KR100332502B1 - Propylene elastomer - Google Patents

Abstract

PURPOSE: Provided is a propylene elastomer which has excellent mechanical properties and optical properties including heat resistance, impact absorptivity, transparency, gloss, heat-sealability and blocking resistance. CONSTITUTION: The propylene elastomer has the following characteristics: (a) the elastomer contains 50-95 mol% of propylene units and 5-50 mol% of ethylene units; (b) the triad tacticity of three propylene unit chains formed by head-to-tail bonds is 90.0% or more when measured by 13C-NMR; (c) the ratios of stereo-irregular units generated by 2,1-insertion and 1,3-insertion of propylene monomers, based on the total propylene insertion, are 0.5% or more and 0.05% or less, respectively, when measured by 13C-NMR; and (d) the intrinsic viscosity is 0.1 to 12 dl/g when measured in decahydronaphthalene at 135 deg.C.

Description

Propylene Elastomer {PROPYLENE ELASTOMER}

The present invention relates to a novel transition metal compound, an olefin polymerization catalyst component of the transition metal compound, an olefin polymerization catalyst containing the catalyst component, and an olefin polymerization method using the olefin polymerization catalyst. The present invention also relates to high-propylene tripropylene tacticity propylene homopolymers, propylene copolymers and propylene elastomers. Well known homogeneous catalysts are, for example, the so-called kaminsky catalyst.

By using this catalyst, a polymer having a very high polymerization activity and a narrow molecular weight distribution can be obtained.

Ethylene bis (indenyl) -zirconium dichloride and ethylene bis (4,5,6,7-tetrahydrointenyl) zirconium dichloride in Kaminsky catalysts as described in Japanese Patent Application Laid-Open No. 61-130134 It is known as a transition metal compound for producing isotactic polyolefins. However, polyolefins prepared using such catalysts generally have low stereoregularity and low molecular weight.

There is a method for producing a high-stereoregular and high molecular weight polyolefin using such a catalyst, but there is a method for producing at a low temperature, this method has a problem of low polymerization activity.

In addition, Journal of Molecular Catalysis, 56 (1989), pp. If hafnium compounds are used instead of zirconium compounds as described in 237-247, high molecular weight polymers can be prepared, but this method also has a problem of low polymerization activity.

In addition, Japanese Patent Laid-Open No. Hei 1-301704 and 'Polymer Preprints',' Japan, Vo1. 39, No. 6, pp. As described in 1,614-1,616 (1980), dimethylsilylbissubstituted cyclopentadienyl zirconium dichloride is also known, but there is a problem that high polymerization activity, high stereoregularity and high molecular weight cannot be simultaneously satisfied.

There are several proposals to solve this problem. For example, Japanese Patent Laid-Open No. 4-268307 describes a polymerization catalyst composed of a metallocene compound and an aluminoxane represented by the following formula as a catalyst capable of producing a high molecular weight polyolefin, but the molecular weight of the resulting polyolefin is sufficient. Not.

In addition, EP 0 530 648 A1 describes an olefin polymerization catalyst comprising a metallocene compound and an aluminoxane represented by the following formula.

In the formula, A is a lower alkyl group.

Since the molecular weight of the polyolefin obtained by this catalyst is high and industrially satisfactory, and the melting point of polyolefin (for example, polypropylene) is also high, it is suitable for manufacture of the stereoregular polyolefin with high melting point.

However, it is unsuitable for stereoregular polyolefins (particularly copolymers) having high molecular weight and low melting point, and the quality of the polymer or copolymer obtained is not satisfactory.

EP 0 537 686 also describes an olefin polymerization catalyst consisting of a metallocene compound and an aluminoxane represented by the following formula.

R ¹ and R ² in the formula are each a methyl group or hydrogen, X is Si (CH _{3) 2} group or an ethylene group. However, the molecular weight of the polyolefin obtained by this catalyst is low and cannot be used practically.

Under the above circumstances, an olefin polymerization catalyst and an olefin polymerization method excellent in olefin polymerization activity and excellent in the properties of a polyolefin obtained are required. There is also a need for a novel transition metal compound that can be an olefin polymerization catalyst component and an olefin polymerization catalyst component used in such a catalyst. The present inventors have made diligent research in consideration of the conventional situation and found that a transition metal compound having two indenyl groups bonded to a hydrocarbon group, a silicon-containing group and the like and having a specific substituent can satisfy the above requirements.

Propylene polymers are used in all fields because of their excellent mechanical and optical properties.

For example, propylene polymers are used in various industrial parts, containers, films and nonwoven fabrics because of their excellent rigidity, surface hardness, heat resistance, gloss and transparency. Propylene / ethylene random copolymers containing a small amount of ethylene units are used in films and containers because of their excellent transparency, rigidity, surface hardness, heat resistance and heat sealing. Propylene elastomers are excellent in shock absorption, heat resistance and heat sealing, so they are used alone in films or as modifiers of thermoplastic resins.

However, the conventional propylene polymer is not necessarily sufficient transparency, impact resistance, etc. depending on the intended use, it is required to emerge a propylene polymer excellent in rigidity, heat resistance, surface hardness, gloss, transparency and impact strength.

Conventional propylene / ethylene random copolymer does not necessarily have sufficient transparency, heat sealing, anti-blocking, outflow resistance, impact strength, etc. depending on the intended use, so that transparency, rigidity, surface hardness, heat resistance, and heat sealing resistance The emergence of this excellent propylene / ethylene random copolymer is required. Conventional propylene elastomers are not necessarily sufficient for heat sealing, anti-blocking and heat resistance when used alone in certain applications, and are not necessarily sufficient for improving impact resistance even when used as a modifier. In addition, the effect of improving antiblocking and impact resistance is required.

In view of the above situation, the present inventors conducted further studies, and the triad taxity measured by ¹³ C-NMR of the propylene chain composed of head-to-tail bonds was high, and the position of a specific ratio. It has been found that propylene polymers with irregular propylene units and specific intrinsic viscosities excel in the properties described above. The present inventors also found that propylene copolymers containing a small amount of ethylene units and having a high triad taxity as measured by ¹³ C-NMR of a propylene chain composed of iron-bonds, having a specific proportion of irregular propylene units and a specific intrinsic viscosity It has also been found that is excellent in the above-described properties. The present inventors also found that a propylene ERA containing a specific amount of ethylene units, and having a high triad taxity as measured by ¹³ C-NMR of a propylene chain composed of a double bond, having a specific proportion of irregular propylene units and a specific intrinsic viscosity It has also been found that the Stormer is excellent in the properties described above.

Furthermore, the present inventors have found that propylene polymers, propylene copolymers and propylene elastomers can be produced by using an olefin polymerization catalyst containing a specific transition metal compound as a catalyst component.

An object of the present invention is to provide a novel transition metal compound useful for an olefin polymerization catalyst component having excellent polymerization activity of an olefin, and at the same time, to provide an olefin polymerization catalyst component of the transition metal compound.

Another object of the present invention is to provide an olefin polymerization catalyst containing the catalyst component for olefin polymerization and to provide a polymerization method of olefins using the olefin polymerization catalyst. Another object of the present invention is to provide a propylene polymer having excellent properties.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a step of a method for producing the first and second olefin polymerization catalysts according to the present invention.

2 is a view showing a process of the method for producing the third and fourth olefin polymerization catalysts according to the present invention.

Figure 3 is a view showing a step of the production method of the fifth and sixth olefin polymerization catalyst according to the present invention.

The novel transition metal compound according to the present invention is a transition metal compound represented by the following general formula (I).

M in the formula is a transition metal of Periodic Tables IVa, Va, and VIa;

R ¹ and R ² each contain a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus group Group;

R ³ is an alkyl group of 2 to 20 carbon atoms;

R ⁴ is an alkyl group of 1 to 20 carbon atoms;

X ¹ and X ² are each a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen containing group or a sulfur containing group;

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon containing group, a divalent germanium containing group, a divalent tin containing group, -0-,-CO- , -S-,-SO-,-SO ₂ -,-NR ⁵ -,-P (R ⁵ )-,-P (O) (R ⁵ )-,-BR ⁵ -or -A1R ^5- (R ⁵ Is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, or a halogenated hydrocarbon group of 1 to 20 carbon atoms).

The catalyst component for olefin polymerization according to the present invention is a transition metal compound represented by the general formula (I).

The first catalyst for olefin polymerization according to the present invention

(A) the transition metal compound represented by the general formula (I); And

(B)

(B-1) an organoaluminum oxy compound, and

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs.

The second catalyst for olefin polymerization according to the present invention

(A) the transition metal compound represented by the general formula (I);

(B)

(B-1) an organoaluminum oxy compound, and

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs; And

(C) It is an organoaluminum compound.

The third catalyst for olefin polymerization according to the present invention

Particulate carriers;

(A) the transition metal compound represented by the general formula (I), and

(B)

(B-1) an organoaluminum oxy compound, and

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs, the transition metal compound (A) and

The at least one compound (B) is supported on the particulate carrier.

The fourth catalyst for olefin polymerization of the present invention

Particulate carriers;

(A) the transition metal compound represented by the general formula (I) and

(B)

(B-1) an organic aluminum oxy compound and

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs, wherein the transition metal compound (A) and the at least one compound (B) A solid catalyst component supported on the particulate carrier;

(C) It is an organoaluminum compound.

The fifth olefin polymerization catalyst according to the present invention

Particulate carriers;

(A) the transition metal compound represented by the general formula (I);

(B)

(B-1) organoaluminum oxy compound and

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs; And

It becomes a prepolymer olefin polymer produced by a prepolymer.

The sixth catalyst for olefin polymerization according to the present invention

Particulate carriers;

(A) the transition metal compound represented by the general formula (I);

(B)

(B-1) an organoaluminum oxy compound, and

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs;

(C) an organoaluminum compound, and

It becomes a prepolymer olefin polymer produced by a prepolymer.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of any one of the first to sixth olefin polymerization catalysts.

The catalyst for olefin polymerization according to the present invention has high polymerization activity, and the olefin polymer obtained using the catalyst has a narrow molecular weight distribution and a narrow composition distribution. When the catalyst is used to polymerize α-olefins having 3 or more carbon atoms, polymers having lower melting points can be obtained when the molecular weights of these polymers are the same as compared with those obtained using conventional metallocene catalysts. In addition, when a copolymer or an elastomer containing ethylene or propylene as a main component is produced, a high molecular weight polymer is obtained.

By using such a catalyst, a low melting point copolymer can be obtained even if the amount of comonomer units is small.

Propylene polymer according to the present invention

(a) more than 90.0% of the triadtaxity of the 3 propylene unit chain of a dumi bond measured by ¹³ C-NMR;

(b) Positional irregularity based on 2,1-insertion of propylene monomer in all propylene insertions.Proportion of propylene units is not less than 0.7% by ¹³ C-NMR and positional irregularity based on 1,3-insertion of propylene monomer. The proportion of propylene units is 0.05% or less as measured by ¹³ C-NMR; And

(c) Intrinsic viscosity is 135 degreeC and it measures in detahydro naphthalene, and has a characteristic of 0.1-12 dl / g.

Such a propylene polymer is excellent in rigidity, heat resistance, surface hardness, gloss, transparency, and impact strength.

Propylene copolymer according to the present invention

(a) the copolymer contains 95 to 99.5 mole% of propylene units and 0.5 to 5 mole% ethylene units;

(b) more than 90.0% of the triadtacticity of the 3 propylene unit chain of the dumi-bond as measured by ¹³ C-NMR;

(c) Positional irregularity based on 2,1-insertion of propylene monomer during all propylene insertions The proportion of propylene units is not less than 0.5% as measured by ¹³ C-NMR, and positional irregularity by 1,3-insertion of propylene monomer. The proportion of propylene units is 0.05% or less as measured by ¹³ C-NMR; And

(d) Intrinsic viscosity is measured in 135 degreeC and decahydro naphthalene, and has a characteristic of 0.1-12 dl / g.

Such copolymers are excellent in transparency, rigidity, surface hardness, heat resistance, heat sealing resistance, bleed resistance and impact resistance.

Propylene elastomer according to the present invention

(a) the elastomer contains 50 to 95 mole percent propylene units and 5 to 50 mole percent ethylene units;

(b) more than 90% of the triadtacticity of the 3 propylene unit chain consisting of dumi bonds measured by ¹³ C-NMR;

(c) Positional irregularity based on 2,1-insertion of propylene monomer in all propylene insertions.Proportion of propylene units is not less than 0.5% by ¹³ C-NMR and positional irregularity based on 1,3-insertion of propylene monomer. The proportion of propylene units is 0.05% or less by ¹³ C-NMR measurement; And

(d) Intrinsic viscosity is measured in 135 degreeC and decahydro naphthalene, and has a characteristic of 0.1-12 dl / g.

Such elastomers are excellent in heat resistance, shock absorption, transparency, heat sealing and anti-blocking properties.

A novel transition metal compound according to the present invention, an olefin polymerization catalyst component of the transition metal compound, an olefin polymerization catalyst containing the olefin polymerization catalyst component, an olefin polymerization method using the olefin polymerization catalyst, a propylene polymer, The propylene copolymer and the propylene elastomer will be described in detail below.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the process of the manufacturing method of the 1st and 2nd olefin polymerization catalysts by this invention. 2 is a view showing the process of the method for producing the third and fourth olefin polymerization catalysts according to the present invention. 3 is a view showing a step of the process for producing the fifth and sixth olefin polymerization catalysts according to the present invention.

