Agro-Industrial Chemical Unit UMR 1010 - INRA/INP-ENSIACET
Workshop on Glycerol Marketing, Uses and ChemistryWorkshop on Glycerol Marketing, Uses and Chemistry
Glycerol / FiveGlycerol / Five‐‐Membered Cyclic Glycerilic Carbonates: Membered Cyclic Glycerilic Carbonates: New Tandems for Ring New Tandems for Ring –– Opening Oligomerisation into Opening Oligomerisation into
Glycerilic Oligocarbonates, Oligoglycerols and NonGlycerilic Oligocarbonates, Oligoglycerols and Non‐‐Isocyanates OligohydroxyurethanesIsocyanates Oligohydroxyurethanes
Dr Zéphirin MOULOUNGUIh iResearch Director INRA
Milan 18 & 19 octobre 20121
Milan, 18 & 19 octobre 2012
New applications for refined glycerine, with volumes estimates2006-2010, in ‘000MT
2006 2007 2008 2009 20102006 2007 2008 2009 2010
Epichlorohydrin 5 95 250 300 500
Propylene glycol ‐ ‐ ‐ 50 200Propylene glycol 50 200
Glycerol carbonate
Di‐butoxyl glycerine
‐ 5 70 80 100
Di butoxyl glycerine
GTBE (Glycerine Ter Butyl Ether)
Acrolein
Others
TOTAL 5 100 320 430 800
Source: Heming J. World glycerine market up to 2010, with emphasis on News USES for glycerines,PIPOC ; Kuala Lumpur, Août 2007 2
Chemical Building Blocks Concept from Glycerol / Glycerol CarbonateChemical Building Blocks Concept from Glycerol / Glycerol Carbonate
OH
C‐OHFatty acid
C‐ORO O
Fatty methyl ester
OLEOCHEMICAL
HOOH
OH
Glycerol
Fatty acid Fatty methyl ester
C‐O‐M+
OO‐H
O
Fatty alcoholSoaps
O O
OH
IntermediatePlatform
5‐memberedglycerilic cyclicMouloungui et al., 2000/6025504
Glycerol carbonateOH 1st generation carbonate
O O
O
Intermediate 5‐memberedMouloungui Z., Pelet S.,E J Li id S i T h l
O O
OC‐R
OGlycerol Carbonate Esters
IntermediatePlatform
2nd generation
5‐memberedglycerilic cycliccarbonate
Eur. J. Lipid Sci. Technol,2000, 103, 216‐222
3
Our StrategyValorization of glyceroli t l l b t
ObjectiveTo develop C‐3
Glycerol
into glycerol carbonateas platform molecule toobtain :
glycerol/glycerol carbonatechemistry to consumptionthe glycerol into oligo‐ and
‐ Top glycerolcarbonate derivativesmonomers
the glycerol into oligo andpolymers materials.
To improve the economy ofbi di l d ti d monomers
‐ Glycerilicoligocarbonate/
biodiesel production andoleochemical industry bysustainable the glycerine
Glycerol CarbonateCAS: 931‐40‐8
oligoglycerol by ringopening five memberedglycerilic cyclic
g ysupply/ demand balance
glycerilic cycliccarbonates
‐ Glycerilic oligo‐ andl h d th b
C3‐monomersC3‐oligomers
C3‐polymers
C OO CRO
polyhydroxyurethanes byisocya‐nate free‐route[ CH‐CH2‐O‐C‐O ] [ CH2‐CH‐CH2‐O ]
CH2OH
OHn m
OPoly [aminoesters glycerilic
polyhydroxyurethane]O O
O‐CR
5‐membered glycerilic cyclic carbonates
Oligocarbonate/oligoglycerolO O
O O
OHN‐R‐NH
R‐NH
O
4
Glycerolcarbonate
CAS Number: 931-40-8EINECS Number: 213-235-0
Catalytic Process of Glycerol Carbonate Synthesis
By: Integrated carbonation approach
In: Slurry three phase catalytic reactorIn: Slurry three phase catalytic reactor
5
Technology of synthesis of C3 AgroTechnology of synthesis of C3 Agro‐‐SynthonsSynthons
Technology of synthesis of the glycerol carbonate
Technology : Catalytic carbonylation of glycerol by reaction of the urea with the glycerol
* Catalytic process in consecutive two steps in situ
One-pot >>> C b l ti C b l tiReactions >>> Carbamoylation Carbonylation
