JP2007197736A - Modifier for polyolefin-based resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin modifier comprising 1-butene-based polymer having uniform composition, controlled stereoregularity, high flowability and high flexibility. <P>SOLUTION: The modifier for polyolefin-based resin comprises a 1-butene-based polymer satisfying following (1) to (3). (1) The intrinsic viscosity [η] as measured in tetralin solvent at 135°C is 0.01 to 0.5 dL/g. (2) The crystalline resin has a melting point (Tm-D) of 0 to 100°C, wherein the melting point is defined as the top of the peak observed on the highest-temperature side in a melting endothermic curve obtained with a differential scanning calorimeter (DSC) in a test in which a sample is held in a nitrogen atmosphere at -10°C for 5 min and then heated at a rate of 10°C/min. (3) The stereoregularity index ä(mmmm)/(mmrr+rmmr)} is 30 or lower. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a 1-butene polymer having a good balance of high flow, further fluidity, tensile elastic modulus and elongation, and secondary processability, a method for producing the 1-butene polymer, and the 1-butene system. The present invention relates to a resin modifier comprising a polymer and a hot melt adhesive containing the 1-butene polymer.
The 1-butene polymer of the present invention is suitable for applications such as hot melt adhesives, sealing agents, resin / elastomer modifiers, wax blending agents, filler blending agents and the like.

Conventionally, propylene homopolymers or olefin polymers obtained by copolymerizing propylene with ethylene or 1-butene have been known as polymers having relatively low molecular weight and crystallinity and used as hot melt adhesives. Yes.
However, such a polymer lacks uniformity because of its wide molecular weight distribution and composition distribution.
Until now, 1-butene polymers have been produced with magnesium-supported titanium catalysts (Patent Document 1), but the composition was non-uniform and had adverse effects on physical properties such as stickiness and reduced transparency.

In this regard, in recent years, 1-butene polymers having a uniform composition have been obtained with metallocene catalysts (Patent Documents 2 to 6).
Patent Document 7 discloses a highly fluid 1-butene polymer.
However, in any case, since a non-crosslinked metallocene compound is used, a liquid non-crystalline 1-butene polymer is obtained. In this 1-butene polymer, surface characteristics are deteriorated. There was a problem that caused.
In addition, hot melt adhesives used in hot melt bonding, which melts and bonds polymers with heat, are excellent in high-speed coating properties, fast curing properties, solvent-free properties, barrier properties, energy savings, economic efficiency, etc. Use is expanding in various fields.

Conventional hot melt adhesives include natural rubber, ethylene-vinyl acetate copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and other base polymers such as tackifier resins and plastics. The resin which mix | blended the agent is mainly used.
However, since the base polymer as described above contains a large amount of double bonds, the hot melt adhesive compounded using the base polymer has poor thermal stability during heating, and is oxidized and gelated during coating. There have been problems such as causing aging, decomposition, coloring, etc., and causing the strength of the bonded portion to change over time.
In addition, there is a drawback that the adhesiveness to low polar substances such as polyethylene and polypropylene is poor.

For such low-polarity substances, there have been resins based on polypropylene or the like, but these are excellent in thermal stability, but the base polymer has too high hardness and poor fluidity, so that the temperature is high. There is a problem that it is necessary to apply the coating underneath, the thermal stability at high temperature is low, and sufficient adhesion cannot be obtained.
In this regard, as described above, the polymer used as the base polymer of the hot melt adhesive has a relatively low molecular weight and crystallinity obtained by copolymerizing propylene homopolymer or propylene with ethylene or 1-butene. Olefin polymers are known (Patent Document 8).

However, these polymers have a good balance of fluidity, flexibility, and secondary processability, but have poor toughness, so that when used as an adhesive between an elastic body and a nonwoven fabric, the adhesive strength may be inferior. was there.
For example, in order to increase the toughness of the polymer, there is a method of reducing the stereoregularity and using a low crystallinity (Patent Document 9), but if the stereoregularity is too low, the crystal part which is a physical crosslinking point In short, the toughness is reduced.
On the other hand, if the molecular weight is increased in order to develop toughness due to polymer entanglement, the toughness is high but the fluidity is poor.
As described above, in the hot melt adhesive, it is necessary to adjust the balance between fluidity and toughness of the base polymer.

JP 7-145205 A Japanese Patent Laid-Open No. 62-119214 Japanese Patent Laid-Open No. 62-121707 JP 62-121708 A Japanese Patent Laid-Open No. 62-119213 JP-A-8-225605 JP-A-63-57615 JP 7-145205 A JP 2002-322213 A

The present invention has been made in view of the above circumstances. A 1-butene polymer having a uniform composition, controlled stereoregularity, high fluidity and high flexibility, a method for producing the 1-butene polymer, and An object of the present invention is to provide a resin modifier comprising the 1-butene polymer.
Furthermore, the present invention solves the problem of lack of toughness in the base polymer for hot melt adhesives, has an excellent balance between fluidity and toughness, and has excellent thermal stability at high temperatures and adhesion to low polar substances. And it aims at providing the hot-melt-adhesive containing this 1-butene type polymer which the adhesive surface is excellent also in heat resistance.

As a result of intensive studies to achieve the above object, the present inventors have reacted with (A) a specific transition metal compound and (B) (B-1) the transition metal compound of the (A) component. A highly active 1-butene polymer can be produced by using a polymerization catalyst containing at least one component selected from compounds capable of forming an ionic complex and (B-2) aluminoxane. The obtained 1-butene polymer was found to have an appropriate molecular weight distribution and composition distribution, and a good balance of fluidity, physical properties (elastic modulus), and secondary processability (melting point).
Further, the present inventors have found that a 1-butene polymer having a zero shear viscosity η ^{0 as} an index of fluidity of 300 Pa · s or less and a tensile elongation at break of 100% or more as an index of toughness flows. The present invention has been found to be excellent as a base polymer for hot melt adhesives because of its excellent balance between workability and toughness and excellent secondary workability (melting point).
The present invention has been completed based on such findings.
That is, the present invention provides the following 1-butene polymer, a method for producing a 1-butene polymer, a resin modifier comprising the polymer, and a hot melt adhesive containing the 1-butene polymer. It is to provide.

1. A highly fluid 1-butene polymer satisfying the following (1) to (3).
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 0.5 deciliter / g.
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. 1. A crystalline resin having a melting point (Tm-D) of 0 to 100 ° C. defined as the peak top of the observed peak (3) Stereoregularity index {(mmmm) / (mmrr + rmmr)} is 30 or less. A highly fluid 1-butene polymer satisfying the following (1), (2) and (3 ′).
(1) Intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.25 to 0.5 deciliter / g
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The mesopentad fraction (mmmm) determined from the crystalline resin (3 ′) nuclear magnetic resonance (NMR) spectrum having a melting point (Tm-D) of 0 to 100 ° C. defined as the peak top of the observed peak is 68 to 73. %
3. 3. The high fluid 1-butene polymer as described in 2 above, wherein the zero shear viscosity η ⁰ is 300 Pa · s or less and the tensile elongation at break is 100% or more.
4). 3. The highly fluid 1-butene polymer according to 1 or 2 that satisfies the following (4) and (5).
(4) Molecular weight distribution (Mw / Mn) measured by gel permeation chromatograph (GPC) method is 4 or less (5) Weight average molecular weight (Mw) measured by GPC method is 10,000 to 100,000
5). (A) a transition metal compound represented by the following general formula (I), and (B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex, and (B-2) 1-butene is homopolymerized in the presence of a polymerization catalyst containing at least one component selected from aluminoxane, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms ( However, 1-butene is excluded). A method for producing a highly fluid 1-butene polymer.

