JP2000095820A - Propylene-based polymer and composition including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-based polymer useful as a substitute for non- rigid vinyl chloride resin and to provide a propylene-based polymer composition capable of imparting film and molded products excellent in transparency and rigidity. SOLUTION: When a propylene-based polymer is a polypropylene homopolymer, it has 30-80% isotactic pentad fraction (mmmm fraction) showing stereoregularity, <=3.5 molecular weight distribution (Mw/Mn) and 0.8-5 dL/g intrinsic viscosity [η]. When a propylene-based polymer is a copolymer from propylene and ethylene (and/or a 4-20C α-olefin), it has 55-90 mol% stereoregularity parameter (P), <=3.5 molecular weight distribution (Mw/Mn) and 0.8-5 dL/g intrinsic viscosity [η]. A propylene-based polymer composition is prepared by adding >=1,000 ppm nucleating agent to the above propylene-based polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymer having a low stickiness component, a low elastic modulus, a soft, transparent molded product, and a useful substitute for a soft vinyl chloride resin, and its production. A method and a molded body comprising the same,
The present invention relates to a propylene-based polymer composition which is excellent in low-temperature heat sealability and moldability, and is capable of producing a film and a molded article having excellent transparency and rigidity, and a molded article, a film and a laminate comprising the same.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resin has been widely used as a soft synthetic resin. However, it is known that vinyl chloride resin generates harmful substances in the burning process. The development of alternatives is desired. As a substitute for the soft vinyl chloride resin, there is a propylene-based polymer. A propylene-based polymer has resin characteristics such that the degree of supercooling required to initiate crystallization is large and a crystallization temperature is low even at the same melting point, as compared with an ethylene-based polymer. For this reason, there is a problem that a molding failure phenomenon is likely to occur particularly in a heat sealing grade having a low melting point. In order to lower the heat sealing temperature, a method of reducing the stereoregularity of the propylene-based polymer or a copolymer with another olefin has been used. Among them, the conventional low-order propylene-based polymer obtained by using a Ziegler catalyst system has a wide stereoregular distribution and a large amount of sticky components when trying to be soft (that is, low elastic modulus). A sticky component derived from atactic polypropylene (hereinafter referred to as APP) causes a decrease in the physical properties of the low-order propylene polymer, for example, when the propylene polymer is molded, deteriorates the surface properties of the molded product. It was a factor to make it. The deterioration of the surface characteristics causes various problems when a molded article in the form of a sheet, a film, or the like is developed for food, medical use, and the like. Therefore,
A propylene-based polymer having an improved balance between a low elastic modulus and the amount of a sticky component is desired. In addition, it has a very low melting point and an extremely narrow stereoregularity distribution possessed by a low-order propylene-based polymer, exhibits excellent transparency, low-temperature heat sealability, and has high rigidity in films, fibers, sheets, and molded articles. It is desired to obtain.

[0003]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that an isotactic pentad fraction (mmmm fraction), a molecular weight distribution and an intrinsic viscosity produced in the presence of a specific catalyst. A propylene homopolymer having [η] in a specific range, a propylene copolymer prepared in the presence of a specific catalyst and having a tacticity index (P), a molecular weight distribution and an intrinsic viscosity [η] in a specific range. Coalescence, found that the balance between the low elastic modulus and the amount of the sticky component is improved, and also, a propylene-based polymer composition to which a specific amount of a nucleating agent is added, has a high crystallization temperature. Therefore, it has excellent low-temperature heat sealability and moldability comparable to linear low-density polyethylene, and found that a film formed from this composition has excellent transparency and rigidity. To complete Was.

That is, the present invention relates to (1) a propylene homopolymer having a stereoregular isotactic pentad fraction (mmmm fraction) of 30 to 80% and a molecular weight distribution (Mw / Mw / Mn) is 3.5 or less, intrinsic viscosity [η] is from 0.8 to 5 deciliters / g of a propylene-based polymer, (2) propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms. A propylene-based copolymer having a stereoregularity index (P) of 55 to 9
A propylene polymer having a molecular weight distribution (Mw / Mn) of 3.5 or less and an intrinsic viscosity [η] of 0.8 to 5 deciliters / g; (3) (A) (I)

[0005]

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[Wherein M is group 3-10 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
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And 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-, -NR^{twenty four}-, -PR^{twenty four}
-, -P (O) R^{twenty four}-, -BR^{twenty four}-Or-AlR^{twenty four}-
And R^{twenty four}Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
Hydrocarbon groups, halogen-containing hydrocarbons having 1 to 20 carbon atoms
Denote groups, which may be the same or different
No. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. Transition metallization represented by
And (B) (B-1) Transition metallization of the component (A)
Reacts with the compound or its derivative to form an ionic complex
And (B-2) aluminoxane
Propylene alone in the presence of a polymerization catalyst containing
The propylene-based product according to the above (1), which is polymerized.
A method for producing a polymer, (4) represented by the above general formula (I)
A transition metal compound, and (B) (B-1) the component (A)
Reacts with transition metal compounds or their derivatives to form ionic complexes
A compound capable of forming a body and (B-2) an aluminoxane
In the presence of a polymerization catalyst containing components selected from
And ethylene and / or α-O having 4 to 20 carbon atoms
The above (2), wherein the olefin is copolymerized.
Method for producing propylene-based polymer, (5) propylene as described above
(6) The propyle of the above (1)
Propylene obtained by adding a nucleating agent of 10 ppm or more to
Len-based polymer composition, (7) propylene-based composition of (2) above
Propylene in which a nucleating agent is added at 10 ppm or more to a polymer
-Based polymer composition, (8) propylene-based polymer,
The crystallization temperature (Tc (° C)) measured by a scanning calorimeter and
The melting point (Tm (° C.)) satisfies the following relational expression (1): Tc ≧ 0.75 Tm−15 (1)
Pyrene polymer composition, (9) any of (6) to (8) above
Molded articles comprising any of the propylene-based polymer compositions; and
A film, and (10) any of the above (6) to (8)
At least one layer comprising at least one propylene polymer composition
It is intended to provide a laminated body.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene polymer of the present invention comprises
It is composed of propylene alone or propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms. As the α-olefin having 4 to 20 carbon atoms, ethylene, 1-butene, 1-pentene, 4-methyl-1-
Pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
Examples thereof include 1-octadecene and 1-eicosene, and in the present invention, one or more of these can be used. As the propylene-based polymer of the present invention, a propylene homopolymer is preferable.

