KR100332503B1 - Propylene elastomer - Google Patents

Abstract

PURPOSE: Provided is a propylene elastomer which has excellent rigidity, heat resistance, surface hardness, transparency, gloss, heat-sealability, impact strength 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 at least 90.0% when measured by 13C-NMR; (c) the ratio of stereo-irregular units generated by 2,1-insertion of propylene monomers, based on the total propylene insertion, is 0.05% to 0.5%, 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, a catalyst component for olefin polymerization of the transition metal compound, an olefin polymerization catalyst containing the catalyst component and an olefin polymerization method using the olefin polymerization catalyst. The invention also relates to propylene homopolymers, propylene copolymers and propylene elastomers, which have a high triad tacticity of propylene unit chains and a low amount of irregular site units.

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.

As described in Japanese Patent Application Laid-Open No. 61-130134, ethylenebis (indenyl) -zirconium dichloride and ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride are used in the Kaminsky catalyst. It is known as a transition metal compound for producing a soottic polyolefin. 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. 1-301704 and 'Polymer Preprints',' Japan, Vol. 39, No. 6, pp. As described in 1,614-1,616 (1990), 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.

Various proposals have been made to solve this problem. For example, Japanese Patent Laid-Open No. Hei 4-268307 describes a polymerization catalyst composed of a metallocene compound represented by the following formula and an aluminoxane as a catalyst capable of producing a high molecular weight polyolefin.

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.

However, the stereoregularity and molecular weight of the polyolefins obtained using these catalysts are not satisfactory and the amount of irregularity unit is still too large.

In addition, '40 YEARS ZIEGLER CATALYST IN HONOR OF KARL ZIEGLER AND WORKSHOP (Sep. 1-3, 1993), in which the catalyst component (wherein A is a phenyl or naphthyl group in the metallocene compound described above), is published by Hoechst. It was announced at.

EP 0 576 970 A1 also discloses olefin polymerization catalysts made of metallocene compounds and aluminoxanes represented by the following formulae.

Wherein M ¹ is a transition metal atom, R ¹ and R ² are each a hydrogen atom, R ³ is an alkyl group of 1 to 10 carbon atoms, R ⁴ to R ¹² is an alkyl group of 1 to 10 carbon atoms, and R ¹³ is a hydrocarbon Group or silicone-containing group.

However, the stereoregularity of the polyolefins obtained by the use of these catalysts is not satisfactory, and the amount of irregularity unit is still too large.

In view of this prior art as described above, the inventors have found that the polymerization activity of the catalyst component of the transition metal compound described above is determined according to the type of substituents on the indenyl group, and the positional irregularity and stereoregularity of the resulting polyolefin It was found to be significantly different.

In addition, the inventors of the present invention can provide an olefin polymerization catalyst capable of producing an olefin polymer having an indenyl group containing a specific substituent as a ligand and having excellent olefin polymerization activity, high stereoregularity, and low positional irregular unit amount. It turned out that

Propylene polymers, especially propylene homopolymers, have been used in applications such as industrial parts, containers, films and nonwovens because of their excellent stiffness, surface hardness, heat resistance, gloss and transparency.

However, the conventional propylene homopolymer is insufficient in transparency, impact resistance, etc., and therefore is unsuitable for some applications, and therefore, the emergence of a propylene polymer excellent in rigidity, heat resistance, surface hardness, gloss, transparency, and impact strength is desired.

In addition, since the physical properties of propylene and copolymers of α-olefins other than propylene vary depending on their composition, monomer content derived from α-olefins other than propylene is generally divided to about 5 mol%. Propylene copolymers containing up to 5 mol% of monomer units derived from α-olefins other than propylene are suitable for various applications such as containers and packaging materials (eg films) because of their excellent stiffness, surface hardness, heat resistance, transparency and heat sealing properties. Was used.

However, using the copolymer as a film, the produced film was not sufficiently transparent, heat-sealing, anti-blocking, anti-bleed out and impact strength. Therefore, a propylene copolymer has been desired that further improves transparency, stiffness, surface hardness, heat resistance and heat sealing, and also has excellent antiblocking property and antibleed out property.

In contrast, propylene copolymers containing an amount of at least 5 mol% of monomer units derived from α-olefins other than propylene are not suitable for the heat treatment of films and laminated films due to their excellent transparency, low temperature heat sealing, environmental aging and impact absorption ability. It was used for various applications such as a modifier for improving the impact resistance and anti-heat sealing property of the sealing layer and the thermoplastic resin. However, the conventional propylene copolymer has insufficient transparency, heat sealing property, bleed out resistance, impact strength, etc. in some applications, and the effect of improving low temperature heat sealing property and impact strength as a modifier is not sufficient. Therefore, there has been a demand for a propylene copolymer having an effect of further improving transparency, environmental aging and impact strength, and also improving low temperature heat sealing and impact strength.

In view of the above circumstances, the present inventors have steadily researched the propylene homopolymer obtained by homopolymerization of propylene in the presence of an olefin polymerization catalyst containing a specific transition metal compound, and α- of ethylene and carbon atoms of 4-20. It has been found that the propylene copolymer obtained by the copolymerization of propylene with at least one kind of α-olefin selected from the group consisting of olefins satisfies the above requirements.

Propylene / ethylene random copolymers containing a small amount of ethylene units are used in films, containers and the like because they are excellent in transparency, rigidity, surface hardness and heat resistance.

Until now, a method of using a titanium catalyst system composed of a titanium compound and an organoaluminum compound, and a method of using a metallocene compound consisting of a metallocene compound (eg, zirconocene and hafnocene) and an alkyl aluminoxane or an ionic compound Processes for producing propylene / ethylene random copolymers containing small amounts of ethylene units such as are known.

However, propylene / ethylene random copolymers obtained using titanium catalyst systems do not have sufficient heat sealing in some applications and also insufficient antiblocking, bleed out and impact strength. On the other hand, the propylene / ethylene random copolymer obtained using the metallocene catalyst system has insufficient rigidity, surface hardness, and heat resistance. Therefore, the emergence of propylene / ethylene random copolymers having good balance with these two advantages has been required.

In view of the above circumstances, the inventors have continued to study that the triadtaxity of the propylene chains of the iron-bonded bonds measured by ¹³ C-NMR is high, and the ratio and specific intrinsic viscosity of specific positional propylene units are high. It was found that propylene copolymers containing a specific amount of ethylene units were excellent in transparency, stiffness, surface hardness, heat sealing, antiblocking property, antibleed out property and impact strength.

In addition, propylene elastomer is used alone for the film and also used as a thermoplastic resin modifier because of its excellent impact absorption, heat resistance and heat sealing.

However, the films produced when conventional propylene elastomers were used alone for the films did not have sufficient heat sealing, antiblocking and heat resistance. When the elastomer was used as a modifier, the effect of improving the impact strength was insufficient. Therefore, the emergence of propylene elastomers having excellent impact strength and effectively improving heat resistance, transparency, heat sealing, anti-blocking property, anti-bleed out property and impact strength has been required.

In view of the above situation, the inventors have continued to study that ethylene having a high triadtaxity of a propylene chain of a dumi-bonded propylene chain measured by ¹³ C-NMR, having a specific positional propylene unit ratio and a specific intrinsic viscosity The present invention was completed by finding that the propylene / ethylene random copolymer containing a specific amount of the unit was excellent in the above-described characteristics.

It is an object of the present invention to provide a novel transition metal compound useful for a catalyst component for olefin polymerization which has an excellent olefin polymerization activity and is capable of providing an olefin polymer having high stereoregularity and a low order irregular unit amount. To provide a catalyst component for olefin polymerization.

It is another object of the present invention to provide a catalyst for olefin polymerization containing the catalyst component for olefin polymerization, and to provide a polymerization method for olefins using the catalyst for olefin polymerization.

Still another object of the present invention is to provide a propylene homopolymer having excellent stiffness and transparency, a propylene copolymer having excellent impact strength and transparency, and a propylene elastomer having excellent impact strength and transparency.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the process of the manufacturing method of the catalyst for olefin polymerization by this 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 1Va, Va, V1a;

R ¹ is a hydrocarbon group of 2 to 6 carbon atoms, R ² is a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms, an organosilyl group or an aryl group of 6 to 16 carbon atoms which may be substituted with a halogen atom,

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, -O-, -CO-, -S-,- SO-, -SO _2- , -NR ^3- , -P (R ³ )-, -P (O) (R ³ )-, -BR ³ -or -AlR ^3- (R ³ is 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.

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) A compound which forms an ion pair by reacting with the transition metal compound

At least one compound selected from the group consisting of

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) 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) organoaluminoxane compound

It becomes

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) 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 the transition metal compound (A) and the at least one compound (B) It is supported on the particulate carrier.

The fourth olefin polymerization catalyst of the present invention

Particulate carrier,

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

(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, wherein the transition metal compound (A) and the at least one compound (B) A solid catalyst component supported on the particulate carrier;

(C) organoaluminum compound

It becomes

The fifth 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) 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 | generated 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) and

(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;

(C) an organoaluminum compound and

It becomes a prepolymer olefin polymer produced by prepolymerization.

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

The catalyst for olefin polymerization according to the present invention has a high polymerization activity, and the olefin polymer obtained by using the catalyst has a narrow molecular weight distribution, a narrow compositional distribution, and a large molecular weight. When the catalyst is used to polymerize α-olefins having 3 or more carbon atoms, polymers having high stereoregularity, low positional irregular unit amount, and excellent heat resistance and rigidity can be obtained.

The first propylene homopolymer according to the present invention is obtained by polymerizing propylene in the presence of the olefin polymerization catalyst according to the present invention consisting of the following.

(A) the transition metal compound represented by 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;

The first propylene copolymer according to the present invention is at least one α- selected from the group consisting of propylene, ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to the present invention. Obtained by copolymerizing an olefin.

(A) the transition metal compound represented by 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;

The propylene homopolymer of the present invention is excellent in rigidity, heat resistance, surface hardness, gloss, transparency, and impact strength.

The second propylene homopolymer according to the present invention

(i) the triadtaxity of the propylene unit chain is at least 99.0% as measured by ¹³ C-NMR;

(ii) the proportion of positional propylene units based on 2,1-insertion of propylene monomer during all propylene insertions is not more than 0.20% as measured by ¹³ C-NMR; And

(iii) Intrinsic viscosity measured in decahydronaphthalene at 135 degreeC, and has a characteristic like 0.1-20 dl / g.

Such propylene polymers are excellent in stiffness, heat resistance, surface hardness, gloss, transparency, and impact strength.

The second propylene homopolymer according to the present invention

(i) the copolymer contains up to 50 mole% ethylene units;

(ii) more than 98.0% of the triadtaxity of the propylene unit chain of the dumi-bond as measured by ¹³ C-NMR;

(iii) the proportion of positional propylene units based on 2,1-insertion of the propylene monomer during all propylene insertions is not more than 0.20% as measured by ¹³ C-NMR;

(iv) Intrinsic viscosity measured in decahydro naphthalene at 135 degreeC, and has a characteristic like 0.1-20 dl / g.

Such copolymers (units of monomers derived from α-olefins other than propylene are 5 mol% or less) are excellent in transparency, rigidity, surface hardness, heat resistance, heat sealing, antiblocking, antibleed out and impact resistance. Do. The propylene copolymer according to the present invention (the amount of monomer units derived from α-olefins other than propylene is 5 mol% or more) is excellent in transparency and environmental aging, and is effective in improving low temperature heat sealing and impact properties.

The third propylene copolymer according to the present invention

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

(ii) more than 95% of the triadtacticity of the propylene unit chain of the dumi-bond, measured by ¹³ C-NMR;

(iii) the proportion of positional propylene units based on 2,1-insertion of the propylene monomer during all propylene insertions is 0.05% to 0.5% as determined by ¹³ C-NMR;

(iv) Intrinsic viscosity measured in decahydro naphthalene at 135 degreeC and has a property like 0.1-12 dl / g.

Such a propylene copolymer has excellent transparency, rigidity, surface hardness, heat resistance, heat sealing, antiblocking property, and antibleed out property.

Propylene elastomer according to the present invention

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

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

(iii) the proportion of positional propylene units based on 2,1-insertion of propylene monomers in all propylene insertions, measured by ¹³ C-NMR, from 0.05% to 0.5%;

(iv) Intrinsic viscosity measured in decahydro naphthalene at 135 degreeC and has a property like 0.1-12 dl / g.

Such propylene elastomers are excellent in heat resistance, impact absorption, transparency, heat sealing and antiblocking properties.

Novel transition metal compound according to the present invention, catalyst component for olefin polymerization of the transition metal compound, olefin polymerization catalyst containing the catalyst component for olefin polymerization, olefin polymerization method using this olefin polymerization catalyst, propylene homopolymer The propylene copolymer and the propylene elastomer will be specifically described below.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the process of the manufacturing method of the catalyst for olefin polymerization by this 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 periodic table IVa, Va, and VIa group. Examples of transition metals include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, among which titanium, zirconium and hafnium are preferred, and zirconium is particularly preferred.

R ¹ is a hydrocarbon group of 2 to 6 carbon atoms, for example ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Sec-butyl, tert-butyl, n-pentyl, neopentyl and n-hexyl And alkyl groups such as cyclohexyl, cycloalkyl groups such as cyclohexyl, and alkenyl groups such as vinyl and propenyl. Among these, an alkyl group having a carbon atom bonded to an indenyl group is preferred, and an alkyl group having 2 to 4 carbon atoms is better. Ethyl group is particularly good.

R ² is an aryl group having 6 to 16 carbon atoms, for example phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, prenyl, acenaphthyl, phenenyl, aceanthrenyl, tetrahydro Naphthyl, indanyl and biphenylyl, among others, phenyl, naphthyl, anthracenyl or phenanthryl.

These aryl groups may be substituted with halogen atoms such as fluorine, chlorine, cancellation or iodine, hydrocarbon groups of 1 to 20 carbon atoms, for example methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dode Alkyl groups, such as an alkyl group, such as a yarn, an ecosyl, a norbornyl, and adamantyl, an alkenyl group, such as vinyl, propenyl, and cyclohexenyl, an aryl alkyl group, such as benzyl, phenylethyl, and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl And aryl groups such as ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl and phenanthryl or organosilyl groups such as trimethylsilyl, triethylsilyl and triphenylsilyl.

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 halogen atoms and hydrocarbon groups having 1 to 20 carbon atoms, and halogenated hydrocarbon groups having 1 to 20 carbon atoms include, for example, halogenated groups of the aforementioned hydrocarbon groups having 1 to 20 carbon atoms. Can be.

Oxygen-containing groups include, for example, alkoxy groups such as hydroxy groups, methoxy, ethoxy, propoxy and butoxy, aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, phenylmethoxy and phenylethoxy And an arylalkoxy group.

Sulfur-containing groups are, for example, groups obtained by replacing oxygen with sulfur in the oxygen-containing group described above.

As the sulfur-containing group, methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, penta Sulfonate groups such as fluorobenzenesulfonate; And sulfinate groups such as methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate and pentafluorobenzene sulfinate. Of these, halogen atoms or hydrocarbon groups of 1 to 20 carbon atoms are preferable.

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, -O-, -CO-, -S-,- SO-, -SO _2- , -NR ^3- , -P (R ³ )-, -P (O) (R ³ )-, -BR ³ -or -AlR ^3- (R ³ is a hydrogen atom, a halogen atom Or 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 carbon 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; And arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

Examples of the divalent halogenated hydrocarbon group include a group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene.

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

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

Examples of the atoms and groups represented by R ³ include the halogen atoms exemplified above, hydrocarbon groups of 1 to 20 carbon atoms, and halogenated hydrocarbon groups of 1 to 20 carbon atoms.

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

Examples of the transition metal compound represented by the formula (I) are as follows.

rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (0-methylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (0-chlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2,6-dichlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (4-bromophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (4-biphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4- (4-trimethylsilylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,

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

rac-dimethylsilyl-bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-propyl-4- (8-methyl-9-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-s-butyl-4- (2-methyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-s-butyl-4- (5-acenaphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-s-butyl-4- (9-anthracenyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-pentyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-butyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-butyl-4- (β-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-butyl-4- (5-acenaphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-butyl-4- (9-phenanthryl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-butyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-butyl-4- (β-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-butyl-4- (2-methyl-1-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-butyl-4- (5-acenaphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-naphthyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-naphthyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-hexyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2-ethyl-4-phenylindenyl} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2-ethyl-4-phenylindenyl} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2-ethyl-4- (4-biphenyl) indenyl} zirconium dichloride,

rac-methylene-bis {1- (2-ethyl-4-phenylindenyl} zirconium dichloride,

rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,

rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-ethylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-dimethylgeryl-bis {1- (2-ethyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylgeryl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl} zirconium dichloride,

rac-dimethylgeryl-bis {1- (2-n-propyl-4-phenylindenyl} zirconium dichloride,

Among the compounds exemplified above, a transition metal compound obtained by substituting vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal or tungsten metal instead of zirconium metal, titanium metal or hafnium metal may be used.

