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.

Propylene polymerizations were carried out with f2C(Flu)(Cp)ZrCl2 and SiMe2(Ind)2ZrCl2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f2C(Flu)(Cp)ZrCl2, SiO2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereoregularity.

Neste trabalho, o desempenho dos catalisadores SiMe2(Ind)2ZrCl2, Et(Ind)2ZrCl2, SiMe2(Ind)2HfCl2 e Et(Ind)2HfCl2 na polimerização de propileno usando MAO como cocatalisador empregando-se um Planejamento estatístico de experimentos foi avaliado. As polimerizações foram realizadas em diferentes temperaturas e razões molares alumínio/metal de transição. O efeito destas variáveis na atividade de cada catalisador e nas características do polipropileno obtido foi melhor investigado utilizando-se os modelos propostos para cada variável. Foram observadas influências significativas das condições experimentais principalmente na atividade catalítica, bem como no peso molecular ponderal médio, temperatura de fusão e percentagem de isotaticidade dos polímeros obtidos. A partir dos modelos propostos através do tratamento estatístico realizado pode-se observar que os catalisadores a base de zircônio são os de maior atividade catalítica, enquanto que os hafnocenos produzem polipropileno com peso molecular mais elevado. Os complexos com ponte dimetil-silânica produziram polipropileno com maior peso molecular, estereorregularidade e maior temperatura de fusão do que os similares com ponte etilidênica.

In this work, the performance of the catalysts SiMe2(Ind)2ZrCl2, Et(Ind)2ZrCl2, SiMe2(Ind)2HfCl2 e Et(Ind)2HfCl2 on propylene polymerization using MAO as cocatalyst and employing a Statistic Experimental Planning Model was evaluated. The polymerizations were carried out at different temperatures and aluminum/transition metal molar ratios. The effect of these variables on the catalyst activity and on the polymer characteristics was investigated using the proposed models for each variable. A significant influence was observed of the experimental conditions on the catalyst activity in particular, but also on the weight-average molecular weight, melting point and isotacticity of the polypropylenes produced; the statistical analysis with the proposed models indicated higher catalyst activity for the zirconocenes, while the hafnocenes produced polypropylene with higher molecular weight. The complexes with dimethylsilane bridge produced polypropylene with higher molecular weight, stereoregularity and higher melting temperature in comparison with the corresponding polymers using the ethylidene bridge.

Polypropylene with special properties can be obtained by metallocenic catalysts. These catalytic systems represent the beginning of a new age in polyolefins technology. In this work, the influence of the addition of a syndiotactic polypropylene (s-PP) on the processability and mechanical properties of a commercial isotactic polypropylene (i-PP) obtained by metallocenic catalysts was evaluated. Increasing addition of s-PP promoted better processability, with an increase in the impact strength and a decrease in the stress at break. A reduction of the crystallinity in the polymeric blends was verified. The more significant influence of the s-PP addition was observed for the mi-PP, compared to the ZNi-PP.

O monômero eteno foi polimerizado através dos sistemas catalíticos Cp2ZrCl2/SiO2 e Cp2ZrCl2/MAO/SiO2. Foi elaborado um planejamento estatístico de experimentos a fim de se identificar as melhores condições de preparo dos catalisadores heterogêneos. As variáveis utilizadas foram a concentração de metilaluminoxano (MAO) no pré-tratamento do suporte, a concentração e a temperatura de imobilização do metaloceno. Os catalisadores suportados foram analisados por espectrometria de emissão com plasma acoplado indutivamente e as resinas produzidas foram caracterizadas por cromatografia de permeação em gel (GPC) e calorimetria de varredura diferencial (DSC). Foi observado que quanto maior a concentração de zircônio fixada na superfície do suporte, menor foi a atividade catalítica, na faixa de variáveis estudadas.

Ethylene was polymerized with the catalytic systems Cp2ZrCl2/SiO2 and Cp2ZrCl2/MAO/SiO2. A experimental planning model was developed in order to identify the best conditions for the preparation of metallocene heterogeneous catalysts. The variables used were methylaluminoxane (MAO) concentration of the support treatment, concentration and temperature of metallocene immobilization. The supported catalysts were analyzed by inductively coupled plasma emission spectometry and the polyethylene (PE) produced was characterized by gel permeation calorimetry (GPC) and differential scanning calorimetry (DSC). It was observed that the higher the zirconium concentration fixed on the support surface, the lower the catalyst activity, in the studied variables range.

Este trabalho apresenta uma discussão sobre aspectos gerais da nova tecnologia de síntese de polímeros com microestrutura e propriedades controladas, obtidos via sistema catalítico metaloceno/MAO. Mostra a importância da heterogeneização desses sistemas para possibilitar o seu emprego na produção industrial de uma ampla classe de materiais poliméricos. São discutidas ainda as principais características dos suportes mais empregados para esses catalisadores.

This work presents a discussion about the general aspects of the new technology for the synthesis of polymers with controlled microstructure and properties, obtained by metallocene/MAO catalyst system. It shows the relevance of heterogenization of these systems to allow their application for industrial production of a large range of polymer materials. The characteristics of the more used supports for these catalysts are also discussed.