JP5382982B2 - Propylene polymer and molded article obtained from the polymer - Google Patents

Description

  The present invention relates to a propylene polymer and a molded product obtained from the polymer, and more particularly to a syndiotactic propylene polymer and a molded product obtained from the polymer.

  Polypropylene includes isotactic polypropylene, syndiotactic polypropylene, etc. Among them, isotactic polypropylene is inexpensive and is widely used in various applications because of its rigidity, heat resistance and surface gloss. Yes.

  On the other hand, syndiotactic polypropylene is known to be obtained by low-temperature polymerization in the presence of a catalyst comprising a vanadium compound, ether and organoaluminum. The polymer obtained by this method has low syndiotacticity, and it was difficult to say that the polymer exhibited the original syndiotactic properties.

In recent years, a high tacticity polypropylene having a syndiotactic pentad fraction exceeding 0.7 can be obtained by a transition metal catalyst having an asymmetric ligand and aluminoxane by JA Ewen et al. Since its first discovery (J. Am. Chem. Soc., 1988, 110, 6255-6256 (Non-patent Document 1)), many achievements relating to syndiotactic polypropylene have been published. For example, JP-A-8-67713 (Patent Document 1)
A catalyst comprising rac-2,2-dimethylpropylidene (1-η ⁵ -cyclopentadienyl) (1-η ⁵ -fluorenyl) dichlorometallocene of titanium, zirconium, hafnium and vanadium and a cocatalyst is used, A method for producing syndiotactic polypropylene is disclosed. Further, the applicant of the present invention can produce a syndiotactic polypropylene satisfying a specific property using a polymerization catalyst composed of 1,4-cyclohexanediylidenebis [(cyclopentadienyl-9-fluorenyl) zirconium dichloride]. Is disclosed. (Japanese Patent Laid-Open No. 4-802147 (Patent Document 2))
Syndiotactic polypropylene has extremely high transparency and surface gloss compared to conventional isotactic polypropylene, and also has excellent flexibility. Therefore, syndiotactic polypropylene is a film, sheet, fiber, In addition to uses such as injection-molded bodies and blow-molded bodies, new uses that could not be applied with isotactic polypropylene are expected. However, the syndiotactic polypropylene obtained by the method described in the above publication has a problem that the crystallization speed is slower than that of isotactic polypropylene, and the molding processability is inferior because the crystallization temperature is low. For example, syndiotactic polypropylene is difficult to crystallize during the pelletization stage during continuous operation, and coupled with the low crystallization temperature, the time required to cool an injection molded article or extruded film or sheet is isotactic. Much longer than tick polypropylene. This property delayed the production rate of the molded body, resulting in increased energy costs. Further, there is room for further improvement not only in moldability but also in the balance of heat resistance, transparency, rigidity and strength as a molded body.
JP-A-8-67713 JP-A-4-802147 J. Am. Chem. Soc., 1988, 110, 6255-6256

The problem to be solved by the present invention is to provide a syndiotactic propylene copolymer with improved problems as described above, and a molded product obtained therefrom. Specifically, it is to provide a syndiotactic propylene polymer excellent in moldability by improving the crystallization speed and crystallization temperature, and also excellent in heat resistance, transparency, balance between mechanical properties and strength. It is to provide a molded body.

The propylene polymer of the present invention contains 90 mol% to 10 mol of structural units derived from propylene.
And 0 mol% to 10 mol% of structural units derived from ethylene and one or more selected from ethylene and α-olefins having 4 to 20 carbon atoms (provided that the total amount of structural units is 100 mol%). A syndiotactic propylene polymer that satisfies all the following requirements [1] to [3]. (In the following description, the term “propylene polymer” may be used as a term encompassing not only a propylene homopolymer but also a copolymer with the α-olefin described above. (The polymer may be referred to as “syndiotactic propylene polymer (A)”.)
[1] The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more.
[2] The melting point (Tm) determined by a differential scanning calorimeter is 145 ° C. or higher and the heat of fusion (ΔH) is 40 mJ / mg or higher.
[3] When isothermal crystallization temperature obtained with a differential scanning calorimeter is T _iso , and the half crystallization time at the isothermal crystallization temperature T _iso is t _1/2 , a range of 110 ≦ T _iso ≦ 150 (° C.) In the following formula (Eq-1)
Meet.

