Mechanical and Thermal Properties of Thermoplastic Random Copolyesters Made from Lipid- Derived Medium and Long Chain Poly (x-hydroxyfatty acid) s

The physical properties of novel thermoplastic random copolyesters [-(CH2)(n)-COO-/-(CH2)(n)-COO-](x) made of long (n=12) and medium (n=8) chain length -hydroxyfatty esters [HO-(CH2)(n)-COOCH3] derived from bio-based vegetable oil feedstock are described. Poly(-hydroxy tridecanoate/-hydroxy nonanoate) P(-Me13-/-Me9-) random copolyesters (M-n=11,000-18,500 g/mol) with varying molar ratios were examined by TGA, DSC, DMA and tensile analysis, and WAXD. For the whole range of P(-Me13-/-Me9-) compositions, the WAXD data indicated an orthorhombic polyethylene-like crystal packing. Their melting characteristics, determined by DSC, varied with composition suggesting an isomorphic cocrystallization behavior. TGA of the P(-Me13-/-Me9-)s indicated improved thermal stability determined by their molar compositions. The glass transition temperature, investigated by DMA, was also found to vary with composition. The crystallinities of P(-Me13-/-Me9-)s however, were unaffected by the composition. The stiffness (Young's modulus) of these materials was found to be related to their degrees of crystallinity. (c) 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40492.

Thermoplastic polyesters and Co-polyesters derived from vegetable oil: synthesis and optimization of melt polycondensation for medium and long chain poly(omega-hydroxyfatty acid)s and their ester derivatives

The synthesis of a series of omega-hydroxyfatty acid (omega-OHFA) monomers and their methyl ester derivatives (Me-omega-OHFA) from mono-unsaturated fatty acids and alcohols via ozonolysis-reduction/crossmetathesis reactions is described. Melt polycondensation of the monomers yielded thermoplastic poly(omega-hydroxyfatty acid)s [-(CH2)(n)-COO-](x) with medium (n = 8 and 12) and long (n = 17) repeating monomer units. The omega-OHFAs and Me-omega-OHFAs were all obtained in good yield (>= 80%) and purity (>= 97%) as established by H-1 NMR, Fourier Transform infra-red spectroscopy (FT-IR), mass spectroscopy (ESI-MS) and high performance liquid chromatography (HPLC) analyses. The average molecular size (M-n) and distribution (PDI) of the poly(omega-hydroxyfatty acid)s (P(omega-OHFA)s) and poly(omega-hydroxyfatty ester) s (P(Me-omega-OHFA) s) as determined by GPC varied with organo-metallic Ti(IV) isopropoxide [Ti(OiPr)(4)] polycondensation catalyst amount, reaction time and temperature. An optimization of the polymerization process provided P(omega-OHFA) s and P(Me-omega-OHFA) s with M-n and PDI values desirable for high end applications. Co-polymerization of the long chain (n = 12) and medium chain (n = 8) Me-omega-OHFAs by melt polycondensation yielded poly(omega-hydroxy tridecanoate/omega-hydroxy nonanoate) random co-polyesters (M-n = 11000- 18500 g mol(-1)) with varying molar compositions.

Environmental effects on viscoelastic behavior of carbon fiber/PEKK thermoplastic composites

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influence of monomeric and polymeric structure on the physical properties of thermoplastic polyesters derived from hydroxy fatty acids

The physical properties of three vegetable oil derived medium and long chain poly(-hydroxy fatty ester)s (P(Me--OHFA)s), namely poly(-hydroxynonanoate) [P(Me--OHC9)], poly(-hydroxytridecanoate) [P(Me--OHC13)] and poly(-hydroxyoctadecanoate) [P(Me--OHC18)] (n = 8, 12 and 17, respectively), of the [-(CH2)(n)-COO-](x) polyester homologous series are presented. The effect of M-n (M-n 10-40 kg mol(-1)) and n on the crystal structure and thermal and mechanical properties of the P(Me--OHFA)s were investigated by wide-angle X-ray diffraction (WAXD), TGA, DSC, dynamic mechanical analysis (DMA) and tensile analysis and are discussed in the context of the [-(CH2)(n)-COO-](x) polyester homologous series, contrasted with linear polyethylene (PE). For all P(Me--OHFA)s the WAXD data indicated an orthorhombic crystal phase reminiscent of linear PE with crystallinity (X-c = 50%-80%) depending strongly on M-n. The glass transition temperature and Young's modulus for P(Me--OHFA)s increased with X-c. The DSC, DMA and TGA studies for P(Me--OHFA)s (n = 8, 12 and 17) indicated strong correlations between the melting, glass transition and thermal degradation behavior and n. The established predictive structure relationships can be used for the custom engineering of polyester materials suitable for specialty and commodity applications. (c) 2014 Society of Chemical Industry

