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PROGRAMME DE COOPÉRATION TRANSFRONTALIÈRE
GRENSOVERSCHRIJDEND
SAMENWERKINGSPROGRAMMA
Cofinancie
ring
AVEC LE SOUTIEN DU FONDS EUROPÉEN DE DÉVELOPPEMENT RÉGIONAL
MET STEUN VAN HET EUROPEES FONDS VOOR REGIONALE ONTWIKKELING
AVEC LE SOUTIEN DU FONDS EUROPÉEN DE DÉVELOPPEMENT RÉGIONAL
MET STEUN VAN HET EUROPEES FONDS VOOR REGIONALE ONTWIKKELING 1
New biobased TPEs developped
during the ELASTOPLAST project
Adrian Gainar, Wim Thielemans (KULAK)
Stijn Corneillie (Centexbel)
Julien Cayuela (Materia Nova)
Robert Mundil, Franck Kayser, Julie Meimoun, Audrey Favrelle, Grégory Stoclet,
Philippe Zinck (ULille)
2
Why biobased TPE ?
• Use of renewable feedstock - Depletion of fossil resources
• Consumers pressure
• New / alternative building blocks provide new structures
Oilseed biomass based monomers
Cyclic ester
Building Blocks for BiobasedSynthetic Elastomers
-decalactone Laurylmethacrylate
Long chain (meth)acrylate
Castor oil
Lauryl alcohol fromPalm kernel oil
Coconut oil
4
New biobased TPE’s :
Background and strategy
• Implementation
• Using commercial biobased monomers
• PMMA as the hard block
• Reasonnably high Tg around 110°C
• Immiscible with PDL and PLMA (checked)
• Feasibility in terms of chemistry
• One pot approach : block copolymerization
-decalactone
Tg PDL -60°C
Lauryl methacrylate
Tg PLMA -55°C
Higher temperature of use than
e.g SBS (partial miscibility)
5
New decalactone based TPE
• Organocatalysis : an old tool brought up to date
• Phosphazene bases as catalyst for PMMA synthesis
• Recent progress : also for lactones
• Our idea : Use this chemistry with the biobased decalactone to make
block copolymer with PMMA
Seebach et al.
Angew. Chem. 1993 32 716
Hadjichristidis et al.Polym. Chem. 2014 5 5471
6
• First step : can phospazenes polymerize DL ?
• Yes they can !
New decalactone based TPE
DL ROH P=N
Catalyst
Conversion
(%)
Mn SEC
g/mol
D Mn calc.
g/mol
100 1 0.2 2 nd nd -
100 1 0.4 35 8 300 1.26 6 000
100 1 0.6 65 11 300 1.31 11 100
100 1 0.8 100 14 400 1.39 17 000
100 1 1 100 12 200 1.54 17 000
1h reaction
THF
25°C
7
• Optimization
• Kinetic study
• Very fast reaction : less than 5 min at room temperature
New decalactone based TPE
0 1 2 3 4 5 6 7 80
20
40
60
80
100
co
nve
rsio
n [
mo
l %
]
t [min]
1.0 eq. t-BuP4
0.8 eq. t-BuP4
8
New decalactone based TPE
• Second step : can we block copolymerize DL with MMA ?
• Yes we can !
• Full conversion for both steps
ε-DL
homopol.
100 eq.
ε-DL
MMA
homopol.
100 eq.
MMA
16 18 20 22 24 26 28
RI dete
cto
r
t [min]
PDL
PDL-b-PMMA
Mn = 24k
Ð = 1.58
Mn = 38k
Ð = 1.94
ε-decalactone content : 66 wt%
5 min
RT !
35 min
RT
9
SAXS analysis
(Small Angle X-Ray)
Nanostructuration is clearly confirmed
0.01 0.10.1
1
10
100
Inte
nsit
y [
a.u
.]
q [Å-1]
New decalactone based TPE
10
AFM analysis
(Atomic Force Microscopy)
Separation of 2 phases
New decalactone based TPE
Mechanical tests
0 50 100 150 200
0.2
0.4
0.6
0.8
1.0
1.2
1.4
no
rma
l s
tre
ss [
MP
a]
strain [%]
a)
0 25 50 75
0.1
0.2
0.3
0.4
0.5
no
rma
l s
tre
ss [
MP
a]
strain [%]
b)
tensile testing
tensile modulus 8.5 MPastrain at break 200%
recovery experiment
recovery ratio of 50%
New decalactone based TPE
• Work published in Chem. Com. 2020, 56, 8067
Manuscript available online :
https://interreg-elastoplast.eu/sites/default/files/2021-01/Publicatie_ULille_2020_3.pdf
12
• PMMA – PLMA – PMMA TPEs shows a very low elongation at break, range 10-100%
Attributed to strain-induced crystallization (Mandal et al., Macromolecules, 2006, 39, 91920)
• Our idea to improve :
to insert a low fraction of MMA in the soft PLMA block to hamper cristallisation
New lauryl methacrylate based TPE
Background and strategy
PLMA – Poly(lauryl methacrylate)
Tg -55°C
-0,01
0,04
0,09
0,14
0,19
0,24
0,29
0,34
0,39
0,44
17 18 19 20 21 22 23 24
RI d
etec
tor
time [min]MMA pol.
Lauryl methacrylate content : 75 wt%
P(LMA/MMA)-b-
PMMA
RM041_2
Mn = 34.5 k
Ð = 1.18
100% conversion
RT; 15 min
P(LMA/MMA)
RM041_1
Mn = 27.8 k
Ð = 1.20
100% conversion
RT; 120 min
LMA/MMA
pol.
70 eq. MMA
Catalyst
LMA
80 eq.
Catalyst
MMA
30 eq.+
New lauryl methacrylate
based TPE
14
AFM analysis
New lauryl methacrylate
based TPE
15
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New lauryl methacrylate
based TPE
Tensile tests
• Elongation at break > TPE with pure PLMA as the soft block (literature)
• Concept of hampering the cristallisation validated ?
• WAXS Analyses to be done
16
DMA
Dynamical mechanical analyses
• Good damping properties
• High tackiness : Potential applications for patch, PMMA adhesion
New lauryl methacrylate
based TPE
Projectl
eider
Chef de
file
Partners
Partenaires
Geassocieerde
partners
Partenaires
associés
17
Thank you for your attention !
