Kuliah I : Teknologi Polimer Maju

Sri Agustina, ST., MT., ME., PhD

Jurusan Teknik Kimia Untirta

2021

AKREDITASI INSTITUSI

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About this course….

• Materials that are utilized in high-technology application

• High-tech, a device or product that operates or
functions using relatively intricate and sophisticated
principles
• They might be of all material types whose properties
have been enhanced or newly developed

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 Advanced 
Modify polymers 
materials

L]HVSTLSFMGEPP]IRHQ SHMJMIHTSP]Q IVW

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Polymeric Nanoparticles

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che.untirta.ac.id Integrated Smart and Green University
Smart Polymers

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3D printed polymers

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Hybrid Polymers

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Rules apply…

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Grading…

•Absensi : syarat mengikuti UAS, minimal

10 kali kehadiran dalam kelas
•Latihan Soal di kelas (30%)
•UTS (30%)
•UAS (40%)

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Content
• Polymer Chemistry
• Polymer Physics
• Polymer Synthesis : Heterogenous
Polymerization, Ionic Polymerization, Radical
Polymerization, PISA
• Advanced Polymers Materials
• Polymeric Nanoparticles
• Functional Polymers
• Smart Polymers
• Hybrid Polymers

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 Introduction :
Polymer Chemistry

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 Introduction to polymers : The world of polymers

Polymers changed the world. Many articles that were made from wool, wood,
leather, metal or glass are replaced by articles made from synthetic polymers.
Clothes are made from polyester or nylon, articles in our daily life are made
from polymers (sports articles, container for food or detergent, coatings of
(kitchen) furniture, electrical cords, ………).

The presence of polymers can be very evident, but sometimes the use of
polymers is very hidden. Did you know that you can use polymers as a carrier
for your drug to control the release in your body? Do you know that polymers
can be synthetic metals and can be conducting? Or liquid-crystalline polymers
that can be used for rewriteable disks or optical fibres?

Each year 7*1010 kg of polymers are produced!!!

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History of polymers

• Natural polymers have always been used since prehistoric time (wool,
wood, horn, amber)
• Synthetic polymer appear first when natural rubber was heated with
sulphur to give a stable rubbery product (Goodyear 1839). But the
product is based on the expensive natural rubber

• A cheaper product made from Cellulose was first presented by

Alexander Parkes at the 1862 Great International Exhibition in London

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During the latter part of the 19th century, a rush was on
to find a replacement for ivory in billiards balls. The
game became so popular that thousands of elephants
were killed so that their valuable ivory could be
obtained. John Wesley Hyatt, an American, finally came
upon the solution in 1866 with celluloid.

Baekeland developed a hard resin

based on phenol and formaldehyde 3
in the early 20th century. Bakelites
achieved main commercial
significance in the 1920s.
Wallace Hume Carothers- head of
Dupont Lab- discovered Nylon and
many products were now produced
from the synthetic fibre in the 1930s.

Herman Staudinger investigated the structure of

these and many others macromolecules. Many of his
colleagues told him in the 1920s: “ there is no such
thing as a macromolecule, you are wasting your
time…”
Herman Staudinger received the Noble price
for his pioneering work in polymer chemistry
in 1953.

16
 What are polymers?- Definitions
Polymers are macromolecules, which are built up from repeating
units= monomers

Linear
x homopolymer
with x repeating
units

The word comes from Greek: poly means `many' and mer comes from
merous which means `parts'. Our word polymeric comes directly from the
Greek polumeres which simply means `having many parts'

If the number of repeating units is very small we talk about oligomers

17
A polymer is therefore a long
chain and can look quite
complex!

Polymers can also be build up by different monomers: Copolymer

Linear copolymer

18
Copolymers are made from two or more different monomers. Three types of
copolymers can be found:

1. Statistical copolymer
A-A-B-B-B-A-B-A-B-B-A-A A-ran-B
No definite sequence of monomers exists. Random copolymers are the
most common copolymers. Random copolymers behave usually different
from those of related homopolymers

2. Alternating copolymers
A-B-A-B-A-B-A-B-A-B-A-B- A-alt-B
These polymer can be prepared under very special circumstances

3. Block copolymers
A-A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B A-block-B
retain usually the physical properties of their homopolymers
7
Another type of copolymer are graft copolymers:

A mixture of two homopolymers prepared by simple mixing or

processing is called blend. Blends can have properties that are
different from their homopolymers. However, many homopolymers are
not miscible with each other and tend to phase separate

20
Linear polymers have a long chain as a skeleton. The monomers have
the functionality f=2. Consequently, each repeating unit is connected to
two other units

Branched polymers can be obtained by using polymers with functionality

f>2. Branched polymers contain a unit that is connected to more than two
other repeating units.

