Professional Documents
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Polymer
Characterization
Agenda
2006 Waters Corporation
Characteristics of polymers
Polymer analysis techniques
Definitions
2006 Waters Corporation
Common Monomers
2006 Waters Corporation
Vinyl Chloride :
H2C
CH
Styrene :H2C
CH
Cl
Ethylene :
H2C CH2
Propylene :
H2C
CH CH3
Types of Polymers
2006 Waters Corporation
Synthetic polymers
Polyethylene (PE), polypropylene (PP), polyhexamethylene
adipamide (Nylon), polystyrene (PS), etc.
Widely used in our daily life (plastics, rubbers, and fibers).
Molecular Characteristics of
Polymers
2006 Waters Corporation
Molecular weight
Composition
Microstructure of copolymers
Architecture
Principles of
Molecular Weight Distribution
2006 Waters Corporation
Definition of MW averages :
A polymer is made of species (chains) of varying lengths. Each
chain is characterized by its molecular weight, Mi, and its
abundance ni. Then :
Mn
Mw
niMi
ni
niMi2
niMi
I=Mw/Mn
Mz
niMi3
Mz+1
niMi2
Mw
Mn
niMi4
niMi3
Mn<Mw<Mz<Mz+1
Molecular Weight/
Physical Property Correlations
2006 Waters Corporation
Property/Processs
Parameter
Impact Strength
Melt Viscosity
Processing Temp
Flex Life
Brittleness
Drawability
Softening Temp
Stress-crack Resistance
Melt Flow
Effect of
High MW
Effect of
Low MW
CH3
CH2 CH2
ethylene unit A
CH2 CH2
propylene unit B
A A A A A A A A A polyethylene
B B B B B B B B B polypropylene
A B A B A A B B ethylene-propylene copolymer
A ethylene
B propylene
A A B A B A A B B random copolymer
A A A A B B B B B block-copolymer
A B A B A B A B A alternating copolymer
< L > - average sequence length
Polymer Branching
2006 Waters Corporation
Linear
Analysis of Polymers
2006 Waters Corporation
MS
LC/MS, GC/MS, MALDI-TOF-MS
Thermal analysis
TGA, DSC
NMR
Fourier Transform Infrared FTIR
Chromatography
2006 Waters Corporation
HPLC
Various separation mechanisms available.
Gradient or isocratic
Could be used to separate molecules based on their
compositions.
GPC Basics
2006 Waters Corporation
GPC Basics
2006 Waters Corporation
Separation Mechanism
2006 Waters Corporation
Separation Mechanism
2006 Waters Corporation
Principles of Separation
2006 Waters Corporation
-------------------
Log(M)
Vt
V0
Ve (or time)
Principles of Separation
2006 Waters Corporation
High MW (polymer)
RI signal
Low MW (additives)
Total volume or
solvent peak
Ve (or time)
Log(M)
Vt
V0
Ve (or time)
Principles of Calculations
Step 1
2006 Waters Corporation
Processing standards:
Obtain Elution volume from data.
Plot of log (M) versus f (Elution volume).
355000
43900
7
6
2800
Log(M)
2890000
5
4
3
2
1
0
0.00
10.00
20.00
30.00
Minutes
40.00
Elution volume
Principles of Calculations
Step 2
2006 Waters Corporation
Processing unknowns:
The signal is cut in slices (width dt)
Each slice is characterized by
Elution volume, Vi
Area Hi.dt = niMi
With the calibration curve Vi gives the MW in each slice, Mi
ni for each slice is determined by the area and Mi
Therefore Mn, Mw can be calculated
10.00
15.00
25.00
20.00
Minutes
30.00
SAMPLE
Sample Name:
Sample Type:
Vial:
Injection #:
Injection Volume:
Run Time:
Sample Set Name:
I NFORMATION
Broad PS
Broad Unknown
4
4
100.00 ul
45.0 Minutes
GPC_Demo
Acquired By:
Date Acquired:
Acq. Method Set:
Date Processed:
Processing Method:
Channel Name:
Proc. Chnl. Descr.:
mV
198029
20.00
DEMO
9/23/97 23:23:03
GPC_Demo
10/17/00 15:34:21
PS 3rd Order
SATIN
410 dRI
Chromatogram
10.00
0.00
-10.00
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
Minutes
0.20
0.00
6.50
6.00
Mn=106645
80.00
60.00
40.00
20.00
Cumulative %
Mz=452828
0.40
Mz+1=749374
dw t/d(logM)
0.80
0.60
100.00
Mw=242297
MP=198029
1.00
Distribution curve
Cumulative curve
0.00
5.50
5.00
4.50
4.00
Slice Log MW
dwt/d(logM)
Cumulative %
Mn
Mw
MP
Mz
Polydispersity
2.272
19:37:23
Requirements for
Successful GPC
Considerations
Mobile Phase
Sample Preparation
Column
Solvent Delivery System (Pump)
Sample Preparation
2006 Waters Corporation
Concentration
About 1mg/ml, usually less than 3mg/ml
Samples with broad molecular weight distribution may require
higher concentrations.
