JP2003096135A - Poly (butene-1) and its production method, and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a poly(butene-1) which imparts softening properties, and has excellent moldability or the like and an excellent physical properties balance while retaining heat resistance, and to provide a production method of the poly(butene-1) and a molding thereof. SOLUTION: The poly(butene-1) has a melting point (TmP) of>=80 deg.C defined using a differential scanning calorimetry (DSC), an intrinsic viscosity of 0.5-4.0 [η](dl/g), and a relationship of the melting point (TmP) ( deg.C) and a melting endotherm (ΔHP) (J/g), which is represented by the formula: TmP>3.07ΔHP+3. The poly(butene-1) is produced using a two crosslinked metallocene catalyst, and a Ti-Mg type catalyst or a non-two crosslinked metallocene catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to poly (butene-
The present invention relates to 1), a method for producing the same, and a molded article, and more specifically, it relates to poly (butene-1) having an excellent physical property balance, a method for producing the same, and a molded article.

[0002]

2. Description of the Related Art A method for producing poly (butene-1) is as follows: a solid catalyst containing magnesium, halogen and tetravalent titanium, a gas phase in the presence of an organoaluminum cocatalyst component and a catalyst obtained from an electron donor. A method for producing by polymerization is known, and JP-A-63-165408 discloses a method of carrying out preliminary polymerization in a specific solvent prior to the main polymerization of the method, and JP-A-64-60613 discloses. A method of conducting homopolymerization or copolymerization of butene-1 after prepolymerization in the absence of a solvent is disclosed in JP-A-64-81.
Japanese Patent No. 804 describes a method for homopolymerizing or copolymerizing butene-1 in the presence of a Ziegler-Natta catalyst composition obtained by prepolymerizing in a specific solvent. Poly (butene-1) obtained by these methods
Has excellent stereoregularity and creep resistance, but has problems in formability such as crystal transformation and lack of dimensional stability and impact resistance, and its application is limited to hot water pipes. There is.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides poly (butene-1) excellent in balance of physical properties by imparting softness while maintaining heat resistance and having excellent moldability, and a method for producing the same. The object is to provide a molded body.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a dibridged metallocene catalyst and a Ti--Mg type catalyst or a non-bisbridged metallocene catalyst are used. By homopolymerizing butene-1, it is possible to impart softness while maintaining heat resistance. Also, since it is a reactor mixed catalyst system, the labor of blending is saved, and it is easy to mix evenly and has an excellent physical property balance. The present invention has been achieved by finding that the above materials can be obtained.

That is, the present invention provides the following poly (butene-1)
And a method for producing the same and a molded body thereof. 1. Poly (butene-1) satisfying the following conditions (1) to (3). (1) Using a differential scanning calorimeter (DSC), the sample was melted in a nitrogen atmosphere at 190 ° C. for 5 minutes, and then at 5 ° C./minute −1.
After cooling to 0 ° C and holding at -10 ° C for 5 minutes, 10 ° C
The melting point (TmP), which is defined as the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by raising the temperature at 1 / min, is 80 ° C. or higher (2) intrinsic viscosity [η] (dl / g) is 0.5 ≦
[Η] ≦ 4.0 (3) The melting point (TmP) (° C.) defined above,
At this time, the relationship between the melting endotherm (ΔHP) (J / g) is
TmP> 3.27 ΔHP + 3 2. (1) Bi-bridged metallocene catalyst and (2a) Ti-Mg
System catalyst or (2b) non-dibridged metallocene catalyst,
Butene-1 is homopolymerized.
The method for producing poly (butene-1). 3. (1) The dibridged metallocene catalyst is (A) the general formula (I).

[0006]

[Chemical 2]

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group and a heterocyclopenta group, respectively. A ligand selected from a dienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which forms a crosslinked structure via A ¹ and A ^2. And they may be the same or different from each other, X represents a σ-bonding ligand, and when there are a plurality of Xs,
Multiple X's may be the same or different, other X's,
It may be crosslinked with E ¹ , E ² or Y. Y represents a Lewis base, and when there are plural Y's, the plural Y's may be the same or different and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, which is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
Germanium-containing group, tin-containing group, -O-, -CO-,
_{-S -, - SO 2 -,} - Se -, - NR 1 -, - PR 1
-, - P (O) R 1 -, - BR 1 - or -AlR ¹ - are shown, R ¹ represents a hydrogen atom, a halogen atom, having from 1 to 20 carbon atoms
Or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. q is an integer of 1 to 5 and represents [(valence of M) -2], and r is an integer of 0 to 3. ] And (B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex, and (B-2) Poly (butene-1) as described in 2 above, which is a catalyst containing a component selected from aluminoxanes.
Manufacturing method. 4. (2a) A Ti-Mg-based catalyst is a catalyst composed of a solid catalyst component obtained by bringing a titanium compound, a magnesium compound and an electron donating compound into contact with each other, an organosilicon compound or a diether compound, and an organoaluminum compound. The method for producing poly (butene-1) according to 2 above. 5. (2b) A non-dibridged metallocene catalyst reacts with a transition metal compound having a cyclopentadienyl ring of Group 4 of the periodic table and methylaluminoxane or a transition metal compound of Group 4 of the periodic table to form an ionic 3. The method for producing poly (butene-1) according to the above item 2, which is a catalyst comprising a complex-forming compound and an organoaluminum compound. 6. Vicat softening point Tv (° C) and tensile elastic modulus E (MP
Molded product Tv of poly (butene-1) in which the relationship of a) satisfies the following relationship: Tv> 0.1989E + 17

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION [1] Poly (butene-
1), [2] poly (butene-1) production method, and [3] molded body will be described in detail in order.

[1] Poly (butene-1) The poly (butene-1) of the present invention has the following (1) to (3).
It satisfies the condition of. (1) Using a differential scanning calorimeter (DSC), the sample was melted in a nitrogen atmosphere at 190 ° C. for 5 minutes, and then at 5 ° C./minute −1.
After cooling to 0 ° C and holding at -10 ° C for 5 minutes, 10 ° C
The melting point (TmP) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at 1 / min is 80 ° C. or higher. (2) Intrinsic viscosity [η] (dl / g ) Is 0.5 ≦
[Η] ≦ 4.0 (3) The melting point (TmP) (° C.) defined above,
At this time, the relationship between the melting endotherm (ΔHP) (J / g) is
TmP> 3.27 ΔHP + 3

First, the poly (butene-1) of the present invention has a melting point (TmP) of 80 ° C. or higher, preferably 9
It is 0 to 130 ° C. This melting point (TmP) is measured by a differential scanning calorimeter (DSC). That is, the melting point (TmP) was measured by using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co., Ltd.), and the sample was previously melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then at 5 ° C./minute until -10 ° C. The endothermic amount obtained by lowering the temperature and holding at −10 ° C. for 5 minutes and then raising the temperature at 10 ° C./min is the melting endothermic amount (Δ
HP) (J / g), and the peak top of the peak observed on the highest temperature side of this melting endothermic curve is the melting point (TmP)
Is defined as If this melting point (TmP) is lower than 80 ° C., the resistance to high-temperature substances such as hot water decreases.

The poly (butene-1) of the present invention has an intrinsic viscosity [η] (dl / g) in the range of 0.5 to 4.0. This intrinsic viscosity [η] is measured in decalin at 135 ° C. If the intrinsic viscosity [η] is less than 0.5, stickiness tends to occur. Intrinsic viscosity [η] is 4.
When it exceeds 0, the fluidity is lowered and the moldability becomes poor.

Further, in the poly (butene-1) of the present invention, the relationship between the melting point (TmP) (° C.) defined above and the melting endotherm (ΔHP) (J / g) at this time is expressed by the following equation. It satisfies. TmP> 3.27ΔHP + 3 When the melting point (TmP) is out of the range of this formula, the heat resistance (hot water resistance) becomes poor.

In addition to the above requirements, the poly (butene-1) of the present invention preferably has a melting endotherm ΔHP of 50 J / g or less as measured by DSC, because it is excellent in flexibility.
It is more preferably 20 J / g or less. ΔHP is an index indicating whether or not it is soft, and when this value becomes large, it means that the elastic modulus is high and the softness is lowered. Note that ΔHP is obtained by the method described above.

