JP4841362B2 - Olefin polymerization catalyst component, catalyst, and process for producing olefin polymer using the same - Google Patents

Description

  The present invention provides a catalyst component and a catalyst for polymerization of olefins, which can maintain a high degree of stereoregularity and yield of a polymer and obtain a high melt flow rate by adding a small amount of hydrogen, so-called good hydrogen response And a process for producing a polymer of olefins using the same.

  Conventionally, in the polymerization of olefins such as propylene, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many methods for polymerizing or copolymerizing olefins in the presence of an olefin polymerization catalyst comprising the solid catalyst composition, an organoaluminum compound and an organosilicon compound have been proposed. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 57-63310) and Patent Document 2 (Japanese Patent Laid-Open No. 57-63311), a magnesium compound, a titanium compound, and an organosilicon compound having a Si—O—C bond are used. In particular, a method for polymerizing olefins having 3 or more carbon atoms using a catalyst composed of a combination has been proposed. However, these methods are not always satisfactory for obtaining a high stereoregularity polymer in a high yield, and further improvement has been desired.

  On the other hand, in Patent Document 3 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, aromatic dicarboxylic acid diester, aromatic hydrocarbon compound and titanium halide is in a powder state. A propylene polymerization catalyst comprising a solid catalyst component prepared by heat treatment with, an organoaluminum compound and an organosilicon compound, and a method for polymerizing propylene have been proposed.

  Moreover, in patent document 4 (Unexamined-Japanese-Patent No. 1-315406), titanium tetrachloride is made to contact the suspension formed with diethoxymagnesium and the alkylbenzene, and phthalic acid chloride is then added and made to react. A solid catalyst component prepared by obtaining a solid product and further contacting the solid product with titanium tetrachloride in the presence of an alkylbenzene, a catalyst for propylene comprising an organoaluminum compound and an organosilicon compound, and the catalyst Propylene polymerization methods in the presence have been proposed.

  Each of the above prior arts has such a high activity that the purpose of removing a so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer can be omitted. Although efforts have been made to improve the yield and to increase the sustainability of the catalyst activity during the polymerization, each of them has achieved results, but improvement of the catalyst for such purpose is still desired.

  By the way, the polymer obtained by using the catalyst as described above is used for various uses such as containers and films in addition to molded articles such as automobiles and home appliances. These melt the polymer powder produced by polymerization and mold it with various molding machines. Especially when producing large molded products by injection molding, the flowability of melted polymer (melt flow rate, MFR) ) Is required, and in order to reduce the cost of a highly functional block copolymer especially for automobile materials, an olefin-based thermoplastic elastomer (hereinafter referred to as “TPO”) is used in the copolymerization reactor. ) A method for producing TPO in the polymerization reactor directly without adding a newly synthesized copolymer after production and producing a copolymer necessary for production, that is, a reactor by direct weight as referred to in the industry In the production of maid TPO, the melt flow rate in the homopolymerization stage is used to keep the melt flow rate of the final product sufficiently large and facilitate injection molding. 200 (g / 10min) may be required to more values, many studies have been made to increase the melt flow rate while maintaining high stereoregularity thereof for polymers.

Melt flow rate is highly dependent on the molecular weight of the polymer. In the industry, it is common to add hydrogen as a molecular weight regulator for the polymer produced in the polymerization of propylene. At this time, in order to produce a low molecular weight polymer, that is, in order to produce a polymer having a high melt flow rate, a large amount of hydrogen is usually added. However, particularly in a bulk polymerization apparatus, the pressure resistance of the reactor is limited due to its safety. There is also a limit to the amount of hydrogen that can be added. Further, even in the gas phase polymerization, in order to add more hydrogen, the partial pressure of the monomer to be polymerized must be lowered, and in this case, the productivity is lowered. In addition, the use of a large amount of hydrogen also causes cost problems. In order to solve this problem, Patent Document 5 (WO 2004-16662) discloses a high melt flow rate by using a compound represented by Si (OR) ₃ (NR′R ″) as a catalyst component for the polymerization of olefins. In addition, it is disclosed that a polymer with high stereoregularity can be produced, and it has given a certain effect.

However, it is not sufficient to fundamentally solve the problem of TPO production by direct weight as described above, and further improvement has been desired.
JP-A-57-63310 (Claims) Japanese Laid-Open Patent Publication No. 57-63311 (Claims) Japanese Laid-Open Patent Publication No. 63-3010 (Claims) JP-A-1-315406 PR (Claims) WO 2004-16662 (Claims)

  Therefore, an object of the present invention is to maintain a high degree of stereoregularity and yield of a polymer and to obtain a high melt flow rate by adding a small amount of hydrogen, that is, a catalyst for polymerization of olefins having a good hydrogen response. It is an object of the present invention to provide a component and a method for producing an olefin polymer using the component.

  In such a situation, the present inventors have conducted extensive studies, and as a result, the amino compound having a specific structure having at least two secondary amino bonds or one secondary amino bond and an ether bond via a plurality of atoms. As a result, the present inventors have found that a catalyst containing an active ingredient as an active ingredient is more suitable as a catalyst ingredient for the polymerization of olefins than the conventional catalysts described above.

（式中、Ｒ¹〜Ｒ^１０は水素原子、ハロゲン原子、炭素数１〜２０の直鎖または分岐のアルキル基、シクロアルキル基またはその誘導体、アリル基、アラルキル基、ビニル基、フェニル基、二級アミノ基、アルコキシ基であり、これらの基の中にヘテロ原子も含有してもよく、また同じでも異なっていてもよく、またＲ¹〜Ｒ^１０の中のいずれか２つの基が相互に結合して環を形成してもよく、Ｒ^１１は炭素数１〜１０の直鎖または分岐のアルキル基、シクロアルキル基またはその誘導体、アリル基アラルキル基、ビニル基、フェニル基であり、これらの基の中にヘテロ原子を含有してもよく、Ｚは二級アミノ基またはアルコキシ基である。但し、式中、少なくとも２個の二級アミノ結合を有するか、または１個の二級アミノ結合とエーテル結合を有する。）で表されるオレフィン類重合用触媒成分を提供するものである。 That is, the present invention provides the following formula (1);

Wherein R ^{1 to} R ¹⁰ are a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a derivative thereof, an allyl group, an aralkyl group, a vinyl group, a phenyl group, two A secondary amino group, an alkoxy group, and these groups may contain a hetero atom, and may be the same or different, and any two groups of R ^{1 to} R ¹⁰ may be mutually bonded. R ¹¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a derivative thereof, an allyl group, an aralkyl group, a vinyl group, or a phenyl group. The group may contain a heteroatom, and Z is a secondary amino group or an alkoxy group, provided that it has at least two secondary amino bonds or one secondary amino bond And Ete With binding.) Is intended to provide an olefin polymerization catalyst component represented by.

  The present invention also provides an olefin polymerization catalyst formed using the olefin polymerization catalyst component as an essential component.

  The present invention also provides a method for producing an olefin polymer, characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst.

  The catalyst for polymerizing olefins of the present invention can maintain a higher degree of polymer stereoregularity and yield than conventional catalysts, and has a high melt flow rate by adding a small amount of hydrogen (hereinafter simply referred to as “hydrogen response”). Is obtained). Therefore, it is possible to provide a general-purpose polyolefin at a low cost due to functions such as reduction in the amount of hydrogen used in polymerization and high catalyst activity, and it is expected to be useful in the production of highly functional olefin polymers. The

The olefin polymerization catalyst component of the present invention is an amino compound represented by the general formula (1). The amino compound has at least two secondary amino bonds, or one secondary amino bond and an ether bond. Moreover, it is preferable that R ¹ and R ² are not a compound in which a ring is formed. If such an amino compound having a specific structure is used as a catalyst component for olefin polymerization, the stereoregularity and yield of the polymer can be maintained at a higher level than conventional catalysts, and the hydrogen response is excellent. In the general formula (1), examples of the hetero atom contained in the ring-forming group include a sulfur atom, an oxygen atom, and a nitrogen atom. The derivative of the cycloalkyl group is a cycloalkyl group having a substituent, and specific examples include an alkyl-substituted cyclopentyl group, an alkyl-substituted cyclohexyl group, and an alkyl-substituted cycloheptyl group.