The propylene homopolymer of the propylene polymer of the present invention must have an isotactic pentad fraction (mmmm fraction) in the range of 30 to 80%, preferably 40 to 80%. 70%, more preferably 50 to 70%. If the isotactic pentad fraction is less than 30%, the crystallinity will be too low, resulting in poor moldability. If it exceeds 80%, it will not be soft and the heat sealing temperature will be high. Occurs. The isotactic pendad fraction (mmmm fraction) used in the present invention is defined as "Macromol by A. Zambelli" or the like.
ecules, 6 , 925 (1973) ", means the isotactic fraction in pentad units in the polypropylene molecular chain as measured by the signal of the methyl group in the ¹³ C nuclear magnetic resonance spectrum. The measurement of the ¹³ C nuclear magnetic resonance spectrum was performed by A. Zamb (A. Zamb).
elli) et al., "Macromolecules,
8 , 687 (1975) "in accordance with the assignment of peaks, using the following apparatus and conditions. Apparatus: JNM-EX400 type ¹³ CN manufactured by JEOL Ltd.
MR 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 total: 10000 times

Further, propylene and ethylene and / or C 4 -C 20 in the propylene-based polymer of the present invention.
The propylene-based polymer comprising the α-olefin of (1) needs to have a stereoregularity index (P) in the range of 55 to 90 mol%, and preferably 65 to 80%. If the stereoregularity index (P) is less than 55%, there is a problem that the crystallinity is too low and the moldability is poor.
%, It is not soft and disadvantageously increases the heat sealing temperature. The propylene-based polymer of the present invention has a ratio M between the weight average molecular weight Mw and the number average molecular weight Mn.
The molecular weight distribution defined by w / Mn is 3.5 or less,
3.0 to 2.0 are preferred. If the molecular weight distribution exceeds 3.5, the molecular weight distribution is too wide, so that satisfactory physical properties cannot be obtained. The 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 gel permeation chromatography (GPC) 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)

Further, the propylene-based polymer of the present invention comprises
It is necessary that the intrinsic viscosity [η] is in the range of 0.8 to 5 deciliter / g, preferably 1 to 3 deciliter / g.
g, more preferably 1.5 to 2.5 deciliter / g. When the intrinsic viscosity [η] is less than 0.8 deciliter / g,
If stickiness occurs, and if it exceeds 5 deciliters / g, the fluidity is reduced, resulting in poor moldability. In the propylene polymer composition of the present invention, the propylene polymer has the following relationship between the crystallization temperature (Tc (° C.)) and the melting point (Tm (° C.)) of the polymer measured by a differential scanning calorimeter. It is preferable that the following formula (1) is satisfied: Tc ≧ 0.75 Tm−15 (1) Tc is "0.75Tm-1
If it is less than 5 ", a molding failure phenomenon is likely to occur, and the object of the present invention may not be achieved. From the viewpoint of making the molding failure phenomenon difficult to occur, Tc ≧ 0.75 Tm−10 is particularly preferred. Is Tc ≧ 0.75 Tm-5 In the propylene-based polymer of the present invention, in addition to the above, the extraction amount of boiling diethyl ether, which is an index of a sticky component, is preferably 0 to 10% by weight, From the viewpoint of suppressing the bleeding of the sticky component on the surface of the molded product, the content is more preferably 0 to 5% by weight.
Heating fractionation (TR), another indicator of the amount of sticky components
From the same point, the dissolution amount of EF) at a dissolution temperature of 25 ° C. or lower is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, and still more preferably 0 to 5% by weight. Further, among the propylene-based polymers of the present invention, the propylene-based polymer comprising propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms is preferably a random copolymer. Further, the structural unit obtained from propylene is preferably at least 90 mol%, more preferably at least 95 mol%. The propylene polymer of the present invention comprises (A) a compound represented by the general formula (I):

[0011]

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And (B) a polymerization catalyst containing a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) or a derivative thereof. , Homopolymerized propylene, or copolymerized with propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms.
In the general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples thereof include titanium, zirconium, hafnium, yttrium,
Vanadium, chromium, manganese, nickel, cobalt,
Palladium and lanthanoid metals can be mentioned, and among these, titanium, zirconium and hafnium are preferred from the viewpoint of olefin polymerization activity and the like. E ¹
And E ² are a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amide group (-N <), and a phosphine group (-P <), respectively. , Hydrocarbon groups [>CR-,> C <] and silicon-containing groups [>SiR-,>
Si <] (wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms or a hetero atom-containing group), and represents a ligand selected from the group consisting of A ¹ and A ² Has formed. E ¹ and E ² may be the same or different. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferred. X represents a σ-binding ligand;
When there are a plurality of Xs, the plurality of Xs may be the same or different, and may be crosslinked with another X, E ¹ , E ² or Y. Specific examples of X include a halogen atom, a carbon number of 1 to 1.
A hydrocarbon group having 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms
A sulfide group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, and the like. 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 crosslinked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like. Next, A ¹ and A ² are divalent cross-linking groups that bind two ligands, and include a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. group, a germanium-containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se
^{-, - NR 24 -, -} PR 24 -, - P (O) R 24 -, - B
R ²⁴ - or -AlR ²⁴ - are shown, R ²⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
It represents 0 halogen-containing hydrocarbon radicals, which may be identical 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

[0013]

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(B is a Group 14 element of the periodic table, and examples thereof include carbon, silicon, germanium, and tin. R ¹
And R ² are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, or may combine with each other to form a ring structure. e shows the integer of 1-4. )), And specific examples thereof include a methylene group, an ethylene group,
Ethylidene group, propylidene group, isopropylidene group,
A cyclohexylidene group, a 1,2-cyclohexylene group,
Vinylidene group (CH ₂ ＣC ＝), dimethylsilylene group,
Examples include a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, and a diphenyldisilylene group. Among them, an ethylene group, an isopropylidene group and a dimethylsilylene group are preferred. q is an integer of 1 to 5 and represents ((valency of M) -2);
Represents an integer of 1 to 3. Among the transition metal compounds represented by the general formula (I), the general formula (II)

[0015]

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A transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following formula as a ligand is preferred. In the general formula (II), M, A ¹ , A ² , q and r are the same as above. X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ are the same as those exemplified in the description of X in the general formula (I). Y
¹ represents a Lewis base, and when there are a plurality of Y ¹ ,
¹ may be the same or different, and may be crosslinked with another 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 ³ to R ⁸ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, having from 1 to 20 carbon atoms
The halogen-containing hydrocarbon group, the silicon-containing group or the hetero atom-containing group, at least one of which must not be a hydrogen atom. R ^{3 to} R ⁸ may be the same or different, and adjacent groups may be bonded to each other to form a ring. 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, , 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, 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-isopropylpropenyl) 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-phenylcyclopentienyl) (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′-dimethyl) Silylene) (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,
2′-dimethylsilylene) (2,1′-methylene) (3
-Methyl-5-phenylcyclopentadienyl) (3 ′
-Methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) (2
1'-methylene) (3-methyl-5-i-propylcyclopentadienyl) (3'-methyl-5'-i-propylcyclopentadienyl) zirconium dichloride,
(1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3′-methyl-5′-i-propylcyclopentadienyl) zirconium Dichloride, (1,2′-methylene) (2,1′-methylene) (3-methyl-5-i
-Propylcyclopentadienyl) (3'-methyl-
5'-i-propylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3-methyl-5-i-propylcyclopentadienyl) (3'- Methyl-5'-i-propylcyclopentadienyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these. In addition, a similar compound of a metal element of another group or a lanthanoid series may be used.

