71 |
Novel fire testing frameworks for Phase Change Materials and hemp-lime insulationMcLaggan, Martyn Scott January 2016 (has links)
Modern buildings increasingly include the usage of innovative materials aimed at improving sustainability and reducing the carbon footprint of the built environment. Phase Change Materials (PCMs) are one such group of novel materials which reduce building energy consumption. These materials are typically flammable and contained within wall linings yet there has been no detailed assessment of their fire performance. Current standard fire test methods provide means to compare similar materials but do not deliver knowledge on how they would behave in the event of a real fire. Thus, the aim of this thesis is to develop a novel testing framework to assess the behaviour of these materials in realistic fire scenarios. For PCMs, a flammability study is conducted in the bench-scale cone calorimeter to evaluate the fire risk associated with these materials. Then, micro-scale Thermogravimetric Analysis (TGA) is used to identify the fundamental chemical reactions to be able to confidently interpret the flammability results. Finally, intermediate-scale standard fire tests are conducted to evaluate the applicability of the bench-scale results to realistic fire scenarios. These take the form of modified Lateral Ignition and Flame spread Test (LIFT) and Single Burning Item (SBI) tests to understand flame spread and compartment fires respectively. Finally, a simplified method to combine this knowledge for use in building design is proposed. This method allows the balancing of potential energy benefits with quantified fire performance to achieve the specified goals of the designer. Hemp-lime insulation is a material which has also becoming increasingly popular in the drive towards sustainability. The porous nature of the material means that smouldering combustions are the dominant reaction mode but there is currently no standardised test method for this type of behaviour. Thus, hemp-lime materials also represent an unquantified risk. The work in this thesis defines a simple, accessible and economically viable bench-scale method for quantifying the fire risk associated with rigid porous materials. This is applicable for both downward opposed flow and upward forward flow smoulder propagation conditions. The behaviour is then interpreted using micro-scale thermogravimetric analysis to understand the underlying pyrolysis and oxidation reactions. Designers can utilise this framework to quantify the smouldering risk associated with hemp-lime materials to enable their usage in the built environment. The holistic fire risk assessment performed in this thesis has quantified the behaviour of PCMs and hemp-lime insulation applicable to realistic fire scenarios. The simplified design method empowers designers to be able to realise innovative buildings through fundamental understanding of the fire behaviour of these materials. The outcomes of this thesis allow designers to mitigate the fire risk associated with these materials and achieve optimised engineering solutions. Furthermore, the novel fire testing frameworks provide the economically viable means to assess the fire performance of future PCMs and hemp-lime products which ensures lasting relevance of this research in the future.
|
72 |
Matrices thermodurcissables époxydes et furaniques biosourcées – conception d’assemblages macromoléculaires / Advanced bio-based epoxies and furanics thermosets – hierarchically assembled macromolecular designPin, Jean-Mathieu 15 June 2015 (has links)
Le travail de recherche présenté dans cette thèse s’est orienté vers l’élaboration de matériaux avancés et la conception de polymères/composites biosourcés. Ce dernier sujet a été entrepris à travers la combinaison de différentes matières premières biosourcées qui sont connues comme ayant un grand potentiel de substitution des monomères pétrosourcés. Tout d’abord, un travail fondamental a été exécuté en combinant l’huile de lin epoxydée (ELO) avec des dérivés d’anhydrides d’acides comme agents de réticulation, afin de relier la réactivité chimique de polymérisation à la structure du réseau formé et aux propriétés thermomécaniques. Afin de devenir économiquement viable, les bio-raffineries doivent urgemment valoriser les sous-produits issus de la conversion de la biomasse. Fort de ce constat, une deuxième étude sur l’incorporation et la copolymérisation d’une quantité importante d’humins (résidu hétérogène obtenu durant la conversion des sucres en hydroxymethylfurfural (HMF)) avec de l’alcool furfurylique (FA) a été réalisée avec succès afin de créer de nouvelles résines thermodures. Une autre voie proposée consiste en la combinaison de ELO et de FA à travers une polymérisation cationique, dans l’idée de créer de nouvelles résines totalement biosourcées, générant ainsi une gamme de matériaux aux propriétés mécaniques modulables. / The research work presented in this thesis was oriented on advanced thermoset materials and also on the conception of bio-based polymers and composites. This last topic has been investigated by the combination of different bio-based raw materials which are well-known to have a great potential to substitute the petroleum monomers. Firstly, a fundamental work has been done on the combination of epoxidized linseed oil (ELO) and anhydrides as cross-linkers, which links the polymerization reactivity with the network structure and thermomechanical properties. For being economically realistic, the bio-refineries are urged to valorize the sidestream products issued from biomass conversion. In that respect, a second study investigated successfully the incorporation and copolymerization of an important amount of humins (heterogeneous residues obtained during the sugar conversion into hydroxymethylfurfural (HMF)) with furfuryl alcohol (FA) in order to create new resins. Another proposed combination, focused on ELO and FA cationic copolymerization with the purpose to create new fully bio-based resins with tailored mechanical properties. Concerning the elaboration of advanced polymers and composites, a reflection around the hierarchically organized natural materials has been achieved in order to adapt the self-organization and structuration concepts to polymeric network.