Branched polymers resemble the corresponding linear polymers in many of

the properties. However, heavily branched polymers might not be soluble
and can only swell in a solvent.
21
All chains are chemically linked in a crosslinked or network polymer. A
network polymer is never soluble but it can swell in solvents.

Swelling in a
solvent

A swollen network is
not a solid nor a liquid.
It behaves like a gel.

22
 Molecular weight of polymers- how big is a polymer?

Polymers typically have molecular weights between 20,000 g/mol (Da) and
2,000,000 g/mol (Da) (1 Dalton= 1 g/mol). This corresponds to around 200
to 20,000 repeating units (assuming a molar mass of 100 g/mol per
repeating unit:
M= X* MRU

M= Molecular weight, X= degree of

polymerisation= number of repeating units,
MRU= molecular weight of repeating units

In contrast to small organic molecules or

biological molecules such as proteins a
polymer does not have a fixed molecular
weight. A polymer consists of a
0 20000 40000 60000 80000 100000
distribution of macromolecules with
Molecular Weight different molecular weights
11
Polymers are polydisperse (in contrast to monodisperse). The broadness
(polydispersity) of the distribution can be decribed by a distribution function.
The polydispersity is dependent on the preparation technique of the polymer.
They are described by an average molecular weight:

The number-average molecular weight Mn uses the number based

statistical weight of each molecular weight

niMi
Mn i
ni
i

The weight-average molecular weight Mw uses the weight based

statistical weight of each molecular weight

wiMi nM 2
i i
i i
Mw
wi nM
i i
i i 12
What is the difference between both molecular weights?
In a distribution the heavier macromolecules might have the same number
as smaller macromolecules but their weight fraction is bigger than that of
smaller molecules. Consider this: you have a distribution with
macromolecules of 100,000 and 10,000 Da. You might have the same
number of molecules of each weight but the heavier molecules are 10
times bigger thus have a weight fraction that is ten times higher!
In polymer science we use the ratio of both average molecular weights to
decribe the polydispersity of a molecular weight distribution:

Mw
Polydispersity index PDI=
Mn

If all your macromolecules have the same molecular weight PDI= 1

(monodisperse)
Typically, most polymerisations have a PDI of 1.5 to 2.5 13
 Let’s have a look at an example! We have the following distribution:

A polymer sample consists of:

500 macromolecules with M= 10000

1000 macromolecules with M= 20000
500 macromolecules with M= 30000

500 * 10000 1000 * 20000 500 * 30000

Mn 20000
500 1000 500
500 * 100002 1000 * 200002 500 * 300002
Mw 22500
500 * 10000 1000 * 20000 500 * 30000

The difference is caused by the heavier statistical weight of larger molecules.

The number-based statistical weight of these 3 macromolecules is 0.25 : 0.5 :
0.25, the weight-based statistical weight is 0.125 : 0.5 : 0.375. 14
Let’s repeat together!
• What kind of copolymers do you know?
•What is the difference between number of repeating
units and degree of polymerisation?
•How does the solubility change from a linear polymer
to a branched polymer and network polymer?
•Can you calculate the polydispersity index of the
following molecular weight distribution?
25 mol-% 10,000 Da, 50 mol-% 50,000 Da, 25 mol-%
100,000 Da

15
Molecular Weight determination methods

• Why is the molecular weight important?

• The molecular weight effects the physical properties
• •Viscosity
• •Glass transition temperature and melting point
• •Modulus

physical property I II III

Molecular Weight
28
Molecular Weight is normally measured in solution
(some exceptions such as MALDI)

Absolute Methods:
The molecular Weight can be calculated directly from the measurement
-Endgroup Analysis
-Methods based on colligative properties
-Light scattering

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

29
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.

30
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)

31
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.

Vi

Vm

A B C
A) the polymers are too big, they cannot diffuse into the pore, polymers
above this size cannot be separated.
upper exclusion limit

C) the polymers are small enough to use all the available pore volume
lower exclusion limit

B) polymer diffuse into the pores according to their hydrodynamic volum2n0

separation occurs
The deeper a polymer can
diffuse into the pores the
longer it takes to pass the
column.
bigger polymers pass
the column faster
The time for a polymer to
pass the column is called
M1 M2
retention time, the
volume of solvent is M1>M2
called retention volume
Ve,1 Ve,2

20 22 24 26 28 30 32 34 36 38 40

Ve in minutes 21
GPC is a relative method:
the particles are separated according their hydrodynamic volume.
We need now a calibration curve to obtain the relationship between
the hydrodynamic volume and the molecular weight!

