JP2012036411A - 1-butene-based copolymer and molding comprising the copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a 1-butene-based copolymer giving a molding with less sticking and excellent in flexibility and transparency, and to provide a molding comprising the copolymer and a resin modifier.SOLUTION: This copolymer is a copolymer of 1-butene and 3-20C α-olefin (excluding 1-butene), satisfying the following (1) to (4); and the molding comprises the copolymer. (1) A crystalline resin having no melting point observed, or having a melting point within the range of 0 to 100°C: (2) the stereoregularity index [(mmmm)/(mmrr+rmmr)] is 20 or less; (3) the molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) is 4.0 or less; (4) the weight-average molecular weight (Mw) measured by GPC is 10,000 to 1,000,000.

Description

  The present invention relates to a 1-butene polymer, a molded body comprising the polymer, and a resin modifier. More specifically, the 1-butene system provides a molded body with less stickiness and excellent flexibility and transparency. The present invention relates to a polymer, a molded body made of the polymer, and a resin modifier.

Conventionally, vinyl chloride resin has been widely used as a soft resin. However, vinyl chloride resin is known to generate harmful substances in the combustion process, and development of alternative products is strongly desired. Until now, 1-butene polymers have been produced using magnesium-supported titanium catalysts (see Patent Document 1), but the composition is non-uniform, and the physical properties such as the occurrence of stickiness and the decrease in transparency have been adversely affected. In this regard, a 1-butene polymer having a uniform composition has recently been obtained with a metallocene catalyst (see Patent Documents 2 to 6). However, the homopolymers disclosed in these prior arts have high stereoregularity and lack flexibility. Therefore, in order to increase flexibility, copolymers of 1-butene and other α-olefins have been proposed. However, even in the case of using a metallocene catalyst, when it is a simple 1-butene copolymer, the composition distribution may be widened, and the occurrence of stickiness and a decrease in transparency could not be effectively prevented. .
In general, 1-butene polymers are known to exhibit different crystal states called I-type crystals and II-type crystals by X-ray diffraction analysis. Conventional 1-butene polymers have disadvantages as products, such as a gradual transition from the II-type crystal state to the I-type crystal state and shrinkage of the molded product.

JP 7-145205 A JP-A-62-1119214 JP 62-121708 A JP 62-121707 A Japanese Patent Laid-Open No. 62-119213 JP-A-8-225605

  The present invention relates to a 1-butene polymer that gives a molded product with less stickiness and excellent softness and transparency, a 1-butene polymer that does not change with time due to crystal modification, and a molded product comprising the polymer. An object of the present invention is to provide a resin modifier.

As a result of intensive studies to achieve the above object, the present inventors have (1) melting point, (2) stereoregularity index {(mmmm) / (mmrr + rmmr)}, (3) molecular weight distribution (Mw / Mn), (4) a 1-butene polymer having a weight average molecular weight (Mw) in a specific range is found to be excellent in the balance between the amount of sticky component, low elastic modulus and transparency, (5) A structural unit derived from 1-butene, (6) a 1-butene polymer having a II-type crystal fraction (CII) in a specific range is found to have no change over time due to crystal modification, The present invention has been completed.
That is, the present invention provides the following 1-butene polymer, a molded product comprising the polymer, and a resin modifier.
1. A 1-butene copolymer which is a copolymer of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) and satisfies the following (1) to (4) (1) 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 (2) 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 20 or less (3) Gel perm The molecular weight distribution (Mw / Mn) measured by an aation chromatograph (GPC) method is 4.0 or less. (4) The weight average molecular weight (Mw) measured by the GPC method is 10,000 to 1,000,000.
2.1 A copolymer of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) and satisfying the following (1 ′) to (4 ′): Polymer.
(1 ′) Using a differential scanning calorimeter (DSC), the sample was melted at 220 ° C. for 3 minutes in a nitrogen atmosphere, then cooled to −40 ° C. at 10 ° C./min, and held at −40 ° C. for 3 minutes. A crystalline resin (2 ′) solid having a melting point (Tm) defined as the peak top of the maximum peak of the melting endothermic curve obtained by raising the temperature at 10 ° C./min or 0 to 100 ° C. Regularity index {(mmmm) / (mmrr + rmmr)} is 20 or less (3 ′) Molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method is 4.0 or less (4 ′) GPC method The weight average molecular weight (Mw) measured by the method is 10,000 to 1,000,000
3. A 1-butene copolymer of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) satisfying the following (1 ″) to (4 ″): Copolymer.
(1 ″) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./minute, and held at −10 ° C. for 5 minutes. Thereafter, the melting point (Tm-P) 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 10 ° C./min is not observed or 0 to 100 ° C. Molecular weight distribution (Mw / Mn) measured by gel permeation chromatograph (GPC) method with a crystalline resin (2 ″) stereoregularity index {(mmmm) / (mmrr + rmmr)} of 20 or less (3 ″) 4.0 or less (4 ″) The weight average molecular weight (Mw) measured by GPC method is 100,000 to 1,000,000.
4. The 1-butene copolymer according to any one of 1 to 3 above, wherein the structural unit derived from 1-butene is 90 mol% or more.
5. 5. The 1-butene copolymer according to 4 above, wherein the following randomness index R obtained from an α-olefin chain is 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.)
6. The 1-butene copolymer according to 5 above, wherein the structural unit derived from 1-butene is 95 mol% or more. A 1-butene copolymer satisfying the following (5) and (6).
(5) A copolymer of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), wherein the structural unit derived from 1-butene is 90 mol% or more (6) 190 7. Melted at 5 ° C. for 5 minutes, rapidly solidified with ice water, allowed to stand at room temperature for 1 hour, and then analyzed by X-ray diffraction to obtain a type II crystal fraction (CII) of 50% or less. Furthermore, the 1-butene-type copolymer of said 7 satisfy | filling following (7).
(7) The weight average molecular weight (Mw) measured by GPC method is 10,000 to 1,000,000.
9. (A) It reacts with the transition metal compound represented by the following general formula (I), and (B) (B-1) the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) in the presence of a polymerization compound containing at least one component selected from (B-2) aluminoxane. 9. The 1-butene copolymer according to any one of 1 to 8 obtained by polymerization.

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, A ligand selected from 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 ; In addition, they may be the same or different, X represents a sigma-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 , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, 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 —A ¹ R ^1- represents, 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. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
10. A molded article formed by molding the 1-butene copolymer according to any one of 1 to 9 above.
11. A 1-butene resin modifier comprising the 1-butene copolymer according to any one of 1 to 9 above.

  The 1-butene copolymer of the present invention and a molded article made of the polymer are less sticky, have excellent softness and transparency, or have no change over time due to crystal modification, and do not cause shrinkage. give. 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 a polyolefin resin.

