JP2003261575A - Organic aluminohydroxy compound and polymerization catalyst using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic aluminohydroxy compound giving a homogeneous catalyst having stable and high activity, and to provide a polymerization catalyst containing the compound and having stable and high catalytic activity. <P>SOLUTION: This organic aluminohydroxy compound has two peaks in<SP>27</SP>Al- nuclear magnetic resonance spectrum, wherein the peaks are found out near 150 ppm and 60 ppm and have each a peak area of A<SB>1</SB>or that of A<SB>2</SB>and A<SB>1</SB>/A<SB>2</SB>is ≤0.1. And another compound has ≤0.5 wt.% insoluble content expressed in terms of aluminum atom in a mixed solvent of 2 pts.vol. toluene with 5 pts.vol. hexane at ≤30°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organoaluminoxy compound and a catalyst for polymer production using the same. More specifically, the present invention has a high catalytic activity and an organoaluminooxy compound which gives a homogeneous catalyst having a stable activity, and a high catalytic activity and stable activity obtained by using the organic aluminooxy compound. The present invention relates to a catalyst for producing a homogeneous polymer.

[0002]

2. Description of the Related Art Conventionally, as a method for polymerizing a polymerizable unsaturated compound such as olefins and styrenes to produce a homopolymer or a copolymer thereof, a transition metal compound is reacted with the transition metal compound. A method using a catalyst composed of an ionic compound or an organic aluminooxy compound capable of forming an ionic complex and an alkyl group-containing metal compound optionally used is well known. In the above homogeneous polymerization catalyst, the organoaluminooxy compound used as one component is a reaction product of an organoaluminum compound and water, and reacts with a transition metal compound to form a coordination polymerization catalyst. However, the conventional catalyst for polymerization using an organic aluminooxy compound has a large variation in its catalytic performance, so that there is a problem in that a polymer cannot be stably produced with high activity.

[0003]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention provides an organic aluminooxy compound which provides a homogeneous polymerization catalyst having high catalytic activity and stable activity, and an organic aluminooxy compound thereof. An object of the present invention is to provide a catalyst for producing a polymer, which contains a high catalytic activity and has stable activity.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, an organic aluminooxy compound having specific properties has a high catalytic activity and is a stable homogeneous catalyst. It has been found that a catalyst for polymer production, in which the organoaluminooxy compound, a transition metal compound and optionally an alkyl group-containing metal compound are combined, has high catalytic activity and stable activity. The present invention has been completed based on such findings.

Namely, the present invention provides a (1) ²⁷ Al- nuclear magnetic resonance spectrum ⁽²⁷ Al-NMR), 150
A line segment connecting a local minimum point existing between continuous curves a and b including peaks appearing in the vicinity of ppm and 60 ppm and a point connecting the curve b to the baseline and the curve b.
The area enclosed by and is A _1, and the area enclosed by the continuous curves a and b and the baseline is A _2.
And the A ₁ / A ₂ ratio is 0.1 or less, the organoaluminooxy compound (I), (2) temperature 3
The amount of insoluble component in a mixed solvent of toluene and hexane at a temperature of 0 ° C. or less and a volume ratio of 2: 5 is 5 in terms of aluminum atom.
% Or more of the organic aluminooxy compound (II), (3) (A) transition metal compound, and (B) the organic aluminooxy compound (I) and / or (II). Catalyst for polymer production, and (4) (A)
A catalyst for polymer production comprising a transition metal compound, (B) the organoaluminoxy compound (I) and / or (II), and (C) an alkyl group-containing metal compound.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The organoaluminoxy compound of the present invention
Object (I) is²⁷Al-nuclear magnetic resonance spectrum (²⁷Al-
NMR) has the following characteristics
It The measuring device is not limited to this description.
Figure 1 shows an organoaluminoxy compound²⁷Al-NMR scan
It is a schematic diagram of a vector, in this figure, 150 pp
A curve including a peak appearing near m is around 60 ppm
The curve including the peak appearing in is set to b. Curves a and b are continuous
A continuous curve is formed and exists between this curve a and b.
The existing minimum point P and the point Q where the curve b touches the baseline
Of the area (shaded area) surrounded by the line segment L connecting the
Area is A ₁And on the other hand, the continuous curves a and b and the base
Area of the area surrounded by the line and A₂And when
Ming organic aluminooxy compound (I) is A₁/ A₂Ratio is
It is less than 0.1.

The peak of ²⁷ AI-NMR shifts depending on the measuring instrument and the state of the aluminoxane in the sample (purity, molecular weight, molecular structure, compounding ratio of aluminoxane such as chain and ring, association state, etc.). To do. Also for the aluminoxane of the present invention, the peak of curve a is usually 150 ppm.
Although it is in the vicinity, it sometimes appears between 140 and 160 ppm, and sometimes it appears between 130 and 170 ppm. The peak of the curve b also usually appears in the vicinity of 60 ppm, but it sometimes appears in the range of 40 to 80 ppm, and in some cases, it also appears in the range of 40 to 100 ppm.

As described above, when the A ₁ / A ₂ ratio is 0.1 or less, the catalyst for polymer production using this organic aluminooxy compound has high activity and its activity is stable. . On the other hand, in the case of an organoaluminooxy compound having an A ₁ / A ₂ ratio of more than 0.1, the activity of the catalyst for polymer production using the same varies, and a polymer can be produced stably and with high activity. It will be difficult.

The above ²⁷ Al-NMR is carried out in a quartz NMR tube having a diameter of 5 mm in an amount of 25 in terms of aluminum atoms.
The organoaluminooxy compound equivalent to mg is toluene.
What was melt | dissolved in 6 milliliters was added, and this was used as a sample and measured under the following conditions. Measuring instrument: JEM-Gx270 manufactured by JEOL Ltd. Observation frequency: 70.282 MHz Observation range: 151515 Hz External standard: Aluminum sulfate aqueous solution (0 ppm) Repetition time: 0.6 sec Accumulated number: 10000 times Also, an organic alumino having the following properties The oxy compound (II) also has the same excellent performance as the above-mentioned organic aluminooxy compound (I).

The organic aluminooxy compound (II) is
Volume ratio of toluene and hexane at a temperature of 30 ° C. or lower 2: 5
The amount of the insoluble component in the mixed solvent of is 5% or more in terms of aluminum atom. As described above, when the amount of the insoluble component is 5% or more, the catalyst for polymer production using the organic aluminooxy compound has high activity and the activity is stable. On the other hand, the amount of the insoluble component is
When the content of the organic aluminooxy compound is less than 5% in terms of aluminum atom, the activity of the catalyst for polymer production using the same varies, and it becomes difficult to produce the polymer stably and with high activity. The insoluble component amount is a value obtained by the method described below.

That is, about 80 in terms of aluminum atoms.
After dissolving an organoaluminoxy compound corresponding to 0 mg in 20 ml of toluene, 50 ml of hexane is added, and the mixture is filtered at 25 ° C. using a Whatman glass filter. Then, the amount (mmole) of aluminum atoms present in the insoluble portion and the soluble portion was measured, and the ratio of the insoluble portion was obtained.

Organoaluminoxy compound (I) of the present invention
The method for producing (II) and (II) is not particularly limited as long as it has the above-mentioned properties, and the method shown below can be used to produce the organic aluminooxy compound (I) or (II). It can be manufactured efficiently and with no variation in performance. The organic aluminooxy compound is obtained by reacting an organic aluminum compound with water, and the water to be reacted is usually water of crystallization contained in a compound such as a metal salt, or an inorganic or organic compound. The adsorbed water or the water itself used is used, but it is advantageous to use water of crystallization of metal salt or water itself as the water to be reacted. Therefore, the method for producing an organoaluminoxy compound of the present invention can be divided into a reaction between an organoaluminum compound and a metal salt containing water of crystallization and a reaction between an organoaluminum compound and water itself.

First, when an organoaluminum compound is reacted with a metal salt containing water of crystallization to react an organoaluminoxy compound, the molar ratio of the amount of water involved in the reaction / the amount of the organoaluminum compound is 0.5 to 0.5. It is essential to react using both components so that the range becomes 1.0. If this molar ratio is less than 0.5, the amount of the insoluble component in the mixed solvent of toluene and hexane is insufficient, and if it exceeds 1.0, it is difficult to stably obtain an organic aluminooxy compound having the desired properties. Become. The amount of water involved in the reaction refers to the amount of water that can react in the crystal water.

