JP5201940B2 - Propylene polymer production method - Google Patents

Description

  The present invention relates to a method for producing a propylene polymer, and more particularly, to a method for producing a propylene polymer having high ethylene and α-olefin uptake efficiency using an olefin polymerization catalyst containing a metallocene compound.

Crystalline polypropylene is widely used in various molding fields because of its excellent mechanical properties and chemical resistance. However, a propylene homopolymer or a random copolymer with a small amount of an α-olefin has high rigidity but may have insufficient impact resistance.
Therefore, a rubber component such as ethylene-propylene rubber (EPR) is added to the propylene homopolymer, or after propylene homopolymerization, the propylene and ethylene or α-olefin are subsequently copolymerized to contain the rubber component. The impact resistance has been improved by producing so-called block copolymers. Furthermore, flexibility and impact resistance can be improved by increasing the amount of the rubber component of the block copolymer.

Another problem is that the propylene block copolymer obtained by polymerization in the presence of a conventional Ziegler-Natta type catalyst has low molecular weight components (oligomer components, etc.) due to the nature of the catalyst. Exists. Particularly in recent years, there is a tendency to improve the moldability of the obtained propylene-based block copolymer by increasing the fluidity.
However, if the fluidity of the rubber part is increased too much, the generation ratio of low molecular weight components increases accordingly, and this low molecular weight component not only causes generation of smoke and odor during processing, but also after processing. It is known to cause various problems such as adverse effects on odor and taste, and deterioration of blocking properties due to stickiness. When the powder property of the polymerized polymer deteriorates, stable production cannot be performed, which is a problem. On the other hand, when the difference in the average molecular weight between the crystalline polypropylene and the rubber part is increased, problems such as an increase in gel during molding and an increase in linear expansion coefficient occur.

On the other hand, it is known that propylene is polymerized to obtain isotactic polypropylene using a metallocene-based catalyst different from the conventional Ziegler-type catalyst system. It is also known to produce a so-called block copolymer by copolymerizing ethylene and propylene after homopolymerization of propylene using the same catalyst (for example, see Patent Documents 1 and 2). Furthermore, a propylene-ethylene block copolymer having good rigidity and impact properties is also disclosed (for example, see Patent Document 3).
In particular, in the propylene-ethylene block copolymer, in order to exhibit high impact resistance, for example, it is necessary to exhibit a lower glass transition temperature. To satisfy this, propylene and ethylene or α -It is said that it is preferable to perform copolymerization with an olefin so that each content may satisfy | fill a certain range (for example, refer nonpatent literature 1).
Many examples of the transition metal compound constituting the metallocene catalyst have already been known. In particular, in order to improve the rigidity of a propylene-ethylene block copolymer, a transition metal compound that gives a homopolypropylene having a high melting point is already known (see, for example, Patent Document 4).

However, when such a propylene-based block copolymer is produced with a metallocene-based catalyst, the following technical problems have arisen due to the difference in reactivity between propylene and other comonomers.
That is, when propylene and ethylene or α-olefin are copolymerized after propylene homopolymerization by a conventional production method using a metallocene catalyst, propylene / (ethylene or α-olefin) gas in the polymerization atmosphere The composition ratio and the polymerization amount ratio of the amount of propylene polymerized under the atmosphere / (ethylene amount or α-olefin amount) are greatly different, and the polymer (ethylene or α-olefin) polymerization amount may decrease. To do. In other words, in order to obtain a copolymer having the desired ethylene or α-olefin content, it is necessary to polymerize by supplying a gas having a monomer ratio greatly different from the content in the copolymer. there were. Furthermore, in extreme cases, a copolymer having a desired content may not be produced due to limitations of the polymerization apparatus.
For example, as an example showing the difference in ethylene content between an ethylene / propylene mixed gas and a polymer, in Example 8 of Patent Document 5, a complex having a methylfuryl group introduced at the 2-position of an indenyl ligand was used. After propylene polymerization with a supported catalyst, a mixed gas of ethylene / propylene = 50/50 is supplied to produce a block copolymer. As a result, the ethylene unit content of the ethylene / propylene copolymer component is 30.9 mol%, which is about 20% lower than the molar ratio of the mixed gas.

Thus, in the catalyst using the metallocene complex, the difference in ethylene content between the ethylene / propylene mixed gas and the polymer is large, and it is strongly desired to develop a production method with high ethylene and α-olefin uptake efficiency that eliminates this difference. ing.
In addition, when a metallocene catalyst known so far is used, when copolymerization of propylene and ethylene or α-olefin is carried out in the gas phase, there is a problem that the molecular weight of the resulting copolymer is low. In order to express high impact resistance in a propylene-ethylene block copolymer, it is necessary that the molecular weight of the copolymer has a certain value or more, and a production method capable of producing a high molecular weight copolymer Is also desired. In addition, development of a catalyst having high rubber activity is also desired in order to reduce the unit cost of the catalyst per unit polymer and to increase the content of the rubber part.
JP-A-4-337308 JP-A-6-287257 JP 2003-206325 A Japanese Patent Laid-Open No. 11-240909 JP 2004-2259 A Polymer, 2001, 42, 9611

An object of the present invention is to provide a propylene-based polymer having higher ethylene and α-olefin uptake efficiency than a conventional metallocene catalyst at the time of copolymerization of propylene and ethylene or α-olefin, in view of the problems of the prior art described above. It is in providing the manufacturing method of.
Another object of the present invention is to provide a method for producing a propylene-based polymer which can contain a high activity and high molecular weight rubber component.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a metallocene compound (a) having zirconium having a specific substituent as a central metal, particularly a metallocene compound having a heteroaromatic group at a specific position. By using a polymerization catalyst containing an acid-treated smectite group ion-exchange layered silicate (b) and an organoaluminum compound (c), a rubber component can be obtained with high ethylene and α-olefin uptake efficiency. By using as the component (a) a metallocene compound in which a specific substituent is introduced at the 4-position of the phenyl group at the 4-position of the indenyl ligand of the metallocene compound, the high molecular weight rubber component is highly active. The present invention was also found based on these findings.

That is, according to the first aspect of the present invention, there is provided a method for producing a propylene polymer using the following catalyst components (a), (b) and (c),
(I) a first step of polymerizing propylene in an amount of 90 to 100% by weight and ethylene or α-olefin in an amount of 0 to 10% by weight with respect to all monomer components; and (ii) 10 propylene with respect to all monomer components. A second step of polymerizing ˜90% by weight and 10% to 90% by weight of ethylene or α-olefin having 4 or more carbon atoms;
A process for producing a propylene-based polymer is provided.
Catalyst component (a): metallocene compound represented by the general formula [I]

[ Wherein Y represents a general formula: R ²⁰ ₂ A
(A is germanium or silicon, and R ²⁰ may be the same as or different from each other, and is hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a halogen having 1 to 6 carbon atoms. A containing alkyl group, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms, which may constitute a 4- to 7-membered ring containing A in both adjacent R ²⁰ , and 5 to 7 (It may contain an unsaturated bond in the member ring.)
It is a bivalent crosslinking group shown by these . X ¹ and X ² are each independently a ligand that forms a σ bond with Zr. R ¹ and R ¹¹ may be the same or different from each other, and have an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a substituent. And a heterocyclic group composed of a 5-membered ring or a 6-membered ring (wherein the heteroatom of the heterocyclic group constituting the 5-membered ring or 6-membered ring is not directly bonded to the alkadienyl group), R ¹ One or both of R ¹¹ and R ¹¹ is necessarily a C 3-6 alkyl group, or a heterocyclic group constituting a 5-membered ring optionally having a substituent. R ^{2 to} R ⁹ and R ^{12 to} R ¹⁹ may be the same as or different from each other, and are hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. A halogen-containing alkyl group, a silicon-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a 5-membered ring optionally having a substituent Or it is a heterocyclic group which comprises a 6-membered ring, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond. ]
Catalyst component (b): Acid-treated smectite group ion-exchange layered silicate Catalyst component (c): Organoaluminum compound

According to the second invention of the present invention, in the first invention, in the general formula [I], R ¹ and R ¹¹ are a furyl group or a thienyl group which may have a substituent. A method for producing a propylene-based polymer is provided.

According to the third invention of the present invention, in the first or second invention, in the general formula [I], R ⁴ and R ¹⁴ are each a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. An alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, a silicon-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms. There is provided a method for producing a propylene-based polymer characterized in that
According to a fourth invention of the present invention, in any one of the first to third inventions, the catalyst component (b) is a montmorillonite treated with an inorganic acid, and a method for producing a propylene-based polymer Is provided.
Furthermore, according to the fifth invention of the present invention, in any one of the first to fourth inventions, the first step is bulk polymerization using propylene as a solvent or gas phase polymerization for keeping the monomer in a gaseous state, The second step is a gas phase polymerization, and a method for producing a propylene polymer is provided.

  According to the method for producing a propylene polymer of the present invention, even in a plant in which the gas composition cannot be high, for example, the ethylene / propylene ratio, the rubber component is increased in ethylene and α in the production of the propylene polymer as compared with the conventional metallocene compound. -It can be polymerized with olefin uptake efficiency, can produce a rubber component with high ethylene content or high α-olefin content, and gives a copolymer with high molecular weight, so it has excellent flexibility and impact resistance A propylene-based polymer can be produced efficiently. For this reason, the manufacturing method of this invention is very useful from an industrial viewpoint.

The method for producing a propylene polymer of the present invention is a method for producing a propylene polymer using catalyst components (a), (b) and (c) described later,
(I) a first step of polymerizing propylene in an amount of 90 to 100% by weight and ethylene or α-olefin in an amount of 0 to 10% by weight with respect to all monomer components; and (ii) 10 to 90% of propylene with respect to all monomer components. A second step of polymerizing 10% to 90% by weight of ethylene or α-olefin having 4 or more carbon atoms,
By this step, the propylene polymer according to the present invention can be produced with high productivity.
Hereinafter, the manufacturing method of the propylene-type polymer of this invention is demonstrated in detail for every item.

1. Catalyst component The production method of the propylene-based polymer of the present invention uses a polymerization catalyst containing the following catalyst components (a), (b) and (c).

(1) Component (a):
The catalyst component (a) used in the present invention is a metallocene complex having zirconium as a central metal having a specific substituent represented by the general formula [I].

