Yes / Functional crosslinked hydrogels were prepared from 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (AA). The acid monomer was incorporated both via copolymerization and chain extension of a branching, reversible addition–fragmentation chain-transfer agent incorporated into the crosslinked polymer gel. The hydrogels were intolerant to high levels of acidic copolymerization as the acrylic acid weakened the ethylene glycol dimethacrylate (EGDMA) crosslinked network. Hydrogels made from HEMA, EGDMA and a branching RAFT agent provide the network with loose-chain end functionality that can be retained for subsequent chain extension. Traditional methods of surface functionalization have the downside of potentially creating a high volume of homopolymerization in the solution. Branching RAFT comonomers act as versatile anchor sites by which additional polymerization chain extension reactions can be carried out. Acrylic acid grafted onto HEMA–EGDMA hydrogels showed higher mechanical strength than the equivalent statistical copolymer networks and was shown to have functionality as an electrostatic binder of cationic flocculants.

In this study, the effects of chain extension and branching on the properties of nanocomposites produced from recycled poly(ethylene terephthalate) and organically modified clay were investigated. As the chain extension/branching agent, maleic anhydride (MA) and pyromellitic dianhydride (PMDA) were used. The nanocomposites were prepared by twin-screw extrusion, followed by injection molding. Recycled poly(ethylene terephthalate), was mixed with 2, 3 and 4 weight % of organically modified montmorillonite. During the second extrusion step, 0.5, 0.75 or 1 weight % of MA or PMDA was added to the products of the first extrusion. As the second extrusion step is reactive extrusion, the anhydrides were added at three different screw speeds of 75, 150, 350 rpm, in order to observe the change of properties with the screw speed. XRD analysis showed that, the interlayer spacing of Cloisite 25A expanded from 19.21 &amp / #506 / to about 28-34 &amp / #506 / after processing with polymer indicating an intercalated structure. PMDA, MA and organoclay content as well as the screw speed did not have a recognizable effect on interlayer distance. In the first extrusion step, nanocomposites containing 3% organoclay content gave significant increase in Young&rsquo / s modulus and decrease in elongation to break values indicating good interfacial adhesion. After the addition of chain extenders, it was observed that both MA and PMDA gave rise to improved mechanical properties of the nanocomposite owing to the branching and chain extending effects that increase the molecular weight. However, PMDA gave better mechanical properties at lower content which makes it a more effective chain extender. DSC analysis showed that MA was more effective in increasing the glass transition temperature and melting temperature in comparison to PMDA.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-07-11T12:48:13Z No. of bitstreams: 1 ANNA RAFAELA DE MATOS COSTA - DISSERTAÇÃO (PPGCEMat) 2015.pdf: 2304206 bytes, checksum: bd88411eb6d2299d2908c8f70fbb9f1c (MD5) / Made available in DSpace on 2018-07-11T12:48:13Z (GMT). No. of bitstreams: 1 ANNA RAFAELA DE MATOS COSTA - DISSERTAÇÃO (PPGCEMat) 2015.pdf: 2304206 bytes, checksum: bd88411eb6d2299d2908c8f70fbb9f1c (MD5) Previous issue date: 2015-02-10 / CNPq / Os polímeros biodegradáveis apresentam-se como uma alternativa ambientalmente correta para a sociedade, uma vez que minimizam problemas ambientais e reduzem acúmulo de resíduos plásticos. O presente trabalho investiga a degradação e a extensão de cadeia do polímero biodegradável, poli(butileno adipato tereftalato) (PBAT) com um aditivo extensor de cadeia epoxídico (Joncryl). O PBAT sem aditivar e aditivado com diferentes concentrações de extensor de cadeia foi processado em um misturador interno de laboratório Haake Rheomix 3000 com rotores tipo “roller”. A variação da massa molar foi estimada a partir de dados de temperatura e torque versus tempo fornecidos pelo equipamento durante o processamento do fundido. O efeito do aditivo depende fortemente da temperatura de processamento. A aditivação durante o processamento do fundido