[PDF] Novel biobased epoxy networks derived from renewable resources

View - Download Novel biobased epoxy networks derived from renewable resources

Previous PDF

Next PDF

N° d"ordre 2012ISAL0051 Année 2012

Thèse

Novel biobased epoxy networks derived from renewable resources : Structure-property relationships

Présentée devant

L"institut national des sciences appliquées de Lyon

Pour obtenir

Le grade de docteur

École doctorale : Matériaux de Lyon

Spécialité : Matériaux Polymères et Composites Par

Marie CHRYSANTHOS

Ingénieur ENSCCF

Soutenue le 21 Juin 2012 devant la Commission d"examen Jury E. BOURGEAT-LAMI Directrice de re cherche CNRS (CPE Lyon)

Rapporteur B. BOUTEVI N Professeur (ENSCM)

J. CHRISTOUD Responsable se rvice Matériaux (Rossignol) J. GALY Directr ic e de recherche CNRS (INSA de Lyon)

P. GOTTIS Docteur (H untsman)

Rapporteur M. LAVORGN A CNR Researcher (ICBM - Naples, Italy)

J.P. PASCAULT Professeur ( IN SA de Lyon)

P. SABRE Renewab le Chemistry Management (Roquette Frères) SIGLE ECOLE DOCTORALE NOM ET COORDONNEES DU RESPONSABLE

CHIMIE

CHIMIE DE LYON

http://www.edchimie-lyon.fr

Insa : R. GOURDON

M. Jean Marc LANCELIN

Université de Lyon - Collège Doctoral

Bât ESCPE

43 bd du 11 novembre 1918

69622 VILLEURBANNE Cedex

Tél : 04.72.43 13 95

directeur@edchimie-lyon.fr

E.E.A.

