Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1999-07-06
2002-11-19
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S127000, C502S152000, C526S129000, C526S160000, C526S943000
Reexamination Certificate
active
06482765
ABSTRACT:
TECHNICAL FIELD
The present invention relates to particles which are useful as a carrier and a catalyst component for olefin polymerization a catalyst for olefin polymerization using the same, and method for producing an olefin polymer using said catalyst for olefin polymerization.
BACKGROUND ARTS
A lot of reports on a method for producing an olefin polymer using a transition metal compound have already been made. As the example of using a metallocene transition metal compound, for example, Japanese Patent Publication (Kokai) No.58-19309 discloses a method of producing an olefin polymer using bis(cyclopentadienyl)zirconium dichloride and methylaluminoxane. Japanese Patent Publication(kohyo) No.1-502036 discloses a method of producing an olefin polymer using bis(pentamethylcyclopentadienyl)zirconium dimethyl and n-butylammonium tetrakisphenylborate. Japanese Patent Publication(Kokai) No.5-178923 discloses a method of producing an olefin polymer using dimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium dimethyl, dimethylanilinumtetrakis(pentafluorophenyl)borate and triethylaluminum. Furthermore, a lot of examples using a non-metallocene transition metal compound are disclosed in J. Amer. Chem. Soc., 115, 8493(1993), Plastics Engineering, March. 77(1996), WO96/23010 and the like.
Since catalysts using these transition metal compounds are soluble in a reaction system, when used in the polymerization accompanying formation of polymer particles (e.g. slurry polymerization, gas phase polymerization, etc.), the shape of the formed polymer is irregular to cause formation of large polymer particles, an agglomerate polymer and fine polymer particles, decrease in bulk density of the polymer, adhesion of the polymer to the polymerization reactor wall. Consequently, poor heat transfer and poor cooling in the reactor, and the like are caused, which results in difficulty in stable operation and lowering of the productivity.
In order to apply the transition metal compound to the polymerization accompanying formation of polymer particles (e.g. slurry polymerization, gas phase polymerization), it is necessary that not only sufficient polymerization activity is exerted but also the polymer excellent in shape and particle properties is obtained. To solve these problems, a method of supporting a transition metal compound on a carrier has been proposed.
As one method, for example, a method of fixing or supporting all or a part of a catalyst component such as metallocene complex, methylaluminoxane or the like on an inorganic metal oxide carrier such as silica or the like has been reported.
For example, Japanese Patent Publication(Unexamined) Nos. 60-35006, 60-35007 and 60-35008 respectively disclose a method of depositing/adhering a soluble metallocene on a typical support (e.g. silica, alumina, polyethylene, etc.) to convert into a supported heterogeneous catalyst and using a combination of the catalyst and aluminoxane in the slurry polymerization or gas phase polymerization.
Japanese Patent Publication (Unexamined) No. 61-108610 discloses a method of producing a polyolefin polymer using a solid catalyst component obtained by adding a calcined silica to bis(cyclopentadienyl)zirconium dichloride and a reaction product of trimethylaluminum and water.
Japanese Patent Publication(Unexamined) No. 61-276805 discloses a method of producing an olefin polymer using an inorganic oxide-containing organoaluminum component, obtained by reacting a mixture of methylaluminoxane and trimethylaluminum with silica, and bis(cyclopentadienyl)zirconium dichloride.
Japanese Patent Publication(Unexamined) No. 61-296008 discloses a method of producing an olefin polymer using a solid catalyst containing aluminum and zirconium, obtained by treating silica in turn with methylaluminoxane and bis(cyclopentadienyl)zirconium chloride.
As the improved method, for example, there have been reported a method of using a solid catalyst component obtained by fixing/supporting all or a part of a catalyst component such as metallocene complex, methylaluminoxane, etc. on an in organic metal oxide carrier such as silica, etc., and aluminoxane or organoaluminum, and a method of using a pre-polymerized catalyst obtained by carrying out prepolymerization. Japanese Patent Publication (Kokai) No.63-51407 discloses a method of producing an olefin polymer using a solid catalyst component obtained by treating silica in turn with methylaluminoxane and bis(cyclopentadienyl)zirconium dichloride, and methylaluminoxane.
Japanese Patent Publication (Kokai) No.63-89505 discloses a method of producing an olefin polymer using a solid catalyst component obtained by treating silica in turn with methylaluminoxane and bis(cyclopentadienyl)zirconium dichloride, and triisobutylaluminum or a method of producing an olefin polymer using a solid catalyst component pre-polymerized with the solid catalyst component and triisobutylaluminum.
In the above prior arts, use of aluminoxane is essential. This aluminoxane must be separately synthesized and a lot of steps are required and are complicated. The aluminoxane is unstable and costly. Regarding the solid catalyst component obtained by combining the aluminoxane with an inorganic metal oxide carrier such as silica, the amount of aluminum used is large and activity per 1 mol of an Al atom was low. To solve these problems, there has been reported a method of producing an olefin polymer using a solid catalyst component obtained by reacting an organoaluminum with water in the presence of an inorganic metal oxide carrier such as silica to form aluminoxane.
For example, Japanese Patent Publication (Kokai) No.61-31404 discloses a method of producing an olefin polymer using a catalyst obtained by adding water, trimethylaluminum and bis(cyclopentadienyl)zirconium dichloride in turn to silica.
Japanese Patent Publication (Kokai) No. 1-1207303 discloses a method of producing an olefin polymer using silica gel powders containing a supported metallocene-methylaluminoxane catalyst complex, obtained by adding silica gel not dehydrated, containing water to trimethylaluminum and treating the resultant with bis(n-butylcyclopentadienyl)zirconium dichloride.
Japanese Patent Publication (Kokai) No. 3-234710 discloses a method of producing an olefin polymer using a prepolymerized solid catalyst, obtained by adding water, trimethylaluminum and bis(methylcyclopentadienyl)zirconium dichloride in turn to silica and further adding ethylene to the mixture, and triisobutylaluminum.
According to these prior arts, synthesis of aluminoxane and fixing of the component to an inorganic metal oxide carrier such as silica or the like can be easily and simply performed. However, these methods require control of the amount of water used and it is difficult. Furthermore, the aluminoxane synthesized by this method and the solid catalyst component obtained by fixing the aluminoxane synthesized by this method have low activity, unlike separately synthesized aluminoxane and a solid catalyst component obtained by fixing the separately synthesized aluminoxane, and the particle properties of the resulting polymer are not preferred.
There has been reported a method of producing an olefin polymer using a solid catalyst component obtained from a metallocene transition metal compound, a boron compound and a carrier, or a solid catalyst component obtained from a metallocene transition metal compound, a boron compound, an organoaluminum compound and a carrier.
For example, Japanese Patent Publication (Kohyo) No.5-502906 discloses a method of producing an olefin polymer using a supported catalyst obtained by adding a reaction product of bis(cyclopentadienyl)zirconium dimethyl and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate to basic alumina.
Japanese Patent Publication (Kokai) No. 6-336502 discloses a method of producing an olefin polymer using a solid catalyst component, obtained from a carrier prepared by treating silica with triethylaluminum, ethylenebisindenyl zirconium dichloride and N,N-dimethylanilinumtetrakis(pentafluorophenyl)borate, and further, trii
Katayama Hiroaki
Ohgane Takuya
Sato Hideki
Birch & Stewart Kolasch & Birch, LLP
Harlan R.
Sumitomo Chemical Company Limited
Wu David W.
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