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No. AN52907
Determination of polymer molecular weight and
composition using picoSpin NMR spectroscopy
Authors:
Katherine Paulsen and Daniel Frasco,
Thermo Fisher Scientific, Madison, WI
Key words
Abstract
Polymer molecular weight determination and copolymer by comparing the resonance signals from repeating
compositional analysis involve the integration of the units to those of end groups, thereby determining the
resonance signals from polymer repeating units and end molecular weight. A similar methodology can be adapted
groups, which are inherently broad. A Thermo Scientific™ for the compositional analysis of copolymers, so long as
picoSpin™ 80 NMR spectrometer is well suited for these the resonance signals from different monomers can be
analyses. In the example of poly (ethylene glycol) (PEG) clearly differentiated.
acetyl triarm, the number average molecular weight
was determined with great ease. In the case of the Due to poor molecular rotation and marginally different
compositional analysis of a commercial PEG-PPG-PEG chemical environments in which the repeating units are
block copolymer, Pluronic® L-35, the PEG/PPG ratio situated, resonance signals from polymer repeating units
determined by a picoSpin 80 NMR agrees well with the often coalesce as a broad peak, even using high-field
manufacturer’s product specification. Furthermore, the NMR spectrometers.3 However, in the molecular weight
analyses using an 82 MHz and a 300 MHz NMR yielded analysis and compositional analysis, collective signals
almost identical results. from polymer repeating units are used for calculation
and monomeric resolution is generally not required. To
Introduction that end, low-field NMR readily lends itself as a low-cost
The control of the molecular weight and molecular weight alternative to high-field instruments, with significant savings
distribution (MWD) is essential to obtain and improve on both instrument procurement and upkeep.
certain desired physical properties in a polymer product,
and is therefore of great importance in material science1. In this application note, molecular weight determination of
In addition to gel permeation chromatography (GPC) poly(ethylene glycol) (PEG) acetyl triarm and compositional
and matrix assisted laser desorption ionization mass analysis of a polyol using a picoSpin NMR spectrometer
spectrometry (MALDI MS)2, end group analysis using are presented. The results of the compositional analysis
nuclear magnetic resonance (NMR) spectroscopy has using an 82 MHz NMR were also compared with those
long been established as a viable analytical technique using a high-field, 300 MHz NMR spectrometer.
for determining the number average molecular weight
(Mn) of polymers. For polymers with a defined end group
structure, the number of repeating units can be deduced
Experimental Results and discussion
The structures of the polymers examined in this study are Number average molecular weight (Mn) determination.
shown in Figure 1. In 1H NMR spectroscopy, the area under each resonance
signal is proportional to the molar concentration of the
A B protons being analyzed. Number average molecular
weight (Mn) determination by end-group analysis using
1
H NMR therefore involves identifying and integrating
distinguishable proton signals originating from end-
groups and repeating units.
Figure 1: Chemical Structures of: A) poly(ethylene glycol) (PEG) acetyl triarm (PEG acetyl
triarm), and B) poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene
glycol) (PEG-PPG-PEG).
known signal in the spectrum. MF =FWIJKLMNOJ JPFQRIM +FWMFS INOTUV + FWrepeating units =41+177+(44×7×3)=1142
integral of methyl protons 3.00
All spectra were acquired using the following acquisition Based on the end
x = group analysis using = an 82 MHz
# of methyl group protons 3
parameters: 90° excitation pulse, 750 ms acquisition time picoSpin NMR x = 1.0 relative moles of propylene glycol
spectrometer, the number average
and 5 second recycle delay. Spectral data were processed molecular weight of the PEG acetyl triarm is 1142 g/mol.
using the Mnova™ NMR analysis software with a standard 7.65 3.00
=
set of processing parameters including: Zero filling and 4y + 3 3
y = 1.16 relative moles of ethylene glycol
phase correction. Apodization was not used.
relative moles PEG×MWefg
weight % PEG = ×100%
relative moles PEG×MWefg + relative moles PPG×MWeeg
1.16×44
= ×100% = 46.8%
1.16×44 + 1.0×58
Compositional analysis of a PEG/PPG block copolymer.
Figure 3 shows the 1H NMR spectra of Pluronic L-35, with a normalized peak area of 3.0, and the CH- and
a PEG-PPG-PEG copolymer, using (a) an 82 MHz CH2-proton signals are located at δ ~ 3.3-3.7 ppm with
picoSpin NMR spectrometer; and (b) a 300 MHz NMR a normalized peak area of 7.77. The minor variances in
spectrometer. The two spectra are very similar. In the chemical shift between the two spectra are likely due
82 MHz spectrum, the signals at δ ~0.8 ppm with a to the difference in sample concentrations. Because of
normalized peak area of 3.0 are attributed to the methyl the higher sensitivity of a 300 MHz NMR instrument,
(-CH3) group of PPG. The CH- and CH2- proton signals the samples were used in a lower concentration; hence,
from both PPG and PEG are located at δ ~ 3.1-3.4 ppm, the difference in chemical shift. The 300 MHz spectrum
with a normalized peak area of 7.65. The contributions also offers greater resolution than the 82 MHz one. The
to these signals include 3 protons from PPG (one CH- increased resolution, however, should have little to no
and one CH2-) and 4 protons from PEG (2 CH2- groups). bearing on the results of the compositional analysis,
The 300 MHz 1H NMR spectrum is essentially the same: because the collective signals are integrated for the
the signal from the methyl group resonates at δ 1.1 ppm ensuing calculations.
