JP2000355612A - Propylene polymer, and production and molded item thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymer which is excellent in melt flowability, is little sticky, and gives a molded item excellent in softness and clarity. SOLUTION: This propylene polymer has such characteristics that: (1) the amount of components eluted in hexane at 25 deg.C is 0-80 wt.%; (2) the polymer does not exhibit its melting point (Tm) in differential scanning calorimetry or, when it exhibits its melting point, then Tm and the absorbed heat of melting ΔH (J/g) satisfy the relation: ΔH>=(6×(Tm-140)); and (3) it has a mol.wt. distribution (Mw/Mn) as measured by gel permeation chromatography of 2.5-14.0 and an intrinsic viscosity [η] at 135 deg.C in decalin of 0.5-15.0 dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel propylene polymer which can replace soft vinyl chloride, a method for producing the same, and a molded product. The present invention relates to a novel propylene-based polymer which gives a molded article having excellent flexibility and transparency, a method for producing the same, and a molded article.

[0002]

2. Description of the Related Art Vinyl chloride resin is widely used as a soft resin. However, vinyl chloride resin is known to generate harmful substances in the combustion process, and there is a strong demand for the development of an alternative resin. I have. In recent years, an olefin polymer produced using a metallocene catalyst has been proposed as an alternative resin. For example, a copolymer of ethylene and an α-olefin may be mentioned. However, when this copolymer is made soft, there is a disadvantage that a sticky component increases. Further, there is a problem that transparency is low and surface properties are inferior. In addition, the metallocene catalyst has a narrow molecular weight distribution of a polymer obtained due to the uniformity of its active site (J. Polym. Sci., Polm.
Chem. Ed. , 23 , 2117 (1985)), which is suitable for precision injection molding, ordinary injection molding, fiber molding, or the like.
Regarding foam and film forming, it was not always satisfactory.

[0003]

SUMMARY OF THE INVENTION The present invention provides a propylene-based polymer which is excellent in melt flowability, has low stickiness, and provides a molded product excellent in softness and transparency, a process for producing the same, and a molded product thereof. With the goal.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, (1) 25 ° C.
The amount of the component eluted in hexane is 0 to 80% by weight,
(2) In the DSC measurement, the melting point is not shown, or when the melting point is shown, the melting point and the melting endotherm satisfy a specific relationship, and (3) the molecular weight distribution is 2.5 to 14.0 and the intrinsic viscosity is 0.5. Propylene polymer satisfying 15.0 deciliters / g is excellent in melt fluidity, less sticky, and gives a molded article excellent in softness and transparency,
Based on this, the present invention has been completed. That is, the present invention provides the following propylene-based polymer, a method for producing the same, and a molded article. 1. A propylene polymer satisfying the following (1) to (3). (1) The amount of the component (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight. (2) In the DSC measurement, if the melting point (Tm (° C.)) is not shown or Tm is shown, And the melting endotherm ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm-140) (3) Gel Permeation Chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by the
The intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent is 0.5 to 15.0 deciliter / g. A propylene homopolymer that satisfies the following (1) to (3). (1) The mesopentad fraction (mmmm) is 20 to 85 mol%. (2) The racemic pentad fraction (rrrr) and (1-mm)
mm) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 (3) Gel Permeation Chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by the
2. The intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent is 0.5 to 15.0 deciliter / g. A propylene-based copolymer satisfying the following (1) and (2). (1) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%. (2) Gel permeation chromatography (GPC)
Molecular weight distribution (Mw / Mn) measured by the
3. The intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent is 0.5 to 15.0 deciliter / g. Frequency ω is 1 by frequency dispersion measurement of melt viscoelasticity
The propylene system according to any one of the above items 1 to 3, wherein the magnitude (η ^* ) (Pa · s) of the complex viscosity and the intrinsic viscosity [η] (deciliter / g) at 00 rad / sec satisfy the following relationship: Polymers, propylene homopolymers or propylene copolymers.

Η ^* <159η + 743 5. (A) reacts with a 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. Of propylene in the presence of a polymerization catalyst containing a compound selected from (B-2) an aluminoxane and propylene, or propylene and ethylene and / or 4-2 carbon atoms.
5. The method for producing a propylene polymer, a propylene homopolymer or a propylene-based copolymer according to any one of the above 1 to 4, wherein the propylene polymer is polymerized by a multi-stage polymerization step having at least a step of copolymerizing 0 α-olefin.

[0006]

Embedded image

[Wherein, M is a member of Groups 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Group, π-bonded hydrocarbon group or silicon-containing group
Ligand, wherein A¹And A^TwoThrough the cross-linking structure
And they are identical but different
X represents a σ-binding ligand;
A plurality of Xs may be the same or different,
X, E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Louis
Indicates a base, and when there are a plurality of Ys,
May be different, other Y, E¹, E^TwoOr crosslinked with X
A¹And A^TwoBinds two ligands
A divalent cross-linking group having 1 to 20 carbon atoms
Groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing
Organic group, germanium-containing group, tin-containing group, -O-, -C
O-, -S-, -SO_Two-, -Se-, -NR¹−, −
PR¹-, -P (O) R¹-, -BR¹-Or-AlR
¹-Indicates R¹Is hydrogen atom, halogen atom, carbon number 1
Containing 20 to 20 hydrocarbon groups or 1 to 20 carbon atoms
Show hydrocarbon radicals, which are identical or different
May be. q is an integer of 1 to 5 [(valence of M)-
2], and r represents an integer of 0 to 3. 6]. A propylene-based polymerization according to any one of the above 1 to 4.
Copolymer, propylene homopolymer or propylene copolymer
A molded body formed by molding.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the propylene-based polymer [1] of the present invention, its production method [2], and the molded article [3] will be described in detail. [1] Propylene Polymer The propylene polymer of the present invention includes the following (1) to (3)
It is a propylene-based polymer which requires. (1) The amount of the component (H25) eluted in hexane at 25 ° C. is from 0 to 80% by weight, and (2) the DSC measurement shows no melting point (Tm (° C.)) or Tm if Tm. And the melting endotherm ΔH (J / g) satisfy the following relationship: ΔH ≧ 6 × (Tm-140) and (3) gel permeation chromatography (GP)
The molecular weight distribution (Mw / Mn) measured by the method C) is 2.
5 to 14.0, and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is 0.5 to 15.0 deciliter /
By satisfying the above relationship, the propylene-based polymer of the present invention, which is g, can provide a molded article having excellent melt fluidity, little stickiness, and excellent softness and transparency.

Next, the above requirements will be described. The propylene-based polymer of the present invention has a component amount (H25) eluted in hexane at 25 ° C. of 0 to 80% by weight. Preferably from 0 to 50% by weight, particularly preferably from 0 to 25% by weight
It is. H25 is an index indicating whether the amount of a so-called sticky component that causes stickiness and a decrease in transparency is large or small, and a higher value indicates a larger amount of the sticky component. When H25 exceeds 85% by weight, the amount of the sticky component is large and the blocking resistance and the transparency are lowered.

[0010] Incidentally, H25 means the weight (W ₀ ) of the propylene-based polymer and the polymer in 200 mL of hexane.
Weight after drying at 25 ° C for 3 days or more (W ₁ )
Is measured and calculated by the following equation. H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%) Further, the propylene-based polymer of the present invention does not show a melting point (Tm (° C.)) or a Tm in DSC measurement.
, Tm and the melting endotherm ΔH (J / g) satisfy the following relationship.

ΔH ≧ 6 × (Tm−140) More preferably, ΔH ≧ 3 × (Tm−120), and particularly preferably ΔH ≧ 2 × (Tm−100).

Note that Tm and ΔH are determined by DSC measurement. That is, using a differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-7), 10 mg of a sample was melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then 0 ° C. at 10 ° C./min.
Cool down to Furthermore, after holding at 0 ° C. for 3 minutes, 10
The peak top of the maximum peak of the melting endothermic curve obtained by increasing the temperature at ° C./min is the melting point: Tm, and the melting endotherm in this case is ΔH.

Further, the propylene-based polymer of the present invention comprises
The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) under the apparatus and conditions described in the examples is 2.5 to 14.0, and the intrinsic viscosity measured at 135 ° C. in a decalin solvent. [η] is 0.5
１５15.0 deciliter / g. Preferably, Mw
/ Mn is 3.0 to 12.0, and [η] is 1.0 to
5.0 deciliter / g, particularly preferably 4.0 to 1
0.0, and [η] is 1.0 to 3.0 deciliter /
g. If the molecular weight distribution (Mw / Mn) is less than 2.5, the moldability will decrease, and if it exceeds 14.0, stickiness will occur. If the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness occurs. 15.0 deciliters /
If it exceeds g, the moldability becomes poor because the fluidity decreases.

Further, in addition to the above requirements, the propylene-based polymer of the present invention has a complex viscosity (η ^* ) (Pa ·) at a frequency ω of 100 rad / sec as measured by frequency dispersion measurement of melt viscoelasticity. s) and intrinsic viscosity [η]
(Deciliter / g) preferably satisfies the following relationship because the melt fluidity is improved.

Η ^* <159η + 743 More preferably, η ^* <159η + 600, and particularly preferably, the relationship of η ^* <159η + 500 is satisfied. (Η ^* ) (Pa · s) is a parallel plate (diameter 25 mm, gap 1 mm) in a rotational type rheometer (ARES) manufactured by Rheometrics Co., Ltd.
The frequency dispersion of the melt viscoelasticity is measured at a temperature of 230 ° C. and an initial strain of 20% or less. (Η ^* )
Is an index representing the fluidity of the molten resin during molding processing,
The smaller this value is, the higher the fluidity is, and the better the moldability is.

