GPC for Students

Size Exclusion
Tools For Polymer Characterization

SIZE EXCLUSION CHROMATOGRAPHY

Gel Permeation / Size Exclusion /
Gel Filtration - GPC / SEC / GFC PRINCIPLE OF SEPARATION SEPARATION PROCESS:

MOBILE STATIONARY
GPC polymers PHASE PHASE
SEC polymers & proteins
GFC proteins

Separation based on molecular size in solution

Order of elution - larger < small
Relatively low resolution method
Very predictable chromatography
If it can be dissolved, it can be analyzed
ELUTION ORDER:
LARGER ELUTE FIRST

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ELUTION ORDER IN
SIZE EXCLUSION (GPC)
How GPC Works
MW

1 2 3
1 100,000
VOID
R 2 50,000 Flow
E
S
P 3 20,000 Flavor
O 0 Stabilizer
N Softener
S
E
Polymer
ELUTION VOLUME (mL)

How GPC Works GPC Example - Chewing Gum

Flow

Polymer Softener Flavor

Stabilizer

Decreasing MW

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MOLECULAR WEIGHT
DISTRIBUTION
Molecular Weight Distribution
Polymers have a distribution of various
chain lengths, and, therefore, molecular R
weights. E
S
Monomers have a single molecular weight, P
O
and are monodisperse. N
This distribution of molecular weights S
E
results in an "Envelope" of elution from a
column set.
ELUTION VOLUME (mL)

Why GPC? Comparison of Results

Bad
"Molecular Weight Distribution Good
correlates with virtually all key
processing characteristics and
performance properties of a
material."

Plastics Technology, May 1986

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Millennium Integration Gel Filtration/Size Exclusion/Gel

Narrow Unknowns Permeation
995
22.00 1933
2884
20.00 344
3776 Polymer distribution
18.00 4592 Mid to High MW 1M 500 K 250 K 100 K 25 K
16.00 5271
Epoxy Resin
14.00
Narrow standards
12.00

10.00

8.00 Calibration
1328 curve
6.00 1M
537 279 Log 500K
4.00 Mw 250K
100K
2.00 25K
26.00 28.00 30.00 32.00 34.00 36.00 38.00 40.00 42.00 44.00
Minutes
Elution Time or Volume

Gel Permeation/Size Exclusion/Gel

GPC Narrow Standards
+ Broad Sample
luded volume -
Filtration
mpound moves through the interstitial
ume of column only. No penetration into
of the packing pores and no adsorption
he packing surface.

80 3 Columns
7.8 x 300mm Calibration Curve
60.
Flow: 1.00
mL/min Included volume -
V 40 RI Detector Elution time for molecules
that totally permeate the
1M
column.
20 500 K
Log 250 K Selective
Mw 100 K
permeation
0 25 K

18.0 22.0 26.0 30.0 34.0 38.0

Minutes
Elution Time or Volume

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THEORETICAL CURVE OF THE STERIC

EXCLUSION
Gel Permeation / Size Exclusion / Gel
TOTAL EXCLUSION
Vi - V0 Filtration - GPC / SEC / GFC
=K
Vt - V0
log PARTIAL
PENETRATION There should be no interaction
MW Vi 0 <= K =< 1 between the media surface and
K
the sample.

The same molecule can have

TOTAL PENETRATION different radii in different
V0
ELUTION VOLUME
Vt solvents.

GPC/SEC Separations Distribution Shapes

Polymers may elute in many different

GPC is a SIZE separation technique.
shapes.
Typical shapes are: Gaussian, Multi-Modal,
Separation is based on size in solution,
Skewed-High, Skewed-Low.
not molecular weight.
The various shapes may define important
characteristics such as processing
Polymer size in solution is dependent on parameters and physical properties.
solvent and temperature.