First, the novel transition metal compound according to the present invention will be described.

The novel transition metal compound of the present invention is a transition metal compound represented by the following general formula (I).

M in Formula (I) is a transition metal of Group IVa, Va, and VIa of the periodic table. Examples of the transition metals include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, among which titanium, zirconium and hafnium are preferable, and zirconium is particularly preferable.

R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or It is a phosphorus containing group.

Halogen atoms are, for example, fluoro, chlorine, bromine and iodine, and hydrocarbon groups of 1 to 20 carbon atoms are for example methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, icosyl, norbor Alkyl groups such as neil and adamantyl; Alkenyl such as vinyl, propenyl and cyclohexenyl; Arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Aryl groups such as phenyl, rollyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl, halogenated hydrocarbon groups are substituted with halogen atoms, for example, in the hydrocarbon group, The silicon-containing group is, for example, monohydrocarbon substituted silyl such as methylsilyl, phenylsilyl; Dihydrocarbon substituted silyl such as dimethylsilyl and diphenylsilyl; Trihydrocarbon substituted silyls such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, trirrolylsilyl and trinaphthylsilyl; Silyloxy of hydrocarbon-substituted silyl such as trimethylsilyloxy; Silicon-substituted alkyl groups such as trimethylsilylmethyl, especially trilower alkylsilylmethyl groups; Silicon substituted aryl groups, such as trimethylphenyl, are especially trilower alkyl silylphenyl group. The hydrocarbon is preferably lower alkyl, cyclohexyl, phenyl, tolyl or naphthyl.

The oxygen-containing group is for example a hydroxy group; Alkoxy groups, such as methoxy, ethoxy, propoxy, butoxy, especially a low alkoxy group; Aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; Arylalkoxy groups such as benzyloxy and phenylethoxy, and the sulfur-containing group is, for example, mercapto, lower alkylthio group; Arylthio group; And sulfur in the oxygen of the oxygen-containing group such as an arylalkylthio group, and the like, and the nitrogen-containing group is, for example, an amino group; Alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; Arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino; It is an alkylarylamino group, and phosphorus containing group is a phosphino group, such as dimethyl phosphino and diphenyl phosphino, Among these, R <^1> is preferably a hydrocarbon group, Especially the alkyl group of 1-3 carbon atoms, such as methyl, ethyl, propyl, etc. Is preferably.

R ² is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

R ³ is an alkyl group having 2 to 20 carbon atoms or an arylalkyl group having 20 or less carbon atoms, and R ⁴ is an alkyl group having 1 to 20 carbon atoms. R ³ is preferably a secondary or tertiary alkyl group. The alkyl group represented by R ³ or R ⁴ may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and silicon-containing group include those exemplified for the above R ¹ and R ² .

Examples of the alkyl group represented by R ³ include ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, dodecyl, icosyl, norbor Linear alkyl groups and cyclic alkyl groups such as neyl and adamantyl; And arylalkyl groups such as benzyl, phenylethyl, phenylpropyl and tolylmethyl.

These groups may be substituted with groups containing a double bond or a triple bond.

Examples of the alkyl group represented by R ⁴ include methyl and the chain alkyl group, cyclic alkyl group, and arylalkyl group exemplified above for R ³ .

X ¹ and X ² are each a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen containing group or a sulfur containing group.

Examples of such atoms and groups include a halogen atom exemplified by R ¹ and R ² , a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, and an oxygen-containing group.

As the sulfur-containing group, methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluoro Sulfonate groups such as robenzenesulfonate; And sulfinate groups such as methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate and pentafluorobenzene sulfinate.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group. -CO-, -S-, -SO-, -SO _2- , -NR ^5- , -P (R ⁵ )-, -P (O) (R ⁵ )-, -BR ⁵ -or -A1R ⁵ ( R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms.

Examples of the divalent hydrocarbon group having 1 to 20 hydrocarbon atoms include alkylene groups such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene and 1,4-tetramethylene; Cycloalkylene groups, such as 1, 2- cyclohexylene and 1, 4- cyclohexylene: Aryl alkylene groups, such as diphenylmethylene and diphenyl-1,2-ethylene, are mentioned.

As an example of a halogenated hydrocarbon group, group obtained by halogenating the said hydrocarbon group of 1-20 carbon atoms, such as chloromethylene, is mentioned.

Examples of the silicon-containing group include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylenediphenylsilylene Alkylsilylene groups such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylene groups, and arylsilylene groups; Alkyl disilyl groups, alkylaryl dissilyl groups, and aryl silyl groups, such as tetramethyl- 1, 2- disilyl and tetraphenyl- 1, 2- disilyl, are mentioned.

The alkylsilylene group is a mono-alkylsilylene group or a di-alkylsilylene group, and the alkyl group is preferably lower alkyl or cycloalkyl having 1 to 4 carbon atoms.

The arylsilylene group is mono-arylsilylene or diarylsilylene, and aryl is preferably phenyl substituted with lower alkyl or halogen.

Examples of the divalent germanium-containing group include a group obtained by substituting germanium for silicon of the divalent silicon-containing group.

As an example of a bivalent tin containing group, group obtained by substituting the silicon of the said silicon containing group by tin is mentioned.

Examples of the atoms and groups represented by R ⁵ include a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, and a halogenated hydrocarbon group of 1 to 20 carbon atoms exemplified by R ¹ and R ² .

Among these, divalent silicon-containing groups, divalent germanium-containing groups, and divalent tin-containing groups are preferable, and silicon-containing groups are particularly preferable. Of the silicon-containing groups, alkylsilylene, alkylarylsilylene and arylsilylene are particularly preferred.

Examples of the transition metal compound represented by the general formula (I) are given below.

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-n-propylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-n-pentylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride,

rac-diethylsilyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (i-propyl) silyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (n-butyl) silyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (cyclohexyl) silyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,

rac-di (p-tolyl) silyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (p-chlorophenyl) silyl-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-ethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride,

rac-diethylsilyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-sec-butylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-phenylethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride,

rac-diethylsilyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (i-propyl) silyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (i-butyl) silyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (cyclohexyl) silyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride

rac-diphenylsilyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride,

rac-di (p-tolyl) silyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-di (p-chlorophenyl) silyl-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl,

rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconiummethyl chloride,

rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (methanesulfonate),

rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium (p-phenylsulfonate),

rac-dimethylsilyl-bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} titanium dichloride, and

rac-dimethylsilyl-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} hafnium dichloride,

Of these, compounds having a branched alkyl group (eg i-propyl, sec-butyl, tert-butyl) at the 4th position are particularly preferred.

In the present invention, a transition metal compound in which zirconium metal is substituted with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten in the above compound may be used.

The indene derivative ligands of the novel transition metal compound according to the present invention can be synthesized using a conventional organic synthesis method through the following reaction route.

The transition metal compound of the present invention can be synthesized from these indene derivatives by a known method, for example, the method described in JP-A 4-268307.

The novel transition metal compound according to the present invention is used as a catalyst component for olefin polymerization in combination with an organoaluminum oxy compound.

The transition metal compound is generally used as a catalyst component for olefin polymerization in the form of racemic, but may also be used in the form of R or S.

Next, the catalyst for olefin polymerization containing the novel transition metal compound described above as a catalyst component will be described.

The term 'polymerization' is used here to include not only 'polymerization' but also 'copolymerization', and 'polymer' may be used to include not only 'polymer' but also 'copolymer'. .

The first and second olefin polymerization catalysts according to the present invention will be described below.

The first catalyst for olefin polymerization of the present invention

(A) the transition metal compound represented by the general formula (I) (hereinafter sometimes referred to as 'component (A)'); And

(B)

(B-1) an organoaluminum oxy compound, and

(B-2) At least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs.

The second catalyst for olefin polymerization of the present invention

(A) the transition metal compound represented by the general formula (I);

(B)

(B-1) an organoaluminum oxy compound, and

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs; And

(C) It is formed with an organoaluminum compound.

The organoaluminum oxy compound (B-1) (hereinafter sometimes referred to as 'component (B-1)') used in the first and second olefin polymerization catalysts of the present invention may be conventionally known aluminoxane. A benzene-insoluble organoaluminum oxy compound as described in Japanese Patent Laid-Open No. 2-78687 may be used.

Conventionally known aluminoxanes can be produced, for example, by the following method.

(1) Organic aluminum, such as trialkylaluminum, in suspensions such as compounds containing adsorbed water or salts containing crystallized water, such as magnesium chloride hydrates, copper sulfate hydrates, aluminum sulfate hydrates, nickel sulfate hydrates, and cerium chloride hydrates. A method of adding and reacting a compound to recover as a solution of a hydrocarbon.

(2) A method of recovering as a solution of a hydrocarbon by directly acting water, ice, or water vapor on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, tetrahydrofuran or the like.

(3) A method of reacting organotin oxides, such as dimethyltin oxide and dibutyltinoxide, with organoaluminum compounds such as trialkylaluminum in a medium such as decane, benzene, or toluene.

This aluminoxane may contain a small amount of organometallic components. In addition, the solvent or the unreacted organic aluminum compound may be distilled off from the recovered solution of aluminoxane and then redissolved in the solvent.

Examples of the organoaluminum compounds used when preparing aluminoxanes include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum and tri trialkyl aluminums such as tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum and tridecyl aluminum;

Tricycloalkyl aluminum, such as tricyclohexyl aluminum and tricyclooctyl aluminum;

Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride;

Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride;

Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; And

Dialkyl aluminum aryl oxide, such as diethyl aluminum phenoxide, etc. are mentioned.

Among the organoaluminum compounds, trialkylaluminum and tricycloalkylaluminum are particularly preferable.

Moreover, the isoprenyl aluminum represented by following General formula (II) can also be used as an organoaluminum compound used when manufacturing aluminoxane.

(iC ₄ H ₉ ) xAly (C ₅ H ₁₀ ) z

X, y, z in the formula is a positive number, Z≥2x.

Such organoaluminum compounds are used alone or in combination.

As a solvent used when manufacturing aluminoxane, Aromatic hydrocarbons, such as benzene, toluene, xylene, cumene, cymene; Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; Petroleum oils such as gasoline, kerosene and diesel; And hydrocarbon solvents such as halides of the aromatic hydrocarbons, aliphatic hydrocarbons and cycloaliphatic hydrocarbons, in particular chlorides and bromide. Other ethers, such as ethyl ether and tetrahydrofuran, can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred.

As an example of a compound which forms an ion pair by reacting with the transition metal compound (A) used in the first and second olefin polymerization catalysts (hereinafter referred to as 'component (B-2)'), Japanese Patent Application Laid-Open Nos. 1-501950 and 1-502036, Japanese Patent Laid-Open No. 3-179005, Japanese Patent Laid-Open No. 3-179006, Japanese Patent Laid-Open No. 3-207703 and Japanese Patent Laid-Open No. 3-207704 and US Patent No. . Lewis acids, ionic compounds and borane compounds and carborane compounds as described in 547718.

Examples of the Lewis acid include Mg-containing Lewis acid, Al-containing Lewis acid, and B-containing Lewis acid. Among them, B-containing Lewis acid is preferable.

As an example of Lewis acid (B containing Lewis acid) containing a boron atom, the compound represented by the following general formula is mentioned.

BR ⁶ R ⁷ R ⁸

In formula, R <^6> , R <^7> and R <^8> respectively independently represents the phenyl group which may have substituents, such as a fluoro atom, a methyl group, and a trifluoromethyl group, or a fluoro atom.

Examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluolphenyl) boron, tris (3,5-difluorophenyl) boron and tris (4-fluoromethylphenyl) boron , Tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron. Of these tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound of the present invention is a salt consisting of a cationic compound and an anionic compound. Anion reacts with the transition metal compound (A) to cationic the transition metal compound (A) and form ion pairs to stabilize the transition metal cation species. Such anions include organoboron compound anion, organoarsenic compound anion, organoaluminum compound anion, and the like. Anion that is relatively bulky and stabilizes transition metal cation species is preferable. Examples of the cation include metal cation, organometallic cation, carbonium cation, trifum cation, oxonium cation, sulfonium cation, phosphonium cation and ammonium cation.

More specifically, triphenyl carbonium cation, tributyl ammonium cation, N, N- dimethyl ammonium cation, and ferrocene cation are mentioned.

Among these, an ionic compound containing a boron compound as an anion is preferable. More specifically, examples of the trialkyl substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) Boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and tri (n-butyl) ammoniumtetra (4-fluorophenyl) boron have.

Examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron and N, N-2,4,6-pentamethylaniyl Linium tetra (phenyl) boron is mentioned.

Examples of the dialkylammonium salts include di (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Triphenyl phosphonium tetra (phenyl) boron, a tri (methylphenyl) phosphonium tetra (phenyl) boron, and a tri (dimethylphenyl) phosphonium tetra (phenyl) boron are mentioned as an example of a triaryl phosphonium salt.