ELECTRONIQUE,

ELECTROTECHNIQUE, AUTOMATIQUE

http://edeea.ec-lyon.fr

Secrétariat : M.C. HAVGOUDOUKIAN

eea@ec-lyon.fr

M. Gérard SCORLETTI

Ecole Centrale de Lyon

36 avenue Guy de Collongue

69134 ECULLY

Tél : 04.72.18 60 97 Fax : 04 78 43 37 17

Gerard.scorletti@ec-lyon.fr

E2M2

EVOLUTION, ECOSYSTEME,

MICROBIOLOGIE, MODELISATION

http://e2m2.universite-lyon.fr

Insa : H. CHARLES

Mme Gudrun BORNETTE

CNRS UMR 5023 LEHNA

Université Claude Bernard Lyon 1

Bât Forel

43 bd du 11 novembre 1918

69622 VILLEURBANNE Cédex

Tél : 04.72.43.12.94

e2m2@biomserv.univ-lyon1.fr EDISS

INTERDISCIPLINAIRE SCIENCES-

SANTE http://ww2.ibcp.fr/ediss

Sec : Safia AIT CHALAL

Insa : M. LAGARDE

M. Didier REVEL

Hôpital Louis Pradel

Bâtiment Central

28 Avenue Doyen Lépine

69677 BRON

Tél : 04.72.68 49 09 Fax :04 72 35 49 16

Didier.revel@creatis.uni-lyon1.fr

INFOMATHS

INFORMATIQUE ET

MATHEMATIQUES

http://infomaths.univ-lyon1.fr

M. Johannes KELLENDONK

Université Claude Bernard Lyon 1

INFOMATHS

Bâtiment Braconnier

43 bd du 11 novembre 1918

69622 VILLEURBANNE Cedex

Tél : 04.72. 44.82.94 Fax 04 72 43 16 87

infomaths@univ-lyon1.fr

Matériaux

MATERIAUX DE LYON

Secrétariat : M. LABOUNE

PM : 71.70 -Fax : 87.12

Bat. Saint Exupéry

Ed.materiaux@insa-lyon.fr

M. Jean-Yves BUFFIERE

INSA de Lyon

MATEIS

Bâtiment Saint Exupéry

7 avenue Jean Capelle

69621 VILLEURBANNE Cédex

Tél : 04.72.43 83 18 Fax 04 72 43 85 28

Jean-yves.buffiere@insa-lyon.fr

MEGA

MECANIQUE, ENERGETIQUE, GENIE

CIVIL, ACOUSTIQUE

Secrétariat : M. LABOUNE

PM : 71.70 -Fax : 87.12

Bat. Saint Exupéry

mega@insa-lyon.fr

M. Philippe BOISSE

INSA de Lyon

Laboratoire LAMCOS

Bâtiment Jacquard

25 bis avenue Jean Capelle

69621 VILLEURBANNE Cedex

Tél :04.72.43.71.70 Fax : 04 72 43 72 37

Philippe.boisse@insa-lyon.fr

ScSo ScSo*

M. OBADIA Lionel

Sec : Viviane POLSINELLI

Insa : J.Y. TOUSSAINT

M. OBADIA Lionel

Université Lyon 2

86 rue Pasteur

69365 LYON Cedex 07

Tél : 04.78.69.72.76 Fax : 04.37.28.04.48

Lionel.Obadia@univ-lyon2.fr

*ScSo : Histoire, Geographie, Aménagement, Urbanisme, Archéologie, Science politique, Sociologie, Anthropologie

Extxendxtx abs

Remerciements

Je tiens dans un premier temps à remercier ma directrice de thèse, Jocelyne GALY,

pour m"avoir confié ce travail de recherches, ainsi que pour sa disponibilité, sa gentillesse, et

son aide au cours de ces années. Je remercie également Jean-Pierre PASCAULT, de s"être

investi dans cette thèse. Merci à lui pour toutes ses idées et remarques qui m"auront aidé à

remettre perpétuell ement en cause mon travail, à avance r et développer ma curios ité

scientifique. Je le remercie également d"avoir accepté de faire partie du jury. Merci enfin à

Jean-François GERARD, et Etienne FLEURY, pour m"avoir accepté dans leur laboratoire. Je ti ens égaleme nt à remercier Mari no LAV ORGNA, et Monsieur Bernar d BOUTEVIN, d"avoir accepté d"être les rapporteurs de ce travail. Merci à Philippe SABRE, de

la soc iété Roquette et Frères, Jacky CHRIS TOUD de la socié té Rossignol, et Philippe

GOTTIS de la société Huntsman, pour leur aide et leur gentillesse tout au long du projet NAFI et d"avoir accepté de faire partie de mon jury. Je remercie, de même, la présidente du jury Elodie BOURGEAT-LAMI. J"en profite également pour adresser mes remerciements à tous les membres du projet NAFI, dont Françoise MECHIN pour son aide bibliographique. Pour leur soutien technique mais surtout leur bonne humeur, leur gentillesse et tous ces moments de fous rires, un grand merci aux dames de la RMN : Fernande BOISSON, Annick WATON et surtout Cécile CHAMIGNON, l"inénarrable. Merci à Raphael BRUNEL pour son aide précieuse en rhéologie ainsi qu"à Guilhem QUINTARD qui n"aura jamais perdu patience et aur a " pr esque » su m e faire apprécier l a ma chine d"ARES. J"aimerai aus si remercier les secrétaires du laboratoire, Mallou et Isabelle, pour leur gentillesse et leur aide précieuse. Merci aussi aux nombreux non-pe rmanents du laboratoir e, thèsards, post-docs et

autres masters, qui auront su égayer ces années de thèse. Un grand merci en particulier à mes

compagnons de burea u ; m erci à Feliks , à Amélie (m a col lègue de voya ge !), à Céline,

Wenyong, Thomas, Komkriss et last but not least, Elie. Merci aux anciens (Morgan, Sandra,

Alexia, Arthur) pour leurs conseils précieux à la débutante que j"étais. Merci à Stéphane

(Pépito !) et Grégoire qui ont partagé cette expérience en même temps que moi. Merci à ceux

qui n"ont pas encore fini (courage) et avec qui j"ai eu plaisir à faire un bout de chemin (Marie-

