POLYMERS & FORMULATION

Step polymerization polymers

A2 + B2 systems

A A B B

Polyesters
Polyamides
Polyurethanes

27.10.2021 Lecture JF STUMBE 1

 POLYMERS & FORMULATION
Polycondensation:
example of polyethylene terephtalate (PET)

O O

HO OH Cat. * O O
OH + O
HO ou *
O O n
300°C, vide
O O

OMe OMe

2 steps: Tg ~70°C
• oligomerisation
• final condensation (HMM) Tm ~264°C

27.10.2021 Lecture JF STUMBE 2

 POLYMERS & FORMULATION

Polyetylene terephtalate (PET)

Characteristics & properties

• 25.000 < Mn < 50.000 g/mol

• highly crystallizable (theoretically)
But
• slow crystallisation rate (Tg ~70°C)
 possibility to obtain 100% amorphous PET (bottles)

• Crystalline PET requires hot mould

• Crystalline PET textile fibers obtained under stretch

A PET bottle which has

been heated by a
candle and has
recrystallized, making it
opaque

27.10.2021 Lecture JF STUMBE 3

 POLYMERS & FORMULATION

Crystallization behavior of PET

 7 PET prepared by cooling down a molten sample at various
cooling rates (from 10K/min to 60 K/min)

PET PET
at glassy state at molten state
(100% amorphous) (viscous liquid)
Example: bottle

Melting:
OR above
Tg
& Tm
Semi-crystalline PET
(max of
crystallization) 6 samples cooled down
Example: fiber
at various cooling rates
From 10K/min to 60K/min

27.10.2021 Lecture JF STUMBE 4

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

 6 PET prepared by cooling down a molten sample at various
cooling rates (from 10K/min to 60 K/min)
 Each sample now analyzed with DSC: all samples heated in
calorimeter at +10K/min

Tm
Heating
10K/min
Tg

Tc

27.10.2021 Lecture JF STUMBE 5

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

Tm

Heating
10K/min
Tg

Tc

27.10.2021 Lecture JF STUMBE 6

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

Tm

Heating
10K/min
Tg

Tc

27.10.2021 Lecture JF STUMBE 7

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

Tm

Heating
10K/min
Tg

Tc

27.10.2021 Lecture JF STUMBE 8

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

Semi-crystalline Semi-crystalline PET
PET (max of PET
(partial crystallization) at molten state
crystallization)

Tm
Tg
A fraction of rubbery Rubbery
Glassy Fully molten
Amorphous
Rubbery Tc amorphous Amorphous
crystalline
Amorphous phase crystallizes phase
phase phase + larger Phase
+ crystalline + crystalline phase  Viscous liquid
phase
+ crystalline phase  Max of crystallization crystalline
phase

27.10.2021 Lecture JF STUMBE 9

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

Tm

Heating
10K/min

Tg

Tc

27.10.2021 Lecture JF STUMBE 10

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

If PET slowly cooled down during processing (10K/min)

 no crystallization observed when heated (during measurement)
Explanation: Plenty of time to crystallize during cooling phase of processing

If PET quickly cooled down during processing (60K/min)

 crystallisation occurs upon heating (during measurement)
Explanation: time to crystallize during cooling phase of processing

27.10.2021 Lecture JF STUMBE 11

 POLYMERS & FORMULATION

Crystallization behavior of PET at various cooling rates

Fast cooling down
(below Tg) PET
at
glassy state
(100%
amorphous)
PET at molten state

slow cooling down

(below Tg) Semi-crystalline
PET
(max of
crystallization)

PET at molten state

27.10.2021 Lecture JF STUMBE 12

 POLYMERS & FORMULATION

Crystallization of Polyetylene terephtalate (PET)

slow cooling down
(below Tg)
Semi-crystalline
PET
(max of
crystallization)

PET at molten state

Less slow
cooling down
Semi-crystalline
(below Tg) PET
(partial
crystallization)

PET at molten state

27.10.2021 Lecture JF STUMBE 13

 POLYMERS & FORMULATION

Crystallization
of PET
under stretch

Extrusion process

27.10.2021 Lecture JF STUMBE 14

 POLYMERS & FORMULATION

Crystallization of PET under stretch

Spinning speed Spinning speed

< 4200 m/min > 6000 m/min

Faster spinning speed (formation of the wire/filament)  higher crystallization ratio

27.10.2021 Lecture JF STUMBE 15
 POLYMERS & FORMULATION

Polyetylene terephtalate (PET)

Applications • Food packaging
• Films (boiling bags,
2/3: fibers trays,…)
¼: bottles • Bottles for mineral water
• Bottles for sodas
• Other drinks
~60 Mio tonnes • Textile fibers, stuffed winter
clothers, …

27.10.2021 Lecture JF STUMBE 16