The transition metal compound according to the present invention can be prepared in the following manner according to the method disclosed in, for example, the specification of the magazine 'Organic Metal Chemistry' 288 (1985), pages 63-67, EP 0 320 762 and examples thereof. have.

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

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

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 the term 'polymer' may be used to include not only 'monopolymer' 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) 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) 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) organoaluminum compound

It is formed.

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

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

(1) Organic compounds such as trialkylaluminum in hydrocarbon medium suspensions such as compounds containing adsorbed water or salts containing crystallized water such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate and cerium chloride hydrate A method in which an aluminum compound is added and reacted to recover as a solution of a hydrocarbon.

(2) A method of recovering as a solution of a hydrocarbon by directly reacting an organoaluminum compound such as trialkylaluminum, such as trialkylaluminum, in water, ice, or water vapor 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 organoaluminum compounds used when preparing aluminoxanes include

Trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, Trialkyl aluminum, such as 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 oxides, such as diethyl aluminum phenoxide

And the like.

Among the organoaluminum compounds, trialkyl aluminum and tricycloalkyl aluminum are particularly preferable.

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

(iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ....... (II)

Where x, y and z are positive numbers and z ≥ 2x.

Such organoaluminum compounds can be 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 Patent No. Lewis acids, ionic compounds and borane compounds and carborane compounds as described in 547,718.

Examples of Lewis acids include Mg-containing Lewis acids, Al-containing Lewis acids, and B-containing Lewis acids. Among them, B-containing Lewis acids are preferable.

As an example of the 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

Meal R⁶, R⁷And R⁸Each independently represents a phenyl group or a fluorine atom which may have substituents such as a fluorine atom, a methyl group and a trifluoromethyl group.

Examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) 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.

Ionic compounds used in the present invention are salts of cationic compounds and anionic compounds. 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 organic boron compounds anions, organic arsenic compounds anions, organoaluminum compounds anions, and the like. Anions that are relatively bulky and stabilize transition metal cation species are 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 carbenium 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) ammoniumtetra (o-tolyl) boron and tri (n-butyl) ammoniumtetra (4-fluorophenyl) boron .

Examples of N, N-dialkylanilinium salts include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (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.

Examples of the triaryl phosphonium salt include triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

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

Moreover, it can use with the following compounds (In the ionic compounds listed below, a counter ion is tri (n-butyl) ammonium, but a 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} decachlorodecarborate, bis {(tri (n-butyl) ammonium} dodecachlorododecaborate, tri (n- Butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carbodecaborate, tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium- 1-trimethylsilyl-1-carbadecarborate and tri (n-butyl) ammonium bromo-1-carbadecaborate.

Borane compounds and carborane compounds may also be used. 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-dicarbound carborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbound carborate, tri (n-butyl) ammonium Decahydride-8-butyl-7,9-dicarboundeborate, Tri (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.

In addition, the following compounds can also be used (in the ionic compounds listed below, the counterion is tri (n-butyl) ammonium, but the counterion is not limited thereto). Salts of metal carboranes and metalborane anions such as tri (n-butyl) ammoniumbis (nonnahydride-1,3-dicarbononanaborate) cobaltate (III), tri (n-butyl) ammoniumbis (unde) Carhydride-7,8-dicarbound carborate) perate (ferrate), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbound carborate) cobaltate (III) , Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundeborate) nickelate (III), tri (n-butyl) ammoniumbis (undecahydride-7,8-dica Rebound carborate) (rate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicaround deborate) aurate (gold salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeborate) ferrate (III), tri (n-butyl) ammoniumbis (nonahydride-7,8 Dime -7,8-dicarbounde carborate) chromate (chromate) (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbounde carborate) cobaltate (III) ), Tri (n-butyl) ammonium bis (dodecahydride dicarbound carborate) -cobaltate (III), bis {tri ((n-butyl) ammonium} bis (dodecahydride dodecaborate)- Nickelate (III), Tris {tri (n-butyl) ammonium} bis (Undecahydride-7-carboundeborate) Chromate (III), Bis {tri (n-butyl) ammonium} bis (Undeca Hydride-7-carbondecaborate) manganate (IV), bis {tri (n-butyl) ammonium} bis (undecahydride-7-carbondecaborate) cobaltate (III) 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 an organoaluminum compound represented by the following general formula (III). There is.

R ⁹ _n AlX _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 an 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 sesquibromide;

Alkyl aluminum dihalide, 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, are mentioned.

Moreover, as an organoaluminum compound (C), the compound represented by the following general formula (IV) can also be used.

R ⁹ _n AlL _3-n ........... (Ⅳ)

R ⁹ in the formula is a hydrocarbon as in the general formula (III); L is -OR ¹⁰ group, -OSiR ₃ ¹¹ group, -OAlR ₂ ¹² group, -NR ¹³ ₂ group, -SiR ¹⁴ ₃ group or -N (R ¹⁵ ) AlR ¹⁶ ₂ group, n is 1 to 2; R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are each methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl and the like; R ¹³ is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, and the like, and R ¹⁴ and R ¹⁵ are methyl, ethyl and the like, respectively.

As an example of such an organoaluminum compound (C)

(1) compounds represented by the general formula R ⁹ _n Al (OR ¹⁰ ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide;

(2) compounds represented by the general formula R ⁹ _n Al (OSiR ¹¹ ₃ ) _3-n , such as Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ ) and (iso-Bu) ₂ Al (OSiEt ₃ );

(3) a compound represented by the general formula R ⁹ _n Al (OAlR ¹² ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ and (iso-Bu) ₂ AlOAl (iso-Bu) ₂ ;

(4) compounds represented by the general formula R ⁹ _n Al (NR ¹³ ₂ ) _3-n , such as Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ and (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ ;

(5) a compound represented by the general formula R ⁹ _n Al (SiR ¹⁴ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe ₃ ; And

(6) a compound represented by the general formula R ⁹ _n Al (N (R ¹⁵ ) AlR ¹⁶ ₂ ) _3-n , such as Et ₂ AlN (Me) AlEt ₂ and (iso-Bu) ₂ AlN (Et) Al (iso -Bu) ₂

Can be heard.

Among the organoaluminum compounds represented by the general formulas (III) and (IV), compounds represented by R ⁹ ₃ Al, R ⁹ nAl (OR ¹⁰ ) _3-n and R ⁹ _n Al (OAlR ¹² ₂ ) _3-n This is preferable, and especially the compound whose R is an isoalkyl group and n = 2 is preferable.

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 preparing the water and the component (B-1) dissolved in the polymerization solvent as described below.

The first catalyst for olefin polymerization of the present invention comprises component (A) and component (B-1) (or component (B-2)) and optionally water (as catalyst component) an 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 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) The concentration of is in the range of about 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-2)) between component (A) and component (B-2) is usually in the range of 0.01-10, preferably in the range of 0.1-5. Is; The concentration of component (A) is in the range of about 10 ⁻⁸ to 10 ⁻¹ mol / liter-media, preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter-media.

In preparing the second olefin polymerization catalyst of the present invention, the atomic ratio (Alc / Al _B− ) of the aluminum atom (Alc) in component (C) and the aluminum atom (Al _B-1 ) in component (B-1) ₁ ) is normally 0.02-20, 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 aluminum atom (Al _B-1 ) and water (H ₂ O) in component ( _B-1 ) is usually 0.5 to 50, preferably Is in the range of 1 to 40.

Each said component may be mixed in a polymerization reactor, and what mixes previously may be added to a 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 preparation 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

And mixtures of these hydrocarbons.

Next, the third and fourth olefin polymerization catalysts 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) A compound which forms an ion pair by reacting with the transition metal compound (A)

At least one compound selected from the group consisting of;

The transition metal compound (A) and at least one compound are formed 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 forms an ion pair by reacting with the transition metal compound (A) used in the third and fourth olefin polymerization catalysts of the present invention may be 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 oxides such as NO ₃ ) ₃ , NaO, K ₂ O and Li ₂ O.

Although the particulate carrier has different properties depending on its type and production method, the particulate carrier preferably used in the present invention has 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 particulate matter 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 this organic compound include (co) polymers prepared from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and vinylcyclohexane or styrene as main components. The (co) polymer manufactured by the above is mentioned.

The fine particle carrier may contain a surface hydroxyl group or water. In this case, it is desired that the surface hydroxyl group is 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 adsorbed water (% by weight) and the amount of surface hydroxyl group (% by weight) are obtained by the following method.

Amount of adsorbed water

The weight loss of the particulate carrier after drying for 4 hours under normal pressure and nitrogen flow at a temperature of 200 ° C is measured and calculated as the ratio after drying to before drying.

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} × 100

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

The component (A) when mixing the respective components are used in amounts of 3 × 10 ^-6 ~10 ^-3 mol Preferably typically 10 ^-6 ~5 × 10 ^-3 mol, per particle consultation body 1g. 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-1) 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.

As an example of the inert hydrocarbon medium (solvent) used for manufacture of the 3rd and 4th olefin polymerization catalysts of this invention, the same thing as the medium used for the 1st and 2nd olefin polymerization catalysts is mentioned.

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 prepared 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 prepared 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 first and second olefin polymerization catalysts described above. 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 produced by prepolymerizing a small amount of olefin to a 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 the like. 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 components of component (A) is usually 10 ^-6 ~5 × 10 ^-3 mol, preferably 3 × 10 ^-6 is used in an amount of to 10 ^-3 mol per 1g particulate carrier; The concentration of component (A) is in the range of about 5 × 10 ⁻⁶ to 2 × 10 ⁻² moles / liter medium, preferably 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 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 while 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 ~2 × 10 ^-2 to mol / liter, preferably 5 × 10 ^-5 ~10 ^-2 is used in an amount of mole / L. 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 mixtures of the same monomers as the monomers used in the polymerization or monomers such as the monomers used for the polymerization and α-olefins.

The catalyst for olefin polymerization of the present invention obtained as described above is about 10 ⁻⁶ to 10 ⁻³ g · atoms, preferably 2 × 10 ⁻⁶ to 3 × 10 ⁻⁴ g · atoms transition metal per 1 g of the particulate carrier. 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 loaded per 1 g of the particulate carrier. In addition, component (B-2) is a boron atom contained in component (B-2) of 5 x 10 ^{-7 to} 0.1 g.atoms, preferably 2 x 10 ^-7 to 3 x 10 ^-2 g. It is hoped that it is supported.

The amount of the prepolymerized polymer produced by the prepolymerization is desirably in the range of about 0.1 to 500 g, preferably 0.3 to 300 g per 1 g of the particulate 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.

Further, when the olefin having 3 or more carbon atoms is polymerized in the presence of the 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, the catalyst is usually 10 ^-8 to 10 ^-3 g, atom / liter, preferably as a concentration of the transition metal atom of component (A) in the polymerization system. The following is used in amounts of 10 ⁻⁷ to 10 ⁻⁴ g · atoms / liter.

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

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 catalyst is usually 10 ^-8 to 10 ^-3 g. Atoms / liter, preferably as a concentration of the transition metal of component (A) in the polymerization system. 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 the support as desired.

In the slurry polymerization method, the polymerization temperature of the olefin is usually in the range of -100 to 100 ° C, preferably -50 to 90 ° C. In the liquid-phase polymerization method, the temperature is usually in the range of -100 to 250 ° C, preferably -50 to 200 ° C. In the gas phase polymerization method, the temperature is usually in the range of -47 to 120 ° C, preferably -40 to 100 ° C. The polymerization pressure is usually in the range of normal pressure to 100 kg / cm 2, preferably 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-hexene, 4-methyl-1pentene, 1-octene, 1-decene, 1-dodecene, 1-detradecene, 1-hexadecene, 1-octa Α-olefins having 2 to 20 carbon atoms such as decene and 1-eicosene; 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.

Styrene, vinylcyclohexane, diene, etc. can also be used.

The olefin polymerization catalyst according to the present invention can be suitably used for homopolymerization of propylene or copolymerization of propylene with at least one α-olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms.

Polyolefins obtained using the olefin polymerization catalyst of the present invention (e.g., the polyolefin is a propylene / ethylene copolymer containing 50 mol% or more of propylene units) typically have a Mw / Mn value of 1.5 to 3.5 and triadtaxity (mm Fractions) of not less than 98.0%, of proportional irregularity units based on 2.1-insertion of propylene monomers of 0.20% or less, and of proportional irregularity units of 1.3-insertion of propylene monomers, of 0.03% or less.

When the obtained polyolefin is a propylene homopolymer, the polymer typically has a Mw / Mn value of 1.5 to 3.5, a triadtaxity (mm fraction) of 99.0% or more, and a proportion of irregular units based on 2.1-insertion of the propylene monomer. Below 0.50%, the proportion of positional irregularity units based on 1.3-insertion of the propylene monomer is below 0.03%.

Hereinafter, the propylene homopolymer, the propylene copolymer, and the propylene elastomer according to the present invention will be described.

Propylene Homopolymer

The first propylene homopolymer according to the present invention is a homopolymer of propylene obtained by homopolymerization of propylene in the presence of the aforementioned olefin polymerization catalyst.

The propylene homopolymer of the present invention has an intrinsic viscosity [?] Measured in decahydronaphthalene at 135 ° C of 0.1 to 20 dl / g, preferably 0.5 to 10 dl / g, more preferably 1 to 5 dl / g, and Mw / The value of Mn is 1.5 to 3.5, preferably 2.0 to 3.0, more preferably 2.0 to 2.5.

The second propylene homopolymer according to the present invention has a triadtaxicity of at least 99.0%, preferably at least 99.2%, more preferably at least 99.5%.

Here, the term 'triadtaxicity' is a chain of 3 propylene unit chains (continuously bonded 3 propylene units) in which the methyl side chains in the total 3 propylene unit chains in the polymer have the same direction and are bonded to each other by a dumi bond. ), Sometimes referred to as 'mm fraction'. In addition, the ratio of the irregular position unit by 2.1-insertion of the propylene monomer is 0.50% or less, preferably 0.18% or less, more preferably 0.15% or less, and intrinsic viscosity [α] measured in decahydronaphthalene at 135 ° C. Is 0.1 to 20 dl / g, preferably 0.5 to 10 dl / g, more preferably 1 to 5 dl / g.

Intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C of not more than 99.0% of triadtacticity (mm fraction), 0.5% or less of irregularity unit by 2: 1-insertion of propylene monomer. Propylene homopolymers of 20 dl / g are novel.

In addition, in the second propylene homopolymer according to the present invention, the ratio of the irregular position unit by 1.3-insertion of the propylene monomer is preferably less than or equal to the minimum limit of detection by ¹³ C-NMR measurement, and the value of Mw / Mn is 1.5 to 3.5. Preferably it is 2.0-3.0, More preferably, it exists in the range of 2.0-2.5.

The second propylene homopolymer of the present invention can be produced, for example, by homopolymerizing propylene in the presence of the olefin polymerization catalyst described above. The polymerization can be carried out by liquid phase polymerization (eg, suspension polymerization and solution polymerization) or gas phase polymerization.

In the liquid phase polymerization, the same inert hydrocarbon solvent as that used in the aforementioned catalyst preparation can be used, or propylene can be used as a solvent.

In suspension polymerization, the propylene polymerization temperature is usually -50 to 100 ° C, preferably 0 to 90 ° C. In solution polymerization, temperature is 0-250 degreeC normally, Preferably 20-200 degreeC is good. In gas phase polymerization, the temperature is usually 0 to 120 캜, preferably 20 to 100 캜. The polymerization pressure is usually from atmospheric pressure to 100 kg / cm 2, preferably from atmospheric pressure to 50 kg / cm 2. The polymerization reaction can be carried out batchwise, semi-continuously or continuously. The polymerization can 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 varying the polymerization temperature and polymerization pressure.

Propylene copolymer

The first propylene copolymer according to the present invention is propylene obtained by copolymerization of propylene with at least one α-olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of the catalyst for olefin polymerization described above. / α-olefin copolymer.

The propylene copolymer is selected from an α-olefin selected from the group consisting of at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, ethylene and an α-olefin having 4 to 20 carbon atoms. The amount of the derived comonomer unit is 50 mol% or less, preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

Α-olefins having 4 to 20 carbon atoms are, for example,

1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 2-ethyl-1-hexene, 1-decene, 1-dodecene, 1-detradecene And 1-eicosene.

Among these, preferred comonomers used for copolymerization include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene.