|
73 |
I. Total synthesis of [plus or minus] ovalicin and its analogues II. Bio-based polymers from vegetable oil III. New synthetic methods of diacetylene fatty acidsZhao, Huiping January 1900 (has links)
Doctor of Philosophy / Department of Chemistry / Duy H. Hua / I. Ovalicin is a natural product isolated from the culture of fungus Pseudorotium ovalis Stolk, it selectively inhibit type 2 methionine amino-peptidase (MetAP 2), which related to many physiological activities such as angiogenesis. Total synthesis of [plus or minus] ovalicin, its C4(S*), C4(S*)C5(S*) stereo-isomers, and C5 regio-isomer were synthesized via an intramolecular Heck reaction of (Z)-3-(t-butyldimethyl silyloxy)-1-iodo-1,6-heptadiene utilizing a catalytic amount of palladium acetate. Subsequent epoxidation, dihydroxylation, methylation (or stereochemistry inversion before or after methylation) and oxidation led to a variety of ketones, key intermediates for synthesis of ovalicin and its analogues. Introduction of side-chain to ketones by lithium (Z)-6-methylhepta-2,5-dien-2-ide and following functional group transformation led to ovalicin and its analogues. Anti-trypanosomal activities of various ovalicin analogues and synthetic intermediates were evaluated.
II. Bio-based polymers from vegetable oils are renewable and environment-friendly materials. Dihydroxylated, trihydroxylate, tetrahydroxylated and hexahydroxylated triglycerides, triamino and triisopropylamino glycerides were synthesized from model triglyceride glyceryl trioleoate. These monomers were cross-linked with 1, 4-phenylene diisocynate to make polyurethanes and polyureas. The physical properties of these polymers were examined by gel content and swelling value measurements, thermodynamic and viscoelastic properties were studied from TGA, DSC and DMA measurements. The structure-property relationship was discussed based on these measurements.
III. Diacetylenic fatty acids were widely applied in material science to regulate alignment on surface and stabilize self-assembled nanomaterials. A novel synthetic method of diacetylenic fatty acids from vegetable oils was developed. Its self-assembling properties on alumina surface were measured and discussed.