The component (B-1) of the component (B) may be any ionic compound that forms an ionic complex by reacting with the transition metal compound of the component (A). Can be used, but the following general formulas (III) and (IV) ([L ¹ -R ⁹ ] ^{k +} ) _a ([Z] ^- ) _b ... (III) ([L ² ] ^{k +} ) _a ([ Z] ^-) _b ··· (IV) (provided that, L ² is ^{M 2, R 10 R 11 M} 3, R 12 3 C or R
^13, which is a M ^3. In the formulas (III) and (IV), L ¹ is a Lewis base, and [Z] ⁻ is
Non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 1 G 1 G 2 ··· G} f ] ^- ( Here, M ¹ is an element belonging to Groups 5 to 15 of the periodic table, preferably ^{13 to 1} of the periodic table.
Shows Group 5 elements. G ^{1 to} G ^f each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon atom having 2 to 4 carbon atoms.
0 dialkylamino group, C1-C20 alkoxy group, C6-C20 aryl group, C6-C20 aryloxy group, C7-C40 alkylaryl group, C7-C40 Arylalkyl group, 1 to 1 carbon atoms
A halogen-substituted hydrocarbon group of 20; an acyloxy group of 1 to 20 carbon atoms; an organic metalloid group; or a heteroatom-containing hydrocarbon group of 2 to 20 carbon atoms. 2 out of G ^{1 to} G ^f
One or more may form a ring. f is [(center metal M
Represents an integer of ¹ valence) +1]. ), [Z ² ] ^-
It represents a conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base generally defined as a superstrong acid. Further, a Lewis base may be coordinated. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, and R ¹⁰ and R ¹¹ are each a cyclopentadienyl group, A cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹² represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹³ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. k is the ionic valence of [L ¹ -R ⁹ ] and [L ² ] and is 1
A is an integer of 1 or more, b = (k × a). M ² contains an element from Groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents an element from Groups 7 to 12 of the periodic table. ] 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 ⁹ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹⁰ and R ¹¹ include cyclopentadienyl group, methylcyclopentadienyl group , Ethylcyclopentadienyl group,
A pentamethylcyclopentadienyl group and the like can be mentioned. Specific examples of R ¹² include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹³ include tetraphenylporphine,
Examples include phthalocyanine, allyl, and methallyl. Specific examples of M ² include Li, Na,
K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ³ include Mn, Fe, Co, Ni,
Zn and the like can be given.

[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, etc.
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, a 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, bis (trimethylsilyl) methyl group, etc. as pentamethylantimony group, trimethylsilyl group, trimethyl Examples include a germyl group, a diphenylarsine group, a dicyclohexylantimony group, and diphenylboron.

In addition, 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 ) ^- , 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 the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, 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) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl 2-phenylopyridinium 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, theolaphenylporphyrin, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate and the like can be mentioned. This (B-
The ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, which is the component 1), may be used alone or in combination of two or more. On the other hand, as the aluminoxane of the component (B-2),
General formula (V)

[0022]

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(Wherein R ¹⁴ is an alkyl group, alkenyl group, aryl group having 1 to 20, 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 ¹⁴ may be the same or different. Aluminoxane represented by the general formula (VI):

[0024]

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(Wherein, R ¹⁴ and w are the same as those in the above 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 performed according to a known method. For example, a method of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organoaluminum compound initially during polymerization and then adding water, and a method of crystal water contained in a metal salt or the like A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in a combination of two or more. The usage ratio of the (A) catalyst component and the (B) catalyst component is as follows:
When the compound (B-1) is used as the catalyst component (B), the molar ratio is preferably from 10: 1 to 1: 100, more preferably from 2: 1 to 1:10. If it deviates, the catalyst cost per unit weight polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1:10.
00000, more preferably 1:10 to 1: 1000
0, more preferably in the range of 1:10 to 1: 1000. 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.

The polymerization catalyst in the production method of the present invention comprises:
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 following general formula (VII): R ¹⁵ _v AlJ _3-v (VII) wherein R ¹⁵ 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, dimethylaluminum Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. Of these, trimethylaluminum, triethylaluminum and triisobutylaluminum are preferred, and triisobutylaluminum is more preferred. These organoaluminum compounds may be used alone or in combination of two or more.
The use ratio of the (A) catalyst component and the (C) catalyst component is as follows:
The molar ratio is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1: 1.
A range from 0 to 1: 1000 is desirable. 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 production method of the present invention, preliminary contact can also be performed using the above-mentioned components (A), (B) and (C). The preliminary contact can be performed by, for example, bringing the component (A) into contact with the component (A), but the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing the catalyst cost, for example, by improving the catalyst activity and reducing the use ratio of the co-catalyst (B) component. Further, by bringing the component (A) into contact with the component (B-2), an improvement in the molecular weight can be seen together with the above-mentioned effects. The pre-contact temperature is usually -20 ° C to 200 ° C, preferably-
The temperature is 10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, the solvent is an inert hydrocarbon,
Aliphatic hydrocarbons and the like can be used. Particularly preferred among these are aromatic hydrocarbons.

In the present invention, at least the catalyst component
One can be used by supporting it on a suitable carrier. The charge
There is no particular limitation on the type of body, inorganic oxide carrier,
Use any other inorganic or organic carrier
Can be formed, but in particular, inorganic oxide carrier or other
Organic carriers are preferred. As the inorganic oxide carrier, specifically,
Is SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO
_Two, Fe_TwoO_Three, B_TwoO_Three, CaO, ZnO, BaO,
ThO_TwoAnd mixtures thereof, such as silica alumina and zeolite.
Olite, ferrite, glass fiber, carbon
And so on. Among them, especially SiO 2_Two, Al
_TwoO _ThreeIs preferred. In addition, the inorganic oxide carrier is used in a small amount.
Carbonate, nitrate, sulfate and the like. one
On the other hand, as a carrier other than the above, MgCl_Two, Mg (OC_Two
H_Five)_TwoGeneral represented by magnesium compounds such as
Formula MgR¹⁶ _XX¹ _yMagnesium compounds represented by
And the like. Where R¹⁶Is carbon
An alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms
A group or an aryl group having 6 to 20 carbon atoms, X¹Is a halogen field
And represents an alkyl group having 1 to 20 carbon atoms;
2, y is 0 to 2 and x + y = 2. Each R¹⁶Passing
And each X¹May be the same or different
Is also good.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Examples thereof include polymers such as polypropylene, substituted polystyrene, and polyarylate, and starch. The carrier used in the present invention includes MgCl ₂ , Mg
Cl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ , SiO ₂ ,
Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually 1 to 300.
μm, preferably 10 to 200 μm, more preferably 2 μm
0 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. Also,
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to 5 c.
m ³ / g, preferably 0.3 to ³ cm ³ / g. When either the specific surface area or the pore volume deviates from the above range,
The catalyst 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 carrier is usually 100 to 1000 ° C., preferably 150 to 80 ° C.
It is desirable to use it after firing at 0 ° 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. On the carrier,
The method for supporting at least one of the component (A) and the component (B) is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with a carrier, and a method of mixing the carrier with an organoaluminum compound Or a method of treating with a halogen-containing silicon compound and then mixing with at least one of the component (A) and the component (B) in an inert solvent, a carrier and the component (A) and / or the component (B) and the organoaluminum compound or A method of reacting 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) with the component (A) and the component (B). For example, a method of mixing the contact reaction product with the carrier with the carrier, and a method of coexisting the carrier during the contact reaction between the component (A) and the component (B) can be used. Note that, in the above and the above reactions,
An organoaluminum compound as the component (C) can be added.

