This article reports the synthesis of two zinc(II) complexes containing phenoxy-imine ligands and their application as initiators of bulk ring opening polymerization (ROP) of L-lactide (LLA). The phenoxy-imine ligands (L1 and L2) were obtained by condensation reactions of salicylaldehyde derivatives with 2,6-diisopropylaniline. The reactions of L1 and L2 with ZnEt2 in the presence of n-BuOH afforded [Zn(L1)(OBu)] (C1) and [Zn(L2)(OBu)] (C2), which were characterized by elemental analysis, FTIR and 1H NMR spectroscopy. In addition, the geometries of both complexes were investigated by DFT (B3LYP/LACV3P**) calculations. C1 and C2 were tested as initiators of ROP of LLA at 180 °C using different LLA/Zn molar ratios, namely 500, 1000 and 2500. Both complexes showed good activity, resulting in conversions up to 90-92% in 2 h. The poly(L-lactide) obtained displayed Mn ranging from 40.000-109.000, relatively low polydispersity (Mw/Mn = 1.2-2.1) and high stereoregularity with Tm = 176 °C.

Nickel-diimine complexes DADNiX2 (DAD= 2,6-iPr2-C6H3-N=C(Me)-C(Me)=N-2,6-iPr2-C6H3) containing the non-chelating pseudo-halide ligands isothyocyanate and isoseleniumcyanate (X= NCS 1 and NCSe 2) were synthesized and used in ethylene polymerization activated by methyaluminoxane (MAO) at temperatures from 0 to 50°C. Polymerizations with these complexes were compared with the analogous Ni-diimines halide (X= Br 3) as non-chelating ligand. All systems were very active in this polymerization. The increase of reaction temperature favored the increase in catalytic activity. The catalyst system 1/MAO was more stable than the others, showing the best catalytic activity at the molar ratio Al/Ni between 200 and 300. System 2/MAO showed to be the less stable and less active, particularly at 50°C. Polyethylenes obtained with systems 1, 2 and 3 show high molecular weights, are branched polymers, and predominately amorphous, but the majority still present DSC endothermal events related to melting of small crystals. When halide (Br) are compared with these pseudo-halides, different activities, polymerization kinetics and characteristics of the final polymer indicated modification in the active species caused by the non-chelating ligand. Polymer molecular weight and branching content was not significantly influenced by the non-chelating ligand, being much more dependent on the MAO/Ni molar ratio and polymerization temperature.

This article reports the synthesis of two bimetallic zinc(II) complexes containing phenoxy-imine ligands and their application as initiators of ring opening polymerization (ROP) of L-lactide (LA). The phenoxy-imine ligands were obtained from salicylaldehyde derivatives and 2,3,5,6-tetramethylphenylenediamine, yielding two bidentate regions per ligand. The reactions of both phenoxy-imine ligands with ZnEt2 in the presence of n-BuOH afforded [Zn2(L1)(OBu)2] and [Zn2(L2)(OBu)2], which were characterized by elemental analysis, Fourier transform infrared (FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopy. In addition, the geometries of both complexes were investigated by DFT (B3LYP/LACVP**) calculations. [Zn2(L1)(OBu)2] and [Zn2(L2)(OBu)2] were tested as initiators of ROP of LA at 180 °C using different LA/Zn molar ratios, namely 500, 1000 and 2500. Both complexes showed good activity, resulting in conversions up to 96% in 2 h. The poly-LLA exhibited average molecular weight (Mw) ranging from 45,000-92,000, relatively low polydispersity (Mw/Mn = 1.6-2.0) and high stereoregularity with melting temperature Tm = 164 °C.

In this paper, chemical functionalization of poly(lactic acid) (PLA) was carried out by using of salicyl aldehyde (SAl) and salicylic acid (SAc) as co-initiators of ring opening polymerization (ROP). Two factorial designs (22) were performed to evaluate the effects of the lactide/catalyst and co-initiator/catalyst molar ratios on the content of aldehyde or carboxylic acid end groups, thermal properties and molecular weight (Mw) of PLA. Tin(II) 2-ethylhexanoate was used as a catalyst. The co-initiator/catalyst molar ratio has a statistically significant influence on the polymer functionalization. The highest co-initiator/catalyst molar ratio of 12/1 allows the best aldehyde or carboxylic acid functionalization, independent on the lactide/catalyst molar ratio. On the other hand, the used lactide/catalyst and co-initiator/catalyst molar ratios did not show a statistically significant influence on the polymer thermal properties. Besides, co-initiator/catalyst molar ratio has a statistically significant influence on the polymer molecular weight. So, the highest co-initiator/catalyst molar ratio used (12/1) in combination with the highest lactide/catalyst ratio (125/1) produced functionalized PLA with higher molecular weights.

