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Lec25 (Cl 27)

NMR for Sequence Isomerism

NMR can also provide clear evidence of sequence isomerism in

polymers. For example, poly(vinylidene fluoride), or PVDF
polymer which contains H-H and T-T sequences.
Because the 19F nucleus has a spin number of 1/2 and its
natural abundance is 100% so 19F NMR spectroscopy is a
powerful tool for studying these fluoropolymers.

NMR for Sequence Isomerism

The F atoms (small yellow balls) with one of the units in backward position,
giving a H-H and T-T sequence. The peaks marked A, B, C and D in the
corresponding 19F NMR spectrum of PVDF correspond to the fluorine atoms
labeled in the Figure below.

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NMR for Sequence Isomerism

NMR for Sequence Isomerism

To know the number fraction of VDF- monomers that are

incorporated backwards into the chain, the relative intensities
of the bands in the spectra is used and we can use probability
theory for this.
If we consider Vinyl monomer CH2=CXY then we define the
probability of "normal" addition as P1{TH} and the probability
of "backward addition as P1{HT}. It can only be one or the
other, so it follows that P1{TH}+P1{HT}=1

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NMR for Sequence Isomerism

If we want to calculate the number or fraction of "backward"

units in a sample, we need to determine P1{HT} = 1 P1{TH}.
This determination will depend upon what information is
available in the NMR spectrum.
For Diads=4 possible sequences,
Traids= 8 possible sequences
Tetrads =16, and so on.
Not all of these are distinguishable. For example, NMR cannot
distinguish between {TH-TH-TH} and {HT-HT-HT}- this is
equivalent to reading the chain in one direction or the other.

NMR for Sequence Isomerism

We should see 3 NMR lines if we are observing diad

information and 4 for triads (there would be 5 lines for tetrads
and 6 for pentads).
Even more interesting, n of the observed NMR lines (assuming
they are resolved in the spectrum) will have the same intensity
if n-ad information is available. This just means that if we have
triad information available, 3 of the 4 observed lines will have
the same intensity as we saw in PMMA example, where 3
bands have the same intensity.

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NMR for Sequence Isomerism

Similarly, the 13C NMR spectrum of polychloroprene, was also

analyzed and the olefinic region is shown here.

NMR for Sequence Isomerism

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IR & NMR for Structural Isomerism

Both NMR and vibrational spectroscopy can be used to detect

and study structuctural isomerism in dienepolymers. For
example, the infrared transmission spectrum of poly (2,3
dimethylbutadiene).
No band near 1660 cm-1 from C=C double bonds, because of
the symmetry in the repeat unit of this polymer. Just like
symmetric stretch in CO2 , which is IR inactive.
But, there is a strong Raman line at 1665 cm-1, therefore we
need both IR and Raman spectra to obtain information about
this polymer.

IR & NMR for Structural Isomerism

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IR & NMR for Structural Isomerism

Polychloroprene, for example, with

largely trans-1,4- units. but how
many cis- 1,4, -1,2 and -3,4 units
are there?
Consider the IR spectra marked A
and B. Sample A was polymerized
at -40C, while sample B was
polymerized at -20C. This results
in a difference in microstructure,
but it can be seen that the spectra
of the two samples are very similar,
simply because there is only a
small difference in the content of
structural irregularities.

IR & NMR for Structural Isomerism

By modem computer-based instruments it is possible to subtract

one spectrum from the other (A - B) to give a difference
spectrum C revealing the presence of bands that can be
assigned to cis-1,4-, 1,2-, and 3,4- units.
For quantitative analysis, we have to use 13C NMR. In addition,
1H NMR is less effective in this case as there is only minimal
chemical shift differences between cis and trans isomers in the
1H NMR spectra of polymers like polybutadiene and
polyisoprene.

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IR & NMR for Structural Isomerism

13C

NMR however, is extremely effective in characterizing

these types of polymers. These spectra not only display wellseparated lines for the various structural isomers that may be
present, but also provide sequence distribution information and
readily allow quantitative analysis.
For example, the proton decoupled 13C NMR spectrum of
polybutadiene will show band that can be assigned to specific
triad sequences. We have marked with arrows those that have
a central cis unit.

