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Natural polymers
Artificial polymers

Synthetic
polymers

Préhistoire XIXème XXème

 Leather, Animal fibers (Wool)
Wood, Paper, Straw
Vegetable fibers (Cotton)
Charles Goodyear (1800-1860)

1842: Vulcanization of rubber

NR (Natural Rubber)
Alexander Parkes (1813-1890)

Pratent 1856 : Parkesine (1866 :

 objects made of Parkesine
CN (Cellulose nitrate)

Parkesine
1862
CN-P

Première
matière
plastique artificielle
Celluloid (CN)
Celluloid (CN)
Brevet 1908 : Insoluble condensation products of phenolhttps://worldwide.espacenet.com
and formaldehyde
Léo Baekeland (1863-1944)
Bakélite : 1 st synthetic plastic (1908)
Hermann Staudinger (1881-1965)
Macromolecular chemistry (1920)
Nobel prize in Chemistry(1953)
21st century, need to bio-source molecules

Lactic acid
Macromolecular chemistry
 Macromolecular chemistry
A macromolecule, or macromolecular chain, is made up of a very large
number of atoms linked by strong bonds.
 Macromolecular chemistry
A polymeric material consists of a very large number of macromolecules
linked together by weak bonds, sometimes strong bonds, and by
entanglement.
Macromolecular chemistry
 Macromolecular chemistry
A macromolecule is the result of chemical reactions that assemble small
molecules, monomers. These reactions constitute polymerization.

C
H
O
N
Cl
F
Macromolecular chemistry
Double bond C=C Chain polymerization

Carboxyle group (acides carboxyliques)

Staged
Hydroxy group (alcools) polymerization
Primary amino group (amines)
R1 to R4 denote an H or and alkyl (-CH3, -CH2-CH3, -CH2-CH2-CH3, etc.)
R denote and alkyl (-CH3, -CH2-CH3, -CH2-CH2-CH3, etc.)
Macromolecular chemistry

Stage
Polymerization
Macromolecular chemistry
Chain polymerization, example of ethylene
Macromolecular
Chain polymerization, example of ethylene
chemistry
 Macromolecular chemistry
Chain polymerization, example of ethylene
Etape 1 : Initiation

Benzoyl peroxide (initiator A) .

Radical (R )

One molecule, the initiator (here a peroxide), breaks down into 2 radicals, very
reactive species.
 Macromolecular chemistry
Chain polymerization, example of ethylene
Step 1 : Initiation

.
+ H2C=CH2 -CH2-CH2

A radical will reat with a monomer. The double bond breaks. The radical moves to
the end of the chain.
 Macromolecular chemistry
Chain polymerization, example of ethylene
Step 2 : Propagation

. .
O-CH2-CH2 + H2C=CH2 O-CH2-CH2-CH2-CH2

. .
O-CH2-CH2 + n H2C=CH2 O-(CH2-CH2)n-CH2-CH2

Each radical species thus formed will in turn react with a monomer. The operation is
repeated n times
 Macromolecular chemistry
Chain polymerization, example of ethylene
Etape 3 : Terminaison

.
O-(CH2-CH2)n-CH2-CH2 +

O-(CH2-CH2)n+1-O

A growing chain can react with one of the radicals initially formed. The
macromolecule is then complete.
 Macromolecular chemistry
Chain polymerizarion, example of ethylene
Step 3 : Terminaison

. .
O-(CH2-CH2)n-CH2-CH2 + CH2-CH2-(CH2-CH2)p-O

O-(CH2-CH2)n+p+2-O

A growing chain can also react with another grwoing chain. The macromolecule is
then complete.
 Macromolecular chemistry
Chain polymerization, example of ethylene

Polyethelene
PE

As the molecules are very large, the ends of chains are not mentioned in the
polymer formula. n is the degree of polymerization.
Macromolecular
Chain polymerization, other examples
chemistry

Propylene
CH3-CH=CH2
Macromolecular chemistry
Chain polymerization, ecample of ethylene

Polypropylene

PP
Macromolecular
Chain polymerization, other examples
chemistry

Styrene
C6H5-CH=CH2
Macromolecular chemistry
Chain polymerization, example of ethylene

Polystyrene
PS
Macromolecular chemistry

Stage
Polymerization
Macromolecular chemistry
Staged polymerization, example of polyesters

Esterification reaction
Macromolecular chemistry
Staged polymerization, example of polyesters

Ethylene glycol Terephathalic acid

Macromolecular chemistry
Staged polymerization, example of polyesters

-
+

+
- H2O

Esterification reaction
Macromolecular chemistry
Staged polymerization, example of polyesters

-
+

+
- H2O

Esterification reaction
Macromolecular chemistry
Staged polymerization, example of polyesters

( )n

Polyethylene terephthalate PET

Macromolecular chemistry
Staged polymerization, example of polyesters

Polyester
fibers

Polyethylene terephthalate PET

Macromolecular chemistry
Staged polymerization, example of polyamides

+ H2O

Amine carboxylic Amide

acid

Amidification reaction
Macromolecular chemistry
Staged polymerization, example of polyamides

