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NMR Spectroscopy

for polymer chemists


Rachel OReilly

CH968
2-5pm
17th February 2014

NMR Theory
Every nucleus has a magnetic moment given
by:

Ih

Gyromagnetic ratio
Nuclear spin

Plancks constant

For a nucleus with spin I there are 2I + 1


possible orientations. Most commonly used
nuclei have I = so there are 2 spin states.

NMR Theory

NMR Theory
The two spin states for I = nuclei are m =
and m = -.
When placed in a uniform magnetic field, B0,
the spins align in one of two opposite
directions.
B0
m=

m = -

NMR Theory
The energy of each spin state is proportional
to the magnetic moment and B0:

hmB0
E E B0
2

m = or -

The selection rule is that m can only change


by one in any transition

NMR Theory
The transition energy is then:

hB0
E
2
The transition is induced by applying radiation
with this energy, or this frequency:

B0
E h
2

NMR Theory
At the resonant frequency, the pulses energy
is absorbed and nuclei are promoted to a
higher energy level.
We try to measure this absorbance.
m = -
m = -
NB

B0
NA

mm==-

NB
e
NA

kT

Very small!

FT NMR
Because of the small difference between NA and NB every
sample has net magnetisation, which is aligned with the
applied field (B0).
Instead of scanning the frequencies, a single pulse containing
all of them is applied over time t.
The length of the pulse is such that the magnetisation is
tipped 90
z
/2 pulse
y

B0
x

FT NMR
The magnetisation now precesses like a top
the time for one revolution round the z axis is
the same as the resonant frequency.
We measure this frequency by positioning a
detector coil along the y axis, this gives us a
cosine wave:

FT NMR
Since all environments are simultaneously excited,
we actually see a superposition of lots of cosines.
The magnetisation also decays over time (i.e. it
returns to being along the z axis).
Both of these give us the Free Induction Decay (FID)
spectrum:

FT NMR
The FID is then converted to the spectrum
with which we are familiar by a Fourier
transform:

A little demonstration

http://www.youtube.com/watch?v=7aRKAXD4dAg&feat
ure=player_detailpage

Things to bear in mind


Higher temperature lower sensitivity
High viscosity poor results
Try increasing the number of acquisitions
rather than the concentration
Possible to use non-deuterated solvents, but
you must add a small amount of deuterated to
provide a lock for the machine

Things to bear in mind


Magnetization of the nuclei by a pulse begins to
return to its original equilm value along the z axis
and the xy plane immediately after the pulse
Return of the Z-component (Mz) to equilm value is
longitudinal relaxation
Return of Mxy to zero is tranverse relaxation
Both are 1st order processes, characterised by the
times T1 and T2

Things to bear in mind


Good data depends on use of appropriate T1
(spin lattice) and T2 (spin-spin) relaxation times
Width of line in NMR spectra determined by T2
Short T2 broad lines

Maximum repetition rate during NMR


acquisition is given by T1 (the delay time should
be at least 5 times the longest T1)

T1 always greater than or equal to T2


In polymers T1 much greater than T2

For small molecules


Relaxation mechanisms
T2 relaxation is caused by fluctuations in any direction
ie molecular motion
Define a correlation time (tc) for a molecule
This is the average time it takes one molecule to rotate
by one radian
Small molecule (Mn < 1000 Da), tc ca. 10-12 sec

For a proton at 300 MHz u0 = 108 (Larmor procession frequency)


Small molecules move too fast to relax by spin-spin relaxation

But polymers do not.