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. Further, in the present invention, a catalyst can be generated by performing an 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 20 kg / cm ² to obtain -20 to 200 A method in which preliminary polymerization is performed at a temperature of 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 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.
If the ratio of the component (B) [component (B-1) or component (B-2)] to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may decrease. is there. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm.
m, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to ⁵ m ² / g.
00 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the carrier 1
The amount of the transition metal in 00 g is usually 0.05 to 10 g, and particularly preferably 0.05 to 10 g.
Preferably, the amount is 1 to 2 g. If the amount of the transition metal is out of the above range, the activity may be low. By supporting on a carrier in this manner, a polymer having an industrially advantageous high bulk density and excellent particle size distribution can be obtained.

In the manufacturing method of the present invention, the above-described weight
Using a joint catalyst, propylene is homopolymerized or
Pyrene and ethylene and / or α- having 4 to 20 carbon atoms
Copolymerize with olefin. In the present invention, the polymerization method
The method is not particularly limited, and may be a slurry polymerization method, a gas phase polymerization method,
Any method such as linear polymerization, solution polymerization, suspension polymerization, etc.
May be used, but slurry polymerization and gas phase polymerization are particularly preferred.
preferable. Regarding the polymerization conditions, the polymerization temperature is usually -10.
0 to 250 ° C, preferably -50 to 200 ° C, more preferably
Or 0 to 130 ° C. Also, the contact with the reactants
The ratio of the solvent used is defined as raw material monomer / component (A) (mol
Ratio) is preferably 1 to 10 ⁸, Especially 100 to 10^FiveTona
Preferably. Further, the polymerization time is usually from 5 minutes to 10 minutes.
Time, reaction pressure is preferably normal pressure to 200 kg / cm^Two
G, particularly preferably normal pressure to 100 kg / cm^TwoG
You. As a method for adjusting the molecular weight of the polymer,
Selection of type, amount used, polymerization temperature, and even in the presence of hydrogen
Polymerization. When using a polymerization solvent, for example,
Benzene, toluene, xylene, ethylbenzene
Aromatic hydrocarbons, cyclopentane, cyclohexane, methyl
Alicyclic hydrocarbons such as rucyclohexane, pentane,
Aliphatic hydrocarbons such as xane, heptane and octane,
Halogenated hydrocarbons such as loroform and dichloromethane
Etc. can be used. These solvents are used alone
May be used, or two or more kinds may be combined.
No. In addition, a monomer such as α-olefin as a solvent
May be used. In addition, depending on the polymerization method, it is carried out without a solvent
be able to.

In the polymerization, preliminary polymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be performed by, for example, 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- having 3 to 20 carbon atoms.
An olefin or a mixture thereof can be mentioned, but it is advantageous to use the same olefin as the olefin used in the polymerization. The prepolymerization temperature is usually -20 to 200C, preferably -10 to 13C.
0 ° C, more preferably 0 to 80 ° 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 of the prepolymerized product [η] (135
C. (measured in decalin) at 0.2 deciliters / g or more, especially 0.5 deciliters / g or more.
The amount of the prepolymerized product per 1 mmol is 1 to 10
It is desirable to adjust the conditions so as to be 000 g, especially 10 to 1000 g. The thus obtained propylene polymer of the present invention can be formed into a molded product by press molding or the like. Further, it can be used as a modifier for imparting flexibility to the resin.

The propylene polymer composition of the present invention comprises the propylene homopolymer [component (a)] or the propylene polymer [(a) comprising the propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms. a ') Component]
And (b) a nucleating agent of 10 ppm or more. The nucleating agent of the component (b) may be any as long as it induces crystal nuclei promptly without lowering the physical properties of the propylene-based polymer and reduces the degree of supercooling required for crystallization to start. Specific examples of the nucleating agent used in the present invention 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 salts, inorganic fine particles, imides, amides, quinacridones, quinones or mixtures thereof. Examples of the high melting point polymer include polyolefins such as polyethylene and polypropylene, polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, and poly3-methylpentene.
1, poly-3-methylbutene-1, polyalkenylsilane and the like. Examples of the metal salt include aluminum benzoate, aluminum pt-butyl benzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like. As the inorganic fine particles, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, alumina, silica, diatomaceous earth,
Examples include titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, and molybdenum sulfide. Among them, inorganic fine particles such as organophosphate metal salts and talc represented by the following general formula (VIII) generate less odor and are suitable when the propylene polymer composition of the present invention is used for food applications.

[0036]

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(Wherein, R ¹⁷ is a hydrogen atom or a carbon number of 1 to 4)
R ¹⁸ and R ¹⁹ 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, and when M is a divalent metal, n represents 1 or 2,
When n is 1, m indicates 1; when n is 2, m indicates 0;
M is 1 and n is 2 when is aluminum. Furthermore, a film formed by molding a propylene-based polymer composition containing inorganic fine particles such as talc has excellent slip properties, so that secondary processing properties such as bag making and printing are improved, and various types of automatic filling and packaging laminating. It is suitable for all general-purpose packaging films in high-speed manufacturing equipment such as. A film formed by molding a propylene-based polymer composition containing dibenzylidene sorbitol or a derivative thereof as a nucleating agent is particularly suitable for packaging toys, stationery, and the like because of its excellent transparency and large display effect. Specific examples of the derivative of dibenzylidene sorbitol include 1,3: 2,4-bis (o-3,4-dimethylbenzylidene) sorbitol and 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. Films formed by molding a propylene polymer composition containing an amide compound as a nucleating agent are particularly excellent in rigidity and are unlikely to cause wrinkles and the like in high-speed bag making. It is suitable as a film. Specific examples of the amide compound include dianilide adipate and dianilide sperate.

