Thermal characterization of the interaction of poly(3-hydroxybutyrate) with maleic anhydride

Poly(3-hydroxybutyrate), PHB, has been structurally modified with maleic anhydride, MA, in the presence of triethylamine, TEA. Glass transition, melting, and crystallization temperature, obtained from DSC curves, and thermal degradation temperatures obtained from TG ones, were employed to evaluate the influence of the MA proportion on the modification in the PHB chain. According to the results, most of chain modification reactions are the 80/20 and 90/10 proportions. Observations suggest that most chain modification reactions occur when the ratio of PHB/MA is 80/20 or 90/10. This suggests that modifications of PHB in the presence of MA involve main chain scission.

Functionalization of isotactic polypropylene with maleic anhydride by reactive extrusion: mechanism of melt grafting

In this work, chemical structures and molecular parameters of grafted materials of PP-g-MAH prepared by melt reactive extrusion were studied by using electrospray ionization-mass spectrometer and gel permeation chromatography. It was found that the initial radicals, due to homolitic scission of dicumyl peroxide could be combined with maleic anhydride (MAH) monomers as well as polypropylene (PP) molecular chains. The homopolymerization of MAH cannot occur and the MAH radicals undergo a dismutational reaction under the processing condition (180-190 degreesC). A modified mechanism of melt grafting MAH onto PP has been proposed tentatively on the basis of our experimental results and other experimental findings published in the literature. (C) 2001 Elsevier Science Ltd. All rights reserved.

Melt rheological properties of polypropylene-polyarnide6 blends compatibilized with maleic anhydride-grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene -polyamide6 (PP-PA6) blends and ternary blends compatibilized with maleic anhydride-grafted PP (PP-PP-g-MAH-PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value delta between these two series of data was obtained. In binary PP-PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and delta was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of delta increased with the dispersed phase composition. In ternary PP-PP-g-MAH-PA6 systems, when the compatibility between PP and PA6 was enhanced by PP-g-MAH, the elongation and break-up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the delta values of the ternary blends and the larger the positive deviation.

Synthesis, characterization and ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Three comb polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and the ionic conductivity of CP/salt complexes is reported. The conductivity of these complexes was about 10(-5)-10(-6) S cm(-1) at room temperature. The conductivity, which displayed non-Arrhenius behaviour, was analysed using the Vogel-Tammann-Fulcher equation. The conductivity maxima appear at lower salt concentration, when CP has longer side chains. Infrared (i.r.) was used to study the cation-polymer interaction. I.r. results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring. (C) 1997 Elsevier Science Ltd.

Ion-conducting polymers based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CPs) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo(oxyethylene) side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. Maximum conductivity close to 1.38 x 10(-4) S/cm was achieved at room temperature and at a [Li]/[EO] ratio (EO = ethylene oxide) of about 0.066. The temperature dependence of ionic conductivity suggested that the ion transport was controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moved to a higher salt concentration as the temperature increased, indicating that a larger number of charge carriers can be transferred through polymer chains, of which free volume is increased at higher temperature. IR results indicated that the ester in CPs might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. CP/salt complexes showed conductivity up to 10(-5)Scm(-1) at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

cis-trans Enantiomerism in the Diels-Alder cycloadducts of 6-arylfulvenes with maleic anhydride: resolution of the exo adducts via the N-((1S)-1-(naphth-1-yl)ethyl)imide derivatives: assignment of the absolute configurations based on the crystal structure of an imide diastereomer

A new case of the uncommon cis-trans enantiomerism is presented. The titled anhydride adducts were prepared in good yields by the known reaction of three 6-arylfulvenes with maleic anhydride (aryl = phenyl, p-tolyl and p-anisyl). The exo adducts were converted to the corresponding imides by reaction with (1S)-1-(naphth-1-yl)ethylamine in similar to 80% yields, and the resulting diastereomeric imides separated by silica gel column chromatography. They were hydrolysed and recyclised to the chiral anhydrides, in `one-pot' with 10% NaOH-EtOH, followed by treatment with 2 M HCl, in similar to 40% yields. The titled anhydrides were thus obtained in homochiral form, in enantiomeric purities (generally) of similar to 90% as indicated by chiral HPLC. The chiral anhydrides were also converted to the corresponding imides (presumably stereospecifically), by treatment with ammonia solution in excellent yields. The crystal structure of one of the above diastereomeric imides (derived from 6-phenylfulvene) was determined, and based on the known (S)-configuration of the naphthylethylamine moiety, the `configurations' of the original anhydride adducts were assigned. (c) 2005 Elsevier Ltd. All rights reserved.