8 22

Polymer standards are

used (polymers with 6

known molecular weight)

and the retention time for log M 4

each standards is
measured 2
injection
calibration curve
0
0 10 20 30 40 50
Ve
 8

6 From the GPC chromatogram to

the molecular weight
distribution
log M

2
injection

0
0 10 20 30 40 50
Ve

10000 20000 30000 40000 50000

Molecular Weight

0 10 20 30 40 50
retention time

35
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.

36
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?

37
The synthesis of polymers
Polymers are usually prepared via polymerisation of monomers via
step-growth or chain growth polymerisation.
Chain growth polymerization:
•Free Radical polymerization: most common polymerization, can
be carried out in bulk, solution, suspension and emulsion
•Ionic polymerization: anionic and cationic
•Insertion polymerization: Ziegler-Natta Polymerization
•Ring-opening polymerization
•Controlled free radical polymerization: RAFT (reversible addition
fragmentation transfer), ATRP (atom transfer radical
polymerization), NMP (nitroxide mediated polymerization)
Step growth polymerization:
26
•Polycondensation and polyaddition
Chain-growth polymerisation
Free radical polymerisation

Most chain-growth polymerisations deal with vinyl polymers derived from

monomers with the general formula: H2C=CR1R2
Vinyl monomers are polymerised leading to the formation of a carbon
atom backbone (homochain)

R1 R1
Polymerisation CH2
n H2C C C

R2 n
R2

Note: Not all compounds with double bonds can be polymerised!

27
The name of the polymer is derived from the monomer by adding the prefix
poly.

Monomer Polymer
ethylene CH2 polyethylene
H 2C CH 2 CH2
n

styrene polystyrene
H 2C CH
CH 2
CH
n

H2C CH acrylonitrile CH2

CH
polyacrylonitrile
n
CN CN
H

O methyl acrylate CH 2
C
n
Poly (methyl acrylate)
O C
O O

CH 3
CH 3

H2C CH vinylchloride CH 2 polyvinylchloride

CH

Cl n
Cl
CH3 CH 3
28
H 2C C methyl CH2
C poly (methyl
methacrylate methacrylate)
C O n
C
O O O

CH3 CH3
 Radical polymerisation (as well as ionic polymerisation) has three
principal steps:
•Initiation of active monomer with radicals
•Propagation or growth of the active (free-radical) chain by sequential
addition of monomer (macroradical)
•Termination of active chains

INITIATION
The polymerisation is started using radicals. Different sources of radicals
are known such as heat, light, -radiation or certain compounds, which are
known to generate radicals.
Note: A radical is a single electron. Instead of an electron pair the molecule
has a single electron, which has a high tendency to react to rebuild the
electron pair and electron octet, respectively.
41
The most common types of initiation of radical polymerisations are:

•Thermal initiation: thermally decomposing initiators, e.g. azo

compounds, peroxides, per-esters
The initiator decomposes into two radicals upon heating
Azoinitiator (Example: 2,2-azobisisobutyronitrile (AIBN))

CH3 CH3 CH3

T
H3C C N N C CH3 2 H3C C N2

CN CN CN

AIBN is the most common azoinitiator. Other azoinitiators are known,

which can decompose at a different rate at different temperatures.

42
 CH3 CH3 O CH3 CH3 O

NC N N CN N N
1. 2,2-azobisisobutyronitrile (AIBN)

CH3 CH3
O
CH3 CH3
O 2. dimethyl 2,2-azobisisobutyrate
(MAIB)
1 2
3. 1,1-azobis(1-cyclohexanenitrile)
CH3 CH3 4. azobis-2,4-dimethylvaleronitrile
N N H3C N N CH3

CN CN CN CN
CH3
CH3

3 4

Peroxides: have two joining oxygen atoms

O O
O O

O O 1. di-tert-butyl peroxide
1
2
2. benzoyl peroxide
O
3. di-tert-butyl peroxalate
O H
O O
O 4. cumene hydroperoxide
O O

O 4

31
3
 Peroxides decompose similar to azocompounds into two radicals:
O O O
heat
2

