Renewable polymers (bioplastics) offer an alternative to petroleum-based polymers and reduced environmental impact through decreased petroleum dependence and a sustainable product lifecycle via renewable, biomass-derived monomers and completely degradable polymers. Applying green chemistry principles, melt polycondensations of 1,3-propanediol with malonic acid and 1,3-propanediol with itaconic acid were performed to produce poly(trimethylene malonte) (PTM) and poly(trimethylene itaconate) (PTI), respectively. Aluminum chloride was used as the catalyst and reaction temperatures from 125-175 °C and reaction times from 2-32 h were attempted in order to produce high yields and molecular weights (Mw). Gravimetric yields ranged from 20-95 wt.% for PTM and 20-85 wt.% for PTI. Both PTM and PTI contained ester and ether backbone bonds, as determined by Fourier transform infrared and nuclear magnetic resonance spectroscopy. Gel permeation chromatography showed both PTM and PTI to have a bi-modal Mw distributions centered at 1.4±0.1 kDa and 35±3 kDa for PTM and 1.0±0.1 kDa and 38±2 kDa for PTI. For PTM, a Tg of -64 °C and a Tm of 29 °C was identified using differential scanning calorimetry (DSC). A crystallization temperature for PTI was found at ~160 °C using DSC. A hydrolytic degradation study was performed at 25 °C on PTM and PTI in pH 5.4, 7, 9, and 11 aqueous solutions for up to 4 weeks. The introduction of K+ ions (in the KOH aq. solutions) interfered with the AAC2 and AAL1 ester hydrolysis mechanisms through acid-base interactions. PTM was found to be susceptible to hydrolytic degradation and lost ~37 wt.% through ester hydrolysis and showed a molecular weight reduction of ~0.8 kDa over 10,000 min for a pH range of 7 to 11. PTI was also found to be susceptible to hydrolytic degradation with ~22 wt.% decrease through ester hydrolysis and molecular weight reduction of ~0.25 kDa over 10,000 min for a pH range of 7 to 11. PTM is a low molecular weight, saturated, linear copolymer and PTI is a low molecular weight, unsaturated, branched copolymer. Both PTM and PTI are renewable copolymers produced using green chemistry and mild reactions conditions and were found to be susceptible to hydrolytic degradation.

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Sustainable polymeric materials put emphasis on mastering the whole life-cycle of polymeric materials. This includes the choice of raw materials, selection of synthesis and processing, environmental impact during long-term use followed by detailed knowledge about recycling and waste management.  Within this large efforts are put in the design and development of new biocomposites using renewable fibres instead of inert ones. The thesis deals with surface modifications of agricultural fibres and the design of biocomposites with optimal long-term properties balancing the potential risk for biodegradation.  The first part of this thesis involved surface modifications of oil palm fibres and production of biocomposites with PP as matrix. The chemical surface modifications of oil palm fibres explored propionylation, PPgMA grafting via solution modification and reactive blending and vinyltrimethoxy silanization as methods. All modified fibre/PP biocomposites showed improvements in the mechanical properties followed also by an improvement of water resistance. In comparison with unmodificed fibres/PP matrix the highest water resistance after the surface modifications of oil palm fibres were observed for silanization followed by PPgMA modified,  PPgMA blending and  propionylation. The second part aimed at producing fully biodegradable biocomposites and analysing the resulting properties with respect to potential risk for biodegradation. Sisal fibres were incorporated in PLA and PHBV and the resulting risk for biodegradation using a fungus, Aspergillus niger, monitored. Neat PLA and PHBV were compared with the corresponding biocomposites and already without fibres both polymers were notably biodegraded by Aspergillus niger. The degree of biodegradation of PLA and PHBV matrices was related to the extent of the growth on the material surfaces. Adding sisal fibres gave a substantial increase in the growth on the surfaces of the biocomposites. Correlating the type of surface modification of sisal fibres with degree of biodegradation, it was demonstrated that all chemically modified sisal/PLA biocomposites were less biodegraded than unmodified sisal biocomposites.  Propionylated sisal/PLA demonstrated the best resistance to biodegradation of all biocomposites while sisal/CA/PLA demonstrated high level of biodegradation after severe invasion by Aspergillus niger. In general, the biodegradation correlated strongly with the degree of water absorption and surface modifications that increase the hydrophobicity is a route to improve the resistance to biodegradation. Designing new biocomposites using renewable fibres and non-renewable and renewable matrices involve the balancing of the increase in mechanical properties, after improved adhesion between fibres and the polymer matrix, with the potential risk for biodegradation. / <p>QC 20130325</p>