The propylene-based polymer of the present invention is not particularly limited as long as it satisfies the above requirements, and examples thereof include a propylene homopolymer and a propylene-based copolymer.
Among them, the propylene-based polymer of the present invention described above is more preferably realized by the following propylene homopolymer [a] or propylene-based copolymer [a ']. [A] Propylene homopolymer The propylene homopolymer of the present invention includes the following (1) to
It is a polymer that requires (3). (1) The mesopentad fraction (mmmm) is 20 to 85 mol%, and (2) the racemic pentad fraction (rrrr)
And (1-mmmm) satisfy the following relationship, and [rrrr / (1-mmmm)] ≦ 0.1 (3) Gel permeation chromatography (GPC)
Molecular weight distribution (Mw / Mn) measured by the
When the propylene homopolymer of the present invention having an intrinsic viscosity [η] of 0.5 to 15.0 deciliter / g as measured at 135 ° C. in a decalin solvent satisfies the above relationship, A molded article having excellent fluidity, low stickiness, and excellent softness and transparency can be obtained.

In the present invention, the mesopendad fraction (mm)
mm fraction) means A. Zambell (A. Zambell)
i) et al., "Macromolecules, 6 , 9
25 (1973) "and ¹³ C-
It is a meso fraction in a pentad unit in a polypropylene molecular chain measured by a signal of a methyl group in an NMR spectrum. When this is increased, it means that stereoregularity is increased. The propylene homopolymer of the present invention has a mesopendad fraction (mmmm fraction) of preferably 30 to 70%, particularly preferably 35 to 60%. The propylene homopolymer of the present invention has a mesopentad fraction (mmmm) of 2
If it is less than 0 mol%, it may cause stickiness. 85 mol%
If it exceeds, the elastic modulus is undesirably high. Similarly, the racemic pendad fraction (rrrr fraction) is a racemic fraction in pentad units in a polypropylene molecular chain.
[Rrrr / (1-mmmm)] is an index obtained from the above-mentioned fraction of the pentad unit and showing the uniformity of the regular distribution of the propylene homopolymer. When this value is increased, the regularity distribution is widened, and high regularity PP and AP like the conventional polypropylene produced using the existing catalyst system.
It becomes a mixture of P, which means that stickiness increases and transparency decreases. The propylene homopolymer of the present invention has a [r
rrr / (1-mmmm)] ≦ 0.08,
[Rrrr / (1-mmmm)] ≦ 0.06 is particularly preferred. The propylene homopolymer of the present invention [rrrr /
(1-mmmm)] exceeds 0.1, it causes stickiness. The measurement method using the ¹³ C-NMR spectrum will be described in detail in Examples.

Further, the propylene homopolymer of the present invention has a molecular weight distribution (Mw) measured by a gel permeation chromatography (GPC) method described in Examples.
/ Mn) is 2.5 to 14.0, and 1 in decalin solvent
The intrinsic viscosity [η] measured at 35 ° C. is 0.5 to 15.0.
It is deciliter / g. Preferably, Mw / Mn is 3.0 to 12.0, [η] is 1.0 to 5.0 deciliter / g, particularly preferably 4.0 to 10.0, and [η] is It is 1.0 to 3.0 deciliter / g.
If the molecular weight distribution (Mw / Mn) is less than 2.5, the moldability will decrease, and if it exceeds 14.0, stickiness will occur. If the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness occurs. On the other hand, if it exceeds 15.0 deciliters / g, the fluidity is reduced and the moldability is poor.

Furthermore, in addition to the above requirements, the propylene homopolymer of the present invention has a complex viscosity (η ^* ) (Pa · s) and intrinsic viscosity [η]
(Deciliter / g) preferably satisfies the following relationship because the melt fluidity is improved.

Η ^* <159η + 743 More preferably, η ^* <159η + 600, and particularly preferably, the relationship of η ^* <159η + 500 is satisfied. (Η ^* ) (Pa · s) is as described above.

Further, the propylene homopolymer of the present invention has a component amount (W25) of the propylene-based polymer eluted at 25 ° C. or lower in a temperature rising chromatography of 20 or less.
Preferably it is １００100% by weight. Particularly preferably, 3
0-100% by weight, most preferably 50-100% by weight. W25 is an index indicating whether or not the propylene-based polymer is soft. When this value is increased, it means that the component having a high elastic modulus is increased and / or the non-uniformity of the stereoregularity distribution is widened. In the present invention, if W25 is less than 20%, flexibility may be lost. In addition, W25 is the amount (weight) of the component that is not adsorbed to the packing material and eluted at the TREF column temperature of 25 ° C. in the elution curve measured and measured by the temperature rising chromatography under the operating method, apparatus configuration and measurement conditions described in Examples. %). In the present invention, W25 is 2
If it is less than 0%, flexibility may be lost.

Further, the propylene homopolymer of the present invention is preferably excellent in flexibility when the melting endothermic amount ΔH measured by DSC is 20 J / g or less. ΔH is an index indicating whether the material is soft or not, and when this value is increased, it means that the elastic modulus is high and the softness is low. Note that ΔH
Is determined by the above method.

Further, the propylene homopolymer of the present invention may or may not have a melting point (Tm) and a crystallization temperature (Tc), but it has no softness or has a low value, especially about Tm. The temperature is preferably 100 ° C. or lower. Note that Tm and Tc are determined by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), 10 mg of a sample is melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then the temperature is lowered to 0 ° C. at 10 ° C./min. The peak top of the maximum peak of the crystallization exothermic curve obtained at this time is the crystallization temperature: Tc. Further, after holding at 0 ° C. for 3 minutes, the temperature is raised at a rate of 10 ° C./minute, and the melting endotherm curve has a maximum peak at the melting point: Tm.

In general, in the polymerization of propylene, the carbon atom on the methylene side of the propylene monomer is bonded to the active site of the catalyst, and the propylene monomer is coordinated and polymerized in the same manner in the order of 1,2. Polymerization of insertion is usually performed, but rarely, 2,1 insertion or 1,3 insertion (also referred to as abnormal insertion) may occur. The homopolymer of the present invention preferably has a small amount of the 2,1 or 1,3 insertion. The ratio of these insertions is expressed by the following relational expression (1) [(m−2,1) + (r−2,1) + (1,3)] ≦ 5.0 (%) (1) [Wherein (m-2,1) is the meso-2,1 insertion content (%) measured by ¹³ C-NMR, and (r-2,1) is the ¹³ C-N
Racemic-2,1 insertion content (%) measured by MR,
(1,3) indicates the 1,3 insertion content (%) measured by ¹³ C-NMR. Is more preferable, and further satisfies the relational expression (2) [(m−2,1) + (r−2,1) + (1,3)] ≦ 1.0 (%) (2) Is more preferable. In particular, those satisfying the relational expression (3) [(m−2, 1) + (r−2, 1) + (1, 3)] ≦ 0.1 (%) (3) are most preferable. This relational expression (1)
If not, the crystallinity may be reduced more than expected, which may cause stickiness.

(M-2,1), (r-2,1) and (1,3) are reported by Grassi et al. (Macromolecule).
s, 21 , p. 617 (1988)) and a report by Busico et al. (Macromolecules, 27 , p. 7538 (1994)).
It is each insertion content determined from the integral intensity of each peak after the assignment of the peak of the ¹³ C-NMR spectrum was determined. That is, (m−2,1) is Pα, γthreth that appears around 17.2 ppm with respect to the integrated intensity in the entire methyl carbon region.
It is the meso-2,1 insertion content (%) calculated from the ratio of the integrated intensity of the peak attributed to o. (R-2,1) is
15.0p for integrated intensity in all methyl carbon region
It is the racemic-2,1 insertion content (%) calculated from the ratio of the integrated intensities of the peaks belonging to Pα and γthreo appearing near pm. (1, 3) is Tβ, which appears near 31.0 ppm relative to the integrated intensity in the entire methine carbon region.
1,3 insertion content (%) calculated from the ratio of the integrated intensity of peaks belonging to γ +.

Furthermore, the propylene homopolymer of the present invention
More preferably, in the measurement of the ¹³ C-NMR spectrum, a peak substantially not observed at the molecular chain end (n-butyl group) derived from the 2,1 insertion is observed. This two
For the molecular chain ends from one insertion, see Jungli
ng et al. (J. Polym. Sci .: Part A: Po1ym. C
^{hem., 33, 13 C-} NMR based on p1305 (1995))
The assignment of peaks in the spectrum is determined, and each insertion content is calculated from the integrated intensity of each peak. In the case of isotactic polypropylene, the peak appearing at around 18.9 ppm is assigned to the unsubstituted methyl group carbon of the n-butyl group.
In addition, ¹³ C-NM concerning abnormal insertion or molecular chain end measurement
The measurement of R may be performed using the above-described apparatus and conditions.

Further, in addition to the above requirements, the propylene homopolymer of the present invention preferably further has a boiling diethyl ether extraction amount, which is an index of the elastic modulus, of 5% by weight or more. The measurement of the boiling diethyl ether extraction amount will be described in Examples.

The propylene homopolymer of the present invention further has a tensile modulus of 100 MPa in addition to the above.
Or less, more preferably 70 MPa
It is as follows. [A '] Propylene-based copolymer The propylene-based copolymer of the present invention includes the following (1) to
The copolymer (2) is a copolymer of propylene, ethylene and / or an α-olefin having 4 to 20 carbon atoms. (1) The stereoregularity index (P) determined by ¹³ C-NMR measurement is 55 to 90 mol%, and (2) the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is 2. 5 to 14.0, and the intrinsic viscosity [η] measured at 135 ° C. in decalin solvent is 0.5 to 1
5.0 deciliter / g When the propylene-based copolymer of the present invention satisfies the above relationship, a molded article having excellent melt fluidity, low stickiness, and excellent flexibility and transparency can be obtained.

The stereoregularity index (P) in the present invention is:
This is a value obtained by measuring a mesotriad (mm) fraction of a propylene chain by a ¹³ C-NMR spectrum, and the larger this value is, the higher the stereoregularity is.
The propylene copolymer of the present invention more preferably has a stereoregularity index (P) of 65 to 80 mol%.
If the stereoregularity index (P) is less than 55 mol%, the elasticity is too low, resulting in poor moldability. 90 mol%
If it exceeds, it will not be soft.