Extxendxtx abs

Laure, Nora, Vincent, Sylvain, Gino, Florent, Thibault, Floriane, Loïc, Cédric, Marie, Hélène,

Marianne). Merci é galement aux pos t-doc pour leur grande " s agesse » et leur soutie n (Nicolas D., Nicolas L., Marco). Merci à Elise, pour m"avoir épaulé et avoir toujours su me redonner confiance. J"ai aussi une pensée affectueuse pour sa famille, pour Jean-Marc et la petite Amandine. Merci à mes amis hors laboratoire : Laure, Saucisse, Yvong, P"ti Nico,

Simon, Anais, Aurélien...

Je re mercie également Max ime, pour m"avoir soutenu tout le long de m es de ux

dernières années de thèse avec patience et humour, et les avoir ainsi rendu plus belles et plus

heureuses. Merci à sa famille pour m "avoir a ccueilli en côte Roa nnaise et m"avoir fa it découvrir les vendanges, ainsi qu"à Charlotte, Moun et Flo. Je remercie enfin chaleureusement ma mère et Serge, mon père, et mes deux frérots pour leur soutien indéfectible au long de ces trois années (et des poussières) de thèse. MERCI

MISOATRA

Extend ea

Abstract:

In recent years, bio-based polymers derived from renewable resources have become increasingly important as s ustainable and eco-e fficie nt products which can repl ace the products based on petrochemical-derived stocks. The objective of our work was to develop novel bio-based reactive systems suitable for high performance composite materials especially epoxy systems. The most commonly used starting monomer to formulate epoxy networks is the diglycidyl ether of bisphenol A, DGEBA, derived from bisphenol A and epichlor ohydrin. Bio-ba sed e pichlor ohydrin is commercially available. So the challenge to obtain a fully bio-based epoxy prepolymer is to replace bisphenol A by a bio-based precursor. Another interest for replacing bisphenol A by a bio-based precursor is that bisphenol A has been known to have estrogenic properties. In this study, we studied different bio-based epoxy systems and compared them to a classical DGEBA base d system using, in a firs t step, isophorone diam ine (IPD) as conventional curing agent. Bio-based epoxy prepolymers were derived from natural sugars, sorbitol and isosorbide respectively. Sorbitol polyglycidyl ether is available commercially, while isosorbide diglycidyl ether was synthesized either via conventional epoxidation (i.e. using epichlorohydrin) or via the diallyl isosorbide intermediate. Another bio-based epoxy prepolymer was derived from cardanol and is also a commercial product. Chemical structure of the bio-based epoxy prepolymers were analyzed by different analytical methods, gelat ion and crossli nking reactions w ere studied using rheological measurements and differenti al s canning calorimetry, respect ively. Propertie s of the cured networks were evaluated using dynamic mechanical analysis and thermo gravimetric analysis. Influence of the bio-based epoxy prepolymer structure on the system properties as well as the influence of the crosslinking agent structure (either derived from renewable resources or bio- based ones) was discussed. Water absorption of the bio-based networks was also studied.

Keywords:

Epoxy net works; bisphenol A; isos orbide; sorbitol ; carda nol; structure-propert ies relationships; reactivity; solid-state properties; water absorption

Extend ea

Résumé:

Récemment, les polymères obtenus à partir de ressources renouvelables ont connus un véritable engouement pour le remplaceme nt de ma tériaux obtenus à partir de ressourc es

pétrolières. L"objectif de notre étude a été de développer de nouveaux systèmes bio-sourcés

réactifs, plus précisément des systèmes époxy, pour des applications dans le domaine des

matériaux composites. Le monomère le plus souvent utilisé pour formuler des réseaux époxy est le diglycidyl éther de bis phenol A , DGEBA, obtenu à par tir du bisphenol A et de

l"épichlorhydrine. L"intérêt pour le remplacement du bisphé nol A par un pr écurseur bio-

sourcé est accentué par la toxicité de ce dernier. Dans cet te étude, nous avons étudié diff érent s syst èmes obtenus à partir de

prépolymères époxy bio-sourcés et les avons comparés à un système classique à base de

DGEBA en utilisant l"isophorone diamine (IPD) comme agent durcisseur.

