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