Os catalisadores lantanídicos são muito eficientes na polimerização estereoespecífica de dienos, principalmente aqueles à base de neodímio. Neste trabalho será apresentado o estudo da polimerização do 2-metil, 1,3-butadieno com catalisadores à base de neodímio, utilizados comercialmente na polimerização do 1,3-butadieno. Foi estudado o efeito da temperatura, do tipo de alquilalumínio e da concentração de catalisador. As reações foram realizadas em reator de aço inox sob atmosfera inerte, usando como solvente o hexano e uma concentração de 2-metil, 1,3-butadieno de 12%. Foram obtidos polímeros com massas molares na faixa de 1,0 a 1,5 × 105 e teor de unidades repetitivas cis em torno de 97%.

The rare earth metals catalysts are very efficient in stereospecific polymerization of dienes, especially those of neodymium. This paper reports on the polymerization of 2-methyl, 1,3-butadiene with catalysts of neodymium, used commercially in polymerization of 1,3-butadiene. Effects were studied from the temperature, type of alkylaluminum, and from the concentration of catalyst. The reactions were carried out in a stainless steel reactor under an inert atmosphere, using hexane as the solvent and a concentration of 12% of 2-methyl, 1,3-butadiene. Polymers were obtained with molecular weight from 1.0 to 1.5 × 105, with ca. 97% of cis repeating units.

Foi utilizado o sistema catalítico tipo Ziegler-Natta modificado, constituído por TiCl4/I2/Al(i-Bu)3 para a síntese de polibutadieno com alto teor de unidades 1,4-cis. Foi estudada a influência da variação da composição do sistema catalítico e da temperatura reacional na atividade catalítica, no massa molar e na microestrutura do polibutadieno. Os polímeros foram caracterizados por espectroscopia na região do infravermelho, cromatografia por exclusão por tamanho e calorimetria diferencial de varredura. Foi obtido polibutadieno com até 92% de unidades 1,4-cis e baixo teor de gel. A massa molar ponderal média variou, com a composição do sistema catalítico e com a temperatura reacional, na faixa de 3 a 50 x 10(4) e a polidispersão variou na faixa de 1,8 a 3,3. A atividade catalítica máxima foi obtida para as razões molares Al/Ti = 5 e I2/Ti = 2.

A modified Ziegler-Natta type catalytic system consisting of TiCl4/I2/Al(i-Bu)3 was used to produce polybutadiene with high content of 1,4-cis repeating units. The influence of the catalytic system composition and temperature on the catalyst activity, molecular weight and microstructure of the polybutadiene was studied. The polymers were characterized by infrared spectroscopy and size exclusion chromatography. Polybutadiene with up to 92% of 1,4-cis repeating units and low gel content was produced. The polymer molecular weight was dependent on the catalytic system composition and reaction temperature. The weight-average molecular weight varied from 3 to 50 x 10(4); the molecular weight distribution was low, ranging, from 1.8 to 3.3. The maximum catalytic activity was achieved at molar ratios Al/Ti = 5 and I2/Ti = 2.

The Ziegler-Natta catalyst and the polymerization thereof are systems which require careful handling and special treatment of chemicals. In spite of the use of inert atmosphere and dry chemicals, some Ziegler-Natta systems may present low activities or even may deactivate because of unsuitable handling. Some features of the TiCl3 synthesis and its characterization when related to the presence of impurities are described. Evidences of poor handling of chemicals and/or laboratory devices while in synthesis of the catalyst are emphasized. The problems arising from butadiene polymerization and some relevant details in propylene polymerization are also presented with teaching objectives.