Lecture AZB - Stumbé 2021-2022 Organic Coatings

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

LPIM-ENSCMu
FRANCE
jean-francois.stumbe@uha.fr
27/10/2021 Cours JF STUMBE 1

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

Thermoplasts vs Thermosets
Elastomers
Thermoplasts Thermosets
(rubber)

Thermosets
Organic coatings Composite materials

Organic coatings
-
Chemistry & applications

Role of organic coatings

 Décoration
 Protection (temporary or long term)
 Functionality
Organic coatings
Definition:
Covering materials, based on organic binder that adhere to surface,
displaying protective and decorating properties
= Material applied to a surface = resulting dry film = application process
Composition:
- Polymer matrix Résins +
- Pigments Solvent crosslinkers Pigments (0-30%)
Water 25-95%
- Fillers & additives
0-70%
- Dispersing phase (optionnal)
Caracteristics:
- Thickness of 20 to 100 μm Fillers
(0-10%)
- Resistance to solvents, to water
- Mechanical resistance
Coating
- Elasticity - hardness Additives (0-3%)

Organic coatings: market information
70
58 %
60
47 %
50
Percentage
40
33 %
29 %
30
20 %
20
13 %
10
0
Volume Value Volume Value Volume Value
Industry Spécialities
Architectural OEM Refinish
OEM: Original Equipment Manufacturing

Organic coatings
Different chemical systems in organic coatings
Binders Crosslinkers / catalysts:
Alkyde resins Isocyanates

Melamines-formaldehyde
Acrylate resins
Amines
PES resins Heat
Epoxy resins O2
UV
Other binders
…..
High diversity of systems !!!!

Organic coatings
Principle of filmification
Physical drying Reactive system
Evaporation
Evaporation
Substract Substrat
Binder Crosslinking
Solvent
Crosslinker Substract

Organic coatings
Industrial coatings
(OEM* & Refinish**)
Reactive paints & varnishes

(Bicomponent systems: binders & crosslinkers)
* OEM: Original Equipment Manufacturing
** Refinish = repare
Organic coatings
I. Polymeric Binders
Main role: bring properties of dry film
- Polyesters
- Polyacrylates
- Epoxies

Organic coatings
Polyesters binders
O
Ester bond
O
Linear block
HO OH Broad variability
 Variable architectures
HO  Variable molecular weights
Star-like
 Relatively low molecular weights
 Mainly aliphatics
OH
HO

Organic coatings
Main components of PES resins (PolyESters)
Diols Triols Diacids & dérivatives
OH
HO
O
HO
Ethylene glycol
O
HO OH
O
OH Trimethylolpropane
HO Phthalic anhydride
1,4-Butanediol
O O
OH OR OR
HO HO OH
1,6-Hexanediol Terephthate
HO OH
O
Pentaerythritol OH
HO OH HO
O
Neopentyl glycol Adipic acid

Organic coatings
Reactive polyester resins
O
OH OH
HO HO
O
(Non
Equilibrated
equation)
O
HO O
O O H
O n
Polyester diol with low molecular weight (500-2000g/mol)

 Reactive polyesters (oligomers)
Mainly aliphatic molecules + low molecular weight  viscous resins

Organic coatings
Polyester resins
 Linear polyesters with various molecular weights
 Linear polyesters with various compositions (Cf monomers list)
 Star polyesters
 Branched polyesters OH
HO
HO OH
HO OH OH
OH
HO OH
HO
OH
HO

Organic coatings
Chemistry of „polyacrylatols“: (radical polymerization)
Radical
polymérisation
Initiators:
polymerization
radicalaire Peroxydes
Control of molecular weight:

Conc. Monomer, initiator, T°,…
R = Alkyl

Organic coatings
II. Crosslinking agents
Main role: chemical binding of « binders»

Organic coatings
Crosslinking agents
(used in mono- and bicomponent systems)
Tri- to hexafunctional Trifunctional

crosslinker crosslinker
Melamine-formaldehyde Clear coat Isocyanates

(MF resins) (PU systems)
Topcoat
NCO
OR OR
R
O N O
N
N N
N N R R
OCN NCO
RO OR O
N N N
isocyanurate
RO OR
Liquid viscous resins Liquid viscous resins

