Polymer Reference Materials-Polystyrene
Introduction
Reference materials are used for calibration and performance evaluation of instruments
used as part of overall quality assurance programs of polymer. These materials support the
development of new measurement methods and characterize new materials. The synthesis
and characterization of our polymer reference materials are achieved meticulously. Above all,
the user can be assured of receiving a well-characterized and quality product.
Chemical Structure of the polymer showing end groups:
_____________________________________________________________
CH3
H3C
CH2
C
CH2
CH
H
n
H
Molecular weight based reference polymers
Polymer Source offers a wide range of reference polymeric materials (RM) for both organic
and aqueous phase applications. New reference polymers are added regularly. A wide range
of polymers with number average molecular masses (Mn) (oligomers to 10 million) have
been covered.
Molecular weight values are characterized by various analytical techniques. Interfacing
chromatographic methods with other analytical techniques can significantly increase the
amount of information available for polymer characterization. The techniques used for
characterization are: size exclusion chromatography (SEC), nuclear magnetic resonance
1
(NMR), intrinsic viscosity, thermal analysis, and Matrix Assisted Laser Desorption
Ionization-Time of Flight-Mass Spectrometry (MALDI-TOF-MS).
Organic phase Polystyrene
soluble
Aqueous phase Polyethylene
soluble
oxide (PEO)
Polymethyl
methacrylate
Polyacrylic acid
Polybutadiene
Polyisoprene
Polystyrene
sulfonic acid
Polystyrene
sodium sulfonate
The polymer standards are available either individually (in the widest range of molecular
weights) or as kits containing wide range of Mn. Care has been taken to develop standards
with the narrowest molecular weight distribution to ensure reliable calibrations of the
instruments or for basic research. A Certificate of analysis that accompanies each product
provides the characterization information indicating the type of end groups and
microstructure of the polymer.
Purification of Polymer samples:
Purification of the polystyrene
catalyst by following steps:
was carried out rigorously to ensure the removal of the
1. Dissolved the polymer in CHCl3 and washed with water to remove insoluble organic
catalyst as side product.
2. Polymer solution in chloroform filtered and passed through a column packed with basic
Al2O3 .
3. Solution was concentrated on rota-evaporator
4. Concentrated solution precipitated in cold methanol.
5. Dried under vacuum for 48h at 38 oC. Further, dissolved in dioxane; filter, and freeze
dried under vacuum.
6. Polymer was packed in a clean vial in dust free environment.
2
Characterization techniques
Gel Permeation or Size Exclusion Chromatography
Gel
permeation chromatography (GPC) also known as size exclusion chromatography
(SEC) is employed to obtain number average molecular masses (Mn) and weight average
molecular weight (Mw). Both these values result to obtain polydispersity index (PDI)
(PDI=Mw/Mn). It guides the application level of reference polymers.
SEC analysis was performed on a Varian liquid chromatograph equipped with refractive
and UV light scattering detectors. Three SEC columns from Supelco (G6000-4000-2000
HXL) were used with a dual detector model 270 from Viscotek Co connected on line in
series with columns. Low angle and at 90 o light scattering were used to determine
absolute molecular weights of the polymer.
Average molecular weight by weight:
Mw 
w M
w
i
i
i
Average molecular weight by number:
Mn 
n M
n
i
i
i
where: wi is the weight in fraction i; ni is the molecular number in fraction i. Mi is the
molecular weight of fraction i.
Mi 
wi
ni
Due to some polymer chains distribution in polymer sample, weight average molecular
weights (Mw) is always greater than number average molecular weights (Mn). The index
of Mw/Mn determine the molecular distribution (polydispersity: PDI) is introduced.
Mw
PI 
Mn
3
If PI=1, all the chain lengths are same. Usually, the sample prepared by living process is
of narrow distribution character, the PI should be less than 1.15.
Mp is the molecular weight at peak maximum.
Intrinsic viscosity [] is the related viscosity exploited to concentration = 0, which is
related to solvent and temperature. The molecular shape is important to the intrinsic
viscosity. When molecular weight is same, the [] of multi-arm (four- or six-arm)
polymer is much lower than that of linear one.
Radius of Gyration (Rgw): the size of macromolecule.