OH H2N = OOH OH
OH
OH
H2N= O
OH
OC-NH2 O
OO
=Cat : ZnSO4
NH3NH3
=
OGlycerol GlycerolUrethane
Glycerol carbonate
Processes patented : ONIDOL/INPT : FR 98 055 47 (30 April 1998) ; US Pat 6 025 504 (15 Feb. 2000)EP 99 390 009 A1 (27 March 2001) 6
Reaction catalyzed by the zinc sulphate
Principle of the glycerol carbonate synthesisPrinciple of the glycerol carbonate synthesisy y p
Multiphase reaction: liquid‐solid‐gaz
Two step reaction: i) carbamoylation, ii) carbonylation
The abstraction of the ammonia is limiting phenomena
The temperature and pressure are important parameters: thermal shock and t i d i ld f l l b t ( Yi ld 86 90% )strong vacuum give a good yield for glycerol carbonate ( Yield= 86‐90% )
Experimental conditions
Molar ratio of urea/glycerol [M = 1]
27.6 g glycerine18.0 g urea0.5g ‐ ZnSO4.H2O
T = 150°C (1h) 140°C (6h)T 150 C (1h) 140 C (6h)
P = 40 mbar (1h) 30 mbar (6h)
7
A Novel Reaction Medium : Hydroxy Thermal MIX FluidGlycerol / Glycerol Carbonate: Glycerol Solubilization in situ of ZnSO4.H2O depending
of thermal condition
Glycerol carbonate Cristallisation in situ of anhydrous ZnSO4 depending of the glycerol carbonate concentration and thermal condition
Hypothesis of thermal treatment of the zinc sulfate and mechanism*
Liquid phase**H
Nucleationzinc sulfate and mechanism
HO
HO
ZnO
SO
Growth
•J W Yoo and Z Mouloungui 3rd Internat Mesostructured
OH
O O
AS/L Separation
Agglomeration
H
O
O
O
•J.W. Yoo and Z. Mouloungui 3 Internat. MesostructuredMaterials Symp. IMMS 2002, Korea** S.J. Angyal, Chem. Soc. Rev., 1980, 9, 415
p
OH
OH HH
Zn2+
CH2O
ZnSO4.H2O(commercial)
S f BET19 1 m2/g
ZnSO4
0.1 m2/g
OH H
HHH
HOB
Surface area BETSurface area t‐plotParticle size
19.1 m /g26.8 m2/g0.09 nm
0.1 m /g1.7 m2/g0.02nm
8
Properties of Hydroxy Solvo Thermal Fluid :Properties of Hydroxy Solvo Thermal Fluid :Glycerol / Glycerol CarbonateGlycerol / Glycerol Carbonate
Glycerol Glycerol carbonate
Molecular mass 92 g/mol 118 g/mol
y / yy / y:
Molecular mass 92 g/mol 118 g/mol
Boiling point 290 °C 351 °C
Melting point ‐ 17,8°C ‐ 66,7°C
Calorific capacity 0,577 cal /K/g 0,408 cal /K/g
Flash point 160°C 212°C
Conductivity (22°) 100.10 ‐6 Ohm‐1.m‐1 144.10 ‐6 Ohm‐1.m‐1
Dielectric constant (22°C) 42,5 121,8
Dipolar moment (25°C) 2 67 D 5 45 DDipolar moment (25°C) 2,67 D 5,45 D
Surface tension (25°C) 63 mN/m 45,5 mN/m1. Heating medium 2. Heat‐transfer fluid
Hydroxy thermal fluid
high compatibility
Non‐flammable
Non‐explosive
N i
Solvent power, Dielectric fluid, Polar activator, Free
fire risks, Low toxicity,
with many uses Non corrosive
Stable liquid
Biodegradability
Source: Mouloungui Z., Yoo J.W., PIPOC, Kuala Lumpur, 2007 9
Glycerol Carbonate asBuilding Block forBuilding Block for Polymersy10
Our « CO2‐philics »2 pglycerilic oligo‐ and l b d l ilipolycarbonates and glycerilic oligo‐ and polyhydroxyurethanesoligo and polyhydroxyurethanes materials from glycerilic cyclic carbonates11
Key question:Key question:How to control the mechanism of direct oligomerization of glycerol carbonate intooligoglycerol carbonate preferentially to the mechanism of decomposition of glycerololigoglycerol carbonate preferentially to the mechanism of decomposition of glycerolcarbonate into oligoglycerols ?
