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
2000-06-08
2002-04-09
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...
C502S110000, C502S111000, C502S152000, C502S156000, C526S160000, C526S165000, C526S128000, C526S151000
Reexamination Certificate
active
06368995
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a solid catalyst for olefin polymerization and to a process for producing olefinic polymers by using the solid catalyst. More particularly, it relates to a solid catalyst for olefin polymerization which requires no deashing treatment because of high polymerization activity and efficiently produces polymers having excellent powder properties such as high bulk density, narrow particle size distribution, low contents of large particles and fine powder and so on, and to a process for producing olefinic polymers by polymerization or copolymerization of olefins by using such a solid catalyst.
BACKGROUND ART
In recent year, Kaminsky type catalysts, which attract attention as general purpose catalysts for olefin polymerization, comprise a metallocene compound and an organoaluminum oxy compound and have features such that they give polyolefins having high activities and narrow molecular weight distributions, and when applied to copolymerization, give polymers having uniform composition. However, the catalysts are homogeneous catalysts so that produced polymer particles are fine, resulting in that not only they are difficult to handle but also they cause fouling. Therefore, it has been practically impossible to apply them to slurry polymerization methods or gas phase polymerization methods, which are major processes of polyolefin production.
To solve these problems, researches have been made to have at least one component of the metallocene compound and organoaluminum oxy compound carried on a solid carrier to improve the properties of powder. For example, Japanese Patent Application Laid-open Nos. Sho 61(1986)-296008 and Sho 63(1988)-280703 disclose solid catalysts for olefin polymerization comprising the above catalyst components carried on porous inorganic oxide carriers such as silica, alumina, and silica-alumina.
Also, Japanese Patent Application Laid-open Nos. Sho 64 (1989)-6003, Sho 64(1989)-6004, Sho 64(1989)-6005, Sho 64(1989)-11104, and Sho 64(1989)-11105 disclose solid catalyst components containing as one component an organic magnesium compound particularly in a liquid state and processes for obtaining olefin polymers having excellent powder properties by using such solid catalyst components. Further, in relation to the improvement of powder properties, Japanese Patent Application Laid-open No. Hei 6(1994)-256411 discloses a solid catalyst containing various metal salts such as anhydrous magnesium carbonate as a carrier, Japanese Patent Application Laid-open No. Hei 7(1995)-268029 discloses a catalyst component for polymerization containing Lewis acid solid such as magnesium dichloride as a carrier, and Japanese Patent Application Laid-open No. Hei 8(1996) -176225 discloses a catalyst for olefin polymerization comprising a solid component obtained by reaction of a specific magnesium compound and an aluminum compound.
Although the catalysts described in these publications are generally improved in adaptivity to slurry polymerization methods and gas phase polymerization methods, they are often accompanied by a decrease in the activity of catalyst and insufficient in improving the powder properties of polymer to a satisfactory level without decreasing the activity of catalyst. In particular, the above references contain only qualitative description on particle size distribution, which together with bulk density is an important feature of powder properties, but fail to disclose data to support its effect specifically. Further, these references disclose nothing on the process for easily controlling particle diameter, which is an important element of the production technology by a slurry polymerization method or gas phase polymerization method.
Accordingly, an object of the present invention is to provide a solid catalyst for olefin polymerization which (1) requires no deashing treatment because of high polymerization activity, (2) produces polymers having excellent powder properties such as high bulk density, narrow particle size distribution and low contents in large particles and fine powder, (3) allows easy control of the particle diameter of the obtained polymer, and (4) shows less fouling on the autoclave upon polymerization. Another object of the present invention is to provide a process for producing olefinic polymers by using such a solid catalyst for olefin polymerization.
DISCLOSURE OF INVENTION
The present inventors have made intensive research in order to solve the above problems and have found that use of a solid reaction product obtained by reacting components such as a specific organic silicon compound and an organic magnesium compound under specific conditions can give rise to a solid catalyst for olefin polymerization that achieves the above objects, thus accomplishing the present invention.
That is, in a first aspect, the present invention provides a solid catalyst [F] for olefin polymerization, obtained by reacting at least one organic silicon compound selected from a hydropolysiloxane compound having a structural unit represented by general formula, R
1
a
H
b
SiO
(4−a−b)/2
(wherein R
1
is a monovalent organic group selected from an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an aryloxy group, a is an integer of 0 to 2, b is an integer of 1 to 3, provided that a+b≦3), a compound composed of silicon atom to which at least one organic group and at least one hydroxyl group are bonded, represented by general formula, R
2
c
Si(OH)
4−c
(wherein R
2
is a monovalent hydrocarbon group having 1 to 18 carbon atoms and c is an integer of 1 to 3) and condensates thereof with an organic magnesium compound represented by general formula (MgR
3
2
)
p
.(R
3
MgX)
q
(wherein R
3
is a hydrocarbon group, X is a halogen atom, p and q are numbers of 0 or 1, provided that p+q=1) to form a reaction product [A], reacting the reaction product [A] with an alcohol having 1 to 4 carbon atoms to obtain an intermediate product [B], reacting the intermediate product [B] with water to obtain a solid reaction product [C], and having an organoaluminum oxy compound [D] and a metallocene compound [E] carried on the solid reaction product [C].
In a second aspect, the present invention provides a process for producing olefinic polymers, characterized by polymerization or copolymerization of olefins in the presence of the above solid catalyst [F] for olefin polymerization and an organoaluminum compound [G].
Hereinafter, the solid catalyst for olefin polymerization (hereafter, sometimes referred to simply as “solid catalyst” for brevity) according to the present invention and a process for producing olefinic polymer using the said solid catalyst will be described concretely.
In the present invention, a group of the organic silicon compounds used in the preparation of the reaction product [A] are hydropolysiloxane compounds having a structural unit represented by the general formula (1)
R
1
a
H
b
SiO
(4−a−b)/2
(1)
wherein R
1
is a monovalent organic group selected from an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an aryloxy group, a is an integer of 0 to 2, b is an integer of 1 to 3, provided that a+b≦3. The degree of polymerization thereof is not particularly limited and either liquid or solid state compound may be used. The terminal of the hydropolysiloxane may be substituted with any inert group, for example, a trialkylsilyl group.
Examples of the hydropolysiloxane compound represented by the general formula (1) include tetramethyldisiloxane, biphenyl disiloxane, trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, ethoxyhydropolysiloxane, cyclooctylhydropolysiloxane, chlorophenylhydropolysiloxane and so on.
Another group of the organic silicon compound used in the preparation of the reaction product [A] are compounds composed of a silicon atom to
Hane Yukiko
Iijima Minoru
Kamiyama Sakae
Takemori Toshifumi
Yamamoto Shigeharu
Lu Caixia
Maruzen Petrochemical Co. Ltd.
Oliff & Berridg,e PLC
Wu David W.
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