|
74 |
Vers des thermodurcissables bio-sourcés : polybenzoxazines à partir de cardanol et composites à base de dialdéhyde cellulose / Towards greener thermosets : cardanol-based polybenzoxazines and dialdehyde cellulose based compositesGanfoud, Rime 10 December 2018 (has links)
L’utilisation et la valorisation de ressources renouvelables dans le domaine de la chimie connait un intérêt grandissant pour remplacer les ressources fossiles. Le travail présenté dans ce manuscrit de thèse est axé sur deux ressources bio-sourcées utilisées pour la préparation de thermodurcissables bio-sourcés : huile végétale et biomasse lignocellulosique. La première partie concerne les polybenzoxazines. A partir d’un monomère à base de phénol, le caractère bio-sourcé est progressivement augmenté par substitution du phenol par du cardanol. Le cardanol est un dérivé phénolique bio-sourcé extrait de l’huile de coque de noix de cajou. Une première étude se concentre sur les effets apportés par cette chaine alkyle sur la réactivité et les propriétés finales du matériau. Par la suite, la réaction de polymérisation du composé de référence est évaluée par des études cinétiques, corrélées aux analyses thermo-mécaniques pour une meilleure compréhension de la réaction de polymérisation. La seconde partie de cette thèse se concentre sur la préparation de composites totalement bio-sourcés, avec des microfibrilles de cellulose (MFC) modifiées pour obtenir des dialdehyde cellulose (DAC). Le poly(alcool furfruylique) (PFA) est une matrice bio-sourcée polymérisée à partir d’alcool furfurylique (FA) et d’anhydride maléique, tous deux obtenus à partir du HMF. Les propriétés du PFA peuvent être modifiées en y incorporant un renfort, tel que la cellulose. La modification de MFC par oxydation génère des fonctions aldéhydes réactives qui améliorent la compatibilité avec la matrice. Cette étude compare différents composites préparés à partir de MFC oxydée à différents DO pour déterminer quel DO entraine une meilleure compatibilité. Pour finir, des matériaux préparés à partir d’une unique source de cellulose, les « all cellulose composites », ont fait l’objet de la dernière étude. Deux différents renforts furaniques ont été utilisés pour contrer les problèmes de sensibilité à l’humidité de la cellulose, et donc augmenter l’hydrophobicité. / To reduce the use of finite petroleum-based resources, interest has grown regarding the valorization of renewable resources in chemistry. The work presented in this thesis focused on two bio-based resources: plant oil and lignocellulosic biomass, for the preparation of greener thermoset materials. The first part discussed about polybenzoxazine thermosets. The bio-based content was gradually increased through substitution of petro-based phenol by bio-based cardanol. Cardanol is a natural phenolic derivative extracted from the cashew nutshell liquid. A first study focused on the effect of this aliphatic side chain and how it can tune the reactivity and the final thermo-mechanical properties of the materials. In the following study the reactivity of polymerization of di-phenol monomer was investigated using advanced isoconversional analyses and thermo-mechanical analyses for a better understanding of the polymerization reaction. The second part discussed about the preparation of fully bio-based composites using modified cellulose microfibrils (MFC). Poly(furfuryl alcohol) (PFA) is a bio-based matrix obtained after polymerization of furfruyl alcohol (FA) with maleic anhydride, both obtained from HMF. The PFA properties can be modified by the introduction of cellulose as a filler. MFC was modified by oxidation to lead to reactive dialdehyde functions. By varying the degree of oxidation (DO), the properties of different composites were studied to determine the most adequate DO for the better PFA/MFC compatibility and the most adequate PFA/MFC ratio. Finally, the last study of this thesis focused on the concept of “all cellulose composites” (ACC), and particularly how to reduce the moisture sensitivity of these materials. Two different furanic compounds were used as cross-linkers to increase the hydrophobicity: a first compound with one furan ring and a second with two furan rings.