The amount of the nucleating agent to be added is usually 10 ppm or more based on the propylene-based copolymer.
000 ppm is preferred. If the addition amount is less than 10 ppm, no improvement in the low-temperature heat sealability is observed, and on the other hand, even if the addition amount of the nucleating agent is increased, the effect corresponding thereto may not be obtained. Although depending on the type of the nucleating agent, the amount of the nucleating agent to be added is generally 1000 ppm or less, and furthermore, 500p from the viewpoints of transparency and impact resistance of the propylene polymer composition.
pm or less is particularly preferred. More specifically, when a sorbitol-based nucleating agent is used, the content of dibenzylidene sorbitol is preferably 3000 ppm or less, more preferably 1500 ppm or less, and particularly preferably 500 ppm or less. For bis (p-methylbenzylidene) sorbitol or bis (dimerbendeliden) sorbitol,
It is preferably 1200 ppm or less, more preferably 600 ppm or less, and particularly preferably 300 ppm or less. In the case of an organic sodium phosphate salt, which is an organic metal phosphate, the content is preferably 500 ppm or less, more preferably 200 ppm or less, and particularly preferably 125 ppm or less. 1900 ppm for organic phosphoric acid Al salt
Or less, further 1500 ppm or less, especially 500 ppm
It is preferable to set the following. In the case of using talc, the talc MMR manufactured by Asada Flour Milling Co. is preferably 4000 ppm or less, more preferably 2000 ppm or less, particularly preferably 1000 ppm. When using an amide-based compound, Nippon Rika's Ngesta-NU-100 has a 3,000 pp
m or less, further 1500 ppm or less, especially 500 pp
m or less.

The propylene-based polymer, propylene-based polymer composition, molded article or film of the present invention may contain a commonly used antioxidant, neutralizing agent, slip agent, antiblocking agent, antifogging agent, or antistatic agent. Agents and the like can be added as necessary. The film comprising the propylene-based polymer composition of the present invention is prepared in advance using a single-screw or twin-screw extruder, a Banbury mixer, or the like, using a propylene-based polymer, a nucleating agent, and various additives used as desired. It can be prepared by melt-kneading an agent and pelletizing and casting to form a film. Alternatively, a film obtained by dry-blending a propylene-based polymer, a nucleating agent, and various additives used as desired with a Henschel mixer or the like can be formed by cast molding. When a high melting point polymer is used as a nucleating agent, a propylene polymer composition can be obtained by simultaneously or sequentially manufacturing a high melting point polymer in a reactor during the production of a propylene polymer.

[0040]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. First, a method for evaluating a propylene-based polymer and a method for evaluating a film will be described. (A) Evaluation method of resin properties (1) Intrinsic viscosity [η] It was measured at 135 ° C in decalin solvent using a VMR-053 type automatic viscometer manufactured by Rigo Co., Ltd. (2) Molecular weight distribution (Mw / Mn) It was measured according to the method described in the text of the specification. (3) Isotactic pentad fraction Measured according to the method described in the specification. (4) Measurement of melting point (Tm) and crystallization temperature (Tc) Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
7) Using 10 mg of a sample in advance in a nitrogen atmosphere,
After melting at 230 ° C. for 3 minutes, 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 was defined as the crystallization temperature. Further, after the sample was kept at 0 ° C. for 3 minutes, the temperature was raised at a rate of 10 ° C./minute. (5) Extraction amount of boiling ether Using a Soxhlet extractor, measurement was performed under the following conditions. Extracted sample: 5 to 6 g Sample shape: powder (Pelletized powder is used by pulverization.) Extraction solvent: diethyl ether Extraction time: 10 hours Number of extractions: 180 or more Extraction amount calculation method: The following formula Is calculated by [Amount (g) extracted in diethyl ether / weight of charged powder (g)] × 100 (6) Temperature rising fractionation chromatography (TREF) The peak top temperature Tp of the main elution peak in the elution curve is as follows. ° C) and the amount of a component which is not adsorbed to the filler and eluted at a TREF column temperature of 25 ° C (weight fraction W _{25 with} respect to the whole copolymer). (a) Operation method The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 25 ° C. at a rate of 5 ° C./hour to adsorb the sample to the filler. Thereafter, the column is heated to 135 ° C. at a rate of 40 ° C./hour to obtain an elution curve. (b) Apparatus configuration TREF column: Silica gel column (4.6 mm x 150 mm) manufactured by GL Sciences Flow cell: 1 mm 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: 3.41 μm Ram Filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C.

(7) Content (α (mol%)) and tacticity index (P (mol%)) of comonomer units (α-olefin units) in the copolymer JNM-EX400 manufactured by JEOL Ltd. A ¹³ C-NMR spectrum was measured using an NMR apparatus 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 Integration count: 4000 times

(A) 1-butene unit content of 1-butene unit in the copolymer (α (mol%))
Was determined from the spectrum measured by ¹³ C-NMR according to the following formula.

[0043]

(Equation 1)

The stereoregularity index (P (mol%)) of the copolymer was determined by the following formula.

[0045]

(Equation 2)

Here, (1), (2)... Indicate the signals of the spectrum of the copolymer of propylene and 1-butene measured by ¹³ C-NMR. Also, I (1), I
(2) ··· indicates the intensity of each signal. Propylene and 1-
Table 1 shows the signals of the spectrum of the butene copolymer measured by ¹³ C-NMR. Incidentally, the signal intensity of P PP chain Sαβ carbon was replaced by P P P chain Sαβ signal strength carbon ((9 signal intensity)).

[0047]

[Table 1]

(8) Tensile Modulus A propylene polymer is press-molded to produce a test piece.
It was measured by a tensile test under the following conditions in accordance with JIS K-7113. Crosshead speed: 50 mm / min Test piece shape: No. 2 type test piece, thickness 1 mm (9) Izod impact strength Using a test piece similar to the above, it was measured at 23 ° C. by a test based on JIS K7110. (10) Transparency The same test piece as described above was visually measured. The evaluation criteria of transparency were ○ when the transparency was good, and △ when the transparency was slightly inferior. (11) Internal haze A propylene-based polymer was press-molded to produce a test piece having a thickness of 1 mm, and silicone oil (KF56, manufactured by Shin-Etsu Silicone Co., Ltd.) was applied to the surface of the test piece in order to remove surface scattering.
After coating, haze measurement according to JIS K7105 was performed. (A) Film molding method From the propylene polymer compositions obtained in Examples and Comparative Examples described below, using a 20 mmφ molding machine manufactured by Tsukada Juki Seisakusho,
A film having a thickness of 50 μm was formed under the following molding conditions. T-die exit resin temperature: 192 ° C Pickup speed: 6.0m / min Chill roll temperature: 40 ° C Chill roll: mirror surface