The isothermal crystallization kinetics of PLA stereocomplex (scPLA) and scPLA/graphene oxide nanocomposites was investigated. scPLA was prepared by symmetric blending the two isomers, PLLA and PDLA and the scPLA nanocomposite by polymerization of the respective lactides in presence of commercial graphene oxide nanoplatelets (GNPO+) followed of blending the two composites. The effect of the filler on the crystallization behavior and thermal properties of scPLA was investigated by using differential scanning calorimetry (DSC). Avrami equation was used to describe the isothermal crystallization kinetics and melting behavior. Addition of 0.5 wt% GNPO+ to PLA matrix increases the crystallization rate, lowering the half-time of crystallization t1/2 to around 5.5 min for scPLA nanocomposites, which is about 2.7 min below that found for scPLA when isothermally crystallized at 165ºC. During the isothermal crystallization, homochiral and stereocomplex crystals are formed, depending on the crystallization temperature. As crystallization temperature reaches 160 and 165ºC, the crystallization of homocrystals become prevented and only stereocomplex crystals are formed.

A aplicação de estruturas tridimensionais bio-reabsorvíveis como suporte temporário na engenharia de tecidos tem crescido nos últimos anos. Neste estudo, estruturas porosas de poli(3-hidroxibutirato) (P(3HB)) foram preparadas pelo método de vazamento e lixiviação de partículas. As amostras foram obtidas pela adição de cloreto de sódio em concentrações de 50, 60, 70, 80 e 90% p/p, a uma solução de P(3HB) em clorofórmio. O tamanho das partículas de sal foi controlado nas faixas de 38-53, 53-75 e 75-150 µm. As propriedades térmicas das matrizes poliméricas foram estudadas via calorimetria diferencial de varredura (DSC) e análise termogravimétrica (TGA). A morfologia das amostras foi observada por microscopia eletrônica de varredura (MEV), onde se constatou a formação de estruturas assimétricas para concentrações de sal de 50, 60 e eventualmente 70%. Os tamanhos dos poros obtidos apresentaram dependência somente com a fração em peso inicial e com o tamanho da partícula do sal empregado. Análises de difração de raios X indicaram que o tipo de sal, a concentração e a granulometria não influenciam as características cristalinas do polímero na estrutura porosa. Pelo teste de bioatividade "in vitro" foi constatada a formação espontânea de uma camada de fosfato de cálcio sobre a superfície das estruturas porosas.

Three-dimensional polymeric scaffolds have been widely employed as support in tissue engineering to reconstruct damaged or lost tissue. In this study porous structures were obtained using P(3HB) solution with five concentrations of sieved sodium chloride 50, 60, 70, 80 and 90 wt %, with particles size in the range of 75 - 150, 53 - 75 and 38 - 53 µm. Thermal properties of the samples were investigated by differential scanning calorimetry and thermo gravimetric analysis, while the morphology was observed by scanning electron microscopy. Asymmetric porous structures were formed for salt concentrations of 50, 60 and in some cases 70wt%. Additionally, porosity increased as the salt weight fraction was increased and pore diameter increased as the salt particle size increased. X-Ray diffraction analysis showed that salt concentration and granulometry did not influence the crystalline characteristics of the porous matrices when compared with the dense polymer film obtained by casting of a solution without salt. The scaffolds promote the spontaneous deposition of a calcium phosphate layer, indicating bioactivity.

As misturas físicas de poliamida 6 (PA6) e policarbonato (PC) processadas a 240 ºC, durante 10, 30 e 60 minutos formam um copolímero de PA6-PC. A alta temperatura e o longo tempo de processamento podem causar modificações nas propriedades dessas misturas e degradar o copolímero, originando grupos isocianato e subseqüentemente CO2 e grupos NH2 terminais. A quantidade de copolímero PA6-PC formado durante o processo de mistura é maior com o aumento da proporção de PC na mistura. As ligações uretânicas de polímeros termoplásticos exibem mais baixas estabilidades térmica e oxidativa, resultando no aumento da concentração de grupos terminais NH2. A reatividade dessas misturas foi investigada através do torque durante o processo de mistura, da titulação potenciométrica dos grupos NH2 terminais e por microscopia eletrônica de varredura.

Polyamide 6 (PA6) and polycarbonate (PC) blends processed at 240 °C, during 10, 30 and 60 minutes produced a copolymer of PA6-PC. The high temperature and long processing time can cause modifications on the properties of these blends and degradation of the copolymer. It can also form isocyanate groups and subsequently CO2 and NH2 "end groups". The amount of PA6-PC copolymer formed during the blending process was found to increase when the PC content is increased. The thermoplastic urethanes normally exhibit smaller thermal and oxidative stability, resulting in an increase in the concentration of NH2 terminal groups. The reactivity of the blends was investigated by monitoring the torque during the blending, potentiometer titration of NH2 terminal groups and scanning electronic microscopy (SEM).