Injection volume
50 100 L/column
Dissolution time
Usually overnight
Sample Preparation
2006 Waters Corporation
150 C
170 C
16.0
17.0
18.0
Minutes
22.0
Sample PE-150C-2h
Sample PE-150C-4h
Sample PE-160C-2h
Sample PE-160C-4h
Sample PE-170C-2h
Sample PE-170C-4h
23.
24.0
25.0
Considerations
Column shipping solvent
Compatible with Mobile phase / Sample solubility
Column effective molecular weight range
Molecular weight range of sample
Known / unknown
Particle size of column packing material
Resolution requirements
Shearing of high molecular weight samples
Temperature requirements
Total sample solubility
Column dimensions
Conventional 7.8 x 300mm
Solvent efficient 4.6 x 300mm
High Speed 6.0 x 150mm
40
30
MV
20
10
0.
-10
7 Minute Run
40 Minute Run
-20
0
10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Minutes
Sample Concentration
2006 Waters Corporation
Molecular
weight
< 5,000
5,000 to
25,000
25,000 to
200,000
200,000 to
2,000,000
> 2,000,000
Sample
concentrati
on column
less than
0.30 w/v%
less than
0.20%
less than
0.10%
less than
0.05%
less than
0.025%
Injection volume
per column
4.6mm i.d. 7.8mm i.d.
20 - 50l
50 to 100l
10 - 30l
Interpreting Results
Interpreting Results
2006 Waters Corporation
Principles of
Molecular Weight Distribution
2006 Waters Corporation
Definition of MW averages :
A polymer is made of species (chains) of varying lengths. Each
chain is characterized by its molecular weight, Mi, and its
abundance ni. Then :
Mn
Mw
niMi
ni
niMi2
niMi
I=Mw/Mn
Mz
niMi3
Mz+1
niMi2
Mw
Mn
niMi4
niMi3
Mn<Mw<Mz<Mz+1
Molecular Weight
Distribution
Mn
Mv
PD = Mw / Mn
Mw
Mz
Increasing MW
Mz+1
Molecular Weight/
Physical Property Correlations
2006 Waters Corporation
Property/Processs
Parameter
Impact Strength
Melt Viscosity
Processing Temp
Flex Life
Brittleness
Drawability
Softening Temp
Stress-crack Resistance
Melt Flow
Effect of
High MW
Effect of
Low MW
Principles of Calculations
2006 Waters Corporation
Processing standards :
Step 1
43900
7
6
2800
Log(M)
2890000
5
4
3
2
1
0
0.00
10.00
20.00
30.00
Minutes
40.00
Elution volume
Step 2
Processing unknowns :
The signal is cut in slices (width dt).
Each slice is characterized by :
Elution volume, Vi.
Area Hi.dt = niMi.
With the calibration curve Vi gives the MW in each
slice, Mi.
ni for each slice is determined by the area and Mi.
Therefore Mn, Mw can be calculated.
