INGENIERIE DES MATERIAUX POLYMERES

Chemistry of Polymers
by
y
Etienne Fleury, Philippe Chaumont and Mohamed Taha

This document is an overview (PDF from PPT presentation)

Cli k here
Click
h
f th
for
the descriptive
d
i ti
f t
feature

Unit Mixte de Recherche 5223

CHEMISTRYOFPOLYMERS

OBJECTIVES
Todevelop
*basicresearchinmacromolecularchemistry
*Chemicaltoolsincooperationtotheotherlab.Activities
(designofmacromoleculararchitecturesand
morphologiesforgivenfunctionality(ies))
Tointegratesustainabilityinresearchapproaches
Togetinnovativeapproachesfordesigningandfunctionalizing
macromoleculararchitectures

CHEMISTRYOFPOLYMERS

COMPETENCES
*MolecularChemistry
Molecular Chemistry
*ChemicalModificationofPolymersandPolysaccharides
* Chemistry of Polymerization
*ChemistryofPolymerization
Polycondensation/Polyaddition
=>PU,Polyepoxy,Polyamide,Polyester,
Ring
RingOpeningPolymerization
=>Lactides,Glycolides,Cyclosiloxane..,
RadicalPolymerization
=>Freeradical,NMP,RAFT,ATRP
=>Free
*PolymerizationProcesses
Polymerization Processes (dispersedmedia,HighT
(dispersed media, High T
T,SolGel,SCCO
, Sol Gel, SC CO2,)
*ChemicalandMicrostructureAnalysis

SPECIFICTOOLS
SPECIFIC TOOLS
Pilot reactor for p
polyesters
y
synthesis
y
(8.5L, 290C, 7bars)

CHEMISTRYOFPOLYMERS

Spectro UV

wave
channel

Pilot reactor for polyamides synthesis

(1L, 350C, 50 bars)

Dryer
Feeders (V, w)
Pumps

NIR & MIR

spectroscopies

Computer-controlled
extruder (P,T, rot., )

TOPICS

CHEMISTRYOFPOLYMERS

TOPIC #I:Molecular&MacromolecularEngineering
I.1MacromolecularEngineeringinMoltenState
l l
i
i i
l
S
I.2PolymerswithControlledArchitecture
I.3 New (macro)molecularChemistryfromSoftConditions
I.3
(macro)molecular Chemistry from Soft Conditions
and/orSelectiveand/orReversibleReactions

TOPIC#II:Chemistry&SustainableDevelopment
II.1ChemistryforReactiveExtrusion
II.2NonToxicProcesses
II.3BiosourcedPolymers
II.4Modificationofpolysaccharides

TOPI
TOPI#III:Surfaces&InterfacesChemistries
#III S f
&I t f
Ch i t i
III.1SynthesisofNanoobjects
III.1SynthesisofNano
III.2 Functionalization of Planar Surfaces
III.2FunctionalizationofPlanarSurfaces
III.3FunctionalizationofFillers

Reagent

Polymer

CHEMISTRYOFPOLYMERS

TOPIC #I:Molecular&MacromolecularEngineering

LDPE+peroxide

I.1MacromolecularEngineeringinMoltenState
H2
C
C
H2

H2
C
C
H2

H2
C
CH

H2
C
C
H2

C
H2

RO

withoutTEMPO
H2
C
C
H2

H2
C
C
H2

H2
C
C
H

H2
C
C
H2

C
H2

Grafted
nitroxide

NO
H2
C
C
H2

H2
C
C
H2

H2
C
CH

withTEMPO

H2
C
C
H2

C
H2

O
N

- Badel T., Beyou E., Bounor-Legare V., Chaumont P. Flat J.J., Michel A.
J. off Polym. Sci.
S Part A (2007)
(
) 5215-5226
- Ibid Macromolecular Material and Engineering (2012)
- Akbar S., Beyou E., Chaumont P., Mazzolini J., Espinosa E., D'Agosto F., Boisson C.
J. of Polym. Sci. Part A (2011) 957-965