[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 represent 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, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a σ-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y 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, 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 - 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 as or different from each other. q is an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
6). 6. The process for producing a highly fluid 1-butene polymer according to 5 above, wherein 1-butene is homopolymerized in the presence of a polymerization catalyst whose component is an organic boron compound.
7). (B) In the presence of a polymerization catalyst whose component is an organic boron compound, 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) are copolymerized. 6. The process for producing a highly fluid 1-butene polymer as described in 5 above.
8). (A) a transition metal compound represented by the following general formula (I), and (B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex, and (B-2) 1-butene is homopolymerized in the presence of a polymerization catalyst containing at least one component selected from aluminoxane, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms ( However, a high fluid 1-butene polymer production method according to the above 1 or 2 is produced by copolymerizing 1) butene).
9. (B) Component is an organoboron compound, The manufacturing method of the high fluid 1-butene polymer of said 8 characterized by the above-mentioned.
10. A highly fluid 1-butene polymer obtained by the production method according to 6 or 7 above.
11. A 1-butene resin modifier comprising the highly fluid 1-butene polymer described in 1 above.
12 3. A hot melt adhesive containing the highly fluid 1-butene polymer described in 2 above.

According to the present invention, a 1-butene polymer having a uniform composition, controlled stereoregularity, high fluidity and high flexibility can be produced.
Further, the 1-butene resin modifier of the present invention gives a molded article that is flexible and has little stickiness and excellent compatibility with the polyolefin resin.
Furthermore, the hot melt adhesive of the present invention is excellent in thermal stability and fluidity at high temperatures, excellent in adhesion to low-polar substances, and its adhesive surface is also excellent in heat resistance.

The present invention is described in detail below.
[1] 1-butene polymer, [2] 1-butene polymer production method, [3] 1-butene resin modifier, [4] hot containing 1-butene polymer The melt adhesive will be described in detail.

[1] 1-butene-based polymer The 1-butene-based polymer of the present invention 1 has the following (1) to (3) as requirements.
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 0.5 deciliter / g.
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Crystalline resin (3) Stereoregularity index {(mmmm) / (mmrr + rmmr)} having a melting point (Tm-D) of 0 to 100 ° C. defined as the peak top of the observed peak is 30 or less. -A butene type | system | group requires following (1), (2) and (3 ') as a requirement.
(1) Intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.25 to 0.5 deciliter / g
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Crystalline resin having a melting point (Tm-D) defined as the peak top of the observed peak of 0 to 100 ° C. (3) Mesopentad fraction (mmmm) of 68 to 73%

The 1-butene polymer of the present invention 1 has an intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent of 0.01 to 0.5 deciliter / g, and this intrinsic viscosity [η] is Preferably it is 0.1-0.5 deciliter / g.
If the intrinsic viscosity [η] is less than 0.01 deciliter / g, the physical properties (strength) decrease, and if it exceeds 0.5 deciliter / g, the fluidity deteriorates.

The 1-butene polymer of the present invention 2 has an intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent of 0.25 to 0.5 deciliter / g, and this intrinsic viscosity [η] is Preferably it is 0.30-0.5 deciliter / g.
When the intrinsic viscosity [η] is less than 0.25 deciliter / g, the polymer for hot melt adhesive lacks the molecules that connect the crystals and the toughness (tensile elongation at break) decreases, and 0.5 deciliter / g If it exceeds, the viscosity will increase too much, and the fluidity will decrease, resulting in molding failure.

The 1-butene polymers of the present invention 1 and 2 require that the melting point (Tm-D) is a crystalline resin of 0 to 100 ° C. by a differential scanning calorimeter (DSC) from the viewpoint of softness. Preferably, it is 0-80 degreeC.
Tm-D is determined by DSC measurement.
That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co., Ltd.), 10 mg of the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere and then heated at 10 ° C./min. The peak top of the peak observed on the highest temperature side of the melting endothermic curve is the melting point: Tm-D.

In the present invention, the crystalline resin refers to a resin in which the above Tm-D is observed.
The 1-butene polymer of the present invention 1 has a stereoregularity index {(mmmm) / (mmrr + rmmr)} of 30 or less, preferably 20 or less, more preferably 15 or less.
When the stereoregularity index exceeds 30, a decrease in flexibility and a decrease in secondary workability occur.
Here, the mesopentad fraction (mmmm) is preferably 20 to 90%, more preferably 40 to 85%, and most preferably 60 to 80%.
If the mesopentad fraction is less than 20%, stickiness of the surface of the molded body and a decrease in transparency may occur.
On the other hand, if it exceeds 90%, flexibility and secondary workability may be deteriorated.

The 1-butene polymer of the present invention 2 has a mesopentad fraction (mmmm) of 68 to 73%, preferably 69 to 73%.
When the mesopentad fraction is less than 68%, the degree of crystallinity is too low, and as a result of insufficient crystals to serve as a physical crosslinking point, the tensile elongation at break is too low for a polymer for hot melt adhesives.
On the other hand, if it exceeds 73%, the physical cross-linking point becomes excessive, so that the flexibility and the tensile elongation at break may be reduced.
In the 1-butene polymers of the present inventions 1 and 2, the 1,4 insertion portion is preferably 5% or less.
If it exceeds 5%, the composition distribution of the polymer is widened, which may adversely affect the physical properties.