Organic coatings
Aminoplastes
OH
MeO OMe PES R R

O
O O
O
MeO N N N OMe
HO OH O O
N N
O O O
N O O O R
OMe OMe
OH OH

Organic coatings
Aminoplastes: formation of a crosslinked network
+ +

Organic coatings
Aminoplastes: formation of a crosslinked network
MeO OMe
MeO N N N OMe
Polymer
N N + HO
n R (Polyol)
N Thermal
&/or acid catalysis
OMe OMe
R R
O O
O N N N O
N N R
R
N
O O
R
R
Organic coatings
Resins’ properties: Characteristics:
- Fonctionnability - Nature of the « amine »

- Flexibility - Degree of methylolation
- Reactivity Aminoplastes - Degree ofe therification
- Polarity / solubility - Nature ofe therification
- Viscosity - Degree of oligomerisation
Coatings’ properties:
- Hardness
- Flexibility
- Weather resistance
(UV, humidity, acidity,…)
- Solvent resistance
- Price
Organic coatings
H
+
Reaction R N C O R'
of isocyanates O
with alcohols H
Catalyst
R N C O + HO R' R N C O R'
Δ
O
H Urethane bond
+
R N C O R'
O
H O
R N C OH
Non desired reaction
Reaction  Avoid water traces
of isocyanates
with water R N C O + HO H R NH2 + CO2
& with amines
H H
R N C O + H2N R R N C N R Urea bond
O

Organic coatings
Bi-component solvent based systems
A B
Crosslinker
Binder
Solvent
Butyle acetate Blend of Standard= Polyacrylatol,

isocyanurates (Macrynal® SM 600)
or Polyesterol,
isocyanates (Desmophen® 680 BA)
Pot life before spaying: 4 hrs

Ratio NCO / OH = 1,1 /1

Organic coatings
Automotive coatings
Specifications: paint / coating to be stable several years
High degree of technology
 Decorative coating (color, gloss, mat, …)

 Protective coatings

Organic coatings
Automotive coatings
Coating
Thickness Function
layer
Appearence, gloss, weather
Clear coat, 30-40m Resistance, scratch resistance,
....
Basecoat, 12-15 m Color (pigments)
Primer 30-40 m Stone / chip resistance,

Leveling
Electrophoretic
coating
20-25 m Corrosion protection
(Electrocoat)
Passivation ~ 2 m
(Phosphate)
Metallic
substract

Organic coatings
Automotive coatings
Coating
Thickness Function
layer
....

Leveling
Electrophoretic
coating
(Electrocoat)
(Phosphate)
Metallic
substract

Organic coatings
Automotive coatings
Coating
Thickness Function
layer
....

Layering,
Electrophoretic
coating
(Electrocoat)
(Phosphate)
Metallic
substract

Organic coatings
Automotive coatings
Coating
Thickness Function
layer
....

Leveling
Electrophoretic
coating
(Electrocoat)
(Phosphate)
Metallic
substract

Organic coatings
Primers
Binding layer between electrophoretic coating
& surface coating (base coat & top coat)
Roles / required qualities:

 « stone chip » resistance
(effect of small stones  damaging adhesion  delamination of coating)
 Adhesion of top coat
Adhesion on electrophoretic coating (CED)
Elastic film
 Leveling
UV resistance
In general, monocomponent system
Main base: polyester Crosslinking agent
- Solution (organic solvent) - Melamine Formaldehyde
(solvent based system)

Organic coatings
Automotive coatings
Coating
Thickness Function
layer
....

Leveling
Electrophoretic
coating
(Electrocoat)
(Phosphate)
Metallic
substract

Organic coatings
Top coat: 1. Base coat
Color
Base coat: polyesters + Melamine formaldehyde crosslinker

Color  effect pigments
Classification of pigments:
Organics
Inorganics
Aluminium
Effect Pigments
TiO2, Carbon black
Functional pigments (corrosion, nanoparticules, …)

Organic coatings
Automotive coatings
Coating
Thickness Function
layer
Appearance, gloss, weather
....

Leveling
Electrophoretic
coating
(Electrocoat)
(Phosphate)
Metallic
substract

Organic coatings
Top coat: 2. Clear coat
Gloss, resistance (scratch, acidity, weather, UV
Numerous technologies acc. to regions in the world:
- Monocomponent solvent based:

- Acrylic / melamine-formaldehyde (130-150°C / 12-20 min)
- Acrylique / mélamine / silane (-O-Si-O-)
- Bicomponent solvent based (EU)

(isocyanurates)