[Wherein Y is a dialkylmethylene group having an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or a divalent bridging group containing a halogenated aryl group having 6 to 18 carbon atoms in the skeleton; Or a divalent bridging group containing a silicon atom, a germanium atom, an oxygen atom, a nitrogen atom, a phosphorus atom or a boron atom, and X ¹ and X ² are each independently a coordination that forms a σ bond with Zr A child.
R ¹ and R ¹¹ may be the same or different from each other, and have an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a substituent. Or a heterocyclic group composed of a 5-membered ring or a 6-membered ring (however, a heteroatom of the heterocyclic group constituting the 5-membered ring or 6-membered ring is not directly bonded to the alkadienyl group). One or both of R ¹ and R ¹¹ is always a C 3-6 alkyl group or a heterocyclic group constituting a 5-membered ring which may have a substituent.
R ^{2 to} R ⁹ and R ^{12 to} R ¹⁹ may be the same as or different from each other, and are hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. A halogen-containing alkyl group, a silicon-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a 5-membered ring optionally having a substituent Or it is the heterocyclic group which comprises a 6-membered ring. Moreover, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond. ]

In the general formula [I], Y is a divalent methylene group having a C 1-6 alkyl group, a C 6-18 aryl group or a C 6-18 halogenated aryl group in the skeleton. A bridging group or a divalent bridging group containing a silicon atom, a germanium atom, an oxygen atom, a nitrogen atom, a phosphorus atom or a boron atom.
Specific examples of Y include dimethylmethylene, diphenylmethylene, bis (4-fluorophenyl) methylene, and examples of the bridging group containing a silicon atom include dimethylsilylene, diethylsilylene, di (n-propyl) silylene, Examples thereof include alkylsilylene groups such as di (i-propyl) silylene and di (cyclohexyl) silylene; alkenylsilylene groups such as divinylsilylene; arylsilylene groups such as diphenylsilylene; alkyl oligosilylene groups such as tetramethyldisilylene. it can. Examples of the crosslinking group containing a germanium atom include an alkylgermylene group in which silicon is substituted with germanium in the crosslinking group containing a silicon atom; an alkenylsilylene group; an arylgermylene group.

Among these, the general formula: R ²⁰ ₂ A
(A is germanium or silicon, and R ²⁰ may be the same as or different from each other, and is hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a halogen having 1 to 6 carbon atoms. A containing alkyl group, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms, which may constitute a 4- to 7-membered ring containing A in both adjacent R ²⁰ , and 5 to 7 (It may contain an unsaturated bond in the member ring.)
Is preferable from the viewpoint of the melting point and molecular weight of the resulting polymer, and dimethylsilylene, diethylsilylene, diphenylsilylene, dimethylgermylene, diethylgermylene, and diphenylgermylene are particularly preferable.

X ¹ and X ² are each independently a ligand that forms a σ bond with M, and are not particularly limited, but preferred X ¹ and X ² are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms. Or a substituted amino group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group. Among these, a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, a dimethylamino group or a diethylamino group is particularly preferable.

In the general formula [I], specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n -Pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like can be mentioned.
The aryl group having 6 to 18 carbon atoms may be substituted with an alkyl group. Specific examples include phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, t-butylphenyl, 1-naphthyl, Examples include 2-naphthyl, acenaphthyl, phenanthryl, and anthryl.
Examples of the halogen atom of the halogen-containing alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the substituent include fluoromethyl, difluoromethyl, trifluoromethyl, Chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, Pentafluoropropyl, nonafluorobutyl, 5-chloropentyl, 5,5,5-trichloropentyl, 5-fluoropentyl, 5,5,5-trifluoropentyl, 6-chlorohexyl, 6,6,6-trichlorohexyl , 6-Fluorohexyl, 6,6,6-trifluoro It can be mentioned hexyl.
Furthermore, examples of the halogen atom include chlorine, bromine, iodine, and fluorine.
Specific examples of the alkenyl group having 1 to 6 carbon atoms include vinyl, propenyl, allyl, butenyl, cyclohexenyl and the like.
Specific examples of the silicon-containing alkyl group having 1 to 6 carbon atoms include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl and the like.
Further, specific examples of the halogen-containing aryl group having 6 to 18 carbon atoms include 2-, 3-, 4-substituted fluorophenyl, 2-, 3-, 4-substituted chlorophenyl, 2-, 3- , 4-substituted bromophenyl, 2,4-, 2,5-, 2,6-, 3,5-substituted difluorophenyl, 2,4-, 2,5-, 2,6-, 3 , 5-substituted dichlorophenyl, 2,4,6-, 2,3,4-, 2,4,5-, 3,4,5-substituted trifluorophenyl, 2,4,6-, 2 3,4-, 2,4,5-, 3,4,5-substituted trichlorophenyl, pentafluorophenyl, pentachlorophenyl and the like.

  The heterocyclic group constituting the 5-membered ring or 6-membered ring which may have a substituent is a hetero atom which is not directly bonded to the alkadienyl group. Specific examples of the heterocyclic ring include pyrrolidyl, Pyridyl, pyrimidyl, quinolyl, isoquinolyl, carbazolyl, furyl, thienyl, thianofuryl, imidazolyl, pyrazolyl, pyrrolyl, oxazolyl, thiazolyl, isothiazolyl, isoxazolyl. Substituent of 6 alkenyl group, C1-C6 halogen-containing alkyl group, C1-C6 silicon-containing alkyl group, C6-C18 aryl group, or C6-C18 halogen-containing aryl group And may form a 5- to 7-membered ring with both adjacent atoms, in which an unsaturated bond is formed. It may be in.

Preferably, it is a heterocyclic ring containing a sulfur atom or an oxygen atom having a 5-membered ring structure, more preferably a furyl group which may have a substituent, or a thienyl group.
Specific examples of the furyl group or thienyl group include 2-furyl, 2- (5-methylfuryl), 2- (5-ethylfuryl), 2- (5-n-propylfuryl), 2- (5-i -Propylfuryl), 2- (5-t-butylfuryl), 2- (5-trimethylsilylfuryl), 2- (5-triethylsilylfuryl), 2- (5-phenylfuryl), 2- (5-tolylfuryl) 2- (5-fluorophenylfuryl), 2- (5-chlorophenylfuryl), 2- (4,5-dimethylfuryl), 2- (3,5-dimethylfuryl), 2-benzofuryl, 3-furyl, 3- (5-methylfuryl), 3- (5-ethylfuryl), 3- (5-n-propylfuryl), 3- (5-i-propylfuryl), 3- (5-t-butylfuryl), 3- (5-trimethylsilylfree) ), 3- (5-triethylsilylfuryl), 3- (5-phenylfuryl), 3- (5-tolylfuryl), 3- (5-fluorophenylfuryl), 3- (5-chlorophenylfuryl), 3- (4,5-dimethylfuryl), 3-benzofuryl, 2-thienyl, 2- (5-methylthienyl), 2- (5-ethylthienyl), 2- (5-n-propylthienyl), 2- (5 -I-propylthienyl), 2- (5-t-butylthienyl), 2- (5-trimethylsilylthienyl), 2- (5-triethylsilylthienyl), 2- (5-phenylthienyl), 2- (5 -Tolylthienyl), 2- (5-fluorophenylthienyl), 2- (5-chlorophenylthienyl), 2- (4,5-dimethylthienyl), 2- (3,5-dimethylthienyl), 2- Nzothienyl, 3-thienyl, 3- (5-methylthienyl), 3- (5-ethylthienyl), 3- (5-n-propylthienyl), 3- (5-i-propylthienyl), 3- (5 -T-butylthienyl), 3- (5-trimethylsilylthienyl), 3- (5-triethylsilylthienyl), 3- (5-phenylthienyl), 3- (5-tolylthienyl), 3- (5-fluoro Phenylthienyl), 3- (5-chlorophenylthienyl), 3- (4,5-dimethylthienyl), 3-benzothienyl, and the like.

In general formula [I], one or both of R ¹ and R ¹¹ is necessarily an alkyl group having 3 to 6 carbon atoms, or a heterocyclic group constituting a 5-membered ring which may have a substituent. It is.
As an example of a C3-C6 alkyl group, the alkyl group may be cyclic, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, i -Pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, etc. can be mentioned. Preferably, it is a heterocyclic group constituting a 5-membered ring which may have a substituent, and more preferably a furyl group or thienyl which may have a substituent in terms of high ethylene incorporation efficiency It is a group.

  In the general formula [I], 6 to 7-membered rings may be constituted by both adjacent Rs, and the 6 to 7-membered ring may contain an unsaturated bond, and the indenyl ring is sterically and electronically environmentally friendly. A complex having a plurality of unique substituents and having a chemical, steric and electronic environment-specific structure is formed.

In general, when a metallocene compound is synthesized, isomers such as racemates and meso isomers are formed in an approximate 1: 1 ratio. Usually, a racemic body is used as the propylene polymerization catalyst, and it is necessary to separate the racemic body from the racemic body / meso body mixture.
However, the metallocene compound according to the present invention in which the 2-position substituents (R ¹ and R ¹¹ ) of the indenyl ring are simultaneously converted to an aryl group, a halogen-containing aryl group, a heterocyclic group or a substituted heterocyclic group is a complex. Since the racemate is produced with a selectivity of 85% or more when separated, and the separation is easy, the racemate can be obtained in a high yield. Such a structure is useful in the synthesis. .

In general formula [I], both or one of R ⁴ and R ¹⁴ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a halogen-containing alkyl group having 1 to 6 carbon atoms. , Having a substituent of a silicon-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a halogen-containing aryl group having 6 to 18 carbon atoms, A rubber component can be obtained, which is preferable.
R ² and R ¹² are hydrogen, and both or one of R ⁶ and R ¹² is a substituent other than hydrogen, preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or 1 carbon atom. A metallocene compound having a halogen-containing alkyl group of ˜6 and a silicon-containing alkyl group of 1 to 6 carbon atoms is also preferable because a rubber component having a high molecular weight can be obtained.
In addition, an alkyl group having 1 to 6 carbon atoms in which R ¹ is bonded to an indenyl ring with carbon having no branch, 3 to 6 alkyl groups in which R ¹¹ is bonded with a carbon having a branch, or a substituent A metallocene compound having a heterocyclic group constituting a 5-membered ring which may have a high activity is preferable because it can produce a rubber component having a high molecular weight. R ¹¹ is particularly preferably a heterocyclic group constituting a 5-membered ring which may have a substituent.