Hereinafter, the 1-butene polymer [1], its production method [2], the 1-butene resin composition [3], the molded product [4] and the 1-butene resin modifier [5] will be described in detail. To do.
[1] 1-Butene Polymer The 1-butene polymer of the present invention includes the following (1) to (4), (1 ′) to (4 ′), (1 ″) to (4 ″). ) Or (5) and (6) as a requirement [hereinafter referred to as 1-butene polymer (I), 1-butene polymer (II), 1-butene polymer (III ) And 1-butene polymer (IV). ].
(1) 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 (2) 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 20 or less (3) Gel perm The molecular weight distribution (Mw / Mn) measured by an aation chromatograph (GPC) method is 4.0 or less. (4) The weight average molecular weight (Mw) measured by the GPC method is 10,000 to 1,000,000.
(1 ′) Using a differential scanning calorimeter (DSC), the sample was melted at 220 ° C. for 3 minutes in a nitrogen atmosphere, then cooled to −40 ° C. at 10 ° C./min, and held at −40 ° C. for 3 minutes. A crystalline resin (2 ′) solid having a melting point (Tm) defined as the peak top of the maximum peak of the melting endothermic curve obtained by raising the temperature at 10 ° C./min or 0 to 100 ° C. Regularity index {(mmmm) / (mmrr + rmmr)} is 20 or less (3 ′) Molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method is 4.0 or less (4 ′) GPC method The weight average molecular weight (Mw) measured by the method is 10,000 to 1,000,000

(1 ″) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./minute, and held at −10 ° C. for 5 minutes. Thereafter, the melting point (Tm-P) 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 10 ° C./min is not observed or 0 to 100 ° C. Molecular weight distribution (Mw / Mn) measured by gel permeation chromatograph (GPC) method with a crystalline resin (2 ″) stereoregularity index {(mmmm) / (mmrr + rmmr)} of 20 or less (3 ″) 4.0 or less (4 ″) The weight average molecular weight (Mw) measured by GPC method is 100,000 to 1,000,000.
(5) A copolymer of 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), wherein the structural unit derived from 1-butene is 90 mol% or more. (6) After being melted at 190 ° C. for 5 minutes, rapidly cooled and solidified with ice water, left at room temperature for 1 hour and then analyzed by X-ray diffraction, the type II crystal fraction (CII) is 50%. Less than

In the present invention, the fact that the melting point (Tm) and the melting point (Tm-P) are not observed with a differential scanning calorimeter (DSC) means that the crystal melting peak cannot be substantially observed because the crystallization rate is very slow in the DSC measurement. Say. In the present invention, the crystalline resin refers to a resin in which at least one of the Tm, Tm-P, and Tm-D peaks is observed.
The 1-butene polymer (I), (II) or (III) of the present invention is the above (1) to (4), (1 ′) to (4 ′) or (1 ″) to (4). '') By satisfying the relationship, the balance between the amount of sticky components such as the obtained molded article, the low elastic modulus and the transparency is excellent. That is, it has a low elastic modulus and excellent softness (also referred to as flexibility), has little sticky component, and excellent surface characteristics (for example, less migration of sticky component to bleed and other products), and There is an advantage of excellent transparency. In addition, the 1-butene polymer (IV) of the present invention has the advantages that, by satisfying the above (5) and (6), there is no change in physical properties due to crystal modification, and shrinkage does not occur in a molded product. is there.

In the present invention, the mesopentad fraction (mmmm) and abnormal insertion content (1,4 insertion fraction) were 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, and the mesopentad fraction and abnormal insertion content in the poly (1-butene) molecule were determined. The 13C nuclear magnetic resonance spectrum was measured with the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. 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-second integration: 10,000 times In the present invention, the stereoregularity index {(mmmm) / (mmrr + rmmr)} is calculated from the values obtained by measuring (mmmm), (mmmrr) and (rmmr) by the above method. did. The racemic triad fraction (rr) was also calculated by the above method.

[A] 1-butene homopolymer The 1-butene homopolymer (I), (II) or (III) of the present invention has a stereoregularity index {(mmmm) / (mmrr + rmmr)} of 20 or less, Preferably it is 18 or less, More preferably, it is 15 or less. When the stereoregularity index exceeds 20, a decrease in flexibility, a decrease in low-temperature heat sealability, and a decrease in hot tack property occur.
The 1-butene homopolymer (I), (II) or (III) of the present invention has a molecular weight distribution (Mw / Mn) measured by GPC method of 4 or less in addition to the above requirements, preferably 3. 5 or less, particularly preferably 3.0 or less. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur.
The 1-butene homopolymer (I), (II) or (III) of the present invention has a weight average molecular weight (Mw) measured by the GPC method of 10,000 to 1,000,000, in addition to the above requirements. Preferably it is 100,000-1,000,000, More preferably, it is 100,000-500,000. If Mw is less than 10,000, stickiness may occur. On the other hand, if it exceeds 1,000,000, the fluidity is lowered and the moldability may be poor.
In addition to the above requirements, the 1-butene homopolymer (I), (II) or (III) of the present invention has a component amount (H25) eluting in hexane at 25 ° C. of 0 to 80% by weight. Is preferable, more preferably 0 to 60% by weight, and most preferably 0 to 50% by weight. H25 is an index indicating whether the amount of so-called stickiness component that causes stickiness, a decrease in transparency, or the like is large or small, and the higher this value, the greater the amount of sticky component. When H25 exceeds 80% by weight, the amount of the sticky component is large, so that blocking occurs, and it may not be used for food or medical products.
H25 is the weight of 1-butene homopolymer (W ₀ ) (0.9 to 1.1 g) and this polymer in 200 ml of hexane at 25 ° C. for 4 days or more and then dried. The weight reduction rate calculated by the following equation after measuring the weight (W1).
H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%)

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 with 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 homopolymer (I) of the present invention has a melting point (Tm-D) of 0 to 5 with a differential scanning calorimeter (DSC) when the Tm and Tm-P are not observed. It is necessary to be a crystalline resin at 100 ° C., preferably 0 to 80 ° C. Tm-D is determined by DSC measurement. That is, using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a 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.
The 1-butene homopolymer (I) having the constitutions (1) to (4) of the present invention has a melting endotherm ΔH-D by DSC measurement of 50 J / g or less in addition to the above requirements. Flexibility is excellent, and it is more preferable that it is 10 J / g or less. ΔH-D is an index that indicates whether or not it is soft, and when this value increases, it means that the elastic modulus is high and the softness is low. ΔH-D is obtained by a method described later.
Further, the 1-butene homopolymer (II) of the present invention is a crystalline resin whose melting point (Tm) is not observed by a differential scanning calorimeter (DSC) from the viewpoint of softness, or is a crystalline resin at 0 to 100 ° C. Is required, and preferably 0 to 80 ° C. Tm is obtained by DSC measurement. That is, using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample is melted at 220 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to −40 ° C. at 10 ° C./min. Furthermore, after maintaining at −40 ° C. for 3 minutes, the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at 10 ° C./min is the melting point: Tm.
The 1-butene homopolymer (II) having the constitutions (1 ′) to (4 ′) of the present invention has a melting endotherm ΔH by DSC measurement of 50 J / g or less in addition to the above requirements. Flexibility is excellent, and it is more preferable that it is 10 J / g or less. ΔH is an index indicating whether or not it is soft, and when this value increases, it means that the elastic modulus is high and the softness is lowered. ΔH is obtained by a method described later.
Further, the 1-butene homopolymer (III) of the present invention is a crystalline resin having a melting point (Tm-P) that is not observed by a differential scanning calorimeter (DSC) from the viewpoint of softness, or is a crystalline resin at 0 to 100 ° C. It is necessary to be, and it is preferably 0 to 80 ° C. Tm-P is determined by DSC measurement. That is, using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample is melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then cooled to −10 ° C. at 5 ° C./min. Furthermore, the melting point: Tm-P is the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by maintaining the temperature at −10 ° C. for 5 minutes and then raising the temperature at 10 ° C./min.
The 1-butene homopolymer (III) having the constitutions (1 ″) to (4 ″) of the present invention has a melting endotherm ΔH-P of 50 J / g by DSC measurement in addition to the above requirements. The flexibility is excellent when it is below, and it is more preferable when it is 10 J / g or below. ΔH-P is an index indicating whether or not it is soft, and when this value increases, it means that the elastic modulus is high and the softness is lowered. ΔH-P is obtained by a method described later.