For small molecules


Chemical shift
Rapid rotation Brownian motion of small molecules
averages out dipolar and other anisotropic magnetic
interactions
Called molecular tumbling
Leads to narrow lines in the NMR spectra
If tumbling (or rotation) is slow relative to the
timescale of the NMR then the signal is broadened
Because different chemical shifts are observed
Brownian motion of molecules decreases with
increasing size
Line width of an NMR signal increases as size increases

Polymers
NMR signals always broad in the 1D NMR of polymers
(each monomer is similar to its neighbours, therefore signals
overlap)
Interactions usually broaden the NMR resonance lines of a
spectrum. In (non-viscous) liquids these interactions are
averaged by rapid isotropic motions of the molecules in
polymers by bond rotations of the backbone and the sidechain or groups. The fast isotropic motions average the
interactions to zero or to a single finite value representing the
average interaction.
Line broadening due to slow relaxation as a result of larger
mass, therefore slower tumbling

How is NMR useful in polymer science

Measurement of polymerisation conversion


End group analysis
Molecular weight determination
Stereochemistry
CMC determination

Conversion by 1H NMR

ATRP

CH3

O
CH3O

(CH2 )2O

CH2

Br

CH2 O

m
H

CH3

(1)

CH3

O
O
CH3

Selection of 1H NMR spectra


recorded during the
polymerization of MMA on
MeOPEG-IX (X = 12, 45, 113).

Cu(I)Br
Toluene

N
C5H13

O
CH3O

(CH2 )2O

CH2

CH3

COOCH3
CH2

CH2 O
CH3

(2)

COOCH3

CH2

CH3

Br
CH3

Alkene signals

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

Compare integration of monomer and polymer signals and work out conversion

Conversion by NMR
Hp = 1.75
Hm = 1
Bromo-styrene
Conversion =

Hp
Hp + Hm

= 1.75/2.75
= 63.5%

Conversion by NMR

Error on this
measurement?

Copolymerizations are more tricky example in the assessment

Copolymerizations are more tricky example in the assessment

Conversion by NMR

RAFT monomer (1-0.31)*100 =


Ethyl monomer (1-(0.72-0.31)*100 =

Conversion by NMR

Error in A0

End Group Analysis


NMR = easiest way to get Mn for your polymer
For reliable numbers you need to ensure that:
1. Polymer signals do not overlap with the end group
2. The end group signal is well resolved
3. The integration is reliable

Note: really only works well for polymers with Mn up to


30,000 Da

End group analysis RAFT example

Ideally, use both end groups for comparison


this may also help you see if the Z group is stable.
TMS can even be incorporated into the CTA!1
Other nuclei may also be useful2
1)
2)

Pach, M.; Zehm, D.; Lange, M.; Dambowsky, I.; Weiss, J.; Laschewsky, A. J. Am. Chem. Soc. 2010, 132, 8757
Godula, K.; Rabuka, D.; Nam, K. T.; Bertozzi, C. R. Angew. Chem., Int. Ed. Engl. 2009, 48, 4973

End group analysis RAFT example

Ideally, use both end groups for comparison


this may also help you see if the Z group is stable.
TMS can even be incorporated into the CTA!1
Other nuclei may also be useful2
1)
2)

Pach, M.; Zehm, D.; Lange, M.; Dambowsky, I.; Weiss, J.; Laschewsky, A. J. Am. Chem. Soc. 2010, 132, 8757
Godula, K.; Rabuka, D.; Nam, K. T.; Bertozzi, C. R. Angew. Chem., Int. Ed. Engl. 2009, 48, 4973

End group analysis


Compare the and signals.

S
O

S
O

31

10

C - can be affected
by grease

2.00

2.16
8.0

ppm (t1)

7.0

6.0

5.0

4.0

3.0

2.0

1.0

End Group Analysis


d
g

a
i
b

c
d

m = 25

f, g

ppm

End Group Analysis


Commercial
polymer end
group
modification

End Group Analysis


Polymer end
group
modification

Norbornene signals

End Group Analysis - ATRP


2 DIFFERENT METAL CATALYSTS, 2 DIFFERENT END GROUPS

End Group Analysis


Isotopic enrichment of the end groups is an
option (albeit expensive) but this makes
determination of Mn trickier.
If you have a protic end group you can
derivatise it to make the protons easier to
see.3
It is possible to use 13C but bear in mind that
this is: a) much less sensitive, and b) the
thiocarbonyl signal usually lies outside the
range of a normal scan.
3)

