CO 2 for Green Polymer Chemistry by Silvio Curia International Conference on Biopolymers and Bioplastics 10 August 2015 San Francisco REFINE project REnewable ID: 472199
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Slide1
Supercritical CO2 for Green Polymer Chemistry
bySilvio Curia
International Conference on
Biopolymers
and
Bioplastics
10
August 2015,
San FranciscoSlide2
REFINE project: REnewable FunctIoNal matErialsfor a sustainable polymer industry
Plastic industry is heavily reliant on petrochemicals.REFINE
aims
to combine:
green raw materialsgreen synthesisgreen processing and modificationSlide3
Plastics: the facts (2014)
Plastics – the Facts 2014
, PlasticsEurope and European Plastics Converters, 201
4
57 Mtonnes in EU
300 Mtonnes globallySlide4
Plastics: the facts (2014)
Plastics – the Facts 2014
, PlasticsEurope and European Plastics Converters, 201
4
<10%
derived from
biodegradable polymers
1
[1] C. Rolando, Biodegradation – Life of Science, 2013 Slide5
CO2 for polymer chemistry
Reduce theviscosity
Energy saving
New green routesSlide6
Polymer processing & synthesis:high viscosity problem
Major obstacle
High Viscosity!Slide7
Major obstacle
High Viscosity!
Solutions
Solvents
✗
Toxic
Polymer processing & synthesis:
high viscosity problemSlide8
Major obstacle
High Viscosity!
Solutions
Solvents
High T
✗
✗
Toxic
Thermal degradation + expensive
Polymer processing & synthesis:
high viscosity problemSlide9
Major obstacle
High Viscosity!
scCO
2
✓
Temporary plasticiser
Non-toxic
Inexpensive
Accessible T
c
& p
c
Solutions
Polymer processing & synthesis:
high viscosity problemSlide10
CO2-induced polymer plasticisation- how does it work?
Polymer chainsSlide11
scCO
2
Polymer chains
CO
2
molecule
Lower viscosity
Lower melting point
CO
2
-induced polymer plasticisation
- how does it work?Slide12
CO
2
-induced polymer plasticisation
- how does it work?
Poly(lactic acid) at 35
o
CSlide13
High Pressure Rheometer
Max Pressure: 300 barSlide14
Oscillatory vs rotational experiments
Oscillation
Full rotation
Stiffness
Melting point
Shear-Viscosity
Flow properties
PolymerSlide15
Elastic modulus of PCL – ambient pressure
P
amb
S. Curia
et al.
,
Polymer
,
2015
Semi-crystalline
Biodegradable
Used for packaging
Suitable for medical applicationsSlide16
P
amb
Soaking time
50 mins
50 bar
Elastic modulus of PCL – in CO
2
S. Curia
et al.
,
Polymer
,
2015Slide17
100 bar
120 bar
70 bar
50 bar
P
amb
Soaking time
50 mins
∼23
o
C
Elastic modulus of PCL – in CO
2
S. Curia
et al.
,
Polymer
,
2015Slide18
Viscosity of PCL 10 kDa: ambient pressure
80
o
C
S. Curia
et al.
,
Polymer
,
2015Slide19
PRESSURE
Viscosity reduction under CO
2
: PCL 10 kDa
80
o
C
S. Curia
et al.
,
Polymer
,
2015Slide20
PRESSURE
Viscosity reduction under CO
2
: PCL 10 kDa
80
o
C
96%
S. Curia
et al.
,
Polymer
,
2015Slide21
Q: can CO2 plasticise higher MW PCL?Slide22
Viscosity: PCL 80
kDa
vs
10
kDa
10
kDa
(ambient
pressure)80 oCShear Rate (s-1)Viscosity (Pa.s)
Longer chains = higher viscosity
S. Curia
et al.
,
Polymer
,
2015Slide23
Polymers: non-Newtonian fluids
log Shear Rate
log Viscosity
Zero Shear ViscositySlide24
80 °C
Viscosity of PCL 80 kDa: ambient pressure
Shear Rate (s
-1
)
Viscosity (Pa.s)
S. Curia
et al.
,
Polymer
,
2015Slide25
PRESSURE
Viscosity reduction under CO
2
: PCL 80 kDa
Shear Rate (s
-1
)
Viscosity (Pa.s)
S. Curia
et al.
,
Polymer
,
2015
, in press
Slide26
PRESSURE
Viscosity reduction under CO
2
: PCL 80 kDa
80
o
C
95%
Shear Rate (s
-1
)Viscosity (Pa.s)
S. Curia
et al.
,
Polymer
,
2015Slide27
Viscosity
vs
pressure
80
o
C
Pressure (bar)
Zero Shear Viscosity (Pa.s)
PCL80
CO
2
Q: can we use another gas?
S. Curia
et al.
,
Polymer
,
2015Slide28
80
o
C
Pressure (bar)
Zero Shear Viscosity (Pa.s)
PCL80
CO
2
vs
N
2
N
2
CO
2
S. Curia
et al.
