functionalization of vegetable oils and their derivatives ... · new bio-based polyurethane ......
TRANSCRIPT
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I A M
Functionalization of vegetable
oils and their derivatives for
new bio-based
polyurethane
coatings
Myriam Desroches
Supervisors B Boutevin
S Caillol
Financial support ANR Greencoat
Collaboration LCPO
Resipoly Chrysor
SEG Dielectriques Journées Chevreul 2012
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Precursors
From oils
Isocyanate free
PU
Partially bio-
based
PU
Strategies
INTRODUCTION
Raw material
Vegetable oils
Glycerin carbonate
PU from biobased
polyols
polyol +
isocyanate
PU from
cyclocarbonates
cyclocarbonate +
amine
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BIO-BASED POLYOLS
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Vegetable oils hydroxylation
TOOL BOX
No thiol
Bio-based reagents
Thiol-ene
« Click chemistry »
Primary alcohol in one step
Trans-esterification / Amidification
Range of precursors
Good yields
Epoxy ring opening
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BIO-BASED POLYOLS POLYOLS BY THIOL-ENE COUPLING
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Protocole
POLYOL IN ONE STEP
Vegetable oil
+ HS(CH2) 2OH
Lamp
Hg
Stirring
Photochemical synthesis
UV intensity 15W/cm2
Initiator free
Solvent free
Thiol excess
Purification
Thermal synthesis
Radical initiator
Mild temperature 60oC
Solvent free
Thiol excess
Purification
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“Click chemistry” but...
POLYOL IN ONE STEP
Desroches et al, Macromolecules, 2011, 44,2489
Boutevin et al, 2012, WO 2012/001315 A1
7
Thiol-ene
onto triglycerides
Main reaction
products
Intramolecular
coupling
Intermolecular
coupling
Disulfide
formation
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To Pilot scale
POLYOL IN ONE STEP
TEP properties:
fm 3
Viscosity 3 Pa.s
Oligomers 21 %wt. (GPC THF)
Thermal synthesis 2 kg
initiator : AIBN
75oC
Thiol / double bonds ratio : 2/1
Liquid-liquid extraction
8
1000 2000 3000 4000 5000 6000
M (g/mol)
huile de soja
huile de soja hydroxylée
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BIO-BASED POLYOLS ”DIOLS” BY THIOL-ENE COUPLING
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Methyl esters
Vegetable oils Esters Glycerin
Diol synthesis based on the ester mixture
- ester/amide functions
- different number of atoms
between the OH functions
“DIOLS” SYNTHESIS
NA
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Several precursors
“DIOLS” SYNTHESIS
11
Desroches et al, EJLST, 2012,114, 1, 84
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Protocole
“DIOLS” SYNTHESIS
Esterification 100 oC, cat. APTS, 7h
yield > 95%mol
Amidification 100 oC, 48h
yield > 98%mol
Thiol-ene coupling 60 oC, AIBN, 8d
yield > 98%mol
By produts
Monoesters/diesters = 20 %wt
Amides = n.d.