Postma, A.; Davis, T. P.; Donovan, A. R.; Li, G.; Moad, G.; Mulder, R.; O'Shea, M. S. Polymer 2006, 47, 1899

Molecular weight - Mn

1H

NMR can also be used to calculate DP by comparing the


integration of polymer to end group
This can in turn be used to calculate Mn, NMR
S
O

Set integration of
A=2
Integration of D
= DP
Mn = (DP x Mr of
monomer) + Mr
of CTA

S
O

31

10

C - can be affected
by grease

B
30.85

2.00
8.0
ppm (t1)

7.0

6.0

5.0

4.0

3.0

2.0

1.0

Ref: J Chem Edu, 2011, 88, 1098

Molecular weight - ATRP


Mn = 5,000 Da

Molecular weight
Poly(ethylene glycol) diacrylate, commercially available from Aldrich

Copolymerisation composition

LCST measurement

A graph to show the ratio of 1H NMR signal intensities for PNIPAM C-H next to
methyl groups (assigned as e in inset, at 3.8 ppm) as a function of temperature in
D2O solution (6 mg/mL) for the PMA27-b-PNIPAM47 diblock copolymer.

Microstructure of polyisoprene

4 DIFFERENT MICROSTRUCTURES

1,4

1,2
3,4

Copolymerisation

13C

NMR
5

RAFT-Ethyl
Ethyl-Ethyl
RAFT-RAFT

ppm

5+6

Fig. 8 13C NMR spectra (100 MHz; CDCl3) of poly(5),


poly(6) and 1:1 copolymer (5:6) in CDCl3.
We can see triad distributions by 13C NMR, this can give you information on
copolymerisation and polymer microstructure

Tacticity
NMR can be used to assess the
stereoregularity of a polymer.
For a given chiral sequence along the polymer
backbone, there is a characteristic peak
pattern.
If you can identify the patterns you can work
out the tacticity of your polymer (this is not
always easy!)

Stereochemistry

Stereochemistry

Odian pages 636-637

NMR measurement, triad level


13C

NMR

Conventional radical polymerization

PMMA

1H

ATACTIC

NMR

SYNDIOTACTIC RICH

Meso (same) isotactic


Racemic (different) - syndiotactic

Syndiotactic bias (3:34:63)

Stereochemistry of Polypropylene

isotactic pendant methyl


groups are on the same side
of the polymer backbone

syndiotactic pendant methyl groups


alternate sides of the polymer backbone

atactic pendant methyl groups are randomly


arranged along polymer backbone

13C

NMR Reveals Polymer Stereochemistry

On a high field NMR instrument, the chemical shift of the methyl groups on the polymer
backbone is sensitive to the relative stereochemistry of its four nearest neighbors (two on
each side).

m = meso (syn)

r = racemo (anti)

13C

NMR Spectra of Various Polypropylenes

Stereochemistry of poly(lactide)

Irradiate at the frequency of the signal that you want to remove coupling to with a 2nd pulse
Like an NOE experiment

Tetrad level

Stereochemistry
Homonuclear decoupling is when the nuclei being irradiated are the same isotope as the
nuclei being observed (analyzed) in the spectrum. ie H-H
iii

TETRAD LEVEL

In DMSO so
signals have
shifted

2D NMR
2D NMR takes longer because you have to record
a number of FIDs (usually about 50-500).
Preparation

evolution
t1

Mixing

detection
t2

Preparation is where the first set of pulses is


applied signals evolve at a particular frequency
a further set of pulses are applied during
Mixing, leading to some transfer of signals
these then evolve at a different frequency during
detection.

