JP2001310903A - Production of propylene homo polymer or propylene/ olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of continuously and stably producing a propylene (co)polymer such as propylene/olefin random copolymer and propylene/olefin block copolymer, especially having a low melting point, which is conventionally difficult in a continuous and stable production. SOLUTION: Propylene or propylene and other olefins are continuously polymerized or copolymerized in a multistage polymerization process in the presence of carried catalyst and organic aluminum compounds. In the process vapor-phase polymerization process consisting of at least the first polymerization zone and the second polymerization zone having two or more horizontal reactors in series with a stirrer rotating around horizontal axis is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a propylene polymer or a propylene / olefin copolymer which has been conventionally difficult to produce by a specific gas phase polymerization process in the presence of a metallocene supported catalyst and an organoaluminum compound. (Hereinafter collectively referred to as a propylene (co) polymer).

[0002]

2. Description of the Related Art Propylene (co) polymers have high crystallinity and are widely used in the field of films, sheets, stretched tapes, fibers, and other molded products as (co) polymers having well-balanced physical properties. It's being used.

[0003] However, propylene homopolymers are
Generally, it has a high melting point. For example, when formed into a film or sheet, the resulting film or sheet has drawbacks such as requiring a high heat sealing temperature. In particular, it has been difficult to apply the method to a field requiring flexibility. In order to solve the above-mentioned problems, a method of randomly copolymerizing propylene and an olefin other than propylene is known, and is industrially practiced.

[0004] For example, a random copolymer of propylene and a small amount of ethylene has a lower melting point than a homopolymer of propylene, and improves the heat sealability and cold resistance of a film or the like obtained when formed into a film or the like. That is already known.

[0005] However, the random copolymers of propylene and ethylene currently on the market have not yet been sufficiently satisfactory in their performance. As a means to solve this, it is thought that by further increasing the content of comonomer such as ethylene, it is possible to lower the melting point of the obtained random copolymer and at the same time to impart impact resistance and flexibility. Can be

However, in the random copolymerization of propylene with ethylene or the like, as the ethylene content is increased to lower the melting point of the copolymer, the bulk specific gravity of the produced copolymer particles increases. Significantly reduced, at the same time,
The amount of by-product amorphous low molecular components increases rapidly. As a result,
In production on an industrial scale, the by-product low-molecular components cause serious obstacles in plant operation such as line blockage, reduced stirring efficiency, and reduced polymerization heat removal efficiency. Therefore, there is naturally a limit in producing a low-melting point random copolymer, that is, a low-crystalline propylene / olefin random copolymer having an increased comonomer content such as ethylene on an industrial scale.

[0007] Various methods have been proposed to overcome this limitation. For example, in the presence of a catalyst composed of titanium trichloride and organic aluminum, 0.1 g to 10 g of ethylene is preliminarily polymerized per 1 g of titanium trichloride, and then propylene and an olefin other than propylene such as ethylene are randomly copolymerized. Polymerization method (JP-A-50-135)
No. 191), and after prepolymerizing 1 to 1000 g of propylene per 1 g of a highly active titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, propylene and ethylene, etc. in the presence of the catalyst component. (Japanese Patent Application Laid-Open No. 59-206424), for example, has been proposed.

[0008] These proposals, compared to previous methods,
Although the amount of by-products of the amorphous low-molecular components is reduced and the bulk specific gravity of the obtained copolymer particles is improved, these methods are still not industrially satisfactory, and have a low melting point. A method for producing a propylene / olefin random copolymer having low crystallinity and high bulk specific gravity with good operability has been desired.

As a method for solving the above problems, for example, JP-A-11-240911 discloses [A] a metallocene compound, [B] an aluminoxane compound or a non-coordinating ionic compound, and [C] an inorganic fine particle carrier. After contacting a catalyst comprising an organoaluminum compound with propylene and prepolymerizing propylene, in the presence of the obtained prepolymerized catalyst and the organoaluminum compound represented by the component (D), A method for producing a low-crystalline polyolefin using a prepolymerized catalyst obtained by preliminarily polymerizing 1-butene by contacting 1-butene has been proposed.

The above proposal proposes that a random copolymer having low melting point, low crystallinity, and high bulk specific gravity can be produced with good operability by performing multistage prepolymerization of propylene and 1-butene. Although improvements have been made, further improvements are desired, including an increase in polymerization activity.
Since there is no clear specification of the random copolymer that can be produced in the specification, it is clearly shown whether a random copolymer having a lower melting point can be produced than the random copolymer produced in the examples. It has not been.

On the other hand, it has been already known to produce a block copolymer of propylene and an olefin by a multistage polymerization method using a metallocene catalyst.
No. 72414, JP-A-6-287257, JP-A-11-228612 and the like.
However, when the block copolymer is produced using a metallocene catalyst, particularly, the propylene / ethylene copolymer produced in the second polymerization step has a very uniform composition, and the current Ziegler-Natta It becomes a completely amorphous copolymer in a wide range of ethylene content as compared with that obtained from a catalyst (hereinafter, referred to as a ZN catalyst). Moreover, these amorphous components are easy to exude to the powder surface during polymerization,
Significantly degrades powder flow. Therefore, according to the knowledge of the present inventors, using a metallocene catalyst,
There has been no example of continuously producing a block copolymer by a multi-stage polymerization method on a scale larger than a so-called pilot polymerization facility.Therefore, from the viewpoint of improving the catalyst, improving the operation method, and improving the polymerization process, such a block copolymer has been developed. The copolymer is continuously
A stable production method was desired.

[0012]

As described above, a metallocene catalyst is used to obtain a low-melting propylene / olefin random copolymer or a propylene / olefin block copolymer. There has been a demand for a method for continuously and stably producing polymers and the like that have been difficult to produce.

[0013]

Means for Solving the Problems The present inventors have found that conventional methods such as low-melting point propylene / olefin random copolymers and propylene / olefin block copolymers can be used without causing the above-mentioned problems. We have been studying a method to continuously and stably produce polymers, etc., for which continuous stable production was difficult. As a result, they found that a method for producing a propylene (co) polymer by a specific gas-phase polymerization process in the presence of a metallocene-supported catalyst and an organoaluminum compound can solve the above problems, and based on this finding, Completed the invention. As is apparent from the above description, the object of the present invention is particularly to provide low-melting propylene /
An object of the present invention is to provide a method for continuously and stably producing a propylene (co) polymer, such as an olefin random copolymer or a propylene / olefin block copolymer, which has heretofore been difficult to continuously produce continuously.

The present invention is represented by the following (1) to (4). (1) In the presence of a metallocene-supported catalyst and an organoaluminum compound, a gas comprising at least a first polymerization zone and a second polymerization zone having two or more horizontal reactors having a stirrer rotating around a horizontal axis therein in series. A method for producing a propylene polymer or a propylene / olefin copolymer, comprising continuously polymerizing or copolymerizing propylene or propylene with another olefin other than propylene by a multistage polymerization method using a phase polymerization process. .

