Lecture AZB - Stumbé 2021-2022 Introduction To Polymers

Year 2021-2022
POLYMERS & FORMULATION
Pr. Jean-François STUMBE
Université de Haute Alsace

LPIM-ENSCMu
FRANCE
jean-francois.stumbe@uha.fr
25/10/2021 Lecture Prof. JF STUMBE 1

Polymers: Everywhere in our day-life !
Plastics Paints
Varnishes Automotive
Adhesives
Construction
Glues
Daily care Cosmetology

Food industry
Medecine Textile
Composites

Elastomers
Adhesives
Foams
Coatings
Sealants


Fate of plastics after use???? Not sustainable
« Plastic continent »
3,5 Mio t (80% Plastic)
750000 pieces / km2

Natural polymers Synthetic polymers

 Polysaccharides
 Thermoplastics
(cellulose, hemicellulose,
 Thermosets
alginates…)
 Functional polymers
 Lignins
 Effect polymers
 Natural rubber (latex)
….
 Proteins
(gelatine, wool, …)

Natural polymers
Natural rubber Cellulose Lignins Vegetable oils
HO OH
OH
R O R
OMe OMe
OH O O
OMe
O MeO
OH HO
O
HO
OH HO
OH O
OH HO
O
O
OH O
O OMe
MeO O
*
* n * HO O O O
OMe
O
OH n * HO OMe
OH O
O
25/10/2021 Polymers Lecture Prof. JF STUMBE Not polymers 7

« Visibles » « non visibles » polymers

Polymeric Materials Formulations / additives
Plastics (PE, PP, PS, PA,..) Functional polymers

Resins (UPES, EP, PU,…) Thickeners / gelifiers
Elastomers (NR, NBR, BR,..) Dispersing / émulsifiers
Stabilizers
Textile (Nylon, coton,..) Complexing agents
Oils (silicones,..) ….
Cellulose, starch

Organization of the lecture
I. Reminders – Definitions – Basics of macromolecular

chemistry
II. Compounding of thermoplastic materials – additives
III. Thermoset materials
IV. Emulsions: from paints to cosmetics
V. Formulation and deformulation

Detailed plan
- General information & definitions about polymers (def, Tg, Tm,…),
introduction to mechanical properties (~3 hrs)
- Thermoplastes: Commodity polymers (plastics) role of additives and

examples additifs (~4hrs)
- thermosets: chemistry of UPES, of epoxies, polyurethanes and

Melamine FA – applications in industrial coatings formulations
(automotive) & composites (1 automotive UPES composite &t 1 EP
windmill composite) + PU foams (~8hrs)
- Emulsions (définition, stabilization, destabilization), molecular &

macromolecular surfactants, cosmetic formulations, shampoos, liquid
soaps and acrylic paints (~6hrs)
- Formulation & deformulation examples (~3hrs)

Reminders
–
Definitions
–
Basics of macromolecular
chemistry

Definitions
Macromolecule = « giant » molecule made of repetition of monomer

units (similar or different) = repeating units
Main feature/characteristic  Molecule with high molecular weight
Polymer = substance constituted of many macromolecules
Monomer = reactive molecule of low molecular weight

Macromolecule = « giant » molecule made of repetition of monomer units

(similar or different) = repeating units
Ex. of species with high molar masses or macromolecules that are

not polymers
Association of small molecules
Micelle: 50-300 molecules (Surfactant)
Associated molecules
into agregates

Macromolecule = « giant » molecule made of repetition of monomer units

(similar or different) = repeating units
Ex. of species with high molar masses or macromolecules that are

not polymers
DNA
Dendrimer
H2N NH2 H2N NH2
NH2 H2N
NH2
H2N N N
N N
NH2
Protein H2N
H2N N N
N N NH2
N
N
N N
N N NH2
H2N
H2N NH2
N
N
NH2
H2N
N NH2
H2N N N
N N
N
N N NH2
H2N N N
H2N NH2
N N
N N
NH2
H2N H2N
NH2 H2N NH2
H2N NH2

In a polymer, many macromolecules with different

molar masses (molecular weights)