(2) Specific examples of metallocene compounds:
Preferred specific examples of the metallocene compound used in the production method of the present invention are shown below.
Dimethylsilylenebis (2- (2-methylfuryl) -4-phenylindenyl) zirconium dichloride,
Dimethylsilylenebis (2- (2-methylfuryl) -4- (4-methylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (2-methylfuryl) -4- (4-i-propylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-methylfuryl) -4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-methylfuryl) -4- (4-biphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-methylfuryl) -4- (3,5-dimethylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-methylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (4,5-dimethylfuryl) -4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-tert-butylfuryl) -4- (4-tert-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-phenylfuryl) -4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (4,5-benzofuryl) -4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (4,5-dimethylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-t-butylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (5-phenylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (4,5-benzofuryl) -4- (3,5-di-t-butylphenyl) indenyl) zirconium dichloride,

Dimethylsilylene (2- (2-methylfuryl) -4-phenylindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4-phenylindenyl) (2-ethyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4- (4-t-butylphenyl) indenyl) (2-methyl-4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4- (4-t-butylphenyl) indenyl) (2-ethyl-4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) (2-methyl-4- (3,5-di-t-butylphenyl) indenyl) zirconium Dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) (2-ethyl-4- (3,5-di-t-butylphenyl) indenyl) zirconium Dichloride,
Dimethylsilylene (2- (2-methylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) (2-i-propyl-4- (3,5-di-t-butylphenyl) indenyl ) Zirconium dichloride,

Dimethylsilylene (2- (2,3-di-methylfuryl) -4-phenylindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4-phenylindenyl) (2-ethyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4-phenylindenyl) (2-i-propyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4- (4-tert-butylphenyl) indenyl) (2-methyl-4- (4-tert-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4- (4-tert-butylphenyl) indenyl) (2-ethyl-4- (4-tert-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4- (4-tert-butylphenyl) indenyl) (2-i-propyl-4- (4-tert-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) (2-methyl-4- (3,5-di-t-butylphenyl) ) Indenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) (2-ethyl-4- (3,5-di-t-butylphenyl) ) Indenyl) zirconium dichloride,
Dimethylsilylene (2- (2,3-di-methylfuryl) -4- (3,5-di-t-butylphenyl) indenyl) (2-i-propyl-4- (3,5-di-t-) Butylphenyl) indenyl) zirconium dichloride,

Dimethylsilylene (2-i-propyl-4-phenylindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2-i-propyl-4-phenylindenyl) (2-ethyl-4-phenylindenyl) zirconium dichloride,
Dimethylsilylene (2-i-propyl-4- (4-t-butylphenyl) indenyl) (2-methyl-4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2-i-propyl-4- (4-t-butylphenyl) indenyl) (2-ethyl-4- (4-t-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2-i-propyl-4- (3,5-di-tert-butylphenyl) indenyl) (2-methyl-4- (3,5-di-tert-butylphenyl) indenyl) zirconium dichloride,
Dimethylsilylene (2-i-propyl-4- (3,5-di-tert-butylphenyl) indenyl) (2-ethyl-4- (3,5-di-tert-butylphenyl) indenyl) zirconium dichloride,

In addition, instead of dimethylsilylene, the cross-linked portion Y of the exemplified compound is a compound of diethylsilylene, diphenylsilylene, dimethylgermylene, diethylgermylene, diphenylgermylene, and X ¹ and X ² are substituted for the exemplified chlorine In addition, compounds in which one or both are substituted with a fluorine atom, a bromine atom, an iodine atom, a methyl group, a phenyl group, a benzyl group, a dimethylamino group, a diethylamino group, or the like can also be exemplified.

(3) Synthesis method of metallocene compound:
The metallocene compound used in the present invention can be synthesized by any method depending on the substituent or the mode of bonding. An example of a typical synthesis route is shown below.

The starting material 1 is lithiated with alkyllithium, then reacted with trialkoxyborane and hydrolyzed to give 2. 3 is obtained by performing the coupling reaction of 2 and 4-bromoindene in the presence of a palladium catalyst or the like. The bromination of 3 to 4 can be performed by the method described in the literature (J. Org. Chem. 1982, 47, 705-709). By performing the coupling reaction of 4 and furylboric acid in the presence of a palladium catalyst or the like, 5 is obtained. 5 is obtained by reaction with YCl ₂ such as dimethyldichlorosilane. After lithiation of 6 with alkyllithium, the desired metallocene compound 7 is obtained by reaction with ZrX ¹ X ² Cl ₂ .
The synthesis of a metallocene compound into which a substituent is introduced can be synthesized by using a corresponding substitution raw material, and by using a corresponding boric acid, such as phenylboronic acid, thienylboric acid, etc., instead of furylboranoic acid. The corresponding 2-position substituent (R ¹ , R ¹¹ ) can be introduced, and when an alkyl group is introduced into the 2-position substituent (R ¹ , R ¹¹ ), as described in the literature (J. Org Chem. 1984, 49, 4226), 4 can be introduced by reacting a Grignard reagent with Ni catalyst.
The synthesis of metallocene compounds with different substituents on the two indenyl rings can be bridged by reacting different substituted indenes with YCl ₂ in turn. Further, a crosslinking aid such as an amine compound (for example, methylimidazole) may be present during crosslinking.

(4) Component (b):
An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Various known silicates are known, and are specifically described in Shiramizu Haruo "Clay Mineralogy" Asakura Shoten (1995).
In the present invention, those used as the component (b) belong to the smectite group, and specific examples include montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite and the like. Among these, montmorillonite is preferable in terms of the activity and molecular weight of the rubber component.
Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (such as quartz and cristobalite) other than ion-exchanged layered silicates. Hybrids may be contained in the smectite silicate.

(5) Granulation of ion exchange layered silicate:
Silicates may be used in a dry state or in a slurry state in a liquid. In addition, the shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or a shape by operations such as pulverization, granulation, and classification. You may use the processed ion exchange layered silicate. Of these, the use of granulated silicate is particularly preferred because it gives good polymer particle properties.
The shape processing of the ion-exchange layered silicate such as granulation, pulverization, and classification may be performed before the acid treatment, or the shape may be processed after the acid treatment.

  Examples of the granulation method used here include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, fluidized bed granulation method, emulsion granulation method. , Submerged granulation method, compression molding granulation method, and the like, but are not particularly limited. Preferably, agitation granulation method, spray granulation method, rolling granulation method, and fluidized granulation method are exemplified, and particularly preferably, agitation granulation method and spray granulation method are exemplified.

  When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium for the raw slurry. Preferably, water is used as a dispersion medium. The concentration of the component (b) in the raw slurry liquid for spray granulation from which spherical particles are obtained is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 10% by weight. . The inlet temperature of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example.

  In granulation, in order to obtain a carrier having high particle strength and to improve propylene polymerization activity, the silicate is refined as necessary. The silicate may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible. Preferably, wet pulverization using water as a dispersion medium and utilizing the swellability of silicate, for example, a method using forced stirring using polytron or the like, a method using dyno mill, pearl mill, or the like. The average particle size before granulation is 0.01 to 3 μm, preferably 0.05 to 1 μm.

  Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation. Examples of the binder used include magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycols and the like.

  The spherical particles obtained as described above preferably have a compression fracture strength of 0.2 MPa or more in order to suppress crushing and fine powder generation in the polymerization step. The particle size of the granulated ion-exchange layered silicate is in the range of 0.1 to 1000 μm, preferably 1 to 500 μm. There is no particular limitation on the pulverization method, and either dry pulverization or wet pulverization may be used.

(6) Acid treatment:
The silicate used in the present invention is used after being subjected to an acid treatment, but may be treated by combining other chemical treatments. Other chemical treatments include alkali treatment, salt treatment, organic matter treatment, and the like.
The acid treatment of the silicate can change the acid strength of the solid. In addition to the effect of ion exchange and removal of surface impurities, the acid treatment also has an effect of eluting part of cations such as Al, Fe, Mg, Li having a crystal structure.
Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Two or more of these may be used simultaneously. Of these, inorganic acids are preferable, sulfuric acid, hydrochloric acid and nitric acid are preferable, and sulfuric acid is more preferable.
A method in which acid treatment and salt treatment are combined is particularly preferable, a method in which acid treatment is performed after salt treatment, a method in which salt treatment is performed after acid treatment, a method in which salt treatment and acid treatment are performed simultaneously, and salt treatment are performed. There is a method in which salt treatment and acid treatment are performed at the same time.

The treatment conditions with the acid are usually selected from the conditions where the acid concentration is 0.1 to 30% by weight, the treatment temperature is the temperature range from room temperature to the boiling point of the solvent used, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the conditions under which at least a part is eluted. The acid is generally used as an aqueous solution. For example, when sulfuric acid is used, the treatment temperature is preferably 80 ° C. to 100 ° C., and the treatment time is preferably 0.5 hours or more and less than 5 hours.
By performing the salt treatment at the same time, the surface area and interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, or the like. For example, a layered substance in a state where the layers are expanded can be obtained by replacing the exchangeable ions between the layers with other large and bulky ions using ion exchange.
When performing the above acid treatment, shape control may be performed by pulverization or granulation before treatment, during treatment, or after treatment. Further, other chemical treatments such as alkali treatment, organic compound treatment, and organometallic treatment may be used in combination.

The salt used for the ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of 1 to 14 atoms, and preferably selected from the group consisting of 1 to 14 atoms. And a compound comprising a cation containing at least one atom and an anion derived from at least one atom or atomic group selected from the group consisting of a halogen atom, an inorganic acid and an organic acid. Is a cation containing at least one atom selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₃ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOC It is a compound comprising at least one anion selected from the group consisting of H, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ . Two or more of these salts may be used simultaneously.