The 1-butene homopolymer (I), (II) or (III) of the present invention preferably has a mesopentad fraction (mmmm) of 20 to 90%, more preferably 30 to 85%, Most preferably, it is -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, when it exceeds 90%, the flexibility, the low temperature heat sealability, and the hot tack property may be lowered.
Further, the 1-butene homopolymer (I), (II) or (III) of the present invention preferably satisfies the relationship (mmmm) ≦ 90-2 × (rr), and (mmmm) ≦ 87. It is more preferable that the relationship of −2 × (rr) is satisfied. If this relationship is not satisfied, stickiness on the surface of the molded body and a decrease in transparency may occur. In the 1-butene homopolymer (I), (II) or (III) of the present invention, 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.
The 1-butene homopolymer (IV) of the present invention was obtained by melting at 190 ° C. for 5 minutes, rapidly solidifying with ice water, leaving it at room temperature for 1 hour, and then analyzing by X-ray diffraction. The type II crystal fraction (CII) is required to be 50% or less, preferably 20% or less, more preferably 0%.
In the present invention, the type II crystal fraction (CII) It was determined in accordance with the method proposed in “Polymer, 7, 23 (1966)” reported by Turner Jones et al. That is, the peak of the type I crystal state and the peak of the type II crystal state were measured by X-ray diffraction analysis, and the type II crystal fraction (CII) in the crystal of the 1-butene homopolymer was determined. X-ray diffraction analysis (WAXD) was performed under the following conditions using an anti-cathode rotor flex RU-200 manufactured by Rigaku Corporation.
Sample state: Melted at 190 ° C. for 5 minutes, rapidly cooled and solidified with ice water, then left at room temperature for 1 hour Output: 30 kV, 200 mA
Detector: PSPC (position sensitive proportional counter)
Integration time: 200 seconds The 1-butene homopolymer (IV) of the present invention has a weight average molecular weight (Mw) measured by the GPC method of 10,000 to 1,000 as a requirement (7) in addition to the above requirements. , 000 is preferable. More preferably, it is 100,000-1,000,000, More preferably, it is 100,000-500,000. If Mw is less than 10,000, stickiness may occur. On the other hand, if it exceeds 1,000,000, the fluidity is lowered and the moldability may be poor. In addition, the measuring method of said Mw / Mn and Mw is the same as the above.
The 1-butene homopolymer (I), (II), (III) or (IV) of the present invention preferably has a tensile modulus measured by a tensile test according to JISK-7113 of 500 MPa or less. More preferably, it is as follows. It is because sufficient softness may not be obtained when it exceeds 500 MPa.

[A ′] 1-butene-based copolymer The 1-butene-based copolymer of the present invention includes the above (1) to (4), (1 ′) to (4 ′), (1 ″) to ( 4 ″) or a copolymer of 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), which satisfy the requirements of (5) and (6) [below These may be referred to as 1-butene copolymer (I), 1-butene copolymer (II), 1-butene copolymer (III), and 1-butene copolymer (IV). . ], 1-butene and a C3-C20 alpha olefin copolymer are preferable.

The 1-butene copolymer (I), (II) or (III) of the present invention is preferably a random copolymer. The structural unit obtained from 1-butene is preferably 90% by mole or more, more preferably 95% by mole or more. When the structural unit derived from 1-butene is less than 90 mol%, stickiness of the surface of the molded article or a decrease in transparency may occur.
Further, the stereoregularity index {(mmmm) / (mmrr + rmmr)} obtained from the (mmmm) fraction and (mmrr + rmmr) fraction of the 1-butene chain portion needs to be 20 or less, preferably 18 Hereinafter, it is more preferably 15 or less. When the stereoregularity index exceeds 20, a decrease in flexibility, a decrease in low-temperature heat sealability, and a decrease in hot tack property occur.
The 1-butene copolymer (I), (II) or (III) of the present invention has a molecular weight distribution (Mw / Mn) measured by gel permeation (GPC) method of 4.0 or less, preferably 3 .5 or less, particularly preferably 3.0 or less. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur.
The 1-butene copolymer (I), (II) or (III) of the present invention has a weight average molecular weight Mw measured by GPC method of 10,000 to 1,000,000, preferably 100,000 to 1. 1,000,000, more preferably 100,000 to 500,000. If the weight average molecular weight is less than 10,000, stickiness may occur, and if it exceeds 1,000,000, the fluidity may decrease and the moldability may be poor. In addition, the measuring method of said Mw / Mn and Mw is the same as the above.
In the 1-butene copolymer (I), (II) or (III) of the present invention, the component amount (H25) eluted in hexane at 25 ° C. is preferably 0 to 80% by weight, more preferably. 0 to 60% by weight, most preferably 0 to 50% by weight. H25 is an index indicating whether the amount of so-called stickiness component that causes stickiness, a decrease in transparency, or the like is large or small, and the higher this value, the greater the amount of sticky component. When H25 exceeds 80% by weight, the amount of the sticky component is large, so that blocking occurs, and it may not be used for food or medical applications. The method for measuring H25 is the same as described above.

In the 1-butene copolymer (II) or (III) of the present invention, the melting point (Tm) or (Tm-P) is not observed with a differential scanning calorimeter (DSC), or 0 to 0 in view of softness. It is necessary to be 100 ° C, and preferably 0 to 80 ° C. Further, when the melting points (Tm) and (Tm-P) are not observed, the [1-butene copolymer (I)] needs to have a melting point (Tm-D) of 0 to 100 ° C. The temperature is preferably 0 to 80 ° C. Tm, Tm-P, and Tm-D are determined by the above-described DSC measurement.
In the 1-butene copolymer (I), (II) or (III) of the present invention, 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 chain.
When the 1-butene polymer (I), (II) or (III) was an ethylene / butene copolymer, the butene content, R, and stereoregularity index 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 EE, EB, and BB chains are T.A. Hsieh and J.H. C. In accordance with the method proposed in Randall, Macromolecules, 1982, 15, 353-336, the Sαα carbon signal of the ¹³ C nuclear magnetic resonance spectrum was measured, and the EE, EB, BB dyad chain content in the copolymer molecular chain was measured. The rate was determined. 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] + [EB] / 2
Randomness index R = 4 [PP] [BB] / [EB] ²
([PP] represents the ethylene chain fraction, [BB] represents the butene chain fraction, and [EB] represents the ethylene-butene chain fraction.)
The stereoregularity index was measured by the method described above. In particular, in the ethylene / butene copolymer, the side chain methylene carbon derived from the BEE chain overlaps the peak of rmmr + mmrr. Correction was made by subtracting from the overlap intensity of the peak and the side chain methylene carbon peak from the BEE chain.
When the 1-butene polymer (I), (II) or (III) was a propylene / butene copolymer, the butene content and R 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 and BB chains are 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.)
When the 1-butene polymer (I), (II) or (III) is an octene / butene copolymer, the butene content and R 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 number: 4000 times Under the above conditions, the Sαα carbon signal of the ¹³ C nuclear magnetic resonance spectrum was measured, and the BB chain observed at 40.8 to 40.0 ppm, 41.3 to 40.40. The OO, OB, and BB dyad chain fractions in the copolymer molecular chain were determined from the peak intensity derived from the OB chain observed at 8 ppm and the OO chain observed at 42.5 to 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.)