Glycerol carbonate
CarbonationGlycerol
Oligomers
Oligomers of glycerol carbonate
Source: Vogdanis L. & al., Synthetic and thermodynamic investigions in the polymerization of ethylene carbonate,Makromol. Chem., 1990, 191, 465‐472 12
Glycerol carbonate oligomerizationGlycerol carbonate oligomerizationOH
Catalyst CH2OH CH2OH O
O O
O
∆Initiator [ ( CH2-CH-O )x / ( CH2-CH - O - C - O )y ]n + n.x CO2
l [( l h h d h l) h lOGlycerol
Carbonate
Poly [(alpha‐hydroxymethyl)oxyethylene‐alt‐ (alpha‐hydroxymethyl)ethylene carbonate
Study of glycerol carbonate oligomerization inStudy of glycerol carbonate oligomerization inoptimal catalytic and thermal conditions
13
TTRANSFERTRANSFERTScale‐up: 250 mL, 2 Liters, 25 Liters, 50 Liters
Phase 1 : Glycerolcarbonate synthesis
Phase 2 : Glycerol carbonateOligomerization
Glycérol + urée
Solid/liquid/gas Solid/liquid/gasevolutionary
systems
Solid Zinc sulfate
Glycerol/glycerol Liquid •Glycerol carbonate
Zinc sulfate
carbonateq y
•Glycerol oligocarbonate•Oligoglycerol•Glyceroly
NH3 : ammoniac Gas CO2 : carbon dioxide
One‐Pot ProcessOne‐Pot Process
GlycerolPhase 1
T, P.Glycerol
carbonatePhase 2
(poly)OligomersCOT,
+ NH3+ CO2
T
Mouloungui Z., Truongh Dinh Ng., Marechal Ph., Glycerol polycarbonate, organic compositions containing same and method for obtaining said compositions. US 2009/0054271 ; PCT FR 2005/002065 14
Ring opening oligomerisation of glycerol Ring opening oligomerisation of glycerol b / l lb / l lcarbonate/glycerolcarbonate/glycerol
Gl l b tO
Glycerol + Glycerol
CatalystP = 30 mbarT = 180°C
•Glycerol carbonate•Glycerol oligocarbonate•Oligoglycerol
Gl l
OHO O
Glycerolcarbonate
+ Glycerol t = 3 h
+ H2O + CO2
•Glycerol
Mouloungui Z., Truongh Dinh Ng., Marechal Ph., Glycerol polycarbonate, organic compositions containing sameg , g g , , y p y , g p gand method for obtaining said compositions, US 2009/0054271 ; PCT FR 2005/002065
15
Formation of different structural units from glycerol Formation of different structural units from glycerol carbonate caracterised by MHcarbonate caracterised by MH++ and (MHand (MH‐‐HH22O)O)++ ionsionscarbonate caracterised by MHcarbonate caracterised by MH and (MHand (MH HH22O)O) ionsions
HO ( CH CH O C O ) HHO ( CH2 - CH - O - C - O )x HCH2OH
O
x 1 2 3 4 5 6 7x 1 2 3 4 5 6 7
MH+ 137 255 373 491 609 727 845
O ( C C O ) O ( C C C O )
CH2OH
y 1 2 3 4 5 6 7 8
HO ( CH2 - CH - O )y H ou HO ( CH2 - CH - CH2-O )y HOH
y 1 2 3 4 5 6 7 8
MH+ 93 167 241 315 389 463 537 61116
Formation of different structural units from glycerol Formation of different structural units from glycerol carbonate caracterised by MHcarbonate caracterised by MH++ and (MHand (MH‐‐HH22O)O)++ ionsions
HO ( CH2 - CH - O - C - O ) ( CH2 - CH - O )y H
OCH2OH CH2OHy 1 2 3 4 5 6 7 8
MH+ 211 285 359 433 507 581 655 729
O
(MH‐H2O)+ 193 267 341 415 489 563 729 711
OHO ( CH2 - CH - O - C - O ) ( CH2 - CH - O ) CH2
OCH2OH CH2OH
O
n 1 2 3 4 5
MH+ 329 403 477 551 625
(MH‐H2O)+ 311 385 459 533 607
cyclique 17
Our «Our « COCO22‐‐philicsphilics » glycerilic oligo» glycerilic oligo‐‐ and and polycarbonates materials from glycerol carbonatepolycarbonates materials from glycerol carbonatepolycarbonates materials from glycerol carbonatepolycarbonates materials from glycerol carbonate
• « CO2‐philics » compounds from «CHO »2CarbonHydrogenOxygenOxygen
by synthesis and characterization of glycerilic oligocarbonate/oligoglycerol
CH2OH O
CH ‐ CH2 ‐ O ‐ C ‐ Ox
CH2 ‐ CH ‐ CH2 ‐ Oy
OH
• The focus of this oligomerisation was to determine 19
Glycerol Carbonate Derivative yas Building Block for Polymers20
Glycerilic Amino Ester GPHUGPHUsMn > 30 000 g/molMn > 30 000 g/mol21