O O O

But the two radicals can decompose further: For example, the
decomposition of benzoyl peroxide leads to the formation of
benzoyloxy and phenyl radicals

-CO2
O

32
•Self initiation (thermal polymerization): monomers themselves can start
free radical polymerization at elevated temperature without added initiators
or initiating impurities, e.g. styrene (this is not the same as spontaneous
polymerization, which can be caused by light or impurities)

-H

(1) (2) (3)

•Redox initiation: redox system, that generates radicals (low activation

energy, therefore suitable for polymerization at lower temperatures)
e.g. Fe2+ + HO-OH Fe3+ +HO- + OH

•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
Initiator I1 + I2 33
 PROPAGATION
The radical is highly reactive and reacts with a monomer (association).
The association or start reaction is usually part of the initiation. This new
radical continues reacting with monomer to form a macroradical. The
monomer is mainly added head-to-tail.

C H3 R1 C H3 R1

H2C C
ka
H3C C H3C C C H2 C

R2
CN CN R
R
R M I-M

tail head C H3 R1 R1 R1
R1
kp
Head: part with H3C C C H2 C n H2C C I C H2 C C H2 C

bigger CN R2 R2 R2
n
R2
substituent
I-M nM I-Mn+1
34
Here is an example with styrene
CH3 CH3 H

H3C C H2C CH
H3C C CH2 C

CN CN

CH3 H CH3 H

H3C C CH2 C H2C CH

CH3 C CH2 CH CH2 C

CN CN

CH3 H CH3 H

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

CN CN

CH3 H CH3 H

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

CN CN

And so on…….. 35
Free radical polymerization is normally not stereospecific. Consequently,
mainly atactic polymer chains are formed.

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
on one side of the backbone or the substituents alter strictly either to one
or the other side.)

48
How long do the chains grow?
Answer: Until they find another radical to react with!

TERMINATION

combination disproportionation

49
Two different kind of termination reactions are known:

A) combination

R1 R1 R1 R1 R1 R1 R1 R1
ktc
I CH 2 C CH 2 C C CH 2 C CH 2 I I CH 2 C CH 2 C C CH 2 C CH 2 I

x y x y
R2 R2 R2 R2 R2 R2 R2 R2

Two macro radical form one chain with the degree of polymerisation x+y
B) disproportionation

R1 R1 R1 R1 R1 R1 R1
ktd R1

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

x y x y
R2 R2
R2 R2 R2 R2 R2 R2

Two macro radicals form two polymer chains with a chain with degree of
polymerisation= x and methyl endgroup and a chain with degree of
polymerisation= y and a double bond endgroup.
50
In radical polymerisation we have 3 steps: Initiation, propagation,
termination.

Let’s take acrylonitrile and try to repeat what

is happening during the polymerisation of
this monomer initiated with benzoyl H2C CH
peroxide!
CN
What is the difference to the polymerisation
initiated with AIBN? How is the end product
different!

Without knowing anything about the kinetics of the polymerisation can

you guess how you could influence the molecular weight or overall
degree of polymerisation of the polymer?

51
Kinetics of free radical polymerisation

We have three parts:

k
Initiation: I→d 2 R
R + M → RM (Start reaction or association)

kp
Propagation: RM + M → RM2
kp
RM2 + M → RM3
kp
RM3 + M → RM4
kp
RMn + M → RMn+1

ktc
Termination: RMn + RMm → RMn+m
ktd
RMn + RMm → RMn + RMm kt= ktc+ktd
52
INITIATION: How many radicals are available?
We might have a certain concentration of initiator in our system but not all
initiator molecules decompose immediately into radicals.

1. Dissociation rate constant kd

The initiator dissociates slowly over time at a certain rate:

I kd 2R
kd is dependent on the environment of the initiator (solvent) and even more
on the temperature
kd= A exp (-Ea/RT)

initiator solvent T/ °C kd/ s-1 Ea/ kJ mol-1

AIBN Benzene 40 5.44×10-7 128
Benzene 70 3.17×10-5
Toluene 70 4.00×10-5 121 41
2. Initiator efficiency f
Not all radicals might be able to initiate a polymerisation. Two radicals
might combine again to form an inactive species