Oligomers due to thiol-ene coupling
≈ 5 %wt
12
10000 20000 30000
M (g/mol)
MED2
DED2
1000 2000 3000
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BIO-BASED POLYOLS POLYOLS BY RING OPENING
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Bio-based carboxylic acids
Lactic acid
Bioassimilation
IIary Alcohol
Glycolic acid
Bioassimilation
Iary Alcohol
Acetic acid
Model
Low price
Polyols with f = 4
14
EPOXYDIZED OILS
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Protocole
Lactic & glycolic acids
Acid/epoxy ratio = 2/4
80 oC, 4h
Solvent free
Initiator free
Extraction
Acetic acid
Acid/epoxy ratio = 5/4
100 oC, 40h
Solvent free
Initiator free
Extraction
Extrapolation 1 kg
15
EPOXYDIZED OILS
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5000 10000 15000 20000 25000 30000
M (g/mol)
ALP
AGP
AAP
Polyol ALP AGP AAP
fm 5,3 4,9 4,3
Conclusion : f > fthéo due to oligomers (GPC THF – RI detection)
Side reactions
triglycerides
oligomers
16
2500 5000 7500 10000 12500 15000
EPOXYDIZED OILS
Desroches et al, J Pol Sci, submitted
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BIO-BASED POLYOLS POLYURETHANES
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Protocole
Hardener Voramer 2093 : MDI prepolymer, mixture
NCO/OH ratio ≈ 1,05
Cross-linking Room temperature
Catalyst free
PU SYNTHESIS
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Tg determination - DSC
0 oC 20 oC 45 oC 60 oC 100 oC
PU-DEDx
PU-TEP PU-MEDx
PU-MADx
PU-ALP
PU-AGP
PU-AAP PU-MAT2
Glass transition temperature parameters
Amide function
Cross-linking density
19
Tg
PU SYNTHESIS
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10 15 20 25 30 35 40
-20
0
20
40
60
80
100
ester alcool
amide alcool
Tg (°C)
lambda
MAT2
MAD2
MAD5
DAD8
MED2
MED4
MED6
DED2 polyol
DED4 DED6
TEP
NA
NA
20
Tg(oC)
Glass transition temperature parameters
Amide function
Cross-linking density
Distance between alcohol functions
PU SYNTHESIS
Tg determination - DSC
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Polymer Gel time
20°C (min)
PU-TEP 170
PU-ALP 490
PU-AGP 370
PU-AAP 690
PU-MAD2 45
21
PU SYNTHESIS
Rheology – gel time
Fast and exothermic cross-linking of TEP/AP
Catalysis of alcohol/isocyanate reaction by amide*
*Arnold et al, Chem Rev, 1957, 57, 47
Sato et al, JACS, 1960, 82, 3893
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Summary
Example text
3 Functionality
2 Amide function
1 Distance OH
Tg
Reaction time
Tg
Hardness Shore
Swelling rate
Tg
Swelling rate
4 OH type
Reaction time
Exothermic
5 Functionalisation
Thiol-ene : soft PU
Epoxy/acid : hard PU
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PU SYNTHESIS
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From soft to hard PU
FORMULATIONS
PU M-TEP M-ALP
Tg (°C) 2 45
Hardness Shore 59 (A) 80 (D)
Td5 % air (°C) 240 290
Char 500 °C air (%) 35 48
εR 23 °C (%) 70 2
σR 23 °C (MPa) 2 660
E 23 °C (Pa) 5 2450
FPU(%wt) 11 40
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ISOCYANATE FREE POLYURETHANES
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Cyclocarbonate dimers
No thiol
Mild conditions
Thiol-ene coupling
« Click chemistry »
Formation of thioethers/ethers
Esterification
No thiol
Range of monomers
Trans-esterification
25
HO
TOOL BOX
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DICYCLOCARBONATES
Different precursors
Thiol-ene coupling
(Trans)esterification
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Solid
Ester/amine side reaction
Liquid
Thioether/ether functions
27 Thiol-ene coupling benefits
DICYCLOCARBONATES
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MATERIALS
Polyhydroxyurethane synthesis
Dicyclocarbonates by thiol grafting
PHU Tg (°C) Td5% (°C) Mn (g/mol) Ip
PHU-DCA -14 230 7000 1,5
PHU-DCG -31 250 9000 3,2
DCA
DCG
28
Benyahya et al, Polym Chem, 2011, 2,2661
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CONCLUSIONS
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CONCLUSIONS
Results - polyols for PU
Building blocks
15 polyols from vegetable oils (f, distance between OH, properties…)
4 polyols at larger scale (>1 kg)
6 dicyclocarbonates from allyl carbonate or bio-based polyacids
Partially « green » PU (isocyanate chemistry) = 70% Cgreen
Wide range of PU (Tg from 0oC to 100 oC)
Totally « green » PU (carbonate chemistry) in progress
2 formulations : various applications
soft PU - thiol-ene coupling
hard PU - epoxy/nucleophile
Test at pilot scale considered (100 m2)
Polyurethanes
Materials
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Thank you for your attention
31 Journées Chevreul 2012