Study on the properties of poly(beta-hydroxybutyrate) grafted with maleic anhydride

The thermal stability, crystallization behavior and biodegradability of poly(beta -hydroxybutyrate) (PHB) grafted with maleic anhydride (MA) were studied by DSC,TGA, optical microscopy and WAXD. The results showed that thermal stability of maleated PHB was obviously improved, comparing with that of pure PHB. The temperature of decomposition was enhanced about 20 degreesC After grafting MA, the crystallization behavior of PHB changed evidently. The rate of spherulite growth decreased, the crystallization temperature from the melt state reduced, and the cold crystallization temperature from the glass state increased. With the increase in graft degree, the banding texture of spherulite became more distinct and orderly. Moreover, the introduction of MA groups promoted the biodegradation of PHB.

Aprovechamiento integral del Cannabis sativa como material de refuerzo/carga del polipropileno

En este trabajo se ha estudiado el potencial tanto los filamentos de cáñamo como de la cañamiza como refuerzo/carga del polipropileno. La modificación de estos materiales se realiza para lograr una mayor compatibilidad con la matriz polimérica. Se evaluaron las propiedades mecánicas de las resistencias a tracción e impacto, de los materiales compuestos reforzados tanto de filamento como de cañamiza. Los filamentos de cáñamo poseen suficiente capacidad de refuerzo en los materiales compuestos basado en polipropileno debido a sus propiedades intrínsecas, siendo una buena alternativa como material de refuerzo. Así, la adición de MAPP (polipropileno modificado con anhídrido maleico) conduce a materiales compuestos con unas resistencias a tracción de hasta el 70% de las que se obtienen con compuestos de PP reforzados con fibra de vidrio. Mientras que la cañamiza ha actuado como una carga en la matriz, incrementado significativamente la rigidez de los materiales compuestos.

Thermal behavior of the maleic anhydride modified poly(3-hydroxybutyrate)

Poly(3-hydroxybutyrate), PHB has been structurally modified through reaction with maleic anhydride, MA. Transesterification reaction was carried out fixing the PHB and MA and besides time and temperature the concentration of the triethylamine (used as catalyst) was changed. Glass transition, melting and crystallization temperature obtained from DSC curves and thermal degradation temperatures obtained from TG traces were used to evaluate the influence of the reaction conditions on the modification of PHB according to factorial design. on the base of the results the optimum conditions are to perform the PHB modification reaction with MA reaction at 110 degrees C for 1 h with 5% v/v triethylamine.

Studies of moisture induced crosslinking in a novel vinyl ether maleic anhydride copolymer

A novel vinyl ether, 2,2-dimethyl-4-vinyioxymethyl-1,3-dioxol (DMVMD), that has a dimethyl ketal protected vicinal diol functionality was synthesizied from readily available starting materials, such as glycerol, acetone and acetylene. Copolymerisation of DMVMD with maleic anhydride (MAH) in various molar ratios was carried out using a free radical initiator. The composition of the copolymer was established by conductometric titration, and was found to be 1:1 irrespective of the monomer feed composition thus establishing its alternating nature. The copolymer formed clear free standing films upon solvent casting which became insoluble upon prolonged exposure to ambeint atmosphere. The insolubility is ascribed to moisture induced crosslinking. A plausible mechanism for the crosslinking involves the hydrolysis of some of the anhydride groups, followed by acid catalysed deketalization, and then by the reaction of the alcoholic groups, thus generated, with the residual anhydride to give ester crosslinks. This hypothesis was confirmed both by model reactions and insitu FT-IR studies.