As the component (b) thus obtained, the pore volume having a radius of 20 mm or more measured by a mercury intrusion method is preferably 0.1 cc / g or more, particularly 0.3 to 5 cc / g. When the component (b) is treated in an aqueous solution, it contains adsorbed water and interlayer water. Here, adsorbed water is water adsorbed on the silicate surface or crystal fracture surface, and interlayer water is water existing between crystal layers.
The silicate is preferably used after removing adsorbed water and interlayer water as described above. The dehydration method is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is a temperature range in which the adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the weight loss of component (b) after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when a silicate having a weight loss adjusted to 3% by weight or less is used, the same weight loss state is maintained even when contacting the component (a) and the component (c). It is preferable to handle them.

(7) Composition after acid treatment of silicate:
The acid-treated silicate which is the component (b) according to the present invention has an Al / Si atomic ratio of 0.01 to 0.29, preferably 0.03 to 0.25, and more preferably. Is preferably in the range of 0.05 to 0.23 in view of the activity of the polymerization catalyst and the molecular weight of the rubber component.
The Al / Si atomic ratio is an index of the acid treatment strength of the clay portion, and the method for controlling the Al / Si atomic ratio is controlled by adjusting the acid species for acid treatment, the acid concentration, the acid treatment time, and the temperature. can do.
Aluminum and silicon in the silicate are measured by a method in which a calibration curve is prepared by a chemical analysis method by JIS method and quantified by fluorescent X-rays.

(8) Component (c):
An example of the organoaluminum compound is represented by the following general formula.
AlR _a X _3-a
In the general formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents hydrogen, halogen, an alkoxy group, or a siloxy group, and a represents a number greater than 0 and 3 or less.
Specific examples of the organoaluminum compound represented by the general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, halogen or alkoxy such as diethylaluminum monochloride, diethylaluminum monomethoxide An alkyl aluminum is mentioned. Of these, trialkylaluminum is preferred. Two or more of the above organoaluminum compounds may be used in combination.

2. Preparation Method of Catalyst In the preparation method of the catalyst for olefin polymerization according to the present invention, the contact method of component (a), component (b) and component (c) is not particularly limited, but the following method is exemplified. be able to. (1) Method of adding component (c) after contacting component (a) and component (b) (2) After contacting component (a) and component (c), component (b) (3) Method of adding component (a) after contacting component (b) and component (c) (4) Contacting components (a), (b), and (c) simultaneously Let

Further, different components may be used as a mixture in each component, or the components may be contacted in different orders. 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.
Alternatively, the components may be divided and brought into contact with each component, such as adding a mixture of component (a) and component (c) after contacting component (b) and component (c).
The contact of each of the components (a), (b), and (c) is preferably performed in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, and xylene in an inert gas such as nitrogen. The contact can be performed at a temperature between −20 ° C. and the boiling point of the solvent, and is preferably performed at a temperature between room temperature and the boiling point of the solvent.

  In the polymerization catalyst according to the present invention, the amount of component (a), component (b) and component (c) used is 0.001 to 10 mmol of the metallocene compound of component (a), preferably 1 to 1 g of component (b), preferably The range is 0.001 to 1 mmol. The amount of the component (c) used is an Al / metallocene compound molar ratio of 0.1 to 100,000, preferably 1 to 10,000. These use ratios show examples of normal ratios, and the present invention is limited by the range of use ratios described above as long as the catalyst meets the purpose of the present invention. Must not.

  Before using the catalyst containing the components (a), (b) and (c) as a catalyst for olefin polymerization (main polymerization), ethylene, propylene, 1-butene, 1-hexene and 1-octene are optionally used. , 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and other olefins may be preliminarily polymerized in a small amount. As the prepolymerization method, a known method can be used.

3. Polymerization method As long as the polymerization catalyst including the component (a), the component (b) and the component (c) and the monomer are in efficient contact with each other, any mode can be adopted.
Specifically, a slurry method using an inert solvent, a bulk polymerization method using propylene as a solvent without substantially using an inert solvent, or a gas phase polymerization method for maintaining each monomer in a gaseous state without using a liquid solvent. Etc. can be adopted. As the polymerization method, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied.
In addition, the combination of polymerization types is not particularly limited, and a mode such as two stages of bulk polymerization, gas phase polymerization after bulk polymerization, and two stages of gas phase polymerization is possible. Is possible.
In order to obtain a polymer with particularly good particle shape, the first step is performed by bulk polymerization and the second step is performed by gas phase polymerization, or both the first step and the second step are performed by gas phase polymerization. preferable.

[First step]:
The first step is a step of polymerizing propylene 100 to 90% by weight and ethylene or α-olefin at 0 to 10% by weight with respect to all monomer components.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is suitably from 0 to 3 MPaG, preferably from 0 to 2 MPaG.
In the case of the bulk polymerization method, the polymerization temperature is 0 to 90 ° C, preferably 60 to 80 ° C. The polymerization pressure is 0 to 5 MPaG, preferably 0 to 4 MPaG.
In the case of gas phase polymerization, the polymerization temperature is 0 to 200 ° C, preferably 50 to 120 ° C, more preferably 60 to 100 ° C. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 0 to 3 MPaG.
Further, ethylene or α-olefin can coexist in the range of 0 to 10% without deteriorating the polymer shape with respect to all monomer components, and the molecular weight, activity and melting point can be adjusted. Moreover, you may use hydrogen as a molecular weight modifier.

[Second step]:
The second step is a step of polymerizing propylene in an amount of 10 to 90% by weight and ethylene or α-olefin in an amount of 10 to 90% by weight with respect to all monomer components, and a rubber component exhibiting suitable impact resistance is produced. be able to. The amount of propylene with respect to the monomer component is preferably 20 to 80% by weight in terms of giving a propylene polymer having high impact resistance.
As polymerization conditions in the second step, slurry polymerization and bulk polymerization are the same as those in the first step. However, in the case of gas phase polymerization, the monomer composition is different from that in the first step. ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C. The polymerization pressure is suitably from 0 to 4 MPaG, preferably from 1 to 3 MPaG. Further, hydrogen may be used as a molecular weight regulator.

  In the second step, when ethylene is used as a monomer, the propylene polymer obtained in the present invention has a portion containing ethylene in a 100 ° C. soluble component in CFC-IR. Improvements in impact resistance and transparency are expected due to the site containing ethylene.

[Polymerization monomer]:
In the present invention, “α-olefin” refers to an olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, styrene, vinylcyclohexane, diene, triene, cyclic olefin and the like.
The monomer used together with propylene is preferably ethylene or 1-butene, and more preferably ethylene. Further, these monomers may be used in combination.

[Analysis of characteristic values of polymerized olefin polymer]
Content of copolymer component (rubber component, hereinafter referred to as “CP”) obtained in the second step in the propylene polymer obtained using the catalyst according to the present invention, ethylene in CP Alternatively, the α-olefin polymerization ratio is determined by the following method.
In addition, although the following examples are when ethylene in CP is used, α-olefins other than ethylene are obtained using a method according to the following examples.

(1) Analytical device to be used (i) Cross fractionation device CFC T-100 manufactured by Dia Instruments
(Ii) Fourier transform infrared absorption spectrum analysis (FT-IR)
・ Perkin Elmer 1760X
A fixed wavelength infrared spectrophotometer attached as a CFC (cross fractionation chromatography) detector is removed, and an FT-IR is connected instead, and this FT-IR is used as a detector.
The transfer line from the outlet of the solution eluted from the CFC to the FT-IR has a length of 1 m and is maintained at 140 ° C. throughout the measurement. The flow cell attached to the FT-IR has an optical path length of 1 mm and an optical path width of 5 mmφ, and the temperature is maintained at 140 ° C. throughout the measurement.
(Iii) Gel permeation chromatography (GPC)
Three GPC columns (AD806MS manufactured by Showa Denko KK) are connected in series to the subsequent stage of the CFC.

(2) CFC measurement conditions (i) Solvent: orthodichlorobenzene (ODCB)
(Ii) Sample concentration: 4 mg / mL
(Iii) Injection volume: 0.4 mL
(Iv) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 40 minutes.
(V) Sorting method:
The fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, and 140 ° C., and fractionation is performed in three fractions in total.
In addition, the elution ratio (unit:% by weight) of the component eluting at 40 ° C. or lower (fraction 1), the component eluting at 40 to 100 ° C. (fraction 2), and the component eluting at 100 to 140 ° C. (fraction 3), respectively It is defined as W40, W100, and W140. W40 + W100 + W140 = 100. Moreover, each fractionated fraction is automatically transported to the FT-IR analyzer as it is.
(Vi) Solvent flow rate during elution: 1 mL / min

(3) Measurement conditions of FT-IR After elution of the sample solution from GPC at the latter stage of the CFC starts, FT-IR measurement is performed under the following conditions, and GPC-IR data is collected for each of the above-described fractions 1 to 3. .
(I) Detector: MCT
(Ii) Resolution: 8 cm ⁻¹
(Iii) Measurement interval: 0.2 minutes (12 seconds)
(Iv) Number of integrations per measurement: 15 times

(4) Post-treatment and analysis of measurement results The elution amount and molecular weight distribution of the components eluted at each temperature are obtained using the absorbance at 2945 cm ⁻¹ obtained by FT-IR as a chromatogram. The elution amount is normalized so that the total elution amount of each elution component is 100%. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
(F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000)

A calibration curve is created by injecting 0.4 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × M ^α ) used at that time.
(I) Calibration curve using standard polystyrene K = 0.000138, α = 0.70
(Ii) Sample measurement of propylene-based block copolymer K = 0.000103, α = 0.78
The ethylene content distribution (distribution of ethylene content along the molecular weight axis) of each eluted component is a ratio of the absorbance of 2956 cm ⁻¹ and the absorbance of 2927 cm ⁻¹ obtained by GPC-IR, and is obtained by using polyethylene, polypropylene, or ¹³ Ethylene polymerization ratio (mol%) by a calibration curve prepared in advance using ethylene-propylene-copolymer (EPR) having a known ethylene content by C-NMR measurement or a mixture thereof. Calculate by converting to

(5) CP content The CP content of the propylene-based block copolymer in the present invention is defined by the following formula (I), and is determined by the following procedure.
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / B100 (I)

In formula (I), W40 and W100 are the elution ratios (unit: weight%) in each of the above-mentioned fractions, and A40 and A100 are the average ethylene content of actual measurement in each fraction corresponding to W40 and W100. (Unit: wt%), and B40 and B100 are the ethylene content (unit: wt%) of CP contained in each fraction. A method for obtaining A40, A100, B40, and B100 will be described later.
The meaning of the formula (I) is as follows.
That is, the first term on the right side of the formula (I) is a term for calculating the amount of CP contained in fraction 1 (portion soluble at 40 ° C.). When fraction 1 contains only CP and does not contain PP, W40 contributes to the CP content derived from fraction 1 as a whole, but fraction 1 contains a small amount of components in addition to CP-derived components. Since components derived from PP (extremely low molecular weight components and atactic polypropylene) are also included, it is necessary to correct the portion. Therefore, by multiplying W40 by A40 / B40, the amount derived from the CP component in fraction 1 is calculated. For example, when the average ethylene content (A40) of fraction 1 is 30% by weight and the ethylene content (B40) of CP contained in fraction 1 is 40% by weight, 30/40 = 3/4 of fraction 1 (Ie, 75% by weight) is derived from CP, and 1/4 is derived from PP. Thus, the operation of multiplying A40 / B40 by the first term on the right side means that the contribution of CP is calculated from the weight% (W40) of fraction 1. The same applies to the second term on the right side, and for each fraction, the CP content is calculated by adding and calculating the contribution of CP.

