Abstract Block copolymers and blends comprised by liquid crystalline oligoester and polystyrene were prepared and their thermal stability were characterized by thermogravimetric analysis (TGA). The samples have shown three main decomposition temperatures due to (1) lost of flexible chain and decomposition of mesogenic segment, (2) decomposition of polystyrene and (3) final decomposition of oligoester rigid segment. Both copolymers and polymer blends presented lower thermal stability compared to polystyrene and oligoester. The residual mass after heating at 600 °C in copolymers and polymer blends were lower than those found in the oligoesters. A degradative process of aromatic segments of oligoester induced by decomposition of polystyrene is suggested.

The formation of the crystalline phase of polypropylene in the presence of four different types of CaCO3 was studied. All composites were prepared by melt mixing and extrusion and the concentration of CaCO3 was maintained at 5 wt %. Furthermore, in another series of composites, 5 wt % of polypropylene-graft-maleic anhydride (PP-g-MA) was added for comparison. The tensile strength, flexural modulus and impact resistance of the composites were determined. The composites were also analyzed by DSC (differential scanning calorimetry) and WAXD (wide angle x-ray diffractometry) in order to understand and quantify the beta crystalline phase. The results indicated that the composite having the smallest CaCO3 size and PP-g-MA presented the best combined mechanical properties, therefore, the highest impact resistance, flexural modulus and tensile strength were observed, which were attributed to the proportionally higher concentration of beta crystalline phase.

This work studies the influence of the film deposition process on light emission performance and on threshold voltage of OLEDs, with architecture glass/ITO/PEDOT:PSS/PVK/Alq3/Al. The commercial PVK was dissolved in different solvents such as: chloroform, tetrahydrofuran, 1,2,4-trichlorobenzene and trimethylpentane. OLEDs were characterized by current-voltage and revealed a significant influence of the solvents, although all devices emitted green electroluminescence. A difference in threshold voltage up to 10 V was observed among OLEDs prepared from different solvents. The 1,2,4-trichlorobenzene showed best performance, presenting lowest treshold voltage (≈ 6 V), followed by tetrahydrofuran (≈ 8 V), trimethylpentane (≈ 14 V) and chloroform (≈ 16 V).

An UV-Ozone reactor was developed with an ignition tube extracted into HID mercury lamp used to irradiation on zinc oxide (ZnO) and fluorinated tin oxide (FTO) films for PLEDs devices. Different exposures times were used. In contact angle measurements revealed better results for ZnO and FTO by 15 and 5 min, respectively. In Diffuse Reflectance Infra-red Fourier Transformed (DRIFT) spectroscopy allowed the observation of water, hydrocarbon and carbon dioxide adsorbed on the untreated TCO surfaces. After the UV-Ozone treatment the contaminants were significantly reduced or eliminated and the PLEDs devices decreased threshold voltages in comparison with respectively untreated TCOs.

Neste trabalho, é mostrada a síntese de homopolímeros de p-acetoxiestireno e copolímeros diblocos de p-acetoxiestireno com isopreno, utilizando um iniciador TEMPO-modificado, por um processo de polimerização "viva" via radical livre. As análises de GPC indicaram a formação de copolímeros em bloco com massas molares e polidispersão mais altas quando comparadas aos dos homopolímeros correspondentes. Os copolímeros em bloco poli(p-acetoxiestireno-b-isopreno) foram preparados com controle de composição e massa molar até 94500 u.m.a. As análises de DSC mostraram que a transição vítrea do bloco de p-acetoxiestireno foi de 5 a 18 °C mais baixa que aquelas obtidas para os homopolímeros correspondentes. A transição vítrea do bloco de isopreno apresentou valores similares àqueles dos homopolímeros de poliisopreno (-67 a -55 °C).

In this work we show the synthesis of homopolymers and diblock copolymers of p-acetoxystyrene and isoprene by using TEMPO-modified free radical initiator. The GPC analyses have shown an increase in the molar masses and in the polydispersity of the copolymers in comparison with their corresponding homopolymer. Poly(p-acetoxystyrene-b-isoprene) were prepared with good control of composition and molar mass up to 94,500 a.m.u. DSC analyses have shown a glass transition temperature decrease of 5-18 °C for the poly(p-acetoxystyrene) segment in copolymers compared to that observed for the parent homopolymer. The glass transition temperature of polyisoprene segment in copolymers remained similar to those observed for the homopolymers (-67 to -55 °C).