nos níveis testados, não somente compensou a discreta degradação da resina durante o processamento no misturador interno como resultou no aumento líquido da massa molar: a massa molar mais que duplicou a 230°C com 2% de aditivo. Para elevadas concentrações de aditivo observaram longos tempos de indução com queda catastrófica do torque, atribuíveis à mistura imperfeita dos componentes. / Biodegradable polymers are an environmentally friendly alternative, as they minimize environmental problems and reduce accumulation of waste plastics. This work is concerned with degradation and chain extension of the biodegradable polymer poly(butylene-adipate-terephthalate) (PBAT) with an epoxidic chain extender additive (Joncryl). The PBAT without and with different concentrations chain extender was processed in a laboratory internal mixer Haake Rheomix 3000 with "roller" type rotors. The variation of molar mass was estimated from temperature and torque data versus time provided by the equipment during melt processing. The effect of the additive depends mostly on processing temperature, less on additive concentration. Incorporation of additive during melt processing not only offset the slight degradation of the resin during processing in the internal mixer, but resulted in net increase of molecular weight. The molecular weight more than doubled at 230°C with 2% additive. For high additive concentrations were observed sometimes long times of induction with catastrophic fall of torque, attributable to imperfect mixing of the components

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-07-12T12:19:19Z No. of bitstreams: 1 ALBANIZA ALVES TAVARES -DISSERTAÇAO (PPGCEMat) 2015.pdf: 2618030 bytes, checksum: e5d264d181ed1552c6946d19110c1c85 (MD5) / Made available in DSpace on 2018-07-12T12:19:19Z (GMT). No. of bitstreams: 1 ALBANIZA ALVES TAVARES -DISSERTAÇAO (PPGCEMat) 2015.pdf: 2618030 bytes, checksum: e5d264d181ed1552c6946d19110c1c85 (MD5) Previous issue date: 2015-02-11 / CNPq / Este estudo visa avaliar a influência de um oligômero multifuncional de estirenoacrílico (POLYAD PR 002), comercializado como extensor de cadeia para polímeros de condensação, no aumento da massa molar do poli (tereftalato de etileno) (PET) e, consequentemente, na restituição de suas propriedades reológicas. O comportamento foi analisado em PET pós-consumo (PETPC) oriundo de garrafas incolores do estado da Paraíba, bem como no PET virgem (PETV) para um parâmetro comparativo. Os polímeros foram processados sem e com a incorporação do aditivo extensor de cadeia em diferentes níveis, para possibilitar o desenvolvimento de diferentes grades de PET. Foi utilizado um misturador interno acoplado ao reômetro de torque Haake Rheomix 3000QC da PolyLab QC, com rotores do tipo roller operando a 265ºC e 60 rpm. Na primeira etapa, o processamento foi realizado em um tempo de 16 min, empregando diferentes concentrações do aditivo (1,5%, 3% e 5% em massa), e na segunda etapa os polímeros sem e com a incorporação do aditivo extensor, nas concentrações 1,5 e 3% em massa, foram processados e reprocessados em um tempo de 30 min. As amostras obtidas foram caracterizadas por reometria de torque. A partir de medições de torque e temperatura obtidas pelo equipamento foi possível realizar uma avaliação das massas molares. De acordo com os resultados, confirma-se que as estimativas com base em medições de torque em tempo real são indicadores rápidos e precisos da eficácia da extensão da cadeia no PET e que a incorporação do aditivo ao PETV e ao PETPC teve uma forte influência no aumento da sua massa molar. / This study is concerned with the effect of a styrene-acrylic multifunctional oligomer (POLYAD PR 002), marketed as a chain extender for condensation polymers, in the increase of molecular weight of poly (ethylene terephthalate) (PET) and, consequently, the restitution of their rheological properties. This behavior was analyzed in post-consumer PET (PETPC) from colorless bottles collected in the State of Paraíba, as well as in virgin PET (PETV) for comparison. The polymers were processed with and without the incorporation of the chain extender additive at different levels to facilitate developing different grades of PET. An internal mixer coupled to the torque rheometer Haake