In the reaction of the organoaluminum compound and the metal salt containing water of crystallization, the contact method of both components is not particularly limited. For example, the metal salt containing water of crystallization is dispersed in a suitable organic solvent. Then, the organoaluminum compound may be added thereto, or a metal salt containing water of crystallization may be added to a solution in which the organoaluminum compound is dissolved in an organic solvent. Further, an organic aluminum compound and a metal salt containing water of crystallization may be simultaneously added to the organic solvent. Since the reaction between the water of crystallization of the metal salt and the organoaluminum compound gradually progresses, the addition of each component may be performed in a single dose without taking time. The reaction temperature is not particularly limited, but is usually -10.
It is selected in the range of 0 to 50 ° C, preferably -78 to 30 ° C, more preferably -10 to 30 ° C. The reaction time depends on the reaction temperature and cannot be determined unconditionally,
It is usually 0.1 to 10 hours, preferably 0.5 to 7 hours.

On the other hand, when the organoaluminum compound is produced by reacting the organoaluminum compound with water itself, the molar ratio of the amount of water used to the amount of the organoaluminum compound used is in the range of 0.5 to 1.0. It is essential that both components be used. If this molar ratio is less than 0.5, the amount of insoluble components in the mixed solvent of toluene and hexane will be insufficient, and
When it exceeds 1.0, it becomes difficult to stably obtain an organic aluminooxy compound having desired properties.

In this reaction, water is added to a solution prepared by dissolving an organoaluminum compound in a suitable organic solvent. At this time, in order to stably obtain an organoaluminooxy compound having a desired performance, the reaction is performed. A method of controlling the temperature of the system or controlling the addition rate of water is used. That is, in the method of controlling the temperature of the reaction system, it is preferable to add water while maintaining the temperature of the reaction system at 0 ° C. or lower.
In this case, the addition rate of water is not particularly limited. In this system, if the temperature of the reaction system when water is added exceeds 0 ° C., an organic aluminooxy compound having desired performance may not be stably obtained. The preferred temperature of the reaction system during the addition of water is selected in the range of -5 to -80 ° C from the viewpoint of obtaining an organic aluminooxy compound having the desired performance stably and efficiently and operability.

On the other hand, in the method of controlling the addition rate of water,
Water is preferably added at a rate of 0.1 mol / min or less per mol of the organoaluminum compound. In this case, the temperature of the reaction system when water is added is not particularly limited. The rate of water addition
If it exceeds 0.1 mol / min, an organic aluminooxy compound having desired properties may not be stably obtained. The preferred addition rate of this water is such that an organoaluminooxy compound having the desired properties can be obtained stably and efficiently, and from a practical standpoint,
It is selected in the range of 0.001 to 0.1 mol / min. Thus, when reacting the organoaluminum compound with water itself, by controlling both the temperature of the reaction system during the addition of water and the addition rate of water, that is, the temperature of the reaction system is reduced to 0.
While maintaining the temperature below ℃, by adding water at an addition rate of 0.1 mol / min or less per 1 mol of the organoaluminum compound, the organoaluminoxy compound having the desired properties can be efficiently dispersed. Can be manufactured without. In order to obtain an organoaluminooxy compound having desired properties in a stable and efficient manner, the temperature of the reaction system during the addition of water is -1 from the practical aspects such as operability and operation time.
0 to 50 ° C, preferably 100 to 0 ° C, more preferably -80 to -5 ° C, and the water addition rate is in the range of 0.001 to 0.1 mol / min per mol of the organoaluminum compound. It is advantageous. Further, in this case, the temperature of the reaction system in the post-reaction after the addition of water is not particularly limited.

The organic solvent used for producing the organoaluminoxy compound of the present invention has, for example, 5 carbon atoms.
~ 18 aliphatic hydrocarbons and alicyclic hydrocarbons, 6 to 6 carbon atoms
20 inert solvents such as aromatic hydrocarbons, specifically n
-Pentane, isopentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more. As the organoaluminum compound, trialkylaluminum represented by the general formula (I) R ₃ Al ... (I) is usually used. R in the general formula (I) is preferably an alkyl group having 1 to 3 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Also 3 R
They may be the same or different.
As examples of such trialkylaluminum, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum and the like are preferably used. These trialkylaluminums may be used alone or in combination of two or more.

When a trialkylaluminum represented by the above general formula (I) is used as the organoaluminum compound, the organoaluminoxy compound obtained as a reaction product of the organoaluminum compound and water has the following structure. Have one or more.

General formula (IIa)

[Chemical 1] Chain aluminoxane represented by

General formula (IIb)

[Chemical 2] Chain aluminoxane with a branch represented by

General formula (III)

[Chemical 3] Cyclic aluminoxane represented by

It is also possible to form a kind of basket type aluminoxane in which two or more aluminoxanes are associated. In the general formulas (IIa), (IIb) and (III), R is the same as above, t is usually a number of 2 to 50, preferably 3 to 30, more preferably 4 to 20. Is a number. x, y, and z each represent an integer of 1 to 50, and satisfy x + y + z ≧ 3. Further, plural Rs in the molecule may be the same or different. The chain aluminoxane of the general formula (IIb) may be a chain aluminoxane having a plurality of branches. Specific examples of the reaction product of the organoaluminum compound and water include methylaluminoxane, ethylaluminoxane, and n.
-Propyl aluminoxane, isopropyl aluminoxane, etc. are mentioned.

The catalyst for producing a polymer of the present invention is (A)
A metal transfer compound, and (B) an organic acid having the above-mentioned specific properties.
Luminooxy compound (I) and / or (IIa), (II
b) and optionally (C) an alkyl group-containing metal compound
Is included. Transition metal compound of the above component (A)
Various items can be used, but usually
The compound represented by the general formula (IV) or the general formula (V) is used
To be     MR¹ _a R^Two _b R^Three _c R^Four _{4- (a + b + c)}    ... (IV)     MR¹ _d R^Two _e R^Three  R^Four _{3- (d + e)}         ... (V) [Wherein M is a metal or lanthanum of Group 3 to 10 of the periodic table
Represents a system metal, R¹, R ^Two , R^Three And R^Four Is it
Alkyl group, alkoxy group, alkylthio group, ant
Group, cyclopentadienyl group, substituted cyclopentadiene
Enyl group, indenyl group, substituted indenyl group, fluore
Nyl group, amino group, amide group, acyloxy group, phosphine
Group, a halogen atom, or a chelating ligand,
a, b, and c each represent an integer of 0 to 4, and d and
e shows the integer of 0-3, respectively. Also R¹ ~ R^Four 
Any two are CH_Two Or Si (CH_Three)_Two Etc.
It may be bridged. ] Periodic Table 3 to M
The Group 10 metal or lanthanum-based metal is preferably
Is a Group 4 metal, especially titanium, zirconium, hafnium
Etc. are used.

There are various titanium compounds, for example, at least one compound selected from titanium compounds represented by the following general formula (VI) or general formula (VII) and titanium chelate compounds. _{^{TiR 5 a R 6 a R 7}} c R 8 4- (a + b + c) ··· (VI) TiR 5 d R 6 e R 7 3- (d + e) ··· (VII) above general formula (VI) or (VII ) In R ⁵ , R ⁶ , R ⁷
And R ⁸ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (specifically, methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group, 2-ethylhexyl group). Group), an alkoxy group having 1 to 20 carbon atoms (specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, etc.), a carbon number of 6 to 20 Aryl group, alkylaryl group, arylalkyl group (specifically, phenyl group, tolyl group, xylyl group, benzyl group, etc.), 6 to 2 carbon atoms
0 aryloxy group (specifically, phenoxy group and the like), C1-20 acyloxy group (specifically,
Acetoxy group, benzoyloxy group, butylcarbonyloxy group, heptadecylcarbonyloxy group, etc., amino group having 1 to 50 carbon atoms (specifically, dimethylamino group, diethylamino group, diphenylamino group, bistrimethylsilylamino group, etc.) ), An amide group (specifically,
Acetamido group, ethylamido group, diphenylamido group, methylphenylamido group, etc.), phosphido group (specifically, dimethylphosphido group, diethylphosphido group, diphenylphosphido group, etc.), cyclopentadienyl group, substituted cyclo Pentadienyl group (specifically, methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, etc.), indenyl group, substitution Indenyl group (specifically, methylindenyl group, dimethylindenyl group, tetramethylindenyl group, hexamethylindenyl group, 4,5,6,7-
Tetrahydro-1,2,3 trimethylindenyl group, etc.), fluorenyl group (specifically, methylfluorenyl group, dimethylfluorenyl group, tetramethylfluorenyl group, octamethylfluorenyl group, etc.), Alkylthio group (specifically, methylthio group, ethylthio group, butylthio group, amylthio group, isoamylthio group, isobutylthio group, octylthio group, 2-ethylhexylthio group, etc.), arylthio group (specifically, phenylthio group,
p-methylphenylthio group, p-methoxyphenylthio group, etc.), chelating ligand (specifically, 2,2′-thiobis (4-methyl-6-t-butylphenyl) group, etc.)
Or halogen atoms (specifically chlorine, bromine, iodine,
Fluorine).