The average ethylene content A40 of fractions 1 to 3, A100, A140, the ethylene content of the weight ratio and each data point for each data point in the chromatogram absorbance 2945cm ^-1 (absorbance 2956Cm ^-1 and 2927cm ^{- (} Obtained from the ratio to the absorbance of ¹ ).
The ethylene content corresponding to the peak position in the differential molecular weight distribution curve of fraction 1 is defined as B40 (unit is% by weight).
Fraction 2 is considered to be completely eluted at 40 ° C. and cannot be defined with the same definition, so in the present invention, it is defined as B100 = 100. B40 and B100 are ethylene contents of CP contained in each fraction, but it is practically impossible to obtain this value analytically. The reason is that there is no means for completely separating and separating PP and CP mixed in the fraction.
As a result of studies using various model samples, B40 can rationally explain the effect of improving material properties when the ethylene content corresponding to the peak position of the differential molecular weight distribution curve of fraction 1 is used. I found that I can do it. Moreover, B100 has crystallinity derived from ethylene chain, and for two reasons that the amount of CP contained in these fractions is relatively smaller than the amount of CP contained in fraction 1, Approximation with 100 is closer to the actual situation, and there is almost no error in calculation. Therefore, the analysis is performed with B100 = 100.
Therefore, the CP content can be determined according to the following formula (II).
CP content (% by weight) = W40 × A40 / B40 + W100 × A100 / 100 (II)

That is, W40 × A40 / B40, which is the first term on the right side of formula (II), indicates the CP content (% by weight) having no crystallinity, and W100 × A100 / 100, which is the second term, represents the crystallinity. The CP content (% by weight) is shown.
The ethylene content in the copolymer component is determined by the following formula (III) using the content of the copolymer component determined by the formula (II).
Ethylene content (% by weight) in copolymer component = (W40 × A40 + W100 × A100 + W140 × A140) / [content of copolymer component (% by weight)] (III)

The significance of setting the three types of fractionation temperatures is as follows.
In the CFC analysis according to the present invention, 40 ° C. means only a polymer having no crystallinity (for example, most of CP or a component having extremely low molecular weight and atactic component among propylene polymer components (PP)). It has the meaning that it is a temperature condition necessary and sufficient for fractionation. 100 ° C. means only components that are insoluble at 40 ° C. but become soluble at 100 ° C. (eg, components having crystallinity due to the chain of ethylene and / or propylene and PP having low crystallinity in CP) The temperature is necessary and sufficient to elute. 140 ° C. is a component that is insoluble at 100 ° C. but becomes soluble at 140 ° C. (for example, a component having particularly high crystallinity in PP and a component having extremely high molecular weight and extremely high ethylene crystallinity in CP ) Only, and the temperature is necessary and sufficient to recover the entire amount of the propylene-based block copolymer used for the analysis.
W140 does not contain any CP component, or even if it is present, it is extremely small and can be substantially ignored. Therefore, it is excluded from the calculation of the CP content and the ethylene content.

(6) Ethylene polymerization ratio The ethylene content in CP is determined by the following formula.
Ethylene content (% by weight) in CP = (W40 × A40 + W100 × A100) / [CP]
However, [CP] is the CP content (% by weight) determined previously.
From the value of the ethylene content (% by weight) in the CP obtained here, the molecular weight of ethylene and propylene is finally used to convert to mol%.

Hereinafter, in order to describe the present invention more specifically and clearly, the present invention will be described in contrast to Examples and Comparative Examples, and the rationality and significance of the constituent elements of the present invention and the superiority over the prior art will be demonstrated. To do.
In the following examples, the complex synthesis step, the catalyst synthesis step, and the polymerization step were all performed under a purified nitrogen atmosphere, and the solvent was dehydrated and then bubbled with purified nitrogen and used after deaeration. In addition, physical property measurement, analysis, and the like in the examples are according to the above-described method and the following method.

(1) MFR measurement:
To 6 g of polymer, 6 g of an acetone solution (0.6 wt%) of a heat stabilizer (BHT) was added. Subsequently, after drying said polymer, it filled with the melt indexer (230 degreeC), and was left to stand on the conditions of a 2.16kg load for 5 minutes. Thereafter, the extrusion amount of the polymer was measured, converted into an amount per 10 minutes, and used as the MFR value (unit: g / 10 minutes).

(2) Measurement of melting point (Tm):
Using DSC (TA2000 model manufactured by DuPont or DSC6200 model manufactured by Seiko Instruments Inc.), the temperature is raised and lowered once from 20 to 200 ° C. at 10 ° C./min, and then the second time at 10 ° C./min. It was determined from the measured value at the time of temperature rise.

[Example 1]
(1-1) Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4-phenyl-indenyl) zirconium dichloride (metallocene compound A) Synthesis was performed with reference to the method described in Example 1 to obtain a racemate (purity 99% or more).

(1-2) Chemical treatment (acid treatment and salt treatment) of smectite group ion-exchange layered silicate
Acid treatment:
Add 1130 g of distilled water and 750 g of 96% sulfuric acid to a separable flask, keep the internal temperature at 90 ° C., and add Benclay SL (average particle size 19 μm, 300 g) manufactured by Mizusawa Chemical Co., Ltd., which is granulated montmorillonite, for 2 hours. Reacted. The suspension was cooled to room temperature in 1 hour and washed with distilled water to pH = 4. The washing magnification at this time was 1/10000 or less.
Salt treatment:
In a separable flask, 210 g of lithium sulfate monohydrate was dissolved in 520 g of distilled water, and filtered acid-treated clay was added thereto, followed by stirring at room temperature for 120 minutes. The slurry was filtered, 3000 ml of distilled water was added to the obtained solid, and the mixture was stirred for 5 minutes at room temperature. The slurry was filtered. To the obtained solid, 2500 ml of distilled water was added, stirred for 5 minutes, and then filtered again. This operation was repeated four more times. The obtained solid was pre-dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain chemically treated montmorillonite. Obtained.
The composition of this chemically treated montmorillonite is Al: 7.5 wt%, Si: 37.6 wt%, Mg: 1.22 wt%, Fe: 1.60 wt%, Li: 0.22 wt%, and Al / Si = 0. 207 [mol / mol].

(1-3) Catalyst preparation using metallocene compound A (catalyst A)
To the flask having an internal volume of 1 L, 10.0 g of the chemically treated montmorillonite obtained above was weighed, 65 ml of heptane and 35 ml (25 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the slurry amount was adjusted to 100 ml. To this, 1.67 ml (1.2 mmol) of a heptane solution of triisobutylaluminum was added and stirred for 10 minutes at room temperature. Further, a solution of 223 mg (293 μmol) of metallocene compound A in 60 ml of toluene was added and stirred at room temperature for 60 minutes.
Next, 340 ml of heptane was added to the above heptane slurry, introduced into a stirring autoclave having an internal volume of 1 L, and propylene was supplied at 40 ° C. at a constant rate of 10 g / hour for 120 minutes. After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours. Thereafter, the residual gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 28.8 g of a solid catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.80.

(1-4) First step of propylene-propylene / ethylene block copolymerization with catalyst A:
After sufficiently replacing the inside of the stirring autoclave with an internal volume of 3 L with propylene, 2.76 ml (2.02 mmol) of n-heptane solution of triisobutylaluminum was added, and 300 ml of hydrogen and then 750 g of liquid propylene were introduced. The temperature was raised to 65 ° C. and the temperature was maintained. Catalyst A was slurried in n-heptane, and 30 mg of catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature inside the tank was maintained at 65 ° C., and after 1 hour from the addition of the catalyst, the remaining monomer was purged, and the inside of the tank was replaced with argon. Stirring was stopped, and while flowing argon, a Teflon (registered trademark) tube was inserted into the tank, and a small amount of polypropylene was extracted. The extracted amount was 15.5 g.

Second step:
Thereafter, propylene was introduced to 0.76 MPa at an internal temperature of 60 ° C., ethylene was subsequently introduced to 1.8 MPa, and the internal temperature was raised to 80 ° C. Thereafter, the polymerization reaction was controlled for 30 minutes while adjusting the internal pressure to 2.0 MPa while introducing a mixed gas of propylene and ethylene prepared in advance.

As a result, 173 g of propylene-propylene • ethylene block copolymer having good particle properties was obtained. The average gas mol composition in the tank during the polymerization of propylene and ethylene was propylene / ethylene = 43/57.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 9 wt%, and the ethylene content in rubber (CP) is 41 wt% (51 mol%). The weight average molecular weight (Mw) of the parts was 121,000, and the ethylene content at 100 ° C. was 0.6%. The rubber polymerization activity (CP activity) was 1,200 (g-CP / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 154 ° C. and an MFR of 162 (dg / min).