Hexamethylenediamine + Adipic acid

-
 Macromolecular chemistry
Staged polymerization, example of polyamides

Hexamethylenediamine +
-
Macromolecular chemistry
Staged polymerization, example of polyamides

( )n

Polyamide 6.6 PA 6.6 (nylon 6.6)

 Macromolecular chemistry
Staged polymerization, example of polyamides

Polyamide (nylon)
Thermoplastic polymers
1 2
Valence 2 monomers

1
2 Linear and saturated macromolecles. The chains are
only linked together by weak bonds
1 2

Thermoplastics
2
1
 Thermoplastic polymers
PS, PVC, PE, PP, PA, PMMA, PTFE,
PET, POM, PC, PLA, etc.
Polymers which plasticize when heated. They are therefore
easy to format and recycle.
Thermoplastic polymers
PS, PVC, PMMA, PET, PC
Transparents

Translucent to opaque, white

PE, PP, PA, PTFE, POM, PLA
 Thermoplastic polymers
PS, PVC, PMMA, PET, PC
Transparents
Polymer PS PVC PMMA PET PC PE PP PA PTFE POM PLA

Tg (°C) 90/100 80/88 100/110 60-84 142-158 -125/-90 -14/-6 44/56 107/123 -18/-8 52/60

Tf (°C) - - - - - 98/137 161/170 210/220 315/339 160/184 145/177

Translucent to opaque, white

PE, PP, PA, PTFE, POM, PLA
Thermoplastic polymers
PS, PVC, PMMA, PET, PC
Amorphous
Transparents

Visible light passes through the material

without being absorbed or scattered.
 Thermoplastic polymers
Amorphous thermoplastics: PS, PVC, PMMA, PET, PC

Low
Glassy state Rubbery state viscosity Degradation

Other
Thermoforming
techniques
20°C Tg

Utilisation forming

Polymer PS PVC PMMA PET PC

Tg (°C) 90/100 80/88 100/110 60-84 142-158

Thermoplastic polymers
Semi-crystalline

Visible light is not absorved but is

diffused by the crystals.

Translucent to opaque, white

PE, PP, PA, PTFE, POM, PLA
Thermoplastic polymers

Translucent to opaque, white

PE, PP, PA, PTFE, POM, PLA
 Thermoplastic polymers
Semi-crystalline thermoplastics: PE, PP, PA, PTFE, POM, PLA

Glassy state Rubbery state molten state Degradation

PTFE PA PP PE forming
PLA POM
Tg Tf
-50°C Utilisation
Utilisation
Polymer PE PP PA PTFE POM PLA

Tg (°C) -125/-90 -14/-6 44/56 107/123 -18/-8 52/60

Tf (°C) 98/137 161/170 210/220 315/339 160/184 145/177

 Thermoplastic polymers
Amorphous thermoplastics: PS, PVC, PMMA, PET, PC
The heat deflection temperature and the Vicat softening temperature are two
properties which provide information on the thermal resistance of a plastic.

For amorphous polymers, they are slightly lower than then Tg.

For semi-crystalline polymers, they will be close to the Tf.

The ISO 75 and ISO 306 standards describe the tests to be carried out to
characterize these properties.
 Thermoplastic polymers
Amorphous thermoplastics: PS, PVC, PMMA, PET, PC
The hot melt index (MFI, MFR or MVR for Melt Flow Index, Melt Flow Rate or Melt Volume
Rate) is the property that tells us about the fluidity of the molten material.

This property is extremely important in qualifying a grade of material for a shaping technique.

The ISO 1133 standard describes the tests to obtain this property.
Thermosetting polymers

The chains are linked together

by strong bonds. They then
form a three-dimensional
network.
The polymer is said to be cross-
linked.
 Thermosetting polymers
PF, MF, UP, EP, PUR, UF, etc.
The materials, once crosslinked, do not plasticize under the
action of heat. Their shaping must therefore be carried out
before crosslinking. It is therefore very difficult to recycle them
They are amorphous materials with Tg. above
ambient temperature.
Thermosetting polymers
Example of unsaturated polyesters (UP)

Maleic Phthalic Ethylene Diethylene

anhydride anhydride glycol glycol
Thermosetting polymers
Example of unsaturated polyesters (UP)

Dissolved in

Dissolved in then chain polymerization with

the addition of an initiator and catalyst,
Thermosetting polymers
Example of polyepoxides (EP)

Bisphénol A Epichlorohydrin

(
Thermosetting polymers
Example of polyepoxides (EP)

Valence 4

(
Valence 2
Thermosetting polymers
Example of phenoplasts (PF)

Formaldehyde Phenol
Thermosetting polymers
Example of aminoplasts (MF)

Formaldehyde Melamine

MF
Thermosetting elastomers (rubbers)

The chains are linked together by

strong bonds, but less than in the
case of a thermosetting polymer.
The polymer is said to be
vulcanized..
 Thermosetting elastomers (rubbers)

NR, IR, CR, BR, IIR, NBR, SI, etc.