The poly (butene-1) of the present invention preferably has a mesopentad fraction (mmmm) of 20 to 90%, more preferably 50 to 90%.
Most preferably, it is 60 to 90%. If the mesopentad fraction is less than 20%, the surface of the molded article may become sticky or the transparency may be reduced. On the other hand, if it exceeds 90%, the flexibility, the low-temperature heat-sealing property, and the hot tack property may deteriorate.

In the present invention, the mesopentad fraction (m
mmm) is V. "M reported by Busico et al.
acromol. Chem. Phys. , 198, 12
57 (1997) ”. That is, the signals of the methylene group and the methine group are measured using ¹³ C nuclear magnetic resonance spectrum, and the mesopentad fraction in the poly (1-butene) molecule is determined. In addition,
^{The 13} C nuclear magnetic resonance spectrum can be measured with the following apparatus and conditions. Device: JEOL Ltd. JNM-EX400 type ¹³ C-N
MR apparatus method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds integration: 10000 times

[2] Method for producing poly (butene-1) As a method for producing poly (butene-1) in the present invention, (1) a dibridged metallocene catalyst and (2a) Ti-Mg are used.
System catalyst or (2b) non-dibridged metallocene catalyst,
A method of homopolymerizing butene-1 can be mentioned.

The (1) dibridged metallocene catalyst used in the method for producing poly (butene-1) of the present invention is, among metallocene catalysts, a transition metal forming a crosslinked structure through two crosslinking groups. It is a metallocene catalyst obtained by combining a compound and a cocatalyst. To give a concrete example, (A)
General formula (I)

[0018]

[Chemical 3]

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopenta group, respectively. A ligand selected from a dienyl group, a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which forms a crosslinked structure via A ¹ and A ^2. And they may be the same or different from each other, X represents a σ-bonding ligand, and when there are a plurality of Xs,
Multiple X's may be the same or different, other X's,
It may be crosslinked with E ¹ , E ² or Y. Y represents a Lewis base, and when there are plural Y's, the plural Y's may be the same or different and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, which is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
Germanium-containing group, tin-containing group, -O-, -CO-,
_{-S -, - SO 2 -,} - Se -, - NR 1 -, - PR 1
-, - P (O) R 1 -, - BR 1 - or -AlR ¹ - are shown, R ¹ represents a hydrogen atom, a halogen atom, having from 1 to 20 carbon atoms
Or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. q is an integer of 1 to 5 and represents [(valence of M) -2], and r is an integer of 0 to 3. ] And (B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex, and (B-2) A method of homopolymerizing 1-butene in the presence of a polymerization catalyst containing a component selected from aluminoxanes can be mentioned.

In the above general formula (I), M represents a metal element of Group 3 to 10 of the periodic table or a lanthanoid series,
Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid-based metals. It is suitable. E ¹ and E ² are respectively a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-N <), a phosphine group (-P <),
Hydrocarbon group [>CR-,> C <] and silicon-containing group [> S
iR-,> Si <] (wherein R is hydrogen or 1 to 2 carbon atoms)
0 is a hydrocarbon group or a hetero atom-containing group) and forms a crosslinked structure via A ¹ and A ² . Further, E ¹ and E ² may be the same or different from each other. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.

X represents a σ-bonding ligand, and when there are a plurality of X's, the plurality of X's may be the same or different and are cross-linked with other X, E ¹ , E ² or Y. May be.
Specific examples of X include a halogen atom and 1 to 20 carbon atoms.
Hydrocarbon group, C1-C20 alkoxy group, C6-C20 aryloxy group, C1-C20 amide group, C1-C20 silicon-containing group, C1-C20 phosphide Group, sulfide group having 1 to 20 carbon atoms, 1 carbon atom
.About.20 acyl groups and the like. On the other hand, Y represents a Lewis base, and when there are plural Y's, the plural Y's may be the same or different and may be cross-linked with other Y or E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines and thioethers.

Next, A ¹ and A ² are divalent bridging groups that bond two ligands, and are a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. , Silicon-containing groups, germanium-containing groups, tin-containing groups, -O-, -C
O -, - S -, - SO 2 -, - Se -, - NR 1 -, -
^{PR 1 -, - P (O} ) R 1 -, - BR 1 - or -AlR
^1- , R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Examples of such a crosslinking group include those represented by the general formula

[0023]

[Chemical 4]

(D is carbon, silicon or tin, R ² and R
Each of ³ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and may be bonded to each other to form a ring structure. e is 1
Indicates an integer of ˜4. ). Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, a diphenyldisililene group and the like. Among these, ethylene group, isopropylidene group and dimethylsilylene group are preferable. q is an integer of 1 to 5 and represents [(valence of M) -2], and r is an integer of 0 to 3. Among the transition metal compounds represented by the general formula (I), the general formula (II)

[0025]

[Chemical 5]

A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by as a ligand is preferable. In the general formula (II), M, A ¹ , A ² , q and r are the same as above. X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ are the same as those exemplified in the description of X in the general formula (I). Y
¹ represents a Lewis base, and when Y ¹ is plural, plural Y
^1's may be the same or different and may be crosslinked with another Y ¹ or X ¹ . Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I). R ^{4 to} R ⁹ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
The halogen-containing hydrocarbon group, the silicon-containing group or the hetero atom-containing group of 1 is shown, but at least one of them is required not to be a hydrogen atom. R ^{4 to} R ⁹ may be the same or different from each other, and adjacent groups may be bonded to each other to form a ring. Among them, it is preferable that R ⁶ and R ⁷ form a ring and that R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , a group containing a hetero atom such as oxygen, halogen and silicon is preferable because the polymerization activity becomes high.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the crosslinking group between the ligands. Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-
Ethylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2'-methylene)
(2,1'-Methylene) -bis (indenyl) zirconium dichloride, (1,2'-isopropylidene)
(2,1'-isopropylidene) -bis (indenyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1'-Ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-ethylene)
(2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2 ′
-Ethylene) (2,1'-ethylene) -bis (4,7-
Diisopropylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
Ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′
-Isopropylidene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'-ethylene) -bis (indenyl) zirconium dichloride, (1,2'-methylene) (2,1'- Isopropylidene) -bis (indenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-Dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-i-propylindenyl) Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ) Screw (3
-Phenylindenyl) zirconium dichloride,
(1,2′-Dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1'-Dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2'-
Dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di) -I-Propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4
-Phenylindenyl) zirconium dichloride, (1
, 2'-Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) ) Screw (5,6
-Benzoindenyl) zirconium dichloride, (1,
2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium dichloride,
(1,2′-Dimethylsilylene) (2,1′-isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-n-butylindenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) ) -Bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Isopropylidene) -bis (3-phenylindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1'-Methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-i-propylindenyl) zirconium dichloride , (1,2 '
-Dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethyl) Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (indenyl) zirconium dichloride, (1,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) )
(2,1'-Methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ( 3-Methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 '-Methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) ( 3-Methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene)
(2,1'-Methylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-
Isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methylcyclopentadienyl) (3'-
Methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride,
(1,2′-isopropylidene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 ′
-Methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) (Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,
2'-Dimethylsilylene) (2,1'-ethylene)
(3,4-dimethylcyclopentadienyl) (3 ′,
4'-Dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3,4-dimethylcyclopentadienyl)
(3 ', 4'-Dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'
-Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-methylene)
(2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropyloxy) Ridene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,
2'-isopropylidene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl)
(3 ', 4'-Dimethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-
Methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,
1'-dimethylsilylene) (3-methyl-5-phenylcyclopentdienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride,
(1,2′-Dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-
Methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,
1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentienyl) zirconium dichloride,
(1,2′-Dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl)
(3'-methyl-5'-ethylcyclopentadienyl)
Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-
i-Propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-
Dimethylsilylene) (2,1'-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene ) (2
1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Methylene) (3-methyl-
5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2'-ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-
i-Propylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5) '-I-propylcyclopentadienyl) zirconium dichloride, (1,
2'-methylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1 , 2'-methylene) (2,
1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i
-Propylcyclopentadienyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-diphenylsilylene) (2,2'-dimethyl) Silylene) bisindenyl zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene) bisindenyl zirconium dichloride, (1,1'-diisopropylsilylene) (2,2 '
-Dimethylsilylene) bisindenyl zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-
Diisopropylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1 ′
-Diphenylsilyleneindenyl) (2,2'-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diphenylsilyleneindenyl) (2,2'-dimethylsilylene-3-trimethylsilylindenyl) Zirconium dichloride,
(1,1′-Dimethylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene) (2,2′-diphenylsilylene) ( Indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilylene)
(2,2'-Dimethylsilylene) (indenyl) (3-
Trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-
Diisopropylsilylene) (2,2'-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-diisopropylsilylene) (indenyl) (3-trimethylsilyl) Indenyl) zirconium dichloride, (1,1′-diisopropylsilylene) (2,2′-diisopropyrylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2 ，
2'-Dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-diphenylsilylene) (2,2'-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium Dichloride,
(1,1′-diphenylsilylene) (2,2′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1 ′)
-Dimethylsilylene) (2,2'-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-diisopropylsilylene) (2,2'-dimethylsilylene) (indenyl) (3 -Trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-dimethylsilylene) (2,2'-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-diisopropylsilylene) Examples include (2,2′-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, and compounds in which zirconium in these compounds is replaced with titanium or hafnium. Of course, it is not limited to these. Further, it may be a compound similar to a metal element of another group or lanthanoid series. Further, in the above compound, (1,1 '-) (2,2'-) is (1,2'-)
It may be (2,1'-) or (1,2 '-) (2
1'-) may be (1,1 '-) (2,2'-).