[Example 2]
(2-1) Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (2-naphthyl) -indenyl) zirconium dichloride (metallocene compound B) 4- (2-naphthylphenyl)- Indene synthesis:
To a 1000 ml glass reaction vessel, 40 g (0.19 mol) of 2-bromo-naphthalene, 200 ml of diethyl ether and 200 ml of hexane were added and cooled to -70 ° C. in a dry ice-methanol bath. To this was added dropwise 265 ml (0.39 mol) of a 1.46 mol / L t-butyllithium-pentane solution. After dropping, the mixture was stirred for 5 hours while gradually returning to room temperature. The solution was cooled again to -70 ° C in a dry ice-methanol bath, and 100 ml of a diethyl ether solution containing 50 ml (0.22 mol) of triisopropyl borate was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After adding 100 ml of distilled water to the reaction solution and stirring for 30 minutes, almost all of the organic phase was distilled off under reduced pressure. (0.15 mol) and 10 g (8.7 mmol) of tetrakis (triphenylphosphino) palladium were sequentially added, and then heated at 80 ° C. for 5 h.
The reaction solution was poured into 1 L of ice water, and then extracted with ether three times. The ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 30 g (yield 81%) of 4- (2-naphthyl) -indene as a pale yellow solid.

Synthesis of 2-bromo-4- (2-naphthyl) -indene:
To a 1000 ml glass reaction vessel, 30 g (0.13 mol) of 4-2 naphthyl) -indene, 300 ml of dimethyl sulfoxide (DMSO) and 9 ml of distilled water are added, and 29 g (0.16 mol) of N-bromosuccinimide is gradually added thereto. And stirred for 1 h at room temperature.
The reaction solution was poured into 1 L of ice water, and extracted from it three times with toluene. The toluene layer was washed with saturated brine, p-toluenesulfonic acid 3.3 g (17 mmol) was added in a 1000 ml glass reaction vessel, and the mixture was heated to reflux for 2 h while removing moisture.
The reaction solution was transferred to a separatory funnel and washed with brine until neutral. Sodium sulfate was added thereto and left overnight, and the reaction solution was dried. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 36 g (yield 89%) of 2-bromo-4- (2-naphthyl) -indene as a pale yellow solid.

Synthesis of 2- (2- (5-methylfuryl))-4- (2-naphthyl) -indene:
To a 1000 ml glass reaction vessel, 14 g (0.11 mol) of methylfuran and 300 ml of DME were added and cooled to −40 ° C. in a dry ice-methanol bath. 104 ml (0.17 mol) of a 1.60 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The solution was cooled again to −40 ° C. in a dry ice-methanol bath, and 100 ml of a DME solution containing 42 ml (0.18 mol) of triisopropyl borate was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
50 ml of distilled water was added to the reaction solution and stirred for 30 minutes, and then 36 g of sodium carbonate-100 ml of distilled water, 2-bromo-4- (2-naphthyl) -indene 36 g (0.11 mol), tetrakis (triphenylphosphino) ) 10 g (8.7 mmol) of palladium was added in order, and then heated while removing low boiling components and heated at 80 ° C. for 3 h.
The reaction solution was poured into 1 L of ice water, and then extracted with ether three times. The ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column, and 30 g of 2- (2- (5-methylfuryl))-4- (2-naphthyl) -indene (yield 82%). Was obtained as colorless crystals.

Synthesis of dimethylbis (2- (2- (5-methylfuryl))-4- (2-naphthyl) -indenyl) silane:
To a 1000 ml glass reaction vessel, 18 g (56 mmol) of 2- (2- (5-methylfuryl))-4- (2-naphthyl) -indene and 250 ml of THF are added, and cooled to -70 ° C. in a dry ice-methanol bath. did. 35 ml (56 mmol) of a 1.60 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was stirred for 2 hours while gradually returning to room temperature. The mixture was cooled again to -70 ° C in a dry ice-methanol bath, 0.2 ml (3 mmol) of 1-methylimidazole was added, and 100 ml of a THF solution containing 3.6 g (28 mmol) of dimethyldichlorosilane was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel, and washed with brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column. Dimethylbis (2- (2- (5-methylfuryl))-4- (2-naphthyl) -indenyl) silane 17 g (yield 87%) of a yellow solid was obtained.

Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (2-naphthyl) -indenyl) zirconium dichloride:
To a 300 ml glass reaction vessel was added 17 g (25 mmol) of dimethylbis (2- (2- (5-methylfuryl))-4- (2-naphthyl) -indenyl) silane and 250 ml of diethyl ether, and dry ice-methanol. Cooled to -70 ° C in bath. Thereto was added dropwise 31 ml (50 mmol) of a 1.60 mol / L n-butyllithium-hexane solution. After dropping, the mixture was stirred for 3 hours while returning to room temperature. The solvent of the reaction solution was distilled off under reduced pressure, 300 ml of toluene and 20 ml of diethyl ether were added, and the solution was cooled to -70 ° C. in a dry ice-methanol bath. Thereto, 5.7 g (25 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized with dichloromethane / hexane, and dimethylsilylenebis (2- (2 ′-(5′-methylfuryl))-4- (2-naphthyl) -indenyl) zirconium dichloride (metallocene compound). 9.4 g (yield 45%) of B) racemate (purity 99% or more) was obtained as yellow-orange crystals.
¹ H-NMR value (CDCl ₃ ) Racemate: δ 1.17 (s, 6H), δ 2.42 (s, 6H), δ 6.06 (d, 2H), δ 6.29 (d, 2H), δ6. 85 (dd, 2H), δ 6.97 (d, 2H), δ 7.12 (s, 2H), δ 7.43-7.47 (m, 6H), δ 7.77-7.91 (m, 8H) , Δ 8.15 (s, 2H).

(2-2) Preparation of catalyst using metallocene compound B (catalyst B)
Catalyst B was obtained in the same manner as the catalyst preparation described in [Example 1] (1-3) except that 255 mg (296 μmol) of metallocene compound B was used instead of metallocene compound A. At that time, the prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.78.

(2-3) Propylene-propylene / ethylene block copolymerization with catalyst B Instead of catalyst A, 30 mg of catalyst B was used, and the average gas mol composition in the tank during propylene / ethylene polymerization in the second step was propylene / ethylene. [Example 1] (1-4), except that the adjustment was made to be 30/70. As a result, 152 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 7 wt%, and the ethylene content in rubber (CP) is 58 wt% (67 mol%). The weight average molecular weight (Mw) of the parts was 134,000, and the ethylene content at 100 ° C. was 0.7%. The rubber polymerization activity (CP activity) was 900 (g-CP / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 153 ° C. and an MFR of 107 (dg / min).

[Example 3]
(3-1) Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) zirconium dichloride (metallocene compound C) 4- (4-t Synthesis of -butylphenyl) -indene:
To a 1000 ml glass reaction vessel, 40 g (0.19 mol) of 1-bromo-4-t-butyl-benzene and 400 ml of dimethoxyethane (DME) were added and cooled to −70 ° C. in a dry ice-methanol bath. 260 ml (0.38 mol) of a 1.46 mol / L t-butyllithium-pentane solution was added dropwise thereto. After dropping, the mixture was stirred for 5 hours while gradually returning to room temperature. The solution was cooled again to -70 ° C. in a dry ice-methanol bath, and 100 ml of a DME solution containing 46 ml (0.20 mol) of triisopropyl borate was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After adding 100 ml of distilled water to the reaction solution and stirring for 30 minutes, an aqueous solution of sodium carbonate 50 g-distilled water 150 ml, 4-bromoindene 30 g (0.15 mol), tetrakis (triphenylphosphino) palladium 5 g (4.3 mmol) Were added in order, and then the low-boiling components were removed, followed by heating at 80 ° C. for 5 hours.
The reaction solution was poured into 1 L of ice water, and then extracted with ether three times. The ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 37 g (yield 98%) of 4- (4-tert-butylphenyl) -indene as a pale yellow liquid.

Synthesis of 2-bromo-4- (4-t-butylphenyl) -indene:
To a 1000 ml glass reaction vessel, 37 g (0.15 mol) of 4- (4-t-butylphenyl) -indene, 400 ml of dimethyl sulfoxide (DMSO) and 11 ml of distilled water were added, and 35 g of N-bromosuccinimide (0. 20 mol) was gradually added, and the mixture was stirred at room temperature for 1 h.
The reaction solution was poured into 1 L of ice water, and extracted from it three times with toluene. The toluene layer was washed with saturated brine, p-toluenesulfonic acid 4.3 g (22 mmol) was added in a 1000 ml glass reaction vessel, and the mixture was heated to reflux for 2 h while removing moisture.
The reaction solution was transferred to a separatory funnel and washed with brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 46 g (yield 95%) of 2-bromo-4- (4-t-butylphenyl) -indene as a pale yellow solid. It was.

Synthesis of 2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indene:
Methylfuran (13.8 g, 0.17 mol) and DME (400 ml) were added to a 1000 ml glass reaction vessel, and cooled to -70 ° C in a dry ice-methanol bath. Thereto was added dropwise 111 ml (0.17 mol) of a 1.52 mol / L n-butyllithium-hexane solution. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The solution was cooled again to -70 ° C. in a dry ice-methanol bath, and 100 ml of a DME solution containing 41 ml (0.18 mol) of triisopropyl borate was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After adding 50 ml of distilled water to the reaction solution and stirring for 30 minutes, sodium carbonate 54 g-distilled water 100 ml aqueous solution, 2-bromo-4- (4-t-butylphenyl) -indene 46 g (0.14 mol), tetrakis (tri Phenylphosphino) palladium (5 g, 4.3 mmol) was sequentially added, and then the mixture was heated while removing low boiling components and heated at 80 ° C. for 3 h.
The reaction solution was poured into 1 L of ice water, and then extracted with ether three times. The ether layer was washed with saturated brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, the residue was purified with a silica gel column, recrystallized with hexane, and 2- (2- (5-methylfuryl))-4- (4-t-butylphenyl). ) -Indene (30.7 g, yield 66%) was obtained as colorless crystals.

Synthesis of dimethylbis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) silane:
To a 1000 ml glass reaction vessel, 22 g (66 mmol) of 2- (2- (5-methylfuryl))-4- (4-tert-butylphenyl) -indene and 200 ml of THF were added, and -70 in a dry ice-methanol bath. Cooled to ° C. To this, 42 ml (67 mmol) of a 1.60 mol / L n-butyllithium-hexane solution was added dropwise. After dropping, the mixture was stirred for 3 hours while gradually returning to room temperature. The mixture was cooled again to -70 ° C in a dry ice-methanol bath, 0.3 ml (3.8 mmol) of 1-methylimidazole was added, and 100 ml of a THF solution containing 4.3 g (33 mmol) of dimethyldichlorosilane was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel, and washed with brine until neutral. Sodium sulfate was added thereto and left overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. Dimethylbis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) 22 g (yield 92%) of a pale yellow solid of silane was obtained.