10.00
15.00
25.00
20.00
Minutes
30.00
I NFORMATION
Broad PS
Broad Unknown
4
4
100.00 ul
45.0 Minutes
GPC_Demo
Acquired By:
Date Acquired:
Acq. Method Set:
Date Processed:
Processing Method:
Channel Name:
Proc. Chnl. Descr.:
DEMO
9/23/97 23:23:03
GPC_Demo
10/17/00 15:34:21
PS 3rd Order
SATIN
410 dRI
198029
20.00
mV
Chromatogram
10.00
0.00
-10.00
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
Minutes
0.20
0.00
6.50
6.00
Mn=106645
80.00
60.00
40.00
20.00
Cumulative %
Mz=452828
0.40
Mz+1=749374
dw t/d(logM)
0.80
0.60
100.00
Mw=242297
MP=198029
1.00
Distribution curve
Cumulative curve
0.00
5.50
5.00
4.50
4.00
Slice Log MW
dwt/d(logM)
Cumulative %
Mn
Mw
MP
Mz
Polydispersity
2.272
19:37:23
GPC
Sample Name:
Date Calibrated:
Processing Method:
Fit Order:
Cal Curve ID:
Calibration
Broad PS
8/23/00 16:28:50
PS 3rd Order
3
1963
Curve
A:
B:
C:
R:
v0:
Information
2.777248e+001
-2.228944e+000
7.528602e-002
0.999807
17.000000
D:
E:
F:
R:
vt:
-9.700817e-004
0.000000e+000
0.000000e+000
0.999614
31.000000
7.00
6.50
6.00
5.50
Log Mol Wt
5.00
4.50
4.00
3.50
3.00
2.50
2.00
18.00
20.00
22.00
24.00
Retention Time
26.00
28.00
30.00
Re te ntion
Tim e (m in)
M ol Wt
(Daltons )
Log
M ol Wt
18.912
1000000
6.0000
963476
3.791
21.197
128000
5.1072
129815
-1.398
23.864
18100
4.2577
18702
-3.220
27.582
1620
3.2095
1633
-0.804
18.019
2180000
6.3385
2386245
20.466
246000
5.3909
22.942
32500
4.5119
%
Re s idual
Re te ntion
Tim e (m in)
Calculate d
We ight
(Daltons )
M ol Wt
(Daltons )
Log
M ol Wt
26.406
3770
3.5763
3539
6.532
19.439
659000
5.8189
584779
12.692
10
21.959
67500
4.8293
72136
-6.427
11
25.030
9130
3.9605
8641
5.659
-8.643
12
29.348
474
2.6758
479
-1.016
236198
4.150
13
29.665
370
2.5682
379
-2.434
35307
-7.950
14
30.152
266
2.4249
262
1.382
Printed 19:45:06
1/9/01
%
Re s idual
8
7
6
PS
PMMA
Log (M)
4
3
17
22
27
Elution volume
32
PS
PMMA
Log[n]M
4
3
17
22
27
Elution volume
32
GPC Calibration
Narrow Standards
2006 Waters Corporation
6.4
6.2
6.0
Calibration:
1. >10 MW standards
2. Standards injected alone or as
a mixture
3. Mixtures should have baseline
resolved
4. Long process ! (But accurate)
5.6
5.4
5.2
5.0
4.8
4.6
4.4
Log Mol Wt
5.8
4.2
4.0
3.8
3.6
3.4
3.2
3.0
2.8
2.6
18
19
20
21
22
23
Time (min)
24
25
9100
190000
1100000
Elution volume
26
27
GPC Calibration
Broad Standards
2006 Waters Corporation
Hamielec Method
A broad sample with known MW data (2 values at least) is
injected
Processed as a Broad Standard
Calibration Curve is calculated
7
6
10.00
30.00
5
Log(M)
Mn
Mw
Mz
Mz+1
4
3
2
1
0
Saves time
Same broad reference for different labs
Elution volume
GPC Calibration
Broad Standards
2006 Waters Corporation
Mol Wt
Log Mol Wt
Cumulative %
1958675
6.291962
0.236
2 19.123
786046
5.895448
3.131
3 20.039
340400
5.531990
21.609
4 20.955
157437
5.197108
54.396
5 21.871
76970
4.886320
81.511
6 22.787
39368
4.595145
93.567
7 23.702
20850
4.319102
97.947
8 24.618
11316
4.053710
99.419
9 25.534
6230
3.794488
99.892
10 26.450
3443
3.536953
100.000
6
5
Log(M)
RT
1 18.207
4
3
2
1
0
Elution volume
Saves time
Same broad reference for different labs
More accurate calibration curve with one injection
GPC Calibration
Broad Standards
2006 Waters Corporation
5
4
3
2
1
0
Elution volume
Saves time
Same broad reference for different labs
More accurate calibration curve with one injection
GPC Calibration
Narrow Standards and Broad Standards
2006 Waters Corporation
Method
Narrow Standards
Advantages
Most Accurate
Disadvantages
Needs many narrow
MWD standards, time
consuming.
Broad Standards
Hamielec Method
Empower Breeze
Broad Standards
Cumulative Match Cal.
Empower Only