,
Polymer
,
2015Slide29
CO
2
vs
N
2
80
o
C
Pressure (bar)
Zero Shear Viscosity (Pa.s)
S. Curia
et al.
,
Polymer
,
2015Slide30
Viscosity of PCL vs T
80 oC1/Temperature (1/K)
180
o
C
Without CO
2
S. Curia
et al.
,
Polymer
,
2015
Zero Shear Viscosity (Pa.s)Slide31
Viscosity of PCL
vs
T
180
o
C
80 kDa
80
o
C
CO2 300 bar10 kDa80 oCCO2 300 bar80 o
C
1/Temperature (1/K)
Zero Shear Viscosity (Pa.s)
300 bar at 80
o
C
in CO
2
= 250
o
C
without CO
2
!
S. Curia
et al.
,
Polymer
,
2015Slide32
Fossil-based resources
Green resources
Monomers
High T
Organic solvents
Toxic catalysts
Polyesters
Low T
No solvents
Enzyme catalysedSlide33
Oleic acid
Barley, rye, wheat
Azelaic acid
Extraction
Ozonolysis
Bio-derived
✓
Non-harmful
✓Slide34
Polymerisation of azelaic acid
T>200
o
C
Metal catalystsSlide35
Oleic acid
Barley, rye, wheat
Azelaic acid
Extraction
Ozonolysis
T
m
≈110
o
C
✗
Insoluble in
apolar
solvents
✗Slide36
Polymerisation of azelaic acid
Can a
green lower T
approach be achieved
in CO2?Slide37
\
CO
2
in
CO
2
out
Mechanical stirrer
HP reaction vessel
(60 mL or 20 mL base)Slide38
Naturally derived
100% bio-content
Low T:
Save €€€/£££
Preserve enzyme
Preserve functionalities
Green Route to Green Functional Materials
S. Curia
et al.
,
Phil Trans A
,
2015
,
accepted
Lipase
Molecular sievesSlide39
End-capped
✓
MW
✓
No side reactions
✓
Sorbic alcohol end-capping: NMR
3
S. Curia
et al.
,
Phil Trans A
,
2015
,
acceptedSlide40
m/z
Intensity (a.u. x 10
4
)
270.4 g/mol
Sorbic alcohol end-capping: MALDI-ToF
S. Curia
et al.
,
Phil Trans A
,
2015
,
acceptedSlide41
m/z
Intensity (
a.u
. x 10
4
)
A=
B=
A
3
A
4
A
5
A
6
A
7
A
8
B
4
Sorbic alcohol end-capping: MALDI-ToF
S. Curia
et al.
,
Phil Trans A
,
2015
,
acceptedSlide42
Further reaction: Diels Alder chain extension
+
Chain extended interpenetrated network
DA
RT, 24 h
2n
n
DA
Swollen in
CHCl
3Slide43
Thermal analysis
40 °C
25 °C
Before curing
After curing
Heat Flow (
endo
down)
Decreased
crystallinitySlide44
Enzyme recycling: propyl oleate synthesis
Fresh enzyme
Enzyme used at 35
o
C/275 bar (CO2)Enzyme used at 110 oC (melt synthesis)Slide45
Enzyme recycling: propyl oleate synthesis
Fresh
S. Curia
et al.
,
Phil Trans A
,
2015
,
acceptedSlide46
Enzyme recycling: propyl
oleate
synthesis
Fresh
CO
2
(35
o
C, 275 bar)
S. Curia
et al.
,
Phil Trans A
,
2015
,
acceptedSlide47
Enzyme recycling: propyl oleate synthesis
Fresh
CO
2
(35
o
C, 275 bar)
Melt process (110
o
C)
S. Curia
et al.
,
Phil Trans A
,
2015
,
acceptedSlide48
ConclusionsCO2 is able to plasticise
PCL with varied MWUsed CO2 as a reaction medium
to achieve a
green low T route
to functional materialsRecycling tests showed that the high-pressure reactions
are
commercially sustainableSlide49
Next StepsTest cross-linking of the green functional polymers (DSC, DMA) + efficiency test (
real time FTIR etc.) (collaboration with KTH)
S. Torron
et al.
,
Macromol Phys and Chem
,
2014Slide50
Next Steps & future outlookRadical chain extension of telechelicA-B-A block copolymer synthesis + analysis
Hydrophilic
Hydrophilic
Hydrophobic
Micelle?
Hydrogel?
Drug delivery?Slide51
Acknowledgments:Prof Steven M Howdle and Dr Derek J IrvineKTH people: Prof Karl Hult, Prof Mats Johansson, Prof Mats Martinelle, Susana Timhagen
, Stefan Semlitsch Mark Guyler, Pete Fields and Richard WilsonHelen CarsonEU, 7th FP and MC
actions
for
fundingSlide52
Thank you!… any questions?