(2) The propylene polymer is a propylene homopolymer, and the propylene / olefin copolymer contains 0.1 to 50% by weight of an olefin other than propylene and olefin other than propylene. 2. The method for producing a propylene polymer or a propylene / olefin copolymer according to the above item 1, wherein the method is a random copolymer, a block copolymer or a random block copolymer.

(3) The propylene polymer or propylene / olefin according to any one of the above (1) or (2), wherein the olefin other than propylene is ethylene and / or 1-butene. A method for producing a copolymer.

(4) A metallocene-supported catalyst (II) or a metallocene-supported catalyst (I-I) prepared by sequentially performing the following steps (a) to (c):
(D) The propylene polymer or propylene / olefin according to any one of the above items 1 to 3, which is a preactivated metallocene-supported catalyst (II) obtained by sequentially performing the steps. A method for producing a copolymer.

(A) a step of reacting a metallocene compound with an aluminoxane in an inert solvent to obtain a metallocene catalyst; and (b) a step of reacting the metallocene catalyst obtained in the above step (a) and the inorganic fine particle carrier with an inert solvent. 85-150 ° C in the presence of
Contacting the metallocene catalyst on the inorganic fine particle carrier to obtain a crude metallocene-supported catalyst (II), (c) the crude metallocene-supported catalyst (II) obtained in the above step (b). Washing the slurry containing at least twice with an aliphatic hydrocarbon at a temperature of −50 to 50 ° C. to obtain a purified metallocene-supported catalyst (II),
(D) The metallocene-supported catalyst obtained in the step (c) (I-
I) is contacted with an olefin to prepolymerize the olefin, and the metallocene-supported catalyst (II) is added in an amount of 0.0
A step of further supporting 1 to 100 kg of an olefin prepolymer on the metallocene-supported catalyst (II) to obtain a preactivated metallocene-supported catalyst (II).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The metallocene-supported catalyst used in the production of the propylene / olefin (co) polymer of the present invention is a metallocene compound, an aluminoxane, a fine particle carrier, and if necessary, an organic aluminum compound. Supported metallocene catalysts (I) and metallocene compounds, ion-exchanged layered compounds or inorganic silicates and, if necessary, metallocene-supported catalysts (II) produced by reacting with organic aluminum compounds. be able to.

The metallocene compound used in the production of the metallocene-supported catalyst (I) or the metallocene-supported catalyst (II) of the present invention is a metallocene compound represented by the following general formula (1).

[0021]

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(Wherein M represents a transition metal, p represents the valence of the transition metal, X may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group, ¹ and R ² represent a π-electron conjugated ligand coordinated to M, wherein R ¹ and R ² may be the same or different, and Q is a divalent group bridging R ¹ and R ² Represents).

Examples of the transition metal represented by M include Y, Sm, Zr, Ti, Hf, V, Nb, Ta and Cr. Preferred transition metals are Y, Sm, Z
r, Ti or Hf, and more preferred transition metals are Zr and Hf.

The π-electron conjugated ligands represented by R ¹ and R ² include η-cyclopentadienyl structure, η-benzene structure, η-cycloheptatrienyl structure and η-cyclooctatetraene. Examples of the ligand include a ligand having a structure, and a particularly preferred ligand is a ligand having an η-cyclopentadienyl structure.

The ligand having the η-cyclopentadienyl structure includes, for example, a cyclopentadienyl group, an indenyl group, an indenyl hydride group, a fluorenyl group, a dihydroazulenyl group and the like. These groups are
A halogen atom, an alkyl, an aryl, an aralkyl, an alkoxy, a hydrocarbon group such as an aryloxy, a hydrocarbon group-containing silyl group such as a trialkylsilyl group, a chain or cyclic alkylene group, and further, a heteroaromatic group,
It may be substituted with a substituted heteroaromatic group or the like.

The group represented by Q is not particularly limited as long as it is a divalent group. Examples thereof include a linear or branched alkylene group, an unsubstituted or substituted cycloalkylene group, an alkylidene group, an unsubstituted or Examples include a substituted cycloalkylidene group, an unsubstituted or substituted phenylene group, a silylene group, a dialkyl-substituted silylene group, a germyl group, and a dialkyl-substituted germyl group.

Examples of the above metallocene compound include dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, rac −
Ethylenebis (indenyl) zirconium dimethyl, r
ac-ethylenebis (indenyl) zirconium dichloride, rac-dimethylsilylenebis (indenyl) zirconium dimethyl, rac-dimethylsilylenebis (indenyl) zirconium dichloride, rac-ethylenebis (tetrahydroindenyl) zirconium dimethyl, rac-dimethylgermylbis (Indenyl) zirconium dimethyl, rac-dimethylgermylbis (indenyl) zirconium dichloride, rac-ethylenebis (tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl, rac-dimethylsilylenebis (tetrahydro Indenyl) zirconium dichloride,

Rac-dimethylgermylbis (tetrahydroindenyl) zirconium dimethyl, rac-dimethylgermylbis (tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-
Methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-dimethylgermylbis (2 -Methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-ethylenebis (2 -Methyl-4,5,6,7-tetrahydroindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-
Methyl-4-phenylindenyl) zirconium dimethyl,

Rac-dimethylgermylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl-4-
Phenylindenyl) zirconium dimethyl, rac-
Dimethylsilylenebis (2-methyl-4-phenylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2
-Methyl-4-naphthylindenyl) hafnium dichloride, rac-dimethylgermylbis (2-methyl-4
-Naphthylindenyl) zirconium dimethyl, rac
-Dimethylgermylbis (2-methyl-4-naphthylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl)
Zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dimethyl, rac-dimethylgermylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride,

Rac-dimethylgermylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,
5-benzoindenyl) hafnium dichloride, rac
-Dimethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl)
Zirconium dimethyl, rac-dimethylgermyl bis (2-ethyl-4-phenylindenyl) zirconium dichloride,

Rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl) hafnium dichloride,
rac-dimethylsilylenebis (2-methyl-4,6-
Diisopropylindenyl) zirconium dichloride,
rac-dimethylsilylenebis (2-methyl-4,6-
Diisopropylindenyl) zirconium dimethyl, r
ac-dimethylgermylbis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, r
ac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) hafnium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride,

Dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3',
5'-dimethylcyclopentadienyl) zirconium dimethyl, dimethylgermyl (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylgermyl (2,4- Dimethylcyclopentadienyl) (3 ', 5'
-Dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride,

Dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Titanium dichloride, dimethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5'-
Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylgermil (2,3 , 5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dichloride, dimethylgermil (2,3,5
-Trimethylcyclopentadienyl) (2 ', 4', 5 '
-Trimethylcyclopentadienyl) zirconium dimethyl,

Dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) Enyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dimethyl, rac-dimethylsilylenebis (2-methyl-4-phenyldihydroazulenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl -4-phenyldihydroazulenyl) zirconium dichloride

