Scribd
Upload
171 views2 pages

Polymer Analysis Using NMR

NMR spectroscopy can be used to characterize the structure of many different polymer types. It provides detailed information about monomers, branching, sequencing, tacticity, molecular weight, and end groups. There are several NMR techniques that can be applied depending on the polymer's physical state. Solid state NMR analyzes insoluble or non-melting polymers, while high temperature NMR and HR-MAS NMR provide information about molten polymers or those in solvent-swollen states. End group analysis using 1H NMR can determine number average molecular weight for polymers under 3000 Da by integrating end group protons compared to repeating unit protons.

Uploaded by

Mavia Naushad
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
171 views2 pages

Polymer Analysis Using NMR

NMR spectroscopy can be used to characterize the structure of many different polymer types. It provides detailed information about monomers, branching, sequencing, tacticity, molecular weight, and end groups. There are several NMR techniques that can be applied depending on the polymer's physical state. Solid state NMR analyzes insoluble or non-melting polymers, while high temperature NMR and HR-MAS NMR provide information about molten polymers or those in solvent-swollen states. End group analysis using 1H NMR can determine number average molecular weight for polymers under 3000 Da by integrating end group protons compared to repeating unit protons.

Uploaded by

Mavia Naushad
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
You are on page 1/ 2

Polymer Analysis using NMR Spectroscopy:

Polymer characterization can also be carried out by using NMR in different states and under a large
variety of conditions. It provides detailed structural information on polymers. NMR can analyze a large
no of polymers like polyethylene (HDPE, LDPE, LLDPE), ethylene, propylene copolymers, polypropylene,
poly acetates, poly acrylates and polyesters, polyisobutene, polyalkylene glycols, phenolic resins, poly
silioxanes, polyurethanes, polyimides, PET, PEEK, polysulphones, polyketones, polymers for packaging
and many additional polymers. NMR polymer analysis provides data for:
 Solid State Nuclear Magnetic Resonance.
 Monomer types, levels and distribution, block or random.
 Polymer chain branching.
 Polymer sequencing.
 Polymer tacticity.
 Polymer molecular weight (MW).
 Polymer end groups.
 Polymeric structure.
 Co-monomer ratios.
Solid state NMR is used to analyze insoluble polymers or those that do not melt. In solid state the
situation is a bit complicated because missing isotropic molecular tumbling causes that anisotropy of
nuclear interaction now plays dominant role in the appearance of NMR spectra. The NMR signals are
very broad and spectra become featureless. In general missing isotropic tumbling leads to severe
broadening of the detected signals. The lack of resolution, however; does not mean the absence of
structure information, it rather reflects its overcrowding in such extent that we are not able to read out
and understand it. Due to this fact various techniques have been proposed to increase spectral
resolution.
High temperature NMR can be applied for studies of molten polymers or materials in special high
temperature solvents and HR-MAS NMR can provide detailed information of polymers in solvent swollen
or semi-rigid states. The high dynamic range of the AVANCE-III system combined with the optimized
probe performance makes NMR the ideal tool to study polymer end-groups, branching and other
features of the material present only in minute quantities.
End-group analysis having Mn values under 3000 by 1H NMR is an easy alternative method for polymer
analysis. In addition, NMR analysis can also be used to accurately determine monomer ratios for various
co-polymers. This technique detects end-group protons which determine the upper limit that can be
measured. In order to use this method, the following criteria must be met:
 Identifiable end-group protons distinguishable from repeating monomer-group protons by NMR
 Accurate integration of both end-group and monomer protons
 Knowledge of monomer formula weights
Once the ratio of protons on the end-groups to protons on the polymer chain is determined, using the
NMR, simple math can be applied to generate the Mn value.

Calculation:
(1) Calculation of integral per proton:
Locate the end-group proton signals integral per proton = sum of vinyl proton integrals of protons in
the two vinyl end groups
(2) Calculation of number of repeating monomer units (n):
Locate the OCH2CH2 proton signals.
n = ((sum of CH2 proton integrals)/No. of CH2 protons)/{integral per proton value}
(3) Calculation of Mn:
Mn = (FW end groups) + (FW repeating unit)(n)

Example:
:

Poly(ethylene glycol) diacrylate

(1) Calculation, integral per proton: Locate the end-group proton signals (ca. 5.8, 6.2 & 6.4 ppm)
integral per proton = sum of vinyl proton integrals # of protons in the two vinyl end groups (10.00 +
9.66 + 10.17)/6 = 4.97 per proton
(2) Calculation, number of repeating monomer units, n:
Locate the OCH2CH2 proton signals (ca. 3.6, 3.7 & 4.3 ppm)
n = ((sum of CH2 proton integrals)/# of CH2 protons)/{integral per proton value}
((20.79 + 151.87)/4)/4.97= 8.69 repeating units, n;
(3) Calculation, Mn:
Mn = (FW end groups) + (FW repeating unit)(n)
= (55.06 + 71.60) + (44.05)(8.69) =509;
Therefore, the Mn of this polymer is approx. 509

You might also like