Chemical modification of wood by mixed anhydrides. Etude de la modification chimique du bois par des anhydrides mixtes.

James Clark

Description

Niveau: Supérieur, Doctorat, Bac+8
THÈSE En vue de l'obtention du DOCTORAT DE L'UNIVERSITÉ DE TOULOUSE Délivré par l'Institut National Polytechnique de Toulouse Discipline ou spécialité : Sciences des Agroressources JURY M. James CLARK (Professeur, The University of York, UK, Rapporteur) M. Alessandro GANDINI (Professeur, Universidade de Aveiro, Portugal, Rapporteur) Mlle Elisabeth BORREDON (Professeur, Institut National Polytechnique de Toulouse) M. Yves CHAUVIN (Membre de l'Académie des Sciences) M. Stéphane GRELIER (Professeur, Université de Bordeaux) Mlle Silham EL KASMI (Responsable R&D LAPEYRE) M. André MERLIN (Professeur, Université de Nancy) M. Carlos VACA GARCIA (Professeur, Institut National Polytechnique de Toulouse) Ecole doctorale : Sciences de la Matière Unité de recherche : Laboratoire de Chimie Agro-industrielle (UMR 1010 INRA/INP-ENSIACET) Directeur de Thèse : Professeur Elisabeth BORREDON Codirecteur de Thèse : Professeur Carlos VACA GARCIA Présentée et soutenue par Jérôme Peydecastaing Le 26 novembre 2008 Titre : Chemical modification of wood by mixed anhydrides. Etude de la modification chimique du bois par des anhydrides mixtes.

• has been


• pilot treatment


• been consumed


• borredon codirecteur de thèse


• growth local species


• fatty cellulose


• has lead


• anhydrides mixtes

Sujets

• List of Revelation Space characters
• Académie des sciences
• Institut national polytechnique de Toulouse
• Nancy-Université
• United Nations
• Chauvin
• Merlin

Informations

• Publié par: profil-feym-2012
• Publié le: 01 novembre 2008
• Nombre de lectures: 40
• Langue: Français
• Poids de l'ouvrage: 5 Mo

Extrait

THÈSE


En vue de l'obtention du

DOCTORAT DE L’UNIVERSITÉ DE TOULOUSE DOCTORAT DE L’UNIVERSITÉ DE TOULOUSE

Délivré par l’Institut National Polytechnique de Toulouse
Discipline ou spécialité : Sciences des Agroressources
Présentée et soutenue par Jérôme Peydecastaing
Le 26 novembre 2008

Titre : Chemical modification of wood by mixed anhydrides.
Etude de la modification chimique du bois par des anhydrides mixtes.


JURY

M. James CLARK (Professeur, The University of York, UK, Rapporteur)
M. Alessandro GANDINI (Professeur, Universidade de Aveiro, Portugal, Rapporteur)
Mlle Elisabeth BORREDON (Professeur, Institut National Polytechnique de Toulouse)
M. Yves CHAUVIN (Membre de l’Académie des Sciences)
M. Stéphane GRELIER (Professeur, Université de Bordeaux)
Mlle Silham EL KASMI (Responsable R&D LAPEYRE)
M. André MERLIN (Professeur, Université de Nancy)
M. Carlos VACA GARCIA (Professeur, Institut National Polytechnique de Toulouse)