In the present invention, the mesopentad fraction (mmmm) and abnormal insertion content (1,4 insertion fraction) are reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum to determine the mesopentad fraction and abnormal insertion content in the poly (1-butene) molecule.
^{The 13} C nuclear magnetic resonance spectrum was measured by the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Complete proton 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: 10,000 times

In the present invention, the stereoregularity index {(mmmm) / (mmrr + rmmr)} was calculated from the values obtained by measuring (mmmm), (mmmr), and (rmmr) by the above method.
In addition to the above requirements, the 1-butene polymers of the present inventions 1 and 2 preferably have a molecular weight distribution (Mw / Mn) measured by GPC method of 4 or less, more preferably 3.5 or less, Especially preferably, it is 3.0 or less.
If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur.
In addition to the above requirements, the 1-butene polymers of Inventions 1 and 2 preferably have a weight average molecular weight (Mw) measured by the GPC method of 10,000 to 100,000.
If Mw is less than 10,000, the physical properties (strength) may decrease.
Moreover, when it exceeds 100,000, since fluidity | liquidity falls, workability may become bad.
In addition, said Mw / Mn is the value computed from the weight average molecular weight Mw and number average molecular weight Mn of polystyrene conversion measured by the following apparatus and conditions with GPC method.
GPC measurement device Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

The 1-butene polymer of the present invention 1 preferably has a tensile modulus measured by a tensile test in accordance with JIS K-7113 of 500 MPa or less, and more preferably 300 MPa or less.
This is because if the tensile modulus exceeds 500 MPa, sufficient softness may not be obtained.
The 1-butene polymer of the present invention 2 has a tensile elongation at break as measured by a tensile test according to JIS K-7113 of 100% or more and a zero shear viscosity η ⁰ of less than 300 Pa · s.
When the tensile elongation is less than 100%, the toughness of the 1-butene polymer is insufficient, so that when it is used as a hot melt adhesive, sufficient adhesive strength may not be obtained, and η ⁰ is 300 Pa · s. If it is as described above, the fluidity of the 1-butene polymer is poor, so that the applicability to the adherend is inferior and molding defects may be caused.
The above η ⁰ is a value measured using the following apparatus and conditions.

That is, RMS800 [parallel disk type rotary rheometer, plate (50 mmφ), plate interval (0.9 mm)] manufactured by Rheometrics Co., Ltd., at an angular frequency ω = 0.1 to 100 / sec at a temperature of 120 ° C. A sinusoidal 20% shear strain was applied, and the absolute value | η * | of the obtained complex viscosity was extrapolated to ω = 0 / sec to calculate the zero shear viscosity η ⁰ .
In hot melt adhesives, the tensile elongation at break and zero shear viscosity of 1-butene polymers are important control factors.
The former factor is controlled by the number of molecules connecting the crystals and the number of crystal parts serving as physical crosslinking points, and is mainly controlled by the intrinsic viscosity [η] or molecular weight and stereoregularity of the 1-butene polymer. The latter can be controlled by intrinsic viscosity [η] or molecular weight.
When the 1-butene polymer of the present invention is a copolymer, a random copolymer is preferable.
The structural unit obtained from 1-butene is preferably 50% by mole or more, more preferably 70% by mole or more.
When the structural unit derived from 1-butene is less than 50 mol%, the secondary workability may be deteriorated.

When the 1-butene polymer of the present invention is a copolymer, the following randomness index R obtained from an α-olefin chain is preferably 1 or less.
R = 4 [αα] [BB] / [αB] ²
([Αα] represents the α-olefin chain fraction, [BB] represents the butene chain fraction, and [αB] represents the α-olefin-butene chain fraction.)
R is an index representing randomness, and the smaller the R, the higher the isolation of the α-olefin (comonomer) and the more uniform the composition.
R is preferably 0.5 or less, and more preferably 0.2 or less.
When R is 0, there is no αα chain, and the α-olefin chain is completely isolated.
The butene content and R when the 1-butene polymer was a propylene / butene copolymer were measured as follows.

Butene content and R were calculated by the following method using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd., measuring a ¹³ C-NMR spectrum under the following conditions.
Sample concentration: 220 mg / NMR solution 3 ml NMR solution: 1,2,4-trichlorobenzene / benzene-d6 (90
/ 10 vol%)
Measurement temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 10 seconds Integration count: 4000 times Under the above conditions, PP, PB, BB chain C. In accordance with the method proposed in Randall, Macromolecules, 1978, 11, 592, the Sαα carbon signal of the ¹³ C nuclear magnetic resonance spectrum was measured, and the PP, PB, and BB dyad chain fractions in the copolymer molecular chain were determined. Asked.

The butene content and the randomness index R were determined from the following formulas from the obtained diat chain fractions (mol%).
Butene content (mol%) = [BB] + [PB] / 2
Randomness index R = 4 [PP] [BB] / [PB] ²
([PP] represents the propylene chain fraction, [BB] represents the butene chain fraction, and [PB] represents the propylene-butene chain fraction.)
The butene content and R when the 1-butene polymer was an octene / butene copolymer were measured as follows.
Butene content and R were calculated by the following method using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd., measuring a ¹³ C-NMR spectrum under the following conditions.
Sample concentration: 220 mg / NMR solution 3 ml NMR solution: 1,2,4-trichlorobenzene / benzene-d6 (90/10 vol%)
Measurement temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 10 seconds Integration count: 4000 times

Under the above conditions, the signal of Sαα carbon in the ¹³ C nuclear magnetic resonance spectrum was measured, and the BB chain observed at 40.8 to 40.0 ppm, the OB chain observed at 41.3 to 40.8 ppm, 42.5 The OO, OB, and BB dyad chain fractions in the copolymer molecular chain were determined from the peak intensity derived from the OO chain observed at ˜41.3 ppm.
The butene content and the randomness index R were determined from the following formulas from the obtained diat chain fractions (mol%).
Butene content (mol%) = [BB] + [OB] / 2
Randomness index R = 4 [OO] [BB] / [OB] ²
([OO] represents the octene chain fraction, [BB] represents the butene chain fraction, and [OB] represents the octene-butene chain fraction.)

[2] Method for Producing 1-Butene Polymer The method for producing a 1-butene polymer in the present invention comprises: (A) the following general formula (I)

[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 represent 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, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a σ-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y 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, 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 - 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 as or different from each other. q is an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
And (B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex and (B-2) an aluminoxane. 1-butene is homopolymerized in the presence of a polymerization catalyst containing at least one component, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) are co-polymerized. This is a production method for polymerization.

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from (A) and a cross-linked structure is formed via A ¹ and A ² .

E ¹ and E ² may be the same as 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, the plurality of Xs may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. .
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X.
Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. 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 —, wherein 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, May be different.
Examples of such a bridging group include a general formula

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and are bonded to each other to form a ring structure. (E may represent an integer of 1 to 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 tetramethyldisylylene group, and a diphenyldisilylene group.
Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable. q is an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the above general formula (II), M, A ¹ , A ² , q and r are the same as described 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 include the same examples as those exemplified in the description of X in formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other 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 each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom.
R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.
Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring.
As R ⁴ and R ⁵ , a group containing a hetero atom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging 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)- (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'-me Len) (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'-dimethylsilyl) ) (2,1′-dimethylsilylene) bis (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'-dimethyl Silylene) bis (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) zyl Nium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) Ridene) -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) zyl Conium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Methylene) -bis (3-trimethylsilylmethylindenyl) 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 dichrome (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′-dimethyl) Lucylylene) (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) 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-dimethylcyclo Pentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-Dimethylcyclopentadienyl) zirconium dichloride, (1,2'-isopropylidene) (2,1'-isopropylidene) (3,4-dimethylcyclopenta Enyl) (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-phenylcyclopentadienyl) (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, ( , 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′-phenylcyclopentadienyl) 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-propylcyclopen Dienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclo) Pentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-i-propylcyclo

Pentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-n-butylcyclo Pentadienyl) (3'-methyl-5'-n-butylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-phenylcyclo Pentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopenta Dienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl) Til-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′-dimethylsilylene) bisindenylzirconium dichloride, (1 1'-dimethylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-diisopropylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1 ' -Dimethylsilylene) (2,2'-diisopropylsilylene) bisindenylzirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-dimethylsilylene) ( Indenyl) (3-trimethylsilylindenyl) zyl Conium dichloride, (1,2'-dimethylsilylene) (2,1'-diphenylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diisopropylsilylene) (2,1'- Dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1, 2'-diisopropylsilylene) (2,1'-diisopropylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (indenyl) ( 3-Trimethylsilylmethylin (Denyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1 '-Dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-diphenylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride , (1,2'-diisopropylsilylene) (2,1'-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-diisopropylsilylene) ) (Indenyl) ( 3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diisopropylsilylene) (2,1'-diisopropylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, and the like, and zirconium in these compounds is titanium. Or the thing substituted by hafnium can be mentioned. Of course, it is not limited to these.

Further, it may be an analogous compound of another group or a lanthanoid series metal element.
In the above compound, (1,1 ′ −) (2,2′−) may be (1,2 ′ −) (2,1′−), or (1,2 ′ −) (2 , 1'-) may be (1, 1'-) (2, 2'-).
As the component (B-1) of the component (B), any compound that can react with the transition metal compound of the component (A) to form an ionic complex can be used. And a coordination complex compound or Lewis acid composed of an anion and a cation in which a plurality of groups are bonded to a metal.
There are various coordination complex compounds composed of an anion and a cation in which a plurality of groups are bonded to a metal. For example, a compound represented by the following general formula (III) or (IV) is preferably used. Can do.

([L ¹ −H] ^{p +} ) _q ([M ² X ³ X ⁴ ... X ⁿ ] ^{(nm) −} ) ₁ ... (III)
([L ² ] ^{p +} ) _q ([M ³ X ³ X ⁴ ... X ⁿ ] ^(nm)- ) ₁ ... (IV)

[Wherein L ¹ is a Lewis base, L ² is M ⁴ , R ¹⁰ R ¹¹ M ⁵ or R ¹² ₃ C described later, and M ² and M ³ are selected from Group 5 to 15 elements of the periodic table. Indicates metal. M ⁴ is a metal selected from Groups 1 and 8 to 12 of the periodic table, M ⁵ is a metal selected from Groups 8 to 10 of the periodic table, and X ^{3 to} X ⁿ are a hydrogen atom and a dialkylamino group, respectively. , An alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metalloid group, or a halogen atom. R ¹⁰ and R ¹¹ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹² represents an alkyl group. m is an integer of 1 to 7 in terms of the valence of M ² and M ³ , n is an integer of 2 to 8, p is an integer of 1 to 7 in terms of ionic valence of L ¹ -H and L ² , and q is 1 or more An integer, l = q × p / (nm). ]

M ² and M ³ are metals selected from Group 5-15 elements of the periodic table, preferably metals selected from Group 13-15 elements of the periodic table, and more preferably boron atoms.
M ⁴ is a metal selected from Groups 1 and 8 to 12 of the periodic table, specific examples are each atom such as Ag, Cu, Na, Li, etc., and M ⁵ is selected from Groups 8 to 10 of the periodic table. Examples of such metals include specific atoms such as Fe, Co, and Ni.
Specific examples of X ^{3 to} X ⁿ include, for example, dimethylamino group and diethylamino group as dialkylamino groups, methoxy group, ethoxy group, n-butoxy group as alkoxy groups, phenoxy group as aryloxy groups, 2, 6 -As a C1-C20 alkyl group, such as a dimethylphenoxy group and a naphthyloxy group, carbon such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group As aryl groups, alkylaryl groups or arylalkyl groups of formulas 6 to 20, phenyl group, p-tolyl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-tert-butyl Phenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, , 4-dimethylphenyl group, 1,2-dimethylphenyl group and the like, F, Cl, Br, I as halogen, pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group as organic metalloid group, And diphenylboron group.

Specific examples of the substituted cyclopentadienyl group represented by each of R ¹⁰ and R ¹¹ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.
In the present invention, specific examples of anions in which a plurality of groups are bonded to a metal include B (C ₆ F ₅ ) ₄ ⁻ , B (C ₆ HF ₄ ) ₄ ⁻ , B (C ₆ H ₂ F ₃ ). ₄ ⁻ , B (C ₆ H ₃ F ₂ ) ₄ ⁻ , B (C ₆ H ₄ F) ₄ ⁻ , B (C ₆ (CF ₃ ) F ₄ ) ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , BF _4- ^{and the} like can be mentioned.
Further, as metal cations, Cp ₂ Fe ⁺ , (MeCp) ₂ Fe ⁺ , (tBuCp) ₂ Fe ⁺ , (Me ₂ Cp) ₂ Fe ⁺ , (Me ₃ Cp) ₂ Fe ⁺ , (Me ₄ Cp) ₂ Fe ⁺ , (Me ₅ Cp) ₂ Fe ⁺ , Ag ⁺ , Na ⁺ , Li ^{+ and the} like, and other cations include pyridinium, 2,4-dinitro-N, N-diethylanilinium, diphenylammonium, Nitrogen-containing compounds such as p-nitroanilinium, 2,5-dichloroaniline, p-nitro-N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, N, N-diethylanilinium, triphenyl carbenium, tri (4-methylphenyl) carbenium, tri (4-methoxyphenyl) carbenium carbenium compounds such as, CH ₃ PH ₃ ^{+, _{2 H 5 PH 3 +, C}} 3 H 7 PH 3 +, (CH 3) 2 PH 2 +, (C 2 H 5) 2 PH 2 +, (C 3 H 7) 2 PH 2 +, (CH 3) ₃ PH ⁺ , (C ₂ H ₅ ) ₃ PH ⁺ , (C ₃ H ₆ ) ₇ PH ⁺ , (CF ₃ ) ₃ PH ⁺ , (CH ₃ ) ₄ P ⁺ , (C ₂ H ₅ ) ₄ P ⁺ , Alkylphosphonium ions such as (C ₃ H ₇ ) ₄ P ⁺ , and C ₄ H ₅ PH ₃ ⁺ , (C ₆ H ₅ ) ₂ PH ₂ ⁺ , (C ₆ H ₅ ) ₃ PH ⁺ , (C ₆ H ^{_{5) 4 P +, (C}} 2 H 5) 2 (C 6 H 5) PH +, (CH 3) (C 6 H 5) PH 2 +, (CH 3) 2 (C 6 H 5) PH +, And arylphosphonium ions such as (C ₂ H ₅ ) ₂ (C ₆ H ₅ ) ₂ P ⁺ .