CH 3

C CH 3
CH 3 CH 3
NC N N
CN -N2
H3C C NC CH 3 + NC CH 3
R
CH 3

AIBN

growing
chain

CH 3 CH 3

NC CN

CH 3 CH 3

stable molecule that cannot initiate

macromolecular growth

54
Solvent effects or high viscosity prevent that the radicals escape from each
other→ two radicals react

heat Cage
effect

AIBN surrounded by Formation of two Recombination of two

monomer/solvent radicals radicals

The initiator efficiency is between 0 (no radicals) and 1 (all possible radicals
available)

The rate of initiation Ri can be expressed as

d[R ]
Ri = = 2fkd [I]
dt

The amount of radicals formed per time unit d[R ]/dt is therefore proportional
to the initiator concentration and the constant kd, which tells you how fast the
initiator decomposes.
55
PROPAGATION: How fast is monomer converted into polymer?

d[M]
RMn + M → RMn+1 Rp k p [M ][M]
dt

The amount of monomer that reacts at any given time is proportional to

the amount of radicals/ macroradicals and the amount of monomer.
This means that the rate of polymerisation Rp is higher in the
beginning of the polymerisation. The polymerisation slows down when
most of the available monomer has been consumed.
The propagation rate coefficients kp is a material constant and tells
you how fast a particular monomer propagates (how fast the monomer is
added to the macroradical)

56
All propagation rate coefficients are temperature dependent
Monomer kp / L mol-1 s-1
Styrene 160 (40 C)
H 2C CH
340 (60 C)
631 (80 C)

methyl methacrylate 472 (40 C)

CH3

H2C C
822 (60 C)
C O

O 1350 (80 C)
CH3

methyl acrylate
H2C CH
22500 (40 C)
C O

O 33700 (60 C)
45
CH3
48000 (80 C)
 TERMINATION: When do two macroradicals react with each
other?
Firstly, two radical have to diffuse towards each other:

Since diffusion is dependent of the size of the chain (molecular weight) or

the viscosity of the solution it gets harder and harder for two chains to
terminate.
But what is more important is the amount of macroradicals available.
With increasing macroradical concentration the termination of two
growing polymer chains is more likely

58
 The rate of termination Rt is therefore proportional to the amount of
macro radicals:
RMn + RMm → RMn+m d[M ] 2
RMn + RMm → RMn + RMm
Rt 2k t [M ]
dt

The rate of the termination reaction, characterized by the termination rate

coefficient kt, depends on a range of factors:
1. the viscosity of the reaction mixture
2. the chain length of the terminating free macroradicals
3. the polymerisation temperature
4. the polymerisation pressure
5. the monomer conversion

59
The higher the monomer to polymer conversion in a given polymerisation,
i.e. the higher the viscosity, the slower the termination reaction

H
CH2
O C

MA n
8 O C
O O
log (kt / L mol-1 s-1)

CH3
CH3

7
MA PMA
H
CH 2
C
O
n

6 DA O
O
C
O

0.0 0.2 0.4 0.6 0.8

Monomer Conversion

DA PDA

60
 With high conversion and therefore the formation of a lot of polymer
the solution gets very viscous. The macroradicals cannot terminate
impossible
becausefor them to diffuse fast enough.
it is

At the same time initiator decomposes and forms radicals. Consequently we

will have more and more radicals in the solution, which can propagate: The
reaction mixture produces more and more heat, the heat leads to higher kp,
the polymerisation goes faster, more heat, higher kp,…………
auto-acceleration: gel or Norrish-Trommsdorff-effect.

Gel effect
Rp

conversion
61
 The gel effect has an influence on the molecular weight.
The molecular weight of the polymers is roughly the same throughout the
polymerisation (small decline).
The chains cannot terminate (kt decreases) but the macroradicals still add
more and more monomer units (the monomers can still diffuse) → higher
molecular weight

Gel effect
Mn

conversion

62
 SUMMARY: The radical polymerisation is divided into 3 steps:
d[R ]
Ri= = 2fkd [I]
A) Initiation dt
d[M]
B) Propagation Rp kp [M ][M]
dt
d[M ] 2kt [M ] 2
C) Termination Rt
dt

t0: monomer and initiator

t1: under the influence of heat or light a initiator

molecule decomposes

63
t3: when AIBN is used two radicals are formed, which add to
a monomer (INITIATION)

the macroradical is growing by adding more and more

monomer (PROPAGATION)

t4: two radicals react with each other under

TERMINATION (by disproportionation or combination)

t5: a new initiator decomposes followed by propagation and

termination

Note: the radical does not live longer than milliseconds.