CHEMISTRYOFPOLYMERS
TOPIC #I:Molecular&MacromolecularEngineering
#I Molecular & Macromolecular Engineering
I.2PolymerswithControlledArchitecture

Deng Y., Bernard J., Alcouffe P., Galy J., Dai L., Grard J. F. J. of Polym. Sci. Part A-Polymer Chemistry (2011) 4343-4352

MNH2=
Biological
derivatives

Fonction
1

N
S

Probes for
bio-imaging

Fonction
2

Fonction
3

Fonction
4

CharreyreM.T.etal.JACS2006,Macromol.Rapid.Commun2007,WO2007/003782

CHEMISTRYOFPOLYMERS
TOPIC #I:Molecular&MacromolecularEngineering
I.3
3 New (macro)molecularChemistryfromSoftConditions
(
) l l Ch i
f
S f C di i
and/orSelectiveand/orReversibleReactions

"Click"

"ClickChemistry" :Sharplessetal.2001=>
chemioselectivity,robusteness,atomeconomy,
1,3dipolarcycloaddition (Huisgen)
Radicaladditionthiolene
DipolarCycloaddition[4
Dipolar Cycloaddition [4+2]
2](DielsAlder)
(Diels Alder)
Oximes/hydrazones

Binauld S., Damiron D., Hawker C. J., Connal L. A., Drockenmuller E. Macromolecular Rapid Communications (2011) 147-168
Magana, S., Zerroukhi, A., Jegat, C., Mignard, N. Reactive & Functional Polymers (2010) 70, 442-448

Polymer Reagent

CHEMISTRYOFPOLYMERS
TOPIC#II:Chemistry&SustainableDevelopment
II.1
II.1ChemistryforReactiveExtrusion
Chemistry for Reactive Extrusion
+

HSi

Si

SiH

Ru3(CO)12
O

2000

Si

Si

Formation de poudre

SiH

Couple (N.cm)

1500
Introduction
PDMS-SiH
1000
EVA

Rticulation EVA

500

i = 0
Gv =

i = 0.39
Gv = 16.7
= 38 mol.m-3

i = 0.91
G = 10.7
Gv
10 7
-3
= 80 mol.m

0
0

temps (mn)

Polyesters
=> PC, PG, PLA
Non reactive
blend EVA/PDMS-SiH

Reactive Blend
EVA/PDMS-SiH

Bonnet J., Bounor-Legar V., Boisson F., Mlis F., Cassagnau P.

J. of Polym. Sci. Part A- (2011) 2899-2907

Starch
Zhao Y., Becquart F., Chalamet Y., Chen J., Taha M.
Macromol. Mater. Eng. (2009) 651-657

CHEMISTRYOFPOLYMERS
TOPIC#II:Chemistry&SustainableDevelopment
II.2NonToxicProcesses
soft segment

HO

OH +

x O=C=N-

polyol

diisocyanate

diisocyanate prepolymer

O=C=N- -N-C-O

-N=C=O

O
soft segment

O-C-N-

-N=C=O

+
H

O=C=N-

-N-C-O

soft segment

O-C-N-

-N-C-O

O-C-N-

O
y

- Residual monomers
- Catalysts

-N=C=O

O=C=N-

-N=C=O

CHEMISTRYOFPOLYMERS
TOPIC#II:Chemistry&SustainableDevelopment
II.3BiosourcedPolymers
HO
HO
HO

N3
O

NH

N
N

HO
HO
HO

J. Chen, S. Chambert, J. Bernard, E. Fleury,

y Y. Queneau,
Sci. China Chem, 2010, 53, 1880-1887.

