Recebido em 12/5/09; aceito em 29/7/09; publicado na web em 8/1/10 BLENDS OF PHB AND ITS COPOLYMERS: MISCIBILITY AND COMPATIBILITY. Poly(hydroxybutyrate) and its copolymers are linear polyesters behaving as conventional thermoplastic materials. However, they are totally biodegradable and produced by a wide variety of bacteria from renewable sources. Some properties and high production cost are still preventing future applications. In an attempt to improve the properties and to reduce cost blending PHB with others polymeric materials is one of the most efficient method. In this paper, miscibility, compatibility, morphological and mechanical aspects of PHB blends will be reviewed. An extensive revision over twenty last years was realized about works of blends based on PHB and its copolymers.Keywords: blends; PHB; miscibility. INTRODUÇÃO Poli(hidroxibutirato) -PHBO PHB e seus copolímeros são produzidos naturalmente por bactérias a partir de fontes renováveis de energia, e são biodegradados por uma enorme quantidade de bactérias e fungos presentes na natureza. 1,2 No Brasil, a produção de PHB foi desenvolvida por uma joint venture entre a Copersucar (Cooperativa dos Produtores de Canade-açúcar do Estado de São Paulo), o IPT (Instituto de Pesquisas Tecnológicas) e pelo ICB (Instituto de Ciências Biomédicas da USP).3,4 A produção de PHB, encontrou condições excepcionalmente favoráveis no Brasil devido às características da indústria de açúcar e álcool, bastante desenvolvida durante o programa PROALCOOL. A disposição de açúcar a baixos preços e grandes quantidades, que é utilizado como substrato para o crescimento das bactérias do PHB, é uma das principais características que favorecem a produção desse polímero.De 1995 a 2000, a primeira produção em planta piloto do PHB no Brasil, utilizando o processo Copersucar-IPT-ICB, foi realizada na usina de açúcar e álcool Usina da Pedra. Os principais objetivos dessa planta piloto foram testar a viabilidade do processo, desenvolvê-lo e realizar uma avaliação econômica do custo de produção de PHB. 4 Em 2000, a produção comercial de PHB se iniciou com a criação da empresa PHB Industrial, em Serrana, próxima à Usina da Pedra. 4 A produção de PHB pela PHB Industrial é a única produção industrial de PHB a partir de cana-de-açúcar e integrada em usina sucroalcooleira. Essa empresa opera desde 2005 com uma planta de capacidade máxima de 60 toneladas de PHB por ano. "Enquanto na Europa, o PHB é produzido a US$10-20,00/kg, no Brasil esses custos estão entre US$2,5-5,00/kg (...)".3 No entanto, esse preço ainda é muito superior aos preços dos polímeros sintéticos da indústria petroquímica, o que desestimula a ampla comercialização do PHB.A biodegradabilidade não pode ser o único atrativo no PHB ou em qualquer polímero biodegradável. Para ser aceito em larga escala, estes polímeros têm de possuir os atrativos dos termoplásticos convencionais como: (i) suprir a demanda do mercado, ou seja, ser produzido em grande quantidade; (ii) correta compostagem para preservar a sua biodegradação; (iii)...

Poly(propylene-co-ethylene) composites with rice husk were prepared in a corotating intermeshing twin-screw extruder using four different coupling agents. While modified maleic anhydrides such as maleated polypropylene (MAPP) and maleated polyethylene (MAPE) are commonly used as compatibilizers to improve interfacial adhesion between lignocellulosic filler and matrix, in this study, polypropylene grafted with acid comonomer (CAPP) and high-density polyethylene grafted with acid comonomer (CAPE) were also used. The morphologies and the thermal and mechanical properties of the composites were characterized using scanning electron microscopy, thermogravimetric analysis, differential scanning analysis, tensile and impact tests. The results indicate that the base resin of the compatibilizer is an important factor in determining the effectiveness of compatibilizers for composites. Composites with PP-based compatibilizers are more effective than PE-based compatibilizers due to the improved wetting of the former compatibilizer in the matrix polymer.