B
A detailed compositional analysis using the 82 MHz NMR Conclusions
spectrum is outlined below.
peak area of repeating units and glycerol linkage
=
peak area of end groups
1
H NMR spectroscopy has been established as a powerful
# of protons in repeating units and glycerol linkage # of protons in end groups
tool for polymer characterization, including molecular
5.78 =.>>
= , n = 6.82 ≈ 7 repeating monomer units
1. peak area of repeating units and glycerol linkage
Determine the
12n + 5 5relative moles of PPG, denoted as x,
peak area of end groups
weight determination and copolymer compositional
MF =FWIJKLMNOJ JPFQRIM +FWMFS INOTUV + FWrepeating units=
=41+177+(44×7×3)=1142
using the signals at δ ~0.8.
# of protons in repeating units and glycerol linkage
peak area of repeating units and glycerol linkage # of protons in end groups
peak area of end groups
analysis. Both analyses involve the integration of the
=
5.78 =.>>
# of protons in repeating units and glycerol linkage
= # of protons in end groups
, n = 6.82 ≈ 7 repeating monomer units resonance signal from polymer repeating units, which are
12n + 5 5
integral of methyl protons 3.00
5.78
MF =FWIJKLMNOJ JPFQRIM
12n + 5 +FW
=.>>
=x = MFS INOTUV
, n = 6.82 =
≈ 7 repeating monomer units
+ FW repeating units =41+177+(44×7×3)=1142
5# of methyl group protons 3
inherently broad. The Thermo Fisher Scientific picoSpin 80
MF =FWIJKLMNOJ JPFQRIMx = 1.0 relative moles of propylene glycol
+FWMFS INOTUV + FWrepeating units =41+177+(44×7×3)=1142 NMR spectrometer is well suited for these investigations.
integral of methyl protons 3.00 In the example of poly(ethylene glycol) (PEG) acetyl triarm,
x = =
2. Determine the # of methyl group protons
relative moles3.00 of PEG,
integral of methyl protons
7.65 3denoted as y,
3.00 the number average molecular weight was determined with
x = = =
x = 1.0 relative moles of propylene glycol
# of methyl group protons 3
using the signals at δ4y + 3~3.1-3,4. 3
great ease. In the case of the compositional analysis of a
x = 1.0 relative moles of propylene glycol
y = 1.16 relative moles of ethylene glycol
commercial PEG-PPG-PEG block copolymer, Pluronic®
7.65 3.00
4y + 3
7.65
=
3
3.00
L-35, the PEG/PPG ratio determined by a picoSpin
=
y = 1.16 relative moles of ethylene glycol
4y + 3 3
relative moles PEG×MW
80 NMR agrees well with the manufacturer’s product
efg
weight % PEG = ×100%
y = 1.16 relative moles of ethylene glycol
relative moles PEG×MW efg + relative moles PPG×MWeeg specification. Furthermore, the analyses using an 82 MHz
3. Calculate
=
the weight
1.16×44 percentages of PEG and PPG.
×100% = 46.8%
and a 300 MHz NMR yielded almost identical results. The
1.16×44 + 1.0×58 relative moles PEG×MWefg
weight % PEG = ×100% Thermo Fisher Scientific picoSpin 80 NMR spectrometer
relative moles PEG×MW efg + relative moles PPG×MWeeg
relative moles PEG×MW
weight % PEG =
1.16×44 relative moles PPG×MW
efg
×100% has proven to be a low-cost alternative to high-field NMR
relative moles PEG×MW efg + relative moles PPG×MW
eeg eeg ×100%
weight % PPG =
= ×100% = 46.8%
1.16×44 relative moles PEG×MW
+ 1.0×58
1.16×44 efg + relative moles PPG×MWeeg spectrometers for polymer molecular weight determination
= ×100% = 46.8%
=
1.0×58
1.16×44 + 1.0×58
×100% = 53.2% and compositional analysis.
1.16×44 + 1.0×58 relative moles PPG×MWeeg
weight % PPG = ×100%
relative moles PEG×MW efg + relative moles PPG×MWeeg
relative moles PPG×MW
weight % PPG =
1.0×58
eeg
relative moles PEG×MWefg + relative moles PPG×MWeeg
×100% References
= ×100% = 53.2%
1.16×44 + 1.0×58
1.0×58
= ×100% = 53.2%
1.16×44 + 1.0×58 1. Higginbotham, C. L.; Izunobi, J.U. J. Chem. Ed. 2011,
88, 1098-1104
Based on the 82 MHz NMR spectrum, Pluronic L-35
copolymer contains 46.8 % of PEG and 53.2 % of PPG. 2. Skoog, D. A.; Holler, J. F.; Crouch, S. R. Principles
The results using the 300 MHz spectrum are essentially the of Instrumental Analysis, 6th ed.; Brooks Cole: Pacific
same: 47.4 % of ethylene glycol and 52.6 % of propylene Grove, 2006.
glycol. Both results are in good agreement with the product
specification4, where PEG/PPG (w/w) = 1. 3. Bovey, F. A.; Mirua, P. A. NMR of Polymers, 1st ed.;
Academic Press: San Diego, 1996.
For Research Use Only. Not for use in diagnostic procedures. © 2016 Thermo Fisher Scientific Inc. All rights
reserved. Mnova is a trademark of Mestralab Inc. All other trademarks are the property of Thermo Fisher Scientific
and its subsidiaries unless otherwise specified. AN52907_E_11/16M