Rac-dimethylsilylenebis (3- (2
-Furyl) -2,5-dimethylcyclopentadienyl)
Zirconium dichloride, rac-dimethylsilylenebis (2- (2-furyl) -3,5-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylenebis (2- (2-furyl) -4,5-dimethylcyclo) Pentadienyl) zirconium dichloride, r
ac-dimethylsilylenebis (3- (2-thienyl)-
2,5-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylenebis (2- (2
-Furyl) -indenyl) zirconium dichloride, r
ac-dimethylsilylenebis (2- (2-thienyl)-
4,5-dimethylcyclopentadienyl) zirconium dichloride,

Rac-dimethylsilylenebis (2- (2
-(5-methyl) -furyl) -4,5-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylenebis (2- (2- (5-t-butyl)-
Furyl) -4,5-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl)-
4,5-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylenebis (2- (2
-(4,5-dimethyl) -furyl) -4,5-dimethylcyclopentadienyl) zirconium dichloride, ra
c-dimethylsilylenebis (2- (2-benzofuryl)
-4,5-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylenebis (2-
(2-thienyl) -indenyl) zirconium dichloride.

Among the above metallocene compounds, particularly preferred compounds are dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride and rac-dimethylsilylenebis (2-methyl-
4-phenylindenyl) zirconium dichloride, r
ac-dimethylgermylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl-4-phenylindenyl) zirconium didichloride, rac-dimethylsilylenebis (2-methyl -4-naphthylindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl-4-naphthylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride ,

Rac-dimethylgermylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl-4-
Phenylindenyl) zirconium dichloride, rac
-Dimethylgermylbis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, rac-dimethylgermylbis (2-methyl -4,6-diisopropylindenyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'
-Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dimethyl, dimethylgermil (2,
4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, dimethylgermyl (2,4-dimethylcyclopentadienyl) (3', 5'-dimethylcyclopentadienyl) ) Zirconium dimethyl,

Dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3', 5 ′
-Dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3 , 5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dimethyl, dimethyl gel mill (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5'-
Trimethylcyclopentadienyl) zirconium dichloride,

Dimethylgermyl (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopenta Dienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,3,
5-trimethylcyclopentadienyl) (2 ′, 4 ′,
5'-trimethylcyclopentadienyl) hafnium dimethyl, rac-dimethylsilylenebis (2-methyl-
4-phenyldihydroazulenyl) zirconium dichloride.

The most preferred metallocene compound is
Dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, dimethylgermyl (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene (2,3,5
-Trimethylcyclopentadienyl) (2 ', 4', 5 '
-Trimethylcyclopentadienyl) hafnium dichloride, as well as rac-dimethylsilylene (2-methyl-4-phenylindenyl) zirconium dichloride.

The above-mentioned racemic compound may contain a corresponding meso compound in an amount of 5 mol% or less.

The aluminoxane used for producing the metallocene-supported catalyst (I) of the present invention is represented by the following general formula (2):
Or a compound represented by (3).

[0044]

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(Wherein R ³ represents a hydrocarbon group having 1 to 6, preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl) Alkyl group such as a group, allyl group, 2-methylallyl group, propenyl group, isopropenyl group, 2-methyl-1-propenyl group, alkenyl group such as butenyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. And R ³ may be the same or different, and among them, an alkyl group is preferable, a methyl group is particularly preferable, and q is an integer of 4 to 30, and is preferable. Is from 6 to 30, particularly preferably from 8 to 30).

As the aluminoxane, a commercially available aluminoxane solution dissolved in an organic solvent can be used. The aluminoxane can also be prepared under various known conditions, and the following preparation method can be specifically exemplified.

(1) A method in which a trialkylaluminum such as trimethylaluminum, triisobutylaluminum or a mixture thereof is directly reacted with water in an organic solvent such as toluene or ether.

(2) A method of reacting a trialkylaluminum such as trimethylaluminum, triisobutylaluminum or a mixture thereof with a salt having water of crystallization such as copper sulfate hydrate or aluminum sulfate hydrate.

(3) water impregnated in silica gel or the like;
A method in which a trialkylaluminum, for example, trimethylaluminum or triisobutylaluminum is reacted individually, simultaneously or sequentially.

There is no particular problem even if unreacted trialkylaluminum remains in the aluminoxane obtained by these methods.

In the present invention, the fine particle carrier used for producing the metallocene-supported catalyst (I) is an inorganic fine particle carrier or an organic fine particle carrier having a particle diameter of 1 to 500 μm, preferably 5 to 300 μm. More preferably, a granular or spherical fine particle solid of 10 to 150 μm is used.

The inorganic fine particle carrier has a specific surface area of 50 to 50.
1,000m ² / g, preferably 100~700m ² / g
And the pore volume is preferably in the range of 0.3 to 2.5 m ³ / g.

As the inorganic fine particle carrier, metal oxides such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , Z
nO, a mixture thereof or a composite oxide thereof is preferable, and a carrier containing SiO ₂ or Al ₂ O ₃ as a main component is particularly preferable. More specific inorganic _{compounds, SiO 2, Al 2 O 3} , MgO, SiO 2 -Al 2 O 3,
SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -Al ₂
O ₃ -MgO and the like are mentioned, and SiO ₂ is particularly preferable.

Prior to use, the inorganic fine particle carrier is usually used at 100 to 1,000 ° C., preferably at 300 to 1,000 ° C.
The one fired at 900 ° C, particularly preferably 400 to 900 ° C, is used. The amount of water adsorbed on the surface of the inorganic fine particle carrier after calcination is 0.1% by weight or less, preferably 0.01% by weight or less, and the surface hydroxyl group content is 1.0% by weight or more, preferably 1.5 to 4.5%. 0% by weight, more preferably 2.0 to
It is in the range of 3.5% by weight. Further, these inorganic fine particle carriers may be subjected to a contact treatment with an organic aluminum compound and / or a halogen-containing silicon compound before use.

Examples of the organic fine-particle carrier include fine-particle organic polymers, for example, fine-particle polymers of polyolefins such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene, and fine-particle polymers such as polystyrene. Examples thereof include polymers.

The organoaluminum compound used as an optional component in the production of the metallocene-supported catalyst (I) or (II) of the present invention is represented by the general formula AlR ⁴ _s R ⁵ _t X _{3-(s + t).} Compound. (Wherein R ⁴ and R ⁵ are each independently a hydrocarbon group such as an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a fluorine atom, a methyl group, a trifluorophenyl group, etc. Represents a phenyl group which may have a substituent, X represents a halogen atom, and s and t are arbitrary integers satisfying 0 <s + t ≦ 3).

As the organic aluminum compound represented by the above general formula, for example, trimethylaluminum, triethylaluminum, triisopropylaluminum,
Triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-
Trialkyl aluminums such as octyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride and diisopropylaluminum chloride; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide, isopropylaluminum sesquichloride and the like And mixtures of two or more of the above. A preferred organoaluminum compound is a trialkylaluminum.

