Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-07-30
2004-04-27
Bell, Mark L. (Department: 1755)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S074000, C526S154000, C526S155000
Reexamination Certificate
active
06727333
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which are high in their polymerization activity and capable of producing an olefin polymer extremely low in its content of lower molecular weight components and low crystallinity components and superior in its powder properties. The invention also relates to a process for producing an olefin polymer, and a process for producing the solid catalyst component,
BACKGROUND OF THE INVENTION
As a catalyst for olefin polymerization, a Ziegler-Natta catalyst composed of a combination of a transition metal component and an organometal component is well known, and as a high activity catalyst for olefin polymerization, there are proposed many catalysts, for example, those comprising an organoaluminum compound and a solid catalyst component obtained by using a titanium compound and a magnesium compound.
However, these catalysts leave problems such that when they are used for the polymerization of &agr;-olefins such as propylene or the copolymerization of ethylene with &agr;-olefins, the resulting polymer contains a lot of lower molecular weight components and low crystallinity components which affect a transparency, an impact resistance and a blocking property of the film or sheet obtained by molding the polymer.
With respect to the polymerization of &agr;-olefins such as propylene, there are proposed a process comprising incorporating an electron donor such as esters and ethers as an internal donor into a solid catalyst component, and a process comprising incorporating an electron donor such as esters, ethers, amines and organosilicone compounds, as an external donor into a catalyst composed of a solid catalyst component and an organoaluminum compound, whereby the stereospecificity of the resulting polymer is improved to decrease the lower molecular weight components and the low crystallinity components contained in the polymer. Whereas, with respect to the copolymerization of ethylene with &agr;-olefins, there are also proposed processes of decreasing the lower molecular weight components and the low ctystallinity components contained in the polymer by using electron donors as the internal or external donor.
However, in the polymerization of &agr;-olefins such as propylene, or the copolymerization of ethylene with &agr;-olefins, such processes of using electron donors as the internal or external donor are not always satisfactory from a viewpoint of decreasing the production of lower molecular weight components and low crystallinity components.
Meanwhile, in the olefin polymerization, it is desired that the resulting powder polymer is superior in its powder properties, that is, high in its bulk density, narrow in its particle size distribution and superior in its flowability, from a viewpoint of an operational stability and operational efficiency.
In recent years, as a new solid catalyst component, there is known a solid catalyst component obtained by fixing a magnesium compound and a titanium compound on a carrier of a functional group-carrying polymer. For example, WO 94/20545 and U.S. Pat. No. 5,409,875 disclose a process for polymerizing ethylene, wherein an organic solvent solution of an ethylene/unsaturated carboxylic acid copolymer is mixed with a poor solvent to precipitate the copolymer, followed by pulverization to form a carrier, and the carrier is contacted with an organomagnesium compound and a transition metal compound to obtain a solid catalyst component, which is used in combination with an organoaluminum compound for the polymerization of ethylene.
The above catalyst obtained by using the carrier is described in the patent specification to exhibit a high activity also in the copolymerization of ethylene with &agr;-olefins. However, the catalyst has been found to be insufficient relating to the content of the lower molecular weight components and the low crystallinity components in the resulting copolymer. Moreover, it has been found that the solid catalyst component obtained by using the carrier contains fine powders to make a particle size distribution broad, and therefore it is not satisfactory also relating to the powder properties of the resulting ethylene/&agr;-olefin copolymer.
Each of the references referred to above is incorporated by reference in its entirety.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a solid catalyst component and catalyst for olefin polymerization, which are high in their polymerization activity and capable of producing olefin polymers that are extremely low in their content of lower molecular weight components and low crystallinity components and that are superior in their powder properties.
Another object of the present invention is to provide a process for producing an olefin polymer.
A further object of the present invention is to provide a process for producing the solid catalyst components of the invention.
The present inventors have undertaken extensive studies to accomplish their objects, and, as a result, have found that desired results can be obtained when a carrier of specific carboxyl group-carrying polymer particles is used, and thereby the present invention has been obtained.
The present invention provides a solid catalyst component (A1) for olefin polymerization, which is obtained by contacting:
(a) a carrier of carboxyl group-carrying polymer particles having an average particle size of from about 1 to 200 &mgr;m,
(b) an organometallic compound of the number 1, 2 or 13 group of metals in the periodic table of elements, and
(c) a transition metal compound of the number 4 group of metals in the periodic table of elements,
The present invention also provides a solid catalyst component (A2) for olefin polymerization, which is obtained by contacting:
(a) a carrier of carboxyl group-carrying polymer particles having an average particle size of from about 1 to 200 &mgr;m,
(b) an organometallic compound of the number 1, 2 or 13 group of metals in the periodic table of elements,
(c) a transition metal compound of the number 4 group of metals in the periodic table of elements, and
(d) a phenol compound,
The present invention further provides a catalyst for olefin polymerization, which is obtained by using any one of the aforementioned solid catalyst components (A1) and (A2), and at least one compound (B) selected from the group consisting of organoaluminum compounds and organoaluminumoxy compounds.
The present invention further provides a process for producing an olefin polymer, which comprises utilizing said catalyst to catalyze a reaction between olefins, diolefins or a mixture thereof.
The present invention furthermore provides a process for producing the solid catalyst components (A1) and (A2), which comprises contacting the aforementioned (a) to (c), or (a) to (d), respectively.
In the above, groups 1, 2 and 13 in the periodic table of elements are those previously referred to as groups 1a, 2a and 3a, respectively. The group 4 in the periodic table of elements is that previously referred to as group 4b.
DETAILED DESCRIPTION OF THE INVENTION
The following description is not to be construed as limiting the present invention, as those of ordinary skill in the art will realize that various changes can be made in the various materials and procedures taught herein, without departing from the spirit or scope of the present inventive discovery. In this respect, the present invention is only limited by the scope of the claims appended hereto, and the equivalents encompassed thereby. The present invention is explained in detail as follows.
(a) Carrier
The carrier used in the present invention comprises polymer particles containing a polymer having a carboxyl group, and the polymer particles having an average particle size of from about 1 to 200 &mgr;m. The polymer particles are preferably spherical or nearly spherical in their shape. Spherical or elliptical particles are particularly preferred. The carrier may be used singly or in a mixture of two or more kinds of polymer particles, and s
Kiuchi Seiki
Miyatake Tatsuya
Nomura Kotohiro
Bell Mark L.
Pasterczyk J.
Stevens Davis Miller & Mosher L.L.P.
Sumitomo Chemical Company Limited
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