Further, the propylene-based copolymer of the present invention has a molecular weight distribution (Mw) measured by a gel permeation chromatography (GPC) method described in Examples.
/ Mn) is 2.5 to 14.0, and 1 in decalin solvent
The intrinsic viscosity [η] measured at 35 ° C. is 0.5 to 15.0.
It is deciliter / g. Preferably, Mw / Mn is 3.0 to 12.0, [η] is 1.0 to 5.0 deciliter / g, particularly preferably 4.0 to 10.0, and [η] is It is 1.0 to 3.0 deciliter / g.
If the molecular weight distribution (Mw / Mn) is less than 2.5, the moldability will decrease, and if it exceeds 14.0, stickiness will occur. If the intrinsic viscosity [η] is less than 0.5 deciliter / g, stickiness occurs. On the other hand, if it exceeds 15.0 deciliters / g, the fluidity is reduced and the moldability is poor.

Further, in addition to the above-mentioned requirements, the propylene-based copolymer of the present invention has a complex viscosity coefficient (η ^* ) (Pa ^* ) at a frequency ω of 100 rad / sec as measured by frequency dispersion measurement of melt viscoelasticity.・ S) and intrinsic viscosity [η]
(Deciliter / g) preferably satisfies the following relationship because the melt fluidity is improved.

Η ^* <159η + 743 More preferably, η ^* <159η + 600, and particularly preferably, the relationship of η ^* <159η + 500 is satisfied. (Η ^* ) (Pa · s) is as described above.

Further, in the propylene copolymer of the present invention, the component amount (W25) of the propylene polymer eluted at a temperature of 25 ° C. or lower in temperature rising chromatography is 20%.
Preferably it is １００100% by weight. Particularly preferably, 3
0-100% by weight, most preferably 50-100% by weight. If W25 is less than 20%, flexibility may be lost. The meaning of W25 and the measuring method are the same as described above.

Further, the propylene copolymer of the present invention is preferably excellent in flexibility when the melting endotherm ΔH measured by DSC is 20 J / g or less. Further, the melting point (Tm)
The crystallization temperature (Tc) may or may not be present, but it is preferable not to consider the softness or to have a low value, particularly, Tm of 100 ° C. or less. Note that ΔH, T
The method for measuring m and Tc is the same as described above.

In addition to the above requirements, the propylene-based copolymer of the present invention preferably further has a boiling diethyl ether extraction amount, which is an index of the elastic modulus, of 5% by weight or more.

The tensile modulus is preferably 100 MPa or less, more preferably 70 MPa or less.

In the propylene copolymer of the present invention, the α-olefin having 4 to 20 carbon atoms includes ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene. , 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene, 1-eicosene and the like can be mentioned, and in the present invention, one or more of these can be used.

Further, the propylene copolymer of the present invention is preferably a random copolymer. Further, the structural unit obtained from propylene is preferably at least 90 mol%, more preferably at least 95 mol%. [2] Method for producing propylene homopolymer [a] and propylene-based copolymer [a ']] The method for producing the propylene homopolymer [a] and the propylene-based copolymer [a'] of the present invention includes: In the presence of a catalyst system called a metallocene catalyst, propylene is homopolymerized, or propylene and ethylene and / or α having 4 to 20 carbon atoms are used.
A method of homopolymerizing or copolymerizing propylene by a multi-stage polymerization step having at least a step of copolymerizing an olefin. Examples of metallocene catalysts include JP-A-58-19309 and JP-A-61-13031.
No. 4, JP-A-3-1630088, JP-A-4-163
No. 300887, Japanese Unexamined Patent Publication No. Hei 4-21694,
A cyclopentadienyl group, a substituted cyclopentadienyl group, and the like, as described in
Examples thereof include a transition metal compound having one or two ligands having an indenyl group, a substituted indenyl group, or the like, and a catalyst obtained by combining a co-catalyst with a transition metal compound in which the ligand is geometrically controlled.

In the present invention, among the metallocene catalysts, it is preferable that the ligand comprises a transition metal compound forming a crosslinked structure via a crosslinking group.
In the presence of a metallocene catalyst obtained by combining a transition metal compound forming a crosslinked structure via two crosslinking groups with a cocatalyst, propylene is homopolymerized, or propylene and ethylene and / or α having 4 to 20 carbon atoms are used. A method of polymerizing by a multi-stage polymerization step having at least a step of copolymerizing an olefin is more preferable. To give a concrete example,
(A) General formula (I)

[0040]

Embedded image

[Wherein M is a group 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Group, π-bonded hydrocarbon group or silicon-containing group
Ligand, wherein A¹And A^TwoThrough the cross-linking structure
And they are identical but different
X represents a σ-binding ligand;
A plurality of Xs may be the same or different,
X, E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Louis
Indicates a base, and when there are a plurality of Ys,
May be different, other Y, E¹, E^TwoOr crosslinked with X
A¹And A^TwoBinds two ligands
A divalent cross-linking group having 1 to 20 carbon atoms
Groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing
Organic group, germanium-containing group, tin-containing group, -O-, -C
O-, -S-, -SO_Two-, -Se-, -NR¹−, −
PR¹-, -P (O) R¹-, -BR¹-Or-AlR
¹-Indicates R¹Is hydrogen atom, halogen atom, carbon number 1
Containing 20 to 20 hydrocarbon groups or 1 to 20 carbon atoms
Show hydrocarbon radicals, which are identical or different
May be. q is an integer of 1 to 5 [(valence of M)-
2], and r represents an integer of 0 to 3. ] Represented by
Transition metal compound and (B) transition of the (B-1) (A) component
Ionic complex by reacting with transfer metal compound or its derivative
From a compound capable of forming an isocyanate and (B-2) aluminoxane
Propylene in the presence of a polymerization catalyst containing the selected components
Homopolymerization of propylene, or propylene and ethylene and / or charcoal
A step of copolymerizing an α-olefin having a prime number of 4 to 20 is reduced.
At least, there is a method of polymerizing by a multi-stage polymerization process.
I can do it.

In the above general formula (I), M is the periodic table
A metal element of group 3 to 10 or a lanthanoid series,
Specific examples include titanium, zirconium, hafnium,
Thorium, vanadium, chromium, manganese, nickel
Metal, cobalt, palladium and lanthanoid metals
Among them, olefin polymerization active among these
Titanium, zirconium and hafnium are preferred
It is. E¹And E^TwoIs a substituted cyclopentadi
Enyl group, indenyl group, substituted indenyl group, heterocy
Clopentadienyl group, substituted heterocyclopentadienyl
Amide group (-N <), phosphide group (-P <),
including π-bonded hydrocarbon groups [> CR-,> C <] and silicon
Organic group [> SiR-,> Si <] (where R is hydrogen or
Hydrocarbon group having 1 to 20 carbon atoms or hetero atom-containing group
Is a ligand selected from the group consisting of¹And A^Two
To form a crosslinked structure. π-bonded hydrocarbon
As the group [> CR-,> C <], a pentadienyl group,
Boratabenzinyl group and the like. Silicon-containing group [> S
iR-,> Si <] represents -CH_Two-Si (C
H _Three) <, -Si (CH_Three) <, Etc. Ma
E¹And E^TwoMay be the same or different
No. This E¹And E^TwoAs a substituted cyclopentadie
Nyl, indenyl and substituted indenyl groups are preferred.
No.

X represents a σ-binding ligand, and when there are a plurality of Xs, a plurality of Xs may be the same or different and are cross-linked to other X, E ¹ , E ² or Y. You may.
Specific examples of X include a halogen atom and a carbon atom having 1 to 20 carbon atoms.
Hydrocarbon group, C1-20 alkoxy group, C6-20 aryloxy group, C1-20 amide group, C1-20 silicon-containing group, C1-20 phosphide Group, sulfide group having 1 to 20 carbon atoms, 1 carbon atom
And 20 acyl groups. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group and an octyl group, a vinyl group, a propenyl group, and a cycloalkyl group. Alkenyl groups such as hexenyl group; arylalkyl groups such as benzyl group, phenylethyl group and phenylpropyl group;
And aryl groups such as phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group and phenanthonyl group. Among them, an alkyl group such as a methyl group, an ethyl group and a propyl group and an aryl group such as a phenyl group are preferable. Examples of the alkoxy group having 1 to 20 carbon atoms include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, a phenylmethoxy group and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include dimethylamide group, diethylamide group, dipropylamide group, dibutylamide group, dicyclohexylamide group, alkylamide group such as methylethylamide group, divinylamide group, dipropenylamide group. And alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; and arylamide groups such as diphenylamide group and dinaphthylamide group. Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group; Tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group,
Trihydrocarbon-substituted silyl groups such as tritolylsilyl group and trinaphthylsilyl group; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; silicon-substituted alkyl groups such as trimethylsilylmethyl group; silicon-substituted aryl groups such as trimethylsilylphenyl group Is mentioned. Among them, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group and the like are preferable. 1-20 carbon atoms
Examples of the sulfide group include methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, alkyl sulfide group such as octyl sulfide group, vinyl sulfide group, propenyl sulfide group,
Alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group and phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethyl phenyl sulfide group, trimethyl phenyl sulfide group, ethyl phenyl And aryl sulfide groups such as a sulfide group, a propylphenyl sulfide group, a biphenyl sulfide group, a naphthyl sulfide group, a methyl naphthyl sulfide group, an anthracenyl sulfide group and a phenanthyl sulfide group. Examples of the sulfoxide group having 1 to 20 carbon atoms include alkylsulfoxide groups such as methylsulfoxide group, ethylsulfoxide group, propylsulfoxide group, butylsulfoxide group, hexylsulfoxide group, cyclohexylsulfoxide group, octylsulfoxide group, vinylsulfoxide group, and propenyl. An alkenyl sulfoxide group such as a sulfoxide group and a cyclohexenyl sulfoxide group; an arylalkyl sulfoxide group such as a benzyl sulfoxide group, a phenylethyl sulfoxide group and a phenylpropyl sulfoxide group; a phenyl sulfoxide group;
Tolylsulfoxide group, dimethylphenylsulfoxide group, trimethylphenylsulfoxide group, ethylphenylsulfoxide group, propylphenylsulfoxide group,
Biphenylsulfoxide group, naphthylsulfoxide group,
And arylsulfoxide groups such as methylnaphthylsulfoxide group, anthracenylsulfoxide group, and phenanthonylsulfoxide group. Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, tearoyl group, alkylacyl group such as oleoyl group, benzoyl group, toluoyl group, salicyloyl group, Examples include arylacyl groups such as cinnamoyl group, naphthoyl group, and phthaloyl group; oxalyl groups, malonyl groups, and succinyl groups derived from dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid.