Ionic compounds containing boron atoms include triphenylcarbenium tetrakis (penta fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and ferrocenium tetrakis (penta fluorophenyl) Borate is also available.

Moreover, the following compounds can also be illustrated. (In the ionic compounds listed below, the counter ion is tri (n-butyl) ammonium, but the counter ion is not limited to this).

Examples of the salts of anions include bis {(tri (n-butyl) ammonium} nonaborate, bis (tri (n-butyl) ammonium} decaborate, bis {tri (n-butyl) ammonium} undecarborate, bis (tri ( n-butyl) ammonium} dodecaborate, bis {tri (n-butyl) ammonium} decachlorodecaborate, bis {tri (n-butyl) ammonium} dodecachlorododecaborate, tri (n-butyl) ammonium- 1-carbadecarborate, tri (n-butyl) ammonium-1-carbodecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-trimethylsilyl -1-carbade caborate and tri (n-butyl) ammonium bromo-1-carbade caborei.

Borane compounds and carborane compounds may also be mentioned. These compounds are used as Lewis acids or ionic compounds.

Examples of borane compounds and carborane compounds include boranes and salts of carborane complexes and carborane anions, such as decaborane (14), 7,8-dicarbondecaborane (13), and 2,7-dicarbondecaborane. (13), undecahydride-7,8-dimethyl-7,8-dicarbondecaborane, dodecahydride-11-methyl-2,7-dicarbondecaborane, tri (n-butyl) Ammonium-6-carbadecarborate (14), tri (n-butyl) ammonium-6-carbadecarborate (12), tri (n-butyl) ammonium-7-carbound carborate (13), tri (n-butyl) ammonium-7,8-dicarboundcarborate (12), tri (n-butyl) ammonium-2,9-dicarbound carborate (12), tri (n-butyl) ammonium dodeca Hydride-8-methyl-7,9-dicarbodecarborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarborate carborate, tri (n-butyl) ammonium Decahydride-8-butyl-7,9-dicarboundeborate, t Li (n-butyl) ammonium decahydride-8-allyl-7,9-dicarbound carborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbound cabo Late and tri (n-butyl) ammonium undehydride-4,6-dibromo-7-carboundeborate;

Carborane and salts of carborane such as 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride- 1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicar Banona Boran is mentioned.

Moreover, the following compounds can also be illustrated. (In the ionic compounds listed below, the counterion is tri (n-butyl) ammonium, but the counterion is not limited to this.)

Salts of metal carboranes and metal borane anions such as tri (n-butyl) ammoniumbis (nonahydride-1,3-dicarbanonaborate) cobaltate (111), tri (n-butyl) ammoniumbis ( Undecahydride-7,8-dicarbodecarborate) ferrate (ferrate), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbodecarborate) cobaltate (111 ), Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbound carborate) nickelate (111), tri (n-butyl) ammoniumbis (undecahydride-7,8- Dicarbound carborate) cuprate (copper acid salt) (111), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbound carborate) aurate (gold salt) (111), Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbodecarborate) ferrate (111), tri (n-butyl) ammoniumbis (nonahydride-7, 8-Dime -7,8-dicarbound carborate) chromate (chromate) (111), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbound carborate) cobaltate (111) ), Tri (n-butyl) ammonium bis (dodecahydride dicarbound carborate) -cobaltate (111), bis {tri ((n-butyl) ammonium} bis (dodecahydride dodecarborate)- Nickelate (111), tris {tri (n-butyl) ammonium} bis (undecahydride-7-carboundecarborate) chromate (111), bis {tri (n-butyl) ammonium} bis (undeca Hydride-7-carbound carborate) manganate (IV), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbound carborate) cobaltate (111) and bis { Tri (n-butyl) ammonium} bis (undecahydride-7-carboundeborate) nickelate (IV).

Compound (B-2) which reacts with the transition metal compound (A) to form an ion pair can be used in combination of two or more kinds.

Examples of the organoaluminum compound (C) (hereinafter sometimes referred to as 'component (C)') used in the second olefin polymerization catalyst of the present invention include organoaluminum compounds represented by the following general formula (III). Can be.

R ⁹ nAlX ₃ -n (III)

R <^9> in a formula is a hydrocarbon group of 1-12 carbon atoms, X is a halogen atom or a hydrogen atom, n is 1-3.

In general formula (III), R <^9> is a hydrocarbon group of 1-12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specific examples are methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl.

Examples of such organoaluminum (C) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri (2-ethylhexyl) aluminum;

Alkenyl aluminum, such as isoprenyl aluminum;

Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide;

Alkyl aluminum seski halides, such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromid;

Alkyl aluminum di halides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; And alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound (C), a compound represented by the following general formula (IV) can also be used.

R ⁹ nA1L ₃ -n (IV)

R in the meal⁹Is a hydrocarbon as in formula (III) above; L is -OR¹⁰-OSiR¹¹ ₃-OA1R¹² ₂group, -NR¹³ ₂-SiR¹⁴ ₃Groups or -N (R¹⁵A1R¹⁶ ₂N is 1 to 2; R¹⁰, R¹¹, R¹²And R¹⁶Are methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl and the like, respectively; R¹³Is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., R¹⁴And R¹⁵Are methyl and ethyl, respectively.

As an example of such an organoaluminum compound (C)

(1) a compound represented by the general formula R ⁹ nA1 (OR ¹⁰ ) ₃ -n such as dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide;

(2) a compound represented by General Formula R ⁹ nA1 (OSiR ¹¹ ₃ ) ₃ -n,

Such as Et ₂ A1 (OSiMe ₃ ), (iso-Bu) ₂ A1 (OSiMe ₃ ) and (iso-Bu) ₂ A1 (OSiEt ₃ );

(3) a compound represented by General Formula R ⁹ nA1 (OA1R ¹² ₂ ) ₃ -n,

Such as Et ₂ A1OA1Et ₂ and (iso-Bu) ₂ A1OA1 (iso-Bu) ₂ ;

(4) a compound represented by General Formula R ⁹ nA1 (NR ¹³ ₂ ) ₃ -n,

Such as Me ₂ A1NEt ₂ , Et ₂ A1NHMe, Me ₂ A1NHEt, Et ₂ A1N (SiMe ₃ ) ₂ and

(iso-Bu) ₂ A1N (SiMe ₃ ) ₂ ;

(5) a compound represented by the general formula R ⁹ nA1 (SiR ¹⁴ ₃ ) ₃ -n, such as (iso-Bu) ₂ A1 SiMe ₃ ; And

(6) a compound represented by formula R ⁹ nA1 (N (R ¹⁵ ) A1R ¹⁶ ₂ ) ₃ -n,

Examples thereof include Et ₂ A1N (Me) A1Et ₂ and (iso-Bu) ₂ A1N (Et) A1 (iso-Bu) ₂ .

In the organoaluminum compounds represented by the general formulas (III) and (IV)

Preferred are the compounds represented by R ⁹ ₃ A1, R ⁹ nA1 (OR ¹⁰ ) ₃ -n and R ⁹ nA1 (OA1R ¹² ₂ ) ₃ -n, particularly preferably a compound in which R is an isoalkyl group and n = 2 .

In the present invention, water may be used as the catalyst component in addition to the component (A), component (B-1), component (B-2) and component (C). The water that can be used in the present invention can exemplify the water or crystalline water contained in the compound or salts used in the preparation of water and component (B-1) dissolved in a polymerization solvent as described below.

The first olefin polymerization catalyst of the present invention comprises component (A) and component (B-1) (or component (B-2)) and, if desired, water (as catalyst component) inert hydrocarbon medium (solvent) or olefin. It can manufacture by mixing in a medium (solvent).

Although the mixing order of these components is arbitrary, it is preferable to mix component (B-1) (or component (B-2)) with water, and then mix component (A).

The second olefin polymerization catalyst of the present invention comprises component (A), component (B-1) (or component (B-2)), component (C) and, if desired, water (as catalyst component) inert hydrocarbon medium. It can manufacture by mixing in a (solvent) or an olefin medium (solvent).

Although the mixing order of these components is arbitrary, when using component (B-1), it is preferable to mix component (B-1) and component (C), and then mix component (A). When using component (B-2), it is preferable to mix component (C) and component (A), and then mix component (B-2).

When mixing each of the above components, the atomic ratio (Al / transition metal) of aluminum in component (B-1) and transition metal in component (A) is usually 10 to 10000, preferably 20 to 5000, and component (A ) Concentration is in the range of 10 ⁻⁸ to 10 ⁻¹ mol / liter medium, preferably 10 ^{−7 to 5} × 10 ⁻² mol / liter medium. When using component (B-2), the molar ratio (component (A) / component (B)) of component (A) and component (B-2) is 0.01-10 normally, Preferably it is the range of 0.1-5, The concentration of (A) is 10 ⁻⁸ to 10 ⁻¹ mol / liter medium, preferably 10 ^{−7 to 5} × 10 ⁻² mol / liter medium.

In preparing the second olefin polymerization catalyst of the present invention, the atomic ratio (Al _C / Al) between the aluminum atom (A1 _C ) in component ( _C ) and the aluminum atom (Al _B-1 ) in component (B-1) _B-1 ) is 0.02-20 normally, Preferably it is the range of 0.2-10.

When water is used as the catalyst component, the molar ratio (Al _B-1 / H ₂ O) between the aluminum atom (Al _B-1 ) and water (H ₂ O) in component ( _B-1 ) is usually 0.5 to 50, preferably The following is the range of 1-40.

Each of the above components may be mixed in the polymerization reactor, or a mixture of the above components may be supplied to the polymerization reactor.

The mixing temperature at the time of mixing the said component beforehand is -50-150 degreeC normally, Preferably it is -20-120 degreeC; The contact time is in the range of 1 to 1000 minutes, preferably 5 to 600 minutes. The mixing temperature may be changed when the components are in mixed contact with each other.

Examples of the medium (solvent) used in the production of the olefin polymerization catalyst according to the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene;

Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane;

Aromatic hydrocarbons such as benzene, toluene and xylene;

Halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; And mixtures of these hydrocarbons. Next, the third and fourth olefin polymerization solvents according to the present invention will be described. The third catalyst for olefin polymerization according to the present invention

Particulate carriers;

(A) the transition metal compound represented by the general formula (I);

(B)

(B-1) organoaluminumoxy compound

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound (A) to form ion pairs;

The transition metal compound (A) and at least one compound (B) are formed by being supported on the particulate carrier.

The fourth catalyst for olefin polymerization according to the present invention

Particulate carrier,

(A) the transition metal compound represented by the general formula (I),

(B)

(B-1) Organic Aluminum Oxy Compound

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound (A) to form ion pairs,

A solid catalyst component formed by supporting said transition metal compound (A) and said at least one compound (B) on a particulate carrier; And

(C) It is formed from an organoaluminum compound.

The transition metal compound (A) used in the third and fourth olefin polymerization catalysts of the present invention is the same as the components used in the above-mentioned first and second olefin polymerization catalysts, and is represented by the general formula (I). Is displayed.

Examples of the organoaluminum oxy compound (B-1) used in the third and fourth olefin polymerization catalysts of the present invention include the same compounds as those used in the first and second olefin polymerization catalysts.

Compound (B-2), which reacts with the transition metal compound (A) used in the third and fourth olefin polymerization catalysts of the present invention to form an ion pair, is added to the first and second olefin polymerization catalysts. Examples include the same compounds as the components used.

The organoaluminum compound (C) used for the 4th olefin polymerization catalyst of this invention can mention the compound similar to the component used for the said 2nd olefin polymerization catalyst.

The particulate carrier used in the third and fourth olefin polymerization catalysts of the present invention is an inorganic or organic compound, which is a granular or particulate solid having a particle size of 10 to 300 µm, preferably 20 to 200 µm. The inorganic carrier is preferably a porous oxide, for example SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof, such as SiO ₂ -MgO , SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O _3, and SiO ₂ -Ti0 ₂ -MgO. Among them, a carrier containing SiO ₂ and / or Al ₂ O ₃ as a main component is preferred.

The inorganic oxide may be a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , Al ( It may contain carbonates, sulfates, nitrates, and oxide components such as NO ₃ ) ₃ , NaO, K ₂ O, and Li ₂ O.

Although particulate carriers vary in performance depending on their type and preparation method, the particulate carriers preferably used in the present invention have a specific surface area of 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, and a pore volume of 0.3. It is preferable that it is -2.5 cm <3> / g. The fine particle carrier is used after firing at a temperature of 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

Moreover, as a particulate carrier which can be used for this invention, the granular or particulate solid of an organic compound whose particle diameter is 10-300 micrometers is mentioned.

Examples of the organic compound include (co) polymers prepared from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butane and 4-methyl-1-pentene, and vinylcyclohexane or styrene as main components. The (co) polymer manufactured by this is mentioned.

The fine particle carrier may contain a surface hydroxyl group or water. In this case, it is desirable for the surface hydroxyl group to be 1.0 wt% or more, preferably 1.5 to 4.0 wt%, more preferably 2.0 to 3.5 wt%. It is desired that the water is 1.0% by weight or more, preferably 1.2 to 20% by weight, more preferably 1.4 to 15% by weight. The water contained in the particulate carrier refers to water adsorbed on the particulate carrier. The amount of the adsorbed water (% by weight) and the amount of the surface hydroxyl group (% by weight) are obtained by the following method.