In the 1-butene copolymer (IV) of the present invention, the structural unit derived from 1-butene needs to be 90 mol% or more, preferably 95 mol% or more. As the combination (IV), a homopolymer is preferable. ].
The 1-butene copolymer (IV) of the present invention is obtained by melting at 190 ° C. for 5 minutes, rapidly solidifying with ice water, leaving it at room temperature for 1 hour, and then analyzing by X-ray diffraction. Further, the type II crystal fraction (CII) is required to be 50% or less, preferably 20% or less, and more preferably 0%. The method for measuring the type II crystal fraction (CII) is the same as described above.
The 1-butene copolymer (IV) of the present invention has a weight average molecular weight (Mw) measured by the GPC method of 10,000 to 1,000,000 as a requirement (7) in addition to the above requirements. Is preferred. The weight average molecular weight is more preferably 100,000 to 1,000,000, and still more preferably 100,000 to 500,000. If Mw is less than 10,000, stickiness may occur. On the other hand, if it exceeds 1,000,000, the fluidity is lowered and the moldability may be poor. In addition, the measuring method of said Mw / Mn and Mw is the same as the above. Regarding the 1-butene copolymer in the present invention, 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-eicocene and the like can be mentioned. In the present invention, one or more of these can be used.
Furthermore, the 1-butene copolymer of the present invention preferably has a tensile modulus measured by a tensile test based on JIS K-7113 of 500 MPa or less, and more preferably 300 MPa or less. It is because sufficient softness may not be obtained when it exceeds 500 MPa.

[2] Method for producing 1-butene homopolymer (a) and 1-butene copolymer (a ′) 1-butene homopolymer (a) and 1-butene copolymer (a ′) in the present invention ) Is a method of homopolymerizing 1-butene using a catalyst system called a metallocene catalyst, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) ) Is copolymerized. Examples of the metallocene catalyst include JP-A-58-19309, JP-A-61-130314, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, and special tables. Transition metal compounds having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and the like, as described in JP-A-1-502036 Examples thereof include a catalyst obtained by combining a transition metal compound whose ligand is geometrically controlled and a promoter.

  In the present invention, among metallocene catalysts, the ligand is preferably composed of a transition metal compound that forms a crosslinked structure via a crosslinking group, and in particular, the crosslinked structure is formed via two crosslinking groups. A method of homopolymerizing 1-butene using a metallocene catalyst obtained by combining a transition metal compound and a cocatalyst formed, or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (however, 1 More preferred is a method of copolymerizing (excluding butene). Specifically, (A) the general formula (I)

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, A ligand selected from 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 ; In addition, they may be the same or different, X represents a sigma-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 , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, 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 —A ¹ R ^1- represents, 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. q represents 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 component (A) or a derivative thereof to form an ionic complex, and (B-2) an aluminoxane. A method of homopolymerizing 1-butene in the presence of a polymerization catalyst containing a component selected from 1 or a copolymerization of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) A method is mentioned.

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 among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same or different. 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 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, and they are identical to each other. But it can 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, and are bonded to each other to form a ring structure. (E represents 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 represents 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 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 or different, 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 heteroatom 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-propylcyclopentadienyl) (3'-methyl-5'- -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-propylcyclopentadi) Enyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopenta Dienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-i-propyl) Cyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bisindenyl zirconium dichloride, ( 1,1′-diphenylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2′- Methylsilylene) bisindenylzirconium dichloride, (1,1'-diisopropylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium 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 indenyl) ( 2,2′-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1 '-Dimethylsilyleneindenyl) (2,2'-diisopropylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diisopropylsilyleneindenyl) (2,2'-diisopropylsilylene-3-trimethylsilylindenyl) ) Zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) Zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2 ′ -Diphenylsil Len-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) Indenyl) (2,2′-diphenylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,1'-dimethylsilyleneindenyl) (2,2'-diisopropylsilylene-3-trimethylmethylsilylindenyl) Zirconium dichloride, (1,1'-diisopropylsilyleneindenyl) (2,2'- Diisopropyl Such as Ren -3-methyl silyl) zirconium dichloride and zirconium in these compounds may include those obtained by substituting titanium or hafnium. 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'-).

Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). The following general formulas (III) and (IV) can be used.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, 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, [Z] ⁻ Is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is an anion having a plurality of groups bonded to the element, ie, [M ¹ G ¹ G ² ... G ^f ] -(Wherein M ¹ represents a group 5 to 15 element of the periodic table, preferably a group 13 to 15 element of the periodic table. G ^{1 to} G ^f represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 20, respectively. Alkyl group, C2-C40 dialkylamino group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C7-C40 alkylaryl Group, an arylalkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, An organic metalloid group or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms, two or more of G ^{1 to} G ^f may form a ring, f is [(atom of central metal M ¹ Valence) +1])), [Z ² ] − is a conjugate base of Bronsted acid alone or a combination of Bronsted acid and Lewis acid having a logarithm (pKa) of reciprocal of acid dissociation constant of −10 or less Or a conjugate base of an acid generally defined as a super strong acid. In addition, 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 are each a cyclopentadienyl group or a substituted group. cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]
What is represented by these can be used conveniently.

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

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, Fe, Co, Ni, and Zn. And so on.

In [Z ¹ ]-, that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al. It is done. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like. Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Oromechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, such as diphenyl boron and the like.

Specific examples of non-coordinating anions, that is, Bronsted acids having a pKa of -10 or less, or conjugate bases [Z ² ]-in combination of Bronsted acids and Lewis acids include trifluoromethanesulfonate anions (CF ₃ SO ₃ )-, bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ )-, trifluoroacetate anion (CF ₃ CO ₂ ) -, hexafluoroantimony anion (SbF ₆₎ -, fluorosulfonic acid anion (FSO ₃₎ -, chlorosulfonic acid anion (ClSO ₃₎ -, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ / SbF ₅₎ -, Fluorosulfonate anion / 5- Arsenic _{(FSO 3 / AsF 5) -} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the component compound (B-1), include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetrapheny Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) tetraethylammonium borate, benzyl (tri-n-butyl) ammonium borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluoro) Phenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate, Dimethylanilinium trakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetrapheni Silver ruborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) ) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) trityl borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Teoraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, tri Examples thereof include silver fluoromethanesulfonate.
(B-1) may be used alone or in combination of two or more.

（式中、Ｒ¹⁵は炭素数１〜２０、好ましくは１〜１２のアルキル基，アルケニル基，アリール基，アリールアルキル基などの炭化水素基あるいはハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。なお、各Ｒ¹⁵は同じでも異なっていてもよい。）
で示される鎖状アルミノキサン、及び一般式（VI) On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

(Wherein R ¹⁵ 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 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the general formula (VI)

（式中、Ｒ¹⁵及びｗは前記一般式（Ｖ) におけるものと同じである。)
で示される環状アルミノキサンを挙げることができる。

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
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 is not particularly limited and may be reacted according to a known method. For example, (i) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (ii) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (iii) a metal There is a method of reacting water adsorbed on salt or the like with water adsorbed on inorganic or organic materials with an organoaluminum compound, (iv) a method of reacting a tetraalkyldialuminoxane with a 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 to (B) catalyst component is preferably 10: 1 to 1: 100 in 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 increases, which is not practical. 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 polymerization catalyst in the production method of the present invention can use an organoaluminum compound as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of component (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ 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 (VII) 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 be carried out using the above-mentioned component (A), component (B) and component (C). The preliminary contact can be performed by, for example, bringing the component (A) into contact with the component (B), but 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 catalyst activity and reducing the proportion of the (B) component that is the promoter. 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 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: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, 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 ¹⁷ _X X ¹ _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) ₂ , or a complex salt thereof can be given. Here, R ¹⁷ 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 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 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 , SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm.
If the particle size is small, fine powder in the polymer increases, and if 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 baking 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, (i) at least one of the component (A) and the component (B) is mixed with the carrier. A method, (ii) a method in which a support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (iii) the support and (A) A method of reacting the component and / or the component (B) with the organoaluminum compound or the halogen-containing silicon compound, (iv) after the component (A) or the component (B) is supported on the carrier, the component (B) or (A ) A method of mixing with the component, (v) a method of mixing the contact reaction product of the component (A) and the component (B) with the carrier, and (vi) a carrier during the contact reaction of the component (A) with the component (B). Can coexist .

In the above reactions (iv), (v) and (vi), 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 removing the solvent once and taking 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 200 A method of preliminarily polymerizing at about 1 minute to 2 hours to form 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 size 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 it is 50-500 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.