On the other hand, Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys 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. Examples of the amines include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine,
Alkylamines such as dipropylamine, dibutylamine, dicyclohexylamine and methylethylamine, and alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine and dicyclohexenylamine; phenylamine, phenylethylamine and phenylpropyne And arylamines such as diamine, diphenylamine and dinaphthylamine. Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether and ethyl allyl ether; anisole Phenetole, phenyl ether,
Benzyl ether, phenylbenzyl ether, α-naphthyl ether, aromatic ether compounds such as β-naphthyl ether, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran,
And cyclic ether compounds such as dioxane. Examples of the phosphines include phosphines having 1 to 20 carbon atoms. Specifically, monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Phosphine, dihydrocarbon-substituted phosphines such as dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine;
Monoalkenyl phosphines such as vinyl phosphine, propenyl phosphine and cyclohexenyl phosphine, and dialkenyl phosphine in which two hydrogen atoms of phosphine are substituted by two alkenyls; trialkenyl phosphine in which three hydrogen atoms of phosphine are substituted by three alkenyls; benzyl phosphine, phenylethyl Arylalkylphosphines such as phosphine and phenylpropylphosphine; diarylalkylphosphine or aryldialkylphosphine in which three hydrogen atoms of phosphine are substituted with three aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, Propylphenylphosphine, biphenylphosphine, naphthylphosphine, methyl Naphthylphosphine, anthracenylphosphine, phenanthylphosphine; di (alkylaryl) phosphine in which two alkylaryls are substituted for phosphine hydrogen atoms; tri (alkylaryl) phosphine in which three alkylaryls are substituted for phosphine hydrogen atoms And aryl phosphines. Examples of the thioethers include the above-mentioned sulfides.

Next, A ¹ and A ² are divalent bridging groups linking two ligands, and include a hydrocarbon group having 1 to 20 carbon atoms and a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. , Silicon-containing group, germanium-containing group, tin-containing group, -O-, -C
O -, - S -, - SO 2 -, - Se -, - NR 1 -, -
PR ^1- , -P (O) R ^1- , -BR ¹ -or -AlR
¹ - are shown, R ¹ represents a hydrogen atom, a halogen atom, a carbon number 1
-20 to 20 or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. At least one of such crosslinking groups is preferably a crosslinking group comprising a hydrocarbon group having 1 or more carbon atoms. As such a crosslinking group, for example, a general formula

[0046]

Embedded image

(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. And e represents an integer of 1 to 4. Specific examples thereof include methylene, ethylene, ethylidene, propylidene, isopropylidene, cyclohexylidene, and the like. 1,2-cyclohexylene group, vinylidene group (CH ₂ ＣC =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldisilylene And the like. Among them, an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred. q is an integer of 1 to 5 [(valence of M)-
2], and r represents an integer of 0 to 3.

In the transition metal compound represented by the general formula (I), when E ¹ and E ² are a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group,
The bond of the crosslinking group of ¹ and A ² is (1,2 ′) (2,
1 ') Double cross-linking type is preferred. Such a general formula (I)
Among the transition metal compounds represented by the general formula (II)

[0049]

Embedded image

A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferable.

In the general formula (II), M, A ¹ , A
² , q and r are the same as above. X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same as those exemplified in the description of X in the general 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 include the same as those exemplified in the description of Y in the general formula (I). R ⁴ to R ⁹ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group, at least one One needs to be not a hydrogen atom. Further, R ^{4 to} R ⁹ may be the same or different, and adjacent groups may be bonded to each other to form a ring. Above all, R
It is preferable that ⁶ and R ⁷ form a ring, and that R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ ,
Groups containing a heteroatom such as oxygen, halogen, silicon and the like are preferred because of their high polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably has a (1,2 ') (2,1') double-bridged ligand.

Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-
Ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene)-
Bis (indenyl) zirconium dichloride, (1,
2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)-
Bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-ethylene) ( 2,1'-ethylene) -bis (4,7-diisopropylindenyl)
Zirconium dichloride, (1,2'-ethylene)
(2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,
2′-ethylene) (2,1′-ethylene) -bis (5
6-benzoindenyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride,
(1,2′-methylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride,
Methylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-i-propylindenyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) 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-propylindene Nyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-dimethylsilylene) 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) zirconium dichloride, (1,
2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylindenyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride , (1,2 '
-Dimethylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethyl (Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (indenyl) zirconium dichloride, (1,
2'-diphenylsilylene) (2,1'-methylene)-
Bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) )
(2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 '-Methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) ( 3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene)
(2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-
Isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3'-
Methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride,
(1,2′-isopropylidene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3 ′
-Methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) (Enyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,
2'-dimethylsilylene) (2,1'-ethylene)
(3,4-dimethylcyclopentadienyl) (3 ′,
4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′
-Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene)
(2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropyl) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,
2'-isopropylidene) (2,1'-isopropylidene) (3,4-dimethylcyclopentadienyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-
Methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-dimethylsilylene) (3-methyl-5-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, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5
-N-butylcyclopentadienyl) (3'-methyl-
5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl)
(3′-methyl-5′-ethylcyclopentadienyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-
Ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-
Dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,
1′-methylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Methylene) (3-methyl-
5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene)
(2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride,
(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2'-Ethylene) (2,1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-
i-propylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5 '-I-propylcyclopentadienyl) zirconium dichloride, (1,
2′-methylene) (2,1′-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium dichloride, , 2'-methylene) (2,
1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i
-Propylcyclopentadienyl) zirconium dichloride and the like in which zirconium in these compounds is replaced with titanium or hafnium. Of course, it is not limited to these. Also,
It may be a similar compound of a metal element of another group or a lanthanoid series.

Next, as the component (B-1) of the component (B), any compound which can react with the transition metal compound of the above component (A) to form an ionic complex can be used. The following general formulas (III), (IV) ([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b ... (III) ([L ² ] ^{k +} ) _a ([Z] ^-) _b ··· (IV) (provided that, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R
A 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] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 G 1 G 2 ··· G} f ] ^- (wherein, M ¹ is the periodic table 5-15 A group element, preferably a group 13 to 15 element of the periodic table, wherein G ^{1 to} G ^f are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, Number 1
An alkoxy group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and having 1 to 20 carbon atoms It represents a halogen-substituted hydrocarbon group, 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. G ¹
Two or more may form a ring of ~G ^f. f represents an integer of [(valence of central metal M ¹⁾ +1]. ),
[Z ^{2] -} is the reciprocal of the acid dissociation constant logarithm (pKa) is -
A conjugate base of 10 or less Brönsted acid alone or a combination of a Bronsted acid and a Lewis acid, or a conjugate base of an acid generally defined as a super strong acid is shown. Further, 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 each represent a cyclopentadienyl group,
A substituted cyclopentadienyl group, indenyl group or fluorenyl group, and R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is [L ¹ -R ¹⁰ ], [L
² ] an ionic valence of 1 to 3; a is an integer of 1 or more;
b = (k × a). M ² is the first to third periodic table of the periodic table
Is intended to include a 1～13,17 group elements, M ³ represents a periodic table 7-12 group element. ] Can be suitably used.

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

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group and trityl group, and specific examples of R ¹¹ and R ¹² include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ¹³ include a phenyl group, a p-tolyl group, a p-methoxyphenyl group and the like, and specific examples of R ¹⁴ include a 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, F
e, Co, Ni, Zn and the like.

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

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , a fluorosulfonic acid anion (FS
O ₃ ) ^- , chlorosulfonic acid anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅₎ ^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the compound of the component (B-1), include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n-butyl) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) , Triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
(1,1'-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, manganese tetrakis (pentafluorophenyl) borate, porphyrin manganese porphyrin, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

As the component (B-1), a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) may be used alone or in combination of two or more. You may.

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

[0062]

Embedded image

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

[0064]

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(Wherein, R ¹⁵ and w are the same as those in formula (V)).

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. The method is not particularly limited, and the reaction may be carried out according to a known method. For example,
A method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and water is added later, water of crystallization contained in a metal salt or the like, an inorganic substance Reacting water adsorbed on organic substances with organic aluminum compounds,
There is a method in which a tetraalkyldialuminoxane is reacted with a trialkylaluminum and then with water. The aluminoxane may be toluene-insoluble.

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

In the production method of the present invention, the polymerization catalyst is
An organoaluminum compound can be used as the component (C) in addition to the components (A) and (B). Here, as the organoaluminum compound of the component (C), a compound represented by the general formula (VII): R ¹⁶ _v AlJ _3-v (VII) wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms, and J is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
And v is an integer of 1 to 3].

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride and dimethylaluminum. Aluminum 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 performed using the above-mentioned components (A), (B) and (C). The preliminary contact can be performed by bringing the component (A) into contact with the component (B), for example, 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 cocatalyst (B) used. 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-mentioned effect. The pre-contact temperature is usually -20C to 200C, preferably -10C to 1C.
The temperature is 50C, more preferably 0C to 80C. In the preliminary contact, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as a 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: 1000 in molar ratio.
0, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1: 1000.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least one of the catalyst components can be used by being supported on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier,
Any of other inorganic carriers and organic carriers can be used, but inorganic oxide carriers and other inorganic carriers are particularly preferred.