Infrared spectrum will give us the difference in the samples qualitatively, due to the
sensibility to impurities. The three samples are chemical identical, as well as the
functionality range.
It is worth to note that all the results listed here might have about ±5% deviation.
Polymers were characterized using a fully integrated GPC instrumentation (combining
refractive index detectors with static light scattering detectors and viscometers) and complete
software packages. A typical combined SEC of a reference polymer having Mn of 90000
dalton is shown below:
162.0
17.0
5
Refractive Index
Right Angle Light Scattering
Low Angle Light Scattering
Viscometer DP
Detector Response (mV)
135.0
108.0
81.0
54.0
27.0
0.0
6.0
8.0
10.0
12.0
14.0
16.0
Retention Volume (ml)
4
18.0
20.0
22.0
24.0
26.0
WF / dLog M vs. Log Molecular Weight
65.15
Log Molecular Weight vs. Retention Volume
6.00
58.64
5.80
52.12
5.60
45.61
5.40
39.09
5.20
5.00
32.58
4.80
26.06
4.60
19.55
4.40
13.03
4.20
6.52
4.00
MnMz
Mw
0.00
16.0
17.0
18.0
19.0
20.0
4.0
5.0
6.0
Typical SEC of Reference Materials
Polystyrene (PS)
Gel permeation chromatography (GPC) of polystyrene Mw ranging from oligomers to 10
millions are shown below.
SEC of selected polystyrene standard
0.4
PS 0.5k
PS 2k
PS 5k
PS 10k
PS 30k
PS 100k
PS 300k
PS 500k
PS 1000k
PS 2000k
PS 5000k
PS 10000k
0.2
0.0
15
18
21
24
Ve (ml)
5
27
30
Polystyrene standard samples
Part No.
Lot No.
Mn
Mw
Mp
PS 0.5K
PS 1K
PS 2K
PS 5k
PS 12k
PS 21k
PS 55K
PS 100k
PS 235K
PS 420K
PS 600K
PS 820K
PS 5,000K
PS 6,500K
PS 7,600k
P8092-S
P8094-S
P8095-S
P2444-S
P5811-S
P486-S
P8647-S
P8070-S
P5712-S
P4699-S
P2577-S
P5654-S
P1104-S
P1105-S
P1099-S
500
950
1900
5,522
12,800
21,000
54,500
99,000
235,000
419,000
600,000
820,000
5,000,000
6,500,000
7,600,000
600
1140
2185
5,910
13,800
23,000
59,300
105,000
256,000
444,000
643,000
878,000
6,500,000
8,200,000
9,300,000
620
950
2000
5,770
13,300
21,000
59,100
100,500
241,500
419,500
632,500
880,000
5,800,000
7,600,000
8,800,000
[] in
THF at
230C
(dl/g)
0.1176
0.2021
0.2828
0.5458
0.8260
1.5880
2.4270
2.8360
3.8860
Mw/Mn
-
Prices
15 polystyrene reference material 500mg each US$ 1000.00
15 polystyrene reference material 1,000mg each US$ 1400.00
6
1.2
1.2
1.15
1.07
1.07
1.09
1.08
1.06
1.09
1.06
1.07
1.07
1.30
1.25
1.22
Characterization report for the each sample analysis:
PS: 500 lot P8092-S
Part No.
Lot No.
Mn
Mw
Mp
PS 0.5K
P8092-S
500
600
620
[] in
THF at
230C
(dl/g)
-
dn
P8092-S
-0
8
10
12
14
16
18
20
22
24
26
28
30
32
Ve (ml)
Size Exclusion Chromatography of polystyrene
2.480
2.466
2.453
1.945
1.932
1.917
0.930
0.96
1.94
1.08
7.356
7.348
7.341
Mn=500, Mw=600, Mw/Mn=1.20
Mn by HNMR: 550
P8092-S
5.00
10.0
ppm (f1)
5.0
7
0.0
Mw/Mn
1.2
Part No.
Lot No.
Mn
Mw
Mp
PS 1K
P8094-S
950
1140
1050
[] in
THF at
230C
(dl/g)
-
dn
P8094-S
-0
8
10
12
14
16
18
20
22
24
26
28
30
Ve (ml)
Size Exclusion Chromatography of polystyrene
Mn=950, Mw=1400, Mp: 1050 Mw/Mn=1.20
Mn by HNMR:
P8094-S
8
0.64
5.0
2.08
1.05
5.00
10.0
ppm (f1)
0.0
32
Mw/Mn
1.2
Lot No.