Next, as the ion-exchangeable layered compound or inorganic silicate used in the production of the metallocene-supported catalyst (II) used in the present invention, an ion-exchanged layered compound excluding silicate (simply a layered compound) Or an inorganic silicate.

Examples of the layered compound include ionic crystalline compounds having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl 2 type, and a CdI 2 type.
As a specific example, α-Zr (HAsO ₄ ) ₂ .H
₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) _2.
3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAs
O ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Z
r (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (N
Crystalline acidic salts of polyvalent metals such as H ₄ PO ₄ ) ₂ .H ₂ O may be mentioned.

The layered compound may be used after being subjected to salt treatment and / or acid treatment, if necessary. A layered compound other than silicate, which has not been subjected to salt treatment or acid treatment, is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force to each other, and contain ions contained therein. Can be exchanged.

Examples of the above inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. They are,
Synthetic products may be used, or naturally occurring minerals may be used. Specific examples of clays and clay minerals include the allophane group such as allophane, the kaolin group such as dickite, nacrite, kaolinite, and anoxite; the halloysite group such as metahaloysite and halloysite; Stone tribe, montmorillonite, sauconite, beidellite,
Non-tronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite,
Examples include mica minerals such as illite, sericite and chlorite, attapulgite, sepiolite, palygorskite, bentonite, Kibushi clay, gairome clay, hissingelite, pyrophyllite, and ryokudeite group. These may form a mixed layer. Examples of the artificially synthesized product include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Among the inorganic silicates, kaolin group, hallocite group, serpentine group, smectite, vermiculite mineral, mica mineral, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite are preferable, and smectite, vermiculite mineral, Synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite are more preferred. These may be used as they are without any particular treatment, or may be used after having been subjected to treatments such as ball milling and sieving. Further, they may be used alone or as a mixture of two or more.

The inorganic silicate can change the acid strength of the solid, if necessary, by salt treatment and / or acid treatment. In the salt treatment, an ion complex,
By forming a molecular complex, an organic derivative, or the like, the surface area or the interlayer distance can be changed. That is, by using the ion exchange property and replacing the exchangeable ion between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

The layered compound and the inorganic silicate may be used without any treatment, but the exchangeable metal cation contained therein is exchanged with a cation dissociated from the following salts and / or acids. Is preferred.

The salts used for the above ion exchange are 1 to
At least one element selected from the group consisting of Group 14 atoms
Is a compound containing a cation containing a proton, preferably
Is at least selected from the group consisting of atoms of groups 1 to 14
A cation containing one type of atom, a halogen atom, an inorganic acid,
At least one element selected from the group consisting of
Consisting of an anion derived from an atom or an atomic group
And more preferably a compound consisting of atoms of groups 2 to 14.
Cation containing at least one atom selected from the group consisting of
And Cl, Br, I, F, PO_Four, SO_Four, NO_Three, C
O_Three, C_TwoO_Four, ClO _Four, OOCCH_Three, CH_ThreeCOCHC
OCH_Three, OCI_Two, O (NO_Three)_Two, O (ClO_Four)_Two, O
(SO_Four), OH, O_TwoCl_Two, OCI_Three, OOCH and O
OCCH_TwoCH_ThreeAt least one member selected from the group consisting of
And a compound comprising: In addition, these salts
May be used in combination of two or more.

The acid used for the above-mentioned ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and two or more of them may be used simultaneously. As a method of combining the salt treatment and the acid treatment, a method of performing an acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of simultaneously performing the salt treatment and the acid treatment,
There is a method of performing salt treatment and acid treatment at the same time after performing salt treatment. In addition, the acid treatment has an effect of removing ions on the surface and ion exchange, and has a crystal structure of Al, Fe, M
It has the effect of eluting some cations such as g and Li.

The conditions for treatment with salts and acids are not particularly limited. However, usually the salt and acid concentrations are at 0.
It is preferable that the treatment is carried out under conditions of 1 to 30% by weight, a treatment temperature of room temperature to the boiling point of the solvent used, a treatment time of 5 minutes to 24 hours, and elution of at least a part of the compound to be treated. In addition, salts and acids are generally used in an aqueous solution.

In the case of performing the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, other chemical treatments such as an alkali treatment, an organic compound treatment, and an organic metal treatment may be used in combination. The layered compound or inorganic silicate obtained in this manner has a pore volume of not less than 0.1 cc / g, particularly not less than 0.3 to 5 cc, having a radius of not less than 20 ° measured by mercury porosimetry.
/ G. Such an inorganic silicate, when treated in an aqueous solution, contains adsorbed water and interlayer water. Here, the adsorbed water is water adsorbed on the surface of an ion-exchangeable layered compound or an inorganic silicate or a crystal fracture surface, and the interlayer water is water existing between crystal layers.

In the present invention, the above-mentioned inorganic silicate is preferably used after removing the above-mentioned adsorbed water and interlayer water. The dehydration method is not particularly limited, and a method such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent is used. The heating temperature is in a temperature range in which adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher. However, high temperature conditions that cause structural destruction are not preferable.
The heating time is at least 0.5 hour, preferably at least 1 hour. At that time, the weight loss of the inorganic silicate after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when a layered compound or an inorganic silicate whose weight loss is adjusted to 3% by weight or less is used, the same weight loss state is maintained even when the layered compound or the organic aluminum compound described below is contacted. It is preferable to handle it.

The metallocene-supported catalyst (I) used in the present invention comprises the above-mentioned metallocene compound and the above-mentioned aluminoxane and the above-mentioned organic aluminum compound which are optional components, in the presence of a particulate carrier. Is usually obtained by reacting a metallocene compound and an aluminoxane, which are soluble in a hydrocarbon solvent, by depositing the metallocene compound and the aluminoxane on a dehydrated particulate carrier. Converted to catalyst. The order in which the metallocene compound and the aluminoxane are added to the fine particle carrier can be arbitrarily changed.
For example, a metallocene compound dissolved in a suitable hydrocarbon solvent can be first added to the particulate support, followed by the aluminoxane. Further, a metallocene compound and an aluminoxane which have been reacted in advance can be added to the fine particle carrier. Alternatively, the aluminoxane can be added first to the particulate carrier, followed by the metallocene compound.

The reaction temperature is usually from -20 to 100.
° C, preferably 0 to 100 ° C, and the time required for the reaction is usually 0.1 min or more, preferably 1 min to 200 min. Further, the metallocene-supported catalyst obtained as described above can be used after being prepolymerized with a small amount of olefin if necessary.

The olefin used for the prepolymerization includes ethylene, propylene, 1-butene, 1-hexene,
Examples thereof include methyl-1-butene and 4-methyl-1-pentene, and two or more monomers can be copolymerized.