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Polyhydroxybutyrate (PHB) is a biodegradable bacterial polyester emerging as a viable substitute for synthetic, semicrystalline, nonbiodegradable polymers. An elastomer terpolymer of acrylonitrile-g-(ethylene-copropylene-co-diene)-g-styrene (AES) was blended with PHB in a batch mixer and in a twin-screw extruder to improve the mechanical properties of PHB. The blends were characterized with differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy, and impact resistance measurements. Despite the narrow processing window of PHB, blends with AES could be prepared via the melting of the mixture without significant degradation of PHB. The blends were immiscible and composed of four phases: poly(ethyleneco-propylene-co-diene), poly(styrene-co-acrylonitrile), amorphous PHB, and crystalline PHB. The crystallization of PHB in the blends was influenced by the AES content in different ways, depending on the processing conditions. A blend containing 30 wt % AES presented impact resistance comparable to that of high-impact polystyrene, and the value was about 190% higher than that of pure PHB.

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The structure of the title compound, C27H32ClN5O, consists of two crystallographically independent conformers differing slightly in all geometric parameters. Both contain nearly planar purine and benzene ring systems [maximum deviations of 0.046 (3) and 0.005 (2) Å, respectively], the dihedral angles between them being 76.44 (6) and 82.39 (6)°, and an adamantane cage consisting of three fused cyclo­hexane rings in almost ideal chair conformations, with C—C—C angles in the range 108.7 (2)–110.6 (2)°. The carbonyl plane and the benzene ring are almost coplanar [dihedral angles of 6.43 (9) and 0.64 (8)° in the two conformers]. The crystal structure is stabilized by inter­molecular N—H⋯N inter­actions that link adjacent mol­ecules into dimers and by some non-bonding contacts of the C—H⋯Cl type.

Blends of poly(methyl methacrylate), PMMA, and the elastomer ASA, a graft copolymer based on poly(acrylonitrile‐co‐styrene) (SAN) and acrylic rubber, were prepared by in situ polymerization and characterized according to structural, mechanical, thermal, and morphological properties. The polymerization conditions, such the presence or absence of a chain transfer agent, stirring and an inert atmosphere, influence the morphological and structural properties of the blends. In spite of the evidences of the partial miscibility between PMMA and SAN phase of the ASA, the blends are heterogeneous and present a complex morphology. The morphology of some PMMA‐ASA blends is made up of an elastomeric dispersed phase in a glassy matrix, with a possible inclusion of the matrix in the elastomeric domains. The selective extraction of the blend components and infrared spectroscopy showed that crosslinking and/or grafting reactions occur on ASA chains during MMA polymerization. The syndiotacticity of PMMA obtained in the presence of ASA increases with the amount of ASA, due to possible interactions between the carbonyl groups of PMMA and the nitrile or phenyl groups of the SAN copolymer. The mechanical properties of the blends were influenced by the compositions of the blends and mainly by the conditions of polymerization. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene) (AES) were prepared by in situ polymerization. AES, a commercial elastomer obtained by radical copolymerization of styrene and acrylonitrile in the presence of ethylene‐propylene‐diene terpolymer (EPDM), was dissolved in methyl methacrylate and the in situ polymerization was conducted at 60 °C. The blends were characterized by CHN analysis, infrared spectroscopy (FTIR), carbon‐13 nuclear magnetic resonance (13C NMR), dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM). These blends are immiscible and present complex phase behavior. Selective extraction of the blends’ components showed that a fraction of the material is crosslinked and grafting reactions on EPDM chains take place during MMA polymerization. Syndiotactic PMMA was obtained in the presence of AES and this syndiotactic‐specificity increased with increasing amount of AES. The morphology of polymerized specimens showed irregular domains of elastomeric phase and in some cases inclusions of PMMA could be observed.