Glycerilic PolyhydroxyUrethane (GPHUs)Glycerilic PolyhydroxyUrethane (GPHUs)Glycerilic PolyhydroxyUrethane (GPHUs)Glycerilic PolyhydroxyUrethane (GPHUs)Non Isocyanate PolyUrethanes based on Glycerilic Non Isocyanate PolyUrethanes based on Glycerilic
C li C b tC li C b tCyclic CarbonatesCyclic Carbonates
1st Aim:1st Aim:Substitution of isocyanate by glycerilic cyclic carbonateSubstitutin of chemistry O = C = N – R – N = C = O +
C C
OH OHIsocyanate
Diol
Chemistry of cyclic carbonate + poly (amine)
O - R + H2N - R - NH2
2nd Aim:
O O
O
Improvment of molecular weight of glycerilic polyhydroxyurethanes ( GPHUs)
22
Synthesis of Glycerilic AminoEsters Synthesis of Glycerilic AminoEsters PolyHydroxyUrethanes by two different routes named PolyHydroxyUrethanes by two different routes named «« two stepstwo steps » and «» and « oneone‐‐potpot »»
O O
OC ‐ CH = CH2 + H2N ‐ R ‐ NH2
O11stst route by «route by « two stepstwo steps »»
O O
O
Glycerilic cyclic carbonate‐amine stoechiometric reaction
OC HO
C ‐ OHO
H2N – R – NH2Polyaddition by
aminolyse reaction
OC H
O O
O
N R NC OH
O O
O
O O N‐R‐N
O
O O
O O
N‐R‐NH H H H
* *
Oaminolyse reaction O
OH OH n
O O N R N
OO
O O
N‐R‐NH H H H*
O
OOH OO
H HO
O O N‐R‐NOH
OO N R N
OH n*
Mouloungui et al., 2012.French Patenting Application
OO N‐R‐N
OHO
O N‐R‐NH H
OH n*
*O
23
Synthesis of Glycerilic AminoEsters Synthesis of Glycerilic AminoEsters PolyHydroxyUrethanes by two different routes namedPolyHydroxyUrethanes by two different routes namedOPolyHydroxyUrethanes by two different routes named PolyHydroxyUrethanes by two different routes named «« two stepstwo steps » and «» and « oneone‐‐stepstep »»22ndnd route by «route by « one stepone step »»22ndnd route by «route by « one stepone step »»
O O
O ‐ C ‐ CH = CH2
O
« One pot » synthesis bycoupling Aza‐Michael reaction H N R NH
O O
Ocoupling Aza Michael reactionand aminolyse reaction in thebulk
O
H2N – R – NH2
O O N‐R‐N
O
OHO O
O O
N‐R‐NH H H H
OH n* *
O
O O N‐R‐N
O
OO
O O
N‐R‐NH H H H
**
OMouloungui et al. 2012
French Patenting Application
OOHO
OO
N‐R‐NH HH H
*O
OH OH n
OO N‐R‐N O
O N R NH H
OH n*
24
Amino Ester PHUs SynthesisAmino Ester PHUs Synthesis
+ H2N‐R‐NH2aT= 90°Ct=2 h bc T=90°C
2 moles 2 moles2 moles 1 moleH OH H
O O
1 mole diamine* O O N
H
O
OH
O
R NH
OO N
H
OHO
R NH *n
NH
O
O
O NH
O
R NH ** O O N
HOHR nBulk Polymerization /Solution P l i ti Viscous media+
OH HO H n
OO N
HO
OHO
* O O NH
OOH
OR N
HR N
H *n
Polymerization Viscous media+
Amino Ester PHUs
Amino Ester PHUs: CaracterizationAmino Ester PHUs: CaracterizationCaracterization by FTIR
62
T.C. alkene = 100%T.C. cycle = 79%
Mn = 25 200M = 29 003
57
n (%
)
Mw = 29 003
47
52
Tran
smis
sion
O(C O)NHOH C-N-
425001000150020002500300035004000
T
Nombre d'onde (cm-1)
résine-O(C=O)NH-
Disapparence of the alkene bandConsumption of cyclocarbonate bandFormation of urethane bands
SummaryIntegrated processes of C‐3 glycerol/glycerol carbonate were successfully developed They contribute to:were successfully developed. They contribute to:
Obtain glycerol carbonate as intermediate platformDevelop an AgriGlyfinery by preparation of « CO2‐evelop an AgriGlyfinery by preparation of CO2
philics » oligo‐/polymers material from « CHO » by synthesis of:
‐ Glycerilic oligocarbonate/oligoglycerol as oligomers‐ Glycerilic oligocarbonate/oligoglycerol as
i t di t l tfintermediate platformDevelop an AgriGlyfinery by preparation of « CO2‐
philics » non isocyanate polyhydroxyurethane (NIPUs) fromphilics » non‐isocyanate polyhydroxyurethane (NIPUs) from « CHON » by synthesis of:
‐ Glycerilic oligohydroxyurethanes as oligomers and as 26
zephirin.mouloungui@ensip g @acet.fr
hi i i d i ll fwww.chimieagroindustrielle.fr