Aluminum compound-containing solid catalyst component,...

Details Aluminum compound-containing solid catalyst component,... Aluminum compound-containing solid catalyst component,...

2000-02-29

2001-12-25

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...

C526S124300, C526S129000, C526S160000, C526S943000, C526S124500, C502S120000, C502S128000, C502S152000, C502S232000, C502S172000

Reexamination Certificate

active

06333388

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an olefin polymerization solid catalyst component supported with a carrier, and a method for producing an olefin polymer using the same. More particularly, the present invention relates to an olefin polymerization catalyst which can be employed in slurry polymerization and gas-phase polymerization to produce an olefin polymer having excellent particle properties with high polymerization activity in that case, and a method for producing an olefin polymer using the same.
2. Prior Arts
A number of methods for producing an olefin polymer using a transition metal compound have already been reported. In the case of a metallocene transition metal compound, JP-58019309-A discloses a method for producing an olefin polymer using a metallocene complex and an aluminoxane. JP-01502036-A discloses a method for producing an olefin polymer using a metallocene complex and a boron compound. WO94/10180 and JP-06329714-A disclose an olefin polymerization catalyst comprising a metallocene complex and a modified aluminumoxy compound and exhibiting a high polymerization activity. However, olefin polymers obtained from the soluble metallocene catalysts proposed have an irregular form and low bulk density. When the metallocene catalyst is employed in slurry polymerization or gas-phase polymerization, problems arise such as poor heat transfer and a decrease in productivity due to formation of an agglomerate polymer and adhesion of a polymer formed on the wall of the polymerization vessel.
In order to solve these problems, methods for supporting a part or all of the catalyst components on an inorganic oxide carrier are proposed in, for example, JP-61108610-A, JP-61276805-A and JP-61296008-A. Further, supporting of catalyst components on an organic carrier such as polystyrene carrier having a polar functional group or the like is proposed in U.S. Pat. No. 5,362,824 and JP-07053623-A. By these methods, olefin polymers excellent in particle properties can be obtained. However, the catalytic activity is still insufficient in these methods and, therefore, a supported catalyst system having high activity has been required.
The present inventors have intensively studied so as to solve the above problems. As a result, the present invention has been accomplished.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an olefin polymerization catalyst which produces an olefin polymer excellent in particle property and exhibits high polymerization activity in slurry polymerization or gas-phase phase polymerization process, and a method for producing an olefin polymer with the catalyst.
The present invention provides an aluminum compound-containing solid catalyst component obtained by contacting a carrier with an organoaluminumoxy compound, followed by contacting with a compound having an electron attractive group.
Further, the present invention also provides a transition metal-containing solid catalyst component obtained by contacting the aluminum compound-containing solid catalyst component with a transition metal compound; a catalyst for olefin polymerization comprising the aluminum compound-containing solid catalyst component and an organoaluminum compound; and a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin using the catalyst for olefin polymerization.
The present invention will be explained in detail.
DETAILED DESCRIPTION OF THE INVENTION
(A) Carrier
The carrier (A) used in-the present invention includes an inorganic carrier and an organic carrier. A plurality of carriers can be used as a mixture, and the carrier may contain a small amount of water as absorbed water or in hydrate form. The carrier is preferably a porous one. The micro pore volume of the porous carrier is preferably not less than 0.1 ml/g, more preferably not less than 0.3 ml/g. The average particle diameter of the carrier is preferably from 5 to 1,000 &mgr;m, more preferably from 10 to 500 &mgr;m.
Examples of the inorganic carrier include inorganic oxides, magnesium compounds, clay minerals and the like. Examples of the inorganic oxide include SiO
2
, Al
2
O
3
, MgO, ZrO
2
, TiO
2
, B
2
O
3
, CaO, ZnO, BaO, ThO
2
and double oxide thereof, e.g. SiO
2
—Al
2
O
3
, SiO
2
—MgO, SiO
2
—TiO
2
, SiO
2
—TiO
2
—MgO. Examples of the magnesium compound include MgCl
2
, MgCl (OEt) and the like. Examples of the clay mineral include kaolin, bentonite, kibushi clay, geyloam clay, allophane, hisingerite, pyrophylite, talc, micas, montmorillonites, vermiculite, chlorites, palygorskite, kaolinite, nacrite, dickite, halloysite and the like.
Examples of the organic carrier include an acrylic polymer, a styrene polymer, an ethylene polymer, a propylene polymer and the like. Among these, an acrylic polymer and a styrene polymer are preferred.
Examples of the acrylic polymer include polymers of acrylic monomers such as acrylonitrile, methyl acrylate, methyl methacrylate, methacrylonitrile and the like, and copolymers of the monomers and crosslinking polymerizable compounds having at least two unsaturated bonds.
Examples of the styrene polymer include polymers of styrene monomers such as styrene, vinyltoluene, ethylvinylbenzene and the like, and copolymers of the monomers and crosslinking polymerizable compounds having at least two unsaturated bonds.
Specific examples of the crosslinking polymerizable compound having at least two unsaturated bonds include divinylbenzene, trivinylbenzene, divinyltoluene, divinylketone, diallyl phthalate, diallyl maleate, N,N′-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and the like.
It is preferred that the organic carrier has a polar functional group. As the polar functional group, primary amino group, secondary amino group, imino group, amide group, imide group, hydrazide group, amidino group, hydroxy group, hydroperoxy-group, carboxyl group, formyl group, methyloxycarbonyl group, carbamoyl group, sulfo group, sulfino group, sulfeno group, thiol group, thiocarboxyl group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group and carbazolyl group are preferred. More preferred are primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfo group and thiol group. Particularly preferred are primary amino group and secondary amino group.
Regarding a method for preparing the organic carrier having a polar functional group, when the organic carrier originally has a polar functional group, the organic carrier can be used as it is. One or more kinds of polar functional groups can also be introduced by subjecting the organic carrier as a matrix to a suitable chemical treatment. The chemical treatment may be any method capable of introducing the polar functional group into the organic carrier. For example, it may be a reaction between an acrylic polymer and a polyalkylenepolyamine such as ethylenediamine, propanediamine, diethylenetriamine, tetraethylenepentamine, dipropylenetriamine or the like.
As the specific method of such a reaction, for example, there is a method of treating an acrylic polymer (e.g. polyacrylonitrile) in a slurry state in a mixed solution of ethylenediamine and water at 100° C. or more, preferably from 120° to 150° C.
The amount of polar functional group per unit gram in the organic carrier having a polar functional group is preferably from 0.01 to 50 mmol/g, more preferably from 0.1 to 20 mmol/g.
(B) Organoaluminumoxy Compound
As the organoaluminumoxy compound (B) used in the present invention, a known organoaluminumoxy compound can be used. Preferred examples include a cyclic aluminoxane having a structure represented by the general formula {—Al(R
1
)—O—}
a
and/or a linear aluminoxane having a structure represented by the general formula R
1
(—Al(R
1
)—O—)
b
AlR
1
2
(R
1
represents a hydrocarbon group having 1 to 8 carbon atoms, and all R
1
may be the same or different; and each of “a” and “b”

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