Amount of adsorbed water

After drying for 4 hours under atmospheric pressure and nitrogen flow at a temperature of 200 ° C, the weight loss of the particulate carrier was measured, and the ratio after drying to drying was calculated.

Amount of surface hydroxyl groups

The weight of the particulate carrier obtained by drying at a temperature of 200 ° C. for 4 hours under normal pressure and nitrogen flow is referred to as X (g). The carrier is calcined at 1000 ° C. for 20 hours to obtain a calcined product containing no surface hydroxyl group. The weight of the fired product thus obtained is referred to as Y (g). The amount (% by weight) of the surface hydroxyl group is calculated by the following equation.

Amount of surface hydroxyl group (wt%) = {(X-Y) / X} X 100

By using the particulate carrier having a specific amount of adsorbed water or surface hydroxyl group as described above, it is possible to obtain a catalyst for olefin polymerization capable of producing an olefin polymer having excellent particle performance and high polymerization activity.

In the third and fourth olefin polymerization catalysts of the present invention, water as described in the first and second olefin polymerization catalysts described above may be used as the catalyst component.

The third olefin polymerization catalyst (for example, a solid catalyst component) of the present invention comprises the particulate carrier, component (A), component (B-1) (or component (B-2)), and water (catalyst as desired). Component) can be produced by mixing in an inert hydrocarbon medium (solvent) or an olefin medium (solvent). You may add further component (C) when these components are mixed. The mixing order of these components can be arbitrarily selected, but preferably, the particulate matter carrier and component (B-1) (or component (B-2)) are mixed and brought into contact with each other, and then component (A) is mixed and brought into contact with each other. To mix water accordingly;

A method of mixing and contacting a mixture of component (B-1) (or component (B-2)) with component (A) and the particulate carrier, followed by mixing water as desired;

And a method in which the particulate matter carrier, component (B-1) (or component (B-2)) and water are mixed and brought into contact with each other, followed by contact with component (A).

When mixing each of the above components, component (A) is usually used in an amount of 10 ⁻⁶ to ⁵ × 10 ⁻³ moles, preferably ³ × 10 ^{−6 to} 10 ⁻³ moles per 1 g of the particulate carrier. The concentration of component (A) is in the range of about ⁵ × 10 ^{−6 to 2} × 10 ⁻² moles / liter medium, preferably ² × 10 ⁻⁵ to 10 ⁻² moles / liter medium. The atomic ratio (Al / transition metal) of aluminum in component (B-1) and transition metal in component (A) is usually in the range of 10 to 3,000, preferably 20 to 2,000. When using component (B-2), the molar ratio (component (A) / component (B-2)) of component (A) and component (B-2) is 0.01-1.0 normally, Preferably it is the range of 0.1-5. to be.

When water is used as the catalyst component, the molar ratio (Al _B-1 / H ₂ O) between aluminum atom (Al _B-1 ) and water (H ₂ O) in component (A) and component (B-2) is 0.5. -50, Preferably it is the range of 1-40.

The mixing temperature at the time of mixing the said component is -50-150 degreeC normally, Preferably it is the range of -20-120 degreeC; The contact time is in the range of 1 to 1000 minutes, preferably 5 to 600 minutes. The mixing temperature can be changed at the time of mixing contact of the components.

The fourth olefin polymerization catalyst according to the present invention is formed of the third olefin polymerization catalyst (solid catalyst component) and the organoaluminum compound (C).

Component (C) is used in an amount of 500 mol or less, preferably 5 to 200 mol, per 1 g atom of the transition metal atom in component (A) contained in the solid catalyst component.

In addition to the above components, the third and fourth olefin polymerization catalysts of the present invention may also contain other components useful for olefin polymerization.

Examples of the inert hydrocarbon medium (solvent) used in the production of the third and fourth olefin polymerization catalysts of the present invention include the same media as those used in the production of the first and second olefin polymerization catalysts.

Next, the fifth and sixth olefin polymerization catalysts according to the present invention will be described.

The fifth olefin polymerization catalyst according to the present invention

Particulate carriers;

(A) the transition metal compound represented by the general formula (I);

(B)

(B-1) Organic Aluminum Oxy Compound

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs; And

It is formed of a prepolymerized olefin polymer produced by prepolymerization.

The sixth catalyst for olefin polymerization according to the present invention

Particulate carriers;

(A) The transition metal compound represented by the general formula (I)

(B)

(B-1) organoaluminumoxy compound

(B-2) at least one compound selected from the group consisting of compounds which react with the transition metal compound to form ion pairs;

(C) an organoaluminum compound; And

It is formed of a prepolymerized olefin polymer produced by prepolymerization.

Examples of the particulate carriers used in the fifth and sixth olefin polymerization catalysts of the present invention include the same carriers used in the third and fourth olefin polymerization catalysts.

The transition metal compound (A) used in the fifth and sixth olefin polymerization catalysts of the present invention is the same compound as the components used in the above-mentioned first and second olefin polymerization catalysts, and the general formula (I) Is displayed.

Examples of the organoaluminum oxy compound (B-1) used in the fifth and sixth olefin polymerization catalysts of the present invention include the same compounds as those used in the first and second olefin polymerization catalysts.

Examples of the compound (B-2) used in the fifth and sixth olefin polymerization catalysts of the present invention to react with the transition metal compound (A) to form ion pairs include the first and second olefin polymerization catalysts. The same compound as the component used can be mentioned.

As an example of the organoaluminum compound (C) which uses the 6th olefin polymerization of this invention for a catalyst, the compound similar to the component used for the 2nd olefin polymerization catalyst is mentioned.

In the fifth and sixth olefin polymerization catalysts of the present invention, water may be used as the catalyst component as described in the above-mentioned first and second olefin polymerization catalysts.

The fifth olefin polymerization catalyst of the present invention can be prepared by prepolymerizing a small amount of olefin in the presence of the solid catalyst component. The solid catalyst component may be prepared by mixing water in an inert hydrocarbon medium (solvent) or an olefin medium (solvent) according to the particulate carrier, component (A), component (B-1) (or component (B-2)), and desired. Obtained.

When mixing these components, the component (C) can also participate further.

The mixing order of these components is arbitrary but preferably

A method of mixing and contacting the particulate matter supporter with component (B-1) (or component (B-2)) followed by mixing and contacting component (A) with water as desired;

A method of mixing and contacting a mixture of component (B-1) (or component (B-2)) with component (A) and the particulate carrier, followed by mixing water as desired;

And a method of mixing and contacting the particulate matter supporter with component (B-1) (or component (B-2)) and water, followed by mixing with component (A).

It is desirable to mix the components under stirring.

When mixing the respective components, component (A) is usually used in an amount of 10 ⁻⁶ to ⁵ × 10 ⁻³ moles, preferably ³ × 10 ^{−6 to} 10 ⁻³ moles per 1 g of the particulate carrier; The concentration of component (A) is about 5X10 ^-5 ~2X10 ^-2 mol / l - in the range of medium-medium, preferably 10 ^-5 to 10 ^-2 mol / liter. The atomic ratio (Al / transition metal) of aluminum in component (B-1) and transition metal in component (A) is usually in the range of 10 to 3000, preferably in the range of 20 to 2000. When using component (B-2), the molar ratio (component (A) / component (B-2)) between component (A) and component (B-2) is usually 0.01 to 10, preferably 0.1 to 5 Range.

When water is used as the catalyst component, the molar ratio (Al _B-1 / H ₂ O) between aluminum atom (Al _B-1 ) and water (H ₂ O) in component ( _B-1 ) is 0.5 to 50, preferably Is in the range of 1 to 40.

The mixing temperature at the time of mixing each component is -50-150 degreeC normally, Preferably it is the range of -20-120 degreeC, and contact time is 1 to 1000 minutes, Preferably it is the range of 5 to 600 minutes. The mixing temperature may be changed when the components are in contact with each other.

The fifth olefin polymerization catalyst of the present invention can be produced by prepolymerizing olefins in the presence of the respective components. Prepolymerization can be carried out by introducing olefins into an inert hydrocarbon medium (solvent) in the presence of each of the above components or in the presence of components (C) as necessary.

Component when the preliminary polymerization (A) is usually from 10 ^-5 to ~2X10 ^-2 mol / liter, and preferably is used in an amount of ^-2 mol / l 5X10 ^-5 ~10. The preliminary polymerization temperature is in the range of -20 to 80 ° C, preferably 0 to 50 ° C; The preliminary polymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours.

The olefins used for the prepolymerization are selected from the olefins used for the polymerization but are preferably monomers such as those used for the polymerization or mixtures of the monomers and α-olefins used for the polymerization.

The olefin polymerization catalyst of the present invention obtained as described above is preferably about 10 ^-6 to ~10 ^-3 g atom and, per particle consultation body 1g is a transition of 2X10 ^-6 ~3X10 ^-4 g atom and the metal is supported; It is desired that an aluminum atom of about 10 ⁻³ to 10 ⁻¹ g · atoms, preferably 2 × 10 ⁻³ to 5 × 10 ⁻² g · atoms, be supported. In addition, component (B-2) is a boron atom contained in component (B-2), which is preferably supported in an amount of 5X10 ^{-7 to} 0.1g atoms, preferably 2X10 ^{-7 to} 3X10 ^-2 g atoms. That's right.

It is desired that the amount of the prepolymerized polymer produced by the prepolymerization is in the range of about 0.1 to 500 g, preferably 0.3 to 300 g per 1 g of the fine particle carrier.

The sixth olefin polymerization catalyst of the present invention is formed of the fifth olefin polymerization catalyst (component) and an organic aluminum compound (C). The organoaluminum compound (C) is used in an amount of 500 mol or less, preferably 5 to 200 mol, per 1 g of the transition metal atom in the component (A).

The fifth and sixth olefin polymerization catalysts of the present invention may contain other components useful for olefin polymerization in addition to the above components.

Examples of the inert hydrocarbon solvent used in the preparation of the fifth and sixth olefin polymerization catalysts of the present invention include the same solvents as those used in the preparation of the first and second olefin polymerization catalysts described above.

The polyolefin obtained by the use of the above olefin polymerization catalyst has a narrow molecular weight distribution and a composition distribution, has a high molecular weight, and the olefin polymerization catalyst has a high polymerization activity.

In addition, when the olefin having 3 or more carbon atoms is polymerized in the presence of an olefin polymerization catalyst, a polyolefin having excellent stereoregularity is obtained.

Next, the polymerization method of the olefin by this invention is demonstrated.

The olefin is polymerized in the presence of the above olefin polymerization catalyst. The polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization or gas phase polymerization.

In the liquid phase polymerization method, the same one as the inert hydrocarbon solvent used at the time of producing the catalyst can be used, and the olefin itself can also be used as the solvent.

When the olefin is polymerized using the first or second olefin polymerization catalyst, such a catalyst is usually 10 ^-8 to 10 ^-3 g, atom / as a concentration of the transition metal atom of component (A) in the polymerization system. It is used in the amount of liters, preferably 10 ^-7 to 10 ^-4 g. Atoms / liters.

When the polymerization is carried out using the third or fourth olefin polymerization catalyst, the catalyst as described above is usually 10 ^-8 to 10 ^-3 g, atom / liter, as a concentration of the transition metal atom of component (A) in the polymerization system. to preferably from 10 ^-7 ~10 ^-4 g and used in an amount of atom / liter.

At this time, you may use the aluminoxane which is not supported by a support as needed.

In the liquid phase polymerization method, the same one as the inert hydrocarbon solvent used at the time of producing the catalyst can be used, and the olefin itself can also be used as the solvent.

When the olefin is polymerized using the first or second olefin polymerization catalyst, the catalyst as described above is usually in the concentration of 10 ^-8 to 10 ^-3 g, atom / of the transition metal atom of component (A) in the polymerization system. It is used in the amount of liters, preferably 10 ^-7 to 10 ^-4 g. Atoms / liters.

Claim of normal and 10 ^-8 ~10 ^-3 g atom / liter as a concentration of 3 or transition metal atom of the catalyst component (A) in the polymerization system as described above, when the polymerization is performed using the catalyst for olefin polymerization of the 4 Use in quantity. At this time, you may use the aluminoxane which is not supported by a support as needed.

When the olefin is polymerized using the fifth or sixth olefin polymerization catalyst, the concentration of the transition metal of component (A) in the polymerization system is usually 10 ⁻⁸ to 10 ⁻³ g · atoms / liter, preferably 10 ^It is used in an amount of ^-7 to 10 ^-4 g, atom / liter. At this time, you may use the aluminoxane which is not supported by the support as desired.

In the slurry polymerization method, the polymerization temperature of the olefin is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. In the liquid-phase polymerization method, the temperature is usually in the range of 0 to 250 ° C, preferably 20 to 200 ° C. In the gas phase polymerization method, the temperature is usually 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is usually in the range of normal pressure to 50 kg / cm 2. The polymerization reaction can be carried out by any of batch wise, semi-continuous or continuous.

Moreover, superposition | polymerization can also be performed dividing into two or more stages in which reaction conditions differ.