As the inorganic oxide carrier, specifically, S
_{iO 2, Al 2 O 3,} MgO, ZrO 2, TiO 2, F
e ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO
₂ and mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like.
Among them, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like.

On the other hand, as a carrier other than the above, MgC
general formula Mg represented by l ₂ , Mg (OC ₂ H ₅ ) _2, etc.
Magnesium compounds and their complex salts represented by R ¹⁷ _{X X} ¹ _y can be exemplified. Here, R ¹⁷ has 1 to 1 carbon atoms.
20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms or aryl groups 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 0, 2 and x + y = 2. Each R ¹⁷ and each X ¹
May be the same or different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.

The carrier used in the present invention includes:
MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC
₂ H _{5) 2,} such as SiO _2, Al ₂ O ₃ is preferred. The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm.
m, more preferably 20 to 100 μm. If the particle size is small, the fine powder in the polymer increases, and if the particle size is large, the coarse particles in the polymer increase, causing a decrease in bulk density and clogging of a hopper.

The specific surface area of the carrier is usually from 1 to 100.
0m^Two/ G, preferably 50 to 500 m^Two/ G, pore volume
The product is usually 0.1-5cm^Three/ G, preferably 0.3-3
cm ^Three/ G.

If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). reference).

Further, the above-mentioned carrier is usually 150 to 100
It is desirable to use by firing at 0 ° C, preferably 200 to 800 ° C.

When at least one of the catalyst components is supported on the carrier, at least one of the catalyst components (A) and (B), preferably the catalyst components (A) and (B)
It is desirable to support both of the catalyst components.

The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the component (A) and the component (B) is mixed with the carrier. Method, a method of treating a carrier with an organoaluminum compound or a halogen-containing silicon compound, and then mixing the carrier with at least one of the component (A) and the component (B) in an inert solvent.
Or a method of reacting the component (B) with an organoaluminum compound or a halogen-containing silicon compound, a method of supporting the component (A) or the component (B) on a carrier, and then mixing the component (B) or the component (A). And a method of mixing the contact reactant of the components (A) and (B) with the carrier, and a method of coexisting the carrier during the contact reaction between the components (A) and (B).

In the above and the above reactions,
An organoaluminum compound as the component (C) can be added.

In the present invention, the above (A), (B),
When contacting (C), an elastic wave may be irradiated to prepare a catalyst. Examples of the elastic wave include a sound wave, particularly preferably an ultrasonic wave. Specifically, the frequency is 1 to 1
000 kHz ultrasonic wave, preferably 10-500 kHz
Ultrasound.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is.

In the present invention, the catalyst can be produced by carrying out the operation of loading at least one of the component (A) and the component (B) on a carrier in 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
A method of adding 0 kg / cm ² and performing prepolymerization at −20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the weight ratio of the component (B-1) to the carrier is preferably 1: 5 to 1:10.
000, more preferably 1:10 to 1: 500, and the use ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000 by weight, more preferably It is desirable to set it as 1: 1 to 1:50. When two or more components (B) are used as a mixture, it is desirable that the use ratio of each component (B) to the carrier be within the above range in terms of weight ratio. Further, the use ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 by weight.

The component (B) [component (B-1) or (B-
2) Component] and carrier, or (A) Component and carrier
If the use ratio with the above deviates from the above range, the activity decreases
Sometimes. The weight according to the present invention thus prepared is
The average particle size of the combined catalyst is usually 2 to 200 μm, preferably
Is 10 to 150 μm, particularly preferably 20 to 100 μm
And the specific surface area is usually 20 to 1000 m^Two/ G, good
Preferably 50-500m ^Two/ G. Average particle size is 2μ
m, the fine powder in the polymer may increase,
If it exceeds 200 μm, coarse particles in the polymer may increase.
There is. Specific surface area is 20m^Two/ G is less than
1000m^Two/ G exceeds polymerization
The bulk density of the body may decrease. In the present invention,
Catalyst, the amount of transition metal in 100 g of the carrier is usually
0.05 to 10 g, preferably 0.1 to 2 g
No. If the amount of the transition metal is outside the above range, the activity will be low.
Sometimes.

By supporting on a carrier as described above, a polymer having a high bulk density and excellent particle size distribution, which are industrially advantageous, can be obtained.

The propylene homopolymer [a] and the propylene-based copolymer [a '] of the present invention are prepared by homopolymerizing propylene or propylene and ethylene and / or It is produced by a method of homopolymerizing or copolymerizing propylene by a multistage polymerization step having at least a step of copolymerizing an α-olefin. Furthermore, the production method of the present invention includes a method in which propylene is homopolymerized or propylene and ethylene as well as/
Alternatively, a method of homopolymerizing or copolymerizing propylene by a multi-stage polymerization step having at least a step of copolymerizing an α-olefin having 4 to 20 carbon atoms may be used. When copolymerization is performed, multi-stage polymerization may or may not be performed. Preferably, it is a method of performing polymerization by multistage polymerization.

In the production method of the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. However, a slurry polymerization method and a gas phase polymerization method are particularly preferred.

Regarding the polymerization conditions for multi-stage polymerization or single-stage polymerization, the polymerization temperature is usually -100 to 250 ° C, preferably-
It is 50-200 ° C, more preferably 0-130 ° C.
The ratio of the catalyst to the reaction raw material is preferably raw material monomer / component (A) (molar ratio) of preferably 1 to 1.
0 ^8, it is preferable that the particular 100 to 10 ^5. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 200 kg / cm ² G, particularly preferably normal pressure to 100 kg / cm ² G.

Methods for adjusting the molecular weight of the polymer include selection of the type and amount of each catalyst component and the amount of polymerization used, and polymerization in the presence of a chain transfer agent. Examples of the chain transfer agent include hydrogen; silane compounds such as phenylsilane and phenyldimethylsilane; and organoaluminum compounds such as trimethylaluminum. Among them, hydrogen is preferred. The amount of the chain transfer agent to be added is 10 times or more, preferably 50 times or more with respect to the transition metal component of the catalyst used. In the case of multi-stage polymerization, it is preferable to change polymerization conditions such as temperature, pressure, polymerization time, amount of chain transfer agent added, and monomer composition ratio between the first stage and the second stage.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and fats such as pentane, hexane, heptane and octane Group hydrocarbons, halogenated hydrocarbons such as chloroform, dichloromethane and the like can be used. These solvents may be used alone or in a combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the polymerization, preliminary polymerization can be carried out using the polymerization catalyst. The prepolymerization can be carried out 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 may be the same as those exemplified above, for example, ethylene, α-α having 3 to 20 carbon atoms.
An olefin or a mixture thereof can be used, but it is advantageous to use the same olefin as the olefin used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0 ° C.
８０80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent.

In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, and the transition metal component in the catalyst is used. The amount of the prepolymerized product per 1 mmol is from 1 to 10,000 g, especially from 10 to 10 g.
It is desirable to adjust the conditions so as to be 00 g.

A nucleating agent may be added to the propylene-based polymer, propylene homopolymer [a] and propylene-based copolymer [a '] of the present invention. The nucleating agent is not particularly limited as long as it has an effect of improving the progress rate 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 the molecular chains of the polymer.

Specific examples of the nucleating agent include a high melting point polymer, an organic carboxylic acid or a metal salt thereof, an aromatic sulfonate or a metal salt thereof, an organic phosphoric acid compound or a metal salt thereof, dibenzylidene sorbitol or a derivative thereof, Rosin acid partial metal salt, inorganic fine particles, imides,
Examples include amides, quinacridones, quinones, and mixtures thereof.

As the high melting point polymer, polyethylene,
Polyolefin such as polypropylene, polyvinylcyclohexane, polyvinylcycloalkane such as polyvinylcyclopentane, syndiotactic polystyrene, poly3-methylpentene-1, poly3-methylbutene-1,
And polyalkenylsilane.

Examples of the metal salt include aluminum benzoate, aluminum pt-butyl benzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like.

As dibenzylidene sorbitol or a derivative thereof, 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 and the like. Further, specifically, Gelol MD and Gelol MD-R (trade name) manufactured by Shin Nippon Rika (manufactured by) are also included.

Examples of the rosin acid partial metal salt include pine crystal KM1600, pine crystal KM1500 and pine crystal KM1300 manufactured by Arakawa Chemical Industries, Ltd.
(Product name) and the like.

Examples of the inorganic fine particles include talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth, titanium oxide, and oxide Examples include magnesium, pumice 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 dianilide adipic acid and dianilide sperate.

One of these nucleating agents may be used, or two or more of them may be used in combination.

In the present invention, it is preferable to use, as a nucleating agent, inorganic fine particles such as an organic metal phosphate salt and / or talc represented by the following general formula, since generation of odor is small,
Suitable for food applications.

[0107]

Embedded image

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

Further, in the present invention, it is preferable to use the above-mentioned inorganic fine particles such as talc as a nucleating agent, because when formed into a film, the film has excellent slip properties and improves characteristics such as printing characteristics. Further, the use of the above-mentioned dibenzylidene sorbitol or a derivative thereof as a nucleating agent is preferable because of excellent transparency. Furthermore, it is preferable to use the above-mentioned amide compound as a nucleating agent because of its excellent rigidity.

In the present invention, a nucleating agent and various additives used as desired 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 polymer is used as a nucleating agent, the polymer may be produced by simultaneously or sequentially adding the high-melting polymer in a reactor during the production of a propylene-based polymer. Various additives used as desired include antioxidants,
Neutralizing agent, slip agent, anti-blocking agent, anti-fog agent,
Or an antistatic agent.