Mn
PS 2K
P8095-S
1900
Mw
Mp
2185
P8095-S
[] in
THF at
230C
(dl/g)
-
2000
dn
Part No.
-0
8
10
12
14
16
18
20
22
24
26
28
Ve (ml)
Size Exclusion Chromatography of polystyrene
Mn=1900, Mw=2200, Mw/Mn=1.19
Mn by HNMR: 1700
P8095-S
5.0
9
0.38
3.28
5.00
10.0
ppm (f1)
0.0
30
32
Mw/Mn
1.15
Part No.
Lot No.
Mn
Mw
Mp
PS 5k
P2444-S
5,522
5,910
5,770
[] in
THF at
230C
(dl/g)
0.1176
Sample ID: P2444-S
2.1713
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
20.00 21.33
22.67
24.00
25.33
26.67
28.00
Sample
29.33
30.67
32.00
Retention Volume (mL)
Mn
34.67
36.00
Mw
Mp
Mw/Mn
5,909
5,771 1.070
37.33
38.67 40.00
IV
Rh
0.1176
2.89
5.00
0.84
1.00
4.67
0.70
0.83
0.56
0.67
0.42
0.50
0.28
0.33
3.33
0.14
0.17
3.00
0.00
0.00
4.33
4.00
3.67
Normaliz ed Mole Frac tion
Log Molec ular Weight
2011-03-29_16;44;25_P2444-S_01.v dt5,522
33.33
34.11 34.54
34.96
2011-03-29_16;44;25_P2444-S_01.v dt:
35.39
35.81
36.24
36.67
Retention Volume (mL)
Log Molec ular Weight
Normaliz ed Mole Frac tion
10
37.09
37.52
37.94
38.37 38.80
Cumulativ e Weight Frac tion
Cumulativ e Weight Frac tion
Concentration
Mw/Mn
1.07
Lot No.
PS 12k
P5811-S
Mn
Mw
Mp
12,800
13,800
Sample ID: P5811-S
13,300
Concentration
1.6279
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
20.00 21.33
22.67
24.00
25.33
26.67
28.00
Sample
29.33
30.67
32.00
Retention Volume (mL)
Mn
Mw
33.33
34.67
36.00
37.33
38.67 40.00
Mp
Mw/Mn
IV
Rh
13,320
1.072
0.2021
4.58
6.00
0.92
1.00
5.50
0.77
0.83
0.61
0.67
0.46
0.50
0.31
0.33
3.50
0.15
0.17
3.00
0.00
5.00
4.50
4.00
Normaliz ed Mole Frac tion
Log Molec ular Weight
2011-03-29_17;45;28_P5811-S_01.v dt12,864 13,787
[] in
THF at
230C
(dl/g)
0.2021
0.00
32.94 33.41
33.88
2011-03-29_17;45;28_P5811-S_01.v dt:
34.35
34.82
35.29
35.76
Retention Volume (mL)
Log Molec ular Weight
36.23
36.70
37.17
37.64 38.11
Cumulativ e Weight Frac tion
Normaliz ed Mole Frac tion
11
Cumulativ e Weight Frac tion
Part No.
Mw/Mn
1.07
Part No.
Lot No.
Mn
Mw
Mp
PS 21k
P486-S
21,000
23,000
21,000
[] in
THF at
230C
(dl/g)
0.2828
Sample ID: P489-S
Concentration
1.4288
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
22.67
24.00
25.33
26.67
28.00
Sample
29.33
30.67
32.00
Retention Volume (mL)
Mn
34.67
36.00
37.33
38.67 40.00
Mw
Mp
Mw/Mn
IV
Rh
23,018
22,129
1.103
0.2818
6.06
5.00
0.71
1.00
4.67
0.59
0.83
0.47
0.67
0.35
0.50
0.24
0.33
3.33
0.12
0.17
3.00
0.00
4.33
4.00
3.67
Normaliz ed Mole Frac tion
Log Molec ular Weight
2011-03-29_18;46;30_P489-S_01.v dt 20,860
33.33
0.00
31.70 32.19
32.67
2011-03-29_18;46;30_P489-S_01.v dt:
33.16
33.65
34.13
34.62
Retention Volume (mL)
35.11
Log Molec ular Weight
35.59
36.08
36.57 37.05
Cumulativ e Weight Frac tion
Normaliz ed Mole Frac tion
12
Cumulativ e Weight Frac tion
20.00 21.33
Mw/Mn
1.09
Part No.
