
its retention time to make a graph of calibration curve as follows:
Mol Wt Log Mol Wt Retention
(Daltons) Time, min
1 43700 4.64048 18.716
2 19500 4.29003 20.518
3 13300 4.12385 21.479
4 9970 3.99870 22.207
5 6520 3.81425 23.371
6 2780 3.44404 25.140
7 1390 3.14301 26.786
8 890 2.94939 27.796
9 580 2.76343 28.310

GPC Distribution Table

Retention Mol Wt Log Mol Area Cumulative dWt/d Vt - Vo
Time Wt % (log m)
1 18.716 43700 4.64048 660 91.053 9417.13 No
2 20.518 19500 4.29003 539 93.374 4545.42 No
3 21.479 13300 4.12385 429 95.258 3225.14 No
4 22.207 9970 3.99870 326 96.723 2493.31 No
5 23.371 6520 3.81425 239 97.815 1709.38 No
6 25.140 2780 3.44404 178 96.619 807.19 No
7 26.786 1390 3.14301 132 99.215 442.25 No
8 27.796 890 2.94939 91 99.646 301.76 No
9 28.310 580 2.76343 47 99.913 209.88 No

Futhermore, we make a figure from table 2, then plot it into graph and we get a calibration curve
equation as a standard equation to determine the molecular weight of sample 2.

6.0

5.0

4.0
Log Mol wt

3.0

2.0
y = -0.1902x + 8.2157
1.0
R² = 0.9975
0.0
15 17 19 21 23 25 27 29
Retention Time, min
Calibration Curve Equation:
Y = -0.1902x + 8.2157
Sample 2: Analysis Result
From experiment done before, we got a figure of GPC analysis graph of sample 2
and a data of Mw, Mn, Mz, Mz+1, and Polydispersity as follows:

Auto-Scaled Chromatogram
140.00

120.00

Peak1 - 16.727
100.00

80.00

60.00

40.00
MV

20.00

0.00

-20.00

-40.00

-60.00

0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00

Minutes
Table 4. GPC Result for Sample 2
RT Mn Mw MP Mz Mz+1 Mv Polydispersity
16.727 41868 41913 41956 41998 1.001052

From experiment, we get the data of retention time of sample 2, then input the value to
calibration curve equation, we can get
y = -0.1902x + 8.2157
y = -0.1902 (16.727) + 8.2157
y = 5.0342246
we get log mol wt of sample 2 value of 5.03422546, after that, substitute the value to anti log
value, and we get
log y = 5.0342246
y = 10^5.0342246
y = 108199.3371
So, the molecular weight of sample 2 is 108199.3371
Number average molecular weight: Mn
From the data, we also got analysis data of Mn is the number average molecular weight is the
statistical average molecular weight of all the polymer chains in the sample, and is defined by:

where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular
weight. Mn can be predicted by polymerization mechanisms and is measured by methods that
determine the number of molecules in a sample of a given weight; for example, colligative
methods such as end-group assay. If Mn is quoted for a molecular weight distribution, there are
equal numbers of molecules on either side of Mn in the distribution. From the data analysis of
sample 2, we got Mn value of 41868.
Weight average molecular weight: Mw
The weight average molecular weight is defined by:

Compared to Mn, Mw takes into account the molecular weight of a chain in determining
contributions to the molecular weight average. The more massive the chain, the more the chain
contributes to Mw. Mw is determined by methods that are sensitive to the molecular size rather
than just their number, such as light scattering techniques. If Mw is quoted for a molecular
weight distribution, there is an equal weight of molecules on either side of Mw in the
distribution. From the data analysis of sample 2, we got Mw value of 41913.
Higher average molecular weights: Mz, Mz+1
In general, a series of average molecular weights can be defined by the equation:

where: n = 1 gives M = Mw
n = 2 gives M = Mz
n = 3 gives M = Mz+1
The higher averages are increasingly more sensitive to high molecular weight polymers and
accordingly are increasingly more difficult to measure with precision. They tend to be
associated with methods that measure the motion of polymer molecules, such as diffusion or
sedimentation techniques. Although the z-averages are not commonly quoted for polymers,
several important methods for measuring the dimensions of chains that yield z-average
molecular weights.
For all synthetic polydisperse polymers:
Mn < Mw < Mz < Mz+1
From data analysis also we can get the polydispersity index (PDI) value of sample 2 of
1.028988, Which the value is comes from
𝑀𝑤
PDI =
𝑀𝑛
41913
PDI =
41868