In the general formula (1), R ^{1 to} R ¹⁰ include a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, sec- butyl, t- butyl group, a 2-ethylhexyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, a benzyl group, a phenyl group, preferably a methyl phenyl group, a methyl group as R ^11, ethyl N-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, cyclopentyl group and cyclohexyl group are preferred. When Z is a secondary amino group, methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, n-butylamino group, iso-butylamino group, sec-butylamino group, t-butyl An amino group is preferable, and in the case of an alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, and a t-butoxy group are preferable.

  In the general formula (1), examples of the compound having at least two secondary amino bonds include 1,1-bis (alkylaminoalkyl) indene, 1,1-bis (alkylaminoalkyl) dialkylindene, 1,1 -Bis (alkylaminoalkyl) trialkylindene, 1,1-bis (alkylaminoalkyl) alkylindene, 1- (alkylaminoalkyl) -1-alkoxyindene, 1- (alkylaminoalkyl) -1-alkoxyalkylindene Of which, 1,1-bis (alkylaminomethyl) indene, 1,1-bis (alkylaminomethyl) alkylindene, 1- (alkylaminomethyl) -1-alkoxyindene, 1- (alkylamino) Methyl) -1-alkoxyalkylindene is preferred.

  In the general formula (1), specific examples of the compound having two secondary amino bonds are 1,1-bis (methylaminomethyl) indene, 1,1-bis (ethylaminomethyl) indene, 1,1 -Bis (n-propylaminomethylindene, 1,1-bis (iso-propylaminomethyl) indene, 1,1-bis (n-butylaminomethyl) indene, 1,1-bis (iso-butylaminomethyl) Indene, 1,1-bis (sec-butylaminomethyl) indene, 1- (methylaminomethyl) -1- (ethylaminomethyl) indene,

  1,1-bis (methylaminomethyl) -2-methylindene, 1,1-bis (ethylaminomethyl) -2-methylindene, 1,1-bis (methylaminomethyl) -2-phenylindene, 1, 1-bis (ethylaminomethyl) -2-phenylindene, 1,1-bis (methylaminomethyl) -2,7-diethylindene, 1,1-bis (ethylaminomethyl) -2,7-diethylindene, 1- (ethylaminomethyl) -1- (methylaminomethyl) -2,7-diethylindene,

  1,1-bis (methylaminomethyl) -2,3,4,5-tetramethylindene, 1,1-bis (ethylaminomethyl) -2,3,4,5-tetramethylindene, 1,1- Bis (n-propylaminomethyl) -2,3,4,5-tetramethylindene, 1,1-bis (iso-propylaminomethyl) -2,3,4,5-tetramethylindene, 1,1- Bis (n-butylaminomethyl) -2,3,4,5-tetramethylindene, 1,1-bis (iso-butylaminomethyl) -2,3,4,5-tetramethylindene, 1- (ethyl Aminomethyl) -1 (methylaminomethyl) -2,3,4,5-tetramethylindene,

  1,1-bis (methylaminomethyl) -3,4-dicyclohexylindene, 1,1-bis (ethylaminomethyl) -3,4-dicyclohexylindene, 1,1-bis (n-propylaminomethyl)- 3,4-dicyclohexylindene, 1,1-bis (iso-propylaminomethyl) -3,4-dicyclohexylindene, 1,1-bis (n-butylaminomethyl) -3,4-dicyclohexylindene, 1,1 -Bis (iso-butylaminomethyl) -3,4-dicyclohexylindene,

  1,1-bis (methylaminomethyl) -2,3,4,5-tetraphenylindene, 1,1-bis (ethylaminomethyl) -2,3,4,5-tetraphenylindene, 1,1- Bis (methylaminomethyl) -2,3,4,5-tetrafluoroindene, 1,1-bis (ethylaminomethyl) -2,3,4,5-tetrafluoroindene, 1,1-bis (methylamino) Methyl) -3,4-dibenzylindene, 1,1-bis (ethylaminomethyl) -3,4-dibenzylindene, 1,1-bis (methylaminomethyl) -3,4-dicyclopentylindene, , 1-bis (ethylaminomethyl) -3,4-dicyclopentylindene,

  1,1-bis (2-methylaminopropyl) indene, 1,1-bis (2-ethylaminopropyl) indene, 1,1-bis (2-propylaminopropyl) indene, 1,1-bis (2- iso-propylaminopropyl) indene, 1,1-bis (2-n-butylaminopropyl) indene, 1,1-bis (2-methylaminopropyl) -2,3,4,5-tetramethylindene, 1 , 1-bis (2-ethylaminopropyl) -2,3,4,5-tetramethylindene, 1,1-bis (2-methylaminopropyl) -3,4-dicyclohexylindene, 1,1-bis ( 2-ethylaminopropyl) -3,4-dicyclohexylindene, 1,1-bis (2-methylaminopropyl) -2,3,4,5-tetraphenylindene, 1,1- (2-ethylaminopropyl) -2,3,4,5-tetraphenylindene, 1,1-bis (2-methylaminopropyl) -2,3,4,5-tetrafluoroindene, 1,1- Bis (2-ethylaminopropyl) -2,3,4,5-tetrafluoroindene,

1,1-bis (2-methylaminopropyl) -3,4-dibenzylindene, 1,1-bis (2-ethylaminopropyl) -3,4-dibenzylindene,
Examples include 1,1-bis (2-methylaminopropyl) -3,4-dicyclopentylindene, 1,1-bis (2-ethylaminopropyl) -3,4-dicyclopentylindene, and the like.

  Preferred compounds having two secondary amino bonds include 1,1-bis (ethylaminomethyl) -2-methylindene, 1,1-bis (ethylaminomethyl) -2-phenylindene, 1, 1-bis (methylaminomethyl) -2,7-diethylindene is mentioned.

  In the general formula (1), examples of the amino ether compound having at least one secondary amino bond and an ether bond include 1- (alkylaminomethyl) -1- (alkylalkoxy) indene, halogen-substituted 1- (alkylaminomethyl) ) -1- (alkylalkoxy) indene and alkyl-substituted 1- (alkylaminomethyl) -1- (alkylalkoxy) indene are preferable, and 1- (alkylaminomethyl) -1-alkoxymethylindene is particularly preferable.

  In the general formula (1), specific examples of the amino ether compound having at least one secondary amino bond and an ether bond include 1- (methylaminomethyl) -1- (methoxymethyl) indene, 1- (methylamino Methyl) -1- (ethoxymethyl) indene, 1- (ethylaminomethyl) -1- (methoxymethyl) indene, 1- (ethylaminomethyl) -1- (methoxymethyl) indene, 1- (ethylaminomethyl) -1- (ethoxymethyl) indene, 1- (n-propylaminomethyl) -1- (methoxymethyl) indene, 1- (n-propylaminomethyl) -1- (ethoxymethyl) indene, 1- (iso- Propylaminomethyl) -1- (methoxymethyl) indene, 1- (iso-propylaminomethyl) -1- (ethoxymethyl) indene, 1- (N-butylaminomethyl) -1- (methoxymethyl) indene, 1- (n-butylaminomethyl) -1- (ethoxymethyl) indene, 1- (iso-butylaminomethyl) -1- (ethoxymethyl) Indene, 1- (sec-butylaminomethyl) -1- (ethoxymethyl) indene,

  1- (methylaminomethyl) -1-methoxymethyl-2-cyclopentylindene, 1- (ethylaminomethyl) -1-methoxymethyl-2-cyclopentylindene, 1- (methylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (methylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetramethylindene, 1- (ethylaminomethyl) -1- (Methoxymethyl) -2,3,4,5-tetramethylindene, 1- (ethylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetramethylindene, 1- (n-propyl) Aminomethyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (n-propylaminomethyl) -1- (ethoxymethyl) -2,3,4,5- Tramethylindene, 1- (iso-propylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (iso-propylaminomethyl) -1- (ethoxymethyl)- 2,3,4,5-tetramethylindene, 1- (n-butylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (n-butylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetramethylindene, 1- (iso-butylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1 -(Iso-butylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetramethylindene,