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Molecular Weight Distribution

Calculation of MW Averages
1.10
1.00
0.90
0.80 Slices (heights, Hi) are drawn from the chromatogram
dwt/d(logM)

0.70
0.60
baseline to the distribution curve, (usually >100).
0.50
Mz+1 = 771950

0.40
Slice heights are multiplied by the corresponding MW's,

Mp = 194240
Mz = 464808

Mw = 248508

Mn = 99962
0.30
0.20
0.10
and summed, (ε [HiMi])
0.00
6.6 6.4 6.2 6.0 5.8 5.6 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6 3.4

log MW
Statistical averages are then calculated to obtain each MW
Slice Table - DOW 1683 moment:
Retention Time Adjusted RT Mol Wt Cumulative %
ε[HiMi^n]/ε [HiMi^n-1];
# Log Mol Wt Area Outside Vo-Vt
(min) (min) (Daltons) (%)

1 19.550 19.550 1690819 6.228097 0.155 498 No Where n=1 is Mn, n=2 is Mw, n=3 is Mz.
2 20.750 20.750 711461 5.852151 4.745 9695 No
3 21.950 21.950 294563 5.469178 28.585 29920 No
4 23.150 23.150 122389 5.087743 67.276 28261 No
5 24.350 24.350 52049 4.716409 89.878 10265 No

Molecular Weight Moments

Calculation of MW Averages
Σ[HiMi n] 1st Moment = Mn (Number Average)
Mx = n=1 (Mn)
Σ[HiMi n-1 ] n=2 (Mw) 2nd Moment = Mw (Weight Average)
Hi
n=3 (Mz) 3rd Moment = Mz (Z Average)
n=4 (Mz+1) 4th Moment = Mz+1 (Z+1 Average)
PD = Mw/Mn Mw/Mn = Dispersity
Moments are related to physical properties.

Retention Time (or Volume)

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Physical Properties
Molecular Weight Distribution
MP Mw Mn is related to brittleness, flow properties,
PD= compression set.
Mw Mn
Mn
Mw is related to strength properties, (tensile,
Mz impact resistance).

Mz+1 Mz is related to elongation and flexibility.

Mz+1 is related to die swell.

Decreasing MW

Importance of MWD
Property/Processs Effect of Effect of
Polymer Concentrations for GPC
Parameter High MW Low MW
Impact Strength MW > 1,000,000 0.007 - 0.02%
Melt Viscosity 500K - 1,000,000 0.02 - 0.07%
Processing Temp 100K - 500K 0.07 - 0.10%
Flex Life 50K - 100K 0.10 - 0.13%
Brittleness 10K - 50K 0.13 - 0.16%
Drawability < 10K 0.16 - 0.20%
Softening Temp
Stress-crack Resistance
Melt Flow

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Sample Preparation Sample Prep (cont'd)

Solvent must allow polymer chains to open up into
the "most relaxed" conformation.
Allow sufficient time for chains to unfold (>3 hours
for some polymers).
The greater the MW and crystallinity, the longer the
time needed.
The polymer solution should be filtered unless there
may be a chance of shear.
To enhance dissolution, some light swirling (no
vigorous shaking) may be done.
Narrow standard solutions need not be filtered, and
high molecular weight standards should not be
shaken at all.

High temperature, may be needed for highly An in-line filter may be used, but a pre-column is not
crystalline polymers. recommended.

ELUTION CURVES OF VARIOUS

Column Selection STATIONARY PHASES

MW 100 - 1,000 50A LINEAR (MIXED BED)

MW 250 - 2,500 100A
MW 1,000 - 18K 500A log PORES
MW 5,000 - 40K 10^3A Log SIZE
MW
MW 106 Å
MW 10K - 200K 10^4A
MW 50K - 1M 10^5A 105 Å

MW 200K - >5M 10^6A 104 Å

103 Å
500K - ~20M 10^7A 500 Å

ELUTION VOLUME
Elution Volume

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GPC and Flow Rate Precision

Plus HR5 Mw
& HR6 Precise solvent flow is essential for precise GPC… Mn

log Molecular Weight Error (%)

60

50

40
Ve
30

20

10

0
0.01
0.02
0.03
0.04
0.05
Waters Flow rate error, mL/min

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