The syndiotactic propylene polymer (A) of the present invention preferably satisfies the following requirement [4] in addition to the above requirement;
[4] The amount of n-decane soluble part is 1% by weight (wt%) or less.

In the following description, a syndiotactic propylene polymer that satisfies the requirement [4] in addition to the requirements [1] to [3] may be particularly referred to as a syndiotactic propylene polymer (A ′).

The syndiotactic propylene polymer (A) of the present invention preferably satisfies the following requirements [a] to [d] in addition to the requirements [1] to [4].
[a] The tensile elastic modulus is in the range of 500 to 2000 MPa.

[b] The tensile strength at break is 20 MPa or more.
[c] The internal haze value of a 1 mm thick press sheet is 50% or less.
[d] The needle penetration temperature is 145 ° C. or higher.

  In the following description, a syndiotactic propylene polymer that satisfies the requirements [a] to [d] in addition to the requirements [1] to [4] is particularly referred to as a syndiotactic propylene polymer (A ″). There is a case.

Furthermore, the present invention provides a syndiotactic propylene polymer (A), (A ′) or
Other also includes a molded article obtained from (A '').
The present invention relates to the syndiotactic propylene polymer (A), (A ′) or (
The sheet obtained from A ″) is also included.
The present invention relates to the syndiotactic propylene polymer (A), (A ′) or (
Also included are unstretched or stretched films obtained from A ″).
The present invention also includes a laminate in which at least one layer is a layer comprising the above-described syndiotactic propylene polymer (A), (A ′) or (A ″).
The present invention relates to the syndiotactic propylene polymer (A), (A ′) or (
A nonwoven fabric obtained from A ″) is also included.

  According to the present invention, a syndiotactic propylene polymer excellent in moldability and heat resistance, in particular, excellent in moldability, heat resistance, transparency, balance between mechanical properties and strength, and a molded body comprising the polymer are provided. be able to.

  Hereinafter, the best mode for carrying out the invention will be described with respect to the syndiotactic propylene polymer (A) according to the present invention and a molded product comprising the propylene polymer. Specifically, the characteristic properties of the syndiotactic propylene polymer (A), a typical production method of the polymer, a method of molding the polymer, and specific examples thereof will be described. .

Syndiotactic propylene polymer (A)
The syndiotactic propylene polymer (A) of the present invention comprises 90 to 100 mol% of structural units derived from propylene and structural units derived from one or more selected from ethylene and an α-olefin having 4 to 20 carbon atoms. Is a propylene polymer containing 0 mol% to 10 mol% (however, the total is 100 mol%).

  The syndiotactic propylene polymer (A) of the present invention is a propylene polymer having the above-mentioned requirements [1] to [3], preferably the requirements [1] to [4], more preferably the requirement [1 ] To [4], as long as the propylene polymer satisfies the requirements [a] to [d], even a homopolypropylene is a propylene / α-olefin having 2 to 20 carbon atoms (excluding propylene) ) A random copolymer or a propylene block copolymer may be used, but preferably a homopolypropylene or a propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) random copolymer. is there. Particularly preferred is a copolymer of propylene and ethylene or an α-olefin having 4 to 10 carbon atoms, and a copolymer of propylene, ethylene and an α-olefin having 4 to 10 carbon atoms.

Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. In addition, the propylene-based polymer of the present invention usually contains 90 mol% to 100 mol% of structural units derived from propylene and 0 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene).
A propylene polymer containing 10 mol% or less (provided that the total of structural units is 100 mol%), preferably 91 mol% or more and 100 mol% of the structural units derived from propylene.
And a propylene polymer containing 0 to 9 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (provided that the total of the structural units is 100 mol%). More preferably, the propylene contains 96 mol% to 100 mol% of structural units derived from propylene and 0 mol% to 4 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is a polymer (however, the total of structural units is 100 mol%).