Next, as the component (B-1) of the component (B), any component can be used as long as it is a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex. The following general formulas (III) and (IV) ([L ¹ -R ¹⁰ ] ^{k +} ) _a ([Z] ^- ) _b ... (III) ([L ² ] ^{k +} ) _{a can also be used.} ([Z] ^- ) _b ... (IV) (where L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R
¹⁴ M ³ . [In the formulas (III) and (IV), L ¹ is a Lewis base, and [Z] ⁻ is
Non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 G 1 G 2 ··· G} f ] ^- ( Here, M ¹ is an element of Groups 5 to 15 of the periodic table, preferably ^{13 to 1} of the periodic table.
Indicates a Group 5 element. G ^{1 to} G ^f are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms and 2 to 4 carbon atoms, respectively.
0 dialkylamino group, C1-20 alkoxy group, C6-20 aryl group, C6-20 aryloxy group, C7-40 alkylaryl group, C7-40 Arylalkyl group, carbon number 1
20 shows a halogen-substituted hydrocarbon group, a C1-C20 acyloxy group, an organic metalloid group, or a C2-C20 hetero atom-containing hydrocarbon group. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(central metal M
Represents an integer of ¹ valence) +1]. ), [Z ^{2] -} is
The logarithm (pKa) of the reciprocal of the acid dissociation constant is a Bronsted acid alone or a conjugated base of a combination of Bronsted acid and Lewis acid, or a conjugate base of an acid generally defined as a super strong acid. Also, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹²
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is an ionic valence of [L ¹ -R ¹⁰ ] and [L ² ] and is an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² contains elements of Groups 1 to 11, 11 to 13 and 17 of the periodic table, and M ³ represents elements of Groups 7 to 12 of the periodic table. ] What is represented by these can be used conveniently.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group and trityl group, and specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopenta group. Examples thereof include a dienyl group, an ethylcyclopentadienyl group and a pentamethylcyclopentadienyl group. Specific examples of R ¹³ include phenyl group, p-tolyl group, p-methoxyphenyl group and the like, and specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Further, specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I ₃ , and specific examples of M ³ include Mn and F.
e, Co, Ni, Zn, etc. can be mentioned.

[Z ¹ ] ^- , that is, [M ¹ G ¹ G
² ... G ^f ], specific examples of M ¹ include B, A
1, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, and a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group. , Hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4- t-
Butylphenyl group, 3,5-dimethylphenyl group, etc.
Fluorine, chlorine, bromine, iodine as a halogen atom, p-fluorophenyl group as a hydrocarbon group containing a hetero atom,
3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl)
Phenyl group, bis (trimethylsilyl) methyl group, etc.
Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron and the like.

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or a combination of conjugate base of a Bronsted acid and Lewis acid [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO ₃₎ ^-, bis (trifluoromethanesulfonyl ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , Chlorosulfonate anion (ClS
O ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ⁻ , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As
F ₅ ) ^- , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{-, and the} like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the component compound of the component (B-1) are as follows.
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, Methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, Methylanilinium tetrakis (pentafluorophenyl) borate, Tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. (B-1) may be used alone or in combination of two or more kinds.

On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (V)

[0035]

[Chemical 6]

(In the formula, R ¹⁵ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. Each R ¹⁵ may be the same or different. ) A chain aluminoxane represented by the general formula (VI)

[0037]

[Chemical 7]

A cyclic aluminoxane represented by the formula (wherein R ¹⁵ and w are the same as those in the general formula (V)) can be mentioned.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other. The means therefor is not particularly limited, and the reaction may be carried out according to a known method. For example,
A method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, water of crystallization contained in a metal salt, an inorganic substance Or a method of reacting water adsorbed on an organic substance with an organoaluminum compound,
There is a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and then reacting with water. The aluminoxane may be insoluble in toluene.

These aluminoxanes may be used alone or in combination of two or more. When the (B-1) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component to the (B) catalyst component is preferably 10: 1 to 1: 100, and Preferably 2: 1
The range of 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer becomes high,
Not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1,000,000,
More preferably, the range of 1:10 to 1: 10000 is desirable. When it deviates from this range, the catalyst cost per unit mass polymer becomes high, which is not practical. As the catalyst component (B), (B-1) and (B-2) can be used alone or in combination of two or more kinds.

In addition to the components (A) and (B), an organoaluminum compound can be used as the component (C) in the polymerization catalyst for producing poly (butene-1). Here, the organoaluminum compound as the component (C) is represented by the general formula (VII) R ¹⁶ _v AlJ _{3 -v} (VII) [wherein, R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, and J is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Is an aryl group or a halogen atom, and v is an integer of 1 to 3] is used. Specific examples of the compound represented by the general formula (VII) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride. , Diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. In the method for producing poly (butene-1), the above-mentioned (A) is used.
Preliminary contact can also be carried out using the component, the component (B) and the component (C). The pre-contact is carried out with the component (A), for example,
It can be carried out by contacting the component (B),
The method is not particularly limited, and a known method can be used. The preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the use ratio of the component (B) which is the cocatalyst. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be seen in addition to the above effects. The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 1
50 degreeC, More preferably, it is 0 degreeC-80 degreeC. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.

The ratio of the (A) catalyst component to the (C) catalyst component used is preferably 1: 1 to 1: 1000 in terms of molar ratio.
The range of 0, more preferably 1: 5 to 1: 2000, and even more preferably 1:10 to 1: 1000 is desirable.
By using the (C) catalyst component, the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. Poly (butene-1)
In the production of, at least one of the catalyst components can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and inorganic oxide carriers, other inorganic carriers and organic carriers can be used,
In particular, an inorganic oxide carrier or another inorganic carrier is preferable.

Specific examples of the inorganic oxide carrier include S
iO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , F
e ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ and mixtures thereof, such as silica-alumina, zeolite, ferrite, and glass fiber.
Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.

On the other hand, as a carrier other than the above, MgC
general formula M represented by l ₂ , Mg (OC ₂ H ₅ ) _{2 and the} like
Examples thereof include magnesium compounds represented by gR ¹⁷ _X X ¹ _y and complex salts thereof. Here, R ¹⁷ has 1 carbon atom
To an alkyl group having 20 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y
Is 0 to 2 and x + y = 2. Each R ¹⁷ and each X
Each ¹ may be the same or different. As the organic carrier, polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly-1-
Examples thereof include polymers such as butene, substituted polystyrene and polyarylate, starch and carbon.

Touches used in the production of poly (butene-1)
As the carrier of the medium, MgCl₂, MgCl (OC
₂H_Five), Mg (OC₂H_Five)₂, SiO₂, Al₂O
₃Are preferred. The nature of the carrier is its type and
Depending on the method, the average particle size is usually 1 to 300 μm,
It is preferably 10 to 200 μm, more preferably 20 to 10 μm.
It is 0 μm. Small particle size increases fines in the polymer
However, if the particle size is large, the number of coarse particles in the polymer increases and the bulk density increases.
Cause deterioration of the hopper and clogging of the hopper. In addition,
Specific surface area is usually 1 to 1000 m²/ G, preferably 5
0-500m²/ G, pore volume is usually 0.1-5 cm³
/ G, preferably 0.3-3 cm ³/ G.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained from the volume of the nitrogen gas adsorbed according to the BET method, for example. further,
When the carrier is an inorganic oxide carrier, it is usually 150.
It is desirable to use the composition after firing at 1000 to 1000 ° C, preferably 200 to 800 ° C. When at least one catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .

The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited, but for example, at least one of the component (A) and the component (B) is mixed with the carrier. Method, method of treating carrier with organoaluminum compound or halogen-containing silicon compound, and then mixing with component (A) and / or component (B) in an inert solvent, carrier and component (A) and / or
Alternatively, a method of reacting the component (B) with an organoaluminum compound or a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing with the component (B) or the component (A). , A method of mixing a contact reaction product of the component (A) and the component (B) with a carrier, and a method of allowing a carrier to coexist in the contact reaction of the component (A) and the component (B).

In the above method and
It is also possible to add an organoaluminum compound as the component (C). In the production of the catalyst used for producing poly (butene-1), the catalyst may be prepared by irradiating an elastic wave when the (A), (B) and (C) are brought into contact with each other.
As the elastic wave, a sound wave is usually used, and an ultrasonic wave is particularly preferable. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably 10 to 500 kHz is used.

The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is. Further, in the production of poly (butene-1), the catalyst can be produced by carrying out the loading operation of at least one of the component (A) and the component (B) on the carrier in the polymerization system.
For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at atmospheric pressure to 2
It is possible to use a method of generating catalyst particles by adding MPa (gauge) and performing prepolymerization at −20 to 200 ° C. for about 1 minute to 2 hours.

The ratio of the component (B-1) and the carrier used in the catalyst used for producing this poly (butene-1) is
The mass ratio is preferably 1: 5 to 1: 10000, and more preferably 1:10 to 1: 500.
-2) The ratio of the component to the carrier used is preferably 1: 0.5 to 1: 1000 by mass ratio, more preferably 1: 1 to 1: 1.
A value of 50 is desirable. When two or more components (B) are mixed and used, it is desirable that the ratio of each component (B) to be used be within the above range in terms of mass ratio. Also,
The use ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000 by mass ratio, more preferably 1:10.
It is desirable to set it to 1: 500.

Component (B) [Component (B-1) or (B-
If the ratio of the component (2)] to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may decrease. The average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 15 μm.
0 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50.
~500m is a ² / g. If the average particle diameter is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. Further, in the catalyst used for producing poly (butene-1), the amount of transition metal in 100 g of the carrier is usually 0.05 to 10 g, and preferably 0.1 to 2 g. If the amount of transition metal is out of the above range, the activity may decrease.

Examples of the Ti-Mg type catalyst (2a) include a solid catalyst component obtained by bringing a titanium compound, a magnesium compound and an electron donating compound into contact with each other, an organosilicon compound or a diether compound, and an organoaluminum compound. It is preferred to use a catalyst system consisting of

The titanium compound is represented by the general formula (IX) TiX ¹ _p (OR ²³ ) _4-p ... (IX) In the general formula (IX), X ¹ represents a halogen atom, and among them, a chlorine atom. And a bromine atom are preferable, and a chlorine atom is particularly preferable. R ²³ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be a linear group, a branched group, or a cyclic group, and further may be sulfur or nitrogen. It may contain a hetero atom such as oxygen, silicon, or phosphorus. Preferably 1 to 1 carbon atoms
Zero hydrocarbon group, especially an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group are preferable, and a linear or branched alkyl group is particularly preferable. When a plurality of —OR ²³ are present, they may be the same or different from each other. Specific examples of R ²³ include methyl group, ethyl group, n-propyl group, isopropyl group and n-
Butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group Group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. p shows the integer of 0-4.

Specific examples of the titanium compound represented by the above general formula (IX) include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraiso. Tetraalkoxytitanium such as butoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium; titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and other tetrahalogenated titanium; methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium tri Trihalogenated alkoxytitanium such as chloride, n-butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-
Dihalogenated dialkoxytitanium such as n-propoxytitanium dichloride and diethoxytitanium dibromide; trimethoxytitanium chloride, triethoxytitanium chloride,
Examples include monohalogenated trialkoxy titanium such as triisopropoxy titanium chloride, tri-n-propoxy titanium chloride, and tri-n-butoxy titanium chloride. Of these, titanium compounds having a high halogen content, particularly titanium tetrachloride, are preferred from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.

As the magnesium compound, a magnesium compound represented by the general formula (X) MgR ²⁴ R ²⁵ ... (X) can be used.
In the above general formula (X), R ²⁴ and R ²⁵ represent a hydrocarbon group, an OR ²⁶ group (R ²⁶ is a hydrocarbon group) or a halogen atom. Here, the hydrocarbon group of R ²⁴ and R ²⁵ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group or the like, and the OR ²⁶ group is R ²⁶ having 1 to 12 carbon atoms. Examples of 12 alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and the like, and halogen atoms include chlorine, bromine, iodine, and fluorine. R ²⁴ and R ²⁵ may be the same or different.

Specific examples of the magnesium compound represented by the above general formula (X) include dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethylbutyl magnesium, diphenyl magnesium and dicyclohexyl magnesium. Alkyl magnesium, aryl magnesium; dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, dihexyloxy magnesium, dioctoxy magnesium, diphenoxy magnesium, dicyclohexyloxy magnesium and other alkoxy magnesium, allyloxy magnesium; ethyl magnesium Chloride, butylmagnesium chloride, hex Le chloride, isopropyl magnesium chloride, isobutyl magnesium chloride, t- butyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride,
Alkyl magnesium halides such as ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium chloride, butyl magnesium iodide, aryl magnesium halides; butoxy magnesium chloride, cyclohexyloxy magnesium chloride, phenoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium bromide, ethoxy magnesium ion Alkoxy magnesium halides such as daid, aryloxy magnesium halides; magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide.

The above magnesium compound can be prepared from metallic magnesium or a compound containing magnesium. The magnesium compound may be in contact with a halide. The halogenated compounds include SiCl ₄ , SiBr ₄ , SnCl ₄ , Sn
Br ₄ and HCl can be used. Of these, SiCl ₄ is particularly preferable. Further, the magnesium compound may be supported on a support such as silica or alumina. The above magnesium compounds may be used alone or in combination of two or more. Further, it may contain halogen such as iodine, other elements such as silicon and aluminum, and may contain electron donating compounds such as alcohols, ethers and esters.

A typical example of the electron-donating compound used for the solid catalyst component is an ester derivative of carboxylic acid,
It is preferably an ester derivative of an aromatic carboxylic acid,
More preferred are ester derivatives of aromatic dicarboxylic acids. The organic group of the ester portion is preferably a linear, branched or cyclic aliphatic hydrocarbon group. Among these, a phthalic acid diester derivative or a malonic acid diester derivative is preferable, and a linear or branched aliphatic hydrocarbon group having 4 or more carbon atoms is particularly preferable as the organic group of the ester portion. Specifically, di-n-butyl phthalate, di-iso-butyl phthalate, di-n-butyl malonate, di-iso-butyl malonate and the like are preferable. These aromatic dicarboxylic acid ester compounds may be used alone or in combination of two or more.

With respect to the solid catalyst component, the above-mentioned magnesium compound, titanium compound and electron-donating compound may be brought into contact with each other by an ordinary method except for temperature, and the contact procedure is not particularly limited. For example, each component may be contacted in the presence of an inert solvent such as hydrocarbon, or each component may be diluted with an inert solvent such as hydrocarbon in advance and contacted.
Examples of the inert solvent include n-octane and n-
Aliphatic hydrocarbons such as decane, methylcyclohexane,
Examples thereof include alicyclic hydrocarbons such as ethylcyclohexane, aromatic hydrocarbons such as toluene and xylene, or a mixture thereof.

Here, the titanium compound is usually used in an amount of 0.5 to 1 with respect to 1 mol of magnesium in the above magnesium compound.
00 mol, preferably 1 to 50 mol is used. If this molar ratio deviates from the above range, the catalytic activity may become insufficient. Further, the electron donor is usually 0.01 to 10 with respect to 1 mol of magnesium of the magnesium compound.
The amount used is preferably 0.05 to 1.0 mol. If this molar ratio deviates from the above range, the catalytic activity and stereoregularity may become insufficient.

