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Molecular Weight determination methods

Molecular Weight is normally measured in solution

• Why is the molecular weight important? (some exceptions such as MALDI)

• The molecular weight effects the physical properties

• •Viscosity Absolute Methods:
• •Glass transition temperature and melting point The molecular Weight can be calculated directly from the measurement
-Endgroup Analysis
• •Modulus -Methods based on colligative properties
-Light scattering
physical property

I II III
Relative Methods:
requires a calibration obtained with polymers of known molecular weight
-GPC (gel permeation chromatography)
-Viscometry

Molecular Weight
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GPC (Gel permeation chromatography)

• Also called size exclusion chromatography (SEC)
• GPC allows the measurement of the molecular
weight and the molecular weight distribution
(polydispersity index).
• GPC is a relative method: a calibration is required to
calculate the molecular weight
• The polymer (which consists of a range of molecular
weights) is separated in the GPC column according to the
hydrodynamic volume of the polymer.
What is in the column?
The column is filled with porous particles
(=stationary phase)
These particles are made from crosslinked
polystyrene, silica gel, porous glass....(the
polymer should not interact with the column
material)
Every solvent can be used for the mobile phase.
However, some solvents are more common: THF,
Toluene, Water
The porous particles and the solvent have to be
compatible.
The solvent is passed through the column with a
certain flow rate (1mL/min)

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How can polymers be separated?

Polymers are separated according to their hydrodynamic volume (which
corresponds to the molecular weight).
The polymer penetrate into the pores of the column material.
The deeper a polymer can
diffuse into the pores the
longer it takes to pass the
Vi
column.
Vm

bigger polymers pass

A B C the column faster
A) the polymers are too big, they cannot diffuse into the pore, polymers The time for a polymer to
above this size cannot be separated. pass the column is called
upper exclusion limit M1 M2
retention time, the
volume of solvent is M1>M2
C) the polymers are small enough to use all the available pore volume called retention volume
lower exclusion limit Ve,1 Ve,2

20 22 24 26 28 30 32 34 36 38 40

B) polymer diffuse into the pores according to their hydrodynamic volum2n0 Ve in minutes 21
separation occurs

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GPC is a relative method:

6 From the GPC chromatogram to
the particles are separated according their hydrodynamic volume. the molecular weight
distribution

log M
We need now a calibration curve to obtain the relationship between
4

the hydrodynamic volume and the molecular weight! 2

injection

0
0 10 20 30 40 50

8 22 Ve

Polymer standards are

used (polymers with 6

known molecular weight) 10000 20000 30000 40000 50000

and the retention time for

Molecular Weight
log M

each standards is
measured 2
injection
calibration curve
0
0 10 20 30 40 50
Ve 0 10 20 30 40 50
retention time

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Important considerations about GPC:
We have to remember that the separation in the GPC occurs according to
their hydrodynamic volume- NOT the molecular weight. However, we will
learn later in this course that the hydrodynamic volume and the molecular
weight of a specific polymer are correlated.
This mean that we can have two different polymers with the SAME
molecular weight, but different hydrodynamic volume:
Polymer 1 Polymer 2
Fully extended chain
Random coil
Furthermore, conditions such as the temperature or the solvent can
influence the hydrodynamic volume.
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We have a polymer (polystyrene) with a molecular
weight of 100,000 g/mol.
We have a GPC system running on Toluene and the
system is calibrated with polystyrene standards. The
oven is set on 40 C. The system was calibrated using
these conditions.
Now somebody was playing around with the settings of
the column oven and increased the temperature.
Polystyrene tends to uncoil at higher temperature (this
is not the case for all polymers) and the hydrodynamic
volume becomes bigger.
How would this affect the retention time and the final
(wrong) result?
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The synthesis of polymers Chain-growth polymerisation

Polymers are usually prepared via polymerisation of monomers via Free radical polymerisation
step-growth or chain growth polymerisation.
Chain growth polymerization: Most chain-growth polymerisations deal with vinyl polymers derived from
monomers with the general formula: H2C=CR1R2
•Free Radical polymerization: most common polymerization, can Vinyl monomers are polymerised leading to the formation of a carbon
be carried out in bulk, solution, suspension and emulsion atom backbone (homochain)
•Ionic polymerization: anionic and cationic
•Insertion polymerization: Ziegler-Natta Polymerization
R1 R1
•Ring-opening polymerization n H2C C
Polymerisation CH2
C

•Controlled free radical polymerization: RAFT (reversible addition R2

R2
n

fragmentation transfer), ATRP (atom transfer radical

polymerization), NMP (nitroxide mediated polymerization) Note: Not all compounds with double bonds can be polymerised!

Step growth polymerization:

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•Polycondensation and polyaddition

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The name of the polymer is derived from the monomer by adding the prefix
poly.

Monomer Polymer Radical polymerisation (as well as ionic polymerisation) has three
principal steps:
ethylene CH2 polyethylene
H 2C CH 2 CH2 •Initiation of active monomer with radicals
n
H2C CH
styrene CH 2
polystyrene •Propagation or growth of the active (free-radical) chain by sequential
addition of monomer (macroradical)
CH
n

•Termination of active chains

H2C CH acrylonitrile CH2
CH
polyacrylonitrile
CN CN
n INITIATION
The polymerisation is started using radicals. Different sources of radicals
H

methyl acrylate Poly (methyl acrylate)

CH 2

O C

are known such as heat, light, -radiation or certain compounds, which are
n
O C
O O

known to generate radicals.