Synthesis of dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) zirconium dichloride:
To a 300 ml glass reaction vessel, 11 g (16 mmol) of dimethylbis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) silane and 200 ml of diethyl ether were added and dried. It cooled to -70 degreeC with the ice-methanol bath. 20 ml (32 mmol) of a 1.60 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was returned to room temperature and stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 200 ml of toluene and 10 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto, 3.7 g (16 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized from dichloromethane / hexane, and dimethylsilylene bis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) zirconium dichloride (metallocene). 1.3 g (yield 9%) of a racemate of compound C) (purity 99% or more) was obtained as yellow-orange crystals.
¹ H-NMR value (CDCl ₃ ) Racemate: δ 1.14 (s, 6H), δ 1.33 (s, 18H), δ 2.41 (s, 6H), δ 6.05 (d, 2H), δ 6. 27 (d, 2H), δ 6.80 (dd, 2H), δ 6.92 (d, 2H), δ 7.08 (s, 2H), δ 7.31 (d, 2H), δ 7.44 (d, 4H ), Δ 7.58 (d, 4H).

(3-2) Catalyst preparation using metallocene compound C (catalyst C)
Catalyst C was obtained in the same manner as in the catalyst preparation described in [Example 1] (1-3), except that 262 mg (300 μmol) of metallocene compound C was used instead of metallocene compound A. The pre-polymerization magnification at that time (a value obtained by dividing the pre-polymerized polymer amount by the solid catalyst amount) was 1.85.

(3-3) Propylene-propylene / ethylene block copolymerization with catalyst C 30 mg of catalyst C was used in place of catalyst A, and the average gas mol composition in the tank during propylene / ethylene polymerization in the second step was propylene / ethylene. = 32/68 The procedure was the same as [Example 1] (1-4) except that adjustment was made. As a result, 350 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 34 wt%, and the ethylene content in rubber (CP) is 47 wt% (57 mol%). The weight average molecular weight (Mw) of the parts was 215,000, and the ethylene content at 100 ° C. was 4.4%. The rubber polymerization activity (CP activity) was 8650 (g-EPR / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 155 ° C. and an MFR of 17 (dg / min).

[Example 4]
(4-1) Dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-tert-butylphenyl) indenyl) zirconium dichloride ( Synthesis of metallocene compound D) Synthesis of dimethyl (2-methyl-4- (1-naphthyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) indenyl) silane :
To a 500 ml glass reaction vessel, 13.5 g (53 mmol) of 2-methyl-4- (1-naphthyl) indene and 100 ml of THF were added and cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added dropwise 33 ml (53 mmol) of a 1.60 mol / L n-butyllithium-hexane solution. After dropping, the mixture was stirred overnight while gradually returning to room temperature to prepare a lithium salt solution of 2-methyl-4- (1-naphthyl) indene.
In another 500 ml glass reaction vessel, 22 g (170 mmol) of dimethyldichlorosilane and 100 ml of THF were added and cooled to -70 ° C. in a dry ice-methanol bath, and 2-methyl-4- (1-naphthyl) prepared previously was added thereto. ) A lithium salt solution of indene was slowly added dropwise. After dropping, the mixture was stirred at room temperature for 1 hour, and the solvent and excess dimethyldichlorosilane were distilled off under reduced pressure. Here, 100 ml of THF was added to prepare a chlorosilane solution.
Further, 17.3 g (53 mmol) of 2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) indene and 200 ml of THF were added to another 500 ml glass reaction vessel, and dry ice-methanol was added. Cooled to -70 ° C in bath. Thereto was added dropwise 33 ml (53 mmol) of a 1.60 mol / L n-butyllithium-hexane solution. After dropping, the mixture was stirred for 4 hours while gradually returning to room temperature. The mixture was cooled again to -70 ° C in a dry ice-methanol bath, 0.4 ml (5 mmol) of 1-methylimidazole was added, and the previously prepared chlorosilane solution was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel, and washed with brine until neutral. Anhydrous sodium sulfate was added and dried overnight. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. Dimethyl (2-methyl-4- (1-naphthyl) indenyl) (2- (2- (5-methylfuryl))- A pale yellow solid of 22.7 g (yield 67%) of 4- (4-t-butylphenyl) indenyl) silane was obtained.

Synthesis of dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) indenyl) zirconium dichloride:
In a 500 ml glass reaction vessel, dimethyl (2-methyl-4- (1-naphthyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) indenyl) silane 12 0.0 g (19 mmol) and 200 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added dropwise 23 ml (37 mmol) of a 1.60 mol / L n-butyllithium-hexane solution. After dropping, the mixture was stirred overnight while gradually returning to room temperature. The solvent of the reaction solution was distilled off under reduced pressure, 300 ml of toluene and 15 ml of diethyl ether were added, and the mixture was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.3 g (19 mmol) of zirconium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized with toluene / hexane, and dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (2- (2- (5-methylfuryl))-4- (4 1.4 g (yield 9%) of orange crystals of racemic-like (purity 97%) of -t-butylphenyl) indenyl) zirconium dichloride were obtained.
¹ H-NMR value (CDCl ₃ ) Racemic like: δ1.24 (s, 3H), δ1.34 (s, 9H), 1.38 (s, 3H), δ2.17 (s, 3H), δ2. 46 (s, 3H), δ 6.10 (d, 1H), δ 6.26 (d, 1H), δ 6.42 (s, 1H), δ 6.78 (s, 1H), δ 6.79 (d, 1H ), Δ 7.08 to 7.88 (m, 16H).

(4-2) Catalyst preparation using metallocene compound D (catalyst D)
Catalyst D was obtained in the same manner as the catalyst preparation described in [Example 1] (1-3) except that 239 mg (298 μmol) of metallocene compound D was used instead of metallocene compound A. The prepolymerization magnification at that time (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.09.

(4-3) Propylene-propylene / ethylene block copolymerization with catalyst D Instead of catalyst A, 20 mg of catalyst D was used, 600 ml of hydrogen was added in the first step, and the inside of the tank during propylene / ethylene polymerization in the second step The same operation as in Example 1 (1-4) was performed except that the average gas mol composition was adjusted to be propylene / ethylene = 25/75. As a result, 435 g of a propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 20 wt%, and the ethylene content in rubber (CP) is 50 wt% (60 mol%). The weight average molecular weight (Mw) of the part was 167,000, and the ethylene content at 100 ° C. was 2.0%. The rubber polymerization activity (activity in the second step) was 10,500 (g-CP / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 155 ° C. and an MFR of 6 (dg / min).

[Example 5]
(5-1) Dimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) indenyl) Synthesis of zirconium dichloride (metallocene compound E) Dimethyl (2-methyl-4- (4-t-butylphenyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) ) Synthesis of indenyl) silane:
To a 500 ml glass reaction vessel, 10.4 g (40 mmol) of 2-methyl-4- (4-t-butylphenyl) indene and 100 ml of THF were added and cooled to −70 ° C. in a dry ice-methanol bath. 26 ml (40 mmol) of a 1.54 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropwise addition, the mixture was stirred overnight while gradually returning to room temperature to prepare a lithium salt solution of 2-methyl-4- (4-t-butylphenyl) indene.
To another 500 ml glass reaction vessel, 25 ml (206 mmol) of dimethyldichlorosilane and 100 ml of THF were added and cooled to -70 ° C. in a dry ice-methanol bath, and the previously prepared 2-methyl-4- (4-t A lithium salt solution of -butylphenyl) indene was slowly added dropwise. After dropping, the mixture was stirred at room temperature for 1 hour, and the solvent and excess dimethyldichlorosilane were distilled off under reduced pressure. Here, 100 ml of THF was added to prepare a chlorosilane solution.
Further, 13.0 g (40 mmol) of 2- (2- (5-methylfuryl))-4- (4-tert-butylphenyl) indene and 100 ml of THF were added to another 500 ml glass reaction vessel, and dry ice-methanol was added. Cooled to -70 ° C in bath. 26 ml (40 mmol) of a 1.54 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was stirred for 4 hours while gradually returning to room temperature. The mixture was again cooled to -70 ° C. in a dry ice-methanol bath, 0.16 ml (2 mmol) of 1-methylimidazole was added, and the previously prepared chlorosilane solution was added dropwise. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel, and washed with brine until neutral. Anhydrous sodium sulfate was added and dried overnight. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column. Dimethyl (2-methyl-4- (4-t-butylphenyl) indenyl) (2- (2- (5-methylfuryl) ))-4- (4-t-butylphenyl) indenyl) silane, 21.5 g (84% yield) of a pale yellow solid.

Synthesis of dimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) indenyl) zirconium dichloride:
In a 500 ml glass reaction vessel, dimethyl (2-methyl-4- (4-t-butylphenyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) Indenyl) silane (17.3 g, 27 mmol) and diethyl ether (300 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. 34 ml (54 mmol) of 1.58 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature. The solvent of the reaction solution was distilled off under reduced pressure, 300 ml of toluene and 20 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 6.2 g (27 mmol) of zirconium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure, recrystallized from dichloromethane / hexane, and dimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2- (2- (5-methylfuryl))- 1.4 g (yield 7%) of orange crystals of racemic-like (purity 97%) of 4- (4-t-butylphenyl) indenyl) zirconium dichloride was obtained.
¹ H-NMR value (CDCl ₃ ) Racemic like: δ 1.21 (s, 3H), δ 1.33 (s, 9H), δ 1.34 (s, 9H), 1.38 (s, 3H), δ2. 26 (s, 3H), δ 2.43 (s, 3H), δ 6.06 (d, 1H), δ 6.17 (d, 1H), δ 6.66 to 6.73 (m, 2H), δ 6.96 (S, 1H), δ 6.08 (s, 1H), δ 7.14 (dd, 1H), δ 7.28 (d, 1H), δ 7.39 (d, 1H), δ 7.44 (d, 4H) , Δ 7.55 (d, 2H), δ 7.62 (d, 2H), δ 7.75 (d, 1H).