Ecole doctorale : Sciences de la Matière
Unité de recherche : Laboratoire de Chimie Agro-industrielle (UMR 1010 INRA/INP-ENSIACET)
Directeur de Thèse : Professeur Elisabeth BORREDON
Codirecteur de Thèse : Professeur Carlos VACA GARCIA
General summary
Foreword ................................................................................................... 5
CHAPTER 1: The characteristics and the durability of wood
1.1 Introduction ..................................................................................................................... 9
1.2 Generalities ..................................................................................................................... 9
1.3 The wood structure ....................................................................................................... 13
1.4 The properties of wood ................................................................................................. 23
1.5 Current strategies to increase wood stability ................................................................ 34
1.6 Conclusions .................................................................................................................... 58
CHAPTER 2: Acetic-fatty anhydrides analysis and synthesis
2.1. Introduction ................................................................................................................... 68
2.2. Quantitative analysis of mixtures of various linear anhydrides and carboxylic acids .... 69
2.3. Consecutive reactions in an oleic acid and acetic anhydride reaction medium ............ 79
2.4. Conclusions .................................................................................................................... 93
CHAPTER 3: Study of the reactivity of mixed anhydrides toward cellulosics
3.1 Introduction ................................................................................................................... 97
3.2 Accurate determination of the DS of long chain cellulose esters (LCCE) ....................... 99
3.3 Mixed acetic-fatty cellulose esters. Part I. Synthesis ................................................... 115
3.4 Mixed acetic-fatty cellulose esters. Part II. Hydrophobicity ........................................ 133
3.5 Mixed acylation of Scots pine sawdust and impact on hydrophobicity ....................... 151
3.6 Conclusions .................................................................................................................. 175
CHAPTER 4: Influence of the treatment conditions on wood properties
4.1 Introduction... 179
4.2 Methodology 180
4.3 Swelling and specific gravity ........................................................................................ 181
4.4 Mechanical properties ................................................................................................. 187
4.5 Dimensional stability ................................................................................................... 195
4.6 Scanning electron microscopy ..................................................................................... 206
4.7 Surface color characteristics ........................................................................................ 208
4.8 The Wood Protect® pilot treatment ............................................................................ 212
4.9 Conclusions .................................................................................................................. 221
General conclusion .................................................................................. 225
Scientific production 2005-2008 ............................................................... 231 Foreword
The industrial era, that has begun two centuries ago, participated in the
frenetic consumption of fossil and renewable resources. In less than two
hundred years of industrial development, about 50% of the fossil resources have
been consumed. Renewable resources which the mains fields of applications are
energy, food, pharmaceutics, textile and raw material in the construction
industry are also concerned due to an increase consumption caused by a
multiplication of the population by four in less than one century.
Wood as a raw material is also concerned. A global deforestation of about
13 millions of hectares has been observed in 2005 by the Food and Agriculture
Organization of the United Nations (FAO). In the past, naturally durable local
wood species were traditionally used in the construction. But the increasing
consumption of these species that present slow growth has lead to consider
them as non renewable. Durable species have then been imported from the
fantastic resources that are the tropical forests leading to an ecological disaster.
That is why biocide treatments such as CCA and creosotes have been developed
to give to fast growth local species an acceptable durability to be use as lumber.
Nevertheless the toxicity of such treatments has lead to restrict or prohibit their
uses by application of new legislations such as the biocides directive.
A need for developing new wood treatment has therefore become urgent to
replace biocides. Wood modification has been initiated since the 1950’s and
encounter an increased interest in last decade. The main purposes of wood
modification are to increase durability by mean of increasing biological
resistance and to enhance wood properties such as dimensional stability and
photostability to respect the specifications of the wood industry and particularly
the one working on joineries.
The main objective of this dissertation will be to present the investigations
made to develop a new wood treatment based on the chemical modification of
wood. This work has been realized in collaboration with a French company
named LAPEYRE, filial of the SAINT-GOBAIN group. LAPEYRE is a joinery
maker which priorities and interest in this work has been to develop a treatment
able to give high dimensional stability to wood. The investigations were carried out in the French Laboratory of Agro-
industrial Chemistry (LCA) located in Toulouse under the direction of the
manageress of the laboratory, Professor Elisabeth Borredon as well as her
colleague, Professor Carlos Vaca-Garcia.
The treatment deals with chemical modification of wood by mixed acetic-
fatty anhydrides. The process developed during this research allowed to file
three patents, one in 2003 under the number WO2003084723 and two in 2007
under the numbers WO2007141445 and WO2007141444. These applications
found an industrial interest and have been commercialized since 2006 under the
®name of Wood Protect .
Four chapters compose this manuscript.
In the first one, an overview of the chemistry of wood and its preservation
will be presented.
The second chapter is composed of two published peer-reviewed articles;
one dealing with the development of an analytical technique to analyze mixed
anhydrides and the other one on the kinetic and thermodynamic study of their
synthesis.
Chapter three is compiling four articles. The first one describes an
analytical method to determine de degree of substitution of cellulose esters, the
second and the third one describe the esterification reaction on cellulose and the
hydrophobic properties obtained. The fourth paper explains the changes of
reactivity occurred when passing from cellulose to a lignocellulosics substrate:
wood sawdust.
Finally, chapter four presents the treatment of wood blocks at both
laboratory and pilot scales. The dimensional stability, the mechanical
properties, as well as weathering and biological protection are discussed.
Each of these chapters will be accompanied by an introduction and a
conclusion in order to facilitate the understanding of the running of the
investigations. 1 CHAPTER 1
The characteristics and the durability of wood

CONTENTS
1.1 Introduction .......................................................................................... 9
1.2 Generalities ..................................................................................