Solid catalyst component and catalyst for olefin polymerization

Details Solid catalyst component and catalyst for olefin polymerization Solid catalyst component and catalyst for olefin polymerization

1999-07-06

2001-05-08

Bell, Mark L. (Department: 1755)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Plural component system comprising a - group i to iv metal...

C502S103000, C502S108000, C502S114000, C502S116000, C502S118000, C502S127000, C526S124200, C526S126000, C526S154000

Reexamination Certificate

active

06228791

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a solid catalyst component and catalyst for polymerization of olefins, which shows high activity and low rate for forming a polymer having a low molecular weight or a low stereoregularity which is soluble in a polymerization solvent and can provide a polymer having a high stereoregularity in a high yield, and further, can provide a copolymer having a excellent property in a high yield in copolymerization of olefins.
TECHNICAL BACKGROUND
Many proposals have been made and known for a solid catalyst component containing magnesium, titanium, an electron donor compound and halogen as essential components and a process for the polymerization or the co-polymerization of olefins in the presence of a catalyst for polymerization of olefins comprising said solid catalyst component, an organic aluminum compound and an organic silicon compound. For example, JP-A-57-63310 and JP-A-57-63311 (The term “JP-A” as used herein means an “unexamined published Japanese patent application”) propose a process for polymerizing an olefin having 3 or more carbon atoms using a catalyst system comprising a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor compound, an organic aluminum compound and an organic silicon compound having Si—O—C bond. However, these processes are not always satisfactory for obtaining highly stereoregular polymers in a high yield, and further improvement has been demanded.
JP-A-63-92614 discloses a solid catalyst component for polymerization of olefins prepared by bringing a dialkoxymagnesium, a diester of an aromatic dicarboxylic acid, an aromatic hydrocarbon, a titanium halide and calcium chloride into contact. On the other hand, JA-A-1-315406 discloses a catalyst system for polymerizing olefins comprising a solid catalyst component prepared by contacting titanium tetrachloride with a suspension formed by diethoxymagnesium with an alkylbenzene, adding phthalic dichloride thereto to react to obtain a solid product, and further contacting the resulting solid product with titanium tetrachloride in the presence of an alkylbenzene, an organic aluminum compound and an organic silicon compound, and a process for polymerizing olefins in the presence of said catalyst system. The foregoing known techniques focus on the development of a catalyst component having a high activity enough to allow the omission of a so-called deashing step, i.e., a step of removing catalyst residues such as chlorine and titanium remaining in the polymer produced as well as on the enhancement of the yield of stereoregular polymer or an improvement in durability of the catalyst activity during polymerization, and achieved excellent results to these purposes.
In the slurry polymerization process which requires a solvent at the polymerization, a polymer having a low molecular weight or a low stereoregularity, which is soluble in a polymerization solvent, is formed, especially in the polymerization of propylene, a polymer so-called “an atactic polypropylene” (hereinafter occasionally referred to as “APP”) is formed. In case of increasing of the forming rate of the APP, it concerns about an undesirable effect to the operation of the process and the production cost of a polymer, because a pipeline may be blocked up during polymerization and a step for removal of APP from a high stereoregular polymer to be a product is required after polymerization. Further, in a copolymerization of olefins, for instance, in a random copolymerization of propylene and ethylene, a content of ethylene in a copolymer has to be increased and randomness has to be improved in order to increase the properties of the resulting copolymer. In case that a content of ethylene is increased, the aforementioned problems occur, because the rate for forming a soluble matter on a polymerization solvent tends to be high very much. However, the use of the catalyst of the foregoing known techniques is not enough to solve the problems.
The objective of the present invention is to solve the foregoing problems remaining in the prior art techniques and to provide a solid catalyst component and a catalyst for polymerization of olefins, which can control the rate of forming a polymer having a low molecular weight and a low stereoregular polymer which is soluble in a polymerization solvent and can obtain a high stereoregular polymer in a high yield, and also can obtain a copolymer having excellent properties in a high yield in the copolymerization of olefins.
DISCLOSURE OF THE INVENTION
As a result of extensive investigations to solve the foregoing problems remaining in the prior art techniques, the present inventors have found that when olefins are polymerized by using a catalyst preparing from a magnesium compound, a tetravalent halogen-containing titanium compound, a diester of an aromatic dicarboxylic acid, an aromatic hydrocarbon and an organic aluminum compound containing a hydroxyl group or aluminum hydroxide, a polymer having a low rate for forming a polymer a low molecular weight polymer or a low stereoregular polymer which is soluble in a polymerization solvent, especially an olefin based polymer having low APP formation rate can be obtained with maintaining a catalyst activity and a stereoregularity of the resulting polymer in a high level, and a copolymer having a excellent property can be obtained in a high yield in copolymerization of olefins with said solid catalyst component.
A solid catalyst component for polymerization of olefins (A) of the present invention to solve the foregoing objective comprises the following components (a) to (e);
(a) a magnesium compound,
(b) a tetravalent halogen-containing titanium compound,
(c) a diester of an aromatic dicarboxylic acid,
(d) an aromatic hydrocarbon and
(e) at least one aluminum compound selected from an organic aluminum compound containing a hydroxyl group represented by the following general formula (I) and aluminum hydroxide;
(R
1
CO
2
)
m
Al(OH)
3-m
  (I)
wherein m represents 1 or 2, R
1
represents hydrogen atom or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 21 carbon atom, and CO
2
represents —C(═O)—O—.
Further, the catalyst for polymerization of olefins of the present invention comprises:
(A) the foregoing solid catalyst component,
(B) an organic aluminum compound represented by the general formula:
R
2
p
AlQ
3-p
 wherein R
2
represents a C
1-4
alkyl group; Q represents a hydrogen or halogen atom; and p represents a real number of from more than 0 to not more than 3; and
(C) an organic silicon compound represented by the general formula:
R
3
q
Si(OR
4
)
4-q
 wherein R
3
represents a C
1-12
-alkyl, cycloalkyl, phenyl, vinyl, allyl or aralkyl group which may be the same or different; R
4
represents a C
1-4
-alkyl, cycloalkyl, phenyl, vinyl, allyl or aralkyl group which may be the same or different; and q represents 0 or an integer of from 1 to 3.
BEST EMBODIMENT FOR IMPLEMENTING THE INVENTION
Preferred examples of the magnesium compound (a) (hereinafter occasionally referred to as “component (a)”) used for preparing a solid catalyst component (A) for polymerization of olefins of the present invention (hereinafter occasionally referred to as “solid catalyst component (A)”) include magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halide and fatty acid salt of magnesium, etc.
Examples of the magnesium dihalide include magnesium dichloride, magnesium dibromide, magnesium diiodide and magnesium difluoride, etc.
Preferred dialkyl magnesium is the compound represented by the general formula R
5
R
6
Mg wherein R
5
and R
6
each represent a C
1-10
alkyl group which may be the same or different. Specific examples of such dialkylmagnesium include dimethylmagnesium, diethylmagnesium, methylethylmagnesium, dipropylmagnesium, methypropylmagnesium, ethylpropylmagnesium, dibutylmagnesium, methylbutylmagnesium and ethylbutylmagnesium, etc. Such dialkylmagnesium may be obtained by react

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