(5-2) Catalyst preparation using metallocene compound E (catalyst E)
Catalyst E was obtained in the same manner as in the catalyst preparation described in [Example 1] (1-3) except that 237 mg (294 μmol) of metallocene compound E was used instead of metallocene compound A. The prepolymerization magnification at that time (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.11.

(5-3) Propylene-propylene / ethylene block copolymerization with catalyst E 20 mg of catalyst E was used in place of catalyst A, and the average gas mol composition in the tank during propylene / ethylene polymerization in the second step was propylene / ethylene. = The operation was performed in the same manner as in [Example 1] (1-4) except that the ratio was adjusted to 38/62. As a result, 375 g of a propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 37 wt%, and the ethylene content in rubber (CP) is 35 wt% (45 mol%). The weight average molecular weight (Mw) of the parts was 201,000, and the ethylene content at 100 ° C. was 1.1%. The rubber polymerization activity (activity in the second step) was 18,100 (g-CP / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 155 ° C. and an MFR of 16 (dg / min).

[Example 6]
(6-1) Propylene-propylene / ethylene block copolymerization with catalyst E Instead of catalyst A, 20 mg of catalyst E was used, and the average gas mol composition in the tank during propylene / ethylene polymerization in the second step was propylene / ethylene. = 68/32 The procedure was the same as [Example 1] (1-4) except that the polymerization temperature was 65 ° C. As a result, 416 g of propylene-propylene • ethylene block copolymer was obtained.
From the result of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 18 wt%, and the ethylene content in rubber (CP) is 14 wt% (19 mol%). The weight average molecular weight (Mw) of the parts was 252,000. The rubber polymerization activity (activity in the second step) was 7,800 (g-CP / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 155 ° C. and an MFR of 13 (dg / min).

[Example 7]
(7-1) Dimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4- (4-t-butylphenyl) indenyl) zirconium dichloride (metallocene compound F) The metallocene compound F was synthesized with reference to the method described in JP-T-2003-533550, to obtain a racemic-like product (purity 99% or more).

(7-2) Catalyst preparation using metallocene compound F (catalyst F)
Catalyst E was obtained in the same manner as in the catalyst preparation described in [Example 1] (1-3) except that 244 mg (322 μmol) of metallocene compound F was used instead of metallocene compound A. At that time, the prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.88.

(7-3) Propylene-propylene / ethylene block copolymerization with catalyst F 20 mg of catalyst F was used instead of catalyst A, and the average gas mol composition in the tank during propylene / ethylene polymerization in the second step was propylene / ethylene. = The operation was performed in the same manner as in [Example 1] (1-4) except that the ratio was adjusted to 36/64. As a result, 435 g of a propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 11 wt%, and the ethylene content in rubber (CP) is 35 wt% (44 mol%). The weight average molecular weight (Mw) of the part was 182,000, and the ethylene content at 100 ° C. was 0.6%. The rubber polymerization activity (activity in the second step) was 2,900 (g-CP / g-Cat / hr). Separately collected propylene homopolymer had a Tm of 155 ° C. and an MFR of 138 (dg / min).

[Comparative Example 1]
(8-1) Synthesis of dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride (metallocene compound G) For the synthesis of metallocene compound G, the method described in Organometallics 1994, 13, 954-963 was referred to. Synthesized to obtain a racemate (purity 99% or more).

(8-2) Catalyst preparation using metallocene compound G (catalyst G)
Catalyst F was obtained in the same manner as in the catalyst preparation described in [Example 1] (1-3) except that 244 mg (322 μmol) of metallocene compound G was used instead of metallocene compound A. The prepolymerization magnification at that time (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.11.

(8-3) Propylene-propylene / ethylene block copolymerization with catalyst E 20 mg of catalyst G was used instead of catalyst A, and the average gas mol composition in the tank during propylene / ethylene polymerization in the second step was propylene / ethylene. = Operation was carried out in the same manner as in [Example 1] (1-4) except that the ratio was adjusted to 33/67. As a result, 136 g of propylene-propylene • ethylene block copolymer was obtained.
From the results of CFC-IR, the block copolymer obtained above has a rubber content (CP content) of 61 wt%, and an ethylene content in rubber (CP) of 39 wt% (49 mol%). The weight average molecular weight (Mw) of the part was 68,000. The rubber polymerization activity (activity in the second step) was 10,200 (g-CP / g-Cat / hr). The Tm of the separately collected propylene homopolymer was 149 ° C., and the MFR was 2 (dg / min).

  Table 1 summarizes the performance of each catalyst described in Examples 1 to 7 and Comparative Example 1.

The metallocene compounds used in Examples / Comparative Examples in Table 1 are shown below.
(Catalyst A): Dimethylsilylenebis (2- (2- (5-methylfuryl))-4-phenyl-indenyl) zirconium dichloride (Catalyst B): Dimethylsilylenebis (2- (2- (5-methylfuryl)) ) -4- (2-naphthyl) -indenyl) zirconium dichloride (catalyst C): dimethylsilylenebis (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) -indenyl) zirconium Dichloride (Catalyst D): Dimethylsilylene (2-methyl-4- (1-naphthyl) indenyl) (2- (2- (5-methylfuryl))-4- (4-t-butylphenyl) indenyl) zirconium dichloride (Catalyst E): Dimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2- (2- (5-methylphenyl) ))-4- (4-t-butylphenyl) indenyl) zirconium dichloride (catalyst F): dimethylsilylene (2-methyl-4- (4-t-butylphenyl) indenyl) (2-i-propyl-4) -(4-t-butylphenyl) indenyl) zirconium dichloride (catalyst G): methylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride

Comparing Example 1 of the present invention with Example 8 described in Patent Document 5, Patent Document 5 uses metallocene compound A and uses a catalyst supported on silica, not component (b), and propylene. -Propylene / ethylene block copolymer is manufactured. At this time, propylene / ethylene composition in the tank at the time of propylene / ethylene polymerization was propylene / ethylene = 50/50, and the ethylene content in CP of the block copolymer obtained at that time was 30.9 mol%. is there. The difference between the ethylene gas mol content during CP polymerization and the ethylene content in the CP of the obtained block copolymer is 19.1 mol%. On the other hand, the difference between the ethylene gas mol content during CP polymerization in Example 1 of the present invention and the ethylene content in the CP of the obtained block copolymer is 6 mol%. Thus, it is clear that the ethylene uptake efficiency was greatly improved by using the acid-treated smectite group ion-exchange layered silicate of component (b) of the present invention.
In addition, Examples 1 to 5 of the present invention used a metallocene compound that has a good ethylene incorporation efficiency, and in particular has a methylfuryl group that is a heterocyclic ring at both or one of the two positions (R ¹ , R ¹¹ ). In Examples 1 to 4, the 2-position (R ¹ , R ¹¹ ) is both in the methyl group as compared with Comparative Example 1, the ethylene incorporation efficiency is good, and the incorporation of ethylene is also achieved by introducing a heterocycle. It can be seen that the efficiency is improved.
Moreover, it turns out that the manufacturing method of this invention can manufacture the propylene-type polymer which has high molecular weight CP part like Examples 1-7.

  By the method for producing a propylene-based polymer of the present invention, propylene-propylene • (ethylene or α-olefin) block copolymer having a high ethylene or α-olefin content in the rubber part can be efficiently produced, and a high molecular weight CP The part can be produced with high activity and is very useful.

Claims (5)

A method for producing a propylene polymer using the following catalyst components (a), (b) and (c),
(I) a first step of polymerizing propylene in an amount of 90 to 100% by weight and ethylene or α-olefin in an amount of 0 to 10% by weight with respect to all monomer components; and (ii) 10 propylene with respect to all monomer components. A second step of polymerizing ˜90% by weight and 10% to 90% by weight of ethylene or α-olefin having 4 or more carbon atoms;
A process for producing a propylene-based polymer.
Catalyst component (a): metallocene compound represented by the general formula [I]

[ Wherein Y represents a general formula: R ²⁰ ₂ A
(A is germanium or silicon, and R ²⁰ may be the same as or different from each other, and is hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a halogen having 1 to 6 carbon atoms. A containing alkyl group, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms, which may constitute a 4- to 7-membered ring containing A in both adjacent R ²⁰ , and 5 to 7 (It may contain an unsaturated bond in the member ring.)
It is a bivalent crosslinking group shown by these . X ¹ and X ² are each independently a ligand that forms a σ bond with Zr. R ¹ and R ¹¹ may be the same or different from each other, and have an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a substituent. And a heterocyclic group composed of a 5-membered ring or a 6-membered ring (wherein the heteroatom of the heterocyclic group constituting the 5-membered ring or 6-membered ring is not directly bonded to the alkadienyl group), R ¹ One or both of R ¹¹ and R ¹¹ is necessarily a C 3-6 alkyl group, or a heterocyclic group constituting a 5-membered ring optionally having a substituent. R ^{2 to} R ⁹ and R ^{12 to} R ¹⁹ may be the same as or different from each other, and are hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. A halogen-containing alkyl group, a silicon-containing alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-containing aryl group having 6 to 18 carbon atoms, or a 5-membered ring optionally having a substituent Or it is a heterocyclic group which comprises a 6-membered ring, 6-7 membered ring may be comprised by both adjacent R, and the 6-7 membered ring may contain the unsaturated bond. ]
Catalyst component (b): Acid-treated smectite group ion-exchange layered silicate Catalyst component (c): Organoaluminum compound In the said general formula [I], R < ¹ > and R < ¹¹ > are the furyl group or thienyl group which may have a substituent, The manufacturing method of the propylene-type polymer of Claim 1 characterized by the above-mentioned. In the general formula [I], R ⁴ and R ¹⁴ are each a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-containing alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. The method for producing a propylene-based polymer according to claim 1 or 2 , which is a silicon-containing alkyl group having 6 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen-containing aryl group having 6 to 18 carbon atoms. . The method for producing a propylene-based polymer according to any one of claims 1 to 3, wherein the catalyst component (b) is montmorillonite treated with an inorganic acid.   5. The method according to claim 1, wherein the first step is bulk polymerization using propylene as a solvent or gas phase polymerization that keeps the monomer in a gaseous state, and the second step is gas phase polymerization. 2. A process for producing a propylene-based polymer according to item 1.