64
From a practical point of view a polymer chemist is interested in two things:
1. The conversion of the polymerisation (how fast is your polymerisation)
2. The molecular weight

1.The rate of polymerisation

d[M]
Rp k p [M ][M]
dt
Rp is the monomer consuming step and tells you how much monomer
polymerises at any point in time (- d[M]/dt).
The central question is now: What is the macroradicals concentration?

65
Bodenstein’s steady state principle (steady state assumption):
Shortly after the polymerization started, as many radicals disappear by
termination as they are generated by initiation. This means that we have a
constant radical concentration throughout the polymerisation:
Ri = Rt

radical concentration in steady state

2 k d f[I]
2fk d [I] 2k t [M ] [M ]
kt

d[M] k d f[I]
Rp k p [M ][M] k p [M]
dt kt

This is an important equation!!!!

66
 Let’s work with this equation:
We polymerise styrene (bulk) at 60 ºC with varying AIBN
concentrations:

f=0.5, kt=1.2·108 L mol-1 s-1, kd=1.2·10-5 s-1, kp= 340 L mol-1

s-1
The concentration of AIBN is 1∙10-2 mol L-1, 1∙10-3 mol L-1 or
1∙10-4 mol L-1
Calculate the monomer conversion x after 2 h reaction time for all three
initiator concentrations. x= ([M]0-[M]t)/[M]0

First, we have to integrate this equation from time= 0 to time t= 2h and

monomer conversion M0 to Mt

d[M] k d f[I] IMPORTANT: We make a big assumption in

kp [M] this calculation: We assume that the
dt kt
concentration of initiator does not change.
This is not true, but we can neglect the
ln[ M] [M]
[M]
t
k p k d f[I] [t]tt 0 changes for this example!
o
kt
67
unknown.
Now, weAshave
a solution, we prepare
the following different
problem: kp ofsamples with different
this polymerisation initiator
may be
concentrations and measure the conversion after a reaction time of 2 h

1.[I]= 0.015 mol/L x= 7.72%

2.[I]= 0.0015 mol/L x= 2.24%
3.[I]= 0.00015 mol/L x= 0.72%
4.[I]= 0.000015 mol/L x= 0.20%
Integrate Rp from [M]0 to [M]t (monomer concentration in the beginning and
at the time t) and from t=0 to t=2h

Plot [I]1/2 against ln [M ]t (=ln 1 , x= conversion)

[M ]0 1 x
Calculate kp from the slope (use f=0.5, kt=1.2·108 L mol-1 s-1, kd=1.2·10-5 s-1)

68
 2. Molecular Weight
The molecular weight is directly related to the kinetic chain length.
The kinetic chain length n is defined as the number of monomer units
consumed per active centres.

Rp Rp
R St Rt
k p [M ][M]
2k t [M ]2

k d f[I]
the macroradical concentration is given as [M ]
kt
kp [M]
2 fk d k t [I]

Now we can calculate how long a chain can grow before being terminated.
The kinetic chain length gives you the number of monomer units added to a
initiating radical unit. 57
The average degree of polymerisation and therefore the molecular weight is
depended on the mode of termination

Xn 2
termination by combination
Xn termination by disproportionation

The mode of termination is determined by the monomer used:

Styrene : mainly combination

Methyl methacrylate: mainly disproportionation

NOTE: The molecular weight can only be calculated from the kinetic
chain length when there are no chain transfer reactions present!

70
 SUMMARY: conversion and molecular
weight of free
radical polymerisation
d[M] k d f[I]
Rp kp [M]
dt kt

[M]: the rate of polymerisation increases with monomer concentration

→dilution with monomer slows the reaction down and at higher
conversion the polymerisation slows down (less monomer)
[I]: a four-fold increase in initiator concentration doubles the rate of
polymerisation

71
In the absence of side reactions the molecular weight can be calculated
from the kinetic chain length

kp [M]
2 fk d k t [I]

→ the molecular weight increases with a high [M] to [I] ratio

A high kp and a small kt leads to high molecular weights

72
 Let’s calculate the molecular weight of polystyrene (assuming
the absence of side reactions):

f=0.5, kt=1.2·108 L mol-1 s-1, kd=1.2·10-5 s-1, kp= 340 L mol-1 s-1

The concentration of AIBN is

a) 1∙10-2 mol L-1
b) 1∙10-3 mol L-1
c) 1∙10-4 mol L-1

What influence on the kinetic chain length would have

a) A decrease of monomer concentration
b) An increase in temperature
c) An increase in viscosity
d) An increase in reaction time
73