The composition of the propylene copolymer in the present invention is measured using ¹³ C-NMR.

The propylene copolymer has an intrinsic viscosity of 0.1 to 20 dl / g, preferably 0.5 to 10 dl / g, more preferably 1 to 5 dl / g, and a Mw / Mn value of 1.5 to 3.5 measured in decahydronaphthalene at 135 ° C. , Preferably it is 2.0-3.0, More preferably, it is 2.0-2.5.

The second propylene copolymer according to the present invention has a propylene unit amount of 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and an ethylene unit amount of 50 mol% or less, preferably 5 40 mol%, More preferably, it is 10-30 mol%.

The propylene copolymer may contain a small amount of structural units derived from olefins other than propylene and ethylene, for example, monomer units derived from other monomers such as α-olepan and dienes having 4 to 20 carbon atoms described above.

The second propylene copolymer according to the present invention has a triadtaxycity (mm fraction) of at least 98.0%, preferably at least 98.2%, more preferably at least 98.5%. In addition, the ratio of the irregular position unit by 2.1-insertion of the propylene monomer is 0.50% or less, preferably 0.18 or less, more preferably 0.15% or less, and the intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C 0.1-20 dl / g, Preferably it is 0.5-10 dl / g, More preferably, it is 1-5 dl / g.

Intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C of not more than 98.0% of triadtacticity (mm fraction), 0.5% or less of irregularity unit by 2.1-insertion of propylene monomer, and 0.1-20 dl / g Phosphorus propylene / ethylene random copolymer is novel.

In the second propylene copolymer according to the present invention, the ratio of the irregular position unit by 2.1-insertion of the propylene monomer is preferably less than or equal to the minimum limit of detection by the measurement of ¹³ C-NMR, and the value of Mw / Mn is 1.5 to 3.5, Preferably it is 2.0-3.0, More preferably, 2.0-2.5 are good.

The second propylene copolymer of the present invention can be prepared, for example, by copolymerizing propylene and ethylene in the presence of the olefin polymerization catalyst described above. Copolymerization can be carried out by liquid phase polymerization (eg, suspension polymerization and solution polymerization) or gas phase polymerization.

In liquid phase polymerization, the same inert hydrocarbon solvent as used in the above catalyst preparation can be used, or propylene and / or ethylene can also be used as the solvent.

In suspension polymerization, the copolymerization temperature of propylene and ethylene is usually -50 to 100 ° C, preferably 0 to 90 ° C. In solution polymerization, temperature is 0-250 degreeC normally, Preferably it is 20-200 degreeC. In gas phase polymerization, the temperature is usually 0 to 120 캜, preferably 20 to 100 캜. The copolymerization pressure is usually atmospheric pressure to 100 kg / cm 2, preferably atmospheric pressure to 50 kg / cm 2. The copolymerization reaction can be carried out batchwise, semicontinuously or continuously. In addition, copolymerization can be carried out in two or more steps having different reaction conditions.

In the third propylene copolymer according to the present invention, the propylene unit amount is 95 to 99.5 mol%, preferably 95 to 99 mol%, more preferably 95 to 98 mol%, and the ethylene unit amount is 0.5 to 5 mol%, Preferably it is 1-5 mol%, More preferably, it contains 2-5 mol%. The propylene copolymer may contain 5 mol% or less of structural units derived from olefins other than propylene and ethylene.

The third propylene copolymer according to the present invention has a triadtaxycity (mm fraction) of at least 95.0%, preferably at least 96.0%, more preferably at least 97.0%. In addition, the ratio of the irregular position unit by 2.1-insertion of the propylene monomer is 0.05 to 0.5%, preferably 0.05 to 0.4%, more preferably 0.05 to 0.3%, and intrinsic measured in decahydronaphthalene at 135 ° C. The viscosity [?] Is 0.1 to 12 dl / g, preferably 0.5 to 12 dl / g, more preferably 1 to 12 dl / g.

In the propylene copolymer of the present invention, the ratio of irregular position unit by 1.3-insertion of the propylene monomer is preferably 0.05% or less.

The third propylene copolymer according to the present invention can be prepared by copolymerizing ethylene and propylene in the presence of an olefin polymerization catalyst such as the following catalyst.

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

(B)

(B-1) organoaluminumoxy compound

(B-2) at least one compound selected from the group consisting of compounds in which the transition metal compound (A) reacts to form an ion pair;

(C) an organoaluminum compound, if necessary

The transition metal compound used in the preparation of the third propylene copolymer according to the present invention is a transition metal compound represented by the following formula (Ia).

In formula (Ia), M is a transition metal atom mentioned in formula (I) above.

R ^a is 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 containing group.

Examples of the halogen atom, the hydrocarbon group of 1 to 20 carbon atoms and the halogenated hydrocarbon group of 1 to 20 carbon atoms include groups and atoms exemplified by X ¹ and X ² in the formula (I).

Examples of the silicon-containing group include dihydrocarbon-substituted silyl such as monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl and tricyclohexylsilyl Silicon such as silyl ether of trifluorosilyl, trimethylsilylmethyl, such as trihydrocarbon-substituted silyl, trimethylsilyl ether such as triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinalylsilyl Silicon substituted aryl groups such as substituted alkyl groups and trimethylphenyl;

Examples of the oxygen-containing group include allyloxy groups such as hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, phenylmethoxy and phenylethoxy And arylalkoxy groups.

Examples of the sulfur-containing group include a group obtained by substituting sulfur for oxygen in the oxygen-containing group described above.

Examples of the nitrogen-containing group include alkyl group such as amino group, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino and Arylamino groups such as methylphenylamino and the like. Examples of phosphorus-containing groups include phosphino groups such as dimethyl phosphino and diphenyl phosphino. Of these, R ^a is preferably a hydrocarbon group, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl.

R ^b is an aryl group having 6 to 16 carbon atoms, for example, is the same as R ^2, and is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a halogen similar to R ^a described above. It is an aryl group substituted with an atom.

X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a hydrogen halide group of 1 to 20 carbon atoms, an oxygen containing group or a sulfur containing group. Examples of those atoms and groups include the following: for halogen atoms, hydrocarbon groups of 1-20 carbon atoms, halogenated hydrocarbon groups of 1-20 carbon atoms, and X ¹ and X ² as described in formula (I) above. Examples include oxygen-containing groups.

Y ¹ 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 ^3- , -P (R ³ )-, -P (0) (R ³ )-, -BR ^3- , or -A1R ^3- ( R ³ is a hydrogen atom, a halogen atom, a hydrocarbon atom of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms)

For example, there are groups mentioned as Y in the above formula (I), and divalent tin-containing groups include groups obtained by substituting tin for silicon in the aforementioned divalent silicon-containing group.

Among these, divalent silicon-containing groups, divalent germanium-containing groups and divalent tin-containing groups are preferred, and divalent silicon-containing groups are better. Of the silicon-containing groups, alkylsilylene, alkylarylsilylene and arylsilylene are particularly preferred. Taking the transition metal compound represented by the formula (Ia) as follows, for example.

rac-dimethylsilyl-bis {1-4-phenylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (n-phenylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (2-anthracenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (o, p-dichlorophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (o-tolyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-i-propylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (m-biphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (p-trimethylsilylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4- (m-trimethylsilylphenyl) indenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-phenyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-n-propyl-4-phenylindenyl} zirconium dichloride,

rac-diethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-di- (i-propyl) silyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-di- (n-butyl) silyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-dichlorohexylyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-methylphenylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-diphenylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-di- (p-tolyl) silyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-di- (p-chlorophenyl) silyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-methylene-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-ethylene-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylgeryl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylstannyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dichloride,

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dibromide,

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium dimethyl,

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium methyl chloride,

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium monochloride mono (trifluoromethanesulfonate),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium di (trifluoromethanesulfonate),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium di (p-toluenesulfonate),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium di (methylsulfonate),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium di (trifluoromethanesulfonate),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium di (trifluoroacetate),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium monochloride (n-butoxide),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium di (n-butoxide),

rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl} zirconium monochloride (phenoxide),

In addition, a transition metal compound obtained by substituting a titanium metal, a hafnium metal, a vanadium metal, a niobium metal, a tantalum metal, a chromium metal, a molybdenum metal, or a tungsten metal in the compound exemplified above may be used.

The transition metal compound is usually used in racemic form as an olefin polymerization catalyst component, but R or S may also be used.

The olefin polymerization catalyst used in the preparation of the propylene copolymer according to the present invention is a catalyst obtained by replacing component (A) of the first to sixth olefin polymerization catalysts with the transition metal compound represented by the above formula (Ia).

The propylene copolymer of the present invention can be prepared, for example, by copolymerizing propylene and ethylene in the presence of the olefin polymerization catalyst described above. The copolymerization may be carried out by liquid phase polymerization (eg suspension polymerization and solution polymerization) or gas phase polymerization.

In liquid phase polymerization, the same inert hydrocarbon solvent as used in the above-mentioned catalyst preparation can be used, and propylene and / or ethylene can also be used as the solvent.

The copolymerization temperature of propylene and ethylene is usually in the range of -50 to 100 DEG C, preferably 0 to 90 DEG C in suspension polymerization, and in the range of 0 to 250 DEG C, preferably 20 to 200 DEG C in solution polymerization. In the range of 0 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually atmospheric pressure-100 kg / cm 2, preferably atmospheric pressure-50 kg / cm 2. The copolymerization reaction may be any of batch, semicontinuous, and continuous, and the copolymerization may be performed in two or more stages having 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 50 to 95 mol% of propylene units, preferably 60 to 93 mol%, more preferably 70 to 90 mol%, and further 5 to 50 mol% of ethylene units, preferably Propylene / ethylene random copolymers containing 7-40 mole%, more preferably 10-30%.

The propylene elastomer may contain up to 10 mol% of structural units derived from olefins other than propylene and ethylene.

In the propylene elastomer of the present invention, the triadtaxity is at least 90.0%, preferably at least 93.0%, more preferably at least 96.0%, and the proportion of irregularity unit by 2.1-insertion of the propylene monomer is 0.05 to 0.5%. , Preferably 0.05 to 0.4%, more preferably 0.05 to 0.3%, intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C of 0.1 to 12 dl / g, preferably 0.5 to 12 dl / g, more preferably 1-12 dl / g is preferable.

Further, in the propylene elastomer according to the present invention, the ratio of the irregular position unit by 1.3-insertion of the propylene monomer is 0.05% or less, preferably 0.03% or less.

The propylene elastomer of the present invention can be prepared by copolymerizing propylene and ethylene in the presence of the above-mentioned olefin polymerization catalyst used in the production of the third propylene copolymer, for example. Copolymerization can be carried out by liquid phase polymerization (eg suspension polymerization and solution polymerization) or gas phase polymerization.

In liquid phase polymerization, the same inert hydrocarbon solvent as used in the above-mentioned catalyst preparation can be used, and propylene and / or ethylene can also be used as the solvent.

The copolymerization temperature of propylene and ethylene is usually in the range of -50 to 100 DEG C, preferably 0 to 90 DEG C in suspension polymerization, and in the range of 0 to 250 DEG C, preferably 20 to 200 DEG C in solution polymerization. In the range of 0 to 120 ° C, preferably 20 to 100 ° C. The copolymerization pressure is usually atmospheric pressure-100 kg / cm 2, preferably atmospheric pressure-50 kg / cm 2. The copolymerization reaction may be any of batch, semicontinuous, and continuous, and the copolymerization may be performed in two or more stages having 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.

In the present invention, the molecular weight distribution (Mw / Mn), triadtactiletite (mm fraction), the ratio of irregular units by 2.1-insertion of propylene monomers, and the ratio of irregular units by 1.3-insertion of propylene monomers are Measure

Molecular Weight Distribution (Mw / Mn)

Mw / Mn is obtained from chromatographs measured using permeation chromatography (GPC) (manufactured by 150-ALC / GPC ^™ Water). The measurement was performed at 140 degreeC using O-dichlorobenzene, GMH-HT, and GMH-HLT type column (both manufactured by Toureda Co., Ltd.) as an elution solvent. From the chromatograph, both the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated by polypropylene conversion by the universal method (however, when the comonomer content is 10 mol% or more in terms of polystyrene), Mw / Mn was calculated. .

Triad Tacity (mm fraction)

The triadtaxity (mm fraction) of the propylene copolymer is the same as the direction of the methyl molecules in the propylene chain when the main chain is represented by a planar zigzag structure, and each propylene unit is composed of three propylene units bonded to each other by a dumi bond. It is calculated | required by defining as ratio of chains. Triadtaxity (mm fraction) of a propylene copolymer can be calculated | required from ¹³ C-NMR spectrum and a following formula.

In the formula, PPP (mm), PPP (mr) and PPP (rr) represent the peak areas derived from the methyl group of the second unit in the following three propylene unit chains in the dumi bond.

^{In a 13} C-NMR sample tube (diameter: 5 mm), the sample was prepared with about 0.5 ml of hexachlorobutadiene, O-dichlorobenzene or 1,2,4-trichlorobenzene and 0.05 ml of deuterated benzene (i.e., lock solvent). After complete dissolution in the mixed solvent, ¹³ C-NMR spectrum was measured at 120 ° C. by quantum perfect coupling method. The measurement was performed under a flip angle of 45 ° and pulse interval conditions of 3.4T ₁ (T ₁ is the longest value of the spin lattice relaxation time of the methyl group). T ₁ of the methylene group and T ₁ of the methine group in the polypropylene, the magnetization recovery of all carbon under this condition is shorter than each a methyl group is more than 99%. The chemical shift was calculated by setting the methyl group of the third unit to 21.593 ppm among the five propylene units of the iron-bonded bond and the compound shift of other carbon peaks based on the above values.

The spectrum is classified into a first region (21.1 to 21.9 ppm), a second region (20.3 to 21.0 ppm), and a third region (19.5 to 20.3 ppm).

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

In the second region, the methyl group of the second unit of the three propylene unit chains represented by PPP (mr) is resonant, and the methyl group (PPE-methyl group) of the propylene unit whose adjacent units are propylene unit and ethylene unit is resonance.

In the third region, the methyl group of the second unit of the three propylene unit chains represented by PPP (rr) resonates, and the methyl group of the propylene unit of the ethylene unit (EPE-methyl group) resonates.

The propylene copolymer also has the following structures (i), (ii) and (iii) containing irregular positions.

Among the peaks derived from the structures (i), (ii) and (iii), the peaks of carbon A and carbon B do not appear in the first to third regions. This is because carbon A resonates at 17.3 ppm and carbon B resonates at 17.0 ppm. Also, since carbon A and carbon B are not related to the three propylene unit chains, these carbons need not be considered in the triadtaxity calculation.

Peaks of carbon C, D and D 'appear in the second region, and peaks of carbon E and E' appear in the third region.

As described above, the peaks of the peaks in the first to third regions, which are not based on the three propylene units constituting the iron bond, are PPE-methyl group (resonance near 20.7 ppm) and EPE-methyl group (resonance near 19.8 ppm). ), Peaks based on carbon C, D, D ', E and E'.

The peak area based on the PPE-methyl group can be obtained by the peak area of the PPE-methyl group (resonance near 30.6 ppm), and the peak area based on the EPE-methyl group is based on the peak area of the EPE-methyl group (resonance near 3.9 ppm). Can be obtained by The peak area based on carbon C can be obtained by the peak area of the adjacent methyl group (resonance near 31.3 ppm), and the peak area based on carbon D is the αβ methylene carbons of structure (ii) (34.3 ppm and 34.5 ppm, respectively). And the peak area based on carbon D 'to the peak of the methine group (resonance near 33.3 ppm) adjacent to the methyl group of carbon E' of structure (iii) described above. The peak area based on carbon E can be obtained by the peak area of adjacent methine groups (resonance near 33.7 ppm), and the peak area based on carbon E 'is determined by the peak area of adjacent methine groups (resonance near 33.3 ppm). It can be obtained by the peak area.

Therefore, by subtracting these peak areas from the total peak areas of the second and third regions, it is possible to obtain peak areas based on the three propylene unit chains (ppp (mr) and ppp (rr)) constituting the dumi bond.

Therefore, since peak areas of PPP (mm), PPP (mr) and PPP (rr) can be obtained, the triadtacticity of the propylene unit chain constituting the dumi bond can be obtained.

The triadtaxity (mm fraction) of the propylene homopolymer is also the same in the direction of the methyl branch in the propylene chain when the main chain is represented in a planar zig-zag structure, with three propylene units in which each propylene unit is bonded to each other by a dumi bond. Defined as the chain ratio, the triadtaxity (mm fraction) of the propylene homopolymer can be obtained from the ¹³ C-NMR spectrum and the following formula.