  1- (methylaminomethyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (methylaminomethyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (ethylaminomethyl) ) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (ethylaminomethyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (n-propylaminomethyl) -1- (Methoxymethyl) -3,4-dicyclohexylindene, 1- (n-propylaminomethyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (iso-propylaminomethyl) -1- (methoxy Methyl) -3,4-dicyclohexylindene, 1- (iso-propylaminomethyl) -1- (ethoxymethyl) -3 4-dicyclohexylindene, 1- (n-butylaminomethyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (n-butylaminomethyl) -1- (ethoxymethyl) -3,4- Dicyclohexylindene, 1- (iso-butylaminomethyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (iso-butylaminomethyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene ,

  1- (methylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (methylaminomethyl) -1- (ethoxymethyl) -2,3,4,5- Tetraphenylindene, 1- (ethylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (ethylaminomethyl) -1- (ethoxymethyl) -2,3 4,5-tetraphenylindene, 1- (n-propylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (n-propylaminomethyl) -1- ( Ethoxymethyl) -2,3,4,5-tetraphenylindene, 1- (iso-propylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (iso- Professional Ruaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetraphenylindene, 1- (n-butylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene 1- (n-butylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetraphenylindene, 1- (iso-butylaminomethyl) -1- (methoxymethyl) -2,3 , 4,5-tetraphenylindene, 1- (iso-butylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetraphenylindene, 1- (methylaminomethyl) -1- (methoxy Methyl) -2,3,4,5-tetrafluoroindene, 1- (methylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (ethylaminomethyl)- 1- (D Kishimechiru) -2,3,4,5-tetrafluoroethane indene, 1- (ethylamino) -1- (methoxymethyl) -2,3,4,5-tetrafluoroethane indene,

  1- (n-propylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (n-propylaminomethyl) -1- (ethoxymethyl) -2,3 4,5-tetrafluoroindene, 1- (iso-propylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (iso-propylaminomethyl) -1- ( Ethoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (n-butylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (n- Butylaminomethyl) -1- (ethoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (iso-butylaminomethyl) -1- (methoxymethyl) -2,3,4,5-tetra Fluoroindene, 1- (i o- butylamino) -1- (ethoxymethyl) -2,3,4,5-tetrafluoroethane indene,

  1- (methylaminomethyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (methylaminomethyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (ethyl Aminomethyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (ethylaminomethyl) -1- (ethoxymethyl) -3,4-dibenzylindene,

  1- (n-propylaminomethyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (n-propylaminomethyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (iso-propylaminomethyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (iso-propylaminomethyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (n-butylaminomethyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (n-butylaminomethyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (iso-butylaminomethyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (iso-butylaminomethyl) -1- (ethoxymethyl) -3,4-dibenzyl Indene, 1- (sec-butylaminomethyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (sec-butylaminomethyl) -1- (ethoxymethyl) -3,4-dibenzyl Indene, 1- (methylaminomethyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (methylaminomethyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene, 1- (Ethylaminomethyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (ethylaminomethyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene,

  1- (n-propylaminomethyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (n-propylaminomethyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene, 1- (iso-propylaminomethyl) (methoxymethyl) -3,4-dicyclopentylindene, 1- (iso-propylaminomethyl) (ethoxymethyl) -3,4-dicyclopentylindene, 1- (n-butyl Aminomethyl) (methoxymethyl) -3,4-dicyclopentylindene, 1- (n-butylaminomethyl) (ethoxymethyl) -3,4-dicyclopentylindene, 1- (iso-butylaminomethyl) (ethoxymethyl) ) -3,4-dicyclopentylindene,

  1- (2-methylaminopropyl) -1- (methoxymethyl) indene, 1- (2-methylaminopropyl) -1- (ethoxymethyl) indene, 1- (2-ethylaminopropyl) -1- (methoxy Methyl) indene, 1- (2-ethylaminopropyl) -1- (ethoxymethyl) indene, 1- (2-propylaminopropyl) -1- (methoxymethyl) indene, 1- (2-propylaminopropyl)- 1- (ethoxymethyl) indene,

  1- (2-iso-propylaminopropyl) -1- (methoxymethyl) indene, 1- (2-iso-propylaminopropyl) -1- (ethoxymethyl) indene, 1- (2-n-butylaminopropyl) ) -1- (methoxymethyl) indene, 1- (2-n-butylaminopropyl) -1- (ethoxymethyl) indene, 1- (methylaminomethyl) -1-methoxymethyl-2,7-diethylindene, 1- (ethylaminomethyl) -1-methoxymethyl-2,7-diethylindene, 1- (methylaminomethyl) -1-methoxy-2-iso-propylindene, 1- (ethylaminomethyl) -1-methoxy 2-iso-propylindene

  1- (2-methylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (2-methylaminopropyl) -1- (ethoxymethyl) -2,3 4,5-tetramethylindene, 1- (2-ethylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (2-ethylaminopropyl) -1- ( Ethoxymethyl) -2,3,4,5-tetramethylindene, 1- (2-propylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (2- Propylaminopropyl) -1- (ethoxymethyl) -2,3,4,5-tetramethylindene, 1- (2-iso-propylaminopropyl) -1- (methoxymethyl) -2,3,4,5 -Tetramethylindene, -(2-Iso-propylaminopropyl) -1- (ethoxymethyl) -2,3,4,5-tetramethylindene, 1- (2-n-butylaminopropyl) -1- (methoxymethyl) -2 , 3,4,5-tetramethylindene, 1- (2-n-butylaminopropyl) -1- (ethoxymethyl) -2,3,4,5-tetramethylindene, 1- (2-iso-butyl) Aminopropyl) -1- (methoxymethyl) -2,3,4,5-tetramethylindene, 1- (2-iso-butylaminopropyl) -1- (ethoxymethyl) -2,3,4,5- Tetramethylindene,

  1- (2-methylaminopropyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (2-methylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (2-ethylaminopropyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (2-ethylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (2 -Propylaminopropyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (2-propylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (2-iso -Propylaminopropyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (2-iso-propyl) Minopropyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (2-n-butylaminopropyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (2-n- Butylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene, 1- (2-iso-butylaminopropyl) -1- (methoxymethyl) -3,4-dicyclohexylindene, 1- (2- iso-butylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclohexylindene,

  1- (2-methylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (2-methylaminopropyl) -1- (ethoxymethyl) -2,3 4,5-tetraphenylindene, 1- (2-ethylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (2-ethylaminopropyl) -1- ( Ethoxymethyl) -2,3,4,5-tetraphenylindene, 1- (2-propylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (2- Propylaminopropyl) -1- (ethoxymethyl) -2,3,4,5-tetraphenylindene, 1- (2-iso-propylaminopropyl) -1- (methoxymethyl) -2,3,4,5 -Tetraph Nylindene, 1- (2-n-butylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetraphenylindene, 1- (2-iso-butylaminopropyl) -1- (methoxymethyl) ) -2,3,4,5-tetraphenylindene,

  1- (2-methylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (2-methylaminopropyl) -1- (ethoxymethyl) -2,3 4,5-tetrafluoroindene, 1- (2-ethylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (2-propylaminopropyl) -1- ( Methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (2-propylaminopropyl) -1- (ethoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (2- iso-propylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (2-iso-propylaminopropyl) -1- (ethoxymethyl) -2,3,4 , 5-Tetraflo Loindene, 1- (2-n-butylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (2-n-butylaminopropyl) -1- (ethoxymethyl) ) -2,3,4,5-tetrafluoroindene, 1- (2-iso-butylaminopropyl) -1- (methoxymethyl) -2,3,4,5-tetrafluoroindene, 1- (2- iso-butylaminopropyl) -1- (ethoxymethyl) -2,3,4,5-tetrafluoroindene,