2D NMR

So a peak in the 2D NMR at coordinates (f1, f2)


means that there is a peak that evolves at
frequency f1 during t1 and is affected by the
mixing period such that the signal is
transferred to another signal that evolved
with frequency f2 during t2.
F1
f1

f2

F2

2D NMR
EXSY = EXchange SpectroscopY (are nuclei
chemically exchanging?)
COSY = COrrelation SpectroscopY (are nuclei
linked by 3J coupling?)
HMQC = Heteronuclear multiple-quantum
correlation (is nucleus B directly attached to
nucleus A?)
HMBC = Heteronuclear multiple-bond correlation
(what other A nuclei are in the vicinity of nucleus
B?)

2D NMR

NOESY = Nuclear Overhauser Effect SpectroscopY


(are nuclei close in space? Actually the same as
EXSY)
ROESY = Rotating frame Overhauser Effect
SpectroscopY (are nuclei close in space?)
TOCSY = TOtal Correlation SpectroscopY (are
nuclei linked by J coupling over longer distances?)
INADEQUATE = Incredible Natural Abundance
Double QUantum Transfer Experiment (what is
the bond order of the nucleus?)

2D NMR
DOSY = Diffusion Ordered SpectroscopY (is
nucleus A in the same molecule as nucleus B?)
Care needs to be taken when recording DOSY spectra as
small effects can wreck your results e.g. convection
within the tube, correct pulse sequence.
The method you use for extracting diffusion coefficients
is important.
Bear in mind that the breadth of the signals in DOSY
has nothing to do with polymer dispersity!
Stokes Einstein equation
D = diffusion time

2D NMR

2D NMR

Polymer-polymer coupling
A mixture or coupling together???

Polymer-polymer coupling - DOSY

Diffusion
coefficient

CMC determination

Fig. 2 600 MHz 2D DOSY NMR spectra obtained at 298K in


CDCl3 solution of (A) poly(ethylene glycol), Mn
= 6000 g mol-1 and (B) poly(lactic acid), Mn = 2100 g mol-1.
1)

Bakkour, Y.; Darcos, V.; Li, S.; Coudane, J. Polym. Chem. 2012, 3, 2006

CMC determination
DOSY

600 MHz 2D DOSY NMR spectrum


recorded at 298K in D2O of
the copolymer PLA12PEG136PLA12.
1)

Bakkour, Y.; Darcos, V.; Li, S.; Coudane, J. Polym. Chem. 2012, 3, 2006

As shown on the DOSY map, only the


spot corresponding to PEG block was
visible, whereas no spot
corresponding to the hydrophobic
PLA block was observed, due to
the limited molecular motion of the
moiety in aqueous solvent.
This phenomenon can be interpreted
by the formation of micelles
or aggregates where the
hydrophobic PLA part of the
copolymer forms the core and the
hydrophilic PEG part forms the shell.

CMC determination
DOSY can be used1:
DOSY

SLS

Excellent agreement between NMR and light


scattering data.
1)

Bakkour, Y.; Darcos, V.; Li, S.; Coudane, J. Polym. Chem. 2012, 3, 2006

DOSY for MW determination


Linear
correlation
of between
LogD and log
MW

Calibration
curves
Determine
Mw

Johnson and Grubbs, Macromolecules, 2012, 45, 9595

DOSY for MW determination


Linear
correlation
of between
LogD and log
MW

Calibration
curves

Johnson and Grubbs, Macromolecules, 2012, 45, 9595

Note: Solid state NMR


Insoluble polymers can be analyzed using solid state NMR
Good for the morphology of a material

References
NMR Theory:
Spectroscopic Methods in Organic Chemistry
Williams & Fleming

http://www-keeler.ch.cam.ac.uk/lectures/
Whole set of lectures goes into a lot of mathematical detail but well explained

NMR Spectroscopy of Polymers


Hatada & Kitayama

Experimental details
http://chem.ch.huji.ac.il/nmr/techniques/expts.html
Quite technical but very full explanations of how all of the NMR experiments actually
work.