Rheomix 3000QC of PolyLab QC, with roller type rotors operating at 265ºC and 60 rpm was used. In the first stage, processing was performed during 16 min, with different additive concentrations (1.5%, 3% and 5% by weight) and in a second stage, polymers with and without the incorporation of additive concentrations 1.5 and 3% by weight were processed and reprocessed during 30 min. The samples were characterized by torque rheometry. From torque and temperature measurements was possible to evaluate molar masses. According to the results, it is evident that estimates based on realtime torque measurement are fast and accurate indicators of the effectiveness of chain extension, and that the incorporation of the additive to PETV and PETPC had a strong effect in increase its molar mass

Ce travail de thèse porte sur l’étude des relations structure/procédés de mise en forme/propriétés finales de matériaux polymères à base de PLA/PBAT. Ces derniers sont destinés à l’emballage alimentaire en vue de remplacer le polyéthylène téréphtalate (PET). Cependant le PLA a certaines limites de processabilité par les technologies de la plasturgie. Le renforcement de ses propriétés à l’état fondu a été obtenu grâce à l’introduction d’un époxyde multifonctionnel capable de réagir avec les bouts de chaînes des polyesters. Aussi, des mélanges à base de PLA/PBAT ont été mis en œuvre en vue de conférer la ductilité au matériau final. La première étape consiste en la compréhension des mécanismes de dégradation thermique et hydrolytique des deux polymères PLA et PBAT au cours des processus de mise en œuvre. En effet, la réaction d’extension des chaînes couplée au branchement induits par l’époxyde multifonctionnel palie cette dégradation. Les mécanismes d’extension de chaînes et de branchements sous-jacents ont été mis en évidence par l’analyse des énergies d’activation, des spectres de relaxation à l’état fondu ainsi que celle des grandeurs physico-chimiques en solution. En outre, les représentations de Van-Gurp-Palmen confirment la co-existence de chaînes macromoléculaires linéaires et aléatoirement branchées. La seconde étape de ce travail a été dédiée à la compatibilisation des mélanges PLA/PBAT par ce même époxyde multifonctionnel. Des études expérimentales modèles basées sur la détermination de la tension interfaciale et la modélisation rhéologique ont montré le rôle majeur de compatibilisant induit par cet agent réactif. Ainsi, la diminution de la tension interfaciale confère à ces matériaux une meilleure cohésion interfaciale et une morphologie fine et homogène de la phase dispersée, accompagnée par l’amélioration des propriétés mécaniques. L’étude des propriétés rhéologiques en cisaillement et en élongation des matériaux modifiés a permis de montrer une meilleure tenue mécanique à l’état fondu. Ainsi, une meilleure aptitude à l’extrusion gonflage a été démontrée en élargissant leurs cartes de stabilité. Parallèlement à ces travaux, des études de bi-étirage des polymères seuls, de leurs homologues modifiés et de leurs mélanges montrent un durcissement structural, dû à la cristallisation induite sous déformation. Les morphologies cristallines ont été analysées finement par des méthodes calorimétriques et spectroscopiques. Enfin, ces études ont été transposées à l’élaboration et à la compréhension des comportements d’une formulation industrielle complexe à base de PLA, PBAT et de farine céréalière plastifiée. / The ultimate aim of the present thesis focuses on the structure/processing/properties relationship of the PLA/PBAT materials. The latters are intended for food packaging in order to replace poly (ethylene terephthalate (PET). However, PLA has a limited processability in conventional technologies of plastics industry. The strengthening of its melt properties has been achieved through the incorporation of a multifunctional epoxide, able to react with the end chains of polyesters. Furthermore, PLA/PBAT blends were prepared to make the final material more ductile. The first part of the study consists on the understanding of thermal and hydrolytic degradation mechanisms of neat PLA and PBAT polymers upon processing. Indeed, the degradation was overcome through the chain extension reaction coupled to branching, induced by the multifunctional