Polymérisation par activation du monomère : application à la synthèse de polyaziridines et polyamides
Language
en
Thèses de doctorat
Date
2018-12-11Speciality
Polymères
Doctoral school
École doctorale des sciences chimiques (Talence, Gironde)Abstract
Cette thèse a pour but la synthèse de nouveaux polymères par polymérisation anionique et organo-catalyse de polymérisation par activation du monomère. Ce sujet s’articule autour de deux axes majeurs : 1) La synthèse de ...Read more >
Cette thèse a pour but la synthèse de nouveaux polymères par polymérisation anionique et organo-catalyse de polymérisation par activation du monomère. Ce sujet s’articule autour de deux axes majeurs : 1) La synthèse de nouveaux polyamides par activation d’amines aromatiques ou de dérivés acrylamides 2) L’étude de l’ouverture de cycle d’aziridines activées catalysée par les carbènes N-heterocycliques. Le but de cette thèse est donc d’étudier les mécanismes mis en jeu lors de ces polymérisations. Les polymères obtenus seront caractérisés par les méthodes d’analyses classiques (RMN, chromatographie par exclusion stérique, analyses thermiques, spectrométrie de masse, etc.)Read less <
English Abstract
In this thesis, the ring-opening polymerization by a monomer activation strategy of heterocyclic monomers such as lactams and aziridines was investigated. In the first part, we described that covalently activated aziridines, ...Read more >
In this thesis, the ring-opening polymerization by a monomer activation strategy of heterocyclic monomers such as lactams and aziridines was investigated. In the first part, we described that covalently activated aziridines, i.e. N-sulfonyl aziridines, could be subjected to the N-heterocyclic carbene organocatalyzed ring-opening polymerization (NHC-OROP) in a living/controlled manner. Secondary activated amine, non-activated secondary amine as well as functional initiators were used to promote the ring-opening polymerization of N-activated aziridines. The high tolerance to various chemical functions and the high level of control of the so-called NHC-OROP have allowed the synthesis of well-defined and original aziridine-based block copolymers. On the other hand, the simultaneous combination of anionic ring-opening of ε-caprolactam and condensation reactions of aminobenzoate derivatives was shown to occur in a « one-step » bulk copolymerization allowing the preparation of aliphatic-aromatic copolyamides with enhanced thermal properties (including the glass transition temperature). Alternatively, other methodologies such as covalent activation of lactams with electron withdrawing group or the hydrogen transfer polymerization of acrylamide derivatives were investigated for the synthesis of new polyamides.Read less <
Keywords
Activation du momonère
Organocatalyse
Polymerisation anionique
Polyamides
Polyaziridines
English Keywords
Monomer activation
Organocatalysis
Anionic polymerization
Polyamides
Polyaziridines
Origin
STAR importedCollections