Horse chestnut (Aesculus hippocastanum L.) starch: Basic physico-chemical characteristics and use as thermoplastic material

Starch isolated from non-edible Aesculus hippocastanum seeds was characterized and used for preparing starch-based materials. The apparent amylose content of the isolated starch was 33.1%. The size of starch granules ranged from 0.7 to 35 pm, and correlated with the shape of granules (spherical, oval and irregular). The chain length distribution profile of amylopectin showed two peaks, at polymerization degree (DP) of 12 and 41-43. Around 53% of branch unit chains had DP in the range of 11-20. A. hippocastanum starch displayed a typical C-type pattern and the maximum decomposition temperature was 317 degrees C.Thermoplastic starch (TPS) prepared from A. hippocastanum with glycerol and processed by melt blending exhibited adequate mechanical and thermal properties. In contrast, plasticized TPS with glycerol:malic acid (1:1) showed lower thermal stability and a pasty and sticky behavior, indicating that malic acid accelerates degradation of starch during processing. (C) 2014 Elsevier Ltd. All rights reserved.

Filling of simulated lateral canals with gutta-percha or thermoplastic polymer by warm vertical compaction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

In situ sonochemical synthesis of ZnO particles embedded in a thermoplastic matrix for biomedical applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation of the genotoxicity of cellulose nanofibers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Polyhydroxybutyrate in Rhizobium and Bradyrhizobium: quantification and phbC gene expression

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Enhancement of thermal stability, strength and extensibility of lipid-based polyurethanes with cellulose-based nanofibers

Cellulose was extracted from lignocellulosic fibers and nanocrystalline cellulose (NC) prepared by alkali treatment of the fiber, steam explosion of the mercerized fiber, bleaching of the steam exploded fiber and finally acid treatment by 5% oxalic acid followed again by steam explosion. The average length and diameter of the NC were between 200-250 nm and 4-5 nm, respectively, in a monodisperse distribution. Different concentrations of the NC (0.1, 0.5, 1.0, 1.5, 2.0 and 2.5% by weight) were dispersed non-covalently into a completely bio-based thermoplastic polyurethane (TPU) derived entirely from oleic acid. The physical properties of the TPU nanocomposites were assessed by Fourier Transform Infra-Red spectroscopy (FTIR), Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD), Dynamic Mechanical Analysis (DMA) and Mechanical Properties Analysis. The nanocomposites demonstrated enhanced stress and elongation at break and improved thermal stability compared to the neat TPU. The best results were obtained with 0.5% of NC in the TPU. The elongation at break of this sample was improved from 178% to 269% and its stress at break from 29.3 to 40.5 MPa. In this and all other samples the glass transition temperature, melting temperature and crystallization behavior were essentially unaffected. This finding suggests a potential method of increasing the strength and the elongation at break of typically brittle and weak lipid-based TPUs without alteration of the other physico-chemical properties of the polymer. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis and physical properties of lipid-based poly(ester-urethane)s, I: Effect of varying polyester segment length

Four aliphatic thermoplastic poly(ester-urethane)s (PEUs) with similar molecular weights but varying polyesters molecular weight (534-1488 g/mol) were prepared from polyester diols, obtained by melt condensation of Azelaic acid and 1,9-Nonanediol, and 1,7-heptamethylene di-isocyanate (HPMDI) all sourced from vegetable oil feedstock. The thermal, and mechanical properties, and crystal structure of PEUs were investigated using DSC, TGA, DMA, tensile analysis and WAXD. For sufficiently long polyester chain, WAXD data indicated no hydrogen bonds polyethylene (PE)-like crystalline packing and for short polyester chains, small crystal domains with significant H-bonded polyamide (PA)-like packing. Crystallinity decreased with decreasing polyester molecular weights. The polymorphism of PEUs and consequently their melting characteristics were found to be largely controlled by polyester segment length. TGA of the PEUs indicated improved thermal stability with decreasing polyester chain length, suggesting a stabilization effect by urethane groups. Mechanical properties investigated by DMA and tensile analysis were found to scale predictably with the overall crystallinity of PEUs. (C) 2012 Elsevier Ltd. All rights reserved.

Efeito da degradação ambiental nas propriedades de cisalhamento de compósitos PPS/fibra de carbono

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliações térmica e reológica da matriz termoplástica PEKK utilizada em compósitos aeronáuticos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação do ciclo térmico de conformação por compressão de peças em poli(sulfeto de fenileno) reforçado com fibras contínuas de carbono

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Análise do efeito higrotérmico no comportamento em fadiga de compósitos de PPS/fibras de carbono

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)