Where PPP (mm) is as defined above, ΣICH ₃ represents the total area of all peaks derived from the methyl group.

The chemical shift is obtained by setting the methyl group of the third unit to 21.593 ppm of the five propylene unit chains constituting the dumi bond, and the chemical shift of the other carbon peaks based on the above values.

In this criterion, the peak of the methyl group of the second unit in the three propylene unit chains expressed in ppp (mm) is in the range of 21.1 to 21.9 ppm, and the peak of the methyl group of the second unit of the three propylene unit chains represented in ppp (mr). The peak is in the range of 20.3 to 21.0 ppm, and the peak of the methyl group of the second unit in the three propylene unit chains represented by ppp (rr) is in the range of 19.5 to 20.3 ppm.

Herein, the propylene homopolymer contains a small amount of a partial structure including the irregular position unit based on 2.1-insertion represented by the above-mentioned structure (i) in addition to the regular structure constituting the propylene unit iron bond.

In the irregular structure showing the structure (i) described above, the above definition of ppp (mm) does not apply to carbons A, B and C. However, carbons A and B resonate in the region of 16.5 to 17.5 ppm, and carbon C resonates near 20.7 ppm (ppp (mr) region).

In substructures containing irregular positions, the peaks of the adjacent methylene and methine groups as well as the peaks of the methyl groups should be identified. Therefore, carbons A, B and C are not included in the ppp (mm) region.

Therefore, the triadtaxity (mm fraction) of a propylene homopolymer can be calculated by the above formula.

Ratio of Irregular Units by 2.1-Insertion of Propylene Monomers

In the polymerization, the propylene monomer is mainly 1.2-inserted (methylene side bonded to the catalyst) but rarely 2.1-inserted. Therefore, the propylene copolymer and the propylene elastomer contain the irregular position unit by 2.1-insertion represented by the above structures (i), (ii) and (iii).

The ratio of irregular position by 2.1-insertion is calculated by the following equation using ¹³ C-NMR.

A: Iαβ [structures and (ii)]

B: Iαβ [structure (ii)]

C: Iαα

D: Iαβ [structure and (ⅲ)]

E: Iαr + Iαβ [structure (ii)] + Iαδ

These peaks were named according to the method by Carmen (Rubber Chem, Tachnolo, 44, 781 (1971)). Iαβ and the like represent peak areas such as αβ-peak and the like.

Homopolymers of propylene contain irregular positions by 2.1-insertion. The ratio of 2.1-propylene monomer insertion to all propylene insertions is calculated from the following equation.

Wherein ∑ICH ₃ is the same as above.

Proportion of Irregular Units by 1.3-insertion of Propylene Monomer

The amount of the three unit chains by 1.3-insertion of propylene in the propylene copolymer and propylene elastomer is obtained from βr-peak (resonance around 27.4 ppm).

The amount of triunit chains by 1.3-insertion of propylene in the propylene homopolymer is obtained from αδ-peak (resonance near 37.1 ppm) and βr-peak (resonance near 27.4 ppm).

Example

The invention is described in detail with reference to the following examples. However, the present invention is not limited to these examples.

In this invention, the intrinsic viscosity [eta] and composition of a copolymer are measured by the following method.

In some embodiments, the heat sealing start temperature and the heat sealing start temperature after heat treatment, the melting point (Tm), the melt flow rate (MFR), the Izod impact strength (IZ) and the film impact strength are measured in the following manner.

Intrinsic Viscosity [η]

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

Composition of the copolymer

The composition of the propylene copolymer was measured by ¹³ C-NMR.

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

30 cm wide and 50 μm fabricated using a single screw extruder having a diameter of 30 mm under a resin temperature of 210 ° C. (temperature of the dicer part of the extruder), a winding speed of 3 m / min, and a temperature of a cooling roll of 25 ° C. For T-die films with thickness, heat sealing of two films is sealed at various sealing bar temperatures using heat and sealing under conditions of heat sealing pressure of 2 kg / cm 2, sealing time of 1 second, and 5 mm width. This produced a sealed film having a width of 15 mm. The sealing film thus produced was left overnight.

The heat sealing start temperature is defined as the temperature when the peeling resistance of the sealed film is 300 g / 25 mm under the conditions of the peeling temperature of 23 ° C., the peeling rate of 200 mm / min and the peeling angle of 180 ° C.

Separately, another sealed film was heat treated at 50 ° C. for 7 days. After the heat treatment, the heat sealing start temperature was measured using a heat treated sample.

Melting Point (Tm)

About 5 mg of the sample placed in the aluminum pan was heated to 200 ° C. at a rate of 10 ° C./min. The melting point was determined from the endothermic curve when heating with. The measurement was carried out using a DSC-7 device manufactured by Perkin Elmer.

Melt FLOW RATE (MFR)

MFR was measured according to ASTMD1238 under a load of 230 ° C. 2.16 kg.

Izod Impact Strength (IZ)

IZ was measured according to ASTM D 256 at a temperature of 23 ° C. using a cutout sample of 12.7 mm (width) × 6.4 mm (thickness) × 64 mm (length).

Dry mixing 20% by weight of the polymer according to the present invention and 80% by weight of polypropylene (HIPOL ^™ , grade J700, melt flow rate: 11 g / 10 min (at 230 ° C.), density: 0.91 Mitsui Petrochemical Industries, Ltd.) The sample was prepared by injection molding at a resin temperature of 200 ° C. and a mold temperature of 40 ° C. using the obtained polypropylene composition and melt kneading at 200 ° C. using a twin screw extruder.

Film Impact Strength

The film impact strength was measured with a film impact tester (shock head bulb: 1/2 inch (12.7 mm Φ), manufactured by Toyo Seiki Co., Ltd.).

Example 1

Synthesis of rac-dimethylsilyl-bis {1-2 (2-ethyl-4-phenylindenyl)} zirconium dichromide

Synthesis of 3- (2-biphenylyl) -2-ethylpropionic acid

In a 500 ml four-necked round flask equipped with a stirrer, a Dimroth condenser, a dropping funnel and a thermometer, 13.46 g (120 mmol) of potassium t-butoxide, 100 ml of toluene and 20 ml of N-methylpyrrolidone Charged.

A solution in which diethylethylmalonate 20.7 g (110 mmol) was dissolved in 50 ml of toluene was added dropwise to the mixture while heating to 60 ° C. under a nitrogen atmosphere.

After the addition was completed, the reaction mixture was stirred at this temperature for 1 hour. Subsequently, a solution in which 20.27 g (100 mmol) of 2-phenylbenzyl bromide was dissolved in 30 ml of toluene was added dropwise to the resultant mixture.

After the addition was completed, the temperature was raised and the resulting mixture was stirred at reflux for 2 hours.

The reaction mixture was poured into 200 ml of water and the resulting mixture was adjusted to pH 1 by addition of 2N HC1. The organic phase was separated and the aqueous phase was extracted three more times with 100 ml of toluene.

The combined organic phases were washed with an aqueous solution of saturated sodium chloride until the product was neutral and then dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to give 36.7 g of yellow orange liquid.

Into a 1 L four-necked circular flask equipped with a stirrer, a dimrose condenser, a dropping funnel and a thermometer, 67.3 g (1.02 mol) of potassium hydroxide and an aqueous solution of methanol (metalol / water = 4/1 (v / v)) were added. Charged. A solution in which the concentrate obtained above was dissolved in 50 ml of aqueous methanol solution (methanol / water = 4/1 (v / v)) at room temperature under nitrogen atmosphere was added dropwise to the mixture.

After the addition was completed, the temperature was raised, and the resulting mixture was stirred at reflux for 4 hours. After that, the temperature was cooled to room temperature, and the resulting precipitate was filtered.

The residue was dissolved in water and acidified to pH 1 by addition of sulfuric acid. The resulting solution was extracted five times with 100 ml of methylene chloride. The organic phases were combined and dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to give 24.2 g of a white solid.

Next, a 300 ml three-necked circular flask equipped with a stirring rod, a dimrose condenser and a thermometer was charged with 24.2 g of the white solid, 56 ml of acetic acid, 37 ml of water, and 56 ml of concentrated sulfuric acid. Stir under reflux for 6 hours under atmosphere. After completion of the reaction acetic acid was evaporated under reduced pressure. 50 ml of water was added to the product, and the mixture was extracted three times with 50 ml of methylene chloride. The combined organic phases were washed with 50 ml of saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure. The residue was chromatographed with silica gel (eluted with hexane / ethyl acetate (2/1) and hexane / ethyl acetate (1/1) (volume part)) to give 13.7 g of a white solid target product (yield: 54%). ).

Synthesis of 3- (2-biphenylyl) -2-ethylpropionylchloride

13.3 g (52.4 mmol) of 3- (2-biphenylyl) -2-ethylpropionic acid and thionyl chloride in a 100 ml three necked flask equipped with a stirring rod, a dimrose condenser, a thermometer and a NaOH trap. ML (355 mmol) was charged and the resulting mixture was stirred for 2.5 h under reflux under a nitrogen atmosphere. After the reaction was completed, unreacted thionyl chloride was distilled off under reduced pressure to obtain 15.2 g of a crude product of a yellow orange liquid.

The acid chloride thus obtained was used in the next reaction without further purification.

IR (knit): 1786cm ^-1 (Vc = 0)

Synthesis of 4-ethyl-2-phenyl-1-indanon

A 200 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel, a thermometer and a NaOH trap was charged with 8.04 g (60.3 mmol) of anhydrous aluminum chloride and 50 ml of carbon disulfide. A solution containing 15.2 g (52.4 mmol) of 3- (2-biphenylyl) -2-ethylpropionyl chloride obtained above in a nitrogen atmosphere at 0 ° C. was added dropwise to the mixture. After the addition was completed, the temperature in the flask was raised to room temperature and the reaction mixture was stirred for 1 hour.

The reaction mixture was poured into 200 mL of ice water and extracted twice with 100 mL of ether.

The combined organic phases were washed with 100 ml of saturated aqueous NaHCO ₃ and 100 ml of saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure. The residue was chromatographed with silica gel (eluted with hexane / ethyl acetate (10/1) and (volume portion)) to give 10.8 g of the target substance as a yellow solid (yield: 88%).

Synthesis of 2-ethyl-1-hydroxy-4-phenylindene

A 200 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer was charged with 0.85 g (22.6 mmol) of sodium borohydride and 28 ml of ethanol.

A solution in which 10.6 g (45.1 mmol) of 2-ethyl-4-phenyl-1-indanone obtained above was dissolved in 20 ml of ethanol at room temperature under a nitrogen atmosphere was added dropwise to the mixture. After the addition was completed the temperature was raised to 50 ° C. and the reaction mixture was stirred for 3.5 hours.

After completion of the reaction, unreacted sodium borohydride was decomposed into acetone. The reaction mixture was then concentrated under reduced pressure, dissolved in 50 ml of water and extracted with 50 ml of ether. After separation of the organic phase, the aqueous phase was extracted twice with 50 ml of ether. The combined organic phases were washed with 100 ml of saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure to obtain 10.67 g of a target substance (two kinds of isomeric mixtures) as a pale yellow liquid (yield: 99%).

Synthesis of 2-ethyl-4-phenylindene

9.78 g (41.3 mmol) of 2-ethyl-1-hydroxy-4-phenylindan and 17.2 ml (123.8 mmol) of triethylamine in a 300 ml four necked flask equipped with a stirring rod, a dropping funnel and a thermometer. ), 0.25 g (2.1 mmol) of 4-dimethylaminopyridine and 98 ml of methylene chloride were charged. A solution of 6.4 ml (82.5 ml) of methanesulfonyl chloride in 6.5 ml of methylene chloride was added dropwise to the mixture under a nitrogen atmosphere at 0 ° C.

After the addition was completed, the reaction mixture was stirred at this temperature for 3.5 hours.

The reaction mixture was poured into 250 ml of ice water, the organic phase was separated and the aqueous phase was further extracted with 50 ml of methylene chloride. The organic phases were combined and washed with saturated aqueous NaHCO ₃ and saturated aqueous sodium chloride solution. Then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure. The residue was chromatographed with silica gel (hexane eluted) to give 6.56 g of the target substance (two types of isomer mixtures) as a pale yellow liquid.

Synthesis of Dimethylsilyl-bis (2-ethyl-4-phenylindene)

In a 200 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer, 5.0 g (22.8 mmol) of 2-ethyl-4-phenylindene and 80 mg (0.63 mmol) of copper thiocyanate ) And 50 ml of anhydrous ether were charged.

15.7 ml (25.1 mmol) of 1.6 M n-butyllithium hexane solution was slowly added dropwise to the mixture under a nitrogen atmosphere at 0 ° C. After the addition was completed, the temperature was raised to room temperature, and a solution of 1.52 ml (12.6 mmol) of dimethyldichlorosilane in 4.5 ml of anhydrous ether was slowly added dropwise to the reaction mixture. After the addition was completed, the reaction mixture was stirred at room temperature for 12 hours. The reaction mixture was filtered through celite and the filtrate was poured into 50 ml of saturated aqueous ammonium chloride solution.

After separation of the organic phase, the aqueous phase was extracted with 50 ml of ether. The combined organic phases were washed with saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure.

The residue was chromatographed with silica gel (eluted with hexane and hexane / methylene chloride (20/1) (volume portion)) to obtain 4.5 g of the target substance (two kinds of isomer mixtures) as a pale yellow solid (yield: 80%).

Synthesis of rac-dimethylsilyl-bis {1-2 (2-ethyl-4-phenylintyl)} zirconium dichloride

A 50 ml three-necked round flask equipped with a stirring rod, a condenser, a dropping funnel and a thermometer was charged with 0.84 g (1.69 mmol) of dimethylsilyl-bis (2-ethyl-4-phenylindene) and 17 ml of anhydrous ether. I was.

2.25 ml (3.56 mmol) of 1.58 M n-butyllithium hexane solution was slowly added dropwise to the mixture at room temperature, and the reaction mixture was stirred for 13.5 hours after the addition was completed. 0.395 g (1.69 mmol) of ZrCl ₄ was slowly added to the resulting solution at -70 ° C.

After the addition was complete the mixture was heated to room temperature overnight. The solvent was then evaporated at room temperature under reduced pressure. 30 ml of methylene chloride was added to the product. The insoluble material was then filtered off and the filtrate was concentrated at room temperature and crystallized. The precipitate was filtered off, and the residue was washed twice with 3 ml of anhydrous ether and dried under reduced pressure to obtain 0.17 g of the target substance as an orange yellow solid (yield: 15%).

Example 2

1.7 liters of toluene were charged into a 2 liter gas passage glass reactor thoroughly washed with nitrogen. The reaction system was sufficiently saturated by cooling the reactor to −30 ° C. and passing propylene at a flow rate of 100 L / hr and hydrogen at a flow rate of 10 L / hr.

Then, 4.25 mmol of triisobutylaluminum, 8.5 mmol of methylaluminoxane (as A1 atom) and 0.017 mmol of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride ( In terms of Zr atoms) was added to the reactor.

The polymerization was carried out for 45 minutes while maintaining the temperature of the reaction system at -30 ° C. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was added to 3 liters of methanol containing a small amount of hydrochloric acid, sufficiently stirred and filtered. The resulting polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours.

The amount of polymer thus obtained was 51.3 g. The polymerization activity was 4.02 Kg-pp / mmol-Zr.hr, the intrinsic viscosity (η) was 3.37 dl / g, and Mw / Mn was 2.22.

In the polymer, triadtaxity is 99.7%, the ratio of irregularity unit by 2,1-insertion of propylene monomer is 0.10%, and the ratio of irregularity unit by 1.3-insertion of propylene monomer is less than the lower limit (0.03% or less). ).

Table 1 (I) and (II) show the result.

Example 3

Propylene and ethylene were passed through at a flow rate of 100 l / hr and 2 l / hr, respectively, with 0.65 mmol of triisobutylaluminum and rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride Polymerization was carried out in the same manner as in Example 2, except that 0.0026 mmol (in terms of Zr atoms) was used to maintain the system at 60 ° C.

The amount of polymer thus obtained was 60.7 g. The polymerization activity was 31.1 Kg-pp / mmol-Zr.hr, intrinsic viscosity {η} was 3.01 dl / g, and Mw / Mn was 2.18. In the polymer, triadtaxity was 99.5%, the ratio of irregular position by 2,1-insertion of propylene monomer was 0.15%, and the ratio of irregular position by 1,3-insertion of propylene monomer was below the lower limit. (0.03% or less).

Table 1 (I) and (II) show the result.

Comparative Example 1

rac-dimethylsilyl-bis (1- (2-methyl-4-phenylindenyl)} zirconium dichloride instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride Polymerization was carried out in the same manner as in Example 3 except for using.