  1- (2-methylaminopropyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (2-methylaminopropyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (2-ethylaminopropyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (2-ethylaminopropyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (2-propylaminopropyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (2-propylaminopropyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (2-iso-propylaminopropyl) -1- (ethoxymethyl) -3,4-dibenzylindene, 1- (2-iso-propylaminopropyl) -1- (methoxymethyl) -3, 4-dibenzylindene, 1- (2-n-butylaminopropyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (2-n-butylaminopropyl) -1- (ethoxymethyl) ) -3,4-dibenzylindene, 1- (2-iso-butylaminopropyl) -1- (methoxymethyl) -3,4-dibenzylindene, 1- (2-iso-butylaminopropyl) -1 -(Ethoxymethyl) -3,4-dibenzylindene,

  1- (2-methylaminopropyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (2-methylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene, 1- (2-ethylaminopropyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (2-ethylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene, 1- (2-propylaminopropyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (2-propylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene, 1- (2-iso-propylaminopropyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (2-iso-propylamino) Nopropyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene, 1- (2-n-butylaminopropyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1- (2- n-butylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene, 1- (2-iso-butylaminopropyl) -1- (methoxymethyl) -3,4-dicyclopentylindene, 1 -(2-iso-butylaminopropyl) -1- (ethoxymethyl) -3,4-dicyclopentylindene,

  Preferred amino ether compounds having one secondary amino bond and ether bond include 1- (ethylaminomethyl) -1- (ethoxymethyl) indene, 1- (ethylaminomethyl) -1-methoxymethyl- Examples include 2-cyclopentylindene, 1- (ethylaminomethyl) -1-methoxymethyl-2,7-diethylindene, and 1- (methylaminomethyl) -1-methoxy-2-iso-propylindene.

  The above compound can be easily synthesized by a known synthetic method such as a chlorine exchange method, a method using an organolithium compound, a method using a Grineer reagent, or a combination thereof. For example, it can be obtained by contacting a halogenated alkyl-substituted indene derivative with a lithium salt of an alkyl-substituted secondary amine and replacing the halogenated alkyl group with the alkyl-substituted secondary amino group.

  In addition, the olefin polymerization catalyst of the present invention is formed using the amino compound represented by the above formula (1) as an essential component. That is, the amino compound can be used as an electron-donating compound (internal donor) of a solid catalyst component that is a constituent element of an olefin polymerization catalyst, and an electron-donating compound (external compound) of an olefin polymerization catalyst. It can also be used as a donor. Among these, when used as an electron donating compound (external donor) of an olefin polymerization catalyst, the effect of the present invention is particularly prominent.

The olefin polymerization catalyst of the present invention comprises (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound,
(B) the following general formula _{^{(2); R 12 p AlQ}} 3-p (2)
(Wherein R ¹² represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) formed from the olefin polymerization catalyst component.

  Further, among the olefin polymerization catalysts of the present invention, the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) contains magnesium, titanium, halogen and an electron donor compound. It can be obtained by contacting a) a magnesium compound, (b) a tetravalent titanium halogen compound and (c) an electron donor compound. Examples of the magnesium compound (hereinafter sometimes simply referred to as “component (a)”) include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. Among these magnesium compounds, dihalogenated magnesium, a mixture of dihalogenated magnesium and dialkoxymagnesium, dialkoxymagnesium are preferable, dialkoxymagnesium is particularly preferable, and specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, Butoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnes Um, and the like, diethoxy magnesium is particularly preferred.

  These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of a halogen-containing organic metal or the like. The above dialkoxymagnesium can be used alone or in combination of two or more.

  Furthermore, dialkoxymagnesium that is preferably used is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as filter clogging in the polymer separation apparatus due to the fine powder contained are solved.

  The spherical dialkoxymagnesium does not necessarily need to be a true sphere, and an elliptical or potato-shaped one can also be used. Specifically, the particle shape is such that the ratio (L / W) of the major axis diameter L to the minor axis diameter W is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .

  The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. Preferably it is 5-150 micrometers. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. Moreover, about the particle size, it is preferable to use a thing with few fine powder and coarse powder and a narrow particle size distribution. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is represented by D90 / D10 (where D90 is the integrated particle size at 90%, D10 is the integrated particle size at 10%), it is 3 or less, preferably 2 or less. .

  For example, JP-A-58-4132, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-4-36891 can be used for producing spherical dialkoxymagnesium as described above. It is illustrated in the 8-73388 gazette etc.

The tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b)”) used for the preparation of the component (A) in the present invention is represented by the general formula Ti (OR ¹³ ) _n X _4-n ( Wherein R ¹³ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4. 1 type or 2 types or more of the compound to be made.

  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride as alkoxytitanium halide. Examples include chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride. The Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

  The electron donating compound (hereinafter sometimes simply referred to as “component (c)”) used in the preparation of the solid catalyst component (A) in the present invention is an organic compound containing an oxygen atom or a nitrogen atom, for example, Examples thereof include alcohols, phenols, ethers, esters, ketones, acid halides, amides, isocyanates, organosilicon compounds containing Si—O—C bonds or Si—N—C bonds.

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyle ether, diphenyl ether, 9, Ethers such as 9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Monomers such as ethyl butyrate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, phenyl cyclohexylbenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate Rubonates, diethyl malonate, dipropyl malonate, dibutyl malonate, diisobutyl malonate, dipentyl malonate, dineopentyl malonate, diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl diisobutyl bromomalonate, diisopromalon Diethyl diethyl, diethyl dibutylmalonate, diethyl diisobutylmalonate, diethyl diisopentylmalonate, diethyl isopropylbutylmalonate, dimethyl isopropylisopentylmalonate, diethyl bis (3-chloro-n-propyl) malonate, bis (3 -Bromo-n-propyl) diethyl malonate, diethyl maleate, dibutyl maleate, diethyl succinate, butyl succinate, dimethyl adipate, diethyl adipate, dip adipate Dicarboxylic acid diesters such as pill, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, phthalate diester, phthalate diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, phthalates Acid chlorides such as acid dichloride, terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, olefinic acid amide, stearic acid Amides such as amides, nitriles such as acetonitrile, benzonitrile and tolylnitrile, methyl isocyanate, ethyl isocyanate Isocyanates such as phenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkylalkylalkoxysilanes, etc., organosilicon compounds containing Si—O—C bonds, bis (alkylamino) dialkoxysilanes And organosilicon compounds containing a Si—N—C bond such as bis (cycloalkylamino) dialkoxysilane, alkyl (alkylamino) dialkoxysilane, dialkylaminotrialkoxysilane, and cycloalkylaminotrialkoxysilane. .

  Among the above electron donating compounds, esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and phthalic acid diester derivatives are particularly preferable. Specific examples of these phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethyl methyl phthalate, Methyl isopropyl phthalate, ethyl phthalate (n-propyl), ethyl phthalate phthalate (n-butyl), ethyl isobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, dihexyl phthalate, Di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, diisodecyl phthalate, phthalate Acid bis (2,2-dimethylheptyl), n-butyl phthalate (isohexyl) ), N-butyl phthalate (2-ethylhexyl), n-pentyl phthalate (hexyl), n-pentyl phthalate (isohexyl), isopentyl phthalate (heptyl), n-pentyl phthalate (2-ethylhexyl), phthalate N-pentyl acid (isononyl), isopentyl phthalate (n-decyl), n-pentyl phthalate (undecyl), isopentyl phthalate (isohexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-phthalate -Hexyl (isononyl), n-hexyl phthalate (n-decyl), n-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (isononyl), n-heptyl phthalate (neo-decyl), phthalic acid 2-ethylhexyl (isononyl) is exemplified, and one of these phthalic acid diesters is Rui is two or more of them is used.

