Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-12-22
2003-03-04
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S114000, C526S115000, C526S117000, C526S118000, C526S160000, C526S166000, C502S103000, C502S113000, C502S117000, C502S129000, C502S130000, C502S131000
Reexamination Certificate
active
06528596
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to particles suited for use as a carrier and a catalyst component for olefin polymerization, a catalyst for olefin polymerization using the same, and a process for producing an olefin polymer using said catalyst for olefin polymerization.
2. Description of Related Arts
Olefin polymers such as polypropylene and polyethylene have widely been used in the fields of various moldings because of excellent mechanical properties and chemical resistance as well as good balance between the properties and economical efficiency. These olefin polymers have hitherto been produced by polymerizing an olefin using mainly a so-called Ziegler-Natta catalyst (multi-site catalyst) obtained by combining a solid catalyst component obtained from a compound of the Group IV metal elements (e.g. titanium trichloride, titanium tetrachloride, etc.) with a compound of the Group XIII metal elements represented by an organoaluminum compound.
There has recently been proposed a process for producing an olefin polymer, which comprises polymerizing an olefin using a so-called single-site catalyst obtained by combining a transition metal compound (e.g. metallocene complex, non-metallocene compound, etc.) different from the solid catalyst component, which has been used for a long time, with aluminoxane. For example, JP-A-58-19309 reports a method of using bis(cyclopentadienyl)zirconium dichloride and methyl aluminoxane. It has also been reported to combine a specific boron compound with such a transition metal compound. For example, JP-A-1-502036 reports a method of using bis(cyclopentadienyl)zirconium dimethyl and tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate. It has been known that an olefin polymer obtained by using the single-site catalyst has a narrow molecular weight distribution as compared with that obtained by using a conventional solid catalyst (multi-site catalyst) and a homogeneous olefin polymer is obtained as compared with the case of using a conventional solid catalyst because a comonomer is copolymerized more uniformly in case of a copolymer.
Since the catalyst obtained from the metallocene complex and non-metallocene compound is usually soluble in a reaction system, when using it in the polymerization which forms polymer particles (e.g. slurry polymerization, gas phase polymerization, etc.), the resulting polymer is unstable in shape to cause formation of coarse polymer particles , agglomerate polymer and finely powdered polymer, reduction of the bulk density of a polymer, and adhesion of a polymer to a polymerization reactor wall. For these reasons, there were problems that poor heat transfer , poor heat removal in the reactor and the like were caused, and difficulty in a stable operation and reduction of productivity resulted.
JP-A-11-193306 has been known as a method of solving such a problem, but a further improvement has been required in view of the molecular weight of the resulting polymer.
Furthermore, these metallocene catalysts have such a drawback that properties of the copolymer obtained by a change of a monomer ratio in the polymerization (e.g. density, melting point, etc.) are liable to change because of a large number of short chain branches (SCB) in the production of the copolymer.
SUMMARY OF THE INVENTION
An object of the present invention is to provide particles which can provide high-molecular polymer excellent in shape and particle properties with a high activity when a transition metal compound is applied to the olefin polymerization accompanied with formation of olefin polymer particles (e.g. slurry polymerization, gas phase polymerization, etc.) by using in combination with the transition metal compound, and which can particularly provide a copolymer containing a relatively small number of short chain branches in the production of an ethylene copolymer; a carrier composed of said particles; a catalyst component for olefin polymerization using said particles; a catalyst for olefin polymerization using said particles; and a process for producing olefin polymer using said catalyst for olefin polymerization.
That is, the present invention provides modified articles obtained by contacting particles (a) with a metal compound (b) selected from the group consisting of compounds of the Group VI metal elements, compounds of the Group VII metal elements, compounds of the Group XIV metal elements and compounds of the lanthanide series of the Periodic Table, and contacting said particles with a compound (c) having a functional group containing an active hydrogen or a non-proton donative Lewis basic functional group and an electron-withdrawing group.
The present invention also provides a carrier composed of said modified particles; a catalyst component for olefin polymerization comprising said modified particles; a catalyst for olefin polymerization obtained by contacting said modified particles (A) with a transition metal compound (B) and optionally an organometallic compound (C); and a process for producing olefin polymer with said catalyst for olefin polymerization.
The present invention will be described below in detail.
DETAILED DESCRIPTION OF THE INVENTION
(a) Particles
Modified articles of the present invention are obtained by contacting particles (a) with a metal compound (b) selected from the group consisting of compounds of the Group VI metal elements, compounds of the Group VII metal elements, compounds of the Group XIV metal elements and compounds of the lanthanide series, and contacting said particles with a compound (c) having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group and an electron-withdrawing group.
The particles (A) are preferably those that are generally used as a carrier. Porous materials having a uniform particle diameter are preferred. Inorganic materials or organic polymers are preferably used.
Examples of the inorganic material used in the particles (A) of the present invention include inorganic oxides, magnesium compounds and the like. Clay and clay minerals can be used as far as they do not cause any problems. They can be used alone or in combination.
Examples of the inorganic oxide are SiO
2
, Al
2
O
3
, MgO, ZrO
2
, TiO
2
, B
2
O
3
, CaO, ZnO, BaO, ThO
2
, and mixtures thereof such as SiO
2
—MgO, SiO
2
—Al
2
O
3
, SiO
2
—TiO
2
, SiO
2
—V
2
O
5
, SiO
2
—Cr
2
O
3
, and SiO
2
—TiO
2
—MgO. Among these inorganic oxides, SiO
2
and/or Al
2
O
3
are preferred. Furthermore, the inorganic oxide may contain a small amount of carbonate, sulfate, nitrate and oxide components, such as Na
2
CO
3
, K
2
CO
3
, CaCO
3
, MgCO
3
, Na
2
SO
4
, Al
2
(SO
4
)
3
, BaSO
4
, KNO
3
, Mg(NO
3
)
2
, Al(NO
3
)
3
, Na
2
O, K
2
O, and Li
2
O.
Examples of the magnesium compound are magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide, or magnesium fluoride; alkoxy magnesium halide such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, or octoxy magnesium chloride; aryloxy magnesium halide such as phenoxy magnesium chloride or methyl phenoxy magnesium chloride; alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, or 2-ethyl hexoxy magnesium; aryloxy magnesium such as phenoxy magnesium or dimethyl phenoxy magnesium; or carboxylates of magnesium such as magnesium laurate or magnesium stearate. Among these magnesium compounds, magnesium halide or alkoxy magnesium are preferred, and magnesium chloride or butoxy magnesium are more preferred.
Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, allophane, hisingerite, pyrophyllite, talc, mica group, montmorillonite group, vermiculite, chlorite group, palygorskite, kaolinite, nacrite, dickite, smectite, saponite, andhalloysite. Among these clays and clay minerals, montmorillonite and saponite are preferred, and montmorillonite and hectorite are more preferred.
It is not necessary for these inorganic materials to remove water when used, but
Miyatake Tatsuya
Takaoki Kazuo
Rabago R.
Sumitomo Chemical Company Limited
Wu David W.
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