The materials, once vulcanized, do not plasticize under the
action of heat. Their shaping must be done before
vulcanization. It is therefore very difficult to recycle them.

They are amorphous materials with a Tg below

room temperature
Thermosetting elastomers (rubbers)
Example of polyisoprenes (NR, IR)

+
Isoprene
Polyisoprene Sulfur
Copolymères
Copolymères
Copolymers

Mixture Additive
 Copolymers
Example of styrene copolymers

Property set 1

Styrene (S) Polystyrene (PS)

Homopolymer (SSSSSSSS)

Property set 2

Butadiene Rubber(BR)
Butadiene (B) Homopolymer
(BBBBBBBB)
 Copolymers
Example of styrene copolymers
SSSSSSSSSSSSBBBBBBBBBBBBBBSSSSSSSSSSSSSSSBBBBBBBBBBBBBBBBB
Block copolymer Property set 3

SSBBBSSSSBSBBSSBBSSBBBBSBBSSBBSSSSSBSSBBBSSSBBBSSBBBBBSBBB
Statistical copolymer(random copolymer)
B Property set 4 B
B B
B B
B B
SSSSSSSSBSSSSSSSSSSSSSSSBSSSSSSSSSSSSSSSSSSSBSSSSSSSSSSSSSSS
B Branched copolymer (graft copolymer) B
B Property set 5
B
 Copolymers
Example of styrene copolymers
SSSSSSSSSSSSSSSSSSSSSSSSSBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB
Block copolymer

SB
 Copolymers
Example of styrene copolymers
SSBBBSSSSBSBBSSBBSSBBBBSBBSSBBSSSSSBSSBBBSSSBBBSSBBBBBSBBB
random copolymer

SBR
 B

Copolymers B
B
Example of styrene copolymers B
SSSSSSSSBSSSSSSSSSSSSSSSBSSSSSSSSSSSSSSSSSSSBSSSSSSSSSSSSSSS

PS-HI
B graft copolymer
B
B
 Copolymers
Example of styrene copolymers

SAN
Styrene AcryloNitrile
 Terpolymers
Example of styrene copolymers

Acrylonitrile (A) Butadiene (B) Styrene (S)

ABS
Acrylonitrile Butadiene Styrene
Block terpolymer
Terpolymers
 Copolymères
Example of styrene copolymers
SSSSSSSSSSSSSSSBBBBBBBBBBBBBBBBBBBBBSSSSSSSSSSSSSSSSSSSSSSSSSS
block copolymer

SBS
TPE :Thermoplastic
elastomer
 Copolymers
Example of propylene / ethylene copolymers (bumper)

(block copolymers)

(random copolymer)
 Copolymers
Two-phase EPR material
in PP matrix
 Polymer mixtures
Polymer A
property set 1

Polymer A+B
Property set 3

Polymer B
property set 2
Polymer mixtures

ABS+PA
Polymer mixtures

TPO : PP+EPDM
TPO : ThermoPlastic Olefins (TPE)
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 Additives
Plasticizers (XX-P)

Phthalate
 Additives
Stabilizers
The degradation of a polymeric material is due to the breaking of chains, itself
due to an input of energy (chemical, thermal, photo- or radiochemical) which
takes place during processing or use.

The different types of degradation:

- Hydrolytic degradation (H2O)

- Oxidative degradation (O2)
- Photochemical degradation (UV)
- Thermal degradation (heat)
- Their combinations (thermo-oxidation, photo-oxidation)
 Additives
Stabilizers
The stabilizers make it possible to slow down or limit this degradation.
These are generally organic molecules used in the formulation of
materials.
 Additives
Flame retardants

The European RoHS directive limits PBBs and PBDEs,

halogenated flame retardants (CMR: carcinogens, mutagens and
reprotoxic) to 0.1%.
polyolefins

PE-LLD PE-LD PE-HD PE-UHMW PE-X

Linear low density PE Low density PE Very high molecular mass PE Crosslinked PE
High density PE

PP fibers PE-E or PP-E Foam

Spectra® fibers PE-UHMW

EPDM
PP (homo) PP (Rand. copo) PP-I (block copo.) Ethylene-Propylene-Diene Monomer
Vinylics

PVC-U PVAC PVB

Unplasticized or rigid PVC Poly (vinyl acetate) Poly (vinyl butyral)
Vinyl chloride / acetate prepared from PVAL
random copolymer
vinyl

EVAC EVOH PVC-P PVC-C

Ethylene-vinyl acetate Ethylene vinyl alcohol Plasticized or flexible Chlorinated
Statistical copolymer PVC PVC
random copolymer of PVAL
Ethylene vinyl alcohol
Styrenics

PS PS-HI SB SAN ASA

PS standard or ‘’cristal’’ Styrene-Butadiene AcryloNitrile-Styrene-
Block copolymer Random copolymer
graft copolymer Acrylate Terpolymer
Styrene-Butadiene Styrene-AcryloNitrile

ABS PS-E
AcryloNitrile-Butadiene-
Expanded PS
Styrene Terpolymer