|
75 |
Contribution à la certification des bâtiments durables au Sénégal : cas d'étude des matériaux de construction biosourcés à base de Typha / Contribution to the certification of sustainable buildings in Senegal : case study of biobased building materials made of Typha AustralisNiang, Ibrahim 25 June 2018 (has links)
Ces travaux de thèse s'inscrivent dans le cadre du projet PNEEB/Typha (Programme National d’Efficacité Energétique des Bâtiments) pour la valorisation d’un roseau invasif, le Typha Australis, comme isolant thermique pour améliorer l’efficacité énergétique des bâtiments au Sénégal. Un agromatériau à base de terre argileuse et de granulats de Typha Australis est élaboré afin d’évaluer l’influence de la morphologie et de la quantité de fibres sur le comportement du matériau. Pour cela, deux modes de production de granulats sont choisis : Une découpe longitudinale et une découpe transversale. Les propriétés physiques sont étudiées (taux de porosité, densité apparente et absolue, microstructure) et la tenue mécanique est déterminée. L'absorption acoustique est également évaluée, de même que les propriétés hygrothermiques et le comportement au feu. Les résultats montrent que la morphologie du granulat de Typha affecte le comportement en flexion, cisaillement et l’absorption acoustique. Son impact sur le comportement de compression est moins prononcé. Une portion plus importante de fibres de Typha réduit la résistance mécanique. En revanche, les performances hygrothermiques sont accrues en raison de la porosité de ces granulats. La fraction transversale de Typha permet d’améliorer la résistance thermique et d’accroitre les phénomènes de transfert de la vapeur d'eau. Cette étude a également permis de montrer que ces matériaux sont d'excellents régulateurs d'humidité. Enfin, les tests au feu révèlent qu’il s’agit de combustibles ininflammables en raison de la présence d'argile. L’influence de la morphologie des granulats n’est pas relevée. / This work is a part of PNEEB/Typha project (National Program for Energy Efficiency of Buildings) for the valorisation of an invasive reed, the Typha Australis, as a thermal insulator to improve the energy efficiency of buildings in Senegal. An agromaterial based on clay soil and Typha Australis is elaborated in order to evaluate the influence of the amount and fibres morphology on the material behaviour. For this, two production mode of granulates are chosen: longitudinal and transversal cut. Physical properties are studied (porosity, apparent, and absolute density, microstructure) and mechanical strength is determined. Sound absorption is also evaluated, as well as hygrothermal properties, and fire behaviour. Results show that granulate morphology affects the mechanical shear and flexure behaviour, as well as the acoustic absorption. Its impact on the compression strength is less pronounced. A greater portion of Typha fibers reduces the mechanical strength. However, hygrothermal performances are increased due to the aggregates porosity. Typha transverse fraction improves thermal resistance and increase water vapor transfer. This study also shows that these materials are excellent moisture regulators. Finally, fire tests reveal that it can be classified as combustible but non-flammable due to the clay presence. The fibres shape does not have a great influence.
|
76 |
Success and Failure Factors for the Adoption of Bio-Based PackagingErdogan, Umit Emre January 2013 (has links)
The purpose of this study is to provide insight into the factors that determine the willingness of key market players in the Indian food industry to adopt bio-based plastic packaging. First, the key market players are identified within the important market segments in the specified industry. After the identification of key players, the literature is surveyed in the context of eco-innovations, innovation adoption in emerging countries and Roger’s market adoption theory. In addition, the sustainability point of packaging and its perceived attributes are elaborated on and analyzed using the selected framework. Semi-structured interviews with the key market players in the food packaging industry are conducted in the context of adoption theory. The results of the survey reveal that there are only two groups in the industry, those that are currently considering bio-based plastic packaging and those that have not yet considered it. Due to the low number of completed questionnaires, advanced multivariate statistical methods cannot be used for data analysis. Nevertheless, the questionnaire is used in the analysis section; for further investigation of important concepts, semi-structured interviews are performed which clarify the environmental strategies and programs of players in the market who expect opportunities for CO2, material, water and energy reduction to emerge in both the short-term and long-term. Their responses also underscore the increasing importance of “Life Cycle Assessment” in decision-making, i.e., as factors that determine the willingness of especially brand owners to adopt bio-based plastic packaging. However, the contribution of bio-based materials to these sustainability programs has not been clearly perceived as a positive attribute. Moreover, there is no significant indication that supports the use of bio-based materials in comparison to conventional plastics