In a polymer, many macromolecules with different

molar masses (molecular weights)
Statistical distribution
MW

In a polymer, all macromolecules entangled with

each others  spaguetti model
25/10/2021
Lecture Prof. JF STUMBE 17
Molecular weight of polymers (Molar mass)
 Average molecular weights
Number average molecular weight Weight average molecular weight
 For same chemical composition, mixture of different molecular weights

 Distribution in molecular weight  polydispersity / Polymolecularity


H H H H
C C
* C C *
H n
H
Styrene Poly(styrene), Polystyrene
Identical repetitive units Homopolymer


2 types of repetitive units Copolymers
H H
H H
C C * C C *
H H n
C C H H H H
H CN C C
* n
*
Acrylonitrile H CN Styrene
Statistical/random
Monomers are randomly distributed
Copolymers

H CH3 H H *
* O
C C * * C C n
H H O O O
O n H O H
Propylene oxyde Ethylene oxyde
Block
Monomers organized in 2 segments
copolymers
Statistical / random copolymers

Linear polymers
Block copolymers
Alternated copolymers


Branched polymers
Star copolymers
Graft copolymers
The blocks display different properties (solubility, etc…)

Polydispersity /polymolecularity
« Classical » pure molecule Polymer
Unique molar mass Different molar masses

 Average molecular weight
Reasons for polydispersity??
 Polymerization = successive addition reaction of monomers on

an active site
 Statistical process (random)
 Initiation – Propagation – terminaison (all random events)

Molecular weight of polymers (Molar mass)

 Average molecular weight = caracteristic of polymers
 For same chemical composition, mixture of different molecular weights
 Distribution in molecular weight  polydispersity / Polymolecularity
 Polymers with same composition (homologues) can display:

- different average molecular weights
- Different molar (molecular) distributions
Mn Mn
States of macromolecular matter

-
Influence on macromolecular structure
and on macroscopic properties
1. The glass transition temperature of polymers (Tg)
1. Crystallization of polymers: melting point (Tm)

Thermoplasts vs Thermosets
Elastomers
Thermoplasts Thermosets
(rubber)

Thermoplasts vs Thermosets
Elastomers Thermosets
Di-sulfide « bridge» Crosslinking
points
Thermoplasts
Semi Amorphous Rigid polymer chains

crystalline (rigide: high Tg)
Flexible polymer chains Crystalline

(flexible: low Tg) domain • High temperature
resistance
• High temperature
resistance
• High chemical
• High abrasion Amorphous resistance
resistance domain
• High tensile
• High flexibility • Transparent stength
• Fusible
• Infusible • Fragile • Infusible
• No Tm

States of macromolecular matter: glass transition

Origine of glass transition temperature: mobility of polymeric chains
Required
energy
4C segment
In polymer chain High energy
required
Rotation around C2-C3
4C molecule
= butane Low energy required

Required
energy Rotation around C2-C3
and C3-C4
Still significant amount

of energy required

Required
energy
 Concerted 3 bonds motion

 2 energy barriers
 Crankshaft-like motion
3 bonds motion
Crankshaft

- Overal reorientation of one

Required segment of the chain
energy
- Connectivity with rest of the

macromolecule to be taken in
account
(requires much more energy)
- Concerted 3 bonds motion

- Crankshaft-like motion
2 energy barriers

Properties changes of a polymer depending on temperature
 Glass transition = phase / state change

 Associated/related to all amorphous phases
What is concerned:
- linear polymers
- linear segments of crosslinked polymers
- amorphous domains of semi-crystalline polymers
Transition from glassy state to liquid or rubbery state
Variation of many physical properties

Properties changes of a polymer depending on temperature

What is concerned:
- linear polymers
- linear segments
of crosslinked polymers
- amorphous domains of semi-crystalline polymers

Measurement of heat capacity with DSC technique
(Differential scaning Calorimetry)
Reference Sample/probe
DSC Instrument
Oven
Temperature
or heat sensors
Oven Thermal
resistance
Heat flow
Heat & cooling system
Mesure of the difference of heat flow between 2 cells (ref + sample)
1  H 
Matter absorbes part of the heat, Cp   
Especially during state transition n0  T P

Monitoring the variation of heat capacity (Cp)