These R⁵ , R⁶ , R⁷ And R⁸ Is
They may be the same or different, or
Two of them are CH_Two Or Si (CH_Three )_Two
It may be crosslinked with, for example. a, b and c are respectively
Is an integer of 0 to 4, and d and e are 0 to 3 respectively.
Indicates an integer. Specific examples of such titanium compounds
Is cyclopentadienyltrimethyl titanium; cyclope
Pentadienyl triethyl titanium; cyclopentadienyl
Tripropyl titanium; cyclopentadienyl tributyl
Titanium; Methylcyclopentadienyl trimethyl tita
1,2-dimethylcyclopentadienyltrimethyl
Titanium; 1,2,4-trimethylcyclopentadienyl
Trimethyl titanium; 1,2,3,4-tetramethylsik
Lopentadienyl trimethyl titanium; pentamethylsik
Lopentadienyl trimethyl titanium; pentamethylsik
Lopentadienyltriethyltitanium; pentamethylsik
Lopentadienyltripropyl titanium; pentamethylsilane
Clopentadienyltributyl titanium; Cyclopentadi
Enylmethyl titanium dichloride; cyclopentadienyl
Ethyl titanium dichloride; pentamethylcyclopentadi
Ethenylmethyl titanium dichloride; pentamethylcyclope
N-dienylethyl titanium dichloride; cyclopentadi
Enyldimethyltitanium monochloride; cyclopentadiene
Nyldiethyl titanium monochloride; cyclopentadiene
Rutitanium trimethoxide; cyclopentadienyl titanium
Triethoxide; cyclopentadienyl titanium tripro
Poxide; cyclopentadienyl titanium triphenoxy
P; pentamethylcyclopentadienyl titanium trimetho
Xide; pentamethylcyclopentadienyl titanium tri
Ethoxide; pentamethylcyclopentadienyl titanium
Tripropoxide; pentamethylcyclopentadienyl
Titanium tributoxide; pentamethylcyclopentadiene
Nyl titanium triphenoxide; cyclopentadienyl
Tantric chloride; pentamethylcyclopentadienyl
Titanium trichloride; cyclopentadienyl methoxyti
Tandichloride; cyclopentadienyl dimethoxy tita
Chloride; pentamethylcyclopentadienylmethoxy
Cytitanium dichloride; cyclopentadienyl tribenz
Rutitanium; pentamethylcyclopentadienylmethyldi
Ethoxy titanium; indenyl titanium trichloride; in
Denyl titanium trimethoxide; indenyl titanium trie
Toxide; Indenyl trimethyl titanium; Indenyl
Ribenzyl titanium; (t-butylamido) dimethyl (te
Tramethyl η⁵ -Cyclopentadienyl) silanetita
Dichloride; (t-butylamido) dimethyl (tetra
Methyl η⁵ -Cyclopentadienyl) silane titanium di
Methyl; (t-butylamido) dimethyl (tetramethyl
η ⁵ -Cyclopentadienyl) silane titanium dimethoxide
Examples include sid.

Further, as the titanium compound, a compound represented by the general formula (VII
I)

[Chemical 4] ^Wherein, R ^{9, R 10} are each a halogen atom, an alkoxy group having 1 to 20 carbon atoms, indicates an acyloxy group, k
Indicates 2 to 20. ] A condensed titanium compound represented by the following may be used. Further, the titanium compound may be used in the form of a complex with an ester or ether.
On the other hand, the trivalent titanium compound represented by the general formula (V) typically includes titanium trihalides such as titanium trichloride and cyclopentadienyl titanium compounds such as cyclopentadienyl titanium dichloride. Other examples include those obtained by reducing a tetravalent titanium compound. These trivalent titanium compounds may be used in the form of a complex with an ester or ether.

Examples of zirconium compounds as transition metal compounds include tetrabenzyl zirconium, zirconium tetraethoxide, zirconium tetrabutoxide, bisindenyl zirconium dichloride, triisopropoxy zirconium chloride, zirconium benzyl dichloride and tributoxy zirconium chloride. There are tetrabenzyl hafnium, hafnium tetraethoxide, hafnium tetrabutoxide, etc. in the hafnium compound, and further in the vanadium compound,
Examples include vanadyl bisacetylacetonate, vanadyltriacetylacetonate, triethoxyvanadyl, and tripropoxyvanadyl. Among these transition metal compounds, titanium compounds are particularly suitable.

As the transition metal compound which is the other component (A), a transition metal compound having two ligands having a conjugated π electron, for example, a compound represented by the general formula (IX) M ¹ R ¹¹ R ¹² R ¹³ R ¹⁴・ There are compounds represented by (IX). M ^{1 in} this general formula (IX)
Indicates titanium, zirconium or hafnium. R ¹¹
And R ¹² are a cyclopentadienyl group and a substituted cyclopentadienyl group (specifically, a methylcyclopentadienyl group; a 1,3-dimethylcyclopentadienyl group; a 1,2,4-trimethylcyclo group). Pentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3-di (trimethylsilyl) cyclopentadienyl group; 1,2,4-tri (trimethylsilyl) cyclopentadienyl group; tert-butylcyclopentadienyl group; 1,3-di (tert-butyl) cyclopentadienyl group; 1,
2,4-tri (tertiarybutyl) cyclopentadienyl group, etc., indenyl group, substituted indenyl group (specifically, methylindenyl group; dimethylindenyl group;
A trimethylindenyl group), a fluorenyl group or a substituted fluorenyl group (for example, a methylfluorenyl group). R ¹¹ and R ¹² may be the same or different, and further, R ¹¹ and R ¹² have 1 carbon atoms.
~ 5 alkylidene group (specifically, methine group, ethylidene group, propylidene group, dimethylcarbyl group, etc.) or alkylsilylene group having 1 to 20 carbon atoms and 1 to 5 silicon atoms (specifically, dimethylsilylene group). Group, a diethylsilylene group, a dibenzylsilylene group, etc.).

On the other hand, R ¹³ and R ¹⁴ are a hydrogen atom and a halogen atom (specifically, chlorine, bromine, iodine,
Fluorine), alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, etc.), 6 to 20 carbon atoms Aryl group (specifically, a phenyl group, a naphthyl group, etc.), an arylalkyl group having 7 to 20 carbon atoms (specifically, a benzyl group, etc.), a carbon number of 1 to 1
20 alkoxy groups (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, etc.), aryloxy group having 6 to 20 carbon atoms (Specifically, a phenoxy group etc.), an amino group or a thioalkoxy group having 1 to 20 carbon atoms is shown. This R ¹³ and R
¹⁴ may be the same or different, and are each a hydrocarbon group having 1 to 5 carbon atoms, 1 to 20 carbon atoms, and 1 to 10 silicon atoms.
It may be crosslinked with an alkylsilylene group having 5 or a germanium-containing hydrocarbon group having 1 to 20 carbons and 1 to 5 germanium.