(C) Evaluation method of film quality After film formation, the film was subjected to an aging treatment at 40 ° C. × 24 hours, and then a temperature of 23 ± 2 ° C. and a humidity of 50 ± 10%.
After conditioning for 16 hours or more, the measurement was performed under the same temperature and humidity conditions. (1) Tensile modulus According to JIS K-7127, it was measured by a tensile test under the following conditions. Crosshead speed: 500 mm / min Load cell: 15 kg Measurement direction: machine direction (MD direction) (2) Impact resistance Evaluated by the impact fracture strength using a 1/2 inch impact head with a film impact tester manufactured by Toyo Seiki Seisakusho. (3) Haze It was evaluated by a test based on JIS K-7105. (4) Heat seal temperature Measured according to JIS Z-1707. The fusion conditions are described below. The temperature of the heat seal bar is calibrated by a surface thermometer. After sealing, it was left at room temperature for 24 hours, and then at room temperature, the peeling rate was 200 mm / min, and the peel strength was measured by a T-type peeling method. The heat sealing temperature was determined by calculating a temperature at which the peel strength was 300 g / 15 mm from a seal strength-peel strength curve. Sealing time: 2 seconds Sealing area: 15 × 10 mm Sealing pressure: 5.3 kg / cm ² Sealing temperature: Measure several points so that heat sealing temperature can be interpolated

Example 1 Preparation of catalyst (1) (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) under a nitrogen stream
Was dissolved in 50 ml of dehydrated ether. -78 ° C
Then, 5.01 ml of a hexane solution having a concentration of 1.57 mol / liter of n-butyllithium (n-butyllithium: 7.87 mmol) was added dropwise over 30 minutes.
The temperature was raised to room temperature and stirred for 8 hours. The ether solvent was distilled off under reduced pressure, and the residue was washed with hexane to obtain 1.12 g (3.02 mmol) of a dilithium salt as an ether adduct. This dilithium salt was dissolved in 50 ml of dehydrated tetrahydrofuran and cooled to -78 ° C.
To this solution was added 0.42 ml of methyl iodide (6.74 ml).
10 mmol of a tetrahydrofuran solution containing the compound (i.m.
Stirring was performed 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 off, and the filtrate is evaporated to dryness under reduced pressure to obtain the target product (1,2′-ethylene) (2,1′-ethylene). ) -Bis (3-methylindene) (0.87 g, 2.78 mmol) (yield 7
0.5%). It was present as an isomer mixture of double bonds in the five-membered ring moiety. (2) (1,2'-ethylene) (2,1'-ethylene)-
Production of dilithium salt of bis (3-methylindene) Under a nitrogen stream, 0.87 g (2.78 g) of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindene)
Mmol) in 35 ml of ether.
Cooled to ° C. 1.57 n-butyllithium was added to this solution.
3.7 ml of a hexane solution having a mol / liter concentration (n-butyllithium: 5.81 mmol) was added dropwise over 30 minutes, and 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 obtain 1.03 g of a dilithium salt as an ether adduct.
(2.58 mmol) was obtained (yield 92.8%). When the ¹ H-NMR of this product was determined, the following results were obtained.
¹ H-NMR (THF-d ₈ ) (δ, ppm): 2.20 (6
H, s), 3.25 (8H, s), 6.0-7.4 (8H,
m) (3) (1,2'-ethylene) (2,1'-ethylene)-
Preparation of bis (3-methylindenyl) zirconium dichloride 1.03 g (2.58 mmol) of an ether adduct of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindene) dilithium salt ) Was suspended in 25 ml of toluene and cooled to -78 ° C. To this, 0.60 g (2.58 mmol) of zirconium tetrachloride in toluene (2
(0 ml) The suspension 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 (1,2′-
0.21 g of ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride was obtained (yield: 17.3%). When the ¹ H-NMR of this product was determined, the following results were obtained. ¹ H-NMR (CDCl ₃ )
: 2.48 (6H, s), 3.33 to 3.85 (8H, m),
6.9 to 7.6 (8H, m) polymerization 5 l of heptane, 5 mmol of triisobutylaluminum, and 19 mmol of methylaluminoxane (manufactured by Albemarle Co.) in a 10-liter stainless steel autoclave were converted to aluminum in the above manner. Prepared (1,2′-ethylene) (2,1′-ethylene)-
A catalyst component obtained by pre-contacting 19 micromoles of bis (3-methylindenyl) zirconium dichloride in toluene for 30 minutes was added, the temperature was raised to 40 ° C, and the total pressure was 8.0 kg.
/ Cm ² G of propylene gas was introduced. During the polymerization, propylene gas was supplied by a pressure regulator so that the pressure became constant, and after 1 hour, the content was taken out and dried under reduced pressure to obtain polypropylene. Evaluation of Physical Properties The evaluation was made by the method described above. The results are shown in Table 2.

Example 2 The procedure of Example 1 was repeated, except that 50 g of 1-butene (comonomer) was additionally charged in the autoclave, and the physical properties were evaluated. The results are shown in Table 2. Example 3 Preparation of Catalyst (1) Production of 2-chlorodimethylsilylindene In a nitrogen stream, 50 ml of THF (tetrahydrofuran) and 2.5 g (41 mmol) of magnesium were added to a 1-liter three-necked flask, and 1 part of the flask was added thereto. Then, 0.1 ml of 2,2-dibromoethane was added and stirred for 30 minutes to activate magnesium. After stirring, the solvent was extracted, and 50 ml of THF was newly added. Here, 5.0 g (25.6 mmol) of 2-bromoindene in THF (20
0 ml) solution was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to -78 ° C, and dichlorodimethylsilane (3.1 ml, 25.6
(100 mmol) in THF (100 ml) was added dropwise over 1 hour, and after stirring for 15 hours, the solvent was distilled off. After extracting the residue with 200 ml of hexane,
The solvent was distilled off to obtain 6.6 g (24.2 mmol) of 2-chlorodimethylsilylindene (yield 9).
4%). (2) Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) THF40 was placed in a 1-liter three-necked flask under a nitrogen stream.
0 ml and 2-chlorodimethylsilylindene 8
g was added and cooled to -78 ° C. To this solution, add LiN
A solution of (SiMe ₃ ) ₂ in THF (1.0 mol) was added dropwise to 38.5 ml (38.5 mmol). After stirring at room temperature for 15 hours, the solvent was distilled off and extracted with 300 ml of hexane. By distilling off the solvent,
2.2 g (6.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) was obtained (yield: 33.4%). (3) Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indenyl) zirconium dichloride In a Schlenk bottle, (1,2′-dimethylsilylene) (2,
2.2 g of 1'-dimethylsilylene) -bis (indene)
(6.4 mmol) and 100 ml of ether, cooled to −78 ° C., and 9.6 ml (15.4 mmol) of n-butyllithium (hexane solution: 1.6 mol) was added. Stir for 12 hours. The solvent was distilled off, and the obtained solid was washed with 20 ml of hexane to obtain a lithium salt (this lithium salt can be obtained quantitatively). The obtained lithium salt was dissolved in 100 ml of toluene, and 1.5 g (6.4 g) of zirconium tetrachloride was placed in another Schlenk bottle.
Mmol) and 100 milliliters of toluene. 5
100 ml of toluene was added to a 00 ml three-necked flask, cooled to 0 ° C., and while stirring, an equal amount of the above lithium salt and zirconium tetrachloride was added dropwise over 1 hour using a cannula. After dropping,
Stirred overnight at room temperature. The solution was filtered and the solvent of the filtrate was distilled off. By recrystallizing the obtained solid with dichloromethane, (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) -bis (indenyl)
1.2 g (2.4 mmol) of zirconium dichloride was obtained (yield 37%). When the ¹ H-NMR of this product was determined, the following results were obtained. ¹ H-NMR (CDC
l ₃ ): 0.85, 1.08 (6H, s), 7.11 (2H,
s), 7.2-7.7 (8H, m) polymerization 5 l of heptane, 5 mmol of triisobutylaluminum, and 10 mmol of methylaluminoxane (manufactured by Albemarle Co.) in a stainless steel autoclave having an internal volume of 10 l in terms of aluminum. And 10 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indenyl) zirconium dichloride prepared above and pre-contacted in toluene for 5 minutes. Temperature to 8.0 at full pressure
Propylene gas was introduced up to kg / cm ² G. During the polymerization, propylene gas was supplied by a pressure regulator so that the pressure became constant. After 2 hours and 30 minutes, the content was taken out and dried under reduced pressure to obtain polypropylene. Mixing and kneading The following additives were formulated into the polypropylene obtained as described above, and a single-screw extruder (TLC35- manufactured by Tsukada Juki Seisakusho) was used.
(Type 20) to obtain pellets. Antioxidant Irganox 1 manufactured by Ciba Specialty Chemicals
010: 1000 ppm and Irgafos 168: 1000 ppm manufactured by Ciba Specialty Chemicals Co., Ltd. Evaluation of physical properties Evaluation was made by the methods described above. The results are shown in Table 2.