The amount of the nucleating agent added in the present invention is usually at least 10 ppm based on the propylene polymer [1], the propylene homopolymer [a] or the propylene copolymer [a '], Preferably 10 to 10000p
pm, more preferably 10 to 5000 pp
m, more preferably 10 to 2500 pp
m. If the amount is less than 10 ppm, no improvement in moldability is observed, while if the amount exceeds 10,000 ppm, the preferable effect may not be increased. [3] Molded article The molded article of the present invention is the above-mentioned propylene-based polymer [1],
A molded article obtained by molding the propylene homopolymer [a] or the propylene-based copolymer [a '] (hereinafter, also referred to as the propylene-based polymer of the present invention). The molded article of the present invention has softness (also referred to as flexibility), high elastic recovery (property to return to the original state even when pulled), and is soft, that is, low in elasticity but less sticky and transparent. There is a feature that is excellent.

Examples of the molded product of the present invention include films, sheets, containers, interior materials for automobiles, housing materials for home electric appliances, and the like. Examples of the film include a food packaging film and an agricultural film (an example of a greenhouse). Examples of the container include a transparent case, a transparent box, a decorative box, and the like because of excellent transparency.

The molding method of the molded article includes an injection molding method,
Examples include 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 is such that the resin melts and flows.
C. to 300.degree. C. and a mold temperature of 60.degree. C. or less. When a film is formed as the molded article of the present invention, a general compression molding method, an extrusion molding method, a blow molding method, a cast molding method, or the like can be used. Also,
The film may or may not be stretched. When stretching, biaxial stretching is preferred. As the conditions for biaxial stretching,
The following conditions are mentioned. Molding conditions during sheet molding Resin temperature 50 to 200 ° C, chill roll temperature 50 ° C or less Longitudinal stretching condition 3 to 7 times stretching temperature, 50 to 100 ° C stretching condition Horizontal stretching condition 6 to 12 times stretching temperature, 50 to 100 ° C stretching temperature The surface of the film may be treated as necessary to increase the surface energy or polarize the surface. For example, examples of the treatment method include a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, and an ozone or ultraviolet irradiation treatment. Examples of the method for making the surface uneven include a sand blast method and a solvent treatment method.

The film may contain, if necessary, commonly used antioxidants, neutralizing agents, slip agents, antiblocking agents, antifogging agents, antistatic agents and the like.

Further, a film containing inorganic fine particles such as talc has excellent slip properties, so that the secondary processing properties such as bag making and printing are improved, and various general-purpose automatic filling packaging laminating and other high-speed manufacturing apparatuses can be used. Suitable for packaging films.

A film formed by molding the above-mentioned propylene-based polymer containing dibenzylidene sorbitol or a derivative thereof as a nucleating agent is particularly suitable for packaging of toys, stationery and the like because of its excellent transparency and large display effect. is there.

A film formed by molding the propylene-based polymer containing an amide compound as a nucleating agent is particularly excellent in rigidity and hardly causes problems such as winding wrinkles in high-speed bag making. Is suitable as any general-purpose packaging film.

The propylene polymer of the present invention is also suitable as a propylene resin modifier. When the propylene-based polymer or the like of the present invention is used as a propylene-based resin modifier, there is an advantage that a molded article having flexibility, low stickiness, and excellent compatibility with a polyolefin resin can be provided. That is, the propylene polymer or the like of the present invention is a specific one, and in particular, has a small amount of crystallinity in a polypropylene chain portion, and therefore has less stickiness as compared with a conventional soft polyolefin resin as a modifier. Further, the propylene-based polymer of the present invention is particularly excellent in compatibility with the polypropylene-based resin. As a result, the surface properties (such as stickiness) are less reduced and the transparency is higher than when a conventional modifier such as ethylene rubber is used.

[0120]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

First, a method for evaluating the resin properties and physical properties of the polymer of the present invention will be described. (1) Measurement of [η] It was measured at 135 ° C. in a decalin solvent using a VMR-053 automatic viscometer manufactured by Rigo Co., Ltd. (2) Measurement of Pentad Fraction and Abnormal Insertion Fraction It was measured by the method described in the text of the specification. That is, the mesopendad fraction (mmmm fraction) and the racemic pentad fraction (rrrr fraction) were determined by A. Zambelli and others using "Macromol".
ecules, 6 , 925 (1973) ", the signal of the methyl group in the ¹³ C nuclear magnetic resonance spectrum was measured, and the meso fraction and the racemic fraction in pentad units in the polypropylene molecular chain were determined. I asked. (M-
(2,1), (r-2,1) and (1,3) are Grass
i's report (Macromolucules, 21 , p. 617 (1988))
And Busico et al. (Macromolucules, 27 , p.
7538 (1994)), the assignment of peaks in the ¹³ C-NMR spectrum was determined, and each insertion content was calculated from the integrated intensity of each peak. (M-2,1) is calculated as the meso-2,1 insertion content (%) of the ratio of the integrated intensity of the peak belonging to Pα, γthreo appearing around 17.2 ppm to the integrated intensity in the entire methyl carbon region. . (R-2,
1) is 1 to the integrated intensity in the entire methyl carbon region.
The ratio of the integrated intensities of peaks belonging to Pα and γthreo appearing at around 5.0 ppm is represented by racemic-2,1 insertion content (%).
It was calculated as (1,3) is the T value that appears around 31.0 ppm relative to the integrated intensity in the entire methine carbon region.
The ratio of the integrated intensities of the peaks belonging to β and γ was calculated as the 1,3 insertion content (%). When peaks to be attributed to meso-2,1 insertion, racemic-2,1 insertion or 1,3 insertion may not be identifiable due to hiding in noise, etc., the content of each heterogeneous bond (m −2, 1), (r−
(2,1) or (1,3) was regarded as 0.

The measurement of the ¹³ C nuclear magnetic resonance spectrum was performed using the following apparatus and conditions.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / mL Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10000 times (3) Content (mol%) of comonomer unit in copolymer
Using a JNM-EX400 type NMR device manufactured by JEOL Ltd., a ¹³ C-NMR spectrum was measured under the following conditions and calculated by the following method.

Sample concentration: 220 mg / NMR solvent 3
ml NMR solvent: 1,2,4-trichlorobenzene / benzene-d6
(90/10 vol%) Measurement temperature: 130 ° C Pulse width: 45 ° Pulse repetition time: 10 seconds Total number of times: 4000 times (a) Ethylene unit ^{13C for} random copolymer of propylene and ethylene
Table 1 shows the chemical shifts and assignments of each signal in the spectrum measured by -NMR.

[0125]

[Table 1]

The content of ethylene units in the copolymer (α (
Mol%)) was determined from the spectrum measured by ¹³ C-NMR according to the following formula (1).

Α = E / S × 100 (1) where S and E are respectively S = I _EPE + I _PPE + I _EEE + I _PPP + I _PEE + I _PEP E = I _EEE +2/3 (I _PEE + I _EPE ) +1/3 (I _PPE + I
_PEP ), and I _EPE = I (12) I _PPE = I (15) + I (11) + (I (14) -I (11)) / 2 + I (1
0) I _EEE = I (18) / 2 + I (17) / 4 I _PPP = I (19) + (I (6) + I (7)) / 2 + I (3) + I (13)
+ I (11) + (I (14) -I (11)) / 2 I _PEE = I (20) I _PEP = (I (8) + I (9) -2 × I (11)) / 4 + I (21 ).

The isotactic triad fraction of the PPP chain was determined as the stereoregularity index (P (mol%)) of the copolymer by the following equation (2).

P = Im / I × 100 (2) where Im and I are respectively Im = I (22) I = I (22) + I (23) + I (24) − ｛(I ( 8) + I (9)) / 2
+ I (10) + 3/2 × I (11) + I (12) + I (13) + I (15)}. Here, I (1), I (2)... Indicate the intensity of the signal,. (4) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by the method described in the text of the specification. That is, Mw / Mn is a value calculated from the weight average molecular weight Mw and the number average molecular weight Mn in terms of polyethylene measured by the GPC method using the following apparatus and conditions. GPC measuring 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 / milliliter Injection amount: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0) (5) DSC measurement It was measured by the method described in the text of the specification. That is, a differential scanning calorimeter (manufactured by Perkin-Elmer, DS
Using C-7), a sample of 10 mg was placed in a nitrogen atmosphere at 230 ° C.
, And then the temperature was lowered to 0 ° C at 10 ° C / minute, and further held at 0 ° C for 3 minutes, and then the temperature was raised at 10 ° C / minute, and the melting endotherm obtained was ΔH. Also,
The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as melting point: Tm. Further, at 230 ° C., 3
After holding for 1 minute, the temperature is lowered to 0 ° C. at a rate of 10 ° C./minute.
The peak top of the maximum peak of the crystallization exothermic curve obtained at this time was defined as crystallization temperature: Tc. (6) Elevated Temperature Separation Chromatograph The amount W25 (% by weight) of the component eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on the filler. Thereafter, the column was heated to 135 ° C at a heating rate of 40 ° C / hour.
The temperature was raised to ℃ to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C. (7) component amount eluted in hexane (H25) H25 was determined by measuring by the measuring conditions below.

Sample: 0.1 to 5 g Sample shape: powder (Pellet is used after crushing and powdering) Solvent: Hexane Elution condition: 25 ° C., standing for 3 days or more Eluted amount calculation method: The following It is calculated by the following equation.

H25 = [(W ₀ −W ₁ ) / W ₀ ] × 100 (%) (8) Measurement of Boiling Diethyl Ether Extraction Measurement was performed using a Soxhlet extractor under the following conditions.

Sample: 1 to 2 g Sample shape: powder (Pellets are crushed,
Extraction solvent: diethyl ether Extraction time: 10 hours Number of extractions: 180 times or more Calculation method of extraction amount: Calculated by the following formula. [Extraction amount into diethyl ether (g) / charged powder weight (g)] × 100 (9) Measurement of frequency dispersion of melt viscoelasticity (η ^* ) (Pa · s) is a rotation type of Rheometrics (manufactured by). Using a parallel plate (diameter 25 mm, gap 1 mm) in a rheometer (ARES), temperature 23
The test was performed under the conditions of 0 ° C. and an initial strain of 20% or less. (10) Tensile modulus A propylene polymer is press-molded to prepare a test piece,
It measured by the tensile test based on JISK-7113.