In addition, when the syndiotactic propylene polymer of the present invention is a propylene / α-olefin random copolymer, the structural unit derived from propylene is 94 to 99.9 mol%, and has 2 to 20 carbon atoms. A structural unit derived from an α-olefin (excluding propylene) is contained in an amount of 0.1 to 8 mol%, preferably 93 structural units derived from propylene.
To 99.9 mol%, and 0.1 to 7 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene), more preferably 94 to 99.9 mol of structural units derived from propylene. %, And a structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is preferably contained in an amount of 0.1 to 6 mol%. Among these syndiotactic propylene polymers, homopolypropylene is more preferable from the viewpoint of heat resistance and the like.

The intrinsic viscosity [η] of the syndiotactic propylene polymer (A) of the present invention measured in decalin at 135 ° C. is usually 0.01 to 10.00 dL / g, preferably 0.10 to 9.00 dL. / G, more preferably 0.50 to 8.00 dL / g, still more preferably 0.95 to 8.00 dL / g, particularly preferably 1.00 to 8.00, and even more preferably 1.40 to 8. It is desirable to be in the range of 00 dL / g, and it is particularly preferable to be in the range of 1.40 to 5.00 dL / g.

The syndiotactic propylene polymer (A) according to the present invention is characterized by satisfying all of the following requirements [1] to [3].
[1] The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more.
[2] The melting point (Tm) determined by a differential scanning calorimeter is 145 ° C. or higher and the heat of fusion (ΔH) is 40 mJ / mg or higher.
[3] When the isothermal crystallization temperature obtained with a differential scanning calorimeter is T _iso , and the half crystallization time in isothermal crystallization is t _1/2 , the following formula is used in the range of 110 ≦ T _iso ≦ 150 (° C.) (Eq-1) is satisfied.

  Such a syndiotactic propylene polymer (A) is excellent in the balance of moldability, heat resistance, transparency, mechanical properties and strength when applied to moldability. The requirements [1] to [3] will be specifically described below.

Requirement [1]
The syndiotactic propylene polymer used in the present invention has a syndiotactic pentad fraction (rrrr fraction, pentad syndiotacticity) measured by NMR method of 85% or more, preferably 90% or more, more preferably. The syndiotactic propylene polymer having an rrrr fraction in this range is excellent in moldability, heat resistance and transparency, and has characteristics as a crystalline polypropylene. Is favorable and preferable. The upper limit of the rrrr fraction is not particularly limited but is 100% or less, and usually 99% or less, for example.

This syndiotactic pentad fraction (rrrr fraction) is measured as follows.
The rrrr fraction is expressed as Prrrr in the ¹³ C-NMR spectrum (absorption intensity derived from the third unit methyl group at the site where 5 units of propylene units are continuously syndiotactically bonded) and Pw (total methyl groups of propylene units). (Absorption intensity derived from the above) is determined by the following formula (1).

rrrr fraction (%) = 100 × Prrrr / Pw (1)
The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And using JEOL GX-500 type NMR measuring device, ¹³ C-NMR at 120 ° C.
Measure. The number of integration is 10,000 times or more.

  A syndiotactic propylene polymer having an rrrr fraction in this range is preferable because it is excellent in moldability, heat resistance and mechanical properties, and has good properties as a crystalline polypropylene. A syndiotactic propylene polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.

Requirement [2]
The syndiotactic propylene polymer has a melting point (Tm) obtained by differential scanning calorimetry (DSC) measurement of 145 ° C. or higher, preferably 150 ° C. or higher, more preferably 155 ° C. or higher, particularly preferably 156 ° C. That's it. The heat of fusion (ΔH) is 40 mJ / mg or more, preferably 50 mJ / mg or more, more preferably 52 mJ / mg or more, and particularly preferably 55 mJ / mg or more. The upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower, for example.

The differential scanning calorimetry is performed as follows, for example. About 5 mg of the sample is packed in a special aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by Perkin Elmer, and held at 200 ° C. for 5 minutes, and then from 200 ° C. to 30 ° C. The temperature is lowered at 10 ° C./min, held at 30 ° C. for 5 minutes, and then the melting point (Tm) is determined from the endothermic curve when the temperature is raised at 10 ° C./min. When a plurality of peaks are detected during DSC measurement, the peak detected on the highest temperature side is defined as the melting point (Tm).