Lot No.
Mn
Mw
Mp
PS 55K
P8647-S
54,500
59,300
59,100
[] in
THF at
230C
(dl/g)
0.5458
Sample ID: P8647-S
Concentration
1.4364
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
22.67
24.00
25.33
26.67
28.00
Sample
29.33
30.67
32.00
Retention Volume (mL)
Mn
34.67
36.00
37.33
38.67 40.00
Mw
Mp
Mw/Mn
IV
Rh
59,358
59,077
1.094
0.5458
10.37
6.00
0.77
1.00
5.67
0.64
0.83
0.51
0.67
0.38
0.50
0.26
0.33
4.33
0.13
0.17
4.00
0.00
5.33
5.00
4.67
Normalized Mole Fraction
Log Molecular Weight
2011-03-29_19;47;33_P8647-S_01.v dt54,275
33.33
0.00
30.58 31.06
31.55
2011-03-29_19;47;33_P8647-S_01.vdt:
32.03
32.51
33.00
33.48
Retention Volume (mL)
Log Molecular Weight
Normalized Mole Fraction
13
33.96
34.45
34.93
35.41 35.90
Cumulative Weight Fraction
Cumulative Weight Fraction
20.00 21.33
Mw/Mn
1.08
Lot No.
PS 100k
P8070-S
Mn
Mw
Mp
99,000
105,000
Sample ID: P8070-S
100,500
Concentration
1.3054
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
20.00 21.33
22.67
24.00
25.33
26.67
28.00
Sample
29.33
30.67
32.00
Retention Volume (mL)
Mn
33.33
34.67
36.00
37.33
38.67 40.00
Mw
Mp
Mw/Mn
IV
Rh
105,753
100,489
1.072
0.8261
14.44
6.00
0.91
1.00
5.67
0.76
0.83
0.61
0.67
0.45
0.50
0.30
0.33
4.33
0.15
0.17
4.00
0.00
5.33
5.00
4.67
Normalized Mole Fraction
Log Molecular Weight
2011-03-29_20;48;35_P8070-S_01.v dt98,636
[] in
THF at
230C
(dl/g)
0.8260
0.00
28.66 29.21
29.76
2011-03-29_20;48;35_P8070-S_01.vdt:
30.31
30.86
31.41
31.97
Retention Volume (mL)
Log Molecular Weight
32.52
33.07
33.62
34.17 34.72
Cumulative Weight Fraction
Normalized Mole Fraction
14
Cumulative Weight Fraction
Part No.
Mw/Mn
1.06
Part No.
Lot No.
Mn
Mw
Mp
PS 235K
P5712-S
235,000
256,000
241,500
[] in
THF at
230C
(dl/g)
1.5880
Sample ID: P5712-S
Concentration
0.7563
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
22.67
24.00
25.33
26.67
Sample
28.00
29.33
30.67
32.00
Retention Volume (mL)
Mn
34.67
36.00
37.33
38.67 40.00
Mw
Mp
Mw/Mn
IV
Rh
256,362
241,320
1.091
1.5881
24.03
7.00
0.84
1.00
6.67
0.70
0.83
0.56
0.67
0.42
0.50
0.28
0.33
5.33
0.14
0.17
5.00
0.00
6.33
6.00
5.67
Normalized Mole Fraction
Log Molecular Weight
2011-03-29_21;49;39_P5712-S_01.v dt234,906
33.33
0.00
27.39 27.83
28.26
2011-03-29_21;49;39_P5712-S_01.vdt:
28.69
29.12
29.56
29.99
Retention Volume (mL)
30.42
Log Molecular Weight
30.85
31.29
31.72 32.15
Cumulative Weight Fraction
Normalized Mole Fraction
15
Cumulative Weight Fraction
20.00 21.33
Mw/Mn
1.09
Part No.
Lot No.