O processamento reativo de poli(naftalato de etileno) (PEN) na presença de fostito de trifenila (TPP) em um misturador interno acoplado ao reômetro de torque foi investigado. O acompanhamento do torque e da temperatura durante o processamento revelou a ocorrência de reações de extensão de cadeia. A massa molecular do poliéster aumentou com o tempo de processamento, passando por um máximo, após o qual começa a decrescer como resultado de degradação molecular acelerada pela presença de subprodutos da extensão de cadeia. A intensidade das reações de extensão de cadeia aumenta com o aumento do teor de TPP, da temperatura e do cisalhamento. Tanto a extensão de cadeia quanto a degradação ocorrem mais lentamente para o PEN que para o poli(tereftalato de etileno). A presença de TPP no material provoca modificações na Tg, devido a um efeito de plastificação, e aumenta a velocidade de cristalização.

The reactive processing of poly(ethylene naphthalate) (PEN) in presence of triphenylphosphite (TPP) was investigated. An internal mixer coupled to a torque rheometer was used to monitor changes of molecular mass and temperature during processing. The torque curves revealed that chain extension reactions took place. During the processing, there is an increase in the molecular weight of the polyester, which reaches a maximum and then decreases due to molecular degradation, accelerated by the presence of chain extention by-products. The intensity of the chain extention reaction increases when TPP content, temperature and shear rate rise. Chain extension and degradation rate are slower in PEN than in poly(ethylene terephthalate). The presence of low molecular weight by-products of chain extension in PEN causes changes in the Tg, due to plasticization effects, and increase the crystallization rate.

Titanocenos são catalisadores solúveis conhecidos para a polimerisação estereoespecífica de olefinas pró-quirais como o estireno. Nesse trabalho descrevemos as relações entre as características do poliestireno e a estrutura do precursor do catalisador, de fato aqueles da família (RCp)2TiCl2 (R = H, etila, iso-propila, n-propila, sec-butila, n-butila, iso-amila e ciclohexila). Todos os catalisadores são ativos para a produção de poliestireno acima de zero graus centígrados. A sindiotaticidade dos polímeros são dependentes da cadeia lateral dos anéis aromáticos do titanoceno e da temperatura da polimerização. A relação entre os fatores estéricos e eletrônicos do precursor do catalisador e os produtos de polimerização são apresentados e discutidos.

Titanocenes are known to be soluble, stereospecific catalysts for the polymerisation of prochiral olefins such as styrene. In this work we shall describe the relations between polystyrene cracteristics and the structure of the catalyst precursor, namely those of the family (RCp)2TiCl2 (R = H, ethyl, iso-propyl, n-propyl, sec-butyl, n-butyl, iso-amyl e ciclohexyl). All catalysts were found to be active for the production of polystyrene at temperatures above zero degrees centigrade. The syndiotacticity of the polymers were found to be dependent on the side chain at the aromatic rings of the titanocene, and onthe temperature of polymerisation. The relationship between steric and electronic factors within the catalyst precursors and the polymerisation products shall be presented and discussed.

Copolímeros de estireno-divinilbenzeno para a aplicação em cromatografia de exclusão por tamanho foram sintetizados através de polimerização em suspensão aquosa modificada pela presença de diluentes. Na síntese dos copolímeros foram variados os seguintes parâmetros reacionais: tipo de diluente, grau de diluição e teor de divinilbenzeno. Os copolímeros obtidos como partículas esféricas com tamanho médio em torno de 10 µm foram caracterizados quanto à porosidade no estado seco e às propriedades de inchamento. Os copolímeros foram utilizados como material de empacotamento de colunas para cromatografia de exclusão por tamanho (SEC). O aumento do grau de diluição na síntese do copolímero aumentou o limite de exclusão da cromatografia, porém a redução do poder solvatante do diluente teve um efeito mais pronunciado sobre esse parâmetro.

Styrene-divinylbenzene copolymers were synthesized by modified suspension polymerization in presence of diluents. In the copolymers synthesis, the following reaction parameters were varied: diluent type, dilution degree and divinylbenzene content. The copolymers obtained as spherical particles with average diameter around 10 µm. were characterized by their porosity in dry state and by their swelling properties. The copolymers were applied as packing material of size exclusion chromatography columns. The increase of dilution degree in the copolymer synthesis increased the chromatography exclusion limit, but the decrease of diluent-copolymer affinity provoked a more accentuated effect on that parameter.