Organic coatings
Automotive coatings
Coating Most often
Thickness Function used systems
layer
Appearence, gloss, weather  Acrylic / MF 1K
Clear coat, 30-40m  Acrylic / PU 2K
Resistance, scratch resistance,
.... (Isocyanurates)
Basecoat, 12-15 m
Color (pigments) PES + MF
Primer 30-40 m Stone / chip resistance, PES + MF
Leveling
Electrophoretic  flexibility
coating
20-25 m Corrosion protection Epoxy
(Electrocoat)
(Phosphate)
Metallic
substract

Organic coatings
Quality tests
Hardness Elasticity, flexibility
& adhesion
Erichsen
Persoz / König
pendulum

Organic coatings
Quality tests
Solvent resistance
Abrasion resistance
(In the presence of detergents)

Organic coatings
Scratch resistance
reflow
gloss after brasion
& thermal treatment (1h 160°C)
Coin’s test
27/10/2021 39
Cours JF STUMBE
Organic coatings
Toxicity issues
Isocyanates Acrylates
Formaldéhyde
Carcinogen
T Harmful Xn, Irritating Xi
categorie 3 « Possible »
Class 1
Nanoparticules Solvants
Proven carcinogen
? Harmful Xn, Irritating Xi

Organic coatings
Environmental & toxicity issues
 Reduction of solvent emissions (VOC)
 Elimination of toxical compounds
 Energy saving, water,…
Reduction of solvent emissions:

 High solid content formulations
 Water based coatings (max. 10-15 % solvent)
 Powder coatings (no VOC)
 UV crosslinking systems (reactive solvents)
Organic coatings
Conclusion
 Versatile chemistry
 Versatile technology
 Essential technologie (surfaces protection,…)
 Formulation of coatings requires broad experience & knowledge

(chemistry, physico-chemistry, formulation, applications,…)

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Year 2021-2022

POLYMERS & FORMULATION

Pr. Jean-François STUMBE

Université de Haute Alsace

27/10/2021 Cours JF STUMBE 1

Organization of the lecture

I. Reminders – Definitions – Basics of macromolecular

27/10/2021 Cours JF STUMBE 2

27/10/2021 Cours JF STUMBE 3

Organic coatings Composite materials

27/10/2021 Cours JF STUMBE 4

27/10/2021 Cours JF STUMBE 5

Role of organic coatings

 Protection (temporary or long term)

= Material applied to a surface = resulting dry film = application process

27/10/2021 Cours JF STUMBE 7

OEM: Original Equipment Manufacturing

27/10/2021 Cours JF STUMBE 8

Binders Crosslinkers / catalysts:

Alkyde resins Isocyanates

High diversity of systems !!!!

27/10/2021 Cours JF STUMBE 10

Reactive paints & varnishes

* OEM: Original Equipment Manufacturing

27/10/2021 Cours JF STUMBE 12

27/10/2021 Cours JF STUMBE 13

27/10/2021 Cours JF STUMBE 14

Polyester diol with low molecular weight (500-2000g/mol)

27/10/2021 Cours JF STUMBE 15

27/10/2021 Cours JF STUMBE 16

Control of molecular weight:

27/10/2021 Cours JF STUMBE 17

II. Crosslinking agents

Main role: chemical binding of « binders»

27/10/2021 Cours JF STUMBE 18

Tri- to hexafunctional Trifunctional

Melamine-formaldehyde Clear coat Isocyanates

Liquid viscous resins Liquid viscous resins

27/10/2021 Cours JF STUMBE 19

MeO OMe PES R R

27/10/2021 Cours JF STUMBE 20

27/10/2021 Cours JF STUMBE 21

Resins’ properties: Characteristics:

- Fonctionnability - Nature of the « amine »

27/10/2021 Cours JF STUMBE 24

Butyle acetate Blend of Standard= Polyacrylatol,

Pot life before spaying: 4 hrs

27/10/2021 Cours JF STUMBE 25

Specifications: paint / coating to be stable several years

High degree of technology

 Decorative coating (color, gloss, mat, …)

27/10/2021 Cours JF STUMBE 26

Basecoat, 12-15 m Color (pigments)

Primer 30-40 m Stone / chip resistance,

27/10/2021 Cours JF STUMBE 27

Basecoat, 12-15 m Color (pigments)

Primer 30-40 m Stone / chip resistance,

27/10/2021 Cours JF STUMBE 28

Basecoat, 12-15 m Color (pigments)

Primer 30-40 m Stone / chip resistance,

27/10/2021 Cours JF STUMBE 29

Basecoat, 12-15 m Color (pigments)

Primer 30-40 m Stone / chip resistance,