Mn
Mw
Mp
PS 420K
P4699-S
419,000
444,000
419,500
Mw/Mn
[] in
THF at
230C
(dl/g)
2.4270
1.06
Sample ID: P4699-S
Concentration
0.7491
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
22.67
24.00
25.33
26.67
Sample
28.00
29.33
30.67
32.00
Retention Volume (mL)
Mn
34.67
36.00
37.33
38.67 40.00
Mw
Mp
Mw/Mn
IV
Rh
443,977
419,305
1.061
2.4272
33.29
7.00
0.85
1.00
6.67
0.71
0.83
0.57
0.67
0.42
0.50
0.28
0.33
5.33
0.14
0.17
5.00
0.00
6.33
6.00
5.67
Normalized Mole Fraction
Log Molecular Weight
2011-03-29_22;50;40_P4699-S_01.v dt418,563
33.33
0.00
24.52 25.21
25.91
2011-03-29_22;50;40_P4699-S_01.vdt:
26.60
27.29
27.98
28.67
Retention Volume (mL)
Log Molecular Weight
Normalized Mole Fraction
16
29.36
30.05
30.74
31.43 32.12
Cumulative Weight Fraction
Cumulative Weight Fraction
20.00 21.33
Part No.
Lot No.
Mn
Mw
Mp
PS 600K
P2577-S
600,000
643,000
632,500
[] in
THF at
230C
(dl/g)
2.8360
Mw/Mn
1.07
Sample ID: P2577-S
Concentration (mg/ml)
2.0014
Sample dn/dc (dl/g)
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
20.00
22.00
24.00
26.00
28.00
30.00
32.00
Retention Volume (mL)
34.00
36.00
38.00
40.00
Sample
Mn
(Daltons)
Mw
(Daltons)
Mp
(Daltons)
Mw/Mn
IV (dl/g)
2011-04-25_15;47;16_P2577-S_01.v dt
600,650
643,453
632,760
1.071
2.8360
24.00 24.59
25.19
25.79
26.38
2011-04-25_15;47;16_P2577-S_01.v dt:
26.98
27.58
28.17
28.77
29.37
Retention Volume (mL)
Log Molec ular Weight
Normaliz ed Mole Frac tion
17
29.96
30.56
31.16
31.75
32.35 32.95
Cumulativ e Weight Frac tion
Lot No.
PS 820K
P5654-S
Mn
Mw
Mp
820,000
878,000
Sample ID: P5654-S
880,000
Concentration
0.9829
Sample dn/dc
0.1850
Method File
PS80-Jan192011-0000.v cm
Column Set
3x PL 1113-6300
System
Sy stem 1
20.00 21.33
22.67
24.00
25.33
26.67
Sample
28.00
29.33
30.67
32.00
Retention Volume (mL)
Mn
34.67
36.00
37.33
Mw
Mp
Mw/Mn
IV
Rh
877,812
880,203
1.070
3.8873
49.07
0.56
1.00
6.67
0.47
0.83
0.37
0.67
0.28
0.50
0.19
0.33
5.33
0.09
0.17
5.00
0.00
6.33
6.00
5.67
0.00
23.46 24.20
24.94
2011-03-30_00;52;45_P5654-S_01.vdt:
25.68
1.07
38.67 40.00
7.00
Normalized Mole Fraction
Log Molecular Weight
2011-03-30_00;52;45_P5654-S_01.v dt820,377
33.33
Mw/Mn
[] in
THF at
230C
(dl/g)
3.8860
26.42
27.16
27.90
Retention Volume (mL)
Log Molecular Weight
Normalized Mole Fraction
18
28.64
29.38
30.12
30.86 31.60
Cumulative Weight Fraction
Cumulative Weight Fraction
Part No.
Part No.
Lot No.
Mn
Mw
Mp
PS 5,000K
PS 6,500K
PS 7,600k
P1104-S
P1105-S
P1099-S
5,000,000
6,500,000
7,600,000
6,500,000
8,200,000
9,300,000
5,800,000
7,600,000
8,800,000
[] in
THF at
230C
(dl/g)
-
Mw/Mn
1.30
1.25
1.22
PS of 5.0M ; 6.5M and 7.6M
7M
6M
5M
0.0
20
Ve (ml)
Polystyrene, of molecular weights of 5,000,000; 6,500,000 and 7,600,000
19