Specific examples of the transition metal compound represented by the general formula (IX) include biscyclopentadienyl titanium dimethyl; biscyclopentadienyl titanium diethyl; biscyclopentadienyl titanium dipropyl;
Bis (cyclopentadienyl) titanium dibutyl; Bis (methylcyclopentadienyl) titanium dimethyl; Bis (tert-butyl cyclopentadienyl) titanium dimethyl; Bis (1,3-dimethylcyclopentadienyl) titanium dimethyl; Bis (1 , 3-Ditertiarybutylcyclopentadienyl) titanium dimethyl; bis (1,2,2
4-trimethylcyclopentadienyl) titanium dimethyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethyl; biscyclopentadienyl titanium dimethyl; bis (trimethylsilylcyclopentadienyl) titanium dimethyl; Bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethyl;
Bis (1,2,4-tris ((trimethylsilyl) cyclopentadienyl) titanium dimethyl; bisindenyl titanium dimethyl; bisfluorenyl titanium dimethyl; methylene biscyclopentadienyl titanium dimethyl; ethylidene biscyclopentadienyl titanium Dimethyl; methylenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; ethylidenebis (2,3,3
4,5-Tetramethylcyclopentadienyl) titanium dimethyl; dimethylsilylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; methylenebisindenyl titanium dimethyl; ethylidene bisindenyl titanium dimethyl; Dimethyl silylene bis indenyl titanium dimethyl; methylene bis fluorenyl titanium dimethyl; ethylidene bis fluorenyl titanium dimethyl; dimethyl silylene bis fluorenyl titanium dimethyl; methylene (tertiary butyl cyclopentadienyl) (cyclopentadienyl) titanium Dimethyl; methylene (cyclopentadienyl) (indenyl) titanium dimethyl; ethylidene (cyclopentadienyl) (indenyl) titanium dimethyl; dimethylsilylene (cyclopentadienyl) (indeni ) Titanium dimethyl; methylene (cyclopentadienyl) (fluorenyl) titanium dimethyl; ethylidene (cyclopentadienyl) (fluorenyl) titanium dimethyl; dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dimethyl; methylene (indenyl) (fluorenyl) ) Titanium dimethyl; ethylidene (indenyl) (fluorenyl) titanium dimethyl; dimethylsilylene (indenyl) (fluorenyl)
Titanium dimethyl; biscyclopentadienyl titanium dibenzyl; bis (tert-butylcyclopentadienyl) titanium dibenzyl; bis (methylcyclopentadienyl) titanium dibenzyl; bis (1,3-dimethylcyclopentadienyl) Titanium dibenzyl; bis (1,2,
4-trimethylcyclopentadienyl) titanium dibenzyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dibenzyl; bispentamethylcyclopentadienyl titanium dibenzyl; bis (trimethylsilylcyclopentadiene Bis (1,3-di- (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; Bis (1,2,4-tris (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; Bisindenyl Titanium dibenzyl; bisfluorenyl titanium dibenzyl; methylene biscyclopentadienyl titanium dibenzyl; ethylidene biscyclopentadienyl titanium dibenzyl; methylene bis (2,3,3
4,5-Tetramethylcyclopentadienyl) titanium dibenzyl; ethylidene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; dimethylsilylene bis (2,3,4,5-tetra Methylcyclopentadienyl) titanium dibenzyl; methylene bis indenyl titanium dibenzyl; ethylidene bis indenyl titanium dibenzyl; dimethyl silylene bis indenyl titanium dibenzyl; methylene bis fluorenyl titanium dibenzyl; ethylidene bis fluorenyl titanium Dibenzyl;
Dimethylsilylene bisfluorenyl titanium dibenzyl;
Methylene (cyclopentadienyl) (indenyl) titanium dibenzyl; ethylidene (cyclopentadienyl)
(Indenyl) titanium dibenzyl; dimethylsilylene (cyclopentadienyl) (indenyl) titanium dibenzyl; methylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; ethylidene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; Dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; methylene (indenyl) (fluorenyl) titanium dibenzyl; ethylidene (indenyl) (fluorenyl) titanium dibenzyl; dimethylsilylene (indenyl) (fluorenyl) titanium dibenzyl; bis Cyclopentadienyl titanium dimethoxide; Biscyclopentadienyl titanium diethoxide; Biscyclopentadienyl titanium dipropoxide; Biscyclopentadienyl titanium dibutoxide Id; biscyclopentadienyl titanium diphenoxide; bis (methylcyclopentadienyl) titanium dimethoxide; bis (1,3-dimethylcyclopentadienyl) titanium dimethoxide; bis (1,2,4- Trimethylcyclopentadienyl) titanium dimethoxide; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethoxide; bispentamethylcyclopentadienyl titanium dimethoxide; bis (trimethylsilylcyclopenta (Dienyl)
Titanium dimethoxide; Bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethoxide; Bis (1,2,4-tris (trimethylsilyl) cyclopentadienyl) titanium dimethoxide; Bisindenyl Titanium dimethoxide; bisfluorenyl titanium dimethoxide; methylene biscyclopentadienyl titanium dimethoxide; ethylidene biscyclopentadienyl titanium dimethoxide; methylene bis (2,3,3
4,5-Tetramethylcyclopentadienyl) titanium dimethoxide; ethylidene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide; dimethylsilylene bis (2,3,4,5) -Tetramethylcyclopentadienyl) titanium dimethoxide; methylenebisindenyl titanium dimethoxide; methylenebis (methylindenyl) titanium dimethoxide; ethylidene bisindenyl titanium dimethoxide; dimethylsilylene bisindenyl titanium dimethoxide Side; methylene bisfluorenyl titanium dimethoxide; methylene bis (methylfluorenyl) titanium dimethoxide; ethylidene bis fluorenyl titanium dimethoxide; dimethylsilylene bisfluorenyl titanium dimethoxide; methylene (cyclopen Dienyl) (indenyl) titanium di methoxide; ethylidene (cyclopentadienyl)
(Indenyl) titanium dimethoxide; dimethylsilylene (cyclopentadienyl) (indenyl) titanium dimethoxide; methylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide; ethylidene (cyclopentadienyl) (fluorenyl) titanium Dimethoxide; dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide; methylene (indenyl) (fluorenyl) titanium dimethoxide; ethylidene (indenyl) (fluorenyl) titanium dimethoxide; dimethylsilylene (indenyl) ( Fluorenyl)
Examples include titanium dimethoxide.

The zirconium compounds include ethylidene biscyclopentadienyl zirconium dimethoxide and dimethylsilylene biscyclopentadienyl zirconium dimethoxide, and the hafnium compounds include ethylidene biscyclopentadienyl hafnium dimethoxide. Examples include methoxide and dimethylsilylene biscyclopentadienyl hafnium dimethoxide. Among these, titanium compounds are particularly preferable. And
In addition to these combinations, 2,2'-thiobis (4-methyl-6-t-butylphenyl) titanium diisopropoxide; 2,2'-thiobis (4-methyl-6-t-butylphenyl) titanium dimethoxy It may be a bidentate-type complex such as a metal complex.

Furthermore, the transition metal compound of the component (A), there is a transition metal compound having a structure represented by the general formula _{(X) R'MX 'p-1} L q ··· (X). In the above general formula (X), R ′ represents a π ligand and represents a condensed polycyclic cyclopentadienyl group in which at least one of the multimembered rings to which the cyclopentadienyl group is condensed and bonded is a saturated ring. .

Examples of such fused polycyclic cyclopentadienyl group include those represented by the general formulas (XI) to (XIII)

[Chemical 5]

[Chemical 6]

[Chemical 7] In the formula, R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and 1 to 2 carbon atoms.
0 alkoxy group, aryloxy group having 6 to 20 carbon atoms,
A thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group or an alkylsilyl group is shown, and each R ¹⁵ , R ¹⁶ and R ¹⁷ is followed. May be the same or different, and w, x, y and z each represent an integer of 1 or more. ] A group represented by the following can be mentioned. Of these, from the viewpoint of catalytic activity and easy synthesis, 4, 5, 6,
The 7-tetrahydroindenyl groups are preferred.