Example 4 Preparation of catalyst (1,2′-dimethylsilylene) in the same manner as in Example 3
(2,1′-dimethylsilylene) -bis (indenyl)
Zirconium dichloride was obtained. Polymerization In a stainless steel autoclave having an internal volume of 10 liters, heptane (6 liters), triisobutylaluminum (6 mmol), and methylaluminoxane (manufactured by Albemarle Co., Ltd.) were prepared at 500 micromoles in terms of aluminum (1,2′-dimethylsilylene). (2,1 '
-Dimethylsilylene) -bis (indenyl) zirconium dichloride, 5 micromoles of a catalyst component preliminarily contacted in toluene for 5 minutes, and then the temperature was raised to 50 ° C., and propylene gas was supplied to a total pressure of 8.0 kg / cm ² G. Introduced. During the polymerization, propylene gas was supplied by a pressure regulator so that the pressure became constant. After 60 minutes, the content was taken out, and the pressure was reduced.
By drying, polypropylene was obtained. Mixing and kneading The same operation as in Example 3 was performed. Evaluation of Physical Properties The evaluation was made by the method described above. The results are shown in Table 2. Example 5 Example 5 was carried out in the same manner as in Example 3, except that Gelol MD (manufactured by Shin Nihon Rika) was added. Table 2 shows the physical property evaluation results. Comparative Example 1 Preparation of Catalyst (1) Preparation of Magnesium Compound A glass reactor (with an internal volume of about 6 liters) equipped with a stirrer was sufficiently replaced with nitrogen gas, and about 2430 g of ethanol, 16 g of iodine and 160 g of metallic magnesium were charged and stirred. The reaction was carried out under reflux conditions until hydrogen gas was no longer generated from the system, thereby obtaining a solid reaction product. The reaction solution containing the solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component In a glass three-necked flask (internal volume: 500 ml) sufficiently purged with nitrogen gas, 16 g of the magnesium compound (not pulverized), 80 ml of purified ethane, 2.4 silicon tetrachloride Milliliter and 2.3 ml of diethyl phthalate were added. After maintaining the inside of the system at 90 ° C and stirring, 77 ml of titanium tetrachloride was added and reacted at 110 ° C for 2 hours, the solid component was separated and washed with purified heptane at 80 ° C. Further, 122 ml of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours, and then sufficiently washed with purified heptane to obtain a solid catalyst component. Polymerization In a 5-liter stainless steel pressure-resistant autoclave, 20 g of polypropylene powder, 2.5 mmol of triisobutylaluminum (TIBA), 1-allyl-3,4-
20 ml of a heptane solution containing 0.125 mmol of dimethoxybenzene (ADMB), 0.2 mmol of diphenyldimethoxysilane (DPDMS) and 0.05 mmol of the above solid catalyst component in terms of titanium atom were added, and
After evacuation for a minute, gas phase polymerization was carried out for 1.7 hours while supplying propylene gas until the total pressure reached 28 kg / cm ² G to obtain a polymer. Evaluation of Physical Properties The evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[0053]

[Table 2]

[0054]

[Table 3]

Example 6 The following additives were formulated into polypropylene obtained in the same manner as in Example 1, and a single-screw extruder (TL manufactured by Tsukada Juki Seisakusho, Ltd .: TL)
(C35-20 type), and pelletized to obtain pellets. Antioxidant Irganox 1010 manufactured by Ciba Specialty Chemicals: 1000 ppm and Irgafos 168 manufactured by Ciba Specialty Chemicals: 1000 ppm Neutralizing agent: calcium stearate: 1000 ppm Antiblocking agent: ····· Silica: 2300 ppm Slip agent ··· Erca amide: 2500 ppm Nucleating agent Gelol MD (dimethylbenzylidene sorbitol) manufactured by Shin Nippon Rika Co., Ltd .: 2300 ppm And the film quality was evaluated by the above method. The results are shown in Table 3. Example 7 The following additives were formulated into a propylene / butene copolymer obtained in the same manner as in Example 2, and extruded and granulated with a single screw extruder (Model TLC35-20, manufactured by Tsukada Juki Seisakusho Seisakusho). To obtain pellets. Antioxidant Irganox 1010 manufactured by Ciba Specialty Chemicals: 1000 ppm and Irgafos 168 manufactured by Ciba Specialty Chemicals: 1000 ppm Neutralizing agent: calcium stearate: 1000 ppm Antiblocking agent: ····· Silica: 2300 ppm Slip agent ··· Erca amide: 2500 ppm Nucleating agent Gelol MD (dimethylbenzylidene sorbitol) manufactured by Shin Nippon Rika Co., Ltd .: 2300 ppm And the film quality was evaluated by the above method. The results are shown in Table 3. Example 8 The following additives were formulated into polypropylene obtained in the same manner as in Example 1, and a single screw extruder (TL manufactured by Tsukada Juki Seisakusho, Ltd .: TL)
(C35-20 type), and pelletized to obtain pellets. Antioxidant Irganox 1010 manufactured by Ciba Specialty Chemicals: 1000 ppm and Irgafos 168 manufactured by Ciba Specialty Chemicals: 1000 ppm Neutralizing agent: calcium stearate: 1000 ppm Antiblocking agent: ····· Silica: 2300 ppm Slip agent ··· Ercaamide: 2500 ppm Nucleating agent Gelol MD (dimethylbenzylidene sorbitol) manufactured by Shin Nippon Rika Co., Ltd .: 500 ppm And the film quality was evaluated by the above method. The results are shown in Table 3. Comparative Example 2 Example 6 was the same as Example 6 except that no nucleating agent was added.
When the film was formed in the same manner as above, the roll lease property was extremely deteriorated during film formation, and film formation was impossible. Comparative Example 3 The same as Example 6 except that E2900 manufactured by Idemitsu Petrochemical Co., obtained using a nonmetallocene catalyst (titanium / magnesium catalyst), was used as the propylene-based polymer, and no nucleating agent was added. I went to. Table 3 shows the physical properties of the obtained film. Comparative Example 4 As a propylene polymer, a non-metallocene catalyst (titanium /
Example 6 was carried out in the same manner as in Example 6, except that E2900 manufactured by Idemitsu Petrochemical Co., Ltd. obtained using a magnesium-based catalyst) was used. Table 3 shows the physical properties of the obtained film.