Cp: Heat capacity (J.K-1.mol-1)
1  H 
Cp   
n0  T P
Viscoelastic
liquid
Glass
Heat flow
Temperature
 Start of the transition
 Inflexion point
 Crossing of tangentes
Phase diagrams of polymers: effect of M & T°
T°
Viscous liquid
Rubbery state
Glass transition
Vitrous/glassy solid
Me (e: entanglement) M (g/mol)

Properties of macromolecular materials
Glass Rubbery state Liquid

T
Tg
Melt flow domain
Thermal energy (kT) below energy of transition

Glassy state of conformations
No molecular mobility
Thermal energy (kT) above energy of

transition of conformations
Rubbery state Local mobility of « liquid »
No melt flow due to entanglements (M > Me)

1. Influence of molecular weight

Short chains Long chains
(given MW)
(MW tends to infinit)
If Mn low, K/Mn non negligible  effect on Tg (decrease compared to Tg infinit)

If Mn high, K/Mn  0; Tg = Tg max

1. Influence of molecular weight

Exemple :
Polystyrene (PS)
Linear
Dependency
H H of T over 1/Mn
* C C *
n
H
« Plateau »
reached for high
molecular weight
(no more increase)

2. Influence of stiffness/flexibility of main chain
Which chain
displays the higher Tg ?

2. Influence of stiffness/flexibility of main chain

Repeating units
Easy rotating bonds

« flexible » chains
Limited rotation
« flexible » chains

3. Influence of solvents, additives & plasticizers
Solvent = molecule in which the

polymer dilutes
Plasticizer = high boiling point solvent
Mobility of
chains
Tg

3. Influence of plasticizers (exemples)

Plasticizer = « solvent » with high boiling point
G’ = shear modulus
Plasticizer concentration (~ measure of stiffness)
Other method to determine Tg
Effect of plasticizer
concentration on glass
transition temperature
 Decay of G’
Materials getting softer

with more plasticizer
Temperature (°C)
3. Influence of plasticizers
Tg of PVC – DOP mixtures
Rigid PVC
Soft/flexible PVC
Di Octyl Phtalate
Mass fraction of DOP

Frequently used plasticizers
• Phtalates: numerous derivatives
DOP = DEHP
> 50%
(Potential endocrine disruption activity)
• Aliphatic dicarboxlic acid esters

(succinates, adipates, sebacates)
•
Frequently used plasticizers
OR
• Phosphates O P OR
OR
• Hydrogenated phtalates Hexamoll® Dinch
(plasticizers for children toys, eraser,
medical tubing & blood bags,…)

States of macromolecular matter: crystallization

X-rays: a tool for evidencing crystallinity

Crystalline
peaks
Debye-Scherrer diagraph
of amorphous polymer
(PS) Diffuse:fuzzy
halo
Debye-Scherrer diagraph of
semi-crystalline polymer
(PE)
Obvious difference between amorphous polymer (a)

& semi-crystalline polymer (b)
Amorphous polymer Semi-crystalline polymer

Diffuse Halo (a) Concentric circles(b)
- -
Non organized state Organized state

DSC Analysis
Case I: Semi-crystalline polymer after slow cooling
Solid state  Melt state
Decomposition
Exo →
Heating material
- Variation of Cp: glass transition

(amorphous fraction:domains)
- Eendothermic peak
← Endo
Glass
transition Melting (melting of crystalline domains)
Tg Tm T
Mix of amorphous & crystalline phases

Melting of crystalline domains
Crystalline lamella Molten polymer
Tm
Desorganization of crystalline structures of a semi-

crystalline polymer takes place at a specific temperature :
the melting temperature Tm

Monitoring crystallization by DSC analysis
Cooling down
10°C/min
- Endothermic peak
(Melting of crystalline domains)
Heating
T>Tf - Exothermic peak
10°C/min
(Partial crystallization at Tcr < Tm)
T>Tg

Molten polymer Cristalline lamella
TC
The organization (from melt state) of polymeric chains
into crystalline structures (lamellae) takes place at a
specific temperature :
The Crystallization temperature Tc (≠Tm)

Conditions for crystallization of polymers
1. Very simple repetition unit

 PE, PTFE, PEO
 not for PMMA
2. Configurational regularity of polymeric chain

Isotactic polymers (ex. iPP) , syndiotactic polymers
(Ziegler Natta, metallocenes)
3. Configurational Simplicity of polymeric chain