Specific examples of R'are 4, 5, 6,
7-tetrahydroindenyl group; 1-methyl-4,5,
6,7-Tetrahydroindenyl group; 2-methyl-4,
5,6,7-tetrahydroindenyl group; 1,2-dimethyl-4,5,6,7-tetrahydroindenyl group;
1,3-dimethyl-4,5,6,7-tetrahydroindenyl group; 1,2,3-trimethyl-4,5,6,7-
Tetrahydroindenyl group; 1,2,3,4,5,6
7-heptamethyl-4,5,6,7-tetrahydroindenyl group; 1,2,4,5,6,7-hexamethyl-
4,5,6,7-tetrahydroindenyl group; 1,3
4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl group; octahydrofluorenyl group;
1,2,3,4-tetrahydrofluorenyl group; 9-methyl-1,2,3,4-tetrahydrofluorenyl group;
9-methyl-octahydrofluorenyl group and the like can be mentioned.

M represents a metal of Group 3 to 6 of the periodic table or a lanthanum-based metal, and examples thereof include titanium, zirconium, hafnium, lanthanoid-based metals, niobium and tantalum. Among these, titanium is preferable from the viewpoint of catalytic activity. Further, X ′ represents a σ ligand, and specifically, a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and 1 carbon atom. ~ 2
0 alkoxy group, aryloxy group having 6 to 20 carbon atoms,
A thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group, an alkylsilyl group and the like can be mentioned.
May be the same or different from each other, and may be bonded to each other via an arbitrary group. Further, specific examples of X'include a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a benzyl group, a phenyl group,
Trimethylsilylmethyl group, methoxy group, ethoxy group,
Examples thereof include a phenoxy group, a thiomethoxy group, a thiophenoxy group, a dimethylamino group and a diisopropylamino group. L is a Lewis base, p is the valence of M,
q represents 0, 1 or 2. When there are a plurality of Ls, each L may be the same or different.

Examples of the transition metal compound represented by the general formula (X) include 4,5,6,7-tetrahydroindenyl titanium trichloride; 4,5,6,7-tetrahydroindenyl titanium trimethyl; 4,5
6,7-Tetrahydroindenyl titanium tribenzyl; 4,5,6,7-Tetrahydroindenyl titanium trimethoxide; 1-Methyl-4,5,6,7-tetrahydroindenyl titanium trichloride; 1-methyl- 4,5,6,7-Tetrahydroindenyl titanium trimethyl; 1-methyl-4,5,6,7-tetrahydroindenyl titanium tribenzyl; 1-methyl-
4,5,6,7-Tetrahydroindenyl titanium trimethoxide; 2-methyl-4,5,6,7-tetrahydroindenyl titanium trichloride; 2-methyl-
4,5,6,7-Tetrahydroindenyl titanium trimethyl; 2-methyl-4,5,6,7-tetrahydroindenyl titanium tribenzyl; 2-methyl-4,
5,6,7-Tetrahydroindenyltitanium trimethoxide; 1,2-Dimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride; 1,2-Dimethyl-4,5,6,7-tetrahydro Indenyl titanium trimethyl; 1,2-dimethyl-4,5,6,7
-Tetrahydroindenyl titanium tribenzyl;
1,2-dimethyl-4,5,6,7-tetrahydroindenyl titanium trimethoxide; 1,3-dimethyl-
4,5,6,7-Tetrahydroindenyl titanium trichloride; 1,3-Dimethyl-4,5,6,7-tetrahydroindenyl titanium trimethyl; 1,3-Dimethyl-4,5,6,7-tetrahydro Indenyl titanium tribenzyl; 1,3-dimethyl-4,5,6
7-Tetrahydroindenyltitanium trimethoxide; 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride; 1,2,3
-Trimethyl-4,5,6,7-tetrahydroindenyl titanium trimethyl; 1,2,3-trimethyl-
4,5,6,7-Tetrahydroindenyl titanium tribenzyl; 1,2,3-trimethyl-4,5,6,7
-Tetrahydroindenyl titanium trimethoxide;
1,2,3,4,5,6,7-heptamethyl-4,5,
6,7-Tetrahydroindenyl titanium trichloride; 1,2,3,4,5,6,7-heptamethyl-4,
5,6,7-Tetrahydroindenyl titanium trimethyl; 1,2,3,4,5,6,7-heptamethyl-
4,5,6,7-Tetrahydroindenyl titanium tribenzyl; 1,2,3,4,5,6,7-heptamethyl-4,5,6,7-tetrahydroindenyl titanium trimethoxide; 1,2 , 4,5,6,7-Hexamethyl-4,5,6,7-tetrahydroindenyltitanium trichloride; 1,2,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindene Nyltitanium trimethyl; 1,2,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyltitanium tribenzyl; 1,2,4,5,6,7-hexamethyl-4,5 , 6,7-Tetrahydroindenyltitanium trimethoxide; 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyltitanium trichloride 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl titanium trimethyl; 1,3,4,5,6,7-hexamethyl-4,5,6,7- Tetrahydroindenyl titanium tribenzyl; 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl titanium trimethoxide; octahydrofluorenyl titanium trichloride; octahydrofluore Nyltitanium trimethyl; Octahydrofluorenyltitanium tribenzyl; Octahydrofluorenyltitanium trimethoxide; 1,2,3,4-Tetrahydrofluorenyltitanium trichloride; 1,2,3,4-Tetrahydrofluore Nyltitanium trimethyl; 1,2,3,4
-Tetrahydrofluorenyl titanium tribenzyl;
1,2,3,4-Tetrahydrofluorenyltitanium trimethoxide; 9-methyl-1,2,3,4-tetrahydrofluorenyltitanium trichloride; 9-methyl-1,2,3,4-tetrahydro Fluorenyl titanium trimethyl; 9-methyl-1,2,3,4-tetrahydrofluorenyl titanium tribenzyl; 9-methyl-1,2,3,4-tetrahydrofluorenyl titanium trimethoxide; 9-methyl -Octahydrofluorenyltitanium trichloride; 9-methyl-octahydrofluorenyltitanium trimethyl; 9-methyl-
Octahydrofluorenyl titanium tribenzyl; 9
-Methyl-octahydrofluorenyltitanium trimethoxide and the like, and those in which titanium in these compounds is replaced with zirconium or hafnium, or similar compounds of other group or lanthanide series transition metal elements. Of course, it is not limited to these. Among these, titanium compounds are preferable from the viewpoint of catalytic activity. In the present invention, one kind of these transition metal compounds (A) may be used,
You may use it in combination of 2 or more type.

In the catalyst for polymer production of the present invention,
As the component (B), the organic aluminooxy compound I or II having the above-mentioned specific properties is used. This organic aluminooxy compound may be used alone or in combination of two or more. Further, as the component (B), a combination of the organic aluminoxy compound and an ionic compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex may be used, if desired. Good. The ionic compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A), which is optionally used, is a coordination complex compound composed of an anion having a plurality of groups bound to a metal and a cation. Can be mentioned.

Anions and cuts in which a plurality of groups are bound to a metal
There are various coordination complex compounds consisting of on.
Is represented by, for example, the following general formula (XIV) or (XV)
The compound can be preferably used.   ([L¹-H]^{g +})_h   ([M^Two X¹ X^Two ... Xⁿ ]^(Nm)-)_i       ... (XIV)   ([L^Two ]^{g +})_h   ([M^Three X¹ X^Two ... Xⁿ ]^(Nm)-)_i         ... (XV) [In Formula (XIV) or (XV), L^Two Is M described later^Four , R
¹⁸R¹⁹M⁵ Or R^{Two 0} _Three C and L¹ Is louis
Base, M^Two And M^Three Are the 5th group of the periodic table
Metals selected from group 15 and M^Four Is the 8th to 1st group of the periodic table
Metals selected from Group 2 and M⁵ Is the 8th to 10th members of the periodic table
Metal selected from the group X¹ ~ Xⁿ Is the hydrogen source
Child, dialkylamino group, alkoxy group, aryloxy
Si group, C1-C20 alkyl group, C6-C20
Aryl group, alkylaryl group, arylalkyl
Group, substituted alkyl group, organic metalloid group or halogen source
Indicates a child. R¹⁸And R¹⁹Are each cyclopenta
Dienyl group, substituted cyclopentadienyl group, indenyl
Group or fluorenyl group, R²⁰Represents an alkyl group. m
Is M^Two , M^Three Is an integer of 1 to 7, and n is 2 to 8
Integer, g is L¹ -H, L ^Two Ion valence of 1 to 7
Number, h is an integer of 1 or more, i = h × g / (nm)
It ]

Specific examples of M ² and M ³ include B and A.
l, Si, P, As, Sb and other atoms, specific examples of M ⁴ include Ag, Cu and other atoms, and specific examples of M ⁵ include Fe, Co, Ni and other atoms. . X ¹
Specific examples of ^Xn are, for example, dimethylamino group, diethylamino group as a dialkylamino group, methoxy group, ethoxy group, n-butoxy group as an alkoxy group, phenoxy group as an aryloxy group, 2,6-dimethylphenoxy group. , Naphthyloxy group, carbon number 1-2
As an alkyl group of 0, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group, a 2-ethylhexyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group. As phenyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl)
Phenyl group, 4-tert-butylphenyl group, 2,
6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 1,2-dimethylphenyl group, F, Cl, Br, I as halogen, pentamethylantimony group as organic metalloid group, trimethylsilyl Group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron group. Specific examples of the substituted cyclopentadienyl group represented by each of R ¹⁸ and R ¹⁹ include a methylcyclopentadienyl group, a butylcyclopentadienyl group,
Examples include a pentamethylcyclopentadienyl group.