The polymer amount thus obtained was 4.7 g. The polymerization activity was 2.4 Kg-pp / mmol-Zr.hr, the intrinsic viscosity [η] was 4.05 dl / g, and Mw / Mn was 2.18. Triadtaxity in the polymer was 98.6%. The positional irregularity unit ratio by 2,1-insertion of the propylene monomer was 0.33%, and the positional irregularity unit ratio by 1,3-insertion of the propylene monomer was less than the lower limit (0.03% or less).

Table 1 (I) and (II) show the result.

Example 4

250 ml of toluene was charged into a 500 ml gas passage glass reactor thoroughly washed with nitrogen. The reactor was cooled to 0 ° C. and the reaction system was sufficiently saturated by passing propylene through at a flow rate of 160 L / hr and ethylene at a flow rate of 40 L / hr. Then, 0.25 mmol of triisobutylaluminum, 0.5 mmol of methylaluminoxane (as A1 atom) and 0.001 mmol of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride ( Zr atom) was added to the reactor. The polymerization was carried out for 10 minutes while maintaining the temperature of the reaction system at 0 ° C. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was poured into 2 liters of methanol containing a small amount of hydrochloric acid, sufficiently stirred and filtered. The resulting polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours.

The polymer thus obtained was 5.62 g. The polymerization activity was 33.7 Kg-polymer / mmol-Zr.hr, ethylene content was 3.9 mol%, intrinsic viscosity [?] Was 1.80 dl / g, Mw / Mn was 2.15, and Tm was 126 ° C.

In the polymer, triadtaxity is 99.3%, the ratio of irregularity unit by 2,1-insertion of propylene monomer is 0.12%, and the ratio of irregularity unit by 1,3-insertion of propylene monomer is less than the lower limit (0.03). %Below).

Table 1 (I) and (II) show the result.

The film of the polymer had a heat sealing start temperature of 129 ° C. and a heat sealing start temperature of 132 ° C. after heat treatment. Table 2 shows the results.

Example 5

The polymerization was carried out in the same manner as in Example 4 except that the reaction system was sufficiently saturated by passing propylene at a flow rate of 140 L / hr and ethylene at a flow rate of 60 L / hr, respectively. The polymer solution thus obtained was poured into 2 L of methanol containing a small amount of hydrochloric acid to precipitate the polymer.

The methanol was sufficiently removed and the resulting polymer was dried at 130 ° C. for 10 hours.

The polymer was thus obtained in an amount of 6.63 g and had a polymerization activity of 39.8 Kg-polymer / mmol-Zr.hr. Ethylene content was 8.7 mol%, intrinsic viscosity {(eta)} was 1.66 dl / g, Mw / Mn was 2.46 and Tm was 105 degreeC. In the polymer, triadtaxity is 99.2%, the ratio of irregularity unit by 2,1-insertion of propylene monomer is 0.12%, and the ratio of irregularity unit by 1,3-insertion of propylene monomer is less than the lower limit. (0.03% or less).

Table 1 (I) and (II) show the result.

The film of the said polymer had the heat-sealing start temperature of 106 degreeC, and the heat-sealing start temperature after heat processing of 109 degreeC.

Table 2 shows the results.

Example 6

The polymerization reaction was carried out in the same manner as in Example 4 except that the reaction system was sufficiently saturated by passing propylene through propylene at a flow rate of 100 L / hr and ethylene at a flow rate of 100 L / hr, respectively. The polymer solution thus obtained was poured into 2 L of methanol containing a small amount of hydrochloric acid to precipitate the polymer.

The methanol was sufficiently removed and the resulting polymer was dried at 130 ° C. for 10 hours. The polymer was thus obtained in an amount of 8.95 g and had a polymerization activity of 53.7 Kg-polymer / mmol-Zr.hr.

The ethylene content was 28.9 mol%, the intrinsic viscosity {η} was 1.34 dl / g, and Mw / Mn was 1.95. In this polymer, triadtaxity is 98.5%, the ratio of irregularity unit by 2,1-insertion of propylene monomer is 0.09%, and the ratio of irregularity unit by 1,3-insertion of propylene monomer is below detection limit. (0.03% or less).

Table 1 (I) and (II) show the result.

The copolymer had an Izod impact strength of 28 Kg.cm/cm and a film impact strength of 5,300 Kg.cm/cm.

The results are shown in Table 2.

Example 7

Synthesis of rac-dimethylsilyl-bis {1- (2-ethyl-4- (1-naphthyl) indenyl)} zirconium dichloride

Synthesis of 3- (2-bromophenylyl) -2-ethylpropionic acid

A 2 liter four necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer was charged with 44.2 g (394 mmol) of potassium t-butoxide, 392 ml of toluene and 30 ml of N-methylpyrrolidone. .

A solution of 61.2 g of diethylethyl malonate dissolved in 61 ml of toluene at 60 ° C. under a nitrogen atmosphere was added dropwise to the mixture, and after the addition was completed, the reaction mixture was stirred at this temperature for 1 hour. Then, a solution obtained by dissolving 75.4 g (302 mmol) of 2-bromobenzyl bromide in 75 ml of toluene was added dropwise to the resulting mixture.

After the addition was completed, the temperature was raised and the resulting mixture was stirred at reflux for 5 hours. The reaction mixture was poured into 300 ml of water and adjusted to pH 1 with 10% sulfuric acid. The organic phase was separated and the aqueous phase was extracted three times with 100 ml of ether. The organic phases were combined, washed three times with 200 ml of saturated aqueous sodium bicarbonate solution and 150 ml of saturated aqueous sodium chloride solution, and dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure to give 111.1 g of a yellow liquid concentrate.

A 2 liter four necked flask equipped with a stirrer, a dimrose condenser, a dropping funnel and a thermometer was charged with 195 g (2.96 mol) of potassium hydroxide and 585 ml of an aqueous methanol solution (methanol / water = 4/1 (v / v)). Charged. The concentrated solution obtained above at room temperature under a nitrogen atmosphere was added dropwise to the mixture. After the addition was completed, the temperature was raised and the resulting mixture was stirred at reflux for 3 hours. The temperature was then cooled to room temperature and the precipitated solid was filtered off. The filtrate was concentrated and cooled to give a second product. The same procedure as above was repeated to obtain a third product. The products were combined and suspended in hexanes and filtered. The solid thus obtained was dried to obtain 101.5 g of a white powder.

The white powder was dissolved in 400 ml of water and the resulting solution was acidified to pH 1 by addition of aqueous H ₂ SO ₄ solution. The resulting mixture was extracted five times with 200 ml of methylene chloride. The organic phases were combined and concentrated under reduced pressure to give 74.2 g of a hard white solid.

Then, the white solid obtained above was filled into a 300 ml three necked flask equipped with a stirring rod, a dimrose condenser, and a thermometer. The solid was then heated to 200 ° C. and stirred for 5 hours in a nitrogen atmosphere. After the reaction was completed, the reaction product was cooled to room temperature to obtain 61.2 g of the target product as a pale yellow solid. (Yield 79%)

Synthesis of 3- (2-bromophenyl) -2-ethylpropionylchloride

60.86 g (237 mmol) of 3- (2-bromophenylyl) -2-ethylpropionic acid in a 300 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer and a NaOH trap. 40 ml of benzene and 120 ml of thionyl chloride were charged.

The mixture was stirred at reflux for 1.5 h in a nitrogen atmosphere. After the reaction was completed, the unreacted thionyl chloride was distilled off under reduced pressure to obtain a crude product of a yellow liquid.

The acid chloride thus obtained was used in the next reaction without further purification.

Synthesis of 4-bromo-2-ethyl-1-indanon

A 1 L three-necked round flask equipped with a stirring rod, a dimrose condenser, a dropping funnel, a thermometer, and a NaOH trap was charged with 36.3 g (272 mmol) of anhydrous aluminum chloride and 280 ml of carbon disulfide.

A solution obtained by dissolving 3- (2-bromophenyl) -2-ethylpropionyl chloride obtained above in 50 ml of carbon disulfide was added dropwise to the mixture under a nitrogen atmosphere at 0 ° C. After the addition was completed, the temperature in the flask was raised to room temperature and the reaction mixture was stirred for 1 hour.

The reaction mixture was poured into 1 L of ice water and extracted twice with 300 mL of ether.

The combined organic phases were washed with saturated aqueous NaHCO ₃ and saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure to obtain 56.9 g of the target substance as a viscous red liquid. The ketones thus obtained were used in the next reaction without further purification.

Synthesis of 4-bromo-2-ethyl-1-trimethylsilyloxyindan

4.97 g (118 mmol) of sodium borohydride and 200 ml of ethanol were charged into a 500 ml three-necked circular flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. A solution in which 56.93 g of 4-bromo-2-ethyl-1-indanone obtained above was dissolved in 85 ml of ethanol at room temperature under a nitrogen atmosphere was added dropwise to the mixture. After the addition was completed, the reaction mixture was further stirred for 4 hours. After the reaction was completed, the reaction mixture was cooled and the unreacted sodium borohydride was decomposed into acetone.

The reaction mixture was then concentrated under reduced pressure, dissolved in 300 ml of water and extracted with 300 ml of ether. After separating the organic phase, the aqueous phase was extracted three times with 100 ml of ether. The combined organic phases were washed three times with 150 ml of saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure to give 58.92 g of a skin solid.

A 500 ml four necked circular flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer, 58.91 g (244 mmol) of solid, 43.3 ml (307 mmol) of triethylamine, and 280 ml of methylene chloride Charged.

A solution in which 37.2 ml (293 mmol) of Me ₃ SiC1 was dissolved in 15 ml of methylene chloride was slowly added dropwise to the mixture under a nitrogen atmosphere at 0 ° C.

After the addition was completed, the temperature was raised to room temperature and the reaction mixture was further stirred for 3.5 hours.

The reaction mixture was poured into 100 ml of water, the organic phase was separated and the aqueous phase was extracted twice with 100 ml of methylene chloride. The combined organic phases were washed three times with 100 ml of water and dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure, and the residue was distilled off under reduced pressure to obtain 69.9 g of a target substance (diisomeric mixture) as a colorless liquid. (Total yield: 95% from 3- (2-bromophenylyl) -2-ethylpropionic acid)

Synthesis of 2-ethyl-4- (1-naphthyl) phenylindene

11.4 g (36.4 m mol) of 4-bromo-2-ethyl-1-trimethylsilyloxyindan and PdCl _{2 in} a 300 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. (dppf) 0.13 g (0.18 mmol) and 35 ml of anhydrous ether were charged. 101 ml (72.8 mmol) of an ether / benzene solution of 0.72 M of 1-naphthyl magnesium bromide was added dropwise to the resultant mixture at room temperature under a nitrogen atmosphere.

After the addition was completed, the reaction mixture was stirred for 1 hour. The flask was then heated to 50-51 ° C. and the reaction mixture stirred for another 5 hours.

After completion of the reaction, 135 mL of 5N hydrochloric acid was added to the reaction mixture at 0 ° C. to decompose the excess Grignard reagent, and the resulting mixture was extracted twice with 100 mL of Etec. The combined organic phases were washed with saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure to give 20.5 g of a red colored liquid.

The reddish red liquid obtained above was then distilled off with 20 ml of tetrahydrofuran. To the mixture of 5 ml of 12% hydrochloric acid was added and the reaction mixture was stirred overnight at room temperature. After completion of the reaction, 100 ml of ether was added and the organic phase was separated.

The organic phase was washed with saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure and the residue was chromatographed with silica gel (eluted with MERCK, Inc. silica gel 60, 70-230 mesh, hexane and hexane / ethyl acetate (1/3 volume part)) to give a yellow solid. 9.0g of (dimeric mixture) was obtained (yield: 98%).

Synthesis of Dimethylsilyl-bis {1- (2-ethyl-4- (1-naphthyl) indene}

4.97g (18.4m mol) of 2-ethyl-4- (1-naphthyl) indene and 50ml co-amide in a 200ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. (0.51 mmol) and 53 mL of anhydrous ether were charged. 12.8 ml (20.2 mmol) of 1.58 M n-butyllithium hexane solution was slowly added dropwise to the mixture in a nitrogen atmosphere at -10 ° C.

After the addition was completed, the temperature was raised to room temperature and the reaction mixture was stirred for 4 hours.

Then, a solution in which 1.24 ml (10.1 mmol) of dimethyldichlorosilane was dissolved in 5 ml of anhydrous ether was slowly added dropwise to the reaction mixture. After the addition was completed, the reaction mixture was stirred at room temperature for 15 hours. The reaction mixture was poured into 50 ml of saturated aqueous ammonium chloride solution and filtered through celite. The organic phase was separated and the aqueous phase was extracted with 50 ml of ether.

The combined organic phases were washed with saturated aqueous sodium chloride solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure. The remaining residue was chromatographed with silica gel (eluted with hexane) to obtain 3.2 g of the target substance (di-isomeric mixture) as a yellow solid (yield: 58%).

rac-dimethylsilyl-bis {1- (2-ethyl-4- (1-naphthyl) indenyl)} zirconium dichloric

In a 100 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer, 2.0 g (3.36 m mol) of dimethylsilyl-bis (2-ethyl-4- (1-naphthyl) indene and 40 ml of anhydrous ether was charged under argon atmosphere 4.58 ml (7.06 mmol) of a hexane solution of 1.54 M n-butyllithium was slowly added dropwise to the mixture at room temperature.

After the addition was completed, the reaction mixture was stirred for 17.5 hours. The resulting reaction solution was cooled to -75 ° C. Then 0.83 g (3.56 mmol) ZrCl ₄ was slowly added to the solution.

After the addition was completed, the mixture was warmed to room temperature overnight.

The red-yellow reaction slurry thus obtained was filtered and washed with 45 ml of anhydrous ether.

60 ml of methylene chloride and 40 ml of anhydrous ether were added to the residue and the insolubles were filtered off. The filtrate was concentrated to dryness at room temperature. The residue was dissolved in 15 ml of methylene chloride and concentrated to about one third of the total volume of the mixture. Then 2 ml of anhydrous ether was added to precipitate. The precipitate was filtered, washed with 2 ml of anhydrous ether, and dried under reduced pressure to obtain 0.12 g of the target substance as a yellow orange powder (yield: 5%).

Example 8

Rac-dimethylsilyl-bis {1- (2-ethyl-4- (1) instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride as a transition metal compound catalyst component Polymerization was carried out in the same manner as in Example 3 except for using -naphthyl) indenyl)} zirconium dichloride.

The polymer amount thus obtained was 20.2 g and the polymerization activity was 10.4 kg-pp / m mol-Zr.hr.

Intrinsic viscosity [] was 3.08 dl / g and Mw / Mn was 2.09. In this polymer, triadtaxity is 99.7%, the positional irregularity ratio by propylene monomer 2,1-insertion is 0.12%, and the irregularity unit ratio by propylene monomer 1,3-insertion is less than (0.03% or less) detected. It was.

The results are shown in Table 1 (I) and (II).

Example 9

Rac-dimethylsilyl-bis {1- (2-ethyl-4- (1) instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride as a transition metal compound catalyst component The polymerization reaction was carried out in the same manner as in Example 5 except that naphthyl) indenyl)} zirconium dichloride was used.

The polymer amount thus obtained was 2.08 g and the polymerization activity was 12.5 Kg-polymer / m mol-Zr.hr. The ethylene content was 7.9 mol%, the intrinsic viscosity [η] was 1.39 dl / g, Mw / Mn was 2.33, and Tm was 109 ° C. In this polymer, the triadtaxity is 99.2%, the irregular unit ratio by 2,1-insertion of propylene monomer is 0.10%, and the irregular unit ratio by 1,3-insertion of propylene monomer is lower than detection limit (0.03% or less). )

The results are shown in Table 1 (I) and (II).

The polymer film had a heat sealing start temperature of 106 ° C. and a heat sealing start temperature of 110 ° C. after the heat treatment.

The results are shown in Table 2.

Example 10

Synthesis of rac-dimethylsilyl-bis {1- (2-n-propyl-4- (1-naphthyl) indenyl)} zirconium dichloride.

Synthesis of 3- (2-bromophenyl) 2-n-propylpropionic acid

1 l four-necked round flask equipped with a stirrer, dimrose condenser, dropping funnel and thermometer, 37g (330m mol) of potassium t-butoxide, 32ml (334m mol) of N-methylpyrrolidone and 400ml of toluene A solution in which 60.7 g (300 mmol) of n-diethylpropyl malonic acid was dissolved in 50 ml of toluene was added dropwise to the mixture while stirring in an ice bath at a reaction temperature of 5 to 10 ° C. for 30 minutes. After the addition was completed the mixture was stirred at 45 ° C. for 30 minutes and further at 65 ° C. for 1 hour. Immediately after heating, the resulting solution turned to a creamy color heterogeneous material.