Comparative Example 5 Preparation of Catalyst In the same manner as in Example 1, (1,2′-ethylene) (2,
1′-ethylene) -bis (3-methylindenyl) zirconium dichloride was obtained. Polymerization Example 1 In a stainless steel oclave having an internal volume of 10 liters, 5 liters of toluene and 20 mmol of methylaluminoxane (manufactured by Albemarle) were converted to aluminum in terms of aluminum.
20 μmol of (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride prepared in the above step were sequentially added, and the temperature was raised to 50 ° C. Propylene gas was introduced up to 7 kg / cm ² . During the polymerization, propylene gas was supplied by regulating the pressure so that the pressure became constant. After one hour, the content was taken out and dried under reduced pressure to obtain polypropylene. Mixing and kneading The same operation as in Example 8 was carried out. Evaluation of Physical Properties When evaluated by the above-described method, film breakage occurred during film formation, and film formation was impossible.

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

According to the present invention, the balance between the low elastic modulus and the amount of the sticky component is improved, and a propylene-based polymer useful as a substitute for a soft vinyl chloride resin can be obtained. A propylene-based polymer composition exhibiting low-temperature heat-sealing properties and moldability comparable to low-density polyethylene and capable of producing films and molded articles having excellent transparency and rigidity can be obtained.

Claims (10)

[Claims] An isotactic pentad fraction (mmmm) which is a propylene homopolymer and exhibits stereoregularity.
Fraction) is 30 to 80%, and the molecular weight distribution (Mw / M
A propylene polymer having n) of 3.5 or less and an intrinsic viscosity [η] of 0.8 to 5 deciliter / g. 2. A propylene polymer comprising propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms, having a stereoregularity index (P) of 55 to 90 mol% and a molecular weight distribution (Mw). / Mn) is 3.5 or less, and the intrinsic viscosity [η] is 0.8 to 5 deciliter / g. (A) General formula (I)[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, hydrocarbon
A ligand selected from a group and a silicon-containing group,
¹And A^TwoTo form a cross-linked structure through
May be the same or different, and X is a σ bond
A plurality of X are the same when there are a plurality of Xs
But may be different, other X, E¹, E^TwoOr with Y
It may be crosslinked. Y represents a Lewis base;
In some cases, a plurality of Y may be the same or different,
Y, E¹, E^TwoOr X may be cross-linked,¹Passing
And A^TwoIs a divalent bridging group connecting the two ligands.
A hydrocarbon group having 1 to 20 carbon atoms;
Hydrogen-containing hydrocarbon group, silicon-containing group, germanium-containing
Group, tin-containing group, -O-, -CO-, -S-, -SO_Two
-, -Se-, -NR^{twenty four}-, -PR^{twenty four}-, -P (O) R
^{twenty four}-, -BR^{twenty four}-Or-AlR^{twenty four}-Indicates R^{twenty four}Is hydrogen
Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, charcoal
A halogen-containing hydrocarbon group having a prime number of 1 to 20;
They may be the same or different. q is 1-5
[(V of M) -2] is represented by an integer, and r is an integer of 0 to 3.
Indicates a number. A transition metal compound represented by the formula:
(B-1) The transition metal compound of the component (A) or a derivative thereof.
A compound capable of forming an ionic complex by reacting with
(B-2) containing a component selected from aluminoxanes
Homopolymerization of propylene in the presence of a polymerization catalyst
The method for producing a propylene-based polymer according to claim 1, wherein
Law. (A) General formula (I)[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, hydrocarbon
A ligand selected from a group and a silicon-containing group,
¹And A^TwoTo form a cross-linked structure through
May be the same or different, and X is a σ bond
A plurality of X are the same when there are a plurality of Xs
But may be different, other X, E¹, E^TwoOr with Y
It may be crosslinked. Y represents a Lewis base;
In some cases, a plurality of Y may be the same or different,
Y, E¹, E^TwoOr X may be cross-linked,¹Passing
And A^TwoIs a divalent bridging group connecting the two ligands.
A hydrocarbon group having 1 to 20 carbon atoms;
Hydrogen-containing hydrocarbon group, silicon-containing group, germanium-containing
Group, tin-containing group, -O-, -CO-, -S-, -SO_Two
-, -Se-, -NR^{twenty four}-, -PR^{twenty four}-, -P (O) R
^{twenty four}-, -BR^{twenty four}-Or-AlR^{twenty four}-Indicates R^{twenty four}Is hydrogen
Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, charcoal
A halogen-containing hydrocarbon group having a prime number of 1 to 20;
They may be the same or different. q is 1-5
[(V of M) -2] is represented by an integer, and r is an integer of 0 to 3.
Indicates a number. A transition metal compound represented by the formula:
(B-1) The transition metal compound of the component (A) or a derivative thereof.
A compound capable of forming an ionic complex by reacting with
(B-2) containing a component selected from aluminoxanes
In the presence of a polymerization catalyst, propylene and ethylene and / or
Or copolymerization of an α-olefin having 4 to 20 carbon atoms.
The propylene-based polymer according to claim 2, wherein
Construction method. 5. A molded article comprising the propylene-based polymer according to claim 1. 6. A propylene polymer composition comprising (a) the propylene polymer according to claim 1 and (b) at least 10 ppm of a nucleating agent. 7. A propylene polymer composition obtained by adding (b) 10 ppm or more of a nucleating agent to (a ′) the propylene polymer according to claim 2. 8. The propylene polymer has a crystallization temperature (Tc (° C.)) and a melting point (T c) measured by a differential scanning calorimeter.
m (° C.)) and the following relational expression (1): Tc ≧ 0.75 Tm−
The propylene-based polymer composition according to claim 6, which satisfies (1). 9. A molded article and a film comprising the propylene-based polymer composition according to claim 6. 10. A laminate comprising the propylene-based polymer composition according to claim 6 as at least one layer component.