In the present invention, a coordination complex compound comprising any combination of the above metal cation and anion is exemplified.
Among the compounds of the general formulas (III) and (IV), specifically, the following can be used particularly preferably.
Examples of the compound of the general formula (III) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, Examples include tetrakis (pentafluorophenyl) methyldiphenylammonium borate.
On the other hand, as the compound of the general formula (IV), for example, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, decamethyl ferroborate tetrakis (pentafluorophenyl) borate Cenium, tetrakis (pentafluorophenyl) acetylferrocenium borate, tetrakis (pentafluorophenyl) formylferrocenium borate, tetrakis (pentafluorophenyl) cyanoferrocenium borate, silver tetraphenylborate, tetrakis (pentafluorophenyl) Examples include silver borate, trityl tetraphenylborate, tetrakis (pentafluorophenyl) trityl borate, and silver tetrafluoroborate.
Suitable coordination complex compounds are those comprising a non-coordinating anion and a substituted triarylcarbenium, and examples of the non-coordinating anion include those represented by the general formula (V)
(M ¹ X ² X ³ ... X ⁿ ) ^{(nm) −} (V)
[Wherein, M ¹ represents a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table, more preferably a boron atom. X ^{2 to} X ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group), or an alkylaryl group. , An arylalkyl group, a substituted alkyl group, an organic metalloid group, or a halogen atom, m is a valence of M ¹ , and n is an integer of 2 to 8. ]
Can be mentioned.

A compound generally called carborane is also a non-coordinating anion.
On the other hand, examples of the substituted triarylcarbenium include, for example, the general formula (VI)
[CR ¹³ R ¹⁴ R ¹⁵ ] ⁺ ... (VI)
Can be mentioned.
R ¹³ , R ¹⁴ and R ¹⁵ in the general formula (VI) are aryl groups such as a phenyl group, a substituted phenyl group, a naphthyl group and an anthracenyl group, and they may be the same or different from each other. However, at least one of them is a substituted phenyl group, a naphthyl group, or an anthracenyl group.
The substituted phenyl group includes, for example, the general formula (VII)
C ₆ H _5-k R ¹⁶ _k (VII)
It can be expressed as

R ¹⁶ in the general formula (VII) represents a hydrocarbyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, an amino group, an amide group, a carboxyl group, or a halogen atom, and k is It is an integer of 1-5.
When k is 2 or more, the plurality of R ¹⁶ may be the same or different.
Specific examples of the non-coordinating anion represented by the general formula (V) include tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate. , Tetrakis (pentafluorophenyl) borate, tetrakis (trifluoromethylphenyl) borate, tetra (toluyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] Examples thereof include borates and tridecahydride-7,8-dicarbaoundecaborate.
On the other hand, specific examples of the substituted triarylcarbenium represented by the general formula (VI) include tri (toluyl) carbenium, tri (methoxyphenyl) carbenium, tri (chlorophenyl) carbenium, tri (fluorophenyl) carbenium, tri (Xylyl) carbenium, [di (toluyl), phenyl] carbenium, [di (methoxyphenyl), phenyl] carbenium, [di (chlorophenyl), phenyl] carbenium, [toluyl, di (phenyl)] carbenium, [methoxyphenyl, And di (phenyl)] carbenium and [chlorophenyl, di (phenyl)] carbenium.
In addition, the component (B-1) of the catalyst of the present invention includes the following general formula:

BR ¹⁷ R ¹⁸ R ¹⁹ (VIII)
[In formula, R <^17> , R < ¹⁸ > and R < ¹⁹ > are a C1-C20 alkyl group or a C6-C20 aryl group. ]
There is no particular limitation as long as it is a boron compound in which an alkyl group or an aryl group is bonded as a substituent to boron, and any compound can be used.
Here, the alkyl group includes a halogen-substituted alkyl group, and the aryl group includes a halogen-substituted aryl group and an alkyl-substituted aryl group.
R ¹⁷ , R ¹⁸ and R ¹⁹ in the general formula (VIII) each represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, These are alkyl groups such as propyl group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group and 2-ethylhexyl group, or aryl groups such as phenyl group, fluorophenyl group, tolyl group, xylyl group and benzyl group.

Here, R ^{17 to} R ¹⁹ may be the same as or different from each other.
Specific examples of the compound represented by the general formula (VIII) include triphenyl boron, tri (pentafluorophenyl) boron, tri (2,3,4,5-tetrafluorophenyl) boron, tri (2 , 4,5,6-tetrafluorophenyl) boron, tri (2,3,5,6-tetrafluorophenyl) boron, tri (2,4,6-trifluorophenyl) boron, tri (3,4,5 -Trifluorophenyl) boron, tri (2,3,4-trifluorophenyl) boron, tri (3,4,6-trifluorophenyl) boron, tri (2,3-difluorophenyl) boron, tri (2, 6-difluorophenyl) boron, tri (3,5-difluorophenyl) boron, tri (2,5-difluorophenyl) boron, tri (2-fluorophenyl) phospho Boron, tri (3-fluorophenyl) boron, tri (4-fluorophenyl) boron, tri [3,5-di (trifluoromethyl) phenyl] boron, tri [(4-fluoromethyl) phenyl] boron, diethyl Boron, diethylbutyl boron, trimethyl boron, triethyl boron, tri (n-butyl) boron, tri (trifluoromethyl) boron, tri (pentafluoroethyl) boron, tri (nonafluorobutyl) boron, tri (2, 4, 6-trifluorophenyl) boron, tri (3,5-difluorophenyl) boron, di (pentafluorophenyl) fluoroboron, diphenylfluoroboron, di (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di (N-butyl) fluoroboron, Pentafluorophenyl) difluoro boron, phenyl fluoro boron, (pentafluorophenyl) Jikurorohou arsenide, difluoromethyl boron, difluoromethyl boron, and the like (n- butyl) difluoro borate.
Of these, tri (pentafluorophenyl) boron is particularly preferred.
On the other hand, as the aluminoxane of the component (B-2), the general formula (IX)

(Wherein R ²⁰ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to ²⁰ carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2-50, preferably 2-40, wherein each R ²⁰ may be the same or different.
A chain aluminoxane represented by the general formula (X)

(Wherein R ²⁰ and w are the same as those in the general formula (IX)).
The cyclic aluminoxane shown by these can be mentioned.
Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) metal There are a method for reacting water adsorbed on salt and the like, water adsorbed on inorganic and organic substances with an organoaluminum compound, and (4) a method for reacting tetraalkyldialuminoxane with trialkylaluminum and further reacting with water. .
The aluminoxane may be insoluble in toluene.

These aluminoxanes may be used alone or in combination of two or more.
The use ratio of (A) catalyst component and (B) catalyst component is preferably 10: 1 to 1: 100 in terms of molar ratio when (B-1) compound is used as (B) catalyst component. Preferably, the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer becomes high, which is not practical.
Further, when the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000.
When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical.

Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).
The use ratio of the component (A) and the component (B) is preferably a molar ratio of preferably 10: 1 to 1: 100, more preferably 1: 1 to 1:10. The catalyst cost per unit mass polymer becomes high and is not practical.
In the method for producing a 1-butene polymer of the present invention, an ionic complex can be formed by reacting with (A) a specific transition metal compound and (B-1) the transition metal compound of the component (A). By using a polymerization catalyst containing a compound, particularly a boron atom, the 1-butene polymer of the present invention 1 is produced with significantly higher activity than when aluminoxane is used as component (B-2). be able to.
Moreover, as a manufacturing method of 1-butene polymer of this invention 2, it is preferable to use the polymerization catalyst which contains aluminoxane as (A) specific transition metal compound and (B-2) component.

In addition to the component (A) and the component (B), the polymerization catalyst in the production method of the present invention can use an organoaluminum compound as the component (C).
Here, as the organoaluminum compound of component (C), the general formula (X)
R ²¹ _v AlJ _3-v (XI)
[In the formula, R ²¹ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.
Specific examples of the compound represented by the general formula (XI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

In the production method of the present invention, preliminary contact can also be performed using the above-described component (A), component (B) and component (C).
The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used.
These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the proportion of the (B) component that is the promoter.
Further, by bringing the component (A) and the component (B) into contact with each other, an effect of improving the molecular weight can be seen together with the above effect.
The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C.
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 use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2500 in terms of molar ratio.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.
In the present invention, 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 any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include 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, a magnesium compound represented by the general formula MgR ²² _x X ^q _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) ₂ or the like, or a complex salt thereof can be used.
Here, R ²² represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ^q 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 ²² and each X ₁ may be the same or different.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-butene, substituted polystyrene, and polyarylate, starch, and carbon.

As the carrier used in the present invention, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) _{2 and the} like are preferable.
Moreover, although the property of a support | carrier changes with the kind and manufacturing method, an average particle diameter is 1-300 micrometers normally, Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers.
When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there.
When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease.
The specific surface area and pore volume can be determined from the volume of nitrogen gas adsorbed according to the BET method, for example.

Further, when the carrier is an inorganic oxide carrier, it is usually desirable to use it after firing at 150 to 1000 ° C, preferably 200 to 800 ° C.
When at least one kind of 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 for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (1) at least one of the component (A) and the component (B) is mixed with the carrier. (2) A method in which the support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the components (A) and (B) in an inert solvent, (3) the support and (A (4) Method of reacting component and / or component (B) with organoaluminum compound or halogen-containing silicon compound, (4) After supporting component (A) or component (B) on a carrier, component (B) or ( (A) Method of mixing with component, (5) Method of mixing contact reaction product of (A) component and (B) component with carrier, (6) Upon contact reaction of component (A) and component (B) Method of coexisting carriers It can be used.

In the above reactions (4), (5) and (6), an organoaluminum compound (C) can also be added.
In the present invention, when contacting the (A), (B), and (C), the catalyst may be prepared by irradiating elastic waves.
Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave.
Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
The catalyst thus obtained may be used for polymerization after once removing the solvent and taken out as a solid, or may be used for polymerization as it is.
Moreover, in this invention, a catalyst can be produced | generated by performing the carrying | support operation to the support | carrier of at least one of (A) component and (B) component within a 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 normal pressure to 2 MPa (gauge), and -20 to 20 A method of preliminarily polymerizing at 200 ° C. for about 1 minute to 2 hours to produce catalyst particles can be used.

In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. -2) The use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio.
When using 2 or more types as a component (B), it is desirable that the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio.
In addition, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.
If the ratio of component (B) [component (B-1) or component (B-2)] and the carrier, or component (A) and carrier is outside the above range, the activity may decrease. is there.
The average particle diameter of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g.
If the average particle size 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.
When the specific surface area is less than 20 m ² / g, the activity may decrease, and when it exceeds 1000 m ² / g, the bulk density of the polymer may decrease.

In the catalyst of the present invention, the amount of transition metal in 100 g of the support is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g.
If the amount of transition metal is outside the above range, the activity may be lowered.
A polymer having a high bulk density and an excellent particle size distribution which are industrially advantageous can be obtained by supporting the carrier.
The 1-butene polymer of the present invention is obtained by homopolymerizing 1-butene or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (provided that 1-butene is used). And (butene is excluded).
Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned, and one or more of these can be used in the present invention.

In the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. A phase polymerization method is particularly preferred.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC.
The ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , particularly 100 to 10 ⁵ , preferably from raw material monomer / component (A) (molar ratio).
Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).
Examples of the method for adjusting the molecular weight of the polymer include selection of the type of each catalyst component, the amount used, and the polymerization temperature, and further polymerization in the presence of hydrogen.

When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and 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.
Moreover, you may use monomers, such as an alpha olefin, as a solvent.
Depending on the polymerization method, it can be carried out without solvent.
In the polymerization, prepolymerization can be performed using the polymerization catalyst.
The prepolymerization can be performed, for example, 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 for the prepolymerization is not particularly limited, and examples thereof include those similar to those exemplified above, for example, ethylene, an α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as used in
Moreover, prepolymerization temperature is -20-200 degreeC normally, Preferably it is -10-130 degreeC, More preferably, it is 0-80 degreeC.
In the prepolymerization, an aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent.
Of these, aliphatic hydrocarbons are particularly preferred.
Moreover, you may perform prepolymerization without a solvent.

  In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, and per 1 millimole of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10000 g, particularly 10 to 1000 g.

[3] 1-butene resin modifier The 1-butene resin modifier of the present invention is a resin modifier comprising the 1-butene polymer of the present invention 1.
The 1-butene-based resin modifier of the present invention is characterized in that it has a low melting point, is soft, has little stickiness, and can give a molded article excellent in compatibility with a polyolefin resin.
That is, the 1-butene-based resin modifier of the present invention is a specific 1-butene-based polymer, and in particular, there are some crystalline portions in the poly 1-butene chain portion. Compared to the soft polyolefin resin that is an agent, it is less sticky and has excellent compatibility.

Furthermore, the 1-butene resin modifier of the present invention is excellent in compatibility with polyolefin resins, particularly polypropylene resins.
As a result, the surface properties (stickiness, etc.) are less deteriorated and transparency is higher than in the case of using ethylene-based rubber as a conventional modifier.
Due to the above characteristics, the 1-butene resin modifier of the present invention 1 can be suitably used as a physical property improver having flexibility and transparency.
Furthermore, it can be suitably used as an improving agent for heat sealability and hot tackiness.

[4] Hot Melt Adhesive The 1-butene polymer of the present invention 2 is suitable as a hot melt adhesive base polymer, and is blended with a tackifier resin, a plasticizer, and the like, so that the heat stability at high temperatures is achieved. In addition, it can be used as a polyolefin-based hot-melt adhesive having excellent fluidity, excellent adhesion to a low-polarity substance, and excellent adhesion resistance.
As a tackifying resin used for a polyolefin hot melt adhesive using the 1-butene polymer of the present invention 2 as a base polymer, α obtained from rosin resin made from raw pine crab, pine essential oil -Perene, terpene resin made from β-pinene, petroleum resins obtained by polymerizing a fraction containing unsaturated hydrocarbons produced as a by-product by thermal decomposition such as petroleum naphtha, and hydrogenated products thereof Etc.