  Further, as the phthalic acid diester derivative, one or two hydrogen atoms of the benzene ring to which the two ester groups of the above phthalic acid diester are bonded are an alkyl group having 1 to 5 carbon atoms, or a chlorine atom, bromine atom and fluorine. Examples thereof include those substituted with a halogen atom such as an atom. The solid catalyst component prepared using the phthalic acid diester derivative as an electron-donating compound can improve the effect of obtaining a high melt flow rate by adding a small amount of hydrogen, that is, the hydrogen response. Even if the amount of hydrogen to be used is the same or small, the melt flow rate of the polymer can be improved. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4, neodimethyl dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-butyl 4-chlorophthalate , Dineopentyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-butyl 4-bromophthalate, dineopentyl 4-bromophthalate, 4-bromophthalate Diisobutyl acid, diisohexyl 4-bromophthalate, diisooctyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl 4,5-dichlorophthalate, diisohexyl 4,5-dichlorophthalate, , 5-dichloro-phthalic acid diisooctyl, can be mentioned, of which 4-bromophthalic acid dineopentyl, 4-bromophthalic di -n- butyl, and 4-bromophthalic acid diisobutyl are preferred.

  The above esters are also preferably used in combination of two or more, and the esters are combined when the total number of carbon atoms of the ester alkyl group used is 4 or more compared to other esters. It is desirable.

  Moreover, the amino compound of the said General formula (1) can also be used as an electron-donating compound (internal donor) in a solid catalyst component. In addition, an electron-donating compound containing an ester such as the above phthalate ester is first used for the preparation of the solid catalyst component, and the obtained solid catalyst component is treated with the amino compound of the general formula (1), It is also preferable to prepare a solid catalyst component by containing an amino compound.

  In the present invention, the above (a), (b), and (c) are contacted in the presence of the aromatic hydrocarbon compound (d) (hereinafter sometimes simply referred to as “component (d)”). The method of preparing the component (A) by the method is a preferred embodiment. Specifically, as the component (d), specifically, an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. such as toluene, xylene, or ethylbenzene is preferably used. . Moreover, these may be used independently or may be used in mixture of 2 or more types.

  As a particularly preferred method for preparing the component (A) in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. The preparation method by making the mixed solution formed from b) and component (d) contact this suspension, and making it react after that can be mentioned.

In the preparation of the solid catalyst component (A) of the present invention, it is preferable to use a polysiloxane (hereinafter sometimes simply referred to as “component (e)”) in addition to the above components. As a result, the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced. Polysiloxane is a polymer having a siloxane bond (—Si—O bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm ² / s ( ^{2 to} 10,000 centistokes). It is a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

  As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid groups. Examples thereof include substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.

  In the present invention, the components (a), (b), and (c) and, if necessary, the component (d) or the component (e) are contacted to form the component (A). A method for preparing the component (A) will be described. Specifically, the magnesium compound (a) is suspended in an alcohol, a halogen hydrocarbon solvent, a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d), and an electron donating property such as phthalic acid diester is used. The method of obtaining a component (A) by contacting a compound (c) and / or a tetravalent titanium halogen compound (b) is mentioned. In this method, by using a spherical magnesium compound, a spherical component (A) having a sharp particle size distribution can be obtained, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device. By forming particles by a so-called spray-drying method in which a turbid liquid is sprayed and dried, a spherical component (A) having a sharp particle size distribution can be obtained.

  The contact of each component is performed with stirring in a container equipped with a stirrer in a state where moisture and the like are removed under an inert gas atmosphere. The contact temperature is the temperature at the time of contact of each component at the time of contact of each component, and may be the same temperature as the reaction temperature or a different temperature. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or is dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if it exceeds 130 ° C, evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  A preferred method for preparing component (A) of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d). , A method of preparing component (A) by reacting, or component (a) is suspended in component (d), and then component (c) is contacted and then component (b) is contacted and reacted The method of preparing a component (A) can be mentioned by this. Moreover, the performance of the final solid catalyst component can be improved by bringing the component (A) thus prepared into contact with the component (b) or the component (b) and the component (c) again or multiple times. it can. At this time, it is desirable to carry out in the presence of the aromatic hydrocarbon compound (d).

  As a preferred method for preparing component (A) in the present invention, a suspension is formed from component (a), component (c), and aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and component (b) And a mixed solution formed from the component (d) is brought into contact with the suspension and then reacted.

  Preferred methods for preparing component (A) in the present invention include the methods shown below. A suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A mixed solution is formed from the component (c) and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction treatment (first reaction treatment). After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the solid substance after washing is used as a solid product. Thereafter, the washed solid material is further brought into contact with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C., and the temperature is raised. It is also possible to obtain a component (A) obtained by repeating a reaction treatment (secondary reaction treatment) and washing with a liquid hydrocarbon compound at room temperature after completion of the reaction 1 to 10 times.

  Based on the above, a particularly preferred method for preparing the solid catalyst component (A) in the present invention is to suspend dialkoxymagnesium (a) in an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. After bringing the tetravalent titanium halogen compound (b) into contact with the suspension, a reaction treatment is performed. At this time, before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension, one or more electron donating compounds (c) such as phthalic acid diesters are added at −20 to 20 Contact at 130 ° C. and contact with component (e) as necessary to carry out a reaction treatment to obtain a solid product (1). At this time, it is desirable to conduct the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds. This solid product (1) was washed with a liquid hydrocarbon compound at room temperature (intermediate washing), and then the tetravalent titanium halogen compound (b) was again -20 to 100 ° C in the presence of the aromatic hydrocarbon compound. To obtain a solid product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid product (2) is washed with a hydrocarbon compound that is liquid at room temperature by decantation to obtain the solid catalyst component (A).

  The ratio of the amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method, and thus cannot be determined unconditionally. For example, a tetravalent titanium halogen compound (b) per mole of the magnesium compound (a) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donating compound (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol. More preferably, it is 0.02 to 0.6 mol, and the aromatic hydrocarbon compound (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol. The polysiloxane (e) is 0.01 to 100 g, preferably 0.05 to 80 g, more preferably 1 to 50 g.

  Further, the content of titanium, magnesium, halogen atom and electron donating compound in the solid catalyst component (A) in the present invention is not particularly defined, but preferably 0.5 to 8.0% by weight, preferably 1% of titanium. 0.0-8.0 wt%, more preferably 2.0-8.0 wt%, magnesium is 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, still more preferably Is 15 to 25% by weight, halogen atoms are 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, and the total amount of electron-donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight in total, and particularly preferably 2 to 20% by weight in total.

The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (2). If there is no particular limitation, R ¹² is preferably an ethyl group or an isobutyl group, Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and p is preferably 2 or 3, and 3 is particularly preferable. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.

  As the amino compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention, a compound represented by the above general formula (1) is used. . Specific examples of the compound include those described above.