L'attractivité des matériaux polymères issus de ressources renouvelables augmente continuellement en raison de la prise de conscience environnementale de la société. Dans ce contexte, l’acide polylactique (PLA) est un biopolymère qui possède d’indéniables atouts (notamment en termes de rigidité et résistance en traction/flexion) permettant d’envisager des applications à grande échelle, par exemple pour l’automobile. Cependant, les applications durables du PLA sont encore considérablement restreintes à cause de sa fragilité et de sa stabilité thermique limitée. Dans cette thèse, nous nous sommes focalisés sur la conception de nouveaux matériaux à base de PLA pour des applications dans l’automobile, en travaillant notamment sur l’amélioration des propriétés thermiques et mécaniques (notamment la ductilité), y compris sous haute vitesse de déformation. Ainsi, la composition optimale permettant d’atteindre le meilleur compromis entre différentes propriétés (ductilité, résistance et rigidité, résilience, stabilité thermique…), tout en étant composée d’au moins 50% de matériaux biosourcés est déterminée. D'autres stratégies visant à améliorer la capacité ou la vitesse de cristallisation des compositions à base de PLA ont également été étudiées. Dans tous ces développements, une attention particulière est portée sur l’étude des interactions entre structure, propriétés et process. / The interest to use polymeric materials derived from renewable resources increases continuously due to considerably improved environmental awareness and the expected depletion of petrochemical ressources. In this regard, Poly(lactic acid), PLA, is a biopolymer that can respond to the demand for such materials for a wide range of applications, thanks to interesting mechanical properties such as high tensile/flexural strength and rigidity, in particular. However, in many cases, durable applications of PLA have been significantly limited by its inherent brittleness and limited thermal stability. In this dissertation, we focused on the design of new biobased PLA materials for automotive parts subjected to severe loading and environmental conditions, by improving thermal and mechanical properties, including under high strain rate loadings. Thus, the most promising compound is selected as the one that offers the best balance between different properties (ductility, strength and stiffness, impact toughness, good thermal stability…) with a content of bio-sourced polymer in the blend at least equal to 50%. Other strategies to improve crystallinity of PLA-based compounds are also studied. In all those developments, a particular attention is paid to the study of structure-process-properties interactions.

Tailored fluoropolymers remain the leading choice for a wide variety of advanced high-performance applications, including electronic/optical and energy conversion, owing to their unique blend of complementary high-performance properties. Amorphous semi-fluorinated polymers exhibit improved solubility and melt processability when compared to traditional perfluoropolymers. A leading class of semi-fluorinated aryl ether polymers includes perfluorocyclobutyl (PFCB), perfluorocycloalkenyl (PFCA), and fluoroarylene vinylene ether (FAVE) polymers. Monomers containing aromatic trifluorovinyl ethers (TFVE) are used to synthesize PFCB polymers via radical-mediated [2+2] cyclodimerization. On the other hand, FAVE and PFCA polymers are polymerized via base-mediated nucleophilic addition/elimination of bisphenols with TFVE monomers and decafluorocyclohexene respectively. The use of different monomer cores (aromatic, aliphatic, contorted, and renewable) should help to develop general structure/property relationships for this versatile and expanding approach to semi-fluorinated aryl ether polymers. The enchainment of polycyclic aromatic hydrocarbon (PAH) cores with functional fluorocarbon groups (or segments) recently afforded a new class of semi- fluorinated polymers in the continuing quest for novel organic materials for potential applications in optoelectronic, gas-separation, and advanced composites. Chapter 2 details the incorporation of commercially available acenaphthenequinone was achieved to afford PFCB aryl ether polymers with excellent solubility, high thermal stability, and film-forming capability. Chapter 3 represents base-promoted nucleophilic addition/elimination of commercial bisphenols with TFVE-triphenylene monomers affording FAVE aryl ether polymers possessing excellent solution processability, high thermal stability and photostability. In addition, triphenylene-enchained FAVE polymers exhibit extreme thermal-oxidative photostability and emit blue light after heating in air at 250 °C for 24 h. Further, time-dependent density functional theory (TD-DFT) computations were performed to understand electronic polymer structures. In one case, post-polymerization Scholl coupling converted the central triphenylene core to afford a hexabenzocoronene containing semi-fluorinated polymer with new optoelectronic properties. Chapter 4 demonstrates synthesis and characterization of renewable semi-fluorinated polymers obtained using aliphatic diol isosorbide. This renewable diol readily polymerizes with bis-TFVE derivatives of bisphenol A and 6F to provide high molecular weight thermoplastics exhibiting excellent solubility and tough, transparent film-forming capability. Finally, Chapter 5 presents synthesis of TFVE enchained corannulene which gave blue-light emission and outstanding processability. Synthesis and characterization, including the new materials' optical, thermal, and electronic properties, is presented.