A solution of 75 g (300 mmol) of 2-bromobenzyl bromide dissolved in 50 ml of toluene was added dropwise to the product at a reaction temperature of 5 to 15 ° C. for 30 minutes in an ice bath.

After the addition was completed, the mixture was stirred at 65 ° C. for 30 minutes. The temperature was raised and the reaction mixture was heated at reflux for 1 hour. The color of the reaction slowly turned gray.

After cooling the reaction was poured into 500 ml of water and the mixture was adjusted to pH 1 by addition of 10% aqueous sulfuric acid solution. The organic phase was separated and the aqueous phase was extracted five times with 100 ml of toluene.

The combined organic phases were washed four times with 200 mL of aqueous NaCl solution and then dried over MgSO ₄ . The solvent was evaporated to give 114 g of a brown liquid.

A 1 L four-necked circular flask equipped with a stirrer, a dimrose condenser, a dropping funnel and a thermometer was charged with 200 ml of the liquid and methanol obtained above. A solution in which 237 g (content: 85%, 3.59 mol) of potassium hydroxide was dissolved in 520 ml of methanol and 180 ml of water was added to the mixture. The flask was then heated to 90 ° C. and the mixture was refluxed for 5 hours. Then almost all methanol was evaporated using an evaporator and 500 ml of water was added to obtain a homogeneous solution. The homogeneous solution was adjusted to pH 1 by adding 10% aqueous sulfuric acid solution while cooling with ice. The resulting white precipitate was isolated by filtration. The organic phase was then separated from the filtrate and the aqueous phase was extracted six times with 200 ml of ether. The organic phases were combined and dried over MgSO ₄ . The solvent was evaporated to give 94 g of an off white semisolid.

The semisolid was then charged into a 1 L round flask and heated at 180 ° C. for 10 minutes. After heating, the product was cooled to give 78.0 g of the target substance which is a brown transparent liquid (yield: 96%).

Synthesis of 3- (bromophenyl) 2-n-propylpropionylchloride

200 ml 3- (bromophenyl) -2-propylpropionic acid (277m mol) and thionyl chloride in a 500 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer and a NaOH trap. Charged. The mixture was heated at reflux for 2 hours. Excess thionyl chloride was then removed by distillation, and the residue was distilled off under reduced pressure to give 77.4 g of a crude product which was a light brown transparent liquid having a boiling point of 130 to 135 ° C / l mmHg. This acid chloride was used in the next reaction without further purification.

Synthesis of 4-bromo-2-n-propyl-1-indanon

A 1 L four-necked round flask equipped with a stirring rod, a dimrose condenser, a dropping funnel, a thermometer, and a NaOH trap was charged with 74.5 g (559 m mol) of anhydrous aluminum chloride and 400 ml of carbon disulfide.

The solution obtained by dissolving the acid chloride obtained above in 100 ml of carbon disulfide while cooling in an ice bath was slowly added dropwise to the mixture. After the addition was completed, the mixture was stirred at 0 ° C. for 3 hours. The reaction solution was then poured into 600 ml of ice water. The organic phase was separated and the aqueous phase was extracted four times with 200 mL of ether. The combined organic phases were washed four times with 300 ml of saturated sodium bicarbonate solution and dried over anhydrous MgSO ₄ . The solvent was evaporated to give 66.7 g of a brown liquid.

This ketone was used in the next reaction without further purification.

Synthesis of 4-bromo-2-n-propyl-1-trimethylsilyloxyindan

A 1 L four-necked circular flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer was charged with 4.96 g (131 m mol) of sodium borohydride and 200 ml of ethanol.

A solution obtained by dissolving 4-bromo-2-n-propyl-1-n-propyl-indanone obtained above in 200 ml of ethanol while cooling in an ice bath was added dropwise to the mixture. After the addition was completed, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was added to 200 ml of ice water and almost all ethanol was evaporated using an evaporator. The residue was transferred to a separatory funnel using 300 mL of ether to separate the organic phase, and the aqueous phase was extracted three times with 200 mL of ether. The organic phases were combined and dried over anhydrous MgSO ₄ . The solvent was then evaporated to give 66.50 g of a yellowish white powder.

Then, the yellowish white powder obtained above, 200 ml of ether and 47 ml (337 mmol) of triethylamine were charged into a 1-neck four-necked circular flask. A solution in which 39 ml of trimethicylyl chloride was dissolved in 50 ml of ether while cooling in an ice bath was added to the mixture.

The reaction mixture was stirred for 7 hours, and the reaction mixture was poured into 400 ml of saturated aqueous sodium bicarbonate solution, and the organic phase was separated.

The aqueous phase was then extracted three times with 200 ml of ether. The combined organic phases were washed with 400 mL saturated aqueous NaCl solution and dried over anhydrous MgSO ₄ . Then the solvent was evaporated to give a tan liquid. The liquid was distilled off under reduced pressure to obtain 76.00 g of a target substance of an off-white transparent liquid having a boiling point of 120 to 125 ° C / 2 mmHg. The total yield of this liquid from the 3- (2-bromophenyl) -2-n-propylpropionic acid was 81%.

Synthesis of 2-n-propyl-4-1 (1-naphthyl) indene

In a 300 ml four necked flask equipped with a stirring rod, a dropping funnel and a thermometer, 10 g (30.5 m mol) of 4-bromo-2-n-propyl-1-trimethylsilyloxyindan and 50 ml of dry ether And PdCl ₂ (dppf) 112 mg (0.153 mmol) were charged. 85 mL (61 mmol) of ether / benzene solution containing 0.72 M of 1-naphthyl magnesium bromide was added dropwise to the mixture at room temperature. The temperature in the flask was then raised to 48 ° C. and the mixture was stirred at reflux for 4 hours.

The reaction product was then poured into 300 mL of saturated aqueous ammonium chloride solution and extracted four times with 200 mL of ether. The organic phase was washed with saturated aqueous NaC1 solution and then dried over anhydrous MgSO ₄ . The solvent was evaporated to give 17.83 g of a yellowish-brown semisolid.

50 ml of the above-mentioned yellowish-brown semisolid and ether were charged into a 300 ml three necked flask.

60 ml of 5N aqueous hydrochloric acid solution was added dropwise to the mixture, followed by vigorous stirring. After 2 hours the mixture was transferred to a separatory funnel and extracted three times with 50 ml of ether.

The combined organic phases were washed twice with 100 ml of saturated aqueous sodium bicarbonate solution and dried over anhydrous MgSO ₄ . The solvent was evaporated to give a brown semisolid. The semisolid thus obtained was purified by silica gel chromatography (eluted with hexane / ethyl acetate = 50 / 1-51 / 5) to obtain 8.40 g of an off-white powder.

Then, 80 ml of the white powder, methylene chloride anhydrous, 11.3 ml (81 m mol) of triethylamine and 165 ml (1.35 m mol) of 4-dimethylaminopyridine were charged into a 200 ml round neck flask. . While cooling with an ice bath, a solution of 4.2 ml of methanesulfonyl chloride in 20 ml of anhydrous methylene chloride was slowly added dropwise to the mixture. After complete addition the temperature was raised to room temperature and the mixture was stirred overnight.

The reaction product was then poured into 100 ml of ice water and extracted three times with 100 ml of methylene chloride. The combined organic phases were washed three times with 100 ml of saturated aqueous sodium bicarbonate solution and dried over anhydrous MgSO ₄ . The solvent was evaporated to give a brown liquid. The brown liquid thus obtained was chromatographed with silica gel (silica gel 200g, hexane / ethyl acetate = 50/1) to give 6.51 g of the target substance as a white solid (yield: 75%).

Synthesis of Dimethylsilyl-bis- (2-n-propyl-4- (1-naphthyl) indene

In a 200 ml four necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer, 6.27 g (22.0 m mol) of 2-n-propyl (1-naphthyl) indene and 120 ml of dry ether 60 mg of coanide was charged. 15 ml (24.5 mmol) of 1.63 M n-butyllithium hexane solution was added dropwise to the mixture while cooling with an ice bath. After the addition was completed the mixture was stirred at reflux for 30 minutes.

Then, a solution of 1.5 ml (12.4 mmol) of dimethyldichlorosilane in 5 ml of dry ether was added dropwise to the resulting mixture while cooling with an ice bath. After complete addition the mixture was stirred overnight at room temperature. The reaction mixture was then poured into saturated aqueous ammonium chloride solution. After filtration the organic phase of the filtrate was separated and the aqueous phase was extracted twice with 50 ml of ether. The combined organic phases were washed with 100 mL of saturated aqueous NaC1 solution and then dried over anhydrous MgSO ₄ . The solvent was evaporated to give a yellow oil. The yellow oil obtained above was purified by silica gel chromatography (silica gel 200 g, hexane / ethyl acetate = 50/1) to obtain 5.80 g of the target substance as an off-white powder. (Yield 84%)

Synthesis of rac-dimethylsilyl-bis {1- (2-n-propyl-4 (1-naphthyl) indenyl)} zirconium dichloride

2.5 g of dimethylsilyl-bis {1- (2-n-propyl-4 (1-naphthyl) indene)} in a 100 ml four necked flask equipped with a stirring rod, a condenser, a dropping funnel and a thermometer. 4.00m mol) and 50 ml of dry ether were charged. 5.15 mL (8.40 mmol) of a 1.63M hexane solution of n-butyllithium was added dropwise to the mixture in a water bath. After the addition was completed, the mixture was stirred at room temperature overnight, and then 1.00 g (4.29 m mol) of ZrCl ₄ was added to the resultant mixture at -78 ° C. After the addition was completed, the mixture was allowed to stand overnight. The resulting orange reaction slurry was filtered and the filtrate was washed with 40 ml of dry ether and 40 ml of dry methylene chloride. The mixture was filtered and the filtrate was concentrated to about one third of the total volume of the filtrate. The precipitate was dissolved in 10 ml of methylene chloride and crystallized from 20 ml of dry ether. The precipitate was filtered, washed with 5 ml of dry ether, and dried under reduced pressure to obtain 0.09 g of the target substance as a yellow powder (yield: 3%).

Example 11

Synthesis of rac-dimethylsilyl-bis {1- (2-n-propyl-4 (9-phenanthryl) indenyl)} zirconium dichloride

Synthesis of 2-n-propyl-4 (9-phenanthryl) indene

10 g (30.5 mmol) of 4-bromo-2-n-propyl-1-trimethylsilyloxyindane synthesized in Example 10 in a 300 ml four-necked circular flask equipped with a stirring rod, a dropping funnel and a thermometer. And 50 ml of dried ether and 112 mg (0.153 mmol) of PdCl ₂ (dppf) were charged. 42 ml (61 mmol) of an ether / benzene solution containing 1.45 M of 9-phenanthtolyl magnesium bromide at room temperature was added dropwise to the mixture while stirring. The temperature in the flask was then raised to 42 ° C. and the mixture was stirred at reflux for 10 hours. The reaction mixture was then poured into 300 mL of saturated aqueous ammonium chloride solution and extracted four times with 200 mL of ether. The combined organic phases were washed with saturated aqueous NaCl solution and dried over anhydrous MgSO ₄ . The solvent was evaporated to give 20.3 g of a brown colored liquid.

The brown liquid and 50 ml of ether obtained above were charged into a 300 ml four necked flask. 60 ml of 5N aqueous hydrochloric acid solution was added dropwise to the flask at room temperature and the mixture was vigorously stirred for 6.5 hours. The product was transferred to a separatory funnel and washed four times with 50 ml of ether. The organic phase was washed twice with 100 ml of saturated aqueous sodium bicarbonate solution and then dried over anhydrous MgSO ₄ .

The solvent was evaporated to give a brown semisolid. The brown semi-solid thus obtained was purified by silica gel chromatography to obtain 10.75 g of a yellow powder. Then, the yellow powder obtained above, 80 ml of anhydrous methylene chloride, 12.8 ml (92.0 mmol) of triethylamine, and 187 ml (1.53 mmol) of 4-dimethylaminopyridine were charged into a 200 ml round neck flask. . A solution in which 4.72 ml (61.0 mmol) of methanesulfonyl chloride was dissolved in 20 ml of anhydrous methylene chloride was added dropwise to the mixture while cooling with an ice bath. After the addition was completed, the temperature was raised to room temperature and the mixture was stirred for 4 hours.

The reaction product was then poured into 100 ml of ice water and extracted three times with 100 ml of methylene chloride. The combined organic phases were washed three times with 100 ml of saturated sodium bicarbonate solution and dried over anhydrous MgSO ₄ . The solvent was evaporated to give a reddish brown semisolid. The reddish brown semisolid thus obtained was purified by silica gel chromatography to obtain 7.20 g of the target substance as an off-white powder (yield: 71%).

Synthesis of Dimethylsilyl-bis {1- (2-n-propyl-4- (9-phenanthryl) indene

6.20g (18.5mmol) of 2-n-propyl-4- (9-phenanthryl) indene and dry ether 120 50 ml of simultaneous amide was charged with ml. 12.5 ml (20.4 mmol) of 1.63 M n-butyllithium hexane solution was added dropwise to the mixture while cooling with an ice bath. After the addition was complete the mixture was stirred at reflux for 1.5 h. Then, a solution in which 1.34 ml (11.1 mmol) of dimethyldichlorosilane was dissolved in 100 ml of dry ether was added dropwise to the mixture. After the addition was completed, the mixture was stirred overnight at room temperature and the reaction mixture was poured into 200 ml of saturated aqueous ammonium chloride solution. After filtration the filtrate was extracted three times with 100 ml of ether. The organic phase was washed with 200 mL saturated aqueous NaCl solution and dried over anhydrous MgSO ₄ . The solvent was evaporated to give an off white powder. The powder thus obtained was purified by silica gel chromatography to obtain 3.80 g of the target substance as an off-white powder (yield: 54%).

Synthesis of rac-dimethylsilyl-bis {1- (2-n-propyl-4- (9-phennaltryl) indenyl)} zirconium dichloride

Dimethylsilyl-bis (1- (2-n-propyl-4- (9-phenaltolyl) indene) in a 200 ml four necked flask equipped with a stirring rod, a condenser with beads, a dropping funnel and a thermometer. } 2.9 g (4.00 mmol) and 60 ml of dry ether were charged. 5.15 ml (8.40 mmol) of 1.63 M n-butyllithium hexane solution was added dropwise to the mixture while cooling with an ice bath. After complete addition the mixture was stirred overnight at room temperature. 1.00 g (4.29 mmol) of ZrCl ₄ were then added dropwise to the product mixture at -78 ° C. After the addition was complete the mixture was warmed to room temperature. The resulting orange reaction mixture was filtered and washed with 100 ml of dry methylene chloride. The filtrate was concentrated to dryness and dissolved in 100 ml of dry methylene chloride. The solution was precipitated by addition of dry ether, filtered, and the precipitate was washed with 15 ml of dry ether and dried under reduced pressure to yield 0.10 g of the target substance as a yellow powder (yield: 2.8%).

Example 12

Synthesis of rac-dimethylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride

Synthesis of 2-ethyl-1-hydroxy-4- (9-phenanthryl) indane

11.54 g (36.8 mmol) of 4-bromo-2-ethyl-1-trimethylsilyloxyindane and PdCl _{2 in} a 200 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. (dppf) 0.135 g (0.184 mmol) and 35 ml of dry ether were charged. 51.5 mL (73.7 mmol) of ether / benzene solution containing 1.45 M of 9-phenantholyl magnesium bromide was added dropwise to the mixture at room temperature under a nitrogen atmosphere. After the addition was completed the temperature in the flask was raised to 42 ° C. and the mixture was stirred at reflux for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the excess Gringnaard reagent was decomposed by the slow addition of 100 ml of water. After addition of 50 ml of ether, the organic phase was separated and filtered using celite and the filtrate was washed with 100 ml of saturated aqueous NaCl solution and dried over anhydrous MgSO ₄ . The solvent was evaporated under steaming to give 25 g of reddish brown liquid.