The above-mentioned magnesium compound, titanium compound and electron donating compound are brought into contact with each other in the temperature range of 120 to 150 ° C., preferably 125 to 140 ° C., after adding these components. If the contact temperature is out of the above range, the catalytic activity and the stereoregularity may not be sufficiently improved. The contact is usually 1 minute to 24 hours,
It is preferably carried out for 10 minutes to 6 hours. The pressure at this time is
When using a solvent, depending on its type, contact temperature, etc.,
Although the range varies, it is usually 0 to 5 MPaG, preferably 0 to 1 MPaG. Further, during the contact operation, it is preferable to perform stirring from the viewpoint of contact uniformity and contact efficiency. Further, it is preferable that the titanium compound is contacted twice or more so that the titanium compound is sufficiently supported on the magnesium compound which serves as a catalyst carrier. When a catalyst is used in the contacting operation, it is usually 5,000 ml or less, preferably 10 ml, based on 1 mol of the titanium compound.
Use ~ 1,000 milliliters of solvent. If this ratio deviates from the above range, contact uniformity and contact efficiency may be deteriorated.

The solid catalyst component obtained by the above contact is washed with an inert solvent at a temperature of 100 to 150 ° C, preferably 120 to 140 ° C. If the washing temperature is out of the above range, the catalytic activity and the stereoregularity may not be sufficiently improved. As this inert solvent,
For example, aliphatic hydrocarbons such as n-octane and n-decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated tetrachloroethane and chlorofluorocarbons. Hydrocarbons or mixtures thereof can be mentioned. Of these, aliphatic hydrocarbons are preferably used. The cleaning method is not particularly limited,
A method such as decantation or filtration is preferable. The amount of the inert solvent used, the washing time, and the number of washings are not particularly limited, but usually 1 mol is used per 1 mol of the magnesium compound.
00 to 100,000 ml, preferably 1,000
~ 50,000 ml solvent is used, usually 1 min ~
It is carried out for 24 hours, preferably 10 minutes to 6 hours. 0 mol,
It is preferably used in an amount of 0.005 to 5.0 mol. If this molar ratio deviates from the above range, cleaning may be incomplete.
The range of pressure varies depending on the type of solvent, washing temperature, etc., but is usually 0 to 5 MPaG, preferably 0 to 1 M.
Perform in the range of PaG. Further, during the washing operation, it is preferable to perform stirring from the viewpoint of washing uniformity and washing efficiency. The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as hydrocarbon.

As the organosilicon compound used together with the solid catalyst component of the Ti-Mg type catalyst (2a), a compound represented by the following general formula (VIII) is used. ^{_{SiR 21 m (OR 22) 4}} -m ··· (VIII) ( wherein, R ²¹ is branched chain hydrocarbon group having 1 to 20 carbon atoms,
A linear hydrocarbon group or a cyclic hydrocarbon group is shown, and R ²² is a linear hydrocarbon group having 1 to 4 carbon atoms or a branched chain hydrocarbon group. R ²¹ and R ²² may be the same or different from each other. m represents an integer of 0 to 3. )

In the organosilicon compound represented by the general formula (VIII), R ²¹ is preferably a branched hydrocarbon group having 1 to 20 carbon atoms or a saturated cyclic hydrocarbon group. R ²¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group,
A vinyl group, an aryl group, etc. are mentioned, C1-C2
A tertiary alkyl group of 0 and a cycloalkyl group are preferable. R
^Examples of ²² include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.

Specific examples of the organosilicon compound represented by the general formula (VIII) include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane and isobutyltrimethoxysilane. , T-butyltrimethoxysilane, thexyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, t-butyltriethoxysilane , Thexyltriethoxysilane, propyltripropoxysilane,
Dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, ethylmethyldimethoxysilane, t-butylmethyldimethoxysilane, trimethylmethoxysilane, triethyl Alkylalkoxysilanes such as methoxysilane, tripropylmethoxysilane, triisopropylmethoxysilane, tributylmethoxysilane, di-t-butyldiethoxysilane; cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, dicyclopentyldimethoxy. Silane, dicyclohexyldimethoxysilane, dicyclopentyldiethoxysila , Cycloalkylalkoxysilanes such as dicyclohexyldiethoxysilane; phenylalkylalkoxysilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane; cyclopentylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclopentylthexyldimethoxysilane, cyclohexyl Thexyldimethoxysilane, t-butylcyclopentyldimethoxysilane, t-butylcyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, t-butylcyclopentyldiethoxysilane, t
-Butylcyclohexyldiethoxysilane, cyclopentylthexyldiethoxysilane, cyclohexyltexyldiethoxysilane, cyclohexylcyclopentyldiethoxysilane and the like can be mentioned. These organosilicon compounds may be used alone or in combination of two or more. Among these, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, di-t-butyldimethoxysilane, t-butylcyclopentyldimethoxysilane, t-butylcyclohexyldimethoxysilane, cyclopentylthexyldimethoxysilane, cyclohexylthexyldimethoxysilane, cyclohexylcyclopentyl Dimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, di-t-butyldiethoxysilane, t-butylcyclopentyldiethoxysilane, t-
Butylcyclohexyldiethoxysilane, cyclopentylthexyldiethoxysilane, cyclohexyltexyldiethoxysilane and cyclohexylcyclopentyldiethoxysilane are preferred.

Examples of the diether compound used in place of the above organosilicon compound include compounds represented by the following general formula (XI).

[0068]

[Chemical 8]

In the formula, n is an integer of 2 to 10 and R ³³ to
R ⁴⁰ is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and R ³⁶ and R ³⁷ may be the same or different from each other. . Any of R ^{33 to} R ⁴⁰ , preferably R ³⁶ and R ³⁷ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon.

Specific examples of the diether compound represented by the above general formula (XI) include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane and 2 -Butyl-1,3-
Dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2 −
(2-Phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3
-Dimethoxypropane, 2- (diphenylmethyl)-
1,3-dimethoxypropane, 2- (1-naphthyl)-
1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2-
(P-t-butylphenyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1 , 3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2 -Propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,
3-dimethoxypropane, 2-methyl-2-phenyl-
1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) ) -1,
3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2
-Ethylhexyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane,
2,2-dibenzyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2 -Isopropyl-
1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,
3-dimethoxypropane, 2,2-di-s-butyl-
1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-
2-isopentyl-1,3-dimethoxypropane, 2-
Phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,
3-dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-
Benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1 , 3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2
-Isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3- Dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxy Butane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-
Bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-
Dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1, 5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane,
1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3- Dimethoxypropane, 2,2-
Pentamethylene-1,3-dimethoxypropane, 2,2
-Hexamethylene-1,3-dimethoxypropane, 1,
2-bis (methoxymethyl) cyclohexane, 2,8-
Dioxaspiro [5,5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5- Oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,2
2,1] heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2- Cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3
-Dimethoxycyclohexane, 2-cyclohexyl-2
-Methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-
Dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-
Cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2- Isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3
-Dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane, Cyclohexyl-t-butylbis (methoxymethyl) silane, i-propyl-t-butylbis (methoxymethyl)
Examples include silane.

Of these, 1,3-diethers are preferably used, and particularly 2,2-diisobutyl-1,3
-Dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2 -Cyclohexyl-2-isopropyl-1,3
-Dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane are preferred. Used. Further, these compounds may be used alone or in combination of two or more kinds.

Examples of the organoaluminum used with the solid catalyst component of the Ti-Mg type catalyst (2a) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Trialkyl aluminum such as trioctyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride,
Dialkylaluminum chlorides such as diisobutylaluminum chloride and dioctylaluminum chloride;
Alkyl aluminum dichlorides such as methyl aluminum dichloride and ethyl aluminum dichloride; dialkyl aluminum fluorides such as dimethyl aluminum fluoride; dialkyl aluminum hydrides such as diisobutyl aluminum hydride and diethyl aluminum hydride; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride be able to. These organoaluminum compounds may be used alone or in combination of two or more.

As the non-dibridged metallocene catalyst (2b) used in place of the Ti-Mg type catalyst of (2a), a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and methylaluminoxane or A catalyst composed of a compound that reacts with a transition metal compound of Group 4 of the periodic table to form an ionic complex and an organoaluminum compound is used.

The transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring as a main catalyst is a cycloalkadienyl group or a substituted product thereof, specifically, an indenyl group, a substituted indenyl group and a portion thereof. Zirconium, titanium and hafnium compounds having a multidentate coordination compound in which at least two groups selected from the group consisting of hydrides are bonded via a lower alkylene group or a silylene group as a ligand. That is, the transition metal compound is HHBrintzin
ger et al, J. Organometal. Chem., 288, 63 (1985) described ethylene-bis- (indenyl) zirconium dichloride and J. Am. Chem. Soc., 109, 6544 (1987) described ethylene-
Bis- (indenyl) hafnium dichloride, H.Yamaza
ki et al, Chemistry Letters, 1853 (1989), dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride or these. Is a stereorigid chiral compound of zirconium and hafnium compounds such as hafnium dichloride in the complex of.

Specifically, ethylene bis (indenyl) zirconium dichloride, ethylene bis (4,
5,6,7-Tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-
Methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,3)
-Dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (4,5,5)
6,7-Tetrahydro-1-indenyl) hafnium dichloride, ethylenebis (4-methyl-1-indenyl) hafnium dichloride, ethylenebis (5-methyl-1-indenyl) hafnium dichloride, ethylenebis (6-methyl-1- Indenyl) hafnium dichloride, ethylenebis (7-methyl-1-indenyl) hafnium dichloride, ethylenebis (2,3-dimethyl-
1-indenyl) hafnium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) hafnium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl)
Hafnium dichloride, dimethylsilylenebis (4-methylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) hafnium dichloride, dimethylsilylenebis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,2) 4,5-Trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl)
Zirconium dichloride, dimethyl silylene bis (3-
Methylcyclopentadienyl) hafnium dichloride,
Dimethyl silylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethyl silylene bis (benzoindenyl) zirconium dichloride, dimethyl silylene bis {1,1 '-(2-methyl-4-phenyl-4H-azulenyl) } Zirconium dichloride etc. can be mentioned.

As the compound which reacts with the transition metal compound of Group 4 of the periodic table of the cocatalyst to form an ionic complex, triphenylcarbinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Anilinium tetrakis (pentafluorophenyl) borate,
Compounds containing tetra (pentafluorophenyl) borate anion such as lithium tetrakis (pentafluorophenyl) borate, triphenylcarbinium tetrakis (pentafluorophenyl) aluminate, N,
A tetra (pentafluorophenyl) aluminate anion-containing compound such as N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate or lithium tetrakis (pentafluorophenyl) aluminate is preferably used.

As the organoaluminum compound,
It has at least one Al-C bond in the molecule. Specific examples of the organoaluminum compound include triethylaluminum, triisobutylaluminum, trialkylaluminum such as trihexylaluminum, diethylaluminum halide, dialkylaluminum halide such as diisobutylaluminum halide, a mixture of trialkylaluminum and dialkylaluminum halide, tetraethyl. Examples include alkylalumoxane such as dialumoxane and tetrabutylalumoxane.

Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, and alkylalumoxane are preferable, and triethylaluminum,
Triisobutylaluminum, a mixture of triethylaluminum and diethylaluminium chloride and tetraethyldialumoxane are preferred. As the organic aluminum, triethyl aluminum, triisobutyl aluminum and the like are preferably used.

In the above-mentioned production of poly (butene-1) of the present invention, it is needless to say that components common to each catalyst component, such as a component which serves as a cocatalyst for a dibridged metallocene catalyst and a non-dibridged metallocene catalyst, should be used in common. You can Since the poly (butene-1) of the present invention is produced by the mixed catalyst system of the same reactor (reactor), it is possible to save the trouble of blending, and to obtain a material which is easily mixed uniformly and has an excellent physical property balance. Can be advantageously manufactured

As the polymerization method of poly (butene-1), any of a gas phase polymerization method, a liquid phase polymerization method, a slurry polymerization method, a bulk polymerization method and the like can be applied. Further, this polymerization may be carried out in two or more steps,
Each may be performed by different polymerization methods. The catalyst during the polymerization is ethylene, propylene, 1-butene, 1
It is also possible to use one that has been prepolymerized with an α-olefin such as hexene.

Regarding the polymerization conditions, the polymerization temperature is usually -10.
It is 0 to 250 ° C, preferably -50 to 200 ° C, more preferably 0 to 130 ° C. The ratio of the catalyst to the reaction raw material is preferably 1 to 10 ^{8 of} raw material monomer / component (A) (molar ratio), and more preferably 100 to 10 ⁵ . The polymerization time is usually 5 minutes to 10 hours, the reaction pressure is preferably normal pressure to 20 MPa (gauge),
More preferably, the atmospheric pressure is 10 MPa (gauge).

The method for controlling the molecular weight of the polymer includes selection of the type and amount of each catalyst component, polymerization temperature, and further polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane. , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent. Depending on the polymerization method, it can be carried out without a solvent.

Upon polymerization, preliminary polymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be performed by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used in the prepolymerization is not particularly limited, and the same olefins as those exemplified above, such as ethylene and α-C 3-20 can be used.
Examples thereof include olefins and mixtures thereof, but it is advantageous to use the same olefin as that used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0
~ 80 ° C. In the prepolymerization, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferable. Further, the prepolymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] of the prepolymerized product (measured in decalin at 135 ° C.) is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, and the transition metal component in the catalyst is 1 mmol. It is desirable to adjust the conditions so that the amount of the prepolymerized product with respect to 1 to 10000 g, particularly 10 to 1000 g.

If desired, various additives may be added to the poly (butene-1) of the present invention. Examples of various additives used as desired include antioxidants, neutralizing agents, slip agents, antiblocking agents, antifogging agents, antistatic agents, and the like. These additives may be used alone or in combination of two or more. Examples of antioxidants include phosphorus-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

Specific examples of phosphorus antioxidants include trisnonylphenylphosphite and tris (2,4-di-).
t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-
t-Butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphonite,
ADEKA STAB 1178 (manufactured by Asahi Denka Co., Ltd.), Sumilizer TNP (manufactured by Sumitomo Chemical Co., Ltd.), JP-135 (manufactured by Johoku Chemical Co., Ltd.), ADEKA STAB 2112 (Asahi Denka Co., Ltd.)
Made), JPP-2000 (made by Johoku Chemical Co., Ltd.), Wes
ton 618 (manufactured by GE), ADEKA STAB PEP-2
4G (manufactured by Asahi Denka Co., Ltd.), ADEKA STAB PEP-36
(Asahi Denka Co., Ltd.), ADEKA STAB HP-10 (Asahi Denka Co., Ltd.), SandstabP-EPQ (Sand Co., Ltd.), Phosphite 168 (Ciba Specialty Chemicals Co., Ltd.), and the like. To be

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol,
n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-]
Hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 4,4'-butylidene bis- (3-
Methyl-6-t-butylphenol), triethyleneglycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-
Bis {2- [3- (3-t-butyl-4-hydroxy-
5-Methylphenyl) propionyloxy] -1,1-
Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Yoshinox BHT (Yoshitomi Pharmaceutical Co., Ltd.)
), Antage BHT (Kawaguchi Chemical Co., Ltd.), Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.), Irganox 1010 (Ciba Specialty Chemicals Co., Ltd.), ADEKA STAB AO-6
0 (manufactured by Asahi Denka Co., Ltd.), Sumilizer BP-101 (manufactured by Sumitomo Chemical Co., Ltd.), Tominox TT (Yoshitomi Pharmaceutical Co., Ltd.)
Made), TTHP (made by Toray Industries, Inc.), Irganox 31
14 (manufactured by Ciba Specialty Chemicals Co., Ltd.),
ADEKA STAB AO-20 (manufactured by Asahi Denka Co., Ltd.), ADEKA STAB AO-40 (manufactured by Asahi Denka Co., Ltd.), Sumilizer BB
MS (Sumitomo Chemical Co., Ltd.), Yoshinox BB (Yoshitomi Pharmaceutical Co., Ltd.), Antage W-300 (Kawaguchi Chemical Co., Ltd.), Irganox 245 (Ciba Specialty Chemicals Co., Ltd.) , ADEKA STAB AO-70
(Asahi Denka Co., Ltd.), Tominox 917 (Yoshitomi Pharmaceutical Co., Ltd.), ADEKA STAB AO-80 (Asahi Denka Co., Ltd.)
Manufactured by Sumitomo Chemical Co., Ltd.).