The most preferred metallocene-supported catalyst used in the production of the propylene (co) polymer of the present invention is a metallocene-supported catalyst prepared by sequentially carrying out the following steps (a) to (c): (II) or a preactivated metallocene-supported catalyst (II) obtained by sequentially performing the following steps (a) to (d).

(A) reacting the metallocene compound (A) with the aluminoxane (B) in an inert solvent to obtain a metallocene catalyst;

(B) The metallocene catalyst obtained in the above step (a) and the inorganic fine particle carrier are mixed with each other in the presence of an inert solvent for 85 to 85 minutes.
The metallocene catalyst was supported on the inorganic fine particle carrier by contact at a temperature of 150 ° C., and the crude metallocene supported catalyst (I-
The step of obtaining I),

(C) A metallocene-supported catalyst obtained by washing the slurry containing the crude metallocene-supported catalyst obtained in the above step (b) at least twice with an aliphatic hydrocarbon at a temperature of -50 to 50 ° C. Obtaining (II),

(D) The metallocene-supported catalyst (II) obtained in the above step (c) is brought into contact with an olefin to prepolymerize the olefin, and 0.01 to 100 kg of olefin per 1 kg of the metallocene-supported catalyst. A step of further supporting the prepolymer on the metallocene-supported catalyst to obtain a preactivated metallocene-supported catalyst (II).

In the above step (a), an aluminum atom of 10 to 10 mol of the metallocene compound is used.
1,000 moles, preferably 20-500 moles, of aluminoxane in an inert solvent at -50 to 100C,
The reaction is carried out preferably at a temperature of 0 to 50 ° C. for 1 minute to 10 hours, preferably 3 minutes to 5 hours to produce a reaction product of the metallocene compound and the aluminoxane, that is, a metallocene catalyst.

The use of the inert solvent is preferred in that the reaction proceeds uniformly and efficiently. The amount of the inert solvent used is not particularly limited, but is usually 10 to 10,000 liters, preferably 10 to 10,000 liters per mole of the metallocene compound.
It is about 1,000 liters.

As the inert solvent used in the above reaction,
For example, benzene, toluene, xylene, aromatic hydrocarbons such as cumene, butane, tetramethylbutane, pentane, ethylpentane, trimethylpentane, hexane,
Methylhexane, ethylhexane, dimethylhexane,
Aliphatic hydrocarbons such as heptane, methylheptane, octane, nonane, decane, hexadecane, octadecane,
Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane, the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons obtained by substituting alicyclic hydrocarbons with halogens, and mixed solvents thereof; No.

Also, ethers such as ethyl ether and tetrahydrofuran can be used. A preferred inert solvent is an aromatic hydrocarbon, and a solvent used in a commercially available aluminoxane solution may be used as it is or may be further added with other aromatic hydrocarbons for the reaction.

In the step (b) following the step (a),
The reaction product of the metallocene compound obtained in the step (a) and the aluminoxane, i.e., the metallocene catalyst and the inorganic fine-particle carrier are subjected to 85 to 150 in the presence of the inert solvent used as the reaction solvent in the step (a). By contacting at a temperature of ° C., a crude metallocene-supported catalyst (II) of a solid product in which the metallocene catalyst is supported on an inorganic fine particle carrier is obtained. In this contact reaction, an inert solvent can be added as needed.

The ratio of the metallocene catalyst obtained in the step (a) to the inorganic fine particle carrier is 1 to 1,000 kg, preferably 5 to 500 kg, per 1 mol of the transition metal atom in the reaction product. is there. The amount of the inert solvent used is 10 to 10,000 per mole of transition metal atom in the reaction product.
00 liters, preferably 10-1,000 liters. The inorganic fine particle carrier used in this step may use the above-mentioned inorganic fine particle carrier.

The contact conditions between the metallocene catalyst and the inorganic fine particle carrier are 85 to 150 ° C., preferably 90 to 13 ° C.
Under a temperature condition of 0 ° C, particularly preferably 95 to 120 ° C,
The contact is carried out for 5 minutes to 100 hours, preferably for 10 minutes to 50 hours. In particular, the temperature condition is an important factor. By bringing the catalyst into contact within the above temperature range, the obtained metallocene-supported catalyst (I-I) has a high polymerization activity. When this catalyst is used for propylene (co) polymerization, The resulting propylene (co) polymer becomes a (co) polymer having a high bulk specific gravity and good particle properties.

In the following step (c), the crude metallocene-supported catalyst containing the inert solvent obtained in step (b) is
By washing at least twice with an aliphatic hydrocarbon at a temperature of 50 to 50 ° C., the purified product is a solid product carrying a reaction product of a metallocene compound (A) and an aluminoxane (B). Metallocene supported catalyst (I
-I) is obtained.

As the aliphatic hydrocarbon used for washing, the aliphatic hydrocarbons exemplified as the inert solvent and a mixed solvent thereof can be mentioned. Preferably, n-hexane, isopentane or a mixture thereof is used.

As a cleaning method in the step (c), for example,
(b) After completion of the step, the inert solvent is separated from the slurry comprising the inert solvent and the crude metallocene-supported catalyst (II) by filtration, centrifugation, decantation, or the like, and then the aliphatic hydrocarbon is removed. Washing the crude metallocene-supported catalyst (I-I) by using the step (b). After the step (b), the aliphatic hydrocarbon is separated from the slurry comprising the inert solvent and the crude metallocene catalyst without separating the inert solvent. And add
After the mixed solvent of the inert solvent and the aliphatic hydrocarbon is separated by the same means as described above, a method of washing the crude metallocene-supported catalyst (II) using the aliphatic hydrocarbon can be employed. The latter method is more preferable.

The washing conditions are as follows: (b)
Using 1 to 500 liters, preferably 10 to 100 liters, of an aliphatic hydrocarbon with respect to 1 kg of the inorganic particulate carrier used in the step, -50 to 50C, preferably -30 to
The washing is repeated at a temperature of 40 ° C, particularly preferably -30 to 30 ° C, until the metallocene catalyst is not eluted in the aliphatic hydrocarbon after washing. It is sufficient to wash at least two times, usually four times or more, but not limited thereto.

The washing temperature condition is an important factor. By washing in the above temperature range, the obtained metallocene-supported catalyst (I-I) has a high polymerization activity. ) When polymerization is performed, the resulting propylene (co) polymer has a high bulk specific gravity and good particle properties.

As described above, the preactivated metallocene-supported catalyst (I-I) used in the present invention comprises, as the step (d), the metallocene-supported catalyst (I-I) obtained in the step (c).
And the olefin are brought into contact with each other to prepolymerize the olefin, and the content of the metallocene-supported catalyst (II) is 0.0
It is obtained by further supporting 1 to 100 kg of an olefin prepolymer.

Preactivated metallocene supported catalyst (II)
As the olefin prepolymer supported on
-20 olefins, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 2-methyl-1-pentene, 1-hexene, 1-
Homopolymers such as octene, 1-decene, and 1-dodecene and copolymers thereof are listed, and ethylene homopolymers, propylene homopolymers, and olefin copolymers mainly containing ethylene or propylene are preferred. . These olefin prepolymers have intrinsic viscosities [η] of 0.1 to 10 dl / g measured in decalin at 135 ° C.,
It is preferably in the range of 0.2 to 7 dl / g.