Test piece (No. 2 dumbbell) Thickness: 1 mm Crosshead speed: 50 mm / min Load cell: 100 kg Example 1 Propylene homopolymer (1) Preparation of catalyst (1,2′-dimethylsilylene) Synthesis of (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride (1,2′-dimethylsilylene) (2,2) was added to a Schlenk bottle.
1′-dimethylsilylene) -bis (indene)
3 g (2.4 mmol) and 50 mL of ether are charged.
After cooling to −78 ° C., n-BuLi (hexane solution 1.6)
After adding 3.1 mL (5.0 mmol) of M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 20 mL of hexane to obtain 1.1 g (2.3 mmol) of a lithium salt as an ether adduct. This lithium salt is dissolved in 50 mL of THF and cooled to -78 ° C. 0.57 mL (5.3 mmol) of n-butyl bromide is slowly added dropwise and stirred at room temperature for 12 hours. After distilling off the solvent and extracting with 50 mL of hexane, the solvent was removed, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindene) was added in 0.8 ml.
1 g (1.77 mmol) was obtained. Next, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. 0.
81 g (1.77 mmol) and 100 mL of ether are charged. After cooling to −78 ° C. and adding 2.7 mL (4.15 mmol) of n-BuLi (hexane solution 1.54 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with hexane to obtain 0.28 g (1.43 mmol) of a lithium salt as an ether adduct.

Under a nitrogen stream, the lithium salt obtained above is dissolved in 50 mL of toluene. Cooled to −78 ° C., and zirconium tetrachloride 0.33 previously cooled to −78 ° C.
g (1.42 mmol) in toluene (50 mL) is added dropwise. After the addition, the mixture is stirred at room temperature for 6 hours. Thereafter, the mixture is filtered, and the solvent of the filtrate is distilled off. By recrystallization from dichloromethane (1,2'-dimethylsilylene)
0.2 g of (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride
(0.32 mmol) was obtained. (Yield 22%) The result of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) was: δ 0.88, 0.99 (12H, dimethylsilylene), 0.7-1.0, 1.1-. 1.5 (18
H, n-Bu), 7.0-7.6 (8H, benzene ring proton). (2) Homopolymerization of propylene A 1 L pressure-resistant autoclave made of sterylene-less with a stirrer was heated to 80 ° C, sufficiently dried under reduced pressure, then returned to atmospheric pressure with dry nitrogen and cooled to room temperature. Under a stream of dry nitrogen, 400 mL of dry deoxygenated heptane and 0.5 mL of a heptane solution of triisobutylaluminum (2.0 M) (1.0 m
mol) and stirred at 350 rpm for a while. On the other hand, toluene (10 mL) and a triisobutylaluminum heptane solution (2 M, 0.5 mL, 1.0 m) were placed in a 50 mL Schlenk tube sufficiently purged with nitrogen under a nitrogen stream.
mol), and a toluene solution of methylaluminoxane (1.43 M, 0.35 mL, 0.5 mmol) and (1,2′-dimethylsilylene) obtained in the above (1).
Heptane slurry of (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride (5 μmol / mL, 0.1 mL, 0.5 μmo
l) was added and stirred at room temperature for 5 minutes. Then, the catalyst slurry was quickly charged into the autoclave. (First-stage polymerization) Thereafter, stirring was started at 400 rpm,
The pressure of propylene was gradually increased to a total pressure of 8.0 kg / cm ² G, and at the same time, the temperature was slowly increased to 70 ° C. 2
Polymerization was carried out for 0 minutes. (Second-stage polymerization) Thereafter, the temperature was lowered to 30 ° C. over 5 minutes, and polymerization was further performed for 35 minutes. After the reaction,
Unreacted propylene was removed by depressurization. The reaction mixture was poured into 2 L of methanol to precipitate polypropylene, followed by filtration and drying to obtain 17 g of polypropylene. The resin properties and physical properties were measured, and the results are shown in Table 2. Example 2 Homopolymerization of propylene (at the time of the second stage polymerization,
(Hydrogen addition) (Catalyst preparation) It carried out similarly to Example 1. (First-stage polymerization) Thereafter, stirring was started at 400 rpm,
Propylene was gradually pressurized to a total pressure of 8.0 kg / cm ² G, and at the same time, the temperature was slowly raised to 50 ° C. 2
Polymerization was carried out for 0 minutes. (Second-stage polymerization) Then, unreacted propylene is removed by 1.0 k
The pressure was released until g / cm ² G was reached. Thereafter, hydrogen was added to 0.
It was charged until it reached 3 kg / cm ² G. Then, propylene was slowly pressurized to a total pressure of 8.0 kg / cm ² G, the polymerization temperature was raised to 70 ° C., and polymerization was carried out for 30 minutes. After the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into 2 L of methanol to precipitate polypropylene, followed by filtration and drying to obtain 32 g of polypropylene. The resin properties and physical properties were measured, and the results are shown in Table 2. [Example 3] Propylene copolymer (1) Preparation of catalyst (a) (1,2'-ethylene) (2,1'-ethylene)
Production of -bis (3-methylindene) 1.12 g (3.94 mmol) of (1,2′-ethylene) (2,1′-ethylene) -bis (indene) in 50 ml of dehydrated ether under a nitrogen stream. Melted. -7
After cooling to 8 ° C., 5.01 ml of a hexane solution having a concentration of 1.57 mol / l of n-butyllithium (n-butyllithium: 7.87 mmol) was added dropwise over 30 minutes, and the temperature was raised to room temperature. Stir for 8 hours. The ether solvent was distilled off under reduced pressure, and the residue was washed with hexane to obtain 1.12 g of a dilithium salt as an ether adduct.
(3.02 mmol) was obtained. This dilithium salt was dissolved in 50 ml of dehydrated tetrahydrofuran, and
Cooled to ° C. To this solution was added dropwise 10 ml of a tetrahydrofuran solution containing 0.42 ml (6.74 mmol) of methyl iodide over 20 minutes, and the mixture was allowed to warm to room temperature and then stirred for 8 hours. After evaporating the solvent under reduced pressure, the residue was extracted with ethyl acetate. The extracted solution is washed with water, the organic layer is dried over anhydrous magnesium sulfate, filtered, and the filtrate is evaporated to dryness under reduced pressure to obtain the desired product (1,2′-ethylene) (2,1′-ethylene). )-
0.87 g (2.78 mmol) of bis (3-methylindene) was obtained with a yield of 70.5%. It was present as an isomer mixture of double bonds in the five-membered ring moiety. (B) (1,2′-ethylene) (2,1′-ethylene)
Production of dilithium salt of -bis (3-methylindene) 0.87 g of (1,2'-ethylene) (2,1'-ethylene) -bis (3-methylindene) (2.
(78 mmol) dissolved in 35 mmol of ether.
Cooled to ° C. To this solution is added n-butyllithium 1.5
3.7 ml of a 7 mol / liter hexane solution (n-butyllithium: 5.81 mmol) was added to 30
After dropwise addition over a period of minutes, the mixture was heated to room temperature and stirred for 8 hours.
After distilling off the solvent under reduced pressure, the residue was washed with hexane to convert the dilithium salt into an ether adduct.
03 g (2.58 mmol) were obtained with a yield of 92.8%.

When ¹ H-NMR of this product was determined,
The following results were obtained. ¹ H-NMR (THF-d ₈ )
(Δ, ppm): 2.20 (6H, s), 3.25 (8H,
s), 6.0 to 7.4 (8H, m) (c) (1,2'-ethylene) (2,1'-ethylene)
Production of -bis (3-methylindenyl) zirconium dichloride 1.03 g (2.58) of an ether adduct of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindene) dilithium salt (Mmol) was suspended in 25 ml of toluene and cooled to -78 ° C. To this, a suspension of 0.60 g (2.58 mmol) of zirconium tetrachloride in toluene (20 ml) was added over 20 minutes, the temperature was raised to room temperature, and the mixture was stirred for 8 hours. The residue was extracted twice with 50 ml of dichloromethane. After distilling off the solvent under reduced pressure, the residue was recrystallized from dichloromethane / hexane to give
0.21 g of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride was obtained at a yield of 17.3%.