A 200 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer was charged with the dark reddish brown liquid obtained above and 50 ml of tetrahydrofuran. 6 ml of 12% aqueous hydrochloric acid solution was added dropwise to the mixture at room temperature under a nitrogen atmosphere. The reaction mixture was stirred for 5 hours. After completion of the reaction, 100 ml of ether was added, the organic phase was separated, washed three times with 100 ml of saturated aqueous sodium bicarbonate solution, and dried over anhydrous MgSO ₄ . The solvent was evaporated to give a dark red liquid residue. The dark red liquid residue thus obtained was purified by silica gel chromatography (eluted with hexane and hexane / ethyl acetate (4/1 volume part)) to obtain 12.33 g of a viscous reddish brown liquid (2 isomer mixture) as a viscous red liquid (yield: 99%). )

FD-MS: 338 (M +)

Synthesis of 2-ethyl-4- (9-phenanthryl) indene

A 300 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer, 12.3 g (36.3 mmol) of 2-ethyl-1-hydroxy-4- (9-phenanthryl) 19.7 mL (142 mmol) of triethylamine and 61.5 mL of methylene chloride were charged. A solution of 3.3 ml (42.6 mmol) of methanesulfonyl chloride in 5 ml of methylene chloride was added dropwise to the mixture at 0 ° C. under a nitrogen atmosphere. After the addition was completed the temperature was raised to room temperature and the reaction mixture was stirred for 4 hours. 80 ml of saturated aqueous sodium bicarbonate solution was added to the reaction mixture. The organic phase was separated and the aqueous phase was extracted twice with 50 ml of methylene chloride. The combined organic phases were washed with water, washed with saturated aqueous sodium chloride solution and dried over anhydrous MgSO ₄ . The solvent was evaporated under reduced pressure. The residue was chromatographed with silica gel (hexane and hexane / ethyl acetate (eluted at 100/1 volume part)) to give 9.61 g of the target substance as a pale yellow green liquid (yield: 83%).

Synthesis of Dimethylsilyl-bis {1- (2-ethyl-4- (9-phenanthryl)} indene

5.3g (16.5mmol) of 2-ethyl-4- (9-phenanthryl) indene and 45mg (0.45g) of copolyamide in a 200ml three-necked circular flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. mmol) and 1.6 ml of dry ether. 11.8 mL (18.2 mmol) of a 1.5M n-butyllithium hexane solution was added dropwise to the mixture at -10 ° C under a nitrogen atmosphere. After the addition was completed, the temperature was raised to room temperature and the reaction mixture was stirred for 5 hours. Then, a solution in which 1.12 ml (9.1 mmol) of dimethyldichlorosilane was dissolved in 5 ml of dry ether while cooling with an ice bath was added dropwise to the reaction mixture. After the addition was completed, the temperature was raised to room temperature and the reaction mixture was stirred for 15 hours. 50 mL of saturated aqueous ammonium chloride solution was added to the reaction mixture. The insoluble material was then filtered through celite and the filtrate was separated into an organic phase and an aqueous phase.

The aqueous phase was extracted with 50 ml of ether. The combined organic phases were washed three times with 50 ml of saturated aqueous NaCl solution and dried over anhydrous MgSO ₄ . The solvent was evaporated under reduced pressure to give a viscous pale yellow liquid residue. The residue thus obtained was purified by silica gel chromatography (hexane and eluted with hexane / ethyl acetate (1000/7 parts by volume)) to obtain 3.19 g of the target substance as a yellow solid (yield: 55%).

Synthesis of rac-dimethylsilyl-bis {1- (2-ethyl-4- (9-phennaltryl) indenyl)} zirconium dichloride

0.06 g (0.86) dimethylsilyl-bis {1- (2-ethyl-4- (9-phentalryl) indene)} in a 100 ml three necked flask equipped with a stirring rod, condenser, dropping funnel and thermometer m mol) and 12 ml of dry ether were charged under an argon atmosphere. 1.18 ml (1.18 mmol) of 1.5 M n-butyllithium hexane solution was added dropwise to the mixture at room temperature.

After the addition was complete the mixture was stirred for 18.5 hours. The pale yellow orange reaction mixture was cooled to -70 ° C. 0.02 g (0.86 mmol) of ZrCl ₄ was then added to the mixture. After the addition was completed the mixture was warmed overnight. The resulting orange-yellow reaction slurry was filtered and the residue was washed with 6 ml of dry ether and five times with 5 ml of methylene chloride. 55 ml of methylene chloride were added to the product and the insolubles were filtered off. The filtrate was concentrated to dryness. The dried material was resuspended in 2 ml of dry ether and dried to give 80 mg of yellow-orange powder.

NRM analysis of this powder showed a mixture of rac / meso (91-9). Then the powder obtained above was resuspended and washed with 2 ml of methylene chloride and 2 ml of dry ether.

The product was then dried under reduced pressure to give 66 mg of the desired product as a yellow-orange powder (yield: 9%).

Example 13

Synthesis of rac-dimethylsilyl-bis {1- (2-i-butyl-4- (1-naphthyl) indenyl)} zirconium dichloride

Synthesis of 2-bromobenzylindene diethylmalonic acid

In a 500 ml three necked flask (Drean & Stark) equipped with a stirring rod, a dimrose condenser, and a thermometer, 74.0 g (400 mmol) of 2-bromobenzaldehyde and 70.48 g (440 mmol) of diethylmalonic acid And 1.6 ml of piperidine, 4.8 ml of acetic acid and 80 ml of benzene.

The mixture was azeotropically dehydrated for 7 hours in an oil bath at 110 ° C. under a nitrogen atmosphere. After the reaction was completed, the temperature was cooled to room temperature, 300 ml of ether was added, and then washed twice with 100 ml of water. The organic phase was dried over anhydrous Na ₂ SO ₄ . The solvent was concentrated under reduced pressure, and the orange liquid concentrate was distilled off under reduced pressure to obtain 117.2 g of the target substance as a yellow liquid (yield: 90%).

Synthesis of 2-bromobenzyl diethylmalonic acid

A 500 ml three necked flask equipped with a stirrer, a dropping funnel and a thermometer was charged with 13.64 g (360.8 mmol) of sodium borohydride and 280 ml of ethanol. Solid 2-bromobenzylidene diethyl malonic acid was added to the mixture under nitrogen atmosphere while cooling with an ice bath.

After the addition was completed, the mixture was further stirred for 1 hour. The resulting white slurry was then filtered and the residue was washed with 50 ml of ethanol.

The combined filtrates were concentrated under reduced pressure and extracted with 200 mL of water and 200 mL of ether. The organic phase was separated and the aqueous phase further extracted with 200 ml ether. The organic phases were combined and washed twice with 200 mL of saturated NaCl aqueous solution and dried over anhydrous MgSO ₄ . The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (eluted with hexane / ethyl acetate (6/1 volume part)) to give 55.4 g of a target substance as a colorless liquid (yield: 47%).

Synthesis of 3- (2-bromophenyl) -2-i-butylpropionic acid

A 1 L four-necked circular flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer was charged with 20.45 g (182.3 mmol) of potassium t-butoxide, 180 ml of toluene and 25 ml of N-methylpyrrolidone. did.

A solution of 50.0 g (151.9 mmol) of 2-bromobenzyl diethylmalonic acid in 40 ml of toluene was added dropwise to the mixture at room temperature under a nitrogen atmosphere. After the addition was completed, the temperature in the flask was raised to 60 ° C., the reaction mixture was stirred for 1 hour, and then a solution of 24.97 g (182.3 mmol) of I-butyl bromide in 30 ml of toluene was added to the resultant mixture at the same temperature as above. . After the addition was completed the temperature was raised and the mixture was stirred at reflux for 18 hours. The reaction mixture was poured into 150 mL of saturated aqueous sodium chloride solution and the mixture was adjusted to pH 3 by addition of 12% hydrochloric acid. The organic phase was separated and the aqueous phase was extracted twice with 100 ml of ether. The combined organic phases were washed with 200 ml of saturated aqueous sodium bicarbonate solution and 150 ml of saturated aqueous sodium chloride solution and dried over anhydrous MgSO ₄ . The solvent was concentrated under reduced pressure to give 64 g of a concentrate of an orange liquid. Then, in a 1 liter four necked round flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer, 110 g (1.52 m mol) of potassium hydroxide and an aqueous methanol solution (methanol / water = 4/1 (v / v) )) 300 ml was charged. The concentrate obtained above was added dropwise to the mixture at room temperature under a nitrogen atmosphere. After the addition was completed the temperature was raised and the reaction mixture was stirred at reflux for 7 hours. After completion of the reaction the methanol was evaporated under reduced pressure. The residue was dissolved in water and adjusted to pH 3 by addition of dilute sulfuric acid. The precipitate was filtered off and washed with 150 ml ether. The filtrates were combined and separated into an oil phase and an aqueous phase, and the aqueous phase was extracted twice with 100 ml of ether. The combined organic phases were washed with 100 ml of saturated aqueous sodium chloride solution and then dried over anhydrous MgSO ₄ . The solvent was concentrated under reduced pressure to give 49.7 g of a viscous orange-brown liquid. The viscous orange-brown liquid obtained above was then charged to a 300 ml flask equipped with a stirring rod and a dimrose condenser, and heated and stirred at 180 ° C. under a nitrogen atmosphere for 1.5 hours.

42.1 g of the desired product in a viscous dark red liquid was obtained (yield: 97%).

The carboxylic acid thus obtained was used in the next reaction without further purification.

Synthesis of 3- (2-bromophenyl) -2-i-butylpropionic acid chloride

42.1 g of 3- (2-bromophenyl) -2-i-butylpropionic acid and 60 ml of thionyl chloride were placed in a 200 ml four necked flask equipped with a stirring rod, a dimrose condenser, a thermometer and a NaOH trap. Charged.

The mixture was stirred under reflux for 1.5 h under nitrogen atmosphere. After completion of the reaction, unreacted thionyl chloride was evaporated under reduced pressure. The residue was distilled off under reduced pressure to obtain 40.3 g of the target substance as a pale orange liquid (yield: 90%).

Synthesis of 4-bromo-2-i-butyl-1-indanon

A 500 ml four-necked circular flask equipped with a stirring rod, a dimrose condenser, a thermometer, and a NaOH trap was charged with 20.33 g (152.5 mmol) of anhydrous aluminum chloride and 70 ml of carbon disulfide. A solution of 40.2 g (132.6 mmol) of 3- (2-bromophenyl) -2-i-butylpropionic acid chloride obtained above in 50 ml of carbon disulfide was added dropwise to the mixture under nitrogen atmosphere while cooling with an ice bath. . After completion of the addition the temperature of the flask was raised and the mixture was stirred for 1 hour. Then, the reaction mixture was poured into 200 ml of ice water, quenched and extracted three times with 100 ml of ether. The combined organic phases were washed with 100 mL of saturated aqueous sodium bicarbonate solution and 100 mL of saturated NaCl aqueous solution, and then dried over anhydrous MgSO ₄ . The solvent was evaporated under reduced pressure to give 37.4 g of an orange liquid. This ketone was used in the next reaction without further purification.

Synthesis of 4-bromo-2-i-butyl-1-hydroxyindene

A 300 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer was charged with 2.51 g (66.3 mmmol) of sodium borohydride and 85 ml of ethanol. A solution of 37.0 g (132.6 mmol) of 4-bromo-2-i-butyl-1-indanone obtained above in 55 ml of ethanol was added dropwise to the mixture at room temperature under a nitrogen atmosphere. After the addition was completed, the mixture was further stirred for 16 hours. The reaction mixture was then concentrated under reduced pressure and extracted with 150 mL of water and 150 mL of ether. The organic phase was separated and the aqueous phase further extracted with 100 ml of ether. The combined organic phases were washed twice with 100 mL of saturated NaCl aqueous solution and then dried over anhydrous MgSO ₄ .

The solvent was evaporated under reduced pressure to give 34.4 g of the desired product (diisomeric mixture) as a pale orange solid. (Yield 96%) This alcohol was used in the next reaction without further purification.

Synthesis of 4-bromo-2-i-butyl-1-trimethylsilyloxyindan

34.4 g (127.8 mmol) of 4-bromo-2-ibutyl-1-hydroxyindan and triethylamine in a 300 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. 23.1 mL (166.2 mmol) and 118 mL methylene chloride were charged. 20 ml of a methylene chloride solution containing 19.45 ml (153.4 mmol) of trimethylsilyl chloride was added dropwise to the mixture under nitrogen atmosphere while cooling with an ice bath. After the addition was completed the temperature was raised to room temperature and the mixture was further stirred for 1.5 hours. The reaction mixture was poured into a mixture of 200 ml of ice water and 20 ml of saturated sodium bicarbonate solution. The organic phase was then separated and the aqueous phase was extracted twice more with 50 ml of methylene chloride. The organic phases were combined and washed with 100 mL of saturated NaCl aqueous solution. The solvent was evaporated under reduced pressure, and the residue was distilled off under reduced pressure to obtain 41.8 g of a target substance (bi-isomeric mixture) as a pale yellow liquid (yield: 96%).

Synthesis of 2-i-butyl-1-hydroxy-4- (1-naphthyl) indene

5.0g (14.65m) 4-bromo-2-i--n-butyl-1-trimethylsilyloxyindane in a 200ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. mol), 53.6 mg (0.073 mmol) of PdCl ₂ (dppf) and 15 ml of dry ether were charged.

40.7 mL (29.3 mmol) of an ether / benzene solution of 0.72 M of 1-naphthyl magnesium bromide was added dropwise to the mixture at room temperature under a nitrogen atmosphere. After the addition was completed the temperature of the flask was raised to 50-51 ° C. and the mixture was stirred under reflux for 18 hours. After completion of the reaction, the temperature was cooled to room temperature. The reaction mixture was then added to a mixture of 100 ml of saturated aqueous ammonium chloride solution and ice in order to decompose the excess Grinnard reagent. The resulting mixture was extracted twice with 50 ml of ether. The combined organic phases were washed with saturated aqueous sodium bicarbonate solution and saturated aqueous NaCl solution and then dried over anhydrous Na ₂ SO ₄ .

The solvent was evaporated to give 12.1 g of a viscous liquid.

The viscous liquid obtained above was then diluted with 24.2 mL of tetrahydrofuran and 7 mL of 12% hydrochloric acid was added. The mixture was stirred for 3 hours at room temperature. After completion of the reaction, the reaction mixture was added to 50 ml of saturated sodium bicarbonate solution and extracted twice with 50 ml of ether. The combined organic phases were washed with saturated aqueous sodium bicarbonate solution and saturated aqueous NaCl solution and then dried over anhydrous Na ₂ SO ₄ .

The solvent was evaporated under reduced pressure. The residue was separated and purified by silica gel chromatography (eluted with hexane / ethyl acetate (20/1 volume part)) to obtain 4.54 g of a target substance (a mixture of two isomers) as a viscous brown liquid (yield: 98%).

Synthesis of 2-i-butyl-4- (1-naphthyl) indene

4.54 g (14.4 mmol) 2-i-butyl-1-hydroxy-4- (1-naphthyl) indene in a 200 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer ), 5.13 g (50.8 mmol) of triethylamine, 0.10 g (0.82 mmol) of 4-dimethylaminopyridine, and 57.7 mL of methylene chloride were charged. A solution of 3.87 ml (33.8 mmol) of methanesulfonyl chloride in 7.7 ml of methylene chloride was added dropwise to the mixture under nitrogen atmosphere while cooling with an ice bath.

After the addition was completed the temperature was raised to room temperature and the mixture was further stirred for 3 hours. The reaction mixture was poured into 100 ml of water. The organic phase was then separated and the aqueous phase was extracted with 50 ml of methylene chloride. The combined organic phases were combined, washed with saturated aqueous NaCl solution and dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure.

The residue was separated and purified by silica gel chromatography (eluted with hexane / ethyl acetate (20/1 volume part)) to obtain 3.98 g of a target substance (a mixture of two isomers) as a viscous pale yellow liquid (yield 93%).

Synthesis of Dimethylsilyl-bis {1- (2-i-butyl-4- (1-naphthyl)} indene

2.37 g (7.95 mmol) of 2-i-butyl-4- (1-naphthyl) indene and copper thiosia in a 100 ml three necked flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. It was charged with 28 mg (0.22 mmol) of Nate and 24 mL of anhydrous ether. 5.54 mL (8.75 mmol) of a 1.58 M n-butyllithium hexane solution was added dropwise to the mixture at room temperature under a nitrogen atmosphere. After the addition was completed, the mixture was further stirred for 15 hours.

Then, a solution in which 0.53 ml (4.37 mmol) of dimethyldichlorosilane was dissolved in 1.6 ml of dry ether was added dropwise to the reaction mixture.

After the addition was completed, the mixture was further stirred at room temperature for 27.5 hours. The reaction mixture was filtered through Celite and 30 ml of water was added to separate the filtrate into an organic phase and an aqueous phase. The organic phase was separated and the aqueous phase was extracted with 30 ml of ether. The combined organic phases were washed with saturated aqueous NaCl solution and then dried over anhydrous Na ₂ SO ₄ . The solvent was evaporated under reduced pressure to give a viscous yellow liquid residue.

The viscous yellow liquid residue thus obtained was separated and purified by silica gel chromatography (eluted with hexane / ethyl acedate (160/1 volume part)) to obtain 1.85 g of a pale yellow solid (2 isomer mixture) as a pale yellow solid (yield: 71%). .