The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

Examples of olefins polymerized using the olefin polymerization catalyst of the present invention include

Ethylene, propylene, 1-butene, 1-pentene, 1-hexane, 4-methyl-1pentene, 1-octene, 1-decene, 1-decadecene, 1-hexadecene, 1-octadecene, 1-eico Α-olefins of 2 to 20 carbon atoms such as sen; And

Cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4-5,8-dimethano-1,2,3,4,4a And cycloolefins of 3 to 20 carbon atoms such as 5,8,8a-octahydronaphthalene.

In addition, styrene, vinylcyclohexane, diene, or the like can also be used.

When at least 3 carbon atoms polymerize α-olefin using the olefin polymerization catalyst of the present invention, a polymer having a lower melting point can be obtained even if the molecular weight of the polymer is about the same as that of a polymer obtained using a conventional metallocene catalyst. . In addition, the use of the catalyst of the present invention yields a low melting point copolymer, although the amount of repeating units derived from the comonomer is small.

When the α-olefin having a carbon atom of 3 or more is polymerized using the olefin polymerization catalyst of the present invention, a large amount of irregular monomer units exist in the molecule of the resulting olefin polymer. The insertion of α-olefins in polymers prepared by the polymerization of α-olefins of 3 or more carbon atoms in the presence of chiral metallocene catalysts is carried out with 2,1-insertions or 1,3-insertions in addition to conventional 1,2-insertions. It is known that this results in the formation of irregular positions such as 2,1-insertion or 1,3-insertion. (See Makromol. Chem., Rapid Commun., 8,305 (1987), by K. Soga, T. Shiono, S. Takemura and W. Kaminsky). It is also known that the presence of stereoregularity in the olefin polymer molecule lowers the melting point of the olefin polymer by the ratio of its stereoregularity (Polymer, 30, 1350 (1989), by T. Tsutsui, N.Ishimura, A. Mizuno, A). Toyota and N. Kashiwa).

In the olefin polymer obtained by polymerizing α-olefin having 3 or more carbon atoms by using the catalyst for olefin polymerization of the present invention, a large amount of back-insertion monomer units exist, so that the melting point of the olefin polymer is almost obtained using a conventional catalyst. It is estimated to be lower than the melting point of the olefin polymer having the same molecular weight.

The propylene polymer, the propylene copolymer, and the propylene elastomer according to the present invention will be described below.

Propylene polymer

Although the propylene polymer of this invention consists of propylene units, you may contain the component unit derived from olefins other than propylene in 0.5 mol% or less, Preferably it is 0.3 mol% or less, More preferably, it is 0.1 mol% or less.

The propylene polymer of the present invention has at least 90%, preferably at least 93%, more preferably at least 95% triadtaxity.

The term 'triadtaxycity' means that the methyl branch in the propylene unit in any three chains of propylene units (ie, chains of three consecutively linked propylene units) in the entire polymer is the same, and each propylene It means the ratio of three chains of propylene units in which a unit is two-unbonded, and may be described below as a "mm fraction."

Triadtaxity is obtained from the ¹³ C-NMR spectrum of the propylene polymer.

¹³ C-NMR spectrum is measured by the following method. 50-60 mg of the sample was placed in an NMR sample tube (diameter: 5 mm) with about 0.5 ml of hexachloro butadiene, 0-dichlorobenzene or 1,2,4-trichloro benzene and about 0.05 ml of deuterated benzene (i.e. ¹³ C-NMR spectrum was measured by proton perfect decoupling method at 120 ° C. after complete dissolution in a mixed solvent containing). The measurement is carried out under conditions of a flip angle of 45 ° and a pulse interval of 3.4 T ₁ (T ₁ is the maximum value of the spin-latticerelaxation time of the methyl group).

T ₁ of the methylene group and T ₁ of the methine group are all carbon magnetization recovery under these conditions, because less than the T ₁ of each group is 99% or more.

The compound shift is composed of two iron bonds, the methyl group of the third unit in the five chains of propylene units having the same methyl branching direction is set to 21.593 ppm, and the chemical shift of other carbon peaks is determined with reference to the above values. Therefore, the peak by the methyl group of the 2nd unit in three propylene unit chain | strands which have PPP (mm) structure appears in the range of 21.1-21.8 ppm. The peak by the methyl group of the second unit in the three propylene unit-chains having the PPP (mr) structure is in the range of 20.2-21.1 ppm, and the second unit in the three propylene unit-chains having the PPP (rr) structure. The peak by the methyl group of appears in 19.4-20.2 ppm.

PPP (mmm), PPP (mr) and PPP (rr) each have the following three propylene unit-chain structures, each of which is a dumi bond.

In addition to the regular structures represented by PPP (mm), PPP (mr) and PPP (rr) described above, the propylene polymer has a structure (i) containing an irregular position unit by 2,1-insertion and a position by 1,3-insertion It has a small amount of structure (ii) containing irregular units.

The mm fraction of the above definition does not apply to propylene units having carbons of A, B, C, and D among the carbons of A to F. Carbon A and carbon B resonate within a range of 16.5 to 17.5 ppm, carbon C resonates near 20.8 ppm (mr region), and carbon D resonates near 20.7 ppm (mr region). However, the peaks of the methyl groups in structures (i) and (ii) as well as the peaks of adjacent methylene and methine groups should be identified.

In the structure (ii),-(CH ₂ ) ₃ -units are generated as a result of the hydrogen transfer polymerization, and the units corresponding to one methyl group disappear.

The mm fraction in the prepolymer chain is therefore represented by the following formula.

∑ICH ₃ in the formula indicates the total area of all peaks derived from the methyl group.

In addition, I and I _{αδ βr} is the area of the area and a resonance in the vicinity of the peak βr 27.3ppm) of each of αδ peak (resonance in the vicinity of 37.1ppm).

These methylene peaks were named according to the Carman method et al. (Rubber Chem. Tachnol. 44 (1971), 781).

In the polymerization to produce the propylene polymer, the 1,2-insertion of the propylene monomer is mainly performed, or the 2,1-insertion or 1,3-insertion is sometimes performed. 2,1-insertion forms irregular position units represented by the above structure (i) in the polymer chain.

The ratio of 2,1-propylene monomer insertion to all propylene insertions is calculated by the following formula.

Similarly, the ratio of the 1,3-propylene monomer insertion represented by the above structure (ii) to the total propylene insertion is calculated by the following equation.

In the propylene polymer according to the present invention, the ratio of the irregularity unit by 2,1-insertion in all the propylene insertions is 0.7% or more, preferably 0.7 to 2.0%, measured by ¹³ C-NMR. Further, in the propylene polymer of the present invention, the ratio of the irregularity unit by 1.3-insertion during the whole propylene insertion is 0.05% or less, preferably 0.04% or less, more preferably 0.03% or less.

The intrinsic viscosity of the propylene polymer of the present invention is 0.1-12 dl / g, preferably 0.5-12 dl / g, more preferably 1-12 dl / g, measured in decahydro naphthalene at 135 ° C.

The propylene polymer of the present invention can be produced, for example, by polymerizing propylene in the presence of the above olefin polymerization catalyst. The polymerization is carried out by liquid phase polymerization (for example, suspension polymerization and solution polymerization) or gas phase polymerization.

In the liquid-phase polymerization method, the same inert hydrocarbon solvent as that used for preparing the catalyst may be used, or propylene may be used as the solvent.

The polymerization temperature of propylene in the suspension polymerization method is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. The polymerization temperature in a solution polymerization method is 0-250 degreeC normally, Preferably it is the range of 20-200 degreeC.

The polymerization temperature in the gas phase polymerization method is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm 2, preferably from atmospheric pressure to 50 kg / cm 2. The polymerization reaction can be carried out in any of batch, semicontinuous or continuous manners. The polymerization may also be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting propylene polymer can be controlled by the presence of hydrogen in the polymerization system or by changing the polymerization temperature and polymerization pressure.

Propylene copolymer

The propylene copolymer of the present invention contains propylene units in an amount of 95 to 99.5 mol%, preferably 95 to 99 mol%, more preferably 95 to 98 mol%, and 0.5 to 5 mol% ethylene units. The following are propylene / ethylene random copolymers containing 1 to 5 mol%, more preferably 2 to 5 mol%.

Such propylene copolymer may contain up to 5 mol% of component units derived from olefins other than propylene and ethylene.

In the propylene copolymer of the present invention, the triadtaxity of the propylene unit chain in the form of dumi-bond is 90% or more, preferably 93% or more, more preferably 96% or more, as measured by ¹³ C-NMR.

Triad takti sheet (mm fraction) of the propylene copolymer is to be calculated by the following formula to the ¹³ C-NMR spectrum of the propylene copolymer.

PPP (mm), PPP (mr) and (rr) in the formulas represent the peak areas derived from the second unit methyl group in the following three propylene unit-chains, respectively, as dumi bonds.

The ¹³ C-NMR spectrum of the propylene copolymer is measured by the method as described for the propylene polymer. The spectrum related to the methyl carbon region (16-23 ppm) is represented by the first region (21.1-21.9 ppm), the second region (20.3-21.0 ppm), the third region (19.5-20.3 ppm), and the fourth region. (16.5-17.5 ppm).

Each peak in the spectrum was designated with reference to Polymr, 30 (1989) 1350.

In the first region, the methyl group of the second unit in the three propylene unit-chains represented by PPP (mm) resonates.

In the second region, the methyl group of the second unit in the three propylene unit-chains represented by PPP (mr) resonates, and the methyl group (PPE-methyl group) of the propylene unit whose adjacent units are propylene unit and ethylene unit (20.7). in the vicinity of ppm).

In the third region, the methyl group of the second unit in the three propylene unit-chains represented by PPP (rr) resonates, and the methyl group (EPE-methyl group) of the propylene unit whose adjacent unit is an ethylene unit (19.8 ppm) In the vicinity).

The propylene copolymer also has the following structures (i) and (iii) containing irregular position units.

Of the carbons labeled A to G, the peak of carbon C and the peak of carbon C 'appear in the second region, the peak of carbon G appears in the third region, and the peak of carbon A and the peak of carbon B appear first. Appears in the area of 4.

Among the peaks shown in the first to fourth regions, the peaks of the three propylene unit-chains which are domi-bonded to PPE-methyl group, EPE-methyl group, carbon C, carbon C ', carbon G, carbon A and carbon B Peak.

The peak area of the PPE-methyl group is determined by the peak area of the PPE-methine group (resonance near 30.6 ppp), and the peak area of the EPE-methyl group is the peak area of the EPE-methine group (resonance near 3.9 ppm). Can be obtained by The peak area due to carbon C is obtained by half of the sum of the peak areas of carbon F and carbon E (resonance near 35.6 ppm and 35.4 ppm, respectively) having an irregular positional structure (structure (i)). Can be. The peak area by carbon C 'can be obtained by ½ of the sum of the peak areas of αβ methylene carbon (resonance near 34.3 ppm and 34.5 ppm, respectively) having an irregular structure (structure (iii)). . The peak area due to carbon G can be determined by the peak area of adjacent methine carbon (resonance near 33.7 ppm).

Therefore, by subtracting these peak areas from the total peak areas of the second and third areas, the peak areas by three propylene unit chains (PPP (mr) and PPP (rr)) in the form of iron are obtained.

The positions of the peaks of carbon A and peaks of carbon B are not related to the peaks of the three propylene unit-chains (PPPs) and need not be considered.

In this way, the triadtacitiity of the propylene unit chain of a dumi bond can be calculated | required by obtaining the peak areas of PPP (mm), PPP (mr), and PPP (rr).

In the propylene copolymer of the present invention, the ratio of the irregularity unit by 2,1-insertion in all propylene insertions is 0.5% or more, preferably 0.5-1.5%, measured by ¹³ C-NMR. In addition, in the propylene copolymer of the present invention, the ratio of the irregular position unit by 1,3-insertion during all propylene insertion is 0.05% or less, preferably 0.04% or less, and more preferably 0.03% or less.

In polymerization, mainly 1,2-insertion of the propylene monomer (ie, methylene side bonded to the catalyst) occurs, but sometimes 2,1-insertion occurs. 2,1-insertion forms irregular units in the polymer.

The ratio of 2,1-insertion to propylene insertion in the propylene copolymer is calculated by the following equation based on Polymer 30 (1989) 1350.

Ratio of irregular location unit by 2,1-insertion (%)

The peak in the above formula was named by the Carman method (Rubber Chem. Technol., 44 (1971), 781). Iαδ indicates the peak area of the αδ peak.

The ratio of three propylene unit chains by 1,3-insertion is 100 divided by the sum of half the area of βr peak (resonance near 27.4 ppm) divided by the sum of the total methyl peak and the half of βr peak. Multiplied.

The intrinsic viscosity of the propylene copolymer of the present invention is 0.1 to 12 dl / g, preferably 0.5 to 12 dl / g, more preferably 1 to 12 dl / g, measured in decahydronaphthalene at 135 ° C.

The propylene copolymer of the present invention can be produced, for example, by copolymerizing propylene and ethylene in the presence of the olefin polymerization catalyst.

The copolymerization can be carried out by liquid phase polymerization (for example, suspension polymerization and solution polymerization) or gas phase polymerization.