  A syndiotactic propylene polymer having a melting point (Tm) in this range is preferable because it is excellent in moldability, heat resistance and mechanical properties, and has good properties as crystalline polypropylene. A syndiotactic propylene polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.

Requirement [3]
The syndiotactic propylene polymer has an isothermal crystallization temperature determined by differential scanning calorimetry (DSC) measurement as T _iso , and a half crystallization time at the isothermal crystallization temperature T _iso is t _1/2.
In the range of 0 ≦ T _iso ≦ 150 (° C.), the following formula (Eq-1) is satisfied,

  Preferably, the following formula (Eq-2) is satisfied,

  More preferably, the following formula (Eq-3) is satisfied.

The half crystallization time (t _1/2 ) determined by isothermal crystallization measurement is the DSC during the isothermal crystallization process.
When the area between the calorie curve and the baseline is defined as the total calorific value, it is the time when the calorific value reaches 50%. [Refer to New Polymer Experiment Laboratory 8 Polymer Properties (Kyoritsu Publishing Co., Ltd.)]
The half crystallization time (t _1/2 ) is measured as follows. About 5 mg of a sample is packed in a special aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by PerkinElmer, and held at 200 ° C. for 5 minutes, then the temperature (200 ° C. ) To each isothermal crystallization temperature is obtained from a DSC curve obtained by lowering the temperature at 320 ° C./min and maintaining the isothermal crystallization temperature. Here, the half crystallization time (t _1/2 ) is obtained as isothermal crystallization process start time (time when the isothermal crystallization temperature is reached from 200 ° C.) t = 0. The syndiotactic propylene polymer of the present invention is t _1/2 as described above.
However, if crystallization does not occur at a certain isothermal crystallization temperature, for example, 110 ° C., several measurements are made at an isothermal crystallization temperature of 110 ° C. or less for convenience, and semi-crystallization is performed from the extrapolated value. Time (t _1/2 ) was determined.

A syndiotactic propylene polymer satisfying the requirement [3] has much better moldability than existing ones. Here, excellent moldability means that when molding such as injection, inflation, blow, extrusion, or press is performed, the time from solidification to solidification is short. Further, such a syndiotactic propylene polymer is excellent in molding cycle property, shape stability, long-term productivity and the like.

A syndiotactic propylene polymer satisfying the requirement [3] can be produced by setting a polymerization condition as described later using a catalyst system as described later.
The syndiotactic propylene polymer (A) of the present invention preferably satisfies the following requirement [4] in addition to the requirements [1] to [3].

Requirement [4]
The amount of the n-decane soluble part of the syndiotactic propylene polymer is 1 (wt%) or less, preferably 0.8 (wt%) or less, more preferably 0.6 (wt%) or less. The amount of the n-decane soluble part is an index closely related to the blocking characteristics of the syndiotactic propylene polymer or the molded product obtained therefrom. Usually, the small amount of the n-decane soluble part means that the amount of the low crystalline component is low. It means less. That is, the syndiotactic propylene polymer (A ′) that also satisfies the requirement [4] has very good blocking resistance.

The syndiotactic propylene polymer (A) of the present invention, preferably the syndiotactic propylene polymer (A ′) preferably satisfies the following requirements [a] to [d].
[a] The tensile elastic modulus is in the range of 500 to 2000 (MPa).

[b] The tensile strength at break is 20 (MPa) or more.
[c] The internal haze value of a 1 mm thick press sheet is 50% or less.
[d] The needle penetration temperature is 145 ° C. or higher.

Hereinafter, requirements [a] to [d] will be described in detail.
Requirement [a]
The tensile elastic modulus of the syndiotactic propylene polymer (A) of the present invention, preferably the syndiotactic propylene polymer (A ′) is in the range of 500 MPa to 2000 MPa, preferably 600 MPa to 1800 MPa, more preferably 600 MPa to 1500 MPa. Range.

  Specifically, this tensile elastic modulus is a value measured by the following procedure. First, a 1 mm-thick press sheet is punched with an JIS No. 3 dumbbell order bell in accordance with JIS K6301, and used as an evaluation sample. For example, using an Instron tensile tester Inston 1123, the tensile modulus is measured at 23 ° C. at a span interval of 30 mm and a tensile speed of 30 mm / min, and the average value of three measurements is obtained.