Specific examples of the sulfur antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate. , Pentaerythritol tetrakis (3-lauryl thiopropionate),
Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox L
(Manufactured by Nippon Oil & Fats Co., Ltd.), Sumilizer TPM (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.)
Antixox M (manufactured by NOF Corporation), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd.), Yoshinox DS
TP (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), Antiox S (manufactured by NOF Corporation), ADEKA STAB AO-412S (manufactured by Asahi Denka Co., Ltd.), SEENOX 412S (manufactured by Cypro Kasei), Sumilizer TDP (Sumitomo) (Chemical Co., Ltd.)
Etc.

A film of the poly (butene-1) of the present invention,
Examples of antioxidants when used for sheets include Irganox 1010: Substance name: pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Irgafos 168:
Material name: tris (2,4-di-t-butylphenyl) phosphite, Irganox 1076: Material name: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, Irganox 133
0: Substance name: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Irganox 3114: Substance name: Tris (3,5 -Di-t-butyl-4-hydroxybenzyl) isocyanurate, P-EPQ: substance name: tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene-di-phosphite, preferable.

When the antioxidant is used in the present invention, 0.001 to 1 part by weight of the antioxidant may be added to 100 parts by weight of poly (butene-1). This is preferable because it can prevent yellowing and the like. Specific examples of the use of the above-mentioned antioxidants are: Example 1 Irganox 1010 1000ppm PEP-Q 1000ppm Example 2 Irganox 1076 1200ppm PEP-Q 600ppm Irgafos 168 800ppm Example 3 Irganox 1010 400-1000ppm Irgafos 168 750 1500ppm etc. are mentioned.

As the neutralizing agent for film and sheet use,
Calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (DHT-4
A): Composition formula: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ 3.5
H ₂ O and the like are particularly preferable. As an anti-blocking agent for films and sheets, "Silysia" manufactured by Fuji Silysia Ltd .: synthetic silica type, Mizusawa Chemical Industry Co., Ltd.
"Mizukasil" manufactured by: synthetic silica type is particularly preferable.

Examples of slip agents for use in films and sheets include erucic acid amide, oleic acid amide, stearic acid amide, behenic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, stearyl erucamide, and oleyl palmitamide. Particularly preferred.
When the nucleating agent is used in the present invention, the amount of the nucleating agent added is usually 10 ppm or more, preferably 10 to 10000 ppm, more preferably 10 to 5000 ppm with respect to poly (butene-1). And more preferably 10 to 2500 ppm. 1
If it is less than 0 ppm, the low-temperature heat-sealing property is not improved. On the other hand, addition of an amount exceeding 10000 ppm does not increase the preferable effect but also causes poor appearance.

[3] Molded Product The molded product of the present invention is a molded product obtained by molding the above-mentioned poly (butene-1), and is characterized by being excellent in flexibility while maintaining heat resistance. That is, the molded article of poly (butene-1) of the present invention has a Vicat softening point Tv (° C).
And tensile elastic modulus E (MPa) satisfy the following relationship. If it deviates from this range, the heat resistance (hot water resistance) may be poor. Tv> 0.1989E + 17 This Vicat softening point Tv is measured according to JIS K7206. The Vicat softening point Tv of the molded product of poly (butene-1) of the present invention is preferably 80 ° C. or higher, and 9
0 ° C. or higher is more preferable. The tensile modulus of the poly (butene-1) molded product of the present invention is 210 to 460.
MPa is preferable, and 300 to 400 MPa is more preferable.

Examples of the molded article of poly (butene-1) of the present invention include films, sheets, containers, interior materials for automobiles, and housing materials for home electric appliances. As a film,
Examples include food packaging films and agricultural films (an example of a greenhouse). Examples of the container include a case, a box, a cosmetic case, and the like.

As the molding method of the molded body, an injection molding method,
A compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, a blow molding method and the like can be mentioned. Molding conditions are not particularly limited as long as the resin is a temperature condition in which the resin melts and flows. Usually, the resin temperature is 50 ° C to 300 ° C,
It can be performed at a mold temperature of 60 ° C. or less. When a film is formed as the molded product of the present invention, it can be carried out by a general compression molding method, extrusion molding method, blow molding method, cast molding method or the like. The film obtained by molding the poly (butene-1) of the present invention may or may not be stretched. When stretching, biaxial stretching is preferred.
The conditions for biaxial stretching include the following conditions. Molding conditions for sheet molding Resin temperature 50 to 200 ° C., chill roll temperature 50 ° C. or less Longitudinal stretching condition Stretching ratio 3 to 7 times, stretching temperature 50 to 100 ° C. Horizontal stretching condition stretching ratio 6 to 12 times, stretching temperature 50 to 100 ° C.

The surface of the film obtained by molding the poly (butene-1) of the present invention may be treated as necessary to increase the surface energy or polarize the surface. . Examples of the treatment method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone and ultraviolet irradiation treatment. Examples of the method of making the surface uneven include a sandblast method and a solvent treatment method. The film obtained by molding the poly (butene-1) of the present invention requires a commonly used antioxidant, neutralizing agent, slip agent, antiblocking agent, antifogging agent, antistatic agent, or the like. Can be blended accordingly. Further, since the film containing inorganic fine particles such as talc has excellent slip properties, secondary processability such as bag making and printing is improved, and various general-purpose packaging films for high-speed manufacturing equipment such as various automatic filling packaging laminates. Suitable for

It is also possible to produce a multilayer film with the poly (butene-1) according to the invention. Poly (butene-
The method for producing the multilayer laminate in 1) is not particularly limited, and examples thereof include a method for producing by a melt coextrusion molding method. Among them, the T die cast molding method, which enables high-speed molding with a large molding machine, is particularly preferable. The take-up speed may be 50 m / min or higher film forming conditions. The thickness of the multilayer laminate is not particularly limited, but is usually about 10 to 5000 μm.

[0098]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples. First, the resin characteristics of the poly (butene-1) of the present invention and the evaluation method of the physical properties of the molded article will be described.

(Resin Properties) (1) Mesopentad Fraction (mmmm) It was measured by the method described in the specification. (2) Intrinsic viscosity [η] (dl / g): measured in decalin at 135 ° C. (3) DSC measurement: Measured by the method described in the specification.

(Evaluation of Physical Properties of Press-Molded Product) (4) Tensile Elastic Modulus: A polymer was press-molded to prepare a test piece, which was measured under the following conditions according to JIS K-7113.・ Test piece (No. 2 dumbbell) thickness: 1 mm ・ Crosshead speed: 50 mm / min (5) Vicat softening point Tv: Test piece 3 × 20 × 20 m
It was measured according to JIS K7206 by using a press plate of m.

Production Example 1 (Synthesis of Complex for Bibridged Metallocene Catalyst) (1,2′-Dimethylsilylene) (2,1′-dimethylsilylene) -bis (used as a catalyst in the production of a polymer by the following method. 3-Trimethylsilylmethylindenyl) zirconium dichloride was prepared. In a Schlenk bottle, 3.0 g (6.97 mmol) of a lithium salt of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to −78 ° C. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Was obtained (yield 84%). Next, in a Schlenk bottle under a nitrogen stream, the (1,2′-dimethylsilylene) (2,
3.04 g (5.88 mmol) of 1'-dimethylsilylene) -bis (3-trimethylsilylmethylindene)
And ether (50 ml) were added, the mixture was cooled to -78 ° C, and n-BuLi hexane solution (1.54M,
7.6 ml (1.7 mmol)) was added dropwise.
After raising the temperature to room temperature and stirring for 12 hours, ether was distilled off. The obtained solid was washed with 40 ml of hexane to give 3.06 g of a lithium salt as an ether adduct.
(5.07 mmol) was obtained (yield 73%). As a result of measurement by ¹ H NMR (90 MHz, THF-d ₈ ), δ was 0.04 (s, 18H, trimethylsilyl); 0.48 (s, 12H, dimethylsilylene);
1.10 (t, 6H, methyl); 2.59 (s, 4H,
Methylene); 3.38 (q, 4H, methylene), 6.2
It was -7.7 (m, 8H, Ar-H). The lithium salt obtained under a nitrogen stream was dissolved in 50 ml of toluene, cooled to -78 ° C, and 1.2 g (5.1 mmol) of zirconium tetrachloride previously cooled to -78 ° C (20 ml of toluene). ) The suspension was added dropwise. After the dropping, the mixture was stirred at room temperature for 6 hours, and the solvent of the reaction solution was distilled off.
By recrystallizing the obtained residue with dichloromethane, (1,2′-dimethylsilylene) (2,1′-
Dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride 0.9 g
(1.33 mmol) was obtained (yield 26%). As a result of measurement by ¹ H NMR (90 MHz, CDCl ₃ ), δ was 0.0 (s, 18H, trimethylsilyl); 1.02, 1.12 (s, 12H, dimethylsilylene); 2.51 (dd, 4H, methylene); 7.1-
It was 7.6 (m, 8H, Ar-H).