regarding the implemented cases of some life cycle assessments. Last but not least, the packaging material is perceived as being highly cost sensitive. One of the important findings is that market players are not willing to pay a premium price for packaging material merely on the basis of it being environmental friendly; therefore, it is necessary to add value to ensure the potential adoption of these environmental materials. Moreover, this obstacle may be overcome with the help of decreased cost by economies of scale in the bio-packaging materials. This thesis concludes by emphasizing that value chain alignment is necessary, originating from the raw material to the end of recycling, for potentially adopted bio-based packaging material. This alignment can be stimulated by legislation; however, in some European countries, there is no signal detected to the contrary specifically for this industry. / <p>ID number <strong><em>2013:13</em></strong><strong><em>1</em></strong></p>
|
77 |
Development Of Bio-Based Thermosetting ResinsGaurangkumar Mistry, Snehaben January 2021 (has links)
Thermoset polymers are widely used polymers in the world, but Increase in global plastic pollution and lack of fossil fuel stimulates intense research towards environmentally sustainable materials. Bio-based unsaturated polyesters (UPs) would be an excellent solution to replace oil-based synthetic polyesters. Most of the unsaturated polyesters have been synthesised by ring opening polymerisation (ROP) of cyclic esters or lactides. In this study, different resins were developed using different initiators such as isosorbide (IS),1,4 butanediol (BD), and cis-2 butene 1,4 diol (C2BD) with monomers like lactide (L) and alpha angelica lactone (AAL) through the ring opening polymerisation process. The produced resins were further characterised by using Fourier Transform Infrared Spectroscopy (FTIR),Nuclear Magnetic Resonance (NMR), Thermogravimetric Analysis (TGA), Differential Scanning Calorimeter (DSC), and Dynamic Mechanical Analysis (DMA). Synthesis of resin with lactone monomer was not successful while with lactide monomer it was successful. IS-based resin showed better thermal properties compared to other obtained resins. Tg value of IS containing resin was 63°C, thermal stability up to 235°C and Storage modulus about 3841 MPa. These values are comparable with other bio-based resins produced using the same monomer.
|
78 |
Supply chain collaboration as a facilitator of circular economy for bio-based food packagingHolesova, Gabriela, Ivashneva, Ekaterina January 2021 (has links)
The amount of food packaging waste is one of the issues associated with increasing global population and corresponding increase in consumption rate of packaged foods. Traditional plastic food packaging derived from fossil fuels imposes a significant environmental threat. There are sustainable bio-based alternatives developed to substitute traditional plastic packaging that are implemented in circular economy business models. These solutions often utilise collaboration to be implemented, however, there is a lack of research on the collaborative processes that enable circular economy in bio-based food packaging. In this thesis we examine what collaborative processes are being used in the bio-based packaging supply chain and how these processes help with facilitating the implementation of circular economy in the packaging production. Moreover, this thesis also investigates what are the barriers that the packaging producers face as they collaborate toward a circular economy. Therefore, we use qualitative interviews with representatives of bio-based food packaging companies and study the theories of supply chain collaboration and circular economy such as resource based view, transaction cost economics and various iterations of circular supply chain management models. We find that bio-based food packaging producers collaborate externally with customers, suppliers and internally among organisational teams to enable the circular economy of bio-based alternatives to conventional plastics. We also find that collaboration for circular economy in bio-based food packaging solutions is challenged by cultural differences, varying regulations among countries, opportunistic behaviour across the supply chain, insufficient organisation of communication between collaborators as well and misalignment of their interests. We contribute empirical evidence of collaborative processes across bio-based food packaging supply chains providing a ground for further research streams across the aspects of collaboration for circular economy.
|
79 |
Etude expérimentale et modélisation multi-échelles du comportement hygro-mécanique des matériaux de construction : cas du bois / Experimental study and multi-scale modeling of the hygro-mechanical behavior of porous building materialsEl Hachem, Chady 27 November 2017 (has links)