  A syndiotactic propylene polymer having a tensile modulus in this range is preferable because it is excellent in mechanical properties and strength, and has good properties as crystalline polypropylene. A polymer having a tensile modulus in this range can be produced by using a catalyst system as described later and setting the polymerization conditions as described later.

Requirement [b]
The tensile rupture strength of the syndiotactic propylene polymer (A) of the present invention, preferably the syndiotactic propylene polymer (A ′) is 20 (MPa) or more, preferably 22 (MPa) or more, more preferably. Is 25 (MPa) or more, more preferably 30 (MPa) or more.

  Specifically, the tensile strength at break is a value measured by the following procedure. First, a 1 mm-thick press sheet is punched with an JIS No. 3 dumbbell order bell in accordance with JIS K6301, and used as an evaluation sample. For example, using an Instron tensile tester Inston 1123, the tensile strength at break is measured at 23 ° C. with a span interval of 30 mm and a tensile speed of 30 mm / min, and the average value of three measurements is obtained.

  A syndiotactic propylene polymer having a tensile strength at break in this range is excellent in mechanical properties and strength, and preferable as crystalline polypropylene. By using a catalyst system as described later and setting the polymerization conditions as described later, a polymer in this range can be produced.

Requirement [c]
The internal haze of the syndiotactic propylene polymer (A) of the present invention, preferably the syndiotactic propylene polymer (A ′), is 50% or less, preferably 45% or less, more preferably 30% or less.

  The value of this internal haze is 2 times when the internal haze is measured with a digital turbidity meter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd. using a 1 mm thick press sheet test piece. Average value of the measurement.

  A syndiotactic propylene polymer having an internal haze in this range is preferable because of its excellent transparency and good properties as crystalline polypropylene. A polymer having an internal haze in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later.

Requirement [d]
The needle penetration temperature of the syndiotactic propylene polymer (A) of the present invention, preferably the syndiotactic propylene polymer (A ′) is 145 ° C. or more, more preferably 1
It is a range of 50 ° C. or higher.

The needle penetration temperature (sometimes referred to as the softening point determined by TMA measurement) can be measured as follows.
Using Seiko SS-120 or TA Instrument Q-400, 1m thick
Using a press sheet test piece of m, a pressure of ² Kgf / cm ² is applied to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min, and the needle penetration temperature (° C.) is determined from the TMA curve.

  Syndiotactic propylene polymers with a needle penetration temperature in this range are excellent in heat resistance, have good properties as crystalline polypropylene, and are resistant to heat without sacrificing the transparency characteristic of syndiotactic propylene. In view of excellent rigidity, material strength and the like, the properties as crystalline polypropylene are favorable and preferable. By using a catalyst system as described later and setting the polymerization conditions as described later, a polymer in this range can be produced.

The present invention provides a molded product obtained by molding the syndiotactic propylene polymer (A), preferably the syndiotactic propylene polymer (A ′), more preferably the syndiotactic propylene polymer (A ″). About.

Production method of syndiotactic propylene polymer As a catalyst in the production of the syndiotactic polypropylene polymer (A) of the present invention,
(K) a bridged metallocene compound represented by the following general formula [1] (also referred to herein as “component (K)”), and (B) (b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and

(b-3) a polymerization catalyst (cat-1) comprising at least one compound selected from organoaluminum compounds, or a polymerization catalyst (cat) in which the catalyst (cat-1) is supported on a particulate carrier -2) is preferably used, but as long as the polymer produced exhibits properties satisfying the requirements [1] to [3], the catalyst used for the production of the syndiotactic propylene polymer (A) The catalyst is not limited at all.

In the general formula [1], R ¹ , R ² , R ³ and R ⁴ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group, and R ² and R ³ are bonded to each other to form a ring. R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R ¹² are selected from hydrogen, hydrocarbon groups and silicon-containing groups, and the two groups R ⁷ and R ¹⁰ are not hydrogen atoms, R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹ are selected from hydrocarbon groups and silicon-containing groups.
^{In a} combination of one or more adjacent groups selected from ¹ and R ¹² , the adjacent groups may be bonded to each other to form a ring.