Production Example 2 (Preparation of solid catalyst component) (1) Distillation of titanium tetrachloride Commercially available titanium tetrachloride (arsenic content: 0.0008% by weight)
Was distilled at a reflux ratio of 1 using a glass continuous multi-stage distillation column having an actual stage of 50 stages, a column diameter of 55 mm, a column height of 4 m, and a perforated plate tray (with downcomer). The arsenic content (atomic conversion) in the obtained titanium tetrachloride was analyzed and found to be 0.000.
It was 16% by weight. (2) Preparation of solid catalyst component After replacing a flask having an internal volume of 0.2 L with nitrogen gas, anhydrous magnesium chloride (7.9 g), n-decane (36 mL) and 2-ethylhexanol (38 mL) were added, and the mixture was heated at 130 ° C for 2 hours. . Add 0.9g of phthalic anhydride and add 1
It heated at 30 degreeC for 2 hours, and obtained the uniform liquid. After replacing another three-necked flask with a stirrer with an internal volume of 0.5 L with nitrogen gas, 200 mL of previously distilled titanium tetrachloride was added,
After cooling to -20 ° C, the liquid prepared above was added dropwise over 1 hour, and the internal temperature was raised to 110 ° C over 4 hours.
Further, 2.4 mL of 2-isobutyl-2-isopropyl-1,3-methoxypropane was added, and the mixture was stirred at 110 ° C. for 2 hours. The obtained solid was filtered off, 275 mL of titanium tetrachloride previously distilled was added, and the mixture was stirred at 110 ° C. for 2 hours.
After the solid was filtered off, it was thoroughly washed with dehydrated decane to obtain a solid catalyst component.

Example 1 (dibridged metallocene catalyst and M
Mixed system of g-Ti-based catalyst) Heptane (200 m
L), butene-1 (200 mL), triisobutylaluminum (1 mmol), and hydrogen 0.05 MPa were introduced. Then, the solid catalyst component (5 μmol in terms of Ti) prepared in Preparation Example 2, methylaluminoxane (1 mmol) manufactured by Albemarle, and the complex (1,
2'-Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl)
Zirconium dichloride (0.5 μmol) was added.
The temperature was raised to 60 ° C. with stirring, and the mixture was stirred for 10 minutes. Then, after adding methanol (20 mL) and depressurizing, the polymerization solution was dried under reduced pressure to obtain poly (butene-1). Table 1 shows the evaluation results of the resin properties of the obtained poly (butene-1) and the physical properties of the press-formed product.

COMPARATIVE EXAMPLE 1 (Only bi-bridged metallocene catalyst) Heptane (200 m) was added to a 1 L autoclave which was dried by heating.
L), butene-1 (200 mL), triisobutylaluminum (1 mmol), and hydrogen 0.03 MPa were introduced. Then, Albemarl-made methylaluminoxane (0.5 mmol) was added, and the temperature was raised to 60 ° C. with stirring.
After the temperature was raised to 1, the complex (1,2 '
-Dimethylsilylene) (2,1'-dimethylsilylene)
-Bis (3-trimethylsilylmethylindenyl) zirconium dichloride (0.5 μmol) was added. Thirty
After stirring for 1 minute, methanol (20 mL) was added and the pressure was released.
Poly (butene-1) was obtained by drying the polymerization solution under reduced pressure.
Got Table 1 shows the evaluation results of the resin properties of the obtained poly (butene-1) and the physical properties of the press-formed product.

Comparative Example 2 (Mg-Ti System Catalyst Only) Heptane (200 m
L), butene-1 (200 mL), triethylaluminum (1 mmol), and hydrogen 0.03 MPa were introduced. Then, the solid catalyst component prepared in Production Example 2 (converted to Ti, 5
μmol) was added and the temperature was raised to 70 ° C. with stirring. Three
After stirring for 0 minutes, methanol (20 mL) was added and the pressure was released, and the polymerization solution was dried under reduced pressure to remove poly (butene-
1) was obtained. Table 1 shows the evaluation results of the resin properties of the obtained poly (butene-1) and the physical properties of the press-formed product.

[0106]

[Table 1]

[0107]

The poly (butene-1) molded product of the present invention has excellent softness while maintaining heat resistance.
It is used in many applications such as films, sheets, containers, interior materials for automobiles, and housing materials for home appliances. In addition, since the poly (butene-1) of the present invention is produced in a reactor mixed catalyst system, the labor of blending can be saved, and a material that is easily mixed uniformly and has an excellent physical property balance can be produced industrially advantageously. be able to

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA21 AA84 AA85 AA87 AA88                       AF20 BB03 BC10                 4J028 AA02A AB01A AB02A AC00A                       AC01A AC05A AC10A AC28A                       AC31A AC39A AC41A AC42A                       AC44A AC45A AC46A AC47A                       AC48A AC49A BA00A BA01B                       BA02B BB00A BB01B BB02B                       BC12B BC15B BC16B BC17B                       BC19B BC25B CA16A CB23A                       CB30A CB57A EB05 EC01                       GA04 GA19 GA26                 4J100 AA04P CA01 DA09 DA23                       DA24 DA49 DA51 FA09 FA10

Claims (6)

[Claims] 1. A poly (butene-1) satisfying the following conditions (1) to (3). (1) Using a differential scanning calorimeter (DSC), the sample was melted in a nitrogen atmosphere at 190 ° C. for 5 minutes, and then at 5 ° C./minute −1.
After cooling to 0 ° C and holding at -10 ° C for 5 minutes, 10 ° C
The melting point (TmP), which is defined as the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by raising the temperature at 1 / min, is 80 ° C. or higher (2) intrinsic viscosity [η] (dl / g) is 0.5 ≦
[Η] ≦ 4.0 (3) The melting point (TmP) (° C.) defined above,
At this time, the relationship between the melting endotherm (ΔHP) (J / g) is
TmP> 3.27 ΔHP + 3 2. A (1) dibridged metallocene catalyst and (2a)
The method for producing poly (butene-1) according to claim 1, wherein homopolymerization of butene-1 is carried out using a Ti-Mg catalyst or (2b) non-dibridged metallocene catalyst. 3. The (1) dibridged metallocene catalyst is (A)
General formula (I) [In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, wherein
¹ and A ² form a crosslinked structure, and they may be the same or different from each other, X represents a σ-bonding ligand, and when there are a plurality of Xs, a plurality of Xs are They may be the same or different and may be crosslinked with other X, E ¹ , E ² or Y. Y represents a Lewis base, and when there are plural Y's, the plural Y's may be the same or different and may be crosslinked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, which is a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O-, -CO-, -S-, -SO ₂
-, - Se -, - NR 1 -, - PR 1 -, - P (O) R
¹ -, - BR ¹ - or -AlR ¹ - indicates, R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, they They may be the same or different. q is 1-5
[(Valence of M) -2], and r represents an integer of 0 to 3. ] The transition metal compound represented by, and (B)
A catalyst comprising (B-1) a compound capable of reacting with the transition metal compound of component (A) or a derivative thereof to form an ionic complex, and (B-2) a component selected from aluminoxane. 2. The method for producing poly (butene-1) according to item 2. 4. (2a) A solid catalyst component obtained by bringing a Ti—Mg-based catalyst into contact with a titanium compound, a magnesium compound and an electron-donating compound, and reacting the same, an organosilicon compound or a diether compound, and an organoaluminum compound. The method for producing poly (butene-1) according to claim 2, which is a catalyst comprising 5. (2b) A non-dibridged metallocene catalyst reacts with a transition metal compound of Group 4 of the Periodic Table having a cyclopentadienyl ring and methylaluminoxane or a transition metal compound of Group 4 of the Periodic Table. The method for producing poly (butene-1) according to claim 2, which is a catalyst comprising a compound which forms an ionic complex and an organoaluminum compound. 6. A molded product of poly (butene-1) in which the relationship between the Vicat softening point Tv (° C.) and the tensile elastic modulus E (MPa) satisfies the following relationship. Tv> 0.1989E + 17