L’habitat sain est le thème central des réflexions contemporaines du domaine du bâtiment élargies à l’environnement. Il comporte des préoccupations notables en matière de santé, de consommation énergétique (la ventilation, le chauffage, la climatisation et l’eau chaude), d’impacts environnementaux et de durabilité des matériaux de construction. Le choix préliminaire des matériaux utilisés pour la construction joue un rôle important dans la réussite d’un projet HQE (Haute Qualité Environnementale). Dans ce contexte, la problématique de prévision des champs de température et d’humidité demeure essentielle à l’intérieur des matériaux poreux de construction, où les matériaux biosourcés font l'objet d'un fort intérêt vu leurs qualités environnementales. Les matériaux biosourcés, étant hygroscopiques, ont tendance à absorber ou à restituer l’humidité, ce qui génère respectivement un gonflement ou un retrait. A l’échelle microscopique, l’humidité prend place soit par l’absorption de l’eau liée par les fibres, soit par l’existence d’eau libre dans les pores. Cette complexité des phénomènes microscopiques dans les matériaux biosourcés mène à une forte interaction entre l’aspect mécanique et les aspects de transferts de masse et de chaleur. L’existence de ce couplage est susceptible de modifier sensiblement les performances thermiques du bâtiment, et même sa durabilité. L’objectif visé par ce travail de thèse est l’étude et l’analyse microscopique du comportement hygrique des matériaux poreux de construction. L’aspect mécanique couplé à l’aspect hygrique est abordé en prenant en considération les déformations locales de gonflement - retrait, et leur impact sur l’hystérésis de teneur en eau. La maîtrise de ce couplage est primordiale tant sur le plan de la prédiction de la qualité des ambiances habitables que sur l’évaluation de la durabilité de ces structures. Le projet de thèse consiste à travailler à la fois sur les aspects modélisation, caractérisation et mesure des transferts hygriques. La quantification de ces phénomènes est réalisée à travers des campagnes de mesures expérimentales basées sur des techniques d’imagerie 3D (micro-tomographie aux rayons X). Le recours à la diffraction aux rayons X (DRX), à la corrélation d’images volumique, ainsi qu’à la résonance magnétique nucléaire (RMN) permet d’avoir une meilleure compréhension des échanges entre la matrice solide et l’eau liée et/ou libre. Tous ces travaux ont mené à une meilleure caractérisation de la morphologie du bois d’épicéa à l’échelle microscopique, ainsi qu’à une meilleure estimation des diverses variations dimensionnelles (gonflement) à l’échelle des parois cellulaires et de leurs constituants chimiques. Les résultats numériques obtenus sur la structure réelle 3D du matériau ont été couplés aux mesures expérimentales à travers la corrélation d’images volumiques (micro-tomographie aux rayons X) afin d’identifier les propriétés intrinsèques des phénomènes et du matériau. Ces travaux de thèse constitueront une base scientifique permettant une meilleure modélisation du couplage mécanique avec les transferts de chaleur et de masse dans les matériaux biosourcés. / Healthy living is a main contemporary concern of the construction field, extended to the environment. It has significant concerns about health, energy consumption, environmental impact and sustainability of building materials. The preliminary selection of materials used for construction plays an important role in the success of high environmental quality projects. In this context, it remains essential to predict the temperature and humidity fields inside porous building materials, where bio-based materials are subject to a strong interest due to their environmental qualities.As bio-based materials are hygroscopic, they tend to absorb or restore moisture, which respectively generates swelling or shrinkage. At the microscopic scale, moisture takes place either by absorption of bound water by the fibers, or by the existence of free water in the pores. The complexity of microscopic phenomena in bio-based materials will lead to strong interactions between the mechanical aspect on one side and heat and mass transfers’ aspects on the other side. The existence of this coupling may significantly alter the building's thermal performance, as well as its durability.The objective of this thesis work is to study the microscopic hygric behavior of porous building materials. The mechanical aspect coupled to the hygric one is studied, taking into consideration the local swelling and shrinkage strains, and their impact on the hysteresis phenomenon. Understanding this coupling is very important in order to improve the quality of habitat and evaluate the durability of these structures.The PhD project consists on working on all aspects, modeling, characterization and measurement of hygric transfers. Quantification of these phenomena is achieved through experimental campaigns based on 3D imaging techniques (X-ray micro-tomography). The use of X-ray diffraction (XRD), digital volume correlation, as well as nuclear magnetic resonance (NMR) allows a better understanding of the interactions between the solid matrix and bound and/or free water. The corresponding results have led to a microscopic morphological characterization of spruce wood, as well as to a better estimation of the various dimensional variations of the cell walls, and their chemical components.The numerical results achieved on the real 3D structure of the material have been coupled to the experimental ones, using digital volume correlation technique (X-ray tomography), in order to identify the intrinsic properties of the material.These thesis works provide a scientific basis allowing the improvement of modeling of the mechanical coupling with heat and mass transfers in bio-based materials.