When ¹ H-NMR of this product was determined,
The following results were obtained. ¹ H-NMR (CDCl ₃ ): 2.4
8 (6H, s), 3.33 to 3.85 (8H, m),
6.9 to 7.6 (8H, m) (2) Copolymerization of propylene / ethylene To a stainless steel autoclave having an internal volume of 2 liters, 1.2 liters of toluene and 1.
5 mmol, methylaluminoxane (manufactured by Albemarle) 10 (Al) mmol, (1,2′-ethylene)
20 micromoles of (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride was charged, the temperature was raised to 30 ° C., and an ethylene / propylene mixed gas (ethylene / propylene molar ratio = 1/100) was added. Introduced. Excess gas was discharged to a total pressure of 7.0 kg / cm ² G, polymerization was performed for 60 minutes while keeping the gas composition ratio in the system uniform, and the contents were taken out and dried under reduced pressure to obtain propylene. A copolymer was obtained. The resin properties and physical properties were measured, and the results are shown in Table 2. Example 4 (1) Preparation of Catalyst A 1-liter pressure-resistant autoclave made of sterylene-less with a stirrer was heated to 80 ° C., sufficiently dried under reduced pressure, returned to atmospheric pressure with dry nitrogen, and cooled to room temperature. Under a stream of dry nitrogen, 400 mL of dry deoxygenated heptane and 0.5 mL of a heptane solution of triisobutylaluminum (2.0 M) (1.0 mmo
l) and dimethylanilinium tetrakis (pentafluorophenyl) borate in a heptane slurry (2 μm
ol / mL, 0.8 mL, 1.6 μmol)
The mixture was stirred at 350 rpm for a while. Then, (1,2′-dimethylsilylene) obtained in (1) of Example 1 above.
Heptane slurry of (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride (5 μmo1 / mL, 0.08 mL, 0.4 μm
ol), and hydrogen was fed up to 0.3 kg / cm ² G. (2) (First-stage polymerization) Thereafter, stirring was started at 400 rpm, propylene was gradually increased to a total pressure of 8.0 kg / cm ² G, and at the same time, the temperature was slowly increased to 70 ° C. for 20 minutes. Polymerization was performed. (Second-stage polymerization) Thereafter, the temperature was lowered to 40 ° C. over 5 minutes, and polymerization was further performed for 35 minutes. After the reaction,
Unreacted propylene was removed by depressurization. The reaction mixture was poured into 2 L of methanol to precipitate polypropylene, followed by filtration and drying to obtain polypropylene. The resin properties and physical properties were measured, and the results are shown in Table 2. Example 5 (1) Preparation of Catalyst Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-ethoxymethylindenyl) zirconium dichloride '-Dimethylsilylene) (2,
3. lithium salt of 1'-dimethylsilylene) -bis (indene); Ig (9.50 mmol) is dissolved in 50 mL of THF (tetrahydrofuran) and cooled to -78 ° C.
1.9 mL of chloromethyl ether ether (20.5 mm
ol) was slowly added dropwise and stirred at room temperature for 12 hours. The solvent is distilled off, 50 mL of ether is added, and the mixture is hydrolyzed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried and the solvent was removed to remove (1,2′-dimethylsilylene) (2,1 ′).
3.43 g (7.40 mmol) of -dimethylsilylene) -bis (3-ethoxymethylindene) were obtained. (Yield: 78%) Next, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-ethoxymethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. 0.43 g (7.40 mmol) and 50 mL of ether are charged. After cooling to −78 ° C. and adding 9.4 mL (14.8 mmol) of n-BuLi (hexane solution 1.57 M), the mixture is stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 50 mL of hexane to give 1.07 g (1.96 mmol) of a lithium salt as an ether adduct.
l) obtained. (Yield 26%) The lithium salt obtained above was mixed with toluene 50 under a nitrogen stream.
Dissolve in mL. Cool to −78 ° C.
0.46 g (1.96 g) of zirconium tetrachloride cooled to
(mmol) in toluene (20 mL) is added dropwise.
After the addition, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. The resulting residue was extracted with 40 mL of hexane to give (1,2′-dimethylsilylene) (2,1 ′).
-Dimethylsilylene) -bis (3-ethoxymethylindenyl) zirconium dichloride 0.24 g (0.
39 mmol). (Yield 20%) (2) Homopolymerization of propylene (1) Instead of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride, (1) , 2'-Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-
Except for using (ethoxymethylindenyl) zirconium dichloride, polymerization was carried out in the same manner as in Example 1 (2) to obtain a propylene homopolymer. The resin properties and physical properties were measured, and the results are shown in Table 2. Example 6 (1) Preparation of Catalyst Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2′-dimethylsilylene) '-Dimethylsilylene) (2,
3.0 g (6.97 mmol) of lithium salt of 1′-dimethylsilylene) -bis (indene) was added to 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. The solvent is distilled off and ether 5
Add 0 mL and wash with saturated ammonium chloride solution.
After liquid separation, the organic phase was dried to remove the solvent, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was 8.04.
g (5.88 mmol) were obtained. (Yield: 84%) Next, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. .04 g (5.88 mmol) and ether 5
Add 0 mL. After cooling to −78 ° C., 7.6 mL (11.7 mmol) of n-BuLi (hexane solution 1.54 M) was added.
l) After addition, stir at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 mL of hexane to obtain 3.06 g of a lithium salt as an ether adduct.
(5.07 mmol) was obtained. (Yield 73%) The result of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) was: 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).

Under a nitrogen stream, the lithium salt obtained above is dissolved in 50 mL of toluene. 1.2 g of zirconium tetrachloride cooled to −78 ° C. and previously cooled to −78 ° C.
A suspension of (5.1 mmol) in toluene (20 mL) is added dropwise. After the addition, the mixture is stirred at room temperature for 6 hours. The solvent of the reaction solution is distilled off. The obtained residue was recrystallized from dichloromethane to give 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) were obtained. Result of measurement by the (26% ^{yield) 1 H-NMR (90MHz,} CDC1 3),: δ0.0 (s, 18H, trimethylsilyl), 1.02,1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-
7.6 (m, 8H, Ar-H). (2) Homopolymerization Instead of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) ( 2,1′-dimethylsilylene) -bis (3-
Except for using (trimethylsilylmethylindenyl) zirconium dichloride, polymerization was carried out in the same manner as in (2) of Example 1 to obtain a propylene homopolymer. The resin properties and physical properties were measured, and the results are shown in Table 2. [Comparative Example 1] Single-stage polymerization of propylene (adding hydrogen) (Preparation of catalyst) The same procedure as in Example 1 was carried out. (Polymerization) Thereafter, hydrogen was introduced until the pressure reached 1.0 kg / cm ² G, and stirring was started at 400 rpm. Next, the pressure of propylene was gradually increased to a total pressure of 8.0 kg / cm ² G, and at the same time, the temperature was slowly increased to 50 ° C., and polymerization was carried out for 60 minutes. After the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into 2 L of methanol to precipitate polypropylene, followed by filtration and drying to obtain 38 g of polypropylene. The resin properties and physical properties were measured, and the results are shown in Table 2. [Comparative Example 2] Single-stage polymerization of propylene (no hydrogen) (Preparation of catalyst) The same procedure as in Example 1 was performed. (Polymerization) Then, stirring was started at 400 rpm. Next, the pressure of propylene was gradually increased to a total pressure of 8.0 kg / cm ² G, and at the same time, the temperature was slowly increased to 30 ° C.
The polymerization was carried out for 60 minutes. After the reaction, unreacted propylene was removed by depressurization. Then, add 2 L of the reaction mixture.
And precipitated by filtration and dried by filtration to obtain 13 g of polypropylene. The resin properties and physical properties were measured, and the results are shown in Table 2.

[0138]

[Table 2]

[0139]

The propylene-based polymer, propylene homopolymer and propylene-based copolymer of the present invention are excellent in melt fluidity, low in stickiness, excellent in softness and transparency, and are suitable for films, sheets, containers and automobiles. It is suitable as an interior material, a housing material for home electric appliances, and the like.

Continued on the front page F-term (reference) 4F071 AA15X AA20 AA20X AA76X AA80 AA81 AA87 AA88 AF30 AF53 BA01 BB05 BB06 BC01 BC07 4J028 AA01A AB00A AB01A AC00A AC01A AC08A AC09A AC26A AC27A AC37AAC38A AC37AAC38A EB04 EB05 EB07 EB08 EB09 EB10 EC01 EC02 ED08 ED09 FA01 FA02 FA03 FA04 FA06 FA07 GA04 GA06 GA15 GA19 GA22 4J100 AA02Q AA03P AA04Q AA04R AA07Q AA07R AA15Q AA15R AA16A AAAAAAAAAAAAAAAAAAA

Claims (6)

[Claims] 1. A propylene polymer satisfying the following (1) to (3). (1) The amount of the component (H25) eluted in hexane at 25 ° C. is 0 to 80% by weight. (2) In the DSC measurement, if the melting point (Tm (° C.)) is not shown or Tm is shown, And the melting endotherm ΔH
(J / g) satisfies the following relationship: ΔH ≧ 6 × (Tm-140) (3) Gel Permeation Chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by the
The intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent is 0.5 to 15.0 deciliter / g. 2. A propylene homopolymer satisfying the following (1) to (3). (1) The mesopentad fraction (mmmm) is 20 to 85 mol%. (2) The racemic pentad fraction (rrrr) and (1-mm)
mm) satisfies the following relationship: [rrrr / (1-mmmm)] ≦ 0.1 (3) Gel Permeation Chromatograph (GPC)
Molecular weight distribution (Mw / Mn) measured by the
The intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent is 0.5 to 15.0 deciliter / g. 3. A propylene copolymer satisfying the following (1) and (2). (1) The stereoregularity index (P) by ¹³ C-NMR measurement is 55 to 90 mol%. (2) Gel permeation chromatography (GPC)
Molecular weight distribution (Mw / Mn) measured by the
The intrinsic viscosity [η] measured at 135 ° C. in a decalin solvent is 0.5 to 15.0 deciliter / g. 4. The magnitude of complex viscosity (η ^* ) (Pa · s) and intrinsic viscosity [η] (deciliter / g) at a frequency ω of 100 rad / sec determined by frequency dispersion measurement of melt viscoelasticity are as follows: The propylene-based polymer, propylene homopolymer or propylene-based copolymer according to any one of claims 1 to 3, which satisfies the following relationship. η ^* <159η + 743 5. A transition represented by the following general formula (I):
Metal compound and (B) (B-1) Transition of component (A)
Reacts with metal compounds or their derivatives to form ionic complexes
Selected from compounds that can be formed and (B-2) aluminoxanes
Propylene in the presence of a polymerization catalyst containing
Is homopolymerized, or propylene and ethylene and / or carbon
The process of copolymerizing α-olefins of Formulas 4 to 20 is reduced.
The polymerization is carried out by a multi-stage polymerization step having at least
4. The propylene polymer according to any one of
A method for producing a homopolymer or a propylene-based copolymer. Embedded image[Wherein, M is a group 3 to 10 of the periodic table or a lanthanoid type
Indicates the metal element of the column, E ¹And E^TwoAre the replacement symbols
Lopentadienyl group, indenyl group, substituted indenyl
Group, heterocyclopentadienyl group, substituted heterocyclo
Pentadienyl group, amide group, phosphide group, π bondability
A ligand selected from hydrocarbon groups and silicon-containing groups
A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. ] 6. A molded product obtained by molding the propylene-based polymer, propylene homopolymer or propylene-based copolymer according to claim 1.