Planar feature of terephtalate (PET)
4. Organization by establishing H bonds

PA6 & PA6-6

Influence of intermolecular interactions

Influence of intermolecular interactions
PVC Tm = 208 °C
(syndio)
Tm = 188 °C
iPP
Phase diagram: effect of M & T°

T
Viscous liquid
Rubbery state
Tf
Melting
Flexible solid Tg
Glass transition
Glassy solid + crystal
Me M
Summary
Amorphous polymer (ex. PS, PMMA)
Service temperature
Glassy state Tg Rubbery Tfl Viscous liquid state

state
Semi-crystalline polymer (ex. PE, PA6,6)

Heterogeneous
Service temperature system
Crystalline phase Crystalline phase Viscous

Tg Tfl Tm
+ Glassy state + Rubbery state liquid state

Summary
Thermoset polymers (ex. EP, UPES)
Service temperature
Glassy state Tg Rubbery Td

state
Elastomers (ex. NR, BR, NBR)
Service temperature
Glassy
Tg Rubbery state Td
state


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Year 2021-2022

POLYMERS & FORMULATION

Pr. Jean-François STUMBE

Université de Haute Alsace

25/10/2021 Lecture Prof. JF STUMBE 1

Polymers: Everywhere in our day-life !

Daily care Cosmetology

25/10/2021 Lecture Prof. JF STUMBE 2

25/10/2021 Lecture Prof. JF STUMBE 3

25/10/2021 Lecture Prof. JF STUMBE 4

Fate of plastics after use???? Not sustainable

25/10/2021 Lecture Prof. JF STUMBE 5

Polymers: Everywhere in our day-life !

Natural polymers Synthetic polymers

25/10/2021 Lecture Prof. JF STUMBE 6

25/10/2021 Polymers Lecture Prof. JF STUMBE Not polymers 7

Polymers: Everywhere in our day-life !

« Visibles » « non visibles » polymers

Plastics (PE, PP, PS, PA,..) Functional polymers

25/10/2021 Lecture Prof. JF STUMBE 8

Organization of the lecture

I. Reminders – Definitions – Basics of macromolecular

25/10/2021 Lecture Prof. JF STUMBE 9

- Thermoplastes: Commodity polymers (plastics) role of additives and

- thermosets: chemistry of UPES, of epoxies, polyurethanes and

- Emulsions (définition, stabilization, destabilization), molecular &

- Formulation & deformulation examples (~3hrs)

25/10/2021 Lecture Prof. JF STUMBE 10

25/10/2021 Lecture Prof. JF STUMBE 11

Macromolecule = « giant » molecule made of repetition of monomer

Main feature/characteristic  Molecule with high molecular weight

Polymer = substance constituted of many macromolecules

Monomer = reactive molecule of low molecular weight

25/10/2021 Lecture Prof. JF STUMBE 12

Macromolecule = « giant » molecule made of repetition of monomer units

Ex. of species with high molar masses or macromolecules that are

25/10/2021 Lecture Prof. JF STUMBE 13

Macromolecule = « giant » molecule made of repetition of monomer units

Ex. of species with high molar masses or macromolecules that are

25/10/2021 Lecture Prof. JF STUMBE 14

Polymer = substance constituted of many macromolecules

In a polymer, many macromolecules with different

25/10/2021 Lecture Prof. JF STUMBE 15

Polymer = substance constituted of many macromolecules

In a polymer, many macromolecules with different

25/10/2021 Lecture Prof. JF STUMBE 16

Polymer = substance constituted of many macromolecules

In a polymer, all macromolecules entangled with

Molecular weight of polymers (Molar mass)

 Average molecular weights

Number average molecular weight Weight average molecular weight

 For same chemical composition, mixture of different molecular weights

25/10/2021 Lecture Prof. JF STUMBE 18

Macromolecule = « giant » molecule made of repetition of monomer

Identical repetitive units Homopolymer

25/10/2021 Lecture Prof. JF STUMBE 19

Macromolecule = « giant » molecule made of repetition of monomer

2 types of repetitive units Copolymers

Macromolecule = « giant » molecule made of repetition of monomer