In the present invention, a plurality of groups are bound to the metal.
The anion specifically includes B (C₆ F₅)_Four ^-
 , B (C₆ HF_Four)_Four ^- , B (C₆ H_Two F_Three)_Four 
^- , B (C₆ H_Three F_Two)_Four ^- , B (C₆ H_Four F)
_Four ^- , B (C₆ CF_Three F_Four)_Four ^-, B (C₆ H₅)_Four 
^- , BF_Four ^- , PF₆ ^- , P (C₆ F₅)₆ ^- , A
l (C₆ HF_Four)_Four ^- Etc. Also, Catio
Cp_Two Fe⁺, (MeCp)_Two Fe
⁺ , (TBuCp)_Two Fe⁺ , (Me_Two Cp)_Two 
Fe⁺ , (Me_Three Cp)_Two Fe⁺ , (Me_Four C
p)_Two Fe⁺ , (Me₅ Cp)_Two Fe⁺ , Ag
⁺ , Na⁺ , Li⁺ Metal cations such as pyridini
Um, 2,4-dinitro-N, N-diethylaniliniu
Mu, diphenylammonium, p-nitroaniliniu
, 2,5-dichloroanilinium, p-nitro-N,
N-dimethylanilinium, quinolinium, N, N-di
Methylanilinium, N, N-diethylanilinium, etc.
Nitrogen-containing compounds of triphenylcarbenium, tri
(4-methylphenyl) carbenium, tri (4-meth)
A carbenium compound such as xylphenyl) carbenium;
CH_Three PH_Three ⁺ , C_Two H₅ PH_Three ⁺, C_Three H₇ 
PH_Three ⁺ , (CH_Three )_Two PH_Two ⁺ , (C_Two H
₅ )_Two PH _Two ⁺ , (C_Three H₇ )_Two PH_Two ⁺ ，
(CH_Three )_Three PH⁺, (C_Two H₅)_Three PH⁺，
(C_ThreeH₇ )_Three PH⁺, (CF_Three )_Three PH⁺，
(CH_Three)_Four P⁺ , (C_Two H₅ )_Four P⁺ , (C_Three
 H₇ )_Four P⁺ Alkylphosphonium Io such as
And C₆ H₅ PH_Three ⁺ , (C₆ H₅ )_Two P
H_Two ⁺ , (C₆ H₅ )_Three PH⁺ , (C₆ H₅ )
_Four P⁺ , (C_Two H₅ )_Two(C₆ H₅ ) PH⁺ ，
(CH_Three ) (C₆ H₅ ) PH_Two ⁺ , (CH_Three ) _Two
 (C₆ H₅ ) PH⁺ , (C_Two H₅ )_Two (C₆ H
₅ )_Two P⁺ Arylphosphonium ions such as
Is mentioned.

Among the compounds of the general formulas (XIV) and (XV),
Specifically, the following can be used particularly preferably. For example, as the compound of the general formula (XIV), triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate and the like can be mentioned. Further, for example, as the compound of the general formula (XV), pyridinium tetrakis (pentafluorophenyl) borate, pyrrolinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (penta) Fluorophenyl) methyldiphenylammonium borate, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
Decamethylferrocenium borate, Tetrakis (pentafluorophenyl) borate acetylferrocenium, Tetrakis (pentafluorophenyl) formylferrocenium borate, Tetrakis (pentafluorophenyl) cyanocyanoferrocenium borate, Silver tetraphenylborate, Tetrakis ( Pentafluorophenyl) silver borate, tetraphenyl trityl borate, tetrakis (pentafluorophenyl)
Examples thereof include trityl borate, silver hexafluoroarsenate, silver hexafluoroantimonate and silver tetrafluoroborate. These ionic compounds may be used alone or in combination of two or more.

In the catalyst for producing a polymer of the present invention,
If desired, an alkyl group-containing metal compound can be used as the component (C). Here, as the alkyl group-containing metal compound, there are various compounds, for example, the general formula (XV
^{_{I) R 21 u Al (OR}} 22) v E 3-u-v ··· (XVI) ^{wherein, R 21} and ^{R 22} are each 1 to carbon atoms
8, preferably 1 to 4 alkyl groups, and E represents a hydrogen atom or a halogen atom. In addition, u is 0 <u ≦
3, preferably 2 or 3, most preferably 3, and v is 0 ≦ v <3, preferably 0 or 1. Alkyl group-containing aluminum compounds or formula _{^{(XVII) R 21 2 Mg ·····}} (XVII) wherein represented ^{by], R 21} is as defined above. ] An alkyl group-containing magnesium compound represented by the general formula (XV
_{^{III) R 21 2 Zn ····· (}} XVIII) ^{wherein, R 21} is as defined above. ] An alkyl group-containing zinc compound represented by

Of these alkyl group-containing compounds, alkyl group-containing aluminum compounds, especially trialkylaluminum and dialkylaluminum compounds are preferred. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dialkyl Dialkylaluminum halides such as n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride and di-t-butylaluminum chloride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and dimethylaluminum ethoxide, Dimethyl aluminum hydride, diethyl aluminum hydride Id, dialkylaluminum hydride such as diisobutylaluminum hydride and the like. Further, dialkyl magnesium such as dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium and diisopropyl magnesium, and dialkyl zinc such as dimethyl zinc, diethyl zinc, di-n-propylethyl zinc and diisopropyl zinc can be mentioned. The alkyl group-containing metal compound as the component (C) may be used alone or in combination of two or more.

The method for preparing the polymer-producing catalyst of the present invention is not particularly limited, and various methods can be applied. For example, when preparing a catalyst solution consisting of components (A), (B) and (C), the components (1), (A) and (B) are brought into contact with each other in an appropriate organic solvent, and C) component addition method, (2) (A) component and (C) component contact, and (B) component addition method
(3) Method of contacting the components (B) and (C) and adding the component (A) thereto, (4) Method of simultaneously contacting the components (A), (B) and (C), etc. Can be used. The addition or contact of each component can be performed not only at the polymerization temperature but also at a temperature of 0 to 100 ° C. The organic solvent used for preparing the catalyst solution for polymer production has, for example, 5 carbon atoms.
~ 18 aliphatic hydrocarbons and alicyclic hydrocarbons, 6 to 6 carbon atoms
20 inert solvents such as aromatic hydrocarbons, specifically n
-Pentane, isopentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more. Moreover, the monomer used for polymerization can also be used depending on the kind.

The thus obtained catalyst for polymer production of the present invention is used for the polymerization of a polymerizable unsaturated compound, and the polymerizable unsaturated compound is one which can be polymerized by the above catalyst for polymer production. It is not particularly limited as long as it is, and examples thereof include olefins, cyclic olefins, cyclic diolefins, chain conjugated diolefins, chain non-conjugated diolefins, aromatic vinyl compounds, and alkynes.

Examples of olefins include ethylene;
Propylene; butene-1; pentene-1; hexene-
1; heptene-1; octene-1; nonene-1; decene-1; 4-phenylbutene-1; 6-phenylhexene-1; 3-methylbutene-1; 4-methylpentene-
1; 3-methylpentene-1; 3-methylhexene-
1; 4-methylhexene-1; 5-methylhexene-
1,3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; 3
5,5-trimethylhexene-1; α-olefins such as vinylcyclohexane, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene; 3-fluoropropene; trifluoroethylene; 3 And halogen-substituted α-olefins such as 4-dichlorobutene-1.