In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.
The 1-butene polymer used in 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 (however, 1 -(Butene is excluded).
In this case, 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, or a suspension polymerization method may be used. A 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, amount used, and polymerization temperature of each catalyst component, 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 that used.

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, per 1 mmol 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 composition The 1-butene resin composition comprises the 1-butene polymer [1], the 1-butene homopolymer [a], or the 1-butene copolymer [ a ′] is a resin composition obtained by adding a nucleating agent. In general, crystallization of a 1-butene polymer consists of two processes: a crystal nucleation process and a crystal growth process. In the crystal nucleation process, the temperature difference from the crystallization temperature, the state of molecular chain orientation, etc. It is said to affect the crystal nucleation rate. In particular, it is known that the rate of crystal nucleation is significantly increased when a substance having an effect of promoting molecular chain orientation exists through molecular chain adsorption or the like. Any nucleating agent may be used as long as it has an effect of improving the progress of the crystal nucleation process. Substances that have the effect of improving the progress rate of the crystal nucleation process include substances that have the effect of promoting molecular chain orientation through the process of adsorbing molecular chains of polymers.

Specific examples of the nucleating agent include high melting point polymers, organic carboxylic acids or metal salts thereof, aromatic sulfonates or metal salts thereof, organic phosphate compounds or metal salts thereof, dibenzylidene sorbitol or derivatives thereof, rosin acid. Examples thereof include partial metal salts, inorganic fine particles, imides, amides, quinacridones, quinones, and mixtures thereof.
Examples of the high melting point polymer include polyolefins such as polyethylene and polypropylene, polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, syndiotactic polystyrene, poly-3-methylpentene-1, poly-3-methylbutene-1, and polyalkenylsilane. Can be mentioned.
Examples of the metal salt include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrolecarboxylate.

  Dibenzylidene sorbitol or derivatives thereof include dibenzylidene sorbitol, 1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-2,4- Dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (o-4-chlorobenzylidene) sorbitol, 1,3: 2,4 -Dibenzylidene sorbitol etc. are mentioned. Specific examples include Gelall MD, Gelall MD-R (trade name) manufactured by Shin Nippon Rika Co., Ltd., and the like. Examples of the rosin acid partial metal salt include Pine Crystal KM1600, Pine Crystal KM1500, Pine Crystal KM1300 (trade name) manufactured by Arakawa Chemical Industries, Ltd.

Inorganic fine particles include talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice stone Examples thereof include powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, and molybdenum sulfide.
Examples of the amide compound include adipic acid dianilide, speric acid dianilide and the like.
One type of these nucleating agents may be used, or two or more types may be used in combination. As the 1-butene resin composition, it is preferable to use organic fine particles of an organic phosphate represented by the following general formula and / or inorganic fine particles such as talc as a nucleating agent with less generation of odor. This 1-butene resin composition is suitable for food applications.

（式中、Ｒ¹⁸は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ¹⁹及びＲ²⁰はそれぞれ水素原子、炭素数１〜１２のアルキル基、シクロアルキル基、アリール基又はアラルキル基を示す。Ｍはアルカリ金属、アルカリ土類金属、アルミニウム及び亜鉛のうちのいずれかを示し、Ｍがアルカリ金属のときｍは０を、ｎは１を示し、Ｍがアルカリ土類金属又は亜鉛のときｎは１又は２を示し、ｎが１のときｍは１を、ｎが２のときｍは０を示し、Ｍがアルミニウムのときｍは１を、ｎは２を示す。）
有機リン酸金属塩の具体例としては、アデカスタブＮＡ−１１やアデカスタブＮＡ−２１（旭電化株式会社（製））が挙げられる。

(In the formula, R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁹ and R ²⁰ represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, respectively. M represents any one of alkali metal, alkaline earth metal, aluminum and zinc, m represents 0 when M is an alkali metal, n represents 1, and M represents an alkaline earth metal or zinc n is 1 or 2, m is 1 when n is 1, m is 0 when n is 2, m is 1 when M is aluminum, and n is 2.)
Specific examples of the organic phosphate metal salt include ADK STAB NA-11 and ADK STAB NA-21 (Asahi Denka Co., Ltd.).

  Furthermore, as the 1-butene-based resin composition, it is preferable to use inorganic fine particles such as talc as a nucleating agent because, when formed into a film, it is excellent in slip properties and improves properties such as printing properties. . Furthermore, it is preferable to use the dibenzylidene sorbitol or a derivative thereof as a nucleating agent because of excellent transparency. Furthermore, it is preferable to use the amide compound as a nucleating agent because it is excellent in rigidity.

  The 1-butene resin composition includes a 1-butene polymer [1], the 1-butene homopolymer [a] or the 1-butene copolymer [a ′], a nucleating agent, and a desired one. The various additives used according to the above may be dry blended using a Henschel mixer or the like. Alternatively, it may be melt kneaded using a single-screw or twin-screw extruder, a Banbury mixer, or the like. Alternatively, when a high melting point polymer is used as the nucleating agent, the high melting point polymer may be simultaneously or sequentially added in the reactor when the 1-butene polymer is produced. Examples of various additives used as desired include an antioxidant, a neutralizing agent, a slip agent, an antiblocking agent, an antifogging agent, and an antistatic agent.

  The addition amount of the nucleating agent is usually 10 ppm or more with respect to the 1-butene polymer [1], the 1-butene homopolymer [a] or the 1-butene copolymer [a ′]. , Preferably it is the range of 10-10000 ppm, More preferably, it is the range of 10-5000 ppm, More preferably, it is 10-2500 ppm. If it is less than 10 ppm, improvement of the moldability is not observed, and on the other hand, even if an amount exceeding 10,000 ppm is added, the preferable effect may not increase.

[4] Molded body The molded body of the present invention is molded from the 1-butene polymer [1], the 1-butene homopolymer [a] or the 1-butene copolymer [a ′]. It is the molded object obtained by the above. The molded article of the present invention is characterized by being soft (also referred to as flexibility), having low stickiness for its low elastic modulus and excellent transparency.
Examples of the molded body of the present invention include a film, a sheet, a container, an automobile interior material, and a housing material for an electrical product. Examples of the film include a food packaging film and an agricultural film (an example of a greenhouse). As a container, since it is excellent in transparency, a transparent case, a transparent box, a decorative box, etc. are mentioned.
When the molded body of the present invention is a packaging material such as a film or a sheet, it has excellent low temperature heat sealing properties, a wide heat sealing temperature range, and excellent hot tack properties. In addition, it has tensile properties similar to polyvinyl chloride films.

Examples of the molding method include an injection molding method, a compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, and a blow molding method.
The molding conditions are not particularly limited as long as the temperature conditions allow the resin to melt and flow, and can usually be performed at a resin temperature of 50 ° C. to 300 ° C. and a mold temperature of 60 ° C. or less.
When forming a film as the molded article of the present invention, it can be performed by a general compression molding method, extrusion molding method, blow molding method, cast molding method or the like.
The film may or may not be stretched. In the case of stretching, biaxial stretching is preferred. Examples of the biaxial stretching conditions include the following conditions.
(i) Molding conditions during sheet molding Resin temperature 50 to 200 ° C, chill roll temperature 50 ° C or less
(ii) Longitudinal stretching conditions Stretching ratio: 3-7 times, stretching temperature: 50-100 ° C
(iii) Transverse stretching conditions Stretching ratio 6-12 times, stretching temperature 50-100 ° C
Moreover, the film may process the surface as needed, may enlarge surface energy, or may make the surface polar. For example, the treatment method includes corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone and ultraviolet irradiation treatment, and the like. Examples of the surface unevenness method include a sand blast method and a solvent treatment method.