Parmi les différents prépolymères époxy bio-sourcés étudiés, certains ont été obtenus à

partir de dérivés polysaccharides tels que le sorbitol et l"isosorbide. Le sorbitol polyglycidyl

éther est disponible co mmercialement , tandis que le diglycidyl éther d"is osorbide a été

synthétisé soit par une voie cl assique fa isant i ntervenir l"épichlorhydrine soi t par

l"intermédiaire du diallyle isosorbide. Un autre prépolymère époxy dérivé du cardanol a été

étudié et est aussi un produit commercial.

Les structures chimiques de ces prépolymères époxy bio-sourcés ont été analysées.

Les phénom ènes de gélific ation et de réticulation des systèm es obtenu s à partir de ces

prépolymères et de l"IPD ont été étudiés. L"influence de la structure du prépolymère bio-

sourcé et de l"agent de réticulation (classique ou dérivé de ressources renouvelables) sur les

propriétés des réseaux ainsi que l"absorption d"eau par ces réseaux ont également été discutés.

Mots-clefs:

Réseaux époxy; bi sphenol A; is osorbide; sorbitol; cardanol ; relation structure propriétés;

réactivité; propriétés des réseaux; absorption d"eau

Extented

Contents

P

absbrci FshrRIDEhFRs GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG C

EAcHhbr F bHRlo hAbrwR(bhhFsa HRiowbr( IbrF/bI grRw rbsb)cTib rb(RDrEb( GGGGGGGGGGGGGGGGGGGGGGGGGGGGG mP

agPae 24135 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP6P

aagP47827a89P4eP04-8P .82-408 aeEP+4DG-820PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggPAP

∆δPβα

δPβα

δP δδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδδ∆!P

SnP8HIPPS !P"!S#$I P!#%S &PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP''P

(nP8HIPPS %)")!P"!S#$I P!#%S &PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'*P

#nPaI #P%IIHI+!",S$I PI-P!HIPH"!HI+!"&PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'.P

aaagP/a40/1081P8+42GPe8 94230PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'6P

∆δP"#

(nP+"!HS"S$I PI-P!HIPH"!HI+!"&P-"IP5!4!$S(+!PI+&PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'AP

#nP8HIP !$6I"7&P)!"5!)P-"IP5!4!$S(+!PI+&PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'8P

)nP5I #+9&I PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP*:P

δP"#

SnP8$"S#$I PI-P#S")S I+P-"IP#S&%!6P 9$P&%!++P+;9)PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP*AP

(nP0 $%!&&PI-P#S")S I+0(S&!)PI I!"&PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP*8P

#nP8HIP !$6I"7&P)!"5!)P-"IP#S")S I+PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP<=P

)nP5I #+9&I &PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP<*P

δP"#

SnP8HIP !$6I"7&P)!"5!)P-"IP&9#"I&!PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP<*P

(nP8HIP !$6I"7&P)!"5!)P-"IPS+$$I+PS )P&I"($I+PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP<6P

#nP8HIP !$6I"7&P)!"5!)P-"IP&I&I"()!gggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP<8P

(δP)α &δP"*#

SnP+%! S+7S !&P#9" 4PS4! $&PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP.AP

(nP2I& 0(S&!)P#9" 4PS4! $&PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP.8P

#nP4$%!"P(I0(S&!)P#9" 4PS4! $&PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP6*P

a7gP53228e Pae130 2a1DP/a40/1081P8+42GP0G0 8-0PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP6 ∆δPβ

δP.

