Agro-Industrial Chemical Unit UMR 1010 - INRA/INP-ENSIACET Workshop on Glycerol Marketing, Uses and Chemistry Workshop on Glycerol Marketing, Uses and Chemistry Glycerol / Five Glycerol / 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 Non Glycerilic Oligocarbonates, Oligoglycerols and Non‐ Isocyanates Oligohydroxyurethanes Isocyanates Oligohydroxyurethanes Dr Zéphirin MOULOUNGUI h i Research Director INRA Milan 18 & 19 octobre 2012 1 Milan, 18 & 19 octobre 2012
27
Embed
Glycerol / Five Membered Cyclic Glycerilic Carbonates ... Z., Pelet S., EJLiidSiThl OC‐R Glycerol Carbonate Esters O Platform 2nd generation glycerilic cyclic carbonate Eur. J. Lipid
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
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
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
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
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 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 »»
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
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