Synthesis of rac-dimethylsilyl-bis {1- (2-i-butyl-4- (1-naphthyl) indenyl)} zirconium dichloride

Dimethylsilyl-bis {1- (2-i-butyl-4- (1-naphthyl) indene) in a 50 ml three-necked circular flask equipped with a stirring rod, a dimrose condenser, a dropping funnel and a thermometer. 1.0 g (1.53 mmol) and 20 ml of dry ether were charged. 2.09 mL (3.22 mmol) of a hexane solution of 1.54 M n-butyllithium was added dropwise to the mixture at room temperature.

After the addition was completed, the mixture was further stirred for 15 hours. The resulting bright red reaction liquid was cooled to -68 ° C. 0.36 g (1.53 mmol) of ZrCl ₄ was added to the solution. After the addition was complete, the mixture was heated to room temperature with stirring overnight. The resulting orange-yellow reaction slurry was filtered and washed twice with dry ether.

25 ml of methylene chloride was added to the residue and the insolubles were filtered off. The filtrate was concentrated to dryness at room temperature. The resulting orange-yellow dry material was dissolved in 8 ml of methylene chloride and the solution was concentrated to about 1/2 of the total solution volume. 1 ml of dry ether was added, filtered and washed with 1 ml of dry ether to obtain a precipitate. The resulting solid was dried under reduced pressure to give 140 mg of orange-yellow powder. Analysis by NMR showed that the powder consisted of a rac / meso (88/12) mixture. The powder obtained above was then dissolved in 3 ml of methylene chloride. 6 ml of dry ether was added to the solution, and the resulting precipitate was filtered, washed with 0.5 ml of dry ether to obtain a precipitate, and then dried under reduced pressure to give 77 mg of the target substance as a yellow-orange powder (yield: 6%).

Example 14

Rac-dimethylsilyl-bis {1- (2-ethyl-4- (phenane) instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride as a transition metal compound catalyst component Polymerization was carried out in the same manner as in Example 2 except for using tolyl) indenyl)} zirconium chloride and changing the flow rate of hydrogen to 3 L / hr.

The polymer was thus obtained in an amount of 23.4 g and had a polymerization activity of 12.0 Kg-pp / m mmol = Zr.hr. Intrinsic viscosity [] was 2.92 ㎗ and Mw / Mn was 2.22. In the polymer, triadtaxity is 99.7%, the irregular unit ratio by 2,1-insertion of propylene monomer is 0.14%, and the irregular unit ratio by 1,3-insertion of propylene monomer is lower than detection limit (0.03 Or less).

The results are shown in Table 1 (I) and (II).

Example 15

Rac-dimethylsilyl-bis {1- (2-butyl-4- (naph) instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride as a transition metal compound catalyst component The polymerization was carried out in the same manner as in Example 2, except for changing the flow rate of hydrogen to 3 l / hr, using butyl) indenyl)} zirconium dichloride.

The polymer was thus obtained in an amount of 24.6 g and had a polymerization activity of 12.6-kg-pp-mmol-Zr.hr. Intrinsic viscosity [] was 3.05 dl / g and Mw / Mn was 2.10.

In the polymer, triadtaxity is 99.2%, the positional irregularity unit ratio by 2, 1-insertion of propylene monomer is 0.19%, and the positional irregularity unit ratio by 1.3-insertion of propylene monomer is less than the lower limit of detection (0.03% or less). It was.

The results are shown in Table 1 (I) and (II).

Example 16

Rac-dimethylsilyl-bis {1- (2-n-propyl-4- () instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride as a transition metal compound catalyst component The polymerization was carried out in the same manner as in Example 2, except that 1-naphthyl) indenyl)} zirconium dichloride was used and the flow rate of hydrogen was changed to 3 L / hr. The polymer was thus obtained in an amount of 19.9 g and had a polymerization activity of 10.2 kg-pp / mmol-Zr.hr. Intrinsic viscosity [] was 3.13 dl / g and Mw / Mn was 2.19. In the polymer, the triadtaxity is 99.5%, the irregular unit ratio by 2,1-insertion of propylene monomer is 0.19%, and the irregular unit ratio by 1,3-insertion of propylene monomer is lower than detection limit (0.03). % Or less). The results are shown in Table 1 (I) and (II).

Example 17

Rac-dimethylsilyl-bis [1- (2-n-propyl-4- instead of rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)] zirconium dichloride as a transition metal compound catalyst component (Phenanthryl) indenyl)} zirconium dichloride was used, and polymerization was carried out in the same manner as in Example 2 except that the flow rate of hydrogen was changed to 3 L / hr. The polymer was thus obtained in an amount of 14.5 g and had a polymerization activity of 7.4 kg-pp / mmol-Zr.hr. Intrinsic viscosity [] was 3.47 dl / g and Mw / Mn was 2.15. In the polymer, triadtaxity is 99.7%, the positional irregularity ratio by 2,1-insertion of propylene monomer is 0.16% and the positional irregularity ratio by 1.3-insertion of propylene monomer is below the lower limit of detection (0.03% or less). It was. The results are shown in Table 1 (I) and (II).

Example 18

A 2 L autoclave thoroughly washed with nitrogen was charged with 920 mL of hexane and 50 g of 1-butene. 1 mmol of triisobutyl aluminum was then added to the autoclave. After raising the temperature of the reaction system to 70 ° C, propylene was fed to the system so that the total pressure was 7 kg / cm 2 -G. 0.28 mmol of methylaluminoxane and rac-dimethylsilyl-bis {1- (2-ethyl-4-phenyl-1-indenyl)} zirconium dichloride 7 × 10 ⁻⁴ mmol (in terms of Zr atoms) were added to the autoclave. The monomer was polymerized for 30 minutes while continuously feeding propylene to add and maintain a total pressure of 7 kg / cm 2 -G. After the polymerization, the autoclave was released and the resulting polymer was recovered in a large amount of methanol and dried at 110 ° C. for 12 hours under reduced pressure. The polymer obtained above was 52.1 g and had a polymerization activity of 149 kg-polymer / mmol Zr.hr. The polymer had a 1-butene content of 20.2 mol%, an intrinsic viscosity [η] of 1.90 dl / g, a Mw / Mn of 2.05 and a melting point of 101.5 ° C. The results are shown in Table 1 (I) and (II).

Example 19

Into a 200-MW gas-pass glass reactor thoroughly washed with nitrogen, 250 ml of toluene and 9.4 ml of 1-octene were charged, and the temperature of the reactor was raised to 50 ° C. The system was sufficiently saturated by feeding propylene at a flow rate of 250 L / hr. Then, 0.1 mmol of triisobutylaluminum, 1.1 mmol of methylaluminoxane and rac-dimethylsilyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride 0.002 mmol (in terms of Zr atom) were added to the autoclave. ) And propylene were continuously fed at a flow rate of 250 L / hr while maintaining the temperature at 50 ° C. to polymerize the monomer for 30 minutes. The polymerization was stopped by adding a small amount of methanol.

The polymer solution was added to 2 L methanol containing a small amount of hydrochloric acid to precipitate the polymer. The precipitated polymer was recovered and dried at 110 ° C. for 12 hours under reduced pressure. The polymer was obtained in an amount of 5.4 g. The polymerization activity was 5.4 kg-polymer / mmol Zr.hr.

The polymer had a 1-octene content of 6.7 mol%, an intrinsic viscosity [η] of 1.44 dl / g, a Mw / Mn of 2.41 and a melting point of 131 ° C. The results are shown in Table 1 (I) and (II).

Example 20

A 200 ml reactor with a stirring blade thoroughly washed with nitrogen was charged with 80 l of hexane, 80 mmol of triisobutyl aluminum, 0.25 l of hydrogen and 0.3 kg of propylene, and then the temperature of the reactor was raised to 70 ° C. 18 mmol of methylaluminoxane and 0.06 mmol (in terms of Zr) of rac-dimethylsilyl-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride were added to the reactor and polymerized at 70 ° C. for 30 minutes. . During the polymerization, 13.7 kg propylene and 0.5 kg ethylene were fed to the reactor, respectively. After the polymerization, the autoclave was released to recover the product polymer with a large amount of methanol, and the resultant was dried at 80 ° C. for 10 hours under reduced pressure. The amount of polymer obtained was 7.0 kg. The polymerization activity was 117 kg-polymer / mmol Zr.hr. The polymer had an ethylene content of 4.7 mol% and an intrinsic viscosity [η] of 2.7 dl / g. In the polymer, the triadtaxity of the propylene-incorporated chain of iron-bonded polymer is 97.5%, the positional irregularity unit ratio by 2,1-insertion of propylene monomer is 0.22%, and the irregularity unit by 1,3-insertion of propylene monomer The ratio was 0.05% or less. The results are shown in Table 1 (I) and (II). The film of the copolymer had a heat sealing start temperature of 120 ° C. and a heat sealing start temperature after heat treatment of 123 ° C. The results are shown in Table 2.

Example 21

900 ml of hexane was charged into a 2 L autoclave washed thoroughly with nitrogen. 1 mmol of triisobutylaluminum was then added to the autoclave. After raising the temperature of the reaction system to 70 ° C., ethylene was supplied to maintain the pressure at 1.5 kg / cm 2 -G and propylene was supplied to the system so that the total pressure was 8 kg / cm 2 -G. To the autoclave, 0.3 mmol of methylaluminoxane and 0.001 mmol (in terms of Zr atom) of rac-dimethylsilbis {1- (2-dimethyl-4-phenylindenyl)} zirconium dichloride were added, and the total pressure was 8 kg / cm 2-. The monomer was polymerized for 7 minutes while continuously feeding propylene to maintain G. After the polymerization, the autoclave was released and the resulting polymer was recovered in a large amount of methanol and dried at 110 ° C. for 10 hours under reduced pressure. The polymer was obtained in an amount of 25.4 g and had a polymerization activity of 25 Kg-polymer / mmol Zr.hr.

The polymer had an ethylene content of 2.5 mol% and an intrinsic viscosity [η] of 3.1 dl / g. In the polymer, the triadtaxity of the propylene unit chain of the iron-bond is 97.6%, the positional irregularity ratio of 2, 1-insertion of propylene monomer is 0.22%, and the irregularity unit ratio of 1,3-insertion of propylene monomer. Was less than 0.05. The results are shown in Table 1 (I) and (II). The copolymer film had a heat sealing start temperature of 134 ° C and a heat sealing start temperature after heat treatment of 134 ° C. The results are shown in Table 2.

Example 22

8 L of hexane was charged to a 17 L autoclave thoroughly washed with nitrogen. The temperature of the reaction system was raised to 60 ° C., and propylene and ethylene were continuously supplied to the system at a flow rate of 250 L / hr and 170 L / hr, respectively, to increase the pressure to 8 kg / cm 2 -G.

Then, 8 mmol of triisobutylaluminum, 1.8 mmol of methylaluminoxane and rac-dimethylsilyl-bis {1- (2-dimethyl-4-phenylindenyl)} zirconium dichloride were added to the autoclave (Zr atom). The monomer was polymerized at 60 DEG C for 45 minutes while continuously supplying a mixed gas of propylene and ethylene (molar ratio: 60/40) to maintain a pressure of 8 kg / cm &lt; 2 &gt; -G. The autoclave was released and the resulting polymer was recovered in a large amount of methanol and dried at 110 ° C. for 10 hours under reduced pressure.

The polymer was obtained in an amount of 860 g and had a polymerization activity of 143 Kg-polymer / mmolZr.hr. The polymer had an ethylene content of 33.6 mol% and an intrinsic viscosity [η] of 1.4 dl / g. The triad tacticity of the propylene unit chain in the polymerized chain in the polymer is 97.5%, the positional irregularity unit ratio by 2,1-insertion of propylene monomer is 0.27%, and the irregularity unit by 1,3-insertion of propylene monomer The ratio was 0.03% or less. The results are shown in Table 1 (I) and (II).

The copolymer had an Izod impact strength of 30 kg.cm/cm, a film impact strength of 5300 kg.cm/cm, and an MFR of 17.8 g / 10 minutes.

The results are shown in Table 2.

Example 23

The polymerization was carried out in the same manner as in Example 22 except that the ethylene supply was changed from 170 L to 60 L and the molar ratio of propylene to ethylene in the mixed gas was changed from 60/40 to 81/19.

The polymer was obtained in an amount of 900 g and had a polymerization activity of 150 kg / -polymer / mmol Zr.hr. The polymer had an ethylene content of 15.4 mol% and an intrinsic viscosity [η] of 1.51 dl / g. In the polymer, the triadtaxity of the propylene unit chain of the iron-bond is 96.7%, the positional irregularity unit ratio by 2,1-insertion of propylene monomer is 0.28%, and the irregularity unit by 1,3-insertion of propylene monomer. The ratio was 0.03% or less. The results are shown in Table 1 (I) and (II).

The copolymer had a heat sealing start temperature of 80 ° C. and a heat sealing start temperature of 83 ° C. after heat treatment.

The results are shown in Table 2.

Example 24

A 17 L autoclave thoroughly washed with nitrogen was charged with 8 L of hexane and 40 mL of hydrogen. The temperature of the reaction system was raised to 70 ° C., and propylene and ethylene were fed to the system at flow rates of 253 L / hr and 22 L / hr, respectively, to raise the pressure to 6.5 kg / cm 2 -G.

Then, 8 mmol of triisobutyl aluminum, 1.8 mmol of methylaluminoxane and rac-dimethylsilyl-bis {1- (2-dimethyl-4-phenylindenyl)} zirconium dichloride 0.006 mmol (in terms of Zr atom) were added to the autoclave. ) Was added to polymerize the monomer at 70 ° C. for 30 minutes while continuously feeding a mixed gas of propylene and ethylene (molar ratio: 92: 8) to maintain a pressure of 6.5 kg cm 2 -G.

After polymerization, the autoclave was released and the resulting polymer was recovered in a large amount of methanol and dried at 110 ° C. for 10 hours under reduced pressure.

The polymer was thus obtained in an amount of 700 g and had a polymerization activity of 117 kg-polymer / mmolZr.hr. The polymer had an ethylene content of 6.0 mol% and an intrinsic viscosity [η] of 2.0 dl / g.

The triad taxity of the propylene unit chain in the polymerized chain in the polymer is 97.5%, the positional irregularity ratio by 2,1-insertion of the propylene monomer is 0.18%, and the positional irregularity by 1,3-insertion of the propylene monomer The unit ratio was 0.03% or less. The results are shown in Table 1 (I) and (II).

The copolymer film had a heat sealing start temperature of 112 ° C. and a heat sealing start temperature after heat treatment of 115 ° C.

The results are shown in Table 2.

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

The olefin polymerization catalyst of the present invention has a high polymerization activity and the polyolefin produced using this catalyst has a narrow molecular weight distribution, a narrow compositional distribution and a high molecular weight. By using an α-olefin having 3 or more carbon atoms, it is possible to obtain a polymer having high stereoregularity, excellent heat resistance and rigidity, and having a low proportion of irregularity units.

The olefin homopolymer according to the present invention has excellent stiffness, heat resistance, surface hardness, glossiness, transparency and impact strength.

The first and second propylene copolymers of the present invention (the amount of monomer units derived from α-olefins other than propylene is 5% or less) have excellent transparency, rigidity, surface hardness, heat resistance, heat sealing, anti-locking properties, It has anti-bleed out property and impact strength.

The propylene copolymer of the present invention (the amount of monomer units derived from α-olefins other than propylene is not less than 5 mol%) has excellent transparency, environmental aging, low temperature heat sealability improvement effect and impact strength.

The third propylene copolymer according to the present invention has excellent stiffness, surface hardness, heat resistance, transparency, heat sealing property, anti blocking property, and anti bleed out property, and thus is suitable for films, sheets, containers, drawn yarns, nonwoven fabrics, and the like.

Propylene elastomer according to the present invention is excellent in heat resistance, shock absorption, transparency, heat sealing and anti-blocking properties can be used alone for films, sheets and the like and can also be suitably used as a modifier of the thermoplastic resin.

Claims (1)

In propylene elastomers, (i) the elastomer contains 50 to 95 mole percent propylene units and 5 to 50 mole percent ethylene units; (ii) the triadtaxity of the propylene unit chain of the dumi-bond is not less than 90.0% as measured by ¹³ C-NMR; (iii) the ratio of the irregular position unit by 2,1-insertion of the propylene monomer in all the propylene insertions is 0.05% to 0.5% as measured by ¹³ C-NMR; (iv) Propylene elastomer having intrinsic viscosity measured in 135 ° C decahydro naphthalene and in the range of 0.1 to 12 dl / g.