PDI = 1.001052
Thus, this value of PDI is indicates polymer chain is close to be monodisperse because the value
is close to 1.
PDI means polydispersity index. In polymer language this usually refers to ratio of weight
average molecular weight (Mw) to number average (Mn) sometimes also called as molecular
weight distribution. PDI is used to indicate distribution of polymer chain molecular weights in
a given polymer. PDI can be obtained by various means: GPC, Rheology, solution viscosity,
membrane osmosis (van't Hoff eq.), light scattering (Zimm plot) etc. Keep in mind that there
may not be an agreement of PDI values obtained by various techniques as they all use different
principles to measure them. A PDI =1 indicates polymer chain to be monodisperse. But
normally it is difficult to synthesizes polymer chains of identical Mw or Mn. therefore, all
polymers will have PDI > 1. Usually radical polymerized systems have very narrow mol wt.
distribution and will have PDI ~ 1.2 to 1.5. Most polymers have broad distribution which helps
in processing a polymer in extruder. narrow PDI polymers are difficult to process as shear
thinning is nominal.
PDI (or dispersity Ð) is simply defined to be a ratio that is always > or = 1. The definition is
Mw/Mn. Mw is a weight average molecular weight for the sample: Mw=(Σ M^2 N)/(Σ M N)
where N is the number of polymer chains with mass M. For a sample Mw represents the
molecular weight above and below which there is an equal MASS of polymer chains. Mn is a
number average molecular weight for the sample: Mn=(Σ M N)/(Σ N) and represents the
molecular weight above and below which there is an equal NUMBER of polymer chains. From
the definitions you can see that Mw is always > or = Mn, so PDI is always > or = 1
Polymers consist of repeat units (monomers) chemically bonded into long chains.
Understanding the physical properties of a polymer (such as mechanical strength, solubility and
brittleness) requires knowledge of the length of the polymer chains. Chain length is often
expressed in terms of the molecular weight of the polymer chain, related to the relative
molecular mass of the monomers and the number of monomers connected in the chain.
However, all synthetic polymers are polydisperse in that they contain polymer chains of unequal
length, and so the molecular weight is not a single value - the polymer exists as a distribution
of chain lengths and molecular weights.
The molecular weight of a polymer must therefore be described as some average molecular
weight calculated from the molecular weights of all the chains in the sample. This overview
describes the commonly used molecular weight averages that can be determined by gel
permeation chromatography (GPC) and size exclusion chromatography (SEC), how they are
defined, and the classical methods originally used to measure them.
 Experience
Gel permeation chromatography (GPC) is an instrument to measure the molecular weight of
polymers. In using the instrument, we have to be extra caution and careful. When injecting the
sample to the instrument, make sure there is no bubble in the syringe. If there is bubble, it will
affect the measurement of the instrument and could make it broke. While taking any samples,
in our case, THF, make sure to do it the hood, because THF is had a smell on it, and it might be
hazardous to inhale it. Also while running the program, make sure to follow the procedure well,
and remember where the file is saved, so that it could be analyzed quickly.
 未命名
SAMPLE INF O R MAT IO N
Sample Name: Sample 1 Acquired By: System
Sample Type: Broad Unknown Sample Set Name:
Vial: 1 Acq. Method Set: Untitled
Injection #: 18 Processing Method: PS_1080304
Injection Volume: 200.00 ul Channel Name: 410
Run Time: 35.0 Minutes Proc. Chnl. Descr.: 410

Date Acquired: 2019/5/20 PM 02:36:30 CST

Date Processed: 2019/5/20 PM 03:13:18 CST

Auto-Scaled Chromatogram

200.00

6530
150.00

100.00
MV

50.00

0.00

-50.00

0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00

Minutes

GPC Results
Dist Name Mn Mw MP Mz Mz+1 Mv Polydispersity MW Marker 1 MW Marker 2
1 6347 6531 6530 6703 6870 1.028988

Reported by User: System Project Name: E2-302

Report Method: 未命名 Date Printed:
Report Method ID:120
120 2019/5/20
Page: 1 of 2 下午 03:14:00 Asia/Taipei
 GPC Calibration Plot

5.50

5.00

4.50
Log Mol Wt

4.00

3.50

3.00

16.00 18.00 20.00 22.00 24.00 26.00 28.00

Retention Time

GPC Calibration Table

Calculated
Mol Wt RT
Weight % Residual
(Daltons) (min)
(Daltons)
1 387000 16.001 387629 -0.162
2 43700 19.014 43507 0.444
3 6520 23.762 6579 -0.904
4 580 28.827 590 -1.753
5 9970 22.541 9953 0.167
6 890 28.251 870 2.254

Reported by User: System Project Name: E2-302

Report Method: 未命名 Date Printed:
Report Method ID:120
120 2019/5/20
Page: 2 of 2 下午 03:14:00 Asia/Taipei
 未命名
SAMPLE INF O R MAT IO N
Sample Name: s2g4w2 Acquired By: System
Sample Type: Broad Unknown Sample Set Name:
Vial: 1 Acq. Method Set: Untitled
Injection #: 2 Processing Method: PS_1080121
Injection Volume: 20.00 ul Channel Name: 410
Run Time: 37.0 Minutes Proc. Chnl. Descr.: 410

Date Acquired: 2019/5/27 PM 02:18:44 CST

Date Processed: 2019/5/27 PM 03:17:50 CST

Auto-Scaled Chromatogram
140.00

120.00

Peak1 - 16.727
100.00

80.00

60.00

40.00
MV

20.00

0.00

-20.00

-40.00

-60.00

0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00

Minutes

GPC Results
Dist Name Mn Mw MP Mz Mz+1 Mv Polydispersity MW Marker 1 MW Marker 2
1 41868 41913 41956 41998 1.001052
2

Reported by User: System Project Name: GPC

Report Method: 未命名 Date Printed:
Report Method ID:120
120 2019/5/27
Page: 1 of 2 下午 03:18:01 Asia/Taipei
 GPC Calibration Plot

4.60

4.40

4.20

4.00
Log Mol Wt

3.80

3.60

3.40

3.20

3.00

2.80

19.00 20.00 21.00 22.00 23.00 24.00 25.00 26.00 27.00 28.00
Retention Time

GPC Calibration Table

Calculated
Mol Wt RT
Weight % Residual
(Daltons) (min)
(Daltons)
1 43700 18.716 43581 0.274
2 6520 23.371 6229 4.670
3 580 28.310 615 -5.653
4 19500 20.518 19753 -1.281
5 2780 25.140 2971 -6.416
6 13300 21.479 13317 -0.131
7 1390 26.786 1384 0.453
8 9970 22.207 9940 0.303
9 890 27.796 819 8.631

Reported by User: System Project Name: GPC

Report Method: 未命名 Date Printed:
Report Method ID:120
120 2019/5/27
Page: 2 of 2 下午 03:18:01 Asia/Taipei