|
80 |
Élaboration de plastifiants ignifugeants à base de dérivés lipidiques pour formulations PVC / Elaboration of lipidic flame retardant plasticizers for PVCBocqué, Maëva 25 November 2015 (has links)
E PVC est l'un des polymères les plus employés dans les matériaux actuels et l'adjonction de plastifiants permet de modifier ses propriétés (température de transition vitreuse, module…) permettant ainsi l'utilisation de ce polymères dans des applications où de la souplesse est requise (textiles enduits, par exemple). Actuellement, les phtalates sont les plastifiants les plus utilisés même s'ils sont de plus en plus décriés du fait de leur toxicité. Le développement de nouveaux agents plastifiants est un domaine de recherches intenses et les matières premières bio-sourcées s'avèrent être une alternative intéressante aux plastifiants pétro-sourcés. Le travail de cette thèse se propose d'investiguer le développement de plastifiants du PVC bio-sourcés de type lipidique possédant de surcroit des propriétés ignifugeantes évitant ainsi l'ajout d'additifs supplémentaires dans les formulations de PVC devant résister au feu. Dans un premier temps, l'oléate, le linoléate de méthyle et le diacide (D18 : 1) ont été fonctionnalisés par modification chimique de leurs groupements ester et/ou de leurs insaturations pour mener à des dérivés lipidiques phosphorés. Cinq candidats plastifiants bio-sourcés ont ainsi pu être synthétisés et le scale up de la synthèse de l'un des candidats à l'échelle du kilogramme a pu être réalisé dans le cadre de cette thèse. Dans un deuxième temps, des tests de plastification du PVC avec divers candidats ont été réalisés en collaboration avec la société Serge FERRARI. L'étude des propriétés thermiques, mécaniques et thermomécaniques des films de PVC plastifiés obtenus, comparativement au plastifiant phtalate DINP et au plastifiant bio-sourcé commercial RADIA 7295, a permis d'éliminer différents candidats pour n'en finalement retenir que deux. Des profils de dégradation thermique satisfaisants, des basses valeurs de Tg, des allongements à la rupture importants (320 et 365 % respectivement) et proches de ceux obtenus avec le DINP, ont confirmé l'efficacité plastifiante de ces deux composés phosphorés bio-sourcés. Les tests au feu LOI et au cône calorimètre ont également prouvé le caractère ignifugeant de ces deux composés qui conduisent à des résultats du même ordre de grandeur que ceux atteints avec le plastifiant phosphonate commercial de référence S141 / Poly(vinyl chloride) is one of the most manufactured and consumed thermoplastics in the world. The addition of plasticizers allows modifying its properties (glass transition temperature, modulus…) and then to use this polymer for applications where flexibility is needed (coated textiles, for instance). Nowadays, phthalates are the main candidates for PVC even if they have been more and more controversed due to their possible toxicity. To substitute these petro-based plasticizers, researches are focused on alternative plasticizers based on bio-based raw materials. This PhD work proposes to investigate the development of new bio-based plasticizers for PVC, from lipidic derivatives, and having simultaneously flame retardant properties, avoiding the addition of any other additives in PVC during compounding. In the first part, methyl oleate, methyl linoleate and diacid D18 : 1 have been functionalized by modification of their ester groups and/or their doubles bonds to give phosphorylated lipidic derivatives. Thus, five bio-based plasticizers have been synthesized and the synthesis of one candidate on the scale of the kilogram has been successfully performed during this PhD work. Secondly, the plasticizing efficiency of several candidates with PVC has been evaluated in collaboration an industrial company. Thermal, mechanical and thermomechanical properties of the obtained soft PVC films were studied, in comparison with those obtained with the phthalate plasticizer DINP and the commercial bio-based plasticizer RADIA 7295. These analyses allowed the disposal of some of the bio-based plasticizers to finally keep only two candidates. Satisfying thermal degradation profiles, low Tg, and important elongation at break values (320 % and 365 % respectively) close to those obtained with DINP, confirmed the plasticizing efficiency of these two bio-based phosphorylated plasticizers. Fire tests like the LOI test and the cone calorimeter also proved the flame retardant properties of these two candidates, leading to similar results than the ones reached with the phosphonate plasticizer S141
|
Page generated in 0.0635 seconds