H
N

O
O
n

HO
OH

O
O
HN

NH

Abdelkader, S. Moebs, J. Bernard, Y. Queneau, E. Fleury,

J Polym.
J.
P l
S
Sci.i P
Pol.l Ch
Chem. 2011
2011, 49,
49 1309-1318
1309 1318

O
HO

S
S

OH
N3

CHEMISTRYOFPOLYMERS

OH
OH
O
HO

H
OH

OH
O
HO

OH
O

TOPIC#II:Chemistry&SustainableDevelopment

O-1,6
OH
O

II
II.4Modificationofpolysaccharides
4 Modification of polysaccharides

HO

-1,4

Galactomannan

Guar esterifications
in ionic liquids
inionic

3%
in H2O
inH

surfactant
f

10%
in CHCl3
inCHCl

Cl
O

DS=0.12

DS=2.70

Cl
O

5%
inBMIMCl

macromonomer

Cl
Cl

Cl

Cl
Cl

Cl

C. Lacroix, E. Sultan, E. Fleury, A. Charlot Polymer Chemistry 2012, 3, 538-546

Chemical network

ATRPmacroinitiator

CHEMISTRYOFPOLYMERS
TOPIC#III:Surfaces&InterfacesChemistries
TOPIC#III:Surfaces&InterfacesChemistries
III.1Synthesis
III.1
Synthesis ofNano
ofNanoobjects
Sol-gel

Self-assembly

O
Si O
Si
HO Si
O
O OH
O
Si
Si
Si O
O
HO
O
OH

in solution
Silylated block
Sol-gel

Self-assembly

&

in bulk

fPS= 62%

PAPTES113-PS489

1)) HCl, 1M
2) Calcination
800C

Beyou et al, cover page, J Polym Sci, Polym Chem. (2011) 4193-4203

CHEMISTRYOFPOLYMERS
TOPIC#III:Surfaces&InterfacesChemistries
TOPIC#III:Surfaces&InterfacesChemistries
III.2Functionalization
III.2
Functionalization ofPlanar
ofPlanar Surfaces
Irradiation

Radical

Grafting from

Fortin N., Albela B., Bonneviot L., Rouif S., Sanchez J.-Y., Portinha D., Fleury E.
Radiation Physics and Chemistry (2011) 10.1016 /j.radphyschem.2011.10.027

Copolymer
(PVDF/PA 6-6)-g-PHEMA

19F

(MEB/EDX)

16O

CHEMISTRYOFPOLYMERS
TOPIC
TOPIC#III:Surfaces&InterfacesChemiseries
#III : Surfaces & Interfaces Chemiseries

III.3Functionalization
III.3
Functionalization ofFillers

N PEG Me

O
O Si
O

N
H

N
NH

O
O Si
O

COOH

C12H25

HO

Si

N
N

H
N

O
n

O
O

OH

NH
O

Elaboration of alkynyl fluorescent silica nanoparticules

by inverse microemulsion
microemulsion.
CC in the same pot using simultaneously two
reactants of various HLB

ColloidalstabilizationofmixedMEGdodecylsilica
nanoparticlesinwater.
MPEG:C12 =100:0(A);75:25(B);50:50(C);25:75(D)
= 100:0 (A); 75:25 (B); 50:50 (C); 25:75 (D)
C. Tissandier, O. Tillement, T. Hamaide. Langmuir 2012, 28 (1), 209-218

N
N
N

(A)

(B)

(C)

C12Content

(D)

CHEMISTRYOFPOLYMERS
PermanentStaff

INSA
SA
JJ. Bernard
B
d
A. Charlot*
J. Dupuy*
F Fenouillot
F.
Fenouillot*
E. Fleury
J. Galy*
J.F.. Gerard*
J.
Ge a d
F. Ganachaud
F. Mechin*
A. Rousseau
D. Portinha

Lyon 1

ENS

UJM

E. B
E
Beyou
V. Bounor-Legar
P. Chaumont*
A. Crepet
E. Drockenmuller
T. Hamaide
N. Sintes
N. Viton*

*
M.T.
M
T Charreyre
Ch
A. Favier*

F. Becquart
F
B
t
Y. Chalamet*
C. Jegat
N. Mignard
M. Taha