In the liquid phase polymerization method, an inert hydrocarbon solvent such as that used when preparing the catalyst may be used, and propylene and / or ethylene may also be used as a solvent.

In the suspension polymerization method, the copolymerization temperature of propylene and ethylene is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. Copolymerization temperature in the solution polymerization method is 0-250 degreeC normally, Preferably it is the range of 20-200 degreeC. The copolymerization temperature in the gas phase polymerization method is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually normal pressure to 100 kg / cm 2, preferably normal pressure to 50 kg / cm 2. The copolymerization reaction can be carried out by any of batch, semicontinuous or continuous methods. In addition, copolymerization can also be performed in two or more stages with different reaction conditions.

The molecular weight of the resulting propylene copolymer can be controlled by the presence of hydrogen in the copolymer or by changing the copolymerization temperature and copolymerization pressure.

Propylene elastomer

The propylene elastomer of the present invention contains an amount of 50 to 95 mol% of propylene units, preferably 60 to 93 mol%, more preferably 70 to 90 mol%, and 5 to 50 mol% of ethylene units. Below are propylene / ethylene random copolymers containing in an amount of 7 to 40 mol%, more preferably 10 to 30%.

Such propylene elastomers may contain up to 10 mole percent of component units derived from olefins other than propylene and ethylene.

In the propylene elastomer of the present invention, the triadtaxity of the propylene unit chain in the form of iron-bond is 90% or more, preferably 92 mol% or more, more preferably 95.0% or more, as measured by ¹³ C-NMR.

The triadtaxity (mm fraction) of the propylene elastomer can be obtained from the ¹³ C-NMR spectrum of the propylene elastomer and the following formula.

PPP (mm), PPP (mr) and PPP (rr) in the formula are the same as defined above.

The ¹³ C-NMR spectrum of the propylene elastomer can be measured by the same method as described for the propylene polymer. The spectrum related to the methyl carbon region (19-23 ppm) can be divided into a first region (21.2-21.9 ppm), a second region (20.3-21.0 ppm), and a third region (19.5-20.3 ppm). Each peak in the spectrum was designated by reference to the document 'Polymer', 30 (1989) 1350.

In the first region, the methyl group of the second unit represented by PPP (mm) in the three propylene unit-chains resonates. In the second region, the methyl group of the second unit represented by PPP (mr) in three propylene units-chains resonates, and the methyl group (PPE-methyl group) of propylene units whose adjacent units are propylene units and ethylene units (20.7) in ppm).

In the third region, the methyl group of the second unit represented by PPP (rr) in the three propylene unit chains resonates, and the methyl group (EPE-methyl group) of the propylene unit whose adjacent unit is ethylene unit is resonance (near 19.8 ppm). in).

The propylene elastomer also has the following structures (iii) and (iii) containing positional irregular units.

Of the carbons marked with C and G, the peak of carbon C 'and the peak of carbon C' appear in the second region, and the peak of carbon G and the peak of carbon G 'appear in the third region.

Among the peaks shown in the first to third regions, the peaks not based on three propylene unit-chains in the form of dumi-bonds are represented in PPE-methyl group, EPE-methyl group, carbon C ', carbon C', carbon G and carbon G '. Peak.

The peak area by PPE-methyl group can be obtained by the peak area of PPE-methyl group (resonance near 30.56 ppm), and the peak area based on EPE-methyl group is the peak of EPE-methyl group (resonance near 3.9 ppm). It calculates by area. The peak area by carbon C 'can be obtained by double the peak area of methine carbon (resonance near 33.6 ppm) to which the methyl group of carbon G is directly bonded, and the peak area based on carbon C' is the adjacent carbon G '. It is calculated | required by the peak area of the methyl carbon (resonance in the vicinity of 33.2 ppm) of the methyl group of. The peak area based on carbon G can be determined by the peak area of adjacent methine carbon (resonance near 33.6 ppm), and the peak area by carbon G 'is also the peak of adjacent methine carbon (resonance near 33.2 ppm). It calculates by area.

Therefore, subtracting these peak areas from the total peak areas of the second and third areas yields the peak areas (PPP (mr) and PPP (rr)) by three propylene unit-chains of iron-bonded bonds. In this way, when the peak areas of PPP (mm), PPP (mr) and PPP (rr) are obtained, the triadtacitiity of the propylene unit chain formed by the iron binding can be obtained.

In the propylene elastomer of the present invention, the ratio of the irregular position unit by 2,1-insertion in all propylene insertions is 0.5% or more, preferably 0.5-2.0%, more preferably 0.5 by ¹³ C-NMR. -1.5%, and in the propylene elastomer of the present invention, the ratio of the irregular position unit by 1,3-insertion is 0.05% or less, preferably 0.03% or less.

The ratio of 2,1-insertion to the total propylene insertion in the propylene elastomer is calculated by the following formula, referring to Polymer, 30 (1989) 1350. Ratio of irregular location unit based on 2,1 insertion (%)

The peak of the above formula was named by the Carman method (Rubber Chem. Tachnol., 44 (1971), 781). Iαδ refers to the area of αδ peaks. If peak areas such as I _αβ cannot be obtained directly from the spectrum due to overlapping peaks, carbon peaks having corresponding areas can be replaced.

The ratio of three propylene-unit chain amounts by 1,3-insertion is 100 divided by the sum of 1/2 the area of the βr peak (resonance near 27.4 ppm) divided by the sum of the half of the all-methyl and βr peaks. Multiply by.

The intrinsic viscosity of the propylene elastomer of the present invention is 0.1 to 12 dl / g, preferably 1 to 12 dl / g, more preferably 1 to 12 dl / g, measured in decahydro naphthalene at 135 ° C.

The propylene elastomer of the present invention can be produced, for example, by copolymerizing propylene and ethylene in the presence of the olefin polymerization catalyst. Copolymerization can be performed by liquid phase polymerization (eg suspension polymerization and solution polymerization) or vapor phase polymerization.

In the liquid phase polymerization method, an inert hydrocarbon solvent such as that used when preparing the catalyst may be used, and propylene and / or ethylene may also be used as a solvent.

The copolymerization temperature of propylene and ethylene in the suspension polymerization method is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. Copolymerization temperature in the solution polymerization method is 0-250 degreeC normally, Preferably it is the range of 20-200 degreeC. The copolymerization temperature in the gas phase polymerization method is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually in the range of normal pressure to 100 kg / cm 2, preferably normal pressure to 50 g / cm 2. The copolymerization reaction can be carried out by any of batch, semicontinuous or continuous methods. Copolymerization can also be carried out in two or more stages with different reaction conditions.

The molecular weight of the resulting propylene elastomer can be controlled by the presence of hydrogen in the copolymerization system or by changing the copolymerization temperature and copolymerization pressure.

Example

The present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples.

In the present invention, the intrinsic viscosity [η], molecular weight distribution ((/ Mn), stereoregularity (mmm), ratio of positional irregular units and melting point (Tm) are measured as follows.

Also, in some embodiments, melt flow rate (MFR), flexural modulus (FR), heat distortion temperature (HDT), heat sealing initiation temperature and heat after heat treatment The sealing starting temperature and the Izod impact strength are measured as follows.

Intrinsic Viscosity [η]

Intrinsic viscosity [η] was measured in decahydro naphthalene at 135 ° C. and expressed in dl / g.

Molecular Weight Distribution (Mw / Mn)

The molecular weight distribution (Mw / Mn) was measured by the following method using GPC-150C manufactured by Millipore.

Using a separation column of TSK-GNG-GT with a diameter of 72 mm and a length of 600 mm, the column temperature was set at 140 ° C., o-dichlorobenzene (made by Wako Junyaku Kogyo KK) as a mobile phase and BHT as an antioxidant Sample (concentration 0.1 wt.%, Amount: 500 microliters) is transferred in a column at 1.0 ml / min using 0.025 wt.% Of chemical industry).

A differential refractometer was used as a detector. As the standard polystyrene, polystyrene manufactured by Tosoh Corp. was used as the molecular weight of Mw <1,000 and Mw> 4 × 10 ⁶ , and polystyrene manufactured by Preser Chemical Co., Ltd. was used as the thing of 1,000 <Mw <4 × 10 ⁶ .

Stereoregularity (mm triadtacency and mmmm pentactacity)

mm triadtaxity was measured as described above. mmmm pentadtaxity was measured by the following method.

About 50 mg of the sample was completely dissolved in a mixed solvent of 0.5 ml of o-dichlorobenzene (or hexachlorobutadiene) and 0.1 ml of deuterated benzene at about 120 ° C. in an NMR sample tube (diameter: 5 mm), followed by ¹³ C-NMR spectra were measured by a G × 500 type NMR measuring instrument (nuclide: ¹³ C, mode: quantum perfect coupling, temperature: 120 ° C.).

^{The area of} the peak resonating at the lowest magnetic field on the ¹³ C-NMR spectrum (A.Zambell; 21.8 ppm according to P. Locatelli, G. Bajo and FA Bovey, 'Macromolecules', 8,687 (1975)) is determined by The value divided by the peak area was taken as mmmm 5 pentadtaxity.

Percentage of Irregular Units

For each of the polymers obtained in Examples 3 and 4 and Comparative Example 1, the ratio of irregular positions based on 2,1-insertion and 1,3-insertion of the propylene monomer present in the propylene chain of the polymer was ¹³ C-NMR spectrum. It calculated | required by the following formula.

Iαα in the formula is the entire area of the αα carbon peak (resonance near 42.0 ppm and 46.2 ppm),

Iα _δ is the area of αδ carbon peaks (resonance near 37.1 ppm).

Peaks (such as αα, etc.) were named according to the Carman classification (C. J Carman and CE. Wilkes, Rubber Chem. Technl.) 44, 781 (1971).

In another embodiment, the ratio of irregular positions was measured by the method described above.

Melting Point (Tm)

Melting point is about 5mg of sample in aluminum dish and heated to 200 ℃ at 10 ℃ / min, maintained at 200 ℃ for 5 minutes, then cooled to room temperature at 20 ℃ / min and then at 10 ℃ / min. It calculated | required from the endothermic curve at the time of heating again.

The measurement used the Perkin Elmer Co DSC-7 type apparatus.

Melt Flow Rate (MFR)

MFR was measured according to ASTM 1238 at 230 ° C. and 2.16 kg load.

Bending Tensile Stress (FM)

FM is a sample of 12.7mm (width) × 6.4 (thickness) × 127mm (length) made by molding at spun distance of 100mm and flexing 2mm / min at resin temperature of 200 ℃ and molding temperature of 40 ℃. Measured according to ASTM D 790 using.

Heating Distortion Temperature (HDT)

HDT was measured according to ASTM D 648 under a load of 4.6 kg / cm 2.

Heat sealing start temperature and heat sealing start temperature after heat treatment

Resin temperature 210 ° C (at dicer position of extrusion machine) using a single screw extruder with a diameter of 30 mm. A T-type film having a width of 30 cm and a thickness of 50 µm was made under a winding speed of 3 m / min and a cooling roll temperature of 25 ° C., and a heat sealing pressure was used to heat seal pressure of 2 kg / cm 2, sealing time of 1 second, and width of 5 mm. The two films were heat-sealed at various sealing temperatures under a cooling film to form a sealing film.

The heat sealing start temperature is defined as the temperature of the heat sealer when the sealing film is peeled at 23 ° C., and the peeling resistance of the sealing film reaches 300 g / 25 mm under the conditions such as peeling speed 200 mm / min and peel angle 180 °. .

Separately, another sealing film is heat-treated at 50 ° C. for 7 days. The heat sealing start temperature after heat treatment is measured using the heat treated sample.

Izod impact strength (IZ)

IZ is measured according to ASTM D 256 using a sample cut into 12.7 mm (width) x 6.4 mm (thickness) x 64 mm (length).

The sample was dry mixed with 20% by weight of the polymer according to the present invention and 80% polypropylene (HIPOL ^™ , J700 grade, manufactured by Mitsui Seiki Yugyo Co., Ltd., melt flow rate; 11 g / 10 min (at 230 ° C.), density: 0.91) It is produced by extrusion molding at a resin temperature of 200 ° C. and a mold temperature of 40 ° C. using a polypropylene composition obtained by melt-kneading at 200 ° C. using a twin screw extruder.

Film Impact Strength

Film impact strength is measured using a film impact tester (manufactured by Dokko Seiki KK, Impact head bulb diameter: 1/2 inch (12.7 mm Ø)).