As tackifying resins, Idemitsu Petrochemical Co., Ltd. Imabu P-125, Imabu P-100, Imabu P-90, Sanyo Chemical Industries Co., Ltd. Umex 1001, Mitsui Chemicals, Inc. Highlets T1115, Examples include Clearon K100 manufactured by Yashara Chemical Co., Ltd., ECR227 manufactured by Tonex Co., Ltd., Escorez 2101, Alcon P100 manufactured by Arakawa Chemical Co., Ltd., Regalrez 1078 manufactured by Hercules Co., Ltd., and the like.
In view of compatibility with the 1-butene polymer, it is preferable to use a hydrogenated product.
Among them, a hydride of petroleum resin having excellent thermal stability is more preferable.
Moreover, in this invention, various additives, such as a plasticizer, an inorganic filler, and antioxidant, can be mix | blended as needed.

As plasticizers, paraffinic process oil, polyolefin wax, phthalates, adipates, fatty acid esters, glycols, epoxy polymer plasticizer, naphthenic oil, etc., inorganic fillers include clay, Antioxidants such as talc, calcium carbonate, and barium carbonate include trisnoniphenyl phosphite, distearyl pentaerythritol diphosphite, Adekastab 1178 (Asahi Denka Co., Ltd.), Sumilizer TNP (Sumitomo Chemical Co., Ltd.), Irgaphos 168 (Ciba Specialty Chemicals Co., Ltd.), Sandstab P-EPQ (Sand Co., Ltd.) and other phosphorus antioxidants, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ', 5'-di-t-butyl-4'- Roxyphenyl) propionate, Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Irganox 1010 (Ciba Specialty Chemicals Co., Ltd.) and other phenolic antioxidants, dilauryl-3,3′-thiodipropionate, pentaerythritol Examples include sulfur-based antioxidants such as Tetrakis (3-laurylthiopropionate), Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.) Antiox L (Nippon Yushi Co., Ltd.), etc. it can.
Polyolefin hot melt adhesive using 1-butene polymer of the present invention 2 as a base polymer is for sanitary materials, packaging, bookbinding, textiles, woodworking, electrical materials, cans, and construction It can be used in various fields such as bag making.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
First, a method for evaluating resin properties and physical properties of a 1-butene polymer obtained by the production method of the present invention will be described.

(1) Preparation of press-molded sheet (a) Preparation of press-molded sample 1-butene polymer 40 g, Irganox 1010 [Ciba Specialty Chemicals Co., Ltd.] as an antioxidant, 1000 ppm and toluene 300 ml, 80 ° C. Mix well to obtain a uniform polymer solution.
This 1-butene polymer solution was dried in a fume hood for 12 hours and then dried in a dryer at 60 ° C. for 8 hours to completely remove toluene, thereby preparing a sample.
(B) Press-molding method 20 g of the sample of (1) above was pressurized at 50 kg / cm ² for 10 minutes at 150 ° C., taking care not to introduce bubbles, then slowly cooled to room temperature, and 200 mm × 200 mm × 1 mm. A sheet was formed.
(2) Measurement of mesopentad fraction, abnormal insertion amount and stereoregularity index Measurement was performed by the method described in the specification.
(3) Measurement of comonomer content The comonomer content was measured by the method described in the text of the specification.
(4) Measurement of intrinsic viscosity [η] The intrinsic viscosity [η] was measured at 135 ° C. in a tetralin solvent using a VMR-053 type automatic viscometer manufactured by Kosei Co., Ltd.
(5) Measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) It measured by the method described in the specification text.
(6) DSC measurement (melting point: measurement of Tm-D)
It was measured by the method described in the text of the specification.
That is, using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample is held at −10 ° C. for 5 minutes in a nitrogen atmosphere and then heated at 10 ° C./min. The peak top of the peak observed on the highest temperature side of the melting endothermic curve was defined as melting point: Tm-D.
Further, the melting endotherm obtained at this time was defined as ΔH−D.
(7) Measurement of tensile modulus and tensile elongation at break A dumbbell-shaped test piece was produced from a sheet press-formed by the method described in (1), and measured under the following conditions by a tensile test based on JIS K-7113.
・ Crosshead speed: 50mm / min
(8) Measurement of zero shear viscosity It was measured by the method described in the text of the specification.

Example 1
(1) Preparation of catalyst (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride Production of (1,2'-dimethylsilylene) ( 3.0 g (6.97 mmol) of lithium salt of 2,1′-dimethylsilylene) -bis (indene) is dissolved in 50 ml of THF (tetrahydrofuran) and cooled to −78 ° C.
2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and 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, the solvent was removed, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. ) Was obtained (yield 84%).

Next, 3.04 g (5.88) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. Millimoles) and 50 milliliters of ether.
After cooling to −78 ° C., a hexane solution of n-BuLi (1.54M, 7.6 ml (1.7 mmol)) was added dropwise.
After stirring at room temperature for 12 hours, ether was distilled off.
The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of lithium salt as an ether adduct (yield 73%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) are as follows: δ: 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), 6.2-7.7 (m, 8H, Ar-H).
The lithium salt obtained under a nitrogen stream was dissolved in 50 ml of toluene.
After cooling to -78 ° C, a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 ml) was added dropwise.
After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off.
The obtained residue was recrystallized from dichloromethane to obtain 0.9 g (1 of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride. .33 mmol) (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows: δ: 0.0 (s, 18H, trimethylsilyl); 1.02, 1.12 (s, 12H, dimethylsilylene); 2.51 (dd 4H, methylene); 7.1-7.6 (m, 8H, Ar-H).

(2) Polymerization To a heat-dried 1 liter autoclave, 200 ml of heptane, 200 ml of 1-butene and 0.5 mmol of triisobutylaluminum were added, and 0.2 MPa of hydrogen was further introduced.
The temperature was raised to 65 ° C. while stirring, and then 0.8 μmol of triphenylcarbenium tetrakispentafluorophenylborate, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3- 0.2 micromol of trimethylsilylmethylindenyl) zirconium dichloride was added and polymerized for 5 minutes.
After completion of the polymerization reaction, 13 g of 1-butene polymer was obtained by drying the reaction product under reduced pressure.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 1.

Example 2
To a heat-dried 1 liter autoclave, 200 ml of heptane, 200 ml of 1-butene and 0.5 mmol of triisobutylaluminum were added, and 0.3 MPa of hydrogen was further introduced.
After stirring the temperature to 65 ° C., propylene was continuously introduced until the total pressure became 0.8 MPa, and triphenylcarbenium tetrakispentafluorophenylborate 0.8 micromol, (1,2 ′ -Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added in 0.2 micromolar and polymerized for 5 minutes.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 14 g of 1-butene copolymer.
About the obtained 1-butene copolymer, the resin characteristic and the physical property were evaluated by the said method. The results are shown in Table 1.