#nP1!"5!)P-"IP#S&%!6P 9$P&%!++P+;9)PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP66P

)nP4$%!"P#I!"#S+P(I0(S&!)P!HIP-I"9+S$I &PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP6:P

ERsEiD(FRs GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG mp

rbgbrbsEb( GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG mu

P

EAcHhbr FFPTFRBTc(bI bHRlo sbh)Rr-( IbrF/bI grRw F(R(RrTFIb GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG PSP

Hcrh FG HrbHcrchFRs csI HrRHbrhFb( Rg TFRBTc(bI bHRlo sbh)Rr-( IbrF/bI grRw F(R(RrTFIb

IFaioEFIoi bhAbr GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG PS

P

agPae 24135 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP:

aagP82+82a-8e 1DP085 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP:6P

∆δP/

δP1α

#%α#2

δPβ

(δP/

aaagP2803D 0P1e1P1a05300a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP:>P

Extented

Pa∆3e868DH 6+48H+423453+.4.46#+9 39+%10D+9013 He 63aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa30I∆

+!#$"0"∆&&∆&!#$"&#∆#%"#$!",$ ∆ββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββ∆=∆

Sa∆3n6+2%3# e8$+4n63aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3'I∆

a∆.251n 2D 3453.H4+De+47 H603423He 3$81n 34535%3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3AP∆

(a∆5e 674*7 De82+D813-64- 6H+ .3453He 32 H46.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3A∆

&a∆5e 67813.H8#+1+H03453He 32 H46.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3A0∆

Hcrh FFG wRibEDicr wRIbiiFsa Rg TFRBTc(bI HRiowbr IbrF/bI grRw F(R(RrTFIb GGGGGGGGGGGGGGGGGGGGGGGGGGGGG uu∆

1∆

Pa∆,64n-3D42H6+#nH+4238293741 Dn186390287+D.3.+7n18H+42.aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3AI∆

Sa∆/41 Dn1863749 11+2%38--1+ 93423-4107 6.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3I!∆

2

α1∆

Pa∆,64n-3D42H6+#nH+4237 He493aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3I∆

Sa∆/41 Dn186390287+D.37 He493aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3I(∆

a∆H68DH+2%36 .n1H.356473.+7n18H+423aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3I&∆

∆1α∆δ

Pa∆,64n-3D42H6+#nH+4236 .n1H.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3I0∆

Sa∆/41 Dn186390287+D.3E/+G36 .n1H.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3I0∆

ERsEiD(FRs GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG C0C∆

rbgbrbsEb( GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG C0=∆

EAcHhbr FFF FsgiDbsEb Rg hAb TFRBTc(bI bHRlo HrbHRiowbr (hrDEhDrb Rs sbh)Rr- HrRHbrhFb( G C0m 2

α1∆

Pa∆/8H 6+81.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3P!0∆

Sa∆g6 -868H+423453 -4032 H46.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3P!'∆

a∆/ 8.n6 7 2H.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3P!'∆

∆1α∆δ

Pa∆3e868DH 6+48H+423453He 39+55 6 2H3 -403-6 -4107 6.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3P!'∆

+!#$"0"∆&&∆&!#$"&#∆#%"#$!",$ ∆ββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββ∆'=8∆

Sa∆3n6+2%3# e8$+4n63aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3PP&∆

∆!$!" $ ∆-∆4!+∆$!∆ββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββ∆''∆

a∆+ H 67+28H+4238293 $41nH+423453%18..3H682.+H+42.3+He3D42$ 6.+423aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3PSP∆

(a∆.251n 2D 3453.H4+De+47 H603423He 3$81n 34535%63aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3PS(∆

&a∆5e 674*7 De82+D813-64- 6H+ .3453He 32 H46.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3PS&∆

∆%!"0!#% #+∆"!"$!&∆-∆$%!∆ !$6"7&∆$∆"∆A∆'∆βββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββ∆'*∆

(∆%!"0!#% #+∆"!"$!&∆-∆

∆∆δ∆ !$6"7&∆$∆)--!"! $∆&$#%!$"∆βββββββββββββββββββββββββββββββββββ∆'*8∆

0a∆5e 67813.H8#+1+H03453He 32 H46.3aaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa3P∆