  In the presence of the olefin polymerization catalyst of the present invention, homopolymerization, random copolymerization or block copolymerization of olefins is carried out. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene, and 1-butene are preferably used. Particularly preferred is propylene. In the case of propylene, copolymerization with other olefins can be performed. Examples of the olefin to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used. Copolymerization of propylene and other olefins includes random copolymerization in one stage using propylene and a small amount of ethylene as a comonomer, and homopolymerization of propylene in the first stage (first polymerization tank). The so-called propylene-ethylene block copolymerization in which propylene and ethylene are copolymerized in a stage (second polymerization tank) or more stages (multistage polymerization tank) is typical. Even in such random copolymerization and block copolymerization, the catalyst of the present invention comprising the component (A), the component (B) and the component (C) is effective, and has catalytic activity, stereoregularity and / or hydrogen. Not only is the response good, but the copolymerization properties and the properties of the resulting copolymer are also good. In the present invention, the component (D) can be used in combination with the catalyst comprising the component (A), the component (B) and the component (C), if necessary, in order to further improve the catalyst performance. Specific examples of the organosilicon compound of the component (D) include di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyl ( Methyl) dimethoxysilane, t-butyl (ethyl) dimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl (methyl) dimethoxysilane, dicyclopentyldimethoxysilane, cyclopentyl (methyl) diethoxysilane, cyclopentyl (ethyl) dimethoxysilane, cyclopentyl (cyclohexyl) dimethoxy Silane, 3-methylcyclohexyl (cyclopentyl) dimethoxysilane, 4-methylcyclohexyl (cyclopentyl) dimethoxysilane, 3,5-dimethylcyclohexyl (cyclope Til) dimethoxysilane, bis (diethylamino) dimethoxysilane, bis (di-n-propylamino) dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, bis (di-t-butylamino) dimethoxysilane, bis ( Dicyclopentylamino) dimethoxysilane, bis (dicyclohexylamino) dimethoxysilane, bis (di-2-methylcyclohexylamino) dimethoxysilane, bis (isoquinolino) dimethoxysilane, bis (quinolino) dimethoxysilane, bis (ethyl-n-propylamino) ) Dimethoxysilane, bis (ethylisopropylamino) dimethoxysilane, bis (ethyl-n-butylamino) dimethoxysilane, bis (ethylisobutylamino) dimethoxysilane, bis (ethyl-t-butylamino) Methoxysilane, bis (isobutyl-n-propylamino) dimethoxysilane, bis (ethylcyclopentylamino) dimethoxysilane, bis (ethylcyclohexylamino) dimethoxysilane, ethyl (diethylamino) dimethoxysilane, n-propyl (diisopropylamino) dimethoxysilane, Isopropyl (di-t-butylamino) dimethoxysilane, cyclohexyl (diethylamino) dimethoxysilane, ethyl (di-t-butylamino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, n-propyl (isoquinolino) dimethoxysilane, isopropyl (isoquinolino) ) Dimethoxysilane, n-butyl (isoquinolino) dimethoxysilane, ethyl (quinolino) dimethoxysilane, n-propyl (quinolino) dimethoxy Silane, isopropyl (quinolino) dimethoxysilane, n-butyl (quinolino) dimethoxysilane, bis (diethylamino) diethoxysilane, bis (di-n-propylamino) diethoxysilane, bis (di-n-butylamino) diethoxy Silane, bis (di-t-butylamino) diethoxysilane, bis (dicyclopentylamino) diethoxysilane, bis (dicyclohexylamino) diethoxysilane, bis (di-2-methylcyclohexylamino) diethoxysilane, bis ( Diisoquinolino) diethoxysilane, bis (diquinolino) diethoxysilane, bis (ethyl-n-propylamino) diethoxysilane, bis (ethylisopropylamino) diethoxysilane, bis (ethyl-n-butylamino) diethoxysilane, Bis (ethyl Isobutylamino) diethoxysilane, bis (ethyl-t-butylamino) diethoxysilane, bis (isobutyl-n-propylamino) diethoxysilane, bis (ethylcyclopentylamino) diethoxysilane, bis (ethylcyclohexylamino) di Ethoxysilane, n-propyl (diisopropylamino) diethoxysilane, ethyl (isoquinolino) diethoxysilane, n-propyl (isoquinolino) diethoxysilane, isopropyl (isoquinolino) diethoxysilane, n-butyl (isoquinolino) diethoxysilane, Ethyl (quinolino) diethoxysilane, n-propyl (quinolino) diethoxysilane, isopropyl (quinolino) diethoxysilane, n-butyl (quinolino) diethoxysilane, texyltrimethoxysilane, die Tylaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, di-n-butylaminotrimethoxysilane, di-t-butylaminotrimethoxysilane, dicyclopentylaminotrimethoxysilane, dicyclohexylaminotrimethoxysilane, di 2-methylcyclohexylaminotrimethoxysilane, isoquinolinotrimethoxysilane, quinolinotrimethoxysilane, diethylaminotriethoxysilane, di-n-propylaminotriethoxysilane, di-n-butylaminotriethoxysilane, ethyl- t-butylaminotriethoxysilane, ethyl-sec-butylaminotriethoxysilane, dicyclopentylaminotriethoxysilane, dicyclohexylaminotriethoxysilane, di-2-methylcyclohexyla Minotriethoxysilane, isoquinolinotriethoxysilane, quinolinotriethoxysilane, bis (t-butylamino) dimethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (t-butylamino) diethoxysilane, bis (cyclohexyl) Amino) diethoxysilane, trivinylmethylsilane, tetravinylsilane, bis (methylamino) dicyclopentylsilane, bis (ethylamino) dicyclopentylsilane, bis (ethylamino) diisopropylsilane, bis (ethylamino) (diethylamino) ethylsilane, Bis (ethylamino) bis (diethylamino) silane, methyl ether, ethyl ether, propyl ether, butyl ether, amyle ether, diphenyl ether, 9,9-bis (methoxymethyl) E) Ethers such as fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are preferably used, and the organosilicon compound (D) can be used alone or in combination of two or more. . In particular, the component (D) described above in addition to the component (C) which is the catalyst component of the present invention is mixed and used, or the component (C) and the component (D) are separately used in a block copolymerization multistage polymerization tank. It can also be used.

  Also, when shifting from homopolymerization of propylene to block copolymerization, known electron donating compounds such as alcohols, oxygen gas or ketones should be added to the polymerization system in order to prevent gel formation in the final product. Can do. Specific examples of alcohols include ethyl alcohol, isopropyl alcohol and the like, and the amount used is 0.01 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of component (B).

  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, component (B) is used per 1 mole of titanium atom in component (A). , 1 to 2000 mol, preferably 50 to 1000 mol. Component (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.1 to 0.5 mol, per mol of component (B). When component (D) is used in combination, 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, is used per mol of component (B). Further, it is used in an amount of 0.001 to 10 mol, preferably 0.01 to 10 mol, particularly preferably 0.01 to 2 mol, per mol of the component (C).

  The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged in the polymerization system, and then the component (C) is contacted, or the components (C) and (D) mixed in advance It is desirable to contact the solid catalyst component (A) by contacting the components (C) and (D) in any order. Alternatively, the organoaluminum compound (B) is first charged into the polymerization system, while the component (A) and the component (C), or the component (C) and the component (D) are contacted in advance, and the components are brought into contact with each other. It is also a preferred embodiment that (A) and component (C) or component (C) and component (D) are charged into and contacted with each other to form a catalyst. Thus, it is possible to further improve the hydrogen response of the catalyst and the crystallinity of the produced polymer by previously treating the component (A) with the component (B) or the component (C) and the component (D). Become.

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used for polymerization in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 150 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 6 MPa or lower. In addition, either a continuous polymerization method or a batch polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

  Furthermore, in polymerizing olefins using the catalyst formed from component (A), component (B) and component (C) in the present invention (also referred to as “main polymerization”), catalytic activity, stereoregularity and production In order to further improve the particle properties and the like, it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used. Specifically, component (A), component (B) and / or component (C) are contacted in the presence of olefins, and 0.1 to 100 g of polyolefin per 1 g of component (A) is preliminarily polymerized. Further, the component (B) and / or the component (C) is further contacted to form a catalyst. When component (D) is used in combination, component (A), component (B) and component (D) are brought into contact with each other in the presence of olefins during the preliminary polymerization, and component (C) is used during the main polymerization. You can also.

  In carrying out the prepolymerization, the order of contacting the components and the monomers is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for carrying out polymerization such as propylene. And then contact component (C) and / or component (D), then contact component (A), and then contact olefin such as propylene and / or one or more other olefins. Let The prepolymerization temperature is arbitrary and is not particularly limited, but is preferably in the range of -10 ° C to 70 ° C, more preferably in the range of 0 ° C to 50 ° C.

  When olefins are polymerized in the presence of the olefin polymerization catalyst of the present invention, high stereoregularity is maintained and hydrogen response is improved as compared with the case where a conventional catalyst is used. Further, depending on the structure of the component (C), the catalytic activity and stereoregularity are improved as compared with the case where a conventional catalyst is used. That is, when the catalyst of the present invention is used for the polymerization of olefins, the structure of component (C) maintains high stereoregularity, improves hydrogen response, and improves catalytic activity and stereoregularity. Was confirmed.

  Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

<Synthesis of amino compounds>
80 ml of a toluene solution containing 0.05 mol of 1,1-di (bromomethyl) -2-methylindene was placed in a well-dried flask purged with nitrogen gas, cooled to 0 ° C., and stirred while stirring. Separately, a mixed slurry of 0.1 mol of ethylamine Li salt THF and hexane prepared by a conventional method was gradually added dropwise to the solution with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 80 ° C. for 3 hours. Heating was continued while trapping THF distilled off during the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the main product 1,1-bis (ethylaminomethyl) -2-methylindene was purified by distillation under reduced pressure. C, H, N elemental analysis of the product was performed. Figures in parentheses are theoretical values. As a result, C was 74.14% (74.17%), H was 11.43% (11.41%), and N was 14.40% (14.42%).