Example 3
To a heat-dried 1 liter autoclave, 200 ml of heptane, 200 ml of 1-butene, 10 ml of 1-octene and 0.5 mmol of triisobutylaluminum were added, and 0.2 MPa of hydrogen was further introduced.
After stirring to a temperature of 65 ° C., 2 μmol of triphenylcarbenium tetrakispentafluorophenylborate, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethyl) 0.5 micromol of indenyl) zirconium dichloride was added and polymerized for 5 minutes.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 13 g of 1-butene copolymer.
About the obtained 1-butene copolymer, the resin characteristic and the physical property were evaluated by the said method. The results are shown in Table 1.

Example 4
To a heat-dried 1 liter autoclave, 4 liters of heptane and 2.5 kg of 1-butene were added, and 0.2 Pa of hydrogen was further introduced.
After the temperature was raised to 80 ° C. with stirring, 5 mmol of triisobutylaluminum, 5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride Then, 25 micromol of dimethylanilinium tetrakispentafluorophenylborate was added and polymerized for 60 minutes.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 1.2 kg of 1-butene polymer.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 1.

Example 5
To a heat-dried 1 liter autoclave, 4 liters of heptane and 2.5 kg of 1-butene were added, and 0.03 Pa of hydrogen was further introduced.
After the temperature was raised to 80 ° C. with stirring, 5 mmol of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-trimethylsilylmethylindenyl) (indenyl) zirconium dichloride 10 μm Mole and 50 micromol of dimethylanilinium tetrakispentafluorophenylborate were added and polymerized for 40 minutes.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 1.3 kg of 1-butene polymer.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 1.

Comparative Example 1
In Example 1, 0.8 micromol of triphenylcarbenium tetrakispentafluorophenylborate was changed to 0.25 mmol of methylaluminoxane, and (1,2'-dimethylsilylene) (2,1'-dimethylsilylene)- Except for changing bis (3-trimethylsilylindenyl) zirconium dichloride to 0.25 micromolar, the polymerization was carried out for 30 minutes in the same manner as in Example 1, followed by drying to obtain 10 g of 1-butene polymer. It was.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 1.
Example 1 and Comparative Example 1 are both production examples of a 1-butene polymer, but Comparative Example 1 using methylaluminoxane instead of the organoboron compound has low catalytic activity. The same tendency is also observed in the production examples of the 1-butene copolymer of Examples 2 to 3 and the production examples of 1-butene polymer of Examples 4 to 5. In Comparative Example 1, the catalytic activity is low.
Moreover, an Example has a low weight average molecular weight and a intrinsic viscosity [(eta)] compared with a comparative example.
That is, in the Examples, a highly fluid 1-butene polymer is obtained.
As seen in Examples 4 to 5, since the catalysts used in the examples are excellent in heat resistance, the polymerization temperature can be increased while maintaining high catalytic activity, and the hydrogen sensitivity is also high. A suitable high fluid 1-butene polymer can be produced.

Example 6
To a heat-dried 10 liter autoclave, heptane 4000 ml, 1-butene 4000 ml, triisobutylaluminum 4.0 mmol and methylaluminoxane 15 mmol were added, and hydrogen 0.4 Pa was further introduced.
After the temperature was raised to 70 ° C. with stirring, 15 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added and polymerized for 120 minutes. did.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 1530 g of 1-butene polymer.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 2.

Example 7
To a heat-dried 1 liter autoclave, 200 ml of heptane, 200 ml of 1-butene, 0.5 mmol of triisobutylaluminum and 0.4 mmol of methylaluminoxane were added, and 0.4 Pa of hydrogen was further introduced.
After the temperature was raised to 60 ° C. with stirring, 0.4 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added, Polymerized for minutes.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 44 g of 1-butene polymer.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 2.

Comparative Example 2
To a heat-dried 10 liter autoclave were added heptane 4000 ml, 1-butene 4000 ml, triisobutylaluminum 4.0 mmol, dimethylanilinium borate 20 micromol, and hydrogen 0.2 Pa was further introduced.
After the temperature was raised to 60 ° C. with stirring, 5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added and polymerized for 60 minutes. did.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 1180 g of a 1-butene polymer.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 2.

Comparative Example 3
980 g of 1-butene polymer was obtained in the same manner as in Example 6 except that the polymerization temperature was changed to 50 ° C. in a polymerization time of 120 minutes.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 2.
Comparative Example 4
To a heat-dried 10 liter autoclave, heptane 4000 ml, 1-butene 4000 ml, triisobutylaluminum 4.0 mmol and methylaluminoxane 5 mmol were added, and 0.6 Pa of hydrogen was further introduced.
The temperature was raised to 50 ° C. with stirring, and 5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added and polymerized for 180 minutes. .
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 450 g of a 1-butene polymer.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 2.

Comparative Example 5
To a heat-dried 1 liter autoclave, 200 ml of heptane, 200 ml of 1-butene, 0.5 mmol of triisobutylaluminum and 0.8 μmol of dimethylanilinium borate were added, and 0.03 Pa of hydrogen was further introduced.
After the temperature was raised to 80 ° C. with stirring, 0.2 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added for 30 minutes. Polymerized.
After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 25 g of 1-butene polymer.
About the obtained 1-butene polymer, the resin characteristic and physical property were evaluated by the said method. The results are shown in Table 2.
In Examples 1 to 7 and Comparative Examples 2 and 4 to 5, a 1-butene polymer having higher fluidity and higher flexibility than that of Comparative Example 1 was obtained. In particular, in Examples 1 and 6 to 7, A 1-butene polymer having high fluidity, high flexibility, and toughness is obtained.
In Comparative Example 2, since the intrinsic viscosity [η] is small, the tensile elongation at break is low. On the other hand, if the intrinsic viscosity [η] is too large as in Comparative Example 3, the tensile elongation at break is good, but the zero shear viscosity is Has increased and the fluidity has decreased.
Since Comparative Example 4 has too high stereoregularity and Comparative Example 5 has too low stereoregularity, the tensile elongation at break is reduced in all cases.

Claims (2)

A polyolefin resin modifier comprising a 1-butene polymer satisfying the following (1) to (3).
(1) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 0.5 deciliter / g.
(2) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. Crystalline resin (3) Stereoregularity index {(mmmm) / (mmrr + rmmr)} having a melting point (Tm-D) defined as the peak top of the observed peak of 0 to 100 ° C. is 30 or less The modifier for polyolefin resin according to claim 1, comprising a 1-butene polymer satisfying the following (4) and (5).
(4) Molecular weight distribution (Mw / Mn) measured by gel permeation chromatograph (GPC) method is 4 or less (5) Weight average molecular weight (Mw) measured by GPC method is 10,000 to 100,000