epoxide. The chain extension and branching mechanisms were highlighted by the analysis of the activation energy and the relaxation spectra in the molten state as well as the physico-chemical properties in solution. Moreover, the Van-Gurp-Palmen plots confirm the co-existence of linear and randomly branched macromolecular chains. The second part has been dedicated to the compatibilization of PLA/PBAT blends by the multifunctional epoxide. Experimental models studies, based on the assessment of the interfacial tension, and the rheological modeling showed the major role of the reactive epoxide agent as a compatibilizer. Thus, the decrease of the interfacial tension gives a better cohesive interface with finer and homogenous morphology of the dispersed phase, accompanied with an improvement of the mechanical properties. The study of the shear and elongation rheological properties of modified materials showed an enhancement of their melt strength. Therefore, a better ability to be blown has been demonstrated, by expanding their stability maps. Besides, biaxial stretching studies of neat polymers, their modified counterparts as well as their blends show a structural strain hardening, due to a strain-induced crystallization. The crystalline phases were analyzed thanks to calorimetric and spectroscopic methods. Finally, the present studies have been used to elaborate and understand the behavior of a complex industrial formulation based on PLA, PBAT and thermoplastic cereal flour.

This dissertation reports the synthesis and characterization of semi-fluorinated polymers derived from the polymerization of bisphenols with fluoroalkenes. A series of diverse bisphenols were chosen from popular commercial bisphenols and new polycyclic aromatic hydrocarbon (PAH) derived bisphenols requiring synthesis. Step-growth condensation polymerization of bisphenols with three different fluoroalkene types was performed while probing polymerization conditions and the structure/properties relationship of the resulting fluoropolymers. The fluoroalkene monomers were chosen from bis(trifluorovinyloxy)biphenyl (TFVE), perfluorocyclohexene (PFCH), and perfluoro acyclic monomers, namely, perfluoro(4-methyl-2-pentene) and 1-perfluoroheptene to undergo this chemistry. This work is divided into four parts based on the polymerization methodology. The first section focuses on the development of a new class of fluorinated arylene vinylene ether (FAVE) and their chain extended polymers prepared via base-catalyzed step-growth polymerization of PAH bisphenols with the TFVE monomer. These reactions afforded polymers containing controlled terminal and enchained fluoroalkenylenes for latent reactivity such as post polymerization functionalization, chain extension, and/or crosslinking. In general, these PAH cores resulted in polymers with improved thermal properties The second portion describes the investigation of step-growth addition/elimination polymerizations of PAH bisphenols and PFCH to prepare a new class of fluoropolymers containing alternating rigid PAH linkages and enchained PFCH vinylene ether moieties in the backbone. The third section covers the preparation and characterization of semi-fluorinated poly(aryl ether sulfone)s by nucleophilic addition/elimination reactions of PFCH with sulfone bisphenols. From commercially bisphenols combined with PAH bisphenols, we introduced the industrially valuable and property enhancing diaryl sulfone unit in a series of semi-fluorinated copolymers. This modular approach greatly expands access to partially fluorinated aryl ether sulfone polymers intended for high performance applications in optoelectronics, separation/purification membranes, and composites. Finally, in the fourth section, a new class of semifluorinated polymers was synthesized via nucleophilic addition/elimination reactions of acyclic perfluoroalkenes with bisphenols. In particular, environmental concerns for biopersistent and highly regulated perfluorooctanoic acid (PFOA) is the driver for using perfluoroheptene, which is derived cleanly by the decarboxylation of these pollutants in one step. This provided a new class of semi-fluorinated materials with promising properties including thermal stable, processability, and transparent film formation.