Example 1

Synthesis of rac-dimethylsilyl-bismu- (4-isopropyl-2,7-dimethylindenyl) zirconium dichloride

Synthesis of 4-isopropyl-2,7-dimethylindene (Compound 1)

90 g (0.67 mole) of aluminum chloride and 150 g of carbon disulfide were injected into a sufficiently nitrogen-substituted 1-liter reactor, followed by 47 ml (0.30 mole) of p-cymene and 33 ml (0.3 mole) of methacryloyl chloride. The solution mixed with 30 ml of carbon was dripped at 20-25 degreeC. The mixture was reacted for 12 hours at room temperature, added to 1 kg of ice, and extracted with ether. The obtained ether solution was washed with saturated sodium bicarbonate water, and further washed with water to concentrate the ether layer to obtain 68 g of oil. The oil was purified by silica gel column chromatography (developing solvent; n-hexane) to obtain a mixture of 2,4-dimethyl-7-propyl-indanonone and 2,7-dimethyl-4-isopropyl-1-indanonone. 42 g of mixture 1) was obtained. (Yield: 67%)

2.82 g (0.075 mol) of lithium aluminum hydride and 200 ml of ether were charged into a 1-liter reactor sufficiently nitrogen-substituted, and a mixture of the mixture (1) 36.5 g (0.18 mol) and 150 ml of ether was added dropwise under ice-cooling. After dropping, the mixture was stirred at room temperature for 30 minutes and then refluxed for 1 hour. After the reaction was completed in the usual work-up, ether extraction. The obtained ether solution was washed with saturated sodium bicarbonate water and water, dried over anhydrous sodium sulfate, and the ether layer was concentrated to give 36 g of solid.

This solid was slurried with 100 ml of n-hexane and the solvent was evaporated to obtain a mixture of 2,4-dimethyl-7-isopropyl-1-indanol and 2,7-dimethyl-4-isopropyl-1-indanol ( 30 g of mixture 2 was obtained (yield: 82%)

25 g (0.12 mol) of mixtures (2) and 500 ml of benzene were injected into a 1-liter reactor sufficiently nitrogen-substituted, and 50 mg (0.55 mmol) of paratoluene sulfonic acid monohydrate was added thereto and refluxed for 1 hour. After the reaction, the mixture was poured into 30 ml of saturated sodium bicarbonate water, the organic layer was washed with water, and dried over anhydrous sodium sulfate.

The organic layer was concentrated and the oil thus obtained was distilled to give 20 g of the target compound (1). (Yield 90%)

Table 1 shows the NMR data of the desired compound (1).

Synthesis of 1,1′-dimethylsilyl-bis (4-isopropyl-2,7-dimethylindene) (Compound 2)

9.5 g (51 mmol) of compound (1) and 60 ml of 7.7 ml (51 mmol) diethyl ether were injected | thrown-in to the 200 ml reactor fully nitrogen-substituted, and it cooled to -10 degreeC. To this solution was added hexane solution (51 mmol) of n-butyllithium. After heating to room temperature, it cooled to -10 degreeC again, 3.1 ml (25.5 mmol) of dimethyl dichlorosilanes were dripped at 30 minutes, and reaction was performed for 1 hour.

After the reaction, the mixture was added to 40 ml of saturated aqueous ammonium chloride solution, extracted with n-hexane, and washed with water and dried over magnesium sulfate. The yellow oil obtained by removing the salt and concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: n-hexane) to give 5.4 g of a compound (2) as a colorless amorphous (yield: 50%).

Table 1 shows the NMR data of the target compound (2).

Synthesis of rac-dimethylsilyl-bisbis1- (4-isopropyl-2,7-dimethylindenyl) zirconium dichloride (Compound 3)

Into a fully nitrogen-substituted 300 ml reactor, 5.4 g (12.6 mmol) of Compound (2) and 100 ml of tetrahydrofuran were injected, cooled to -78 ° C and stirred. 16 ml of n-butyllithium (n-hexane solution, 1.58 N, 25.2 mmol) was added dropwise thereto over 20 minutes, and stirred for 1 hour while maintaining the temperature to prepare an anionic solution, which was then slowly heated to room temperature. .

Separately, 100 ml of tetrahydrofuran was injected into a 300 ml reactor sufficiently nitrogen-substituted, cooled to -78 ° C, and stirred. 2.94 g (12.6 mmol) of zirconium tetrachloride were slowly added thereto, followed by heating to room temperature. The anion solution mentioned above was dripped over 30 minutes, and it stirred at room temperature for 12 hours. After the reaction was concentrated under reduced pressure, the precipitated solid was washed three times with 300 ml of hexane to remove insoluble matters. The obtained hexane solution was concentrated to about 50 ml, and cooled at 6 degreeC for 12 hours.

The obtained solid was analyzed by ¹ H-NMR and found to be 1.78 g of a mixture of racemate and mesosome (4: 1). (Yield 24%). 100 ml of hexane was added to this mixture and recrystallized again to obtain 0.22 g of yellow columnar crystals of the compound (3) (yield: 3%).

In addition, the result of FD mass spectrometry of compound (3) was 588 (M ⁺ ).

Table 1 shows the NMR data of the target compound (3).

Example 2

Synthesis of rac-diphenylsilyl-bisbis1- (4-isopropyl-2,7-dimethyl-1-indenyl) zirconium dichloride (Compound 3)

Synthesis of 1,1′-dimethylsilyl-bis (4-isopropyl-2,7-dimethylindene (Compound 4)

It carried out similarly to the synthesis | combination of the compound (2) of Example 1 except having used 120 mg of copper cyanides instead of tetramethylethylene diamine, and 5.7 ml of diphenyl dichlorosilanes instead of dimethyl dichlorosilane.

7.2g of compound (4) was obtained as a colorless amorphous (yield: 49%)

Table 1 shows the NMR data of the target compound (4).

Synthesis of rac-diphenylsilyl-bis ｛l- (4-isopropyl-2,7-dimethylindenyl) zirconium dichloride (Compound 5)

It carried out similarly to the synthesis | combination of the compound (3) of Example 1 except having replaced compound (2) with compound (4) using 7.1 g (12.9 mmol) and 3.01 g instead of 2.94 g of zirconium tetrachloride.

1.10g of compound (5) was obtained as yellow columnar crystals (yield: 12%). In addition, the result of FD mass spectrometry of compound (5) was 712 (M ⁺ ).

Table 1 shows NMR data of the desired compound (5).

Example 3

500 g of propylene was injected into a 2-liter autoclave sufficiently nitrogen-substituted, and the temperature was raised to 40 ° C. 0.2 mmol of triisobutyl aluminum, 0.2 mmol of methylaluminoxane, and rac-dimethylsilyl-bis ｛1- (2,7-dimethyl 0.01 mmol of 4-isopropyl-1-indenyl) zirconium dichloride (in terms of Zr atoms) was added, and the polymerization was carried out at 50 ° C for 1 hour. After polymerization, the mixture was degassed to remove propylene, and the polymer was dried at 80 ° C for 10 hours.

The polymer was obtained in an amount of 158 g and had a polymerization activity of 158 kg-pp / mmol-Zr, [η] 4.55 dl / g, Mw / Mn 2.2, mmmm pentad value 95.5%, ratio of 2,1-insertion 0.90%, and Tm 147 ° C. It was.

Example 4

500 g of propylene was injected into a 2-liter autoclave sufficiently nitrogen-substituted, and the temperature was raised to 40 ° C., 0.2 mmol of triethylaluminum and rac-diphenylsilyl-bis1- (2,7-dimethyl-4-isopropylindenyl ) Zirconium dichloride 0.001 mmol (in terms of Zr atoms) and 0.002 mmol (in terms of B atoms) of tris (pentafluorophenyl) boron were added and polymerized at 50 ° C. for 1 hour. After polymerization, the mixture was degassed to remove propylene, and the polymer was dried at 80 ° C for 10 hours.

The polymer was obtained in an amount of 94 g and had a polymerization activity of 94 kg / pp / mmol-Zr, [?] 4.75 dl / g, Mw / Mn 2.3, mmmm pentad value of 96.4% and 2.1-insertion ratio of 0.80% Tm of 148 ° C.

Comparative Example 1

500 g of propylene was injected into a 2-liter autoclave sufficiently nitrogen-substituted, and the temperature was raised to 40 ° C., 0.2 mmol of triisobutylaluminum, 0.2 mmol of methyl aluminoxane, and rac-dimethylsilyl-bis-1-1- (2-methyl-4 -Isopropyl indenyl) zirconium dichloride 0.001 mmol (in terms of Zr atom) was added, and polymerization was carried out at 50 ° C for 1 hour. After the polymerization was degassed to remove propylene and the polymer was dried at 80 ℃ for 10 hours.

The polymer obtained was 125 g, having a polymerization activity of 125 kg / pp mmol-Zr, [?] 3.47 dl / g, Mw / Mn 2.1, mmmm pentad value 96.2%, ratio of 2,1-insertion, 0.40%, and Tm 152 占 폚.

Example 5

500 ml of toluene was added to a fully nitrogen-substituted 1-liter glass reactor, propylene was supplied at a rate of 100 l / hour, and the temperature was raised to 50 ° C., 3.5 mmol of methylaluminoxane and rac-dimethylsilyl-bisbis1- (2,7 A solution obtained by pre-contacting 0.01 mmol of dimethyl-4-isopropylindenyl) zirconium dichloride (in terms of Zr atoms) in toluene was added, and then polymerized at 50 ° C. for 20 minutes. After the polymerization, the solution was poured into methanol solution of methanol, and the polymer was filtered through a filter and dried at 80 ° C for 10 hours.

The polymer obtained was 32.6 g, and the polymerization activity was 8.2 kg-pp / millimolar-Zr [?] 1.37 dl / g, Mw / Mn 2.2, and Tm 148 ° C.

Comparative Example 2

rac-dimethylsilyl-bis ｛l- (2,7-dimethyl-4-isopropylinyl)｝ zirconium dichloride instead of rac-ethylenebis ｛1- (2,4,7-trimethylindenyl)｝ zirconium It carried out similarly to Example 5 except having used the dichloride.

The polymer was obtained in an amount of 23.1 g and had a polymerization activity of 5.08 Kg-pp / mmol-Zr, [?] 0.44 dl / g, Mw / Mn 2.3, and Tm 150 ° C. This polymer had a much lower molecular weight than that obtained in Example 5.

Example 6

Preparation of solid catalyst component (a)

Into a 500 ml reactor sufficiently nitrogen-substituted, 25 g of dried silica (F-948, manufactured by Fuji-Divison) at 200 ° C. under nitrogen flow for 6 hours and 310 ml of toluene were injected, and the system was brought to 0 ° C. while stirring. 90 ml of organoaluminum oxy compounds (method by which the methyl aluminoxane manufactured by Schering Company diluted with toluene, 2.1 mol / l) were dripped over 60 minutes in nitrogen atmosphere. Next, it was made to react at this temperature for 30 minutes and 90 degreeC for 4 hours. The reaction system was allowed to cool and the solution floated on the surface at the time point of 60 ° C was removed by decantation, and the residue was then washed three times with 150 ml of toluene at room temperature.

As a result, a solid catalyst component (a) containing 6.8 mmol of A1 was obtained per 1 g of silica.

Preparation of solid catalyst component (b)

50 ml of n-hexane was injected into a sufficiently nitrogen-substituted 200-ml reactor, and 10.5 mmol (in terms of A1 atom) of the solid catalyst component (a) obtained above, rac-dimethylsilyl-bisbis1- (2,7-dimethyl 4-isopropylindenyl) zirconium dichloride 0.03 mmol (in terms of Zr atoms) was added, followed by stirring for 20 minutes. 100 ml of n-hexane was added, and then 0.9 mmol of triisobutylaluminum was added thereto, followed by stirring for 10 minutes, and then propylene gas (2,2 L / hour) was flowed at 20 DEG C for 4 hours to carry out prepolymerization of propylene. The solution on the surface was removed by decantation and washed three times with 150 ml of toluene.

As a result, a solid catalyst component (b) carrying 0.011 mmol of Zr and 4.48 mmol of A1 was obtained per 1 g of the solid catalyst.

polymerization

In a sufficiently nitrogen-substituted 2-liter autoclave, 750 ml of purified n-hexane was added and stirred for 20 minutes at 25 ° C. under a propylene / ethylene mixed gas (ethylene: 3.6 mol%) atmosphere. 1.0 mmol of triisobutylaluminum and 0.002 mmol (in terms of Zr atom) of the solid catalyst component (b) were added to the reaction system, and the temperature was raised to 50 ° C and polymerized at a total pressure of 2 kg / cm 2 -G for 1 hour. After polymerization, the solvent was removed by filtration, washed with hexane and dried at 80 ° C for 10 hours.

The polymer (powder) obtained was 75 g, the polymer (SP) dissolved in a solvent was 1.9 g (2.5 wt%), and the polymerization activity was 38.5 kg-copolymer / mmimolar-Zr, MFR 6.0dg / min, Mw / of the polymer powder. Mn2.6, 2.9 mol% of ethylene content, and Tm = 126 degreeC.

Example 7

50 ml of n-hexane was injected into a sufficiently nitrogen-substituted 200-ml reactor, and 10.5 mmol (in terms of A1 atom) of the solid catalyst component (a) obtained above, and rac-diphenylsilyl-bisbis1- (2,7- Dimethyl-4-isopropylindenyl) zirconium dichloride 0.03 mmol (in terms of Zr atoms) was added and stirred for 20 minutes. 100 ml of n-hexane was added, and then 0.9 millimoles of triisobutyl aluminum were added, followed by stirring for 10 minutes, and then propylene gas (2.2 L / hour) was flowed at 20 DEG C for 4 hours to prepolymerize propylene. The solution which floated on the surface was removed by decantation, and it wash | cleaned 3 times with 150 ml of toluene. As a result, a solid catalyst component (c) carrying 0.011 mmol of Zr and 4.55 mmol of A1 was obtained per 1 g of the solid catalyst.

polymerization

In a sufficiently nitrogen-substituted 2-L autoclave, 750 ml of purified n-hexane was added and stirred for 20 minutes at 25 ° C. under a propylene / ethylene mixed gas (3.6 mol% of ethylene) atmosphere. 1.0 mmol of triisobutyl aluminum in the reaction system, solid catalyst component

(c) 0.002 mmol (in terms of Zr atoms) was added thereto, the temperature was raised to 50 ° C, and polymerization was carried out at a high pressure of 2 kg / cm 2 -G for 1 hour. After the polymerization, the solvent was removed by filtration, washed with hexane, and then dried at 80 ° C for 10 hours.