∆%!"+∆&$(+$∆-∆$%!∆ !$6"7&∆$∆"∆A∆'∆ββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββββ∆'<<∆

∆∆δ∆ !$6"7&∆$∆)--!"! $∆&$#%!$"ββββββββββββββββββββββββββββββββββββββββββββββββββββ∆'<∆

ERsEiD(FRs GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG CSP

rbgbrbsEb( GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG CSp

Extented

EAcHhbr F/ FsgiDbsEb Rg hAb EDrFsa cabsh (hrDEhDrb Rs sbh)Rr- HrRHbrhFb( GGGGGGGGGGGGGGGGGGGGGGGGGGGG CS'P

Hcrh FG FsgiDbsEb Rg hAb (hrDEhDrb Rg cwFsb EDrFsa cabsh( GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG CS'

agPae 24135 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'<>P

aagP82+82a-8e 1DP085 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'.=P

∆δP1

δPβ

aaagP5.1215 82aB1 a4eP4?P/a40/1081P8+42GP0G0 8-0P9a .P712a430P532aeEP1E8e 0PgggggggggggggggggggggggggggggggggggggggggggggggggggggP'. ∆δP7

SnP/I0(S&!)P&&$!&P6$%P#I 5! $I S+P#9" 4PS4! $&PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'.

δP+

δP+

(δP5α*α

a7gP54e5D30a4eP4?P+12 PaPgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'6'P

Hcrh FFG (oshAb(F( Rg bHRlo sbh)Rr-( To IDci ErR((iFs-Fsa rbcEhFRs( GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG Cm=

agPae 24135 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'6*P

aagP82+82a-8e 1DP085 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'6 ∆δP/

SnP1!$!" S$I PI-P$%!P&$I#%I!$"#P"S$IP"A S%C !P-I"P$%!P!HI0S !P"!-!"! #!P&&$!PgggggggggggggggggggggggP'6.P

(nP?I"9+S$I &P&$9)!)PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'6.P

aaagP2803D 0P1e1P1a05300a4e0PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'66P

∆δP* 9 2-%

δP5

(nPE+S&&P$"S &$I P$!H!"S$9"!&P-I"P!HIP !$6I"7&PI($S !)P9& 4P$!"$S"PS !&PggggggggggggggggggggggggggggggggggggP'6>P

δP1

2-:#

(nP0$9)PI-P4!+S$I PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP':*P

#nP1!$!" S$I PI-PS#$5S$I P! !"4PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP':.P

)nP2!S#$I P7 !$#P-I++I6!)P(Pa2PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP':6P

(δP7

a7gP54e5D30a4eP4?P+12 PaaPggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP':>P

ERsEiD(FRs( GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG Cp0P

rbgbrbsEb( GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG Cp=

EAcHhbr /G )chbr cT(RrHhFRs Rg TFRBTc(bI sbh)Rr-( IbrF/bI grRw (RrTFhRi° F(R(RrTFIb csI

EcrIcsRi GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG CpS

agPae 24135 a4ePggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'A

aagP91 82P042+ a4eP/8.17a432PaeP8+42GPe8 94230PgggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'A.P

'gP9S$!"0!HIP !$6I"7P $!"S#$I &PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'A.P

SnP06!++ 4PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'A:P

(nP++S&$#,S$I PggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggP'A:P

quotesdbs_dbs41.pdfusesText_41

[PDF] formule semi développé de l'acide lactique

[PDF] pyruvate formule

[PDF] butanol formule

[PDF] formule semi développée isomère c4h10o

[PDF] formule semi développée c4h10

[PDF] formule semi développée du butane

[PDF] c4h10o isomers

[PDF] schéma d'analyse des champs de force st2s

[PDF] c4h10o formule semi développée

[PDF] formule semi développée butan-2-one

[PDF] formule brute butanone

[PDF] démarche de projet st2s definition

[PDF] formule semi développée 3-ethyl-2-methylpentan-1-ol

[PDF] projet d'action définition st2s

[PDF] butan-2-one