IR & NMR for Structural Isomerism

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Tacticity in Vinyl Polymers

IR may be used though for tacticity of a

polymer but NMR gives in depth details of
the tacticity.
In polypropylene, for example, the ratio of
the intensity of the 988 cm-1 band to that
of the 973 cm-1 band varies from about 1
in a completely isotactic to 0 in atactic
sample. But what the intensity ratio of this
band actually represents is the degree of
chain order in the sample, not the tacticity
as such.
That is where NMR can unleash the details.

Tacticity in Vinyl Polymers

Normally plexiglassR is atactic, although both the isotatctic
(iso-PMMA) and syndiotactic (syn-PMMA) can be polymerised.
Proton NMR spectroscopy has been used to characterize the
tacticity of various vinyl polymers in
solution. In the case of isotactic polymers,
there are two magnetically nonequivalent
protons in PMMA and appearance of
04 bands in NMR spectra.

On the other hand, in syndiotactic

polymers the two methylene protons are
equivalent and we observe only 01 line.

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Tacticity in PMMA

The two hydrogen atoms of the CH2

groups in isotactic PMMA are not
magnetically equivalent. One is always
in the environment of-two methyl
groups, while the other lies between
two ester groups.
In contrast, for a syndiotactic polymer,
the CH2, protons are magnetically
equivalent, each being on one side by
a methyl group and the other by an
ester. Naturally, atactic polymers have
both types of CH2 units.

Tacticity in PMMA

Because the two protons of the methylene group of iso-PMMA,

are not magnetically equivalent, resulting in the four-line
pattern of CH2.
On the other hand, the CH2, protons of the syndiotactic PMMA
are equivalent, there is no spin-spin interaction so only 01 line
in the NMR. An atactic sample should resemble a combination
of these two.
But, we would not be able to tell if the sample was a mixture
of isotactic and syndiotactic chains, or was actually atactic
because the methylene protons are only sensitive to the diad
structures (the stereochemical arrangements of two adjacent
units).

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Tacticity in PMMA

Tacticity in PMMA

The additional splitting observed here is due to

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NMR Spectroscopy:
Molecular mass
13

C NMR is the most important technique for structural

characterization of polymers.
NMR spectra of linear polymers of low molecular mass often
show unique absorptions due to the end groups. By referencing
these absorptions with the nuclei of the repeat units, it is
possible to obtain the ratio of the no. of end groups to the no.
of repeat units, thereby evaluate the no. average molecular
masses of such polymers.

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NMR Spectroscopy:
Molecular mass

13C

NMR is the most important technique for structural

characterization of polymers.
For branched polymers, NMR absorptions due to the branch
points can be identified and reveal the chemical structure of
those branch points, thus leading to a better understanding of
the mechanisms by which the branch form. It is also possible to
calculate the degree of branching by referencing these
absorptions to those of nuclei in the repeat unit.

NMR Spectroscopy:
Copolymer Analysis
13

C NMR and 1H NMR are power tools to characterise the e

structure and composition of copolymers as well.

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Lec 28
Molecular Weight and Branching

Polymers contain mixtures of different molecular sizes. One

way of obtaining the weight is to separate the polymer into a
no. of fractions each of which has a narrow size distribution of
molar mass. The weight and molar mass fraction of each
polymer chain is then determined and molar mass distribution
is displayed as a histogram.
Size exclusion chromatography allows a rapid and power
method to determine molar mass distributions. Gel Permeation
Chromatography (GPC) is a type of SEC that is used to
determine the polymer molar mass distribution in a solvent.

Instrumentation of GPC

A solvent or a mixture of solvents is pumped through the

packed columns. A polymer solution is injected at injection port
at some point in the solvent stream. After passing through the
columns, a detector measures the amount of polymer in what is
called the eluant stream (by measuring the refractive index of
the solution).
Each column is packed with beads of a porous gel (e.g. Si, or
zeolite). The pore size of gel may be 5-105 nm. The small
solvent molecule pass both through and around the beads.
The smallest polymer molecules are able to pass through most
of the pores in the beads and thus have a relatively long flow
path through the column before exit. Therefore small molecules
reach to the end of column in much longer time compared to
larger size molecules.