Examples of the cyclic olefins include cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-
Methyl norbornene; 7-methyl norbornene; 5,
5,6-trimethylnorbornene; 5-phenylnorbornene; 5-benzylnorbornene and the like, and examples of cyclic diolefins include 5-ethylidenenorbornene; 5-vinylnorbornene; dicyclopentadiene; norbornadiene and the like.

Further, as the chain conjugated diolefins,
For example, 1,3-butadiene; isoprene and the like, and as the chain non-conjugated diolefins, for example, 1,
4-hexadiene; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; 5-methyl-
1,4-dienes such as 1,4-heptadiene, 1,5
-Hexadiene; 3-methyl-1,5-hexadiene;
3-Ethyl-1,5-hexadiene; 3,4-Dimethyl-1,5-hexadiene; 1,5-heptadiene; 5-
Methyl-1,5-heptadiene; 6-methyl-1,5-
Heptadiene; 1,5-octadiene; 5-methyl-
1,5-octadiene; 1,5-dienes such as 6-methyl-1,5-octadiene, 1,6-octadiene;
6-methyl-1,6-octadiene; 7-methyl-1,
6-octadiene; 7-ethyl-1,6-octadiene; 1,6-nonadiene; 7-methyl-1,6-nonadiene; 4-methyl-1,6-nonadiene and the like 1,6-
Dienes, 1,7-octadiene; 3-methyl-1,7
-Octadiene; 3-ethyl-1,7-octadiene;
3,4-Dimethyl-1,7-octadiene; 3,5-Dimethyl-1,7-octadiene; 1,7-Nonadiene;
Examples thereof include 1,7-dienes such as 8-methyl-1,7-nonadiene, 1,11-dodecadiene and 1,13-tetradecadiene.

Further, examples of the aromatic vinyl compound include styrene and α-methylstyrene, p-methylstyrene; m-methylstyrene; o-methylstyrene; pt-butylstyrene; p-phenylstyrene. Alkyl or aryl styrenes, p-methoxystyrene; m-methoxystyrene; p-ethoxystyrene; pn-propoxystyrene; alkoxystyrenes such as pn-butoxystyrene, p-chlorostyrene; p-bromostyrene. Halogenated styrenes such as p-iodostyrene, p-trimethylsilylstyrene;
m-trimethylsilylstyrene; o-trimethylsilylstyrene; p-dimethylphenylsilylstyrene; p-
Methyldiphenylsilylstyrene; alkyl- or aryl-group-containing silylstyrenes such as p-triphenylsilylstyrene, p-dimethylchlorosilylstyrene; p
-Methyldichlorosilylstyrene; halogen-containing silylstyrenes such as p-trichlorosilylstyrene, p-
(2-propenyl) styrene; m- (2-propenyl)
Styrene; p- (3-butenyl) styrene; m- (3-
Butenyl) styrene; o- (3-butenyl) styrene;
Alkenyl styrenes such as p- (3-butenyl) -α-methylstyrene, and further 4-vinylbiphenyl; 3
-Vinyl biphenyl; vinyl biphenyls such as 2-vinyl biphenyl, 1- (4-vinylphenyl) naphthalene; vinylphenyl naphthalene such as 2- (3-vinylphenyl) naphthalene; 1- (4-vinylphenyl)
Anthracene; vinylphenylanthracenes such as 2- (4-vinylphenyl) anthracene; 1- (4-vinylphenyl) phenanthrene; vinylphenylphenanthrenes such as 2- (4-vinylphenyl) phenanthrene; 1- (4-vinyl Phenyl) pyrene; 2- (4
Examples thereof include vinylphenylpyrenes such as -vinylphenyl) pyrene. Examples of alkynes include acetylene and phenylacetylene. These polymerizable unsaturated compounds may be used alone or in combination of two or more kinds.

The method for polymerizing the above-mentioned polymerizable unsaturated compound using the catalyst for polymer production of the present invention is not particularly limited, and examples thereof include slurry polymerization method, high temperature solution polymerization method, gas phase polymerization method, bulk polymerization method, and suspension polymerization method. Any polymerization method such as a turbid polymerization method can be adopted. When a polymerization solvent is used, the solvent is, for example, an inert solvent such as an aliphatic hydrocarbon having 5 to 18 carbon atoms, an alicyclic hydrocarbon, or an aromatic hydrocarbon having 6 to 20 carbon atoms, specifically n. -Pentane, isopentane, hexane, heptane, octane, nonane, decane,
Tetradecane, cyclohexane, benzene, toluene,
Examples include xylene and ethylbenzene. These may be used alone or in combination of two or more. Moreover, the monomer used for polymerization can also be used depending on the kind.

The polymerization temperature is not particularly limited, but it is usually selected in the range of 0 to 350 ° C, preferably 20 to 250 ° C. On the other hand, although the polymerization pressure is not particularly limited, it is usually selected in the range of 0 to 150 kg / cm ² G, preferably 0 to 100 kg / cm ² G. Examples of the method for adjusting the molecular weight of the polymer include the type and amount of each catalyst component, the selection of the polymerization temperature, and the introduction of hydrogen.

[0053]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The A ₁ / A ₂ ratio of methylaluminoxane in Examples and Comparative Examples was defined in the text of the specification.
²⁷ is the area ratio in the Al-NMR spectrum. Example 1 (1) Preparation of methylaluminoxane Copper sulfate pentahydrate 20.0 in 200 ml of toluene
After adding g (0.08 mol), 18 g (0.25 mol) of trimethylaluminum was added at -5 ° C and 24 at -5 ° C.
The reaction was carried out for a time to obtain a toluene solution of methylaluminoxane. About this methylaluminoxane, ²⁷ Al-NM
When R was measured and the A ₁ / A ₂ ratio was determined, it was 0.01. The amount of water involved in the reaction / the amount of trimethylaluminum (molar ratio) was 0.8. (2) Polymerization of styrene 10 ml of styrene and 5 μmol of triisobutylaluminum were placed in a 20 ml container which had been dried and replaced with nitrogen, and the container was sealed and the temperature was raised to 70 ° C.
On the other hand, in a 100 ml container that had been dried and purged with nitrogen, the toluene solution of the methylaluminoxane obtained in (1) above was used as methylaluminoxane, 11.2 mmol, triisobutylaluminum 3.8 mmol, and pentamethylcyclopentadienyltitanium. Trimethoxide 15
Charge 0 micromol and toluene, mix at room temperature,
50 milliliters of premixed catalyst solution was prepared. 83 microliters of this catalyst solution was added to the above-mentioned container containing styrene and triisobutylaluminum, and polymerization was carried out at 70 ° C. for 1 hour. After the reaction was completed, the product was dried to obtain 3.11 g of syndiotactic polystyrene (SPS). In this case, the catalytic activity was 285 kg / gTi.

Example 2 (1) Preparation of methylaluminosaxane 18 g (0.25 mol) of trimethylaluminum was added to 200 ml of toluene and cooled to -78 ° C.
Then, 3.4 g (0.189 mol) of deoxygenated water was added to 0.0
The temperature of the reaction system is -2 over 19 minutes at a rate of 1 mol / min.
After adding dropwise while maintaining at 0 ° C, the mixture was further reacted at 20 ° C for 5 hours to prepare a toluene solution of methylaluminoxane. About this methylaluminoxane, ²⁷ A
When 1-NMR was measured and the ratio of A ₁ / A ₂ was obtained,
It was 0.005. The amount of water / the amount of trimethylaluminum (molar ratio) was 0.76. (2) Polymerization of styrene Using the toluene solution of methylaluminoxane obtained in (1) above, styrene was polymerized in the same manner as in Example 1- (2), and 3.20 g of SPS was obtained. In this case, the catalytic activity was 294 kg / gTi.