<Synthesis of amino compounds>
80 ml of a toluene solution containing 0.05 mol of 1,1-di (bromomethyl) -2,7-diethylindene was placed in a well-dried flask purged with nitrogen gas, cooled to 0 ° C. and stirred. Into this solution, a mixed slurry of 0.1 mol of methylamine Li salt THF and hexane separately prepared by a conventional method was gradually added dropwise with a syringe under a nitrogen stream. After completion of the dropping, the temperature was gradually raised and the reaction was carried out at 70 ° C. for 5 hours. Heating was continued while trapping THF distilled off during the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the main product 1,1-bis (methylaminomethyl) -2,7-diethylindene was purified by distillation under reduced pressure. C, H, N elemental analysis of the product was performed. Figures in parentheses are theoretical values. As a result, C was 79.01% (79.02%), H was 10.13% (10.14%), and N was 10.83% (10.84%).

<Synthesis of amino compounds>
80 ml of a toluene solution containing 0.05 mol of 1,1-di (bromomethyl) -2-phenylindene was placed in a well-dried flask purged with nitrogen gas, cooled to 0 ° C., and stirred while stirring. Separately, a mixed slurry of 0.1 mol of ethylamine Li salt THF and hexane prepared by a conventional method was gradually added dropwise to the solution with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 80 ° C. for 4 hours. Heating was continued while trapping THF distilled off during the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the main product 1,1-bis (ethylaminomethyl) -2-phenylindene was purified by distillation under reduced pressure. C, H, N elemental analysis of the product was performed. Figures in parentheses are theoretical values. As a result, C was 82.52% (82.59%), H was 9.03% (9.04%), and N was 8.34% (8.37%).

<Synthesis of amino ether compound>
80 ml of a toluene solution containing 0.05 mol of 1,1-di (chloromethyl) indene is placed in a well-dried flask purged with nitrogen gas, cooled to 0 ° C., and stirred while stirring the solution. Separately, 30 ml of hexane slurry of 0.05 mol ethoxy Li salt prepared by a conventional method was gradually added dropwise with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 60 ° C. for 3 hours. The reaction mixture was then cooled to 0 ° C. To this slurry of the mixture, 60 ml of a mixed slurry of 0.05 mol of ethylamine Li salt THF and hexane separately prepared by a conventional method was gradually added dropwise with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 80 ° C. for 3 hours. Heating was continued while trapping THF, hexane and the like distilled during the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the main product, 1- (ethylaminomethyl) -1- (ethoxymethyl) indene, was purified by distillation under reduced pressure. C, H, N elemental analysis of the product was performed. Figures in parentheses are theoretical values. As a result, C was 77.85% (77.88%), H was 9.12% (9.15%), and N was 6.09% (6.05%).

<Synthesis of amino ether compound>
80 ml of a toluene solution containing 0.05 mol of 1,1-di (chloromethyl) -2,7-diethylindene is placed in a well-dried flask purged with nitrogen gas, cooled to 0 ° C. and stirred. Then, 30 ml of a 0.05 mol methoxy Li salt hexane slurry separately prepared by a conventional method was gradually added dropwise to this solution with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 70 ° C. for 4 hours. The reaction mixture was then cooled to 0 ° C. To this slurry of the mixture, 60 ml of a mixed solvent slurry of THF and hexane of 0.05 mol of ethylamine Li salt separately prepared by a conventional method was gradually added dropwise with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 80 ° C. for 3 hours. Heating was continued while trapping THF, hexane and the like distilled during the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the main product 1- (ethylaminomethyl) -1-methoxymethyl-2,7-diethylindene was purified by distillation under reduced pressure. C, H, N elemental analysis of the product was performed. Figures in parentheses are theoretical values. As a result, C was 79.03% (79.07%), H was 9.93% (9.95%), and N was 5.11% (5.12%).

<Synthesis of amino ether compound>
80 ml of a toluene solution containing 0.05 mol of 1,1-di (chloromethyl) -2-iso-propylindene is placed in a well-dried flask purged with nitrogen gas, cooled to 0 ° C. and stirred. Then, 30 ml of a 0.05 mol methoxy Li salt hexane slurry separately prepared by a conventional method was gradually added dropwise to this solution with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 70 ° C. for 4 hours. The reaction mixture was then cooled to 0 ° C. To this slurry of the mixture, 60 ml of a mixed solvent slurry of THF and hexane of 0.05 mol of methylamine Li salt prepared separately by a conventional method was gradually added dropwise with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 80 ° C. for 3 hours. Heating was continued while trapping THF, hexane and the like distilled during the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the main product 1- (methylaminomethyl) -1-methoxy-2-iso-propylindene was purified by distillation under reduced pressure. C, H, N elemental analysis of the product was performed. Figures in parentheses are theoretical values. As a result, C was 78.30% (78.32%), H was 9.42% (9.45%), and N was 5.70% (5.71%).

<Synthesis of amino ether compound>
80 ml of a toluene solution containing 0.05 mol of 1,1-di (chloromethyl) -2-cyclopentylindene was taken into a flask that had been sufficiently dried and replaced with nitrogen gas, cooled to 0 ° C., and stirred. Into this solution, 30 ml of a 0.05 mol methoxy Li salt hexane slurry separately prepared by a conventional method was gradually added dropwise with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 70 ° C. for 4 hours. The reaction mixture was then cooled to 0 ° C. To this slurry of the mixture, 60 ml of a mixed solvent slurry of THF and hexane of 0.05 mol of ethylamine Li salt separately prepared by a conventional method was gradually added dropwise with a syringe under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 80 ° C. for 3 hours. Heating was continued while trapping THF, hexane and the like distilled during the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, and the main product 1- (ethylaminomethyl) -1-methoxymethyl-2-cyclopentylindene was purified by distillation under reduced pressure. C, H, N elemental analysis of the product was performed. Figures in parentheses are theoretical values. As a result, C was 79.94% (79.95%), H was 9.52% (9.53%), and N was 4.89% (4.91%).

<Preparation of solid catalyst component>
A 2000-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 150 g of diethoxymagnesium and 750 ml of toluene to form a suspension. The suspension was then added to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride, pre-charged in a 2000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. The suspension was then reacted at 5 ° C. for 1 hour. Thereafter, 22.5 ml of n-butyl phthalate was added and the temperature was raised to 100 ° C., followed by reaction treatment with stirring for 2 hours. After completion of the reaction, the product was washed four times with 1300 ml of toluene at 80 ° C., 1200 ml of toluene and 300 ml of titanium tetrachloride were newly added, and the reaction treatment was performed at 110 ° C. for 2 hours with stirring. The intermediate wash and the second treatment were repeated once more. The product was then washed 7 times with 1300 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component. The titanium content in the solid component was measured and found to be 3.1% by weight.

<Formation and polymerization of polymerization catalyst>
Into an autoclave with a stirrer having an internal volume of 2.0 liters, completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum and 1,1-bis (ethylaminomethyl) -2-methylindene obtained in Example 1 were added in an amount of 0.001. 13 mmol and 0.0026 mmol of the solid catalyst component as titanium atoms were charged to form a polymerization catalyst. Thereafter, 4 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. With respect to the obtained polymer, the catalyst index, bulk specific gravity (BD, g / ml), heptane-insoluble part (HI, weight%), and melt flow rate are melt index (MI, g-PP / 10 minutes) according to ASTM. It showed in. The molecular weight distribution of the polymer was also measured. The results are shown in Table 1.

  The catalyst activity indicating the amount of polymer produced (F) g per hour of the polymerization time per 1 g of the solid catalyst component was calculated by the following equation.

  Catalytic activity = product polymer (F) g / solid catalyst component g / 1 hour

  Further, a part (G) g of this polymer was continuously extracted with boiling n-heptane for 6 hours, and then the polymer insoluble in n-heptane was dried, and the weight (H) g was measured. Of boiling heptane insoluble matter (HI,% by weight) was calculated from the following formula.