R ¹⁷ and R ¹⁸ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon atom-containing group, which may be the same or different from each other, and the substituents may be bonded to each other to form a ring. Good.

  M is Ti, Zr or Hf, Y is carbon, Q can be selected from the same or different combinations from halogen, hydrocarbon group, anionic ligand or neutral ligand capable of coordinating with a lone pair of electrons. Often, j is an integer from 1 to 4.

The following are specific examples of the component (K) satisfying this definition:
Cyclopropylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-fluorenyl)
Zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6
-Ditert-fluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (3,6-ditert-fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butyl) Fluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) ) Zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, Di-n-butylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadi) (Enyl) (2,3,6,7-
Tetra-tert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, Di-n-butylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-
Di-tert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium Dichloride,
Diisobutylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl (2,7-di (2,4,6- Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutyl Methylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,3, 6,7-tetra-tert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride Lido, diisobutylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-tert -Butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride [Also referred to as 1,3-diphenylisopropylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride. Benzylmethylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2 , 7-Diphenyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl ) Zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (4 -Methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride Dibenzylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,
Diphenethylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (Cyclopentadienyl) (2,7-
Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, Di (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2 , 7-Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl Fluorenyl) zirconium dichloride, di (cyclohexylmethyl)
Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-
Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride , Di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) Zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methyl Down (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert- butylfluorenyl) zirconium dichloride,
(Benzyl) (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (
Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopropylidene (Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-
(Butylfluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2 , 7-Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride , Cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-diphenyl-3, 6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexyl Silidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dimethyl-3,6- Ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,
Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-
Dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, di-n-butyl Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di ( Trimethylsilyl) -butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di (trimethylsilyl) -butylfluorenyl) zirconium dichloride, dibenzylmethylene (
Cyclopentadienyl) (2,7-dimethyl-3,6-diphenyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-diphenyl- Butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) ( 2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, Di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, Di (m-chlorophenyl) methylene Lopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromo Phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7-Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl Fluorenyl) zirconium dichloride,
Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2 , 7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene Ropentajieniru) (2,7-dimethyl-3,6-di-tert- butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-
Butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3) , 6-Ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Chirufuruoreniru) zirconium dichloride, and the like can be exemplified.

Among the above exemplary compounds, R ⁶ and R ¹¹ are phenyl group, tolyl group, t-butylphenyl group,
Those which are aryl groups or substituted aryl groups such as a dimethylphenyl group, a trimethylphenyl group and a biphenyl group are preferably used because they give a syndiotactic propylene polymer having a high melting point.

  Furthermore, the compounds exemplified above, where “zirconium” is changed to “hafnium” or “titanium”, “dichloride” is “difluoride”, “dibromide”, “diaiodide”, “dichloride” is “dimethyl” The bridged metallocene compound that has become “methylethyl” can be exemplified similarly.

  The (K) bridged metallocene compound described above can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include the production methods described in WO 2001/27124 and WO 2004/087775 by the present applicant. Moreover, such a metallocene compound can be used individually by 1 type or in combination of 2 or more types.

The polymerization catalyst component (B) (also referred to herein as “component (B)”) reacts with (b-1) an organoaluminum oxy compound and (b-2) the bridged metallocene compound (A). It is composed of at least one compound selected from a compound forming an ion pair and (b-3) an organoaluminum compound, and (C) a particulate carrier, if necessary. Hereinafter, each component will be specifically described.

(b-1) Organoaluminum oxy compound (b-1) Organoaluminum oxy compound used in the present invention (also referred to herein as “component (b-1)”) is a known aluminoxane. Can be used as is. Specifically, the following general formula [2]

(In the above formula [2], R is each independently a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.)
And / or general formula [3]

(In the above formula [3], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.)
In particular, a methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with some organoaluminum compounds. In addition, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, and JP-A-3-103407, etc. It can be suitably used.

  Examples of the organoaluminum oxy compound used in the present invention include modified methylaluminoxane as shown in [4] below.