Duas séries de copolímeros triblocos, poli (ácido lático-b-etileno glicol) (PLA-PEO-PLA), foram sintetizados a partir do éster cíclico l,l-lactideo, usando octoato de estanho como iniciador e poli (etileno glicol) (PEG) (Mn = 4000 ou 600), di-hidróxi terminado, como co-iniciador. A ligação química entre os segmentos PEG e PLA foi confirmada pelas técnicas de espectroscopia no infravermelho (FTIR) e Ressonância Magnética Nuclear de Hidrogênio (RMN-¹H) e análise térmica. O grau de polimerização do bloco PLA, DP PLA, no copolímero foi estimado por RMN-¹H e mostrou variação em função da massa molar do PEG e do aumento da concentração relativa de l,l lactídeo na mistura reacional. O aspecto dos copolímeros sintetizados variou de acordo com o tamanho dos blocos hidrofílico e hidrofóbico presentes em sua estrutura. Testes de solubilidade mostraram comportamento anfifílico para o produto sintetizado. Os segmentos de PLA formaram uma fase cristalina enquanto a fase cristalina correspondente aos segmentos PEG não foi observada.

Two series of tri-block copolymers, poly(lactic acid-b-ethylene glycol) (PLA-PEG-PLA), were synthesized from l,l-lactide using stannous di-octoate as initiator and di-hydroxy terminated poly(ethylene glycol) (PEG) (Mn= 600 or 4000) as co-initiator. The chemical linkage between the PEG segment and the PLA segments was confirmed by Fourier transform infrared spectroscopy (FTIR), by proton magnetic resonance spectroscopy (¹H-NMR) and thermal analyses. The polymerization degree of PLA segments in copolymers, DP PLA, was estimated from ¹H-NMR spectra and has shown a dependence on the PEG molar mass and the relative l,l-lactide feed concentration. The physical aspect of copolymers changed according to the hydrophilic and hydrophobic segments lengths. The solubility tests revealed the amphiphilic nature of copolymers. Longer PLA segments in copolymers still presented crystallinity while the crystallization of the PEG segments was suppressed.

O conceito de volume hidrodinâmico pode ser utilizado efetivamente com cromatografia de permeação em gel (GPC) e dados de viscosidade para calcular a massa molar de uma variedade de polímeros. Neste trabalho, as constantes da equação de Mark-Houwink para os homopolímeros de poli(p-acetóxiestireno) (PASt) foram determinadas pela correlação dos valores de massa molar ponderal média (<IMG SRC="/img/revistas/po/v14n2/21574s1.gif">) determinados por cromatografia de permeação em gel (GPC) relativos a padrões de poliestireno, com as correspondentes medidas de viscosidade intrínseca [<IMG SRC="/img/revistas/po/v14n2/21574s3.gif">] em soluções de THF a 25 °C. A massa molar viscosimétrica média (<IMG SRC="/img/revistas/po/v14n2/21574s2.gif">) de qualquer amostra de PASt desconhecida pode ser calculada medindo-se a viscosidade intrínseca da amostra, e aplicando-se então a equação de Mark-Houwink, utilizando-se os valores de K e alfa calculados, 1,442 x 10-2 g/ml e 0,695, respectivamente.

The hydrodynamic volume concept can be used effectively with gel-permeation chromatography (GPC) and viscosity data to estimate the molecular weight of a variety of polymers. In this work, the Mark-Houwink coefficients (alpha and K) for the poly(p-acetoxystyrene) homopolymers (PASt) were determined by correlating their weight average molecular weight (<IMG SRC="/img/revistas/po/v14n2/21574s1.gif">) values, determined by gel-permeation chromatography (GPC) relative to polystyrene standards, with their measured intrinsic viscosity values ([<IMG SRC="/img/revistas/po/v14n2/21574s3.gif">]). The <IMG SRC="/img/revistas/po/v14n2/21574s2.gif">of any unknown PASt sample may be estimated by first measuring the sample's intrinsic viscosity, and then applying these alpha and K values with the Mark-Houwink equation.

O comportamento fotofísico do cromóforo p-fenóxi-metil-estilbeno livre ou como grupamento pendente em cadeia polimérica foi estudado através de espectros de absorção e fotoluminescência em solução e no estado sólido. As características do cromóforo livre foram observadas usando-se o composto modelo p-(p-etil-fenóximetil)estilbeno e as do cromóforo ligado a um esqueleto polimérico foram estudadas com o poli(estireno-co-estilbenil-p-metoxiestireno). Os resultados são interpretados em termos de emissões provenientes do cromóforo isolado ou de agregados formados no estado fundamental

The photophysical behavior of the chromophore p-phenoxymethylstilbene in the free state or when bound to a polymer backbone was studied by absorption spectroscopy and photoluminescence both in solution and in the solid state. The characteristics of the free chromophore were observed by comparison with the model compound p-(p-ethylphenoxymethyl)stilbene and those of the bound chromophore were studied through poly(styrene-co-stilbenyl-p-methoxystyrene). The results were interpreted in terms of the emissions from the isolated chromophore or from aggregates in the ground state.