The film can be blended with an antioxidant, a neutralizing agent, a slip agent, an antiblocking agent, an antifogging agent, an antistatic agent, or the like as required. In addition, films containing inorganic fine particles such as talc also have excellent slip properties, which improves secondary processability such as bag making and printing, and can be used for various general-purpose packaging films in high-speed production equipment such as various automatic filling and packaging laminates. Is preferred.
A film formed by molding a 1-butene-based resin composition containing the dibenzylidene sorbitol or a derivative thereof as a nucleating agent is particularly suitable for packaging toys, stationery, etc. because of its excellent transparency and large display effect. .
As a film formed by molding a 1-butene resin composition containing the amide compound as a nucleating agent, problems such as curling in high-speed bag making are unlikely to occur. Is preferred.
The 1-butene polymer, 1-butene homopolymer, and 1-butene copolymer of the present invention are excellent in compatibility with polypropylene. For this reason, a low-temperature heat-sealable PP film or the like can be produced by blending the polymer of the present invention and polypropylene. In addition, the polymer of the present invention can be blended with polyethylene or EVA resin, and the strength of the film or sheet can be controlled by this blending.

[5] 1-butene resin modifier The 1-butene resin modifier of the present invention is the 1-butene polymer [1], the 1-butene homopolymer [a], or the 1- A resin modifier comprising a butene copolymer [a ′]. The 1-butene-based resin modifier of the present invention is characterized in that it has a low melting point and is flexible and can give a molded article with little stickiness and excellent compatibility with a polyolefin resin. That is, as described above, the 1-butene resin modifier of the present invention is a specific one of 1-butene homopolymer and 1-butene copolymer, and is particularly crystalline in the poly-1-butene chain portion. Since this part is slightly present, the stickiness is less than that of a conventional flexible polyolefin resin, and the compatibility is excellent. Furthermore, the 1-butene resin modifier of the present invention is excellent in compatibility with polyolefin resins, particularly polypropylene resins. As a result, compared with the case where ethylene-based rubber or the like, which is a conventional modifier, is used, the surface characteristics (such as stickiness) are less deteriorated and the transparency is high. Due to the above characteristics, the 1-butene resin modifier of the present invention 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.

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples.
First, a method for evaluating resin properties and physical properties of the polymer of the present invention will be described.
(1) Measurement of mesopentad fraction, racemic triad fraction, abnormal insertion amount, and stereoregularity index The measurement was performed by the method described in the specification text.

(2) Measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) It was measured by the method described in the specification text.
(3) Measurement of comonomer content and randomness index R It was measured by the method described in the specification text.
(4) Measurement of H25 It was measured by the method described in the text of the specification.
(5) DSC measurement (melting point: measurement of Tm)
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 was melted at 220 ° C. for 3 minutes in a nitrogen atmosphere, and then cooled to −40 ° C. at 10 ° C./min. The melting endotherm obtained by keeping the temperature at −40 ° C. for 3 minutes and then raising the temperature at 10 ° C./min was defined as ΔH. The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as the melting point: Tm.
(6) DSC measurement (melting point: measurement of Tm-P and 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 was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then cooled to −10 ° C. at 5 ° C./min. The melting endotherm obtained by maintaining the temperature at −10 ° C. for 5 minutes and then increasing the temperature at 10 ° C./min was defined as ΔH-P. Further, the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time was defined as the melting point: Tm-P.
Using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The amount of heat was ΔH-D. Moreover, the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time was defined as melting point: Tm-D.
(7) Measurement of tensile elastic modulus A polymer was press-molded to prepare a test piece, and measured under the following conditions by a tensile test based on JIS K-7113.
・ Crosshead speed: 50mm / min
(8) An internal haze polymer was press-molded to prepare a test piece of 15 cm × 15 cm × 1 mm, and measured by a test based on JIS K-7105.
(9) Measurement of type II crystal fraction (CII) It was measured by the method described in the specification text.

Reference example 1
(i) Catalyst preparation
(1) Production of 2-chlorodimethylsilylindene Under a nitrogen stream, 50 ml of THF (tetrahydrofuran) and 2.5 g (41 mmol) of magnesium were added to a 1 liter three-necked flask, and 1,2-dibromoethane was added to the flask. .1 ml was added and stirred for 30 minutes to activate the magnesium. After stirring, the solvent was extracted and 50 ml of THF was newly added. A solution of 5.0 g (25.6 mmol) of 2-bromoindene in THF (200 ml) was added dropwise thereto over 2 hours. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to −78 ° C., and a solution of 3.1 mL (25.6 mmol) of dichlorodimethylsilane in THF (100 mL) was added dropwise over 1 hour and stirred for 15 hours. Then, the solvent was distilled off. The residue was extracted with 200 ml of hexane, and then the solvent was distilled off to obtain 6.6 g (24.2 ml) of 2-chlorodimethylsilylindene (yield 94%).
(2) Production of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) Under a nitrogen stream, 400 ml of THF and 8 g of 2-chlorodimethylsilylindene were placed in a 1-liter three-necked flask. Was added and cooled to -78 ° C. To this solution, 38.5 ml (38.5 mmol) of a THF solution (1.0 mol / liter) of LiN (SiMe ₃ ) ₂ was added dropwise. After stirring at room temperature for 15 hours, the solvent was distilled off and extracted with 300 ml of hexane. The solvent was distilled off to obtain 2.0 g (6.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) (yield 33.4%). ).
(3) Production of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indenyl) zirconium dichloride (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) in a Schlenk bottle ) -Bis (indene) (2.2 g, 6.4 mmol) and ether (100 ml) were added, cooled to -78 ° C., and n-butyllithium (hexane solution: 1.6 mol / liter) was added to 9.6 ml. (15.4 mmol) was added, followed by stirring at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with 20 ml of hexane to obtain a lithium salt. The obtained lithium salt was dissolved in 100 ml of toluene, and 1.5 g (6.4 mmol) of zirconium tetrachloride and 100 ml of toluene were added to another Schlenk bottle. To a 500 ml three-necked flask, 100 ml of toluene was added, cooled to 0 ° C., and the same amount of the lithium salt and zirconium tetrachloride was added dropwise over 1 hour using a cannula while stirring. After completion of dropping, the mixture was stirred overnight at room temperature. The solution was filtered and the solvent of the filtrate was distilled off. The obtained solid was recrystallized from dichloromethane to obtain 1.2 g (2.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indenyl) zirconium dichloride. (Yield 37%).
When ¹ H-NMR of this product was determined, the following results were obtained.
¹ H-NMR (CDCl ₃ ): 0.85, 1.08 (6H, s), 7.11 (2H, s), 7.2-7.7 (8H, m)

(ii) Polymerization 200 ml of 1-butene and 5 mmol of methylaluminoxane were added to a heat-dried 1 liter autoclave, and 0.1 MPa of hydrogen was further introduced. The temperature was raised to 65 ° C. with stirring, and 5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indenyl) zirconium dichloride obtained in (i) was added. Polymerized for minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 65 g of 1-butene homopolymer.
About the obtained 1-butene homopolymer, mesopentad fraction (mmmm), stereoregularity index {(mmmm) / (mmrr + rmmr)}, racemic triad fraction (rr), abnormal insertion amount, weight average molecular weight ( Mw), molecular weight distribution (Mw / Mn), melting point (Tm) and melting endotherm (ΔH) were measured. The results are shown in Table 1.

