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Process of preparation of catalytic support and supported metallocene catalysts for production of homopolymers and copolymers of ethylene with alfa - olefins, of high and ultra high molecular weight and with broad molecular weight distribution in slurry, bulk and gas phase processes and products thereof

a technology of supported metallocene and catalyst, which is applied in the field of catalytic support and supported metallocene catalyst, can solve the problems of poor morphology of the polymer material obtained, the use of toluene, which is commonly used in the formulation of aluminoxanes solution, and the general anti-economic effect of poliolefin production in industrial scale based on these catalytic systems

Inactive Publication Date: 2011-04-14
BRASKEM SA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The present invention relates to a process for preparing supported metallocene catalysts based on transition metals of the groups 4 or 5 of the periodic table, containing ligands like monocyclopentadienyl, monoindenyl or monofluorenyl, which can be used in the polymerization of ethylene and α-olefins. The process involves the reaction between a catalytic support and a transition metal complex containing a ligand and an activator. The resulting catalysts have high molecular weight and ultra high molecular weight polymers with broad molecular weight distribution. The process can be carried out in liquid-phase or gas-phase polymerization. The invention also provides the use of these supported metallocene catalysts in the production of ethylene homopolymers and copolymers with α-olefins.

Problems solved by technology

However, the disadvantage, in most cases, is the fact to be required the use of a large excess of aluminoxanes, in relation to the transition metal content of the catalyst, to yield acceptable productivities.
Due to the high cost of the aluminoxane and also to the necessity of extra work of purification of the polymers obtained, the production of poliolefins in industrial scale, based on these catalytic systems, generally becomes anti-economic.
Besides, the use of toluene, which is commonly used in the formulation of aluminoxanes solution, particularly the MAO, is increasingly becoming highly undesirable due to toxicological reasons in relation to the field of application of the polyolefins and storage stability reasons of the highly concentrated formulations (tendency to gel formation).
Other known problem of the use of metallocene catalysts are the “poor” morphology of the polymeric material obtained; this results in apparent low bulk density and heterogeneous polymer.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

a) Preparation of the Catalytic Support

[0136]In a 5 L reactor equipped with mechanical stirring and previously purged with nitrogen, was added 44.5 g (0.462 mol) of MgCl2 and 2.5 L of dried THF. This mixture was heated until 60° C. and stirred at 100 rpm for 5 h for complete solubilization of the MgCl2. The obtained solution was, after this period, cooled down to 35° C. In this solution, 300 g of silica XPO-2402 were added, previously dehydrated at 600° C. and treated with 22.3 ml (0.163 mol) of diluted TEAL in n-hexane for 50 minutes at temperature of 25° C. Once finished the addition of silica, the mixture was heated up to 60° C. and stirred at 100 rpm for 1 h. After this period, we stop the stirring and start the THF evaporation through vacuum until the THF content to be incorporated in the support to reach a range between 8 and 12% wt.

[0137]The catalytic support obtained was characterized, presenting the following characteristics:[0138]THF content: 11.2% wt[0139]Mg content: 2.3%...

example 2

b) Preparation of Supported Metallocene Catalyst

[0152]In a 200-mL reactor equipped with mechanical stirring and previously purged with nitrogen, 6.1 g of the catalytic support prepared in the step a) of the EXAMPLE 1 and 50 mL of n-hexane were added. In this suspension, stirred at 200 rpm and under temperature of 25° C., it was slowly added 0.4 mL (4.1 mmol) of diluted TMAL in n-hexane (Al / THF=0.45). The suspension was stirred for 2 h and, after this period, the solvent was removed by siphonation. The catalytic support obtained, after this treatment, was characterized presenting the following characteristics:[0153]THF content: 3.3% wt

[0154]In a schlenk, equipped with magnetic stirrer and dipped in a heat oil bath, 0.61 g (2.8 mmol) of the CpTiCl3 and 70 mL of n-hexane were transferred. In this suspension heated up to 50° C. and under stirring, 1.4 mL (5.5 mmol) of diluted TIBAL in n-hexane (Al / Ti=2) was slowly added. The dark solution obtained was stirred for 2.5 h at 50° C.

[0155]In...

example 3

b) Preparation of Supported Metallocene Catalyst

[0163]In a 200-mL reactor equipped with mechanical stirring and previously purged with nitrogen, 6.1 g of the catalytic support prepared in the step a) of the EXAMPLE 1 and 50 mL of n-hexane were added. In this suspension, stirred at 200 rpm and the temperature of 25° C., it was slowly added 1.44 mL (4.2 mmol) of diluted TNHAL in n-hexane (Al / THF=0.45). The suspension was stirred for 2 h and after this period, the solvent was removed by siphonation. The catalytic support obtained, after this treatment, was characterized presenting the following characteristics:[0164]THF content: 3.4% wt

[0165]In a schlenk, equipped with magnetic stirrer and dipped in a heat oil bath, 0.61 g (2.8 mmol) of the CpTiCl3 and 70 mL of n-hexane were transferred. In this suspension heated up to 50° C. and under stirring, 1.4 mL (5.5 mmol) of diluted TIBAL in n-hexane (Al / Ti=2) was slowly added. The dark solution obtained was stirred for 2.5 h at 50° C.

[0166]In ...

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Abstract

The present invention relates a process for the preparation of catalytic support and the supported metallocene catalysts used in the production of ethylene homopolymers and ethylene copolymers with α-olefins, of high and ultra high molecular weight with broad molecular weight distribution, in gas or liquid phase polymerization processes, the latter being in slurry, bulk or suspension, and the products obtained from these processes.

Description

CROSS REFERENCE TO RELATED APPLICATIONS[0001]This application is a divisional application, which is based on and claims priority to co-pending U.S. Utility patent application Ser. No. 12 / 163,711, filed on Jun. 27, 2008, which claims priority to co-pending Brazilian Patent Application No. PI 0703586-1 filed Oct. 19, 2007, which is entirely incorporated herein by reference.FIELD OF THE INVENTION[0002]The present invention relates to supported metallocene catalysts and to a process for the preparation of supported metallocene catalysts based on transition metals of the groups 4 or 5 of the Periodic Table and containing groups of monocyclopentadienyl, monoindenyl or monofluorenyl type, substituted or not, in the absence of activators as aluminoxanes or organoboron base compounds, with application in ethylene homopolymerization and ethylene copolymerization with α-olefins. The invention also relates to the catalytic support and to the ethylene homopolymers and ethylene copolymers with α-...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C08F4/52C08F110/02C08F210/02
CPCB01J21/14B01J31/0212C08F210/16C08F110/02C08F10/02C08F4/6592C08F4/65912B01J2531/22B01J37/0209B01J37/0207B01J37/0203B01J31/122B01J31/143B01J31/2208B01J31/2295B01J31/26C08F4/65916C08F4/025C08F2500/18C08F210/08C08F2500/17
Inventor MIRANDA, MARCIA SILVA LACERDAVIEIRA DA CUNHA, FERNANDA OLIVEIRA
Owner BRASKEM SA