Cure Characteristics and Mechanical Properties of Maleic Anhydride Grafted Reclaimed Rubber/ Styrene Butadiene Rubber Blends

Blends of styrene butadiene rubber (SBR) with maleic anhydride grafted whole tire reclaim (MA-g-WTR) have been prepared and the cure and mechanical properties have been studied with respect to the reclaim content. The grafting was carried out in the presence of dicumylperoxide (DCP) in a Brabender Plasticorder at 150'C. The presence of anhydride group on the WTR was confirmed by infrared spectrometry (IR) study. The properties were compared with those of the blends containing unmodified WTR. Though the cure time was marginally higher, the mechanical properties of the blends containing grafted WTR were better than that of the unmodified blends.

Studies - on Maleic Anhydride Grafted Reclaimed Rubber/Acrylonitrile Butadiene Rubber Blends

Blends of Acrylonitrile rubber with Maleic anhydride grafted Whole Tyre Reclaim WTR (MA-g-WTR) have been prepared and the cure and mechanical properties have been studied with respect to reclaim content. Control compounds containing unmodified WTR were also prepared for comparison. Grafting was confirmed by IR studies. Blends containing grafted WTR showed higher minimum torque and (max-min) torque. They also showed longer cure time, scorch time and lower cure rate. Grafting of the WTR with maleic anhydride also resulted in the improved tensile strength, abrasion resistance, compression set and resilience. However, the heat build up under dynamic loading was marginally higher for the blends containing grafted reclaimed rubber.

Caracterização e desenvolvimento de argilas para aplicação em nanocompósitos poliméricos

O Brasil é produtor de argilas e conta com grandes reservas deste recurso natural. Porém, grande parte da sua produção é comercializada seca e moída. O desenvolvimento de argilas para seu uso como reforço em nanocompósitos poliméricos constitui uma opção para os produtores desta matéria prima que teriam assim um produto com maior valor agregado. Este trabalho visa avaliar o potencial uso como nanocarga de duas argilas nacionais provenientes da Bacia de Taubaté, São Paulo, denominadas ALIGRA e SANTA FÉ. As frações de tamanho de partícula médio menor de 0,02 mm, obtidas por peneiramento á úmido da argila homogeneizada e seca, foram utilizadas no desenvolvimento do trabalho experimental. Os estudos de caracterização, envolvendo análise granulométrica, química, mineralógica, morfológica, térmica e textural, revelaram características muito semelhantes em ambas às argilas. Fração argila, maior de 70% em massa. Composição química conforme a definição química de uma argila e os teores de seus componentes mostram valores intermédios entre as apresentadas pelas bentonitas e argila caulinítica usadas com fins de comparação. Ressaltamse boas propriedades adsorventes. Área superficial específica BET ao redor de 120 m2/g, valor maior do que o apresentado por muitas bentonitas naturais (74,5 m2/g). Predominantemente mesoporosas, com poros, maiormente em forma de fenda, característicos da estrutura em camadas das argilas. Baixa capacidade de troca catiônica, 12 meq/100g. Difratogramas de raios-X revelaram a predominância do estratificado ilita/esmectita, caulinita e quartzo na argila ALIGRA, e de ilita, caulinita e quartzo na argila SANTA FÉ. Prosseguiu-se com a argila ALIGRA a preparação da argila organofílica. A argila organofílica foi obtida por troca catiônica com o sal quaternário de amônio: cloro cetril trimetil amônio, depois de homogeneizada em sódio com cloreto de sódio. Análises FTIR e TGA indicaram que houve inserção dos cátions orgânicos. Testes preliminares foram feitas, preparando misturas das argilas com matriz de polipropileno e usando como agente compatibilizante polipropileno enxertado com anidrido maleico. Resultados de ensaios de tração reportam algumas melhoras nas propriedades testadas com as composições preparadas com as argilas purificadas. Com as composições com argilas organofílicas somente foi melhorado o alongamento na rotura. Estudos ais aprofundados são recomendados.