Reference example 2
(i) Catalyst preparation
(1) Production of (1,2′-SiMe ₂ ) (2,1′-SiMe ₂ ) (indenyl) (3-trimethylsilylmethylindenyl) zirconium chloride 3.5 g (10.2 mmol) of (1,2′-SiMe ₂ ) (2,1′-SiMe ₂ ) bis (indene) is added. A hexane solution (1.60M, 12.8 milliliters) of n-butyllithium (n-BuLi) is added dropwise thereto at -78 ° C. After touching at room temperature for 8 hours, the solvent was distilled off, and the obtained solid was dried under reduced pressure to obtain 5.0 g of a white solid. This solid is dissolved in 50 ml of THF, and 1.4 ml of iodomethyltrimethylsilane is added dropwise thereto at room temperature. 10 ml of water are added and the organic phase is extracted with 50 ml of ether. The organic phase is dried and the solvent is distilled off. Here, 50 ml of ether is added, and a hexane solution of n-BuLi (1.60 M, 12.4 ml) is added dropwise at -78 ° C. After raising to room temperature and stirring for 3 hours, the ether is distilled off. The obtained solid is washed with 30 ml of hexane and then dried under reduced pressure. 5.11 g of this white solid is made turbid in 50 ml of toluene, and 2.0 g (8.6 mmol) of zirconium tetrachloride suspended in 10 ml of toluene in another Schlenk is added. After stirring at room temperature for 12 hours, the solvent is distilled off, and the residue is washed with 50 ml of hexane. The residue was recrystallized from 30 ml of dichloromethane to obtain 1.2 g of yellow fine crystals (yield 25%).
¹ H-NMR (90 MHz, CDCl ₃ ): δ-0.09 (s, —SiMe ₃ , 9H); 0.89, 0.86, 1.03, 1.06 (s, —Me ₂ Si—, 12H); 2.20,2.65 (d, -CH 2 -, 2H); 6.99 (s, CH, 1H); 7.0-7.8 (m, ArH, 8H)
(ii) Polymerization 200 ml of 1-butene and 5 mmol of methylaluminoxane were added to a heat-dried 1 liter autoclave, and 0.1 MPa of hydrogen was further introduced. After the temperature was raised to 55 ° C. while stirring, 5 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-trimethylsilylmethylindenyl) (indenyl) zirconium dichloride was added for 30 minutes. Polymerized. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 43 g of 1-butene homopolymer.
About the obtained 1-butene homopolymer, mesopentad fraction (mmmm), stereoregularity index {(mmmm) / (mmrr + rmmr)}, racemic triad fraction (rr), abnormal insertion amount, weight average molecular weight ( Mw), molecular weight distribution (Mw / Mn), melting point (Tm) and melting endotherm (ΔH) were measured. The results are shown in Table 1.

Comparative Example 1
(i) Preparation of magnesium compound After thoroughly replacing the glass reactor with an internal volume of about 6 liters with a stirrer with nitrogen gas, about 2430 g of ethanol, 16 g of iodine and 160 g of metallic magnesium were charged and heated while stirring. The reaction was carried out under reflux conditions until the generation of hydrogen gas from the system ceased to obtain a solid reaction product. The magnesium compound was obtained by drying the reaction liquid containing this solid product under reduced pressure.
(ii) Preparation of solid catalyst component (A) Into a glass reactor having an internal volume of 5 liters sufficiently substituted with nitrogen gas, 160 g of the magnesium compound obtained in (i) above (unground), purified heptane 80 Charge milliliters, 24 ml of silicon tetrachloride and 23 ml of diethyl phthalate, keep the system at 80 ° C, add 770 ml of titanium tetrachloride while stirring and react at 110 ° C for 2 hours. Washed with 90 ° C. purified heptane. Further, 1220 ml of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours, and then thoroughly washed with purified heptane to obtain a solid catalyst component (A).

(iii) Polymerization To a heat-dried 1 liter autoclave, 200 ml of 1-butene, 2 mmol of triethylaluminum and 0.25 mmol of cineol were added, and 0.1 MPa of hydrogen was further introduced. The temperature was raised to 70 ° C. while stirring, and then 5 μmol of the solid catalyst component (A) was added at a Ti concentration to polymerize for 60 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 27 g of 1-butene copolymer.
About the obtained 1-butene homopolymer, mesopentad fraction (mmmm), stereoregularity index {(mmmm) / (mmrr + rmmr)}, racemic triad fraction (rr), abnormal insertion amount, weight average molecular weight ( Mw), molecular weight distribution (Mw / Mn), melting point (Tm · Tm-P), melting endotherm (ΔH · ΔH-P), tensile modulus and internal haze were measured. The results are shown in Table 1.

Reference example 3
(i) Catalyst Preparation In the same manner as in Reference Example 1, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indenyl) zirconium dichloride was produced.
(ii) Polymerization To a 1 liter autoclave that had been dried by heating, 200 ml of 1-butene and 10 mmol of methylaluminoxane were added, and the temperature was raised to 50 ° C. while stirring, and then obtained in (i) (1,2′- 10 micromoles of dimethylsilylene) (2,1′-dimethylsilylene) -bis (indenyl) zirconium dichloride was added and polymerized for 60 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 7 g of 1-butene homopolymer.
About the obtained 1-butene homopolymer, mesopentad fraction (mmmm), stereoregularity index {(mmmm) / (mmrr + rmmr)}, racemic triad fraction (rr), abnormal insertion amount, weight average molecular weight ( Mw), molecular weight distribution (Mw / Mn), melting point (Tm · Tm-P), melting endotherm (ΔH · ΔH-P), tensile modulus and internal haze were measured. The results are shown in Table 1.

Reference example 4
(i) Catalyst Preparation In the same manner as in Reference Example 1, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indenyl) zirconium dichloride was produced.
(ii) Polymerization 200 ml of 1-butene and 10 mmol of methylaluminoxane were added to a heat-dried 1 liter autoclave, and 0.1 MPa of hydrogen and 0.1 MPa of ethylene were further introduced. The temperature was raised to 50 ° C. while stirring, and 10 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indenyl) zirconium dichloride obtained in (i) was added to 60 ° C. Polymerized for minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 20 g of a 1-butene copolymer.
About the obtained 1-butene copolymer, the stereoregularity index, ethylene unit content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), melting point (Tm) and melting endotherm (ΔH ) Was measured. The results are shown in Table 1.

Reference Example 5
(i) Catalyst preparation
(1) (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) Production of zirconium dichloride (1,2'-dimethylsilylene) (2, 3.0 g (6.97 mmol) of the lithium salt of 1′-dimethylsilylene) -bis (indene) is dissolved in 50 ml of THF and cooled to −78 ° C. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane is slowly added dropwise and stirred at room temperature for 12 hours. Evaporate the solvent, add 50 ml of ether and wash with 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) (Yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. ) And 50 ml of ether. Cool to −78 ° C. and add dropwise n-BuLi in hexane (1.54 M, 7.6 mL (1.7 mmol)). After raising to room temperature and stirring for 12 hours, the ether is 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 is dissolved in 50 ml of toluene. After cooling to -78 ° C, a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride preliminarily cooled to -78 ° C in toluene (20 ml) is added dropwise. After dropping, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. The obtained residue was recrystallized with dichloromethane to obtain 0.9 g (1 of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride. .33 mmol) was obtained (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).
(ii) Polymerization 200 ml of 1-butene and 1 mmol of methylaluminoxane were added to a heat-dried 1 liter autoclave, and 0.03 MPa of hydrogen was further introduced. The temperature was raised to 50 ° C. while stirring, and 1 micromole of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added for polymerization for 20 minutes. did. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 21 g of 1-butene copolymer. About the obtained 1-butene copolymer, mesopentad fraction (mmmm), stereoregularity index {(mmmm) / (mmrr + rmmr)}, racemic triad fraction (rr), abnormal insertion amount, weight average molecular weight by the above method. (Mw), molecular weight distribution (Mw / Mn), melting point (Tm · Tm-P), melting endotherm (ΔH · ΔH-P), tensile modulus and internal haze were measured. The results are shown in Table 1.