Example 3 (1) Preparation of methylaluminoxane 18 g (0.25 mol) of trimethylaluminum was added to 200 ml of toluene and cooled to -50 ° C.
Then, 3.4 g (0.189 mol) of deoxygenated water was added to 0.0
The temperature of the reaction system was reduced to −38 at a rate of 05 mol / min for 38 minutes.
After adding dropwise while maintaining at 30 ° C., the mixture was further reacted at 20 ° C. for 5 hours to prepare a toluene solution of methylaluminoxane. About this methylaluminoxane, ²⁷ A
When 1-NMR was measured and the ratio of A ₁ / A ₂ was obtained,
It was 0.08. The amount of water / the amount of trimethylaluminum (molar ratio) was 0.76. (2) Polymerization of Styrene Polymerization of styrene was carried out in the same manner as in Example 1- (2) using the toluene solution of methylaluminoxane obtained in (1) above, and 2.67 g of SPS was obtained. In this case, the catalytic activity was 245 kg / gTi.

Example 4 (1) Preparation of methylaluminoxane Copper sulfate pentahydrate 23.5 in 200 ml of toluene
After adding g (0.094 mol), 18 g (0.25 mol) of trimethylaluminum was added at 0 ° C. and reacted at 0 ° C. for 24 hours to prepare a toluene solution of methylaluminoxane. About this methylaluminoxane, temperature 30 ℃
The amount of insoluble components in the following mixed solvent of toluene and hexane in a volume ratio of 2: 5 was determined, and was 27.7% in terms of aluminum atom. (2) Polymerization of styrene Using the toluene solution of methylaluminoxane obtained in (1) above, styrene was polymerized in the same manner as in Example 1- (2), and 3.16 g of SPS was obtained. In this case, the catalytic activity was 290 kg / gTi.

Example 5 (1) Preparation of methylaluminoxane 18 g (0.25 mol) of trimethylaluminum was added to 200 ml of toluene and cooled to -78 ° C.
Then, deoxidized water (3.6 g, 0.20 mol) was added to 0.00
The temperature of the reaction system is -2 at a rate of 5 mol / min for 40 minutes.
After the solution was added dropwise while maintaining it at 0 ° C., it was further reacted at 25 ° C. for 5 hours to prepare a toluene solution of methylaluminoxane. About this methylaluminoxane, temperature 30
The amount of insoluble components in a mixed solvent of toluene and hexane in a volume ratio of 2: 5 at or below 0 ° C. was calculated to be 14.3% in terms of aluminum atom. The amount of water / the amount of trimethylaluminum (molar ratio) was 0.80. (2) Polymerization of styrene Using the toluene solution of methylaluminoxane obtained in (1) above, styrene was polymerized in the same manner as in Example 1- (2), and 2.86 g of SPS was obtained. In this case, the catalytic activity was 260 kg / gTi.

Example 6 (1) Preparation of methylaluminoxane 18 g (0.25 mol) of trimethylaluminum was added to 200 ml of toluene and cooled to -50 ° C.
Then, deoxidized water (3.6 g, 0.20 mol) was added to 0.00
The temperature of the reaction system was -1 at a rate of 5 mol / min for 40 minutes.
After adding dropwise while maintaining at 0 ° C., the mixture was further reacted at 22 ° C. for 5 hours to prepare a toluene solution of methylaluminoxane. About this methylaluminoxane, temperature 30
The amount of the insoluble component in a mixed solvent of toluene and hexane at a temperature of not higher than 2.degree. C. in a volume ratio of 2: 5 was determined and found to be 6.7% in terms of aluminum atom. The amount of water / the amount of trimethylaluminum (molar ratio) was 0.80. (2) Polymerization of styrene Using the toluene solution of methylaluminoxane obtained in (1) above, styrene was polymerized in the same manner as in Example 1- (2), and 2.40 g of SPS was obtained. In this case, the catalytic activity was 200 kg / gTi.

Example 7 (Polymerization of Ethylene) 400 ml of toluene and 1 mmol of the aluminoxane used in Example 1 as aluminum atoms, and 5 microliters of biscyclopentadienylzirconium dichloride were placed in an autoclave having an internal volume of 1 liter which was replaced with nitrogen. Mols were sequentially added and the temperature was raised to 80 ° C. Next, ethylene was continuously introduced into the autoclave at a pressure of 8 kg.
The polymerization reaction was carried out at 1 / cm ² for 1 hour. After the reaction, methanol was added to decompose the catalyst and then dried to obtain 131 g of polyethylene. The polymerization activity at this time is 287k.
It was g / g · Zr.

Example 8 (Polymerization of Propylene) Except that in Example 7, ethylenebisindenylzirconium dimethyl was used instead of biscyclopentadienylzirconium dichloride, and propylene was used instead of ethylene. The same operation as in Example 7 was performed to obtain 92 g of polypropylene. The polymerization activity at this time was 194 kg / g · Zr. The isotacticity of the obtained polypropylene was 72% in terms of pentad fraction (mmmm fraction).

Comparative Example 1 (1) Preparation of methylaluminoxane 18 g (0.25 mol) of trimethylaluminum was added to 200 ml of toluene and cooled to 5 ° C. Then, deoxidized water (3.6 g, 0.20 mol) was added at a rate of 0.001 mol / min for 4.2 hours to bring the temperature of the reaction system to -5 ° C.
After adding dropwise while maintaining at, the reaction was further carried out at 22 ° C. for 5 hours to prepare a toluene solution of methylaluminoxane. About this methylaluminoxane, ²⁷ Al-N
When the MR was measured and the A ₁ / A ₂ ratio was determined, it was 0.2. The amount of insoluble components in this methylaluminoxane in a mixed solvent of toluene and hexane at a temperature of 30 ° C. or lower at a volume ratio of 2: 5 was calculated to be 4.5% in terms of aluminum atom. The amount of water / the amount of trimethylaluminum (molar ratio) was 0.80. (2) Polymerization of styrene When the toluene solution of methylaluminoxane obtained in (1) above was used to polymerize styrene in the same manner as in Example 1- (2), 1.63 g of SPS was obtained. In this case, the catalytic activity was 150 kg / gTi.

[0062]

The organoaluminoxy compound of the present invention is
It is possible to provide a homogeneous catalyst having specific properties, high catalytic activity, and stable activity. Further, the catalyst for polymer production of the present invention using the organic aluminooxy compound has a high catalytic activity and has stable activity, and an olefin or styrene homopolymer or copolymer is industrially advantageous. Can be given.

[Brief description of drawings]

FIG. 1 is a schematic view of a ²⁷ Al-NMR spectrum of an organic aluminooxy compound for explaining the A ₁ / A ₂ ratio in the organic aluminooxy compound of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H048 AA01 AB40 VA80 VB20 VB90                 4J128 AA01 AB00 AB01 AC01 AC10                       AC13 AC14 AC20 AC25 AC28                       AC32 AC38 AD01 AD02 AD05                       AD06 AD08 AD11 AD13 BA00A                       BA01B BA02B BB00A BB01B                       BB02B BC05B BC09B BC12B                       BC15B BC16B BC24B BC25B                       BC27B EA01 EB02 EB04                       EB05 EB07 EB08 EB09 EB10                       EB12 EB13 EB14 EB17 EB18                       EB21 EB22 FA01 FA02 FA03                       FA04 FA06 FA07 GA12 GB01

Claims (4)

[Claims] 1. A ²⁷ Al-nuclear magnetic resonance spectrum ( ²⁷ Al
-NMR) around 150 ppm and 60 ppm
Let A ₁ be the area of a region surrounded by a line segment connecting a local minimum point existing between continuous curves a and b each including a peak appearing in the vicinity and a point where the curve b is in contact with the baseline and the curve b. when the area of the region surrounded by the above continuous curve a and b and the base line was a _2, organic aluminoxane oxy-compound a ₁ / a ₂ ratio is equal to or more than 0.1. 2. An organic aluminooxy compound characterized in that the amount of insoluble component in a mixed solvent of toluene and hexane at a temperature of 30 ° C. or lower at a volume ratio of 2: 5 is 5% or more in terms of aluminum atom. 3. A catalyst for polymer production comprising (A) a transition metal compound and (B) the organoaluminoxy compound according to claim 1. 4. (A) transition metal compound, (B) claim 1.
Alternatively, a catalyst for polymer production, which comprises the organoaluminoxy compound according to 2 and (C) an alkyl group-containing metal compound.