CH 3
CH 3

H2C CH vinylchloride CH2 polyvinylchloride

CH Note: A radical is a single electron. Instead of an electron pair the molecule
Cl n
Cl has a single electron, which has a high tendency to react to rebuild the
CH 3 CH 3
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H2C C methyl CH2
C poly (methyl electron pair and electron octet, respectively.
methacrylate methacrylate)
C O n
C
O O O
41
CH 3 CH3

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CH3 CH3 O CH3 CH3 O

1. 2,2-azobisisobutyronitrile (AIBN)
The most common types of initiation of radical polymerisations are: NC N N CN N N

CH3 CH3
O
CH3 CH3
O 2. dimethyl 2,2-azobisisobutyrate
(MAIB)
•Thermal initiation: thermally decomposing initiators, e.g. azo 1 2
3. 1,1-azobis(1-cyclohexanenitrile)
compounds, peroxides, per-esters
CH3 CH3 4. azobis-2,4-dimethylvaleronitrile
The initiator decomposes into two radicals upon heating N N H3C N N CH3

Azoinitiator (Example: 2,2-azobisisobutyronitrile (AIBN)) CN CN

CH3
CN CN
CH3

3 4

CH3 CH3 CH3 Peroxides: have two joining oxygen atoms

T O O
H3C C N N C CH3 2 H3C C N2
O O

CN CN CN O O 1. di-tert-butyl peroxide
1
2
2. benzoyl peroxide
O

AIBN is the most common azoinitiator. Other azoinitiators are known, 3. di-tert-butyl peroxalate
O H
O O
which can decompose at a different rate at different temperatures. O 4. cumene hydroperoxide
O O

O 4

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•Self initiation (thermal polymerization): monomers themselves can start

Peroxides decompose similar to azocompounds into two radicals: free radical polymerization at elevated temperature without added initiators
O O O or initiating impurities, e.g. styrene (this is not the same as spontaneous
heat
2 polymerization, which can be caused by light or impurities)
O O O

-H

But the two radicals can decompose further: For example, the
decomposition of benzoyl peroxide leads to the formation of (1) (2) (3)

benzoyloxy and phenyl radicals

•Redox initiation: redox system, that generates radicals (low activation
energy, therefore suitable for polymerization at lower temperatures)
O

e.g. Fe2+ + HO-OH Fe3+ +HO- + OH

-CO2
O

•Photo initiation: Photo initiation is quite similar to thermal initiation, only

that the electromagnetic radiation (h ) is used induce the decay of the
initiator molecule
h
32 Initiator I1 + I2 33

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Here is an example with styrene

PROPAGATION CH3 CH3 H

CH
The radical is highly reactive and reacts with a monomer (association).
H3C C H2C H3C C CH 2 C

The association or start reaction is usually part of the initiation. This new CN CN

radical continues reacting with monomer to form a macroradical. The

monomer is mainly added head-to-tail. CH3 H CH3 H

H2C CH
H3C C CH2 C CH3 C CH2 CH CH 2 C

C H3 R1 C H3 R1 CN CN

H2C C
ka
H3C C H3C C C H2 C
CH3 H CH3 H
R2
CN CN R
R CH3 C CH2 CH CH2 C H2C CH CH3 C CH2 CH CH2 CH CH2 C

R M I-M
CN CN

tail head C H3 R1 R1 R1
R1
kp CH3 H CH3 H

Head: part with H3C C C H2 C n H2C C I C H2 C C H2 C

CH3 C CH2 CH CH2 CH CH2 C H2C CH CH3 C CH2 CH CH2 CH CH2 CH CH2 C

bigger CN R2 R2 R2
n
R2 CN CN
substituent
I-M nM I-Mn+1
34 And so on…….. 35

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Free radical polymerization is normally not stereospecific. Consequently, How long do the chains grow?
mainly atactic polymer chains are formed. Answer: Until they find another radical to react with!

TERMINATION
R H R H H R R H H R H R R H H R

Atactic: the carbon atom on the substituent has either D or L-configuration

randomly distributed.
(In contrast: Syndiotactic or isotactic polymers have the substituent either combination disproportionation
on one side of the backbone or the substituents alter strictly either to one
or the other side.)

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Two different kind of termination reactions are known: In radical polymerisation we have 3 steps: Initiation, propagation,
termination.
A) combination
Let’s take acrylonitrile and try to repeat what
R1 R1 R1 R1
ktc
R1 R1 R1 R1
is happening during the polymerisation of
I CH2 C CH2 C C CH2 C CH2 I I CH2 C CH2 C C CH2 C CH2 I this monomer initiated with benzoyl H2C CH
R2
x
R2 R2 R2
y
R2
x
R2 R2 R2
y peroxide!
CN

Two macro radical form one chain with the degree of polymerisation x+y What is the difference to the polymerisation
initiated with AIBN? How is the end product
B) disproportionation different!

R1 R1 R1 R1 R1 R1 R1
ktd R1

I CH 2 C CH 2 C C CH2 C CH 2 I I CH2 C CH 2 C H C CH C CH2 I

R2
x
R2 R2 R2
y R2
x
R2
R2 R2
y
Without knowing anything about the kinetics of the polymerisation can
you guess how you could influence the molecular weight or overall
Two macro radicals form two polymer chains with a chain with degree of degree of polymerisation of the polymer?
polymerisation= x and methyl endgroup and a chain with degree of
polymerisation= y and a double bond endgroup.
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