Reference Example 6
20 parts by weight of the 1-butene homopolymer obtained in Reference Example 1 and 90 parts by weight of a polypropylene resin (J2000GP) manufactured by Idemitsu Petrochemical Co., Ltd. were used with a single screw extruder (manufactured by Tsukada Juki Seisakusho: TLC35-20). Extrusion granulation was performed to obtain pellets.
About the obtained pellet, the tensile elasticity modulus and the internal haze were measured by the said method. The results are shown in Table 1. As shown in Table 1, the tensile elastic modulus is lower than that of Comparative Example 2 described later, and the effect as a flexibility modifier is shown.

Comparative Example 2
About the polypropylene resin (J2000GP) by Idemitsu Petrochemical Co., Ltd., the tensile elasticity modulus and the internal haze were measured by the above method. The results are shown in Table 1.

Reference Example 7
(i) Catalyst Preparation In the same manner as in Reference Example 1, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was produced.
(ii) Polymerization 200 ml of heptane, 200 ml of 1-butene and 0.5 mmol of triisobutylaluminum were added to a heat-dried 1 liter autoclave, and 0.03 MPa of hydrogen was further introduced. The temperature was raised to 60 ° C. with stirring, 0.5 mmol of methylalmonoxane was added, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis ( 3-Trimethylsilylmethylindenyl) Zirconium dichloride was added at 0.5 micromole and polymerized for 30 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 36 g of 1-butene polymer.
About the obtained 1-butene polymer, mesopentad fraction (mmmm), stereoregularity index {(mmmm) / (mmrr + rmmr)}, racemic triad fraction (rr), abnormal insertion amount, R value, weight by the above method. Measures average molecular weight (Mw), molecular weight distribution (Mw / Mn), melting point (Tm · Tm-D · Tm-P), melting endotherm (ΔH · ΔH-D · ΔH-P), tensile modulus and internal haze did. The results are shown in Table 1.

Example 1
(i) Catalyst Preparation In the same manner as in Reference Example 1, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was produced.
(ii) Polymerization 200 ml of heptane, 200 ml of 1-butene and 0.5 mmol of triisobutylaluminum were added to a heat-dried 1 liter autoclave, and 0.03 MPa of hydrogen was further introduced. While stirring, the temperature was raised to 60 ° C., propylene was introduced, and the total pressure was continuously supplied at 0.2 MPa. Next, 0.5 mmol of methylalmonoxane was added, and (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium obtained in (i) was further added. 0.5 micromol of dichloride was added and polymerized for 30 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 21 g of 1-butene copolymer.
With respect to the obtained 1-butene copolymer, the comonomer content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), melting point (Tm · Tm-D · Tm-P), The amount of heat (ΔH · ΔH-D · ΔH-P), tensile modulus and internal haze were measured. The results are shown in Table 1.

Example 2
(i) Catalyst Preparation In the same manner as in Reference Example 1, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was produced.
(ii) Polymerization To a heat-dried 1 liter autoclave, 300 ml of heptane, 20 ml of 1-octene, 100 ml of 1-butene and 0.5 mmol of triisobutylaluminum were added, and 0.03 MPa of hydrogen was further introduced. While stirring, the temperature was set to 60 ° C., 1-octane was introduced, and the total pressure was continuously supplied at 0.2 MPa. Next, 0.5 mmol of methylalmonoxane was added, and (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium obtained in (i) was further added. 0.5 micromol of dichloride was added and polymerized for 30 minutes. After completion of the polymerization reaction, 13 g of 1-butene copolymer was obtained by drying the reaction product under reduced pressure.
With respect to the obtained 1-butene copolymer, the comonomer content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), melting point (Tm · Tm-D · Tm-P), The amount of heat (ΔH · ΔH-D · ΔH-P), tensile modulus and internal haze were measured. The results are shown in Table 1.

The 1-butene copolymer of the present invention and a molded product made of the polymer have little stickiness, excellent softness and transparency, or no change in physical properties due to crystal modification, and shrinkage does not occur in the molded product. It is suitable as a film, a sheet, a container, an automobile interior material, a housing material for home appliances, and the like. Examples of the film include a food packaging film and an agricultural film, and examples of the container include a transparent case, a transparent box, and a cosmetic box. Moreover, it can be conveniently used as a soft vinyl chloride resin substitute resin.
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 a polyolefin resin.

Claims (11)

A 1-butene copolymer which is a copolymer of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) and satisfying the following (1) to (4).
(1) 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 (2) 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 20 or less (3) Gel perm The molecular weight distribution (Mw / Mn) measured by an aation chromatograph (GPC) method is 4.0 or less. (4) The weight average molecular weight (Mw) measured by the GPC method is 10,000 to 1,000,000. 1-butene and a C3-C20 α-olefin (excluding 1-butene), which is a 1-butene copolymer satisfying the following (1 ′) to (4 ′) .
(1 ′) Using a differential scanning calorimeter (DSC), the sample was melted at 220 ° C. for 3 minutes in a nitrogen atmosphere, then cooled to −40 ° C. at 10 ° C./min, and held at −40 ° C. for 3 minutes. A crystalline resin (2 ′) solid having a melting point (Tm) defined as the peak top of the maximum peak of the melting endothermic curve obtained by raising the temperature at 10 ° C./min or 0 to 100 ° C. Regularity index {(mmmm) / (mmrr + rmmr)} is 20 or less (3 ′) Molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) method is 4.0 or less (4 ′) GPC method The weight average molecular weight (Mw) measured by the method is 10,000 to 1,000,000 A copolymer of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) and satisfying the following (1 ″) to (4 ″): Polymer.
(1 ″) Using a differential scanning calorimeter (DSC), the sample was melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./minute, and held at −10 ° C. for 5 minutes. Thereafter, the melting point (Tm-P) 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 10 ° C./min is not observed or 0 to 100 ° C. Molecular weight distribution (Mw / Mn) measured by gel permeation chromatograph (GPC) method with a crystalline resin (2 ″) stereoregularity index {(mmmm) / (mmrr + rmmr)} of 20 or less (3 ″) 4.0 or less (4 ″) The weight average molecular weight (Mw) measured by GPC method is 100,000 to 1,000,000.   The 1-butene copolymer according to any one of claims 1 to 3, wherein the structural unit derived from 1-butene is 90 mol% or more. The 1-butene copolymer according to claim 4, wherein the following randomness index R obtained from an α-olefin chain is 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.)   The 1-butene copolymer according to claim 5, wherein the structural unit derived from 1-butene is 95 mol% or more. A 1-butene copolymer satisfying the following (5) and (6).
(5) A copolymer of 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene), wherein the structural unit derived from 1-butene is 90 mol% or more (6) 190 Melted at 5 ° C. for 5 minutes, quenched and solidified with ice water, left at room temperature for 1 hour, and then analyzed by X-ray diffraction to obtain a type II crystal fraction (CII) of 50% or less Furthermore, the 1-butene-type copolymer of Claim 7 which satisfy | fills following (7).
(7) The weight average molecular weight (Mw) measured by GPC method is 10,000 to 1,000,000. (A) It reacts with the transition metal compound represented by the following general formula (I), and (B) (B-1) the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. 1-butene and an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) in the presence of a polymerization compound containing at least one component selected from (B-2) aluminoxane. The 1-butene copolymer according to any one of claims 1 to 8, which is obtained by polymerization.

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, A ligand selected from 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 ; In addition, they may be the same or different, X represents a sigma-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 , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, 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 —A ¹ R ^1- represents, 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. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]   The molded object formed by shape | molding the 1-butene type copolymer in any one of Claims 1-9.   A 1-butene resin modifier comprising the 1-butene copolymer according to any one of claims 1 to 9.