In recent years, a compound N-nitrosodimethylamine (NDMA), a probable human carcinogen, has been identified as an emerging disinfection by-product (DBP) since its formation and detection were linked to chlorine-based disinfection processes in several water utilities in the U.S. and Canada. Numerous organic nitrogen compounds present in water may impact the formation of NDMA during disinfection. Amine-based water treatment polymers used as coagulants and flocculants have been suggested as potential NDMA precursors due to the presence of amine functional groups in their structures, as well as the possible presence of dimethylamine (DMA) residues in polymer products. To minimize the potential risk of NDMA associated with water treatment polymers, the mechanisms of how the polymers behave as NDMA precursors and their contribution to the overall NDMA formation under actual water treatment conditions need to be elucidated. This research involved a systematic investigation to determine whether amine-based water treatment polymers contribute to NDMA formation under drinking water and wastewater treatment conditions, to probe the involved reaction mechanisms, and to develop strategies to minimize the polymers NDMA formation potential. The investigation included five research tasks: (1) General screening of NDMA formation potential of commonly used amine-based water treatment polymers, (2) NDMA formation from amine-based water treatment polymers under relevant water treatment conditions, (3) Probing the mechanisms of NDMA formation from polyamine and PolyDADMAC, (4) Effect of water treatment processes on NDMA formation from amine-based water treatment polymers, and (5) Developing strategies to reduce polymers NDMA formation potential. Direct chloramination or chlorination of high doses of polymers in deionized water at longer than typical contact time was used in the general screening of the NDMA formation potential of water treatment polymers and in the studies to identify reaction mechanisms. On the other hand, realistic dosages of chloramines and polymers and contact time were used in simulating representative water treatment conditions to evaluate the contribution of polymers to the overall NDMA formation in real systems. On the basis of the study results, strategies were developed to reduce the NDMA formation potential of amine-based water treatment polymers, which include modification of polymer structures and treatment parameters.

L'objectif de ce travail fut d'intensifier des procédés de polymérisation radicalaire par transfert d'atomes (ATRP) du méthacrylate de 2-(dimétylamino)éthyle (DMAEAMA) au moyen de technologies de microréaction (microréacteurs, micromélangeurs) et de paramètres de procédé (géométrie du réacteur, température, pression ... ).L'impact du prémélange sur les caractéristiques d'un copolymère statistique du DMAEMA et du méthacrylate de benzyle synthétisé dans des microréacteurs hélicoïdaux (CT) fut étudié en utilisant des principes différents de micromélange: bilamination, multilamination interdigitale (!MM) et jet d'impact. Des caractéristiques bien mieux contrôlées ont été obtenues avec !'IMM et l'intensification du procédé (Pl) a été clairement démontrée encomparaison d'un réacteur fermé ; en effet des masses molaires et conversions plus élevées ainsi que de plus faibles indices de polymolécularité (PDI) ont été obtenus pour des temps de passage inférieurs. Pour la production de PMADAME linéaire, le PI a également été réalisé par augmentation de la température et de la pression (jusqu'à 1 OO bars). Toutefois de trop hautes températures se sont avérées préjudiciables notamment pour de longs temps de passage. L'effet de l'augmentation du taux de cisaillement (via la longueur du réacteur) ne fut bénéfique qu'en régime dilué à un stade précoce de la réaction lorsque les masses molaires sont encore faibles. Comparés aux CT, un mélange interne favorisé par une technique d'inversion de flux s'est révélé être une stratégie très efficace pour réduire davantage le PDI et obtenir des masses molaires et conversions plus élevées. Des polymères branchés synthétisés en microréacteurs à inversion de flux (CFI) par ATRP en présence d'inimère présentèrent une structure plus ramifiée soulignant ainsi la supériorité des CFI sur les CT et réacteurs fermés en termes de PDI et d'efficacité de branchement. Considérant les caractéristiques des CFI, l'augmentation d'échelle des microréacteurs fut considérée par accroissement de leur diamètre. La productivité du procédé a été augmentée d'un facteur 4 tout en gardant un bon contrôle sur les caractéristiques macromoléculaires. Ainsi fut-il démontré que l'inversion de flux est un moyen très efficace pour contrebalancer l'effet négatif d'une augmentation du diamètre du microréacteur. / The aim of this work was to intensify Atom Transfer Radical polymerization (ATRP) processes for the production of DMAEMA-based (co)polymers by relying on microreaction technology tools (microreactor, micromixers) and process parameters (reactor geometry, temperature, pressure ... ). Impact of premixing on macromolecular characteristics of P(DMAEMA-co-BzMA) synthesized in coiled tube (CT) microreactors was studied using different micromixing principles: bilamination, interdigital multilamination (IMM) and impact jet.Better controlled characteristics were obtained with !MM and process intensification (PI) was clearly demonstrated in comparison with batch mode as higher molecular weights, increased monomer conversions and lower polydispersity indices (PDI) were obtained for lower residence times. For the production of linear PDAEMA, PI was also achieved by application of elevated temperature and pressure (up to 100 bars). However, high temperature was found to be detrimental for long residence times. Effect of increased shear rate (i.e. reactor length) was found only beneficial in dilute regime at the early stage of the polymerization reaction when molecular weights are low. ln comparison with CT reactors, internal mixing promoted by flow inversion technique was found to be quite an effective strategy to reduce further PDI and obtain higher molecular weights and monomer conversions. Branched polymers synthesized by self condensing vinyl copolymerization (SCVCP) adapted to ATRP in tubular coil flow inverter (CFI) microreactors exhibited higher branched structure highlighting the superiority of CFI microreactor over CT and batch reactors in terms of PD! and branching efficiency. Finally, considering such features of CFI, attempt was made to scale-up microreactors by increasing their diameter. lt was found that process throughput can be increased by more than a factor of 4 while keeping a good control over macromolecular characteristics. Thus itwas demonstrated that flow inversion is quite effective to counter balance the detrimental effect of an increase in microreactor diameter.