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SEC

Instrumentation of GPC

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GPC Mechanism of Separation

Polymer with a range of chain length, each one follow

different path lengths through the column according to its size
and are eluted at different times.

Decreasing chain size

GPC
The concentration of polymer in the eluate is monitored
continuously and a chromatogram is obtained which is a plot of
concentration against the elution volume or time, which provides
a qualitative distribution of the molar mass in a give polymer.
There may be just a small amount of
very high MW material that comes off first,
and small amounts of low MW material
that come off last, and in-between a curve
that reflects the MW distribution of the
sample.

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Separation by Size Exclusion in

GPC

In order to obtain a MW distribution and

to relate MW to the eluted volume,
columns must be calibrated by using
fractions of known MW (standard
monodispersed PS samples).

A calibration curve can then be

constructed by plotting the log of the
MW against the elution volume for these
samples. Once calibrated, the instrument
can be used to determine the MW
distribution of an unknown sample.

Separation by Size Exclusion in

GPC

The volume of the solvent contained in a GPC system from point of injection
to the point of concentration detection can be considered as the sum of a
void volume Vo (volume of solvent outside the porous beads) and an internal
volume Vi (volume of solvent inside the porous beads).
The volume of solvent required to elute a particular polymer species from
the point of injection to the detector is known as its elution volume Ve as
follows,

Ve Vo K seVi

Where Kse is the fraction of the internal pore volume penetrated by certain
polymer molecules.
For small polymer molecules that can penetrate all of the internal voulme
Kse=1 and therefore Ve Vo Vi
For very large polymer molecules that are unable to penetrate the pores
Kse=0, and therefore Ve Vo

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Separation by Size Exclusion in

GPC

SEC data obtained for a

polydisperse, linear, atactic
polystyrene sample appears as the
distribution shown in Fig.
If we cut the curve into narrow slices
of equal increments of elution volume,
V, the polymer eluting in each of
these elements may be regarded as
monodisperse and the total area of
the curve can be regarded as the sum
of the heights of the individual slices.
The weight fraction of any slice is then
given as;

wi

hi
hi

Calculation of MW Distribution in
GPC

The MW of the ith species is then obtained from the calibration

curve at point Vi and the MW averages can be calculated as;
Mn

1
w
Mi
i

M w wi M i

Polymers of the same MW, but

of a different architecture, will elute
from SEC column at different times.
For instance, linear PS will be
eluted at a different time to a
star-shaped PS.

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GPC:
Hydrodynamic Volume

Calculating the MW distribution and MW

averages is valid as long as monodisperse or
very narrow molecular weight standards of
the same polymer are available.
This is because the size of a molecule in
solution, its hydrodynamic volume depends
upon the nature of the polymer/solvent pair
and the temperature.
A linear polystyrene with the same number of
segments as a star-shaped sample occupies a
larger hydrodynamic volume.

GPC:
Hydrodynamic Volume

Fractionation of molecules in SEC is governed by hydrodynamic

volume rather than by molecular weight.
The largest polymers in the solution cannot penetrate the pores
within the cross-linked gel beads, and so they will elute first as
they are excluded and their retention volume is smaller.
The smallest polymer molecules in the solution are retained in
the interstices (or the voids) within the beads, and so require
more time to elute as their retention volume is larger.

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Column Packing
Different types
Semi-rigid, cross-linked macromolecular polymers
Rigid, controlled-pore-size glasses or silica
Semi-rigid polymers: these materials swell slightly
care must be taken during use
limited to a maximum pressure of 300 psi due to bed
compressibility
e.g. styrene divinylbenzene polymers (for compounds of MW
range of 100-500 million) & suspension polymerization of 2hydroxyethyl methacrylate with ethylene dimethacrylate (can
withstand pressure upto 3000 psi)

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