A preferred olefin prepolymerization method is
In this method, a small amount of olefin is introduced into a slurry in which the metallocene-supported catalyst (II) obtained in the step (c) is dispersed in an aliphatic hydrocarbon and brought into contact with the slurry to prepolymerize the olefin. Using the metallocene-supported catalyst (II) as a slurry in which the catalyst is dispersed in an aliphatic hydrocarbon, without separating the catalyst from the aliphatic hydrocarbon, using the catalyst obtained in the washing at the final stage of the step (c). Alternatively, after separation, it may be used by redispersing it in a similar aliphatic hydrocarbon.

The prepolymerization of the olefin can be carried out in a liquid phase using the olefin to be polymerized itself as a solvent or in a gas phase without using a solvent. It is preferable to carry out the prepolymerization in the presence of an aliphatic hydrocarbon solvent in order to proceed uniformly.

The prepolymerization of olefins carried out in an aliphatic hydrocarbon is carried out in an amount of 0.005 to ⁵ m ³ , preferably 0.1 to ⁵ m ^{3 of} aliphatic hydrocarbon per 1 kg of the metallocene-supported catalyst (II).
Olefin is added to a slurry consisting of 0.01 to 1 m ³ in an amount of 0.0
1 to 1,000 kg, preferably 0.1 to 500 kg, is introduced, and at a temperature of -50 to 100 ° C, preferably 0 to 50 ° C, for 1 minute to 50 hours, preferably 3 minutes to 20 hours.
The olefin is prepolymerized for a period of time.

In the above prepolymerization of olefin, since the reaction product of the metallocene compound and the aluminoxane is supported on the metallocene-supported catalyst (II), an organoaluminum compound such as a trialkylaluminum or aluminoxane is newly added. It is not particularly necessary to add a cocatalyst represented by the formula (1), but it can be added if desired. The amount of these cocatalysts to be added is preferably within a range of 1,000 mol or less, preferably 500 mol or less as aluminum atoms per 1 mol of transition metal atoms in the metallocene-supported catalyst.

In the present invention, most preferably, the above-mentioned olefin prepolymerization is carried out in the presence of hydrogen to control the molecular weight of the resulting olefin prepolymer.

As used herein, the term "preactivation" as used with respect to a catalyst refers to the various activities of the catalyst with respect to the polymerization of olefins including propylene, for example, the amount of olefin polymerized per unit weight of the active ingredient of the catalyst. This means that the polymerization activity and the activity affecting the stereoregularity and crystallinity of the resulting olefin polymer are activated before the main polymerization of the olefin. Also, the term "pre-polymerization" of olefins is used to pre-activate the catalyst.
Prepolymerizing a small amount of olefin in the presence of a catalyst prior to the main polymerization of the olefin, and the term "olefin prepolymer" means an olefin polymer that has been prepolymerized prior to the main polymerization of the olefin. .

The metallocene-supported catalyst (II) used in the present invention is prepared by contacting the metallocene compound with a layered compound or an inorganic silicate and, if necessary, an organoaluminum compound. There is no particular limitation, and the following methods can be exemplified.
In addition, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. That is,

(1) A method of contacting a metallocene compound with a layered compound or an inorganic silicate. (2) A method in which a metallocene compound is brought into contact with a layered compound or an inorganic silicate, and then an organic aluminum compound is added and brought into contact. (3) A method in which a metallocene compound and an organoaluminum compound are brought into contact with each other, and then a layered compound or an inorganic silicate is added and brought into contact. (4) A method in which a metallocene compound is added and then brought into contact with a layered compound or an inorganic silicate and an organoaluminum compound. (5) A method of simultaneously contacting a metallocene compound, a layered compound or an inorganic silicate and an organoaluminum compound. It is.

When or after the above-mentioned components are brought into contact, a solid such as a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or may be brought into contact with them.

The above components may be contacted with each other in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact is carried out at a temperature between -20 ° C and the boiling point of the solvent, particularly preferably at a temperature between room temperature and the boiling point of the solvent.

The amounts of the components used are as follows.
That is, the metallocene compound is usually 10 ^{−4 to} 10 mmol, preferably 10 ⁻³ to ⁵ mmol, and the organoaluminum compound is usually 0.01 to 10 ⁴ mmol, preferably 0.1 to 1 g of the layered compound or the silicate.
１００100 mmol. The atomic ratio between the transition metal in the metallocene compound and the aluminum in the organoaluminum compound is usually 1: 0.01 to 10 ⁶ , preferably 1: 1.
0.1 to 10 is ^5. The catalyst thus prepared may be used without washing after preparation, or may be used after washing.

Further, if necessary, an organic aluminum compound may be newly used in combination. That is, when a catalyst is prepared using a metallocene compound, a layered compound or an inorganic silicate and organic aluminum, an organic aluminum compound may be further added to the reaction system separately from the preparation of the catalyst. At this time, the amount of the organoaluminum compound used is usually 1: 0 to 10 ⁴ , preferably 1: 1 to 1 as an atomic ratio of aluminum in the organoaluminum compound to transition metal in the metallocene compound.
It is selected to 10 ³ become like.

In the case of the metallocene-supported catalyst (II) prepared as described above, similarly to the case of the metallocene-supported catalyst (I), the propylene (copolymer) of the present invention is prepared after prepolymerization. ) It can also be used for the production of polymers.

The metallocene-supported catalyst (I) or (II) obtained above is suitably used for the production of the propylene (co) polymer of the present invention in combination with an organoaluminum compound.

As the organoaluminum compound used in combination with the metallocene-supported catalyst (I) or (II) in the propylene (co) polymerization, the above-mentioned organoaluminum compounds are used. The organoaluminum compound used in the propylene (co) polymerization is
It may be the same or different from the one used for producing the metallocene-supported catalyst (I) or (II).

The amount of the organoaluminum compound used in the propylene (co) polymerization is from 1 to 5,000 moles, preferably from 5 to 5 moles of Al atoms in the organoaluminum compound per mole of transition metal atom in the catalyst system. It is in the range of 3,000 mol, particularly preferably 10 to 1,000 mol.

In the present invention, the production of the propylene (co) polymer comprises, in the presence of a metallocene-supported catalyst and an organoaluminum compound, two or more horizontal reactors having a stirrer rotating around a horizontal axis therein in series. Manufactured using a gas phase polymerization process.

The gas-phase polymerization process of the present invention having two or more horizontal reactors having a stirrer rotating around a horizontal axis therein in series comprises at least a first polymerization zone and a second polymerization zone. Each of the first polymerization zone and the second polymerization zone or the like may be constituted by a plurality of polymerization vessels arranged in series.

