Síntese e caracterização da PEAD obtido via catálise Ziegler-Natta em homo e copolimerização de eteno e 1-buteno

Neste trabalho foram sintetizados e caracterizados polietilenos de alta densidade (PEAD) obtidos via homopolimerização de eteno e copolimerização de eteno com 1-buteno, utilizando-se dois sistemas catalíticos baseados em um catalisador Z-N heterogêneo suportado, sintetizado a partir de TiCl4 e etilato de magnésio, que leva à geração in situ de cloreto de magnésio. O objetivo foi avaliar o efeito do 1-buteno sobre as propriedades do PEAD obtido através do catalisador supracitado e IPRA ou TEA como cocatalisadores (estes sistemas catalíticos foram identificados como ZN1-IPRA e ZN1- TEA). Como esperado, observou-se aumento de atividade catalítica quando 1-buteno foi usado como comonômero, conhecido como “efeito comonômero”. Houve redução da densidade do PEAD com a concentração do comonômero no meio reacional na seguinte ordem: homopolímero > copolímero sintetizado com pressão de 1-C4 de 0,5 bar > copolímero sintetizado com pressão de 1-C4 de 0,9 bar. Esta redução da densidade foi acompanhada de um aumento do MFR, de redução de massa molar e polidispersão, esta última também constatada pelas medidas reológicas em reômetro rotacional. Também constatou-se redução de Tc, Tf, cristalinidade, tensão no escoamento, módulo secante a 2 %, resistência à tração por impacto e ESCR. A razão de inchamento foi maior nos homopolímeros obtidos com ambos os sistemas catalíticos, provavelmente devido à maior polidispersão destas resinas, aliado ao fato de também apresentarem maior massa molar. A deconvolução das curvas de GPC e a caracterização das frações de polímero obtidas através do fracionamento preparativo (PREP) provou a existência de uma maior fração de moléculas com alta massa molar no PEAD obtido com o sistema catalítico ZN1-IPRA. Esta fração permitiu explicar, ao menos em parte, as maiores razões de inchamento e a melhor recuperação no teste de fluência dos polímeros obtidos com este sistema catalítico. Não foi possível identificar diferenças significativas na distribuição do comonômero nas cadeias poliméricas dos copolímeros obtidos com ambos os sistemas catalíticos estudados, somente indícios de incorporação diferenciada através da determinação do teor de metilas totais nas frações obtidas por PREP.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.