  HI (wt%) = (H) g / (G) g × 100

  The melt index (MI) value indicating the melt flow rate of the polymer was measured according to ASTM D 1238 and JIS K 7210.

The molecular weight distribution of the polymer is determined by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained by measurement under the following conditions in a cross fractionation chromatograph (CFC) (CFC T-150B manufactured by Mitsubishi Chemical Corporation). evaluated.
Solvent: o-dichlorobenzene (ODCB)
Temperature: 140 ° C (SEC)
Column: Shodex GPC UT-806m ²
Sample concentration: 4 g / l-ODCB (200 mg / 50 ml-ODCB)
Injection volume: 0.5ml
Flow rate: 1.0 ml / min
Measurement range: 0 to 140 ° C

  Example 1 except that 1,1-bis (methylaminomethyl) -2,7-diethylindene obtained in Example 2 was used instead of 1,1-bis (ethylaminomethyl) -2-methylindene The experiment was conducted in the same manner. The obtained results are shown in Table 1.

  Similar to Example 8 except that 1,1-bis (ethylaminomethyl) -2-phenylindene obtained in Example 3 was used instead of 1,1-bis (ethylaminomethyl) -2-methylindene. The experiment was conducted. The obtained results are shown in Table 1.

  The experiment was conducted in the same manner as in Example 8 except that 1- (ethylaminomethyl) -1-ethoxymethylindene obtained in Example 4 was used instead of 1,1-bis (ethylaminomethyl) -2-methylindene. I did it. The obtained results are shown in Table 1.

  Example except that 1- (ethylaminomethyl) -1-methoxymethyl-2,7-diethylindene obtained in Example 5 was used in place of 1,1-bis (ethylaminomethyl) -2-methylindene The experiment was conducted in the same manner as in FIG. The obtained results are shown in Table 1.

  Example except that 1- (methylaminomethyl) -1-methoxymethyl-2-iso-propylindene obtained in Example 6 was used in place of 1,1-bis (ethylaminomethyl) -2-methylindene The experiment was conducted in the same manner as in FIG. The obtained results are shown in Table 1.

  Example 8 except that 1- (ethylaminomethyl) -1-methoxymethyl-2-cyclopentylindene obtained in Example 7 was used instead of 1,1-bis (ethylaminomethyl) -2-methylindene The experiment was conducted in the same manner. The obtained results are shown in Table 1.

<Preparation of solid catalyst component>
A 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas was charged with 4.76 g of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml of 2-ethylhexyl alcohol, and at 130 ° C. for 2 hours. Reaction was performed to obtain a homogeneous solution. Next, 1.11 g of phthalic anhydride was added to the homogeneous solution and reacted at 130 ° C. for 1 hour. The solution was then added dropwise to 200 ml of titanium tetrachloride charged in a 500 ml round bottom flask equipped with a stirrer and fully substituted with nitrogen gas and maintained at -20 ° C over 1 hour. did. Subsequently, after heating up this mixed solution to 110 degreeC over 4 hours, 2.68 ml of diisobutyl phthalate was added and it was made to react for 2 hours. After completion of the reaction, the liquid part is removed by filtration, and the remaining solid component is washed with decane and hexane at 110 ° C. until no free titanium compound is detected, filtered and dried to obtain a powdered solid catalyst component. It was. The titanium content in the solid catalyst component was measured and found to be 3.1% by weight.

<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and polymerized in the same manner as in Example 8 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.

<Preparation of solid catalyst component>
32 g of ground magnesium for Grignard was charged into a 1000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Next, a mixed liquid of 120 g of butyl chloride and 500 ml of dibutyl ether was dropped into the magnesium over 4 hours at 50 ° C., and then reacted at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature and solid content was removed by filtration to obtain a magnesium compound solution. Next, a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 240 ml of hexane, 5.4 g of tetrabutoxytitanium and 61.4 g of tetraethoxysilane to obtain a homogeneous solution. The magnesium compound solution (150 ml) was added dropwise at 5 ° C. over 4 hours to react, and then stirred at room temperature for 1 hour. Next, the reaction solution was filtered at room temperature to remove the liquid portion, and then the remaining solid was washed 8 times with 240 ml of hexane and dried under reduced pressure to obtain a solid product. Then, 8.6 g of the solid product was charged into a 100-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and further 48 ml of toluene and 5.8 ml of diisobutyl phthalate were added. The reaction was allowed to proceed for 1 hour at ° C. Thereafter, the liquid part was removed by filtration, and the remaining solid was washed 8 times with 85 ml of toluene. After completion of washing, 21 ml of toluene, 0.48 ml of diisobutyl phthalate and 12.8 ml of titanium tetrachloride were added to the flask and reacted at 95 ° C. for 8 hours. After completion of the reaction, solid-liquid separation is performed at 95 ° C., and the solid content is washed twice with 48 ml of toluene. Then, the treatment with the above mixture of diisobutyl phthalate and titanium tetrachloride is performed again under the same conditions, and washed with 48 ml of hexane eight times. Filtered and dried to obtain a powdered solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 2.1% by weight.

<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and polymerized in the same manner as in Example 8 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.

Comparative Example 1
A solid catalyst component was prepared in the same manner as in Example 8, except that cyclohexylmethyldimethoxysilane was used instead of 1,1-bis (ethylaminomethyl) -2-methylindene to form and polymerize the polymerization catalyst. Polymerization catalyst formation and polymerization were performed. The obtained results are shown in Table 1.

Comparative Example 2
A solid catalyst component was prepared in the same manner as in Example 8 except that the polymerization catalyst was formed and polymerized using bis (diethylamino) dimethoxy instead of 1,1-bis (ethylaminomethyl) -2-methylindene. The polymerization catalyst was formed and polymerized. The obtained results are shown in Table 1.

Comparative Example 3
A solid catalyst component was prepared in the same manner as in Example 8 except that the polymerization catalyst was formed and polymerized using diisopropylaminotriethoxysilane instead of 1,1-bis (ethylaminomethyl) -2-methylindene. The polymerization catalyst was formed and polymerized. The obtained results are shown in Table 1.

以上の結果から、重合時にアミノ化合物を用いると、高い立体規則性の重合体を収率良く得られ、かつ水素レスポンスが良好であることがわかる。
Comparative Example 4
A solid catalyst component was prepared in the same manner as in Example 8, except that tris (dimethylamino) methoxysilane was used instead of 1,1-bis (ethylaminomethyl) -2-methylindene to form and polymerize the polymerization catalyst. Preparation, polymerization catalyst formation and polymerization were performed. The obtained results are shown in Table 1.

From the above results, it can be seen that when an amino compound is used during the polymerization, a highly stereoregular polymer can be obtained with a good yield and the hydrogen response is good.

It is a flowchart figure which shows the process of preparing the catalyst component and polymerization catalyst of this invention.

Claims (6)

Following formula (1);

Wherein R ^{1 to} R ¹⁰ are a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or a derivative thereof, an allyl group, an aralkyl group, a vinyl group, a phenyl group, two A secondary amino group, an alkoxy group, and these groups may contain a hetero atom, and may be the same or different, and any two groups of R ^{1 to} R ¹⁰ may be mutually bonded. R ¹¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a derivative thereof, an allyl group, an aralkyl group, a vinyl group, or a phenyl group. The group may contain a heteroatom, and Z is a secondary amino group or an alkoxy group, provided that it has at least two secondary amino bonds or one secondary amino bond And Ete Olefin polymerization catalyst component represented by having a bond.).   An olefin polymerization catalyst formed using the olefin polymerization catalyst component according to claim 1 as an essential component. (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound;
(B) the following general formula (2);
_{^{R 12 AlQ 3-p (2}} )
(Wherein R ¹² represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) An olefin polymerization catalyst formed from the olefin polymerization catalyst component according to claim 1.   The olefins according to claim 3, wherein the solid catalyst component is prepared by contacting a magnesium compound (a), a tetravalent titanium halogen compound (b) and an electron donating compound (c). Polymerization catalyst.   A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 2 to 4.   6. The method for producing an olefin polymer according to claim 5, wherein the olefin polymer is a propylene polymer.

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