The simplest case of the gas phase polymerization process of the present invention is, for example, a case where each of the first polymerization zone and the second polymerization zone is constituted by one polymerization vessel.

In carrying out the present invention, it is needless to say that an arbitrary olefin polymerization zone can be added before the first polymerization zone and / or after the second polymerization zone. Included in the present invention.

In the method for producing a propylene (co) polymer of the present invention, the molecular weight and / or the content of olefins other than propylene are the same or different in the first polymerization zone and the second polymerization zone, respectively. Propylene (co) polymers can be produced.

The amount of the metallocene-supported catalyst or the preactivated metallocene-supported catalyst to be supplied to the first polymerization zone is from 1 × 10 ⁻¹⁰ to 1 × 10 ⁻¹⁰ in terms of transition metal atoms in the catalyst system per liter of polymerization volume. 1 × 10 ^-3 mol, preferably 1
It is from × 10 ^-9 to 1 × 10 ^-4 mol. By setting the amount of the catalyst in the above range, an efficient and controlled polymerization reaction rate of olefin can be maintained.

In this specification, the term “polymerization volume” means the volume of the gas phase in the polymerization vessel.

The propylene (co) polymer produced in the present invention contains propylene homopolymer and olefin other than propylene in an amount of 0.1 to 50% by weight, preferably 1 to 40% by weight.
A random copolymer, a block copolymer or a random block copolymer of propylene and other olefins other than propylene containing 3 to 30% by weight, more preferably 3 to 30% by weight.

Here, the random copolymer of propylene and olefin means a copolymer obtained by random copolymerization of propylene and olefin, and the block copolymer of propylene and olefin is Obtained by a two-stage polymerization method, a propylene homopolymer is produced in a first polymerization stage, and subsequently, propylene and an olefin are copolymerized in a second polymerization stage to obtain an olefin content of 10 to 9
0% by weight of a propylene / olefin random copolymer means a copolymer obtained, and a random block copolymer of propylene and an olefin means a first polymerization step of preparing the block copolymer. And a copolymer produced in the same manner as the block copolymer except that a propylene / olefin random copolymer having an olefin content of 50% by weight or less is produced.

Specific examples of the olefin other than propylene used in the copolymerization with propylene include α-olefins having 2 to 20 carbon atoms other than propylene, such as ethylene, 1-butene, and 1-butene. Pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-
Dodecene, 1-hexadecene, 4-methyl-1-pentene and the like.
More than one species may be used. Of these, ethylene and / or 1-butene are preferred.

The conditions for producing the propylene (co) polymer of the present invention are as follows: a polymerization temperature of 20 to 120 ° C. in the presence of the metallocene-supported catalyst and an organoaluminum compound.
Preferably, the temperature is from 40 to 100 ° C and the polymerization pressure is from atmospheric pressure to 9.9.
MPa (gage pressure), preferably 0.4 to 5.0 MPa
(Gage pressure). Propylene (co) obtained by introducing a chain transfer agent such as hydrogen as necessary
The molecular weight of the polymer may be adjusted. Further, when producing a propylene copolymer having an olefin content other than propylene as high as 10 to 90% by weight, an oxygen-containing compound such as oxygen, carbon monoxide, carbon dioxide, or water is used. Can be introduced into the polymerization system in a desired amount. In such a case, the effect is the most effective particularly when it is introduced into the second polymerization zone.

In the method for producing a propylene (co) polymer of the present invention, particularly when a propylene / ethylene block copolymer is produced, particularly, the propylene / ethylene copolymer produced in the second polymerization zone is used. Has an ethylene content of 2
At 0 to 55% by weight, the most excellent effect is exhibited. In addition, in the first polymerization zone, a propylene / ethylene random copolymer is produced, that is, a propylene / ethylene random block copolymer is produced. The first
The best effect is exhibited when the ethylene content in the propylene / ethylene random copolymer produced in the polymerization zone is more than 5% and not more than 15%.

Further, the method for producing a propylene (co) polymer of the present invention comprises the steps of:
In accordance with IS K7210, the condition 14 (21.
Melt flow rate (MFR, unit: g / 10 min) measured under a load of 18N and 230 ° C.) is 100 to 500 g / 10 min, and more preferably 100 to 300 g.
The effect is most exhibited when g / 10 minutes.

After completion of the propylene (co) polymerization of the present invention, unreacted monomers and hydrogen are separated from the polymerization system, and a catalyst deactivation treatment or the like is performed to obtain a particulate propylene (co) polymer. .

The propylene (co) obtained by the method of the present invention
The polymer may contain various additives such as an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a coloring agent, and an inorganic or organic filler, if necessary. After blending various synthetic resins, usually, the mixture is heated and kneaded at a temperature of 190 to 350 ° C. for about 20 seconds to 30 minutes using a melt kneading machine, extruded into strands as necessary, and further shredded. It is used for the production of various molded products in the form of granules, ie, pellets.

[0123]

The present invention will be more specifically described below with reference to examples and comparative examples. In the following production examples, the following various physical properties were evaluated.

(1) Polymerization activity: The amount of polymer formed per gram of the supported catalyst before preactivation. (Unit: g · polymer / g · catalyst)

(2) Ethylene content: Calculated from ¹³ C-NMR.

(3) MFR: A value measured in accordance with JIS K7210 under the conditions 14 of Table 1 (21.18N load, 230 ° C.) (unit: g / 10 minutes).

(4) BD: bulk density of the produced polymer.
(Unit: kg / m ³ )

Example 1 (1) Production of Metallocene-Supported Catalyst A toluene solution of methylaluminoxane (concentration: 3 mol / l, trade name: 1.37 liters (4.11 mol in terms of Al atom) of PMAO, manufactured by Tosoh Akzo Co., Ltd., and chiral dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4) as a bridged metallocene compound ', 5'-Trimethylcyclopentadienyl) zirconium dichloride and its meso form dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2', 3 ', 5'-trimethylcyclopentadienyl) 16.6 mmol of a mixture of zirconium dichloride (meso content: 1 mol%) was charged, and the mixture was stirred and maintained at a temperature of 25 ° C. for 30 minutes. It is reacted to obtain a reaction product of a metallocene compound and an aluminoxane.

Subsequently, in the reactor, as a particulate carrier,
100 g of silica (SYLOPOL® 948, manufactured by Grace Davison) having an average particle size of 51 μm, which was previously calcined at 750 ° C. for 8 hours under reduced pressure, was charged, and the temperature of the reactor was raised to 100 ° C. and stirred. The reaction product obtained above was held for 1 hour to carry out a contact reaction between silica and silica to obtain a slurry containing a solid product carrying the reaction product.

After the temperature of the reactor was cooled to -10 ° C., 2 liters of n-hexane was charged and stirred for 5 minutes, then the stirrer was stopped, and the solvent was separated by decantation. Subsequently, while maintaining the temperature of the reactor at −10 ° C., 2 liters of n-hexane is charged into the reactor and washed with stirring for 5 minutes. Then, the agitator is stopped and the washing solvent is separated by decantation. The operation was repeated four times to obtain a solid product on which a reaction product of the metallocene compound and the aluminoxane was supported, and a metallocene-supported catalyst. Furthermore, n-
Hexane (2 L) was charged into the reactor, and the metallocene-supported catalyst was dispersed to form a slurry.