59 g of the obtained polymer (powder) was 2.5 g (4.0 wt%) of the polymer (SP) dissolved in a solvent, and the polymerization activity was 30.7 kg-copolymer / mmimolar-Zr, MFR5.8dg / min, Mw / Mn of the polymer powder. = 2.6 2.9 mol% of ethylene content and Tm = 127 degreeC.

Comparative Example 3

Preparation of solid catalyst component (d)

50 ml of n-hexane was injected into a sufficiently nitrogen-substituted 200-ml reactor, and 10.5 mmol (in terms of A1 atom) of the solid catalyst component (a) obtained above, rac-dimethylsilyl-bisbis1- (2-methyl-4 -Isopropylindenyl) zirconium dichloride 0.03 mmol (in terms of Zr atoms) was added and stirred for 20 minutes. 100 ml of n-hexane was added, and then 0.09 mmol of triisobutylaluminum was added, the mixture was stirred for 10 minutes, and propylene gas (2.2 L / hour) was passed through at 4 hours and 20 DEG C for prepolymerization of propylene.

The solution which floated on the surface was removed by decantation, and it wash | cleaned 3 times with 150 ml of toluene.

As a result, a solid catalyst component (d) carrying 0.011 mmol of Zr and 4.35 mmol of A1 was obtained per 1 g of the solid catalyst.

polymerization

In a sufficiently nitrogen-substituted 2-L autoclave, 750 ml of purified n-hexane was added and stirred for 20 minutes at 25 ° C. under a propylene / ethylene mixed gas (5.2 mol% of ethylene) atmosphere. 1.0 mmol of triisobutylaluminum and 0.002 mmol of the solid catalyst component (d) (in terms of Zr atoms) were added to the reaction system, and the temperature was raised to 50 ° C, followed by polymerization at a total pressure of 2 kg / cm 2 -G for 1 hour. After the polymerization, the solvent was removed by filtration, washed with hexane, and then dried at 80 ° C for 10 hours.

The polymer (powder) obtained was 67 g and a small amount of polymer attached to the autoclave base wall was observed. The polymer (SP) dissolved in the solvent was 9.0 g (12.0 wt%), and the polymerization activity was 38 kg-copolymer / millimolar-Zr, MFR 12dg / min of the polymer powder, Mw / Mn = 2.5, ethylene content 5.0 mol%, Tm It was 127 degreeC.

It is expected that such a large amount of SP not only lowers the powder yield but also lowers the heat transfer effect due to the walled polymer and increases the solvent viscosity in the industrial scale production, making operation very difficult.

Example 8

500 g of propylene was added to a 2-L autoclave sufficiently nitrogen-substituted, and the temperature of the autoclave was raised to 40 ° C, 0.2 mmol of triisobutylaluminum, 0.2 mmol of methylaluminoxane, and rac-diphenyl silyl-bis-l- ( 2,7-dimethyl-4-isopropylindenyl) zirconium dichloride 0.001 mmol (in terms of Zr atoms) was added to polymerize propylene at 50 ° C for 1 hour. After the polymerization, the autoclave was opened to remove propylene, and the resulting polymer was dried at 80 ° C. under reduced pressure for 10 hours. The obtained propylene polymer was 158g, the polymerization activity was 158kg-polymer / millimolar Zr, and intrinsic viscosity [eta] 4.55 dl / g. The triad taxity of the propylene unit chain of the iron bond was 95.4%. The ratio of irregular position units by 2.1-insertion of propylene monomer was 0.87% and the ratio of irregular position units by 1.3-insertion of propylene monomer was 0.03% or less.

The melt flow rate (MFR) of the polymer was 12.5 g / 10 min, the bending tensile stress coefficient (FM) 12500 kg / cm 2, and the heating distortion temperature was 105 ° C.

Example 9

750 ml of hexane was poured into a 2-L autoclave sufficiently nitrogen-substituted, and stirred for 20 minutes at 25 ° C. under a propylene / ethylene mixed gas atmosphere (ethylene: 2.9 mol%). 0.25 mmol of triisobutylaluminum, 0.5 mmol of methylaluminoxane, rac-diphenyl silyl-bis ｛1- (2,7-dimethyl-4-isopropylindenyl)｝ zirconium dichloride 0.0015 mmol (in terms of Zr atom) ) Was added and the temperature was raised to 50 ° C, and the polymerization was carried out for 1 hour while maintaining the voltage force at 2 kg / cm 2 -G. The polymer taken out of the autoclave after the polymerization was recovered in a large amount of methanol and dried for 10 hours at 80 ℃ under reduced pressure. The amount of the obtained propylene copolymer was 26.9 g, and the polymerization activity was 17.9 kg-polymer / millimolar-Zr, the intrinsic viscosity [η] 2.2 dl / g of the copolymer, and 3.0 mol% of ethylene. In the propylene copolymer, the triad taxity of the propylene unit chains having the iron bonds in the propylene copolymer was 97.3%, the ratio of the positional irregularity unit by 2.1-insertion of the propylene monomer was 0.9%, and the irregular position unit by 1,3-insertion of the propylene monomer. The ratio of was 0.04%.

The heat sealing start temperature of the film of the copolymer was 118 degreeC, and the heat sealing start temperature after heat processing was 120 degreeC.

The results are shown in Table 2.

Example 10

A sufficiently nitrogen-substituted 2-L autoclave was charged with 900 ml of hexane and 1 mmol of triisobutylaluminum was added. After heating up the temperature of the reaction system to 70 degreeC, ethylene was supplied in this system at the pressure of 1.5 kg / cm <2>, and it was supplied at the total pressure of propylene 8 kg / cm <2> -G. Subsequently, 0.3 mmol of methylaluminoxane and 0.001 mmol of rac-dimethyl silyl-bis ｛1- (2,7-dimethyl-4-isopropylindenyl) zirconium dichloride (in terms of Zr atoms) were added to the reaction system. The monomers are polymerized for 20 minutes while feeding continuously to maintain / cm 2 -G. The polymer taken out of the autoclave after the polymerization was recovered in a large amount of methanol and dried for 10 hours at 110 ℃ under reduced pressure. The amount of the obtained propylene copolymer was 21.2 g of polymerization activity of 21 kg-polymer / millimolar-Zr, intrinsic viscosity [η] 1.5 dl / g of copolymer, and 4.7 mol% of ethylene content. In the propylene copolymer, the triad tacticity of the propylene units in the propylene copolymer was 96.9%, the ratio of the positional irregularity unit by 2.1-insertion of the propylene monomer was 1.1%, and the positional irregularity unit by the 1,3-insertion of the propylene monomer. The ratio was 0.04% or less.

The heat-sealing start temperature of the film of the copolymer was 107 degreeC, and the heat-sealing start temperature after heat processing was 111 degreeC.

The results are shown in Table 2.

Example 11

900 ml of hexane was injected into a 2-liter autoclave sufficiently substituted with nitrogen, 1 mmol of triisobutyl aluminum was added, and 60 liters of propylene gas was supplied. After heating up the temperature of the reaction system at 70 degreeC, ethylene was supplied in this system by the total force of 8 kg / cm <2> -G. Then, 0.45 mmol of methylaluminoxane and rac-diphenyl silyl-bis ｛l- (2,7-dimethyl-4-isopropylindenyl)｝ zirconium dichloride were added to the reaction system, and ethylene was added thereto. The monomer was polymerized for 40 minutes while being fed continuously to maintain a voltage of 8 kg / cm 2 -G.

The polymer taken out of the autoclave after the polymerization was recovered in many fields of methanol and dried at 110 ° C. under reduced pressure for 10 hours.

The polymer was obtained in an amount of 47.2 g and had a polymerization activity of 31.5 Kg-polymer / millimolar -Zr, an inherent viscosity [?] Of 2.0 dl / g, and an ethylene content of 27 mol%.

The triad tacticity of the propylene unit chains with the iron bonds in the polymer was 95.4%, the ratio of positional irregularity units by 2.1-insertion of propylene monomer was 0.88%, and the ratio of positional irregularity units by 1,3-insertion of propylene monomer. Was less than 0.05%.

The impact strength of the film of the copolymer was 6000 kgf cm / cm, the IZ of the polypropylene composition was 35 kg cm / cm, and the melt flow rate (MFR) was 9.3 g / 10 min.

The results are shown in Table 2.

Example 12

900 ml of hexane was poured into the 2-liter autoclave fully nitrogen-substituted, and 1 mmol of triisobutyl aluminum was added. After heating up the temperature of the reaction system to 70 degreeC, ethylene was supplied at 2.0 kg / cm <2> in this system, and then propylene was supplied at 8 kg / cm <2> -G of total pressure. Next, 0.3 mmol of methylaluminoxane and rac-dimethyl silyl-bisbis1- (2,7-dimethyl-4-isopropylindenyl) zirconium dichloride were added to 0.001 mmol (in terms of Zr atoms). The monomer was polymerized for 10 minutes while feeding continuously to maintain a high force of 8 kg / cm 2 -G. The polymer taken out of the autoclave after the polymerization was recovered in a large amount of methanol and dried for 10 hours at 110 ℃ under reduced pressure.

The polymer was obtained in an amount of 16.8 g and had a polymerization activity of 16.8 Kg-polymer / millimolar-Zr, an inherent viscosity [?] Of 1.7 dl / g, and an ethylene content of 8.5 mol%.

The triad tacticity of propylene units with iron bonds in the polymer is 95.6%, the ratio of positional irregularity units by 2.1-insertion of propylene monomer is 0.62%, and the ratio of positional irregularity units by 1,3-insertion of propylene monomer is It was 0.05% or less.

The film of the copolymer had a heat sealing start temperature of 90 ° C. and a heat sealing start temperature of 93 ° C. after the heat treatment.

The results are shown in Table 2.

The novel transition metal compound according to the present invention can be used as a catalyst component for olefin polymerization.

The catalyst for olefin polymerization of the present invention is highly active, and the polyolefin produced using this catalyst has a narrow molecular weight distribution and a composition distribution. When the α-olefin having at least 3 carbon atoms is used for the polymerization, a polymer having a low melting point at about the same molecular weight as a polymer using a conventional metallocene catalyst is obtained.

Using the catalyst of the present invention, a copolymer having a low melting point of at least the amount of repeating units derived from a comonomer can be obtained. Moreover, since the produced copolymer has few solvent-soluble components, it is excellent in various performances, such as transparency, heat sealing property, and blocking resistance. In addition, compared to the conventional metallocene catalysts in which polypropylenes having almost the same molecular weight are obtained, the reaction step in the synthesis is less economical.

When producing a copolymerized elastomer mainly containing ethylene units and propylene units using the catalyst for olefin polymerization of the present invention, the produced elastomer has a high molecular weight. Since such copolymerized elastomers have high strength, when used as a modifier, they exhibit excellent effects in improving the impact strength and hardness of polyolefins. The use of copolymerized elastomers in the production of propylene block copolymers increases the molecular weight of the copolymerized elastomers, thereby creating a well-balanced copolymer between heat resistance, stiffness or transparency and impact strength. Also in the production of polyethylene, it is possible to produce polyethylene having excellent mechanical strength such as impact strength, tensile strength and bending strength.

The propylene elastomer of the present invention is excellent in rigidity, heat resistance, surface hardness, gloss, transparency, and impact strength, and thus is suitable for use in various industrial parts, containers, films, nonwoven fabrics, stretched yarns, and the like.

The propylene copolymer of the present invention has excellent transparency, rigidity, surface hardness, heat resistance, heat sealing, blocking resistance, bleed resistance, and impact strength, and thus is suitable for use in films, sheets, containers, drawn yarns, nonwoven fabrics, and the like. .

The propylene elastomer of the present invention has excellent heat resistance, shock absorption, transparency, heat sealing and blocking resistance, and therefore is not only suitable for use in films and sheets, but also effective for use as a modifier for thermoplastic resins.

Claims (1)

In propylene elastomers, (a) the elastomer contains 50 to 95 mol% propylene units and 5 to 50 mol% ethylene units, (b) the triad taxity of three propylene unit-chains of the iron-bond is at least 90.0% as measured by ¹³ C-NMR; (c) The ratio of irregularity unit by 2,1-insertion of propylene monomer in all propylene insertion is 0.5% or more measured by ¹³ C-NMR and the ratio of irregularity unit by 1,3-insertion of propylene monomer. Measured at ¹³ C-NMR or less than 0.05%, (d) Propylene elastomer having intrinsic viscosity measured in 135 ° C. decahydro naphthalene and in the range of 0.1 to 12 dl / g.