A part of the obtained metallocene-supported catalyst / n-hexane slurry was sampled, the solvent was separated, and dried under reduced pressure. The obtained metallocene-supported catalyst was analyzed. 0.61% by weight and 18.2% by weight of Al derived from aluminoxane; and
It has a peculiar peak in the IR spectrum at 1426 cm -1, confirming that the reaction product of the metallocene compound and methylaluminoxane is supported on silica.
The obtained metallocene-supported catalyst was composed of a solid product having a particle size of 350 μm or more, and no bulk catalyst component was observed.

(2) Production of preactivated catalyst 2 l of n-hexane was charged into a 4 dm3 stainless steel reactor equipped with a stirrer and purged with nitrogen, and the temperature of the reactor was kept at 0 ° C. The metallocene-supported catalyst / n-hexane slurry obtained in 1) was transferred. Then, while stirring and maintaining the temperature of the reaction vessel at 0 ° C., propylene gas was supplied at a supply rate of 0.15 mol / min for 90 minutes to perform prepolymerization, and the produced propylene homopolymer was obtained in (1). Supported on a metallocene supported catalyst. During this prepolymerization reaction, unreacted propylene gas was discharged outside the reactor.
After the elapse of the pre-polymerization time, the supply of propylene gas was stopped,
Subsequently, while raising the temperature of the reactor to 25 ° C., the gas phase of the reactor was replaced with nitrogen. After the solvent was separated from the reaction mixture by decantation, 2 liters of n-hexane was added and stirred for 5 minutes to wash the preactivated catalyst, and a washing operation of separating the washing solvent by decantation was repeated four times. . Next, 2 liters of n-hexane was charged into the reactor, and the obtained preactivated catalyst was dispersed in n-hexane to form a slurry.

A portion of the obtained pre-activated catalyst / n-hexane slurry was collected, the solvent was separated, and the pre-activated catalyst obtained by drying under reduced pressure was analyzed. As a result, 0 g / g of the metallocene-supported catalyst was analyzed. 0.7 g of polypropylene was loaded.

[Production of Propylene / Ethylene Block Copolymer by Gas Phase Polymerization Process] Using the metallocene-supported catalyst prepared as described above, an internal volume of 100 L
In a pilot plant having two horizontal reactors having a stirrer rotating about a horizontal axis inside thereof in series,
Production of a propylene / ethylene block copolymer was continuously performed by a gas phase polymerization method. In this embodiment, the first
The second reactor is the first polymerization zone, where, first,
Propylene homopolymerization was carried out, followed by propylene / ethylene copolymerization in the second polymerization zone, the second reactor. As operating conditions, the temperature / pressure of the first reactor was 65 ° C./1.8 MPa gauge pressure, and the temperature / pressure of the second reactor was 50 ° C./1.5
The ethylene / propylene molar ratio in the second reactor supplying the ethylene monomer was set to 1.1 at a MPa gauge pressure. In addition to the above operating conditions, the second
The withdrawal amount of the propylene / ethylene block copolymer from the second reactor was set at 9 kg / hr,
In the second reactor, the metallocene-supported catalyst prepared as described above was mixed with 25 g of triethylaluminum at 1 g / hr based on the metallocene-supported catalyst before preactivation.
Mol / hr, and secondly, the reactor is continuously fed with 4.1 mmol of oxygen while maintaining a steady state while continuously producing the propylene / ethylene copolymer. went. As a result, as final products, MFR 220 g / 10 min, ethylene content 4.
A propylene / ethylene block copolymer having a weight of 4 kg and a BD of 400 kg / m ³ could be stably produced continuously for 5 days. The polymerization activity was 9,000 g · polymer / g · catalyst. In the propylene / ethylene block copolymer, the content of the propylene / ethylene random copolymer produced in the second step is 15% by weight, and the ethylene content in the propylene / ethylene random copolymer is , 30% by weight.

[0135]

According to the production method of the present invention, in the presence of a specific metallocene-supported catalyst and an organoaluminum compound, two or more horizontal reactors having a stirrer rotating around a horizontal axis are provided in series. Conventionally, propylene or propylene and other olefins other than propylene are continuously polymerized or copolymerized by a multistage polymerization method using a gas phase polymerization process comprising at least a first polymerization zone and a second polymerization zone. A propylene (co) polymer which is difficult to produce and difficult to produce continuously can be easily produced.

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Claims (4)

[Claims] 1. The method according to claim 1, wherein at least a first polymerization zone and a second polymerization zone are provided in series with two or more horizontal reactors having a stirrer rotating around a horizontal axis in the presence of a metallocene-supported catalyst and an organoaluminum compound. A propylene polymer or a propylene / olefin copolymer characterized by continuously polymerizing or copolymerizing propylene or propylene with another olefin other than propylene by a multi-stage polymerization method using a gas-phase polymerization process. Production method. 2. The propylene polymer is a propylene homopolymer, and the propylene / olefin copolymer contains 0.1 to 50% by weight of an olefin other than propylene. The method for producing a propylene polymer or a propylene / olefin copolymer according to claim 1, which is a copolymer, a block copolymer or a random block copolymer. 3. The propylene polymer or propylene / olefin copolymer according to claim 1, wherein the olefin other than propylene is ethylene and / or 1-butene. Manufacturing method of coalescence. 4. A metallocene-supported catalyst is prepared by sequentially carrying out the following steps (a) to (c): (II) or the following steps (a) to (d): The propylene polymer or propylene / polypropylene according to any one of claims 1 to 3, which is a preactivated metallocene-supported catalyst (I-I) obtained by performing the method.
A method for producing an olefin copolymer. (A) a step of reacting a metallocene compound with an aluminoxane in an inert solvent to obtain a metallocene catalyst; and (b) a step of reacting the metallocene catalyst obtained in the above step (a) with the inorganic fine particle carrier in the presence of an inert solvent. Contacting the metallocene catalyst on the inorganic fine particle carrier by contacting at a temperature of 85 to 150 ° C. to obtain a crude metallocene supported catalyst (II);
(C) a metallocene carrier purified by washing the slurry containing the crude metallocene-supported catalyst (II) obtained in the above step (b) at least twice with an aliphatic hydrocarbon at a temperature of -50 to 50 ° C. Obtaining a type catalyst (II), (d) above
(c) The metallocene-supported catalyst (II) obtained in the step is brought into contact with an olefin to prepolymerize the olefin, and 0.01 to 100 k / kg of the metallocene-supported catalyst (II).
a step of further supporting g of the olefin prepolymer on the metallocene-supported catalyst (II) to obtain a preactivated metallocene-supported catalyst (II).