(In the above general formula [4], R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n represent an integer of 2 or more.)
This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound [4] is generally called MMAO. Such MMAO may be prepared by, for example, the method described in US4960878, or a commercially available product may be used as it is. Also, from Tosoh Finechem Co., etc., those prepared using trimethylaluminum and triisobutylaluminum and having R as an isobutyl group are commercially produced under the names MMAO and TMAO. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, it is insoluble in benzene such as the compounds represented by the above formulas [2] and [3]. Unlike insoluble aluminoxane, it dissolves in aliphatic hydrocarbons and alicyclic hydrocarbons. The “benzene-insoluble” organoaluminum oxy compound means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% in terms of Al atoms.
The following refers to an organoaluminum oxy compound that is insoluble or hardly soluble in benzene.

(b-2) A compound that reacts with the bridged metallocene compound (K) to form an ion pair A compound that reacts with the bridged metallocene compound (K) to form an ion pair (b-2) (hereinafter referred to as “ionic compound”) Or may be abbreviated as “component (b-2)”). JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, JP-A-3-179006 Issue gazette,
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207703, JP-A-3-207704, US5321106 and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

In the present invention, the ionic compound (b-2) preferably employed is a compound represented by the following general formula [6].

In the formula [6], examples of R ^{e +} include H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{f to} R ⁱ may be the same as or different from each other, and are organic groups, preferably aryl groups.

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-
Butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) Borate, tripropylammonium tetrakis (
Pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-tri Fluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, di Octadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethyl) Tilphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate And dioctadecylmethylammonium.

Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( 3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5- Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, etc. .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, ionic compounds disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can also be used without limitation.
The ionic compound (b-2) as described above can be used as a mixture of two or more.

(b-3) Organoaluminum Compound Forms Olefin Polymerization Catalyst (b-3) Organoaluminum Compound (
Also referred to as “component (b-3)”. ) Can include, for example, organoaluminum compounds represented by the following general formula [7].

R ^a _m Al (OR ^b ) _n H _p X _q ... [7]
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.
Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum;
Tri-branched alkyl aluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
Isoprenyl aluminum represented by general formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y, z are positive numbers, z ≦ 2x), etc. Alkenylaluminum of
Alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _0.5 ;
Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
In the olefin polymerization catalyst according to the present invention, the catalyst component includes (K) a bridged metallocene compound represented by the general formula [1], and (B) (b-1) an organoaluminum oxy compound, (b- 2) a compound that reacts with the bridged metallocene compound (K) to form an ion pair, and (b-3)
A carrier (C) can be used as required together with at least one compound selected from organic aluminum compounds.

(C) Carrier The carrier (C) (also referred to herein as “component (C)”) is an inorganic or organic compound, and is a granular or particulate solid. Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these are used, for example natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained therein can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used. Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

  The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using ion exchangeability. Clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, teniolite and synthetic mica are particularly preferred.

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 3 to 300 μm, preferably 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene A (co) polymer produced mainly from the above, or a polymer having a polar functional group obtained by copolymerizing or graft-polymerizing a polar monomer such as acrylic acid, acrylic ester or maleic anhydride to these polymers, or A metamorphic body can be illustrated. These particulate carriers can be used alone or in combination of two or more.

Further, the polymerization catalyst used in the present invention may contain an organic compound component (D) (also referred to as “component (D)” in the present specification) as necessary.
(D) Organic Compound Component In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compound component (D) include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

Method for Producing Syndiotactic Propylene Polymer (A) In the polymerization of the syndiotactic propylene polymer (A) of the present invention, the method of using each component and the order of addition are arbitrarily selected. A method is illustrated.
(1) A method of adding the component (K) alone to the polymerization vessel.
(2) A method in which component (K) and component (B) are added to the polymerization vessel in any order.
(3) A method in which the component (K) is supported on the carrier (C) and the component (B) is added to the polymerization vessel in any order.
(4) A method in which the component (B) is supported on the carrier (C) and the component (K) is added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which component (K) and component (B) are supported on a carrier (C) is added to a polymerization vessel.

In the above methods (2) to (5), at least two or more of each catalyst component may be contacted in advance.
In the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different.

  The solid catalyst component in which the component (K) is supported on the component (C) and the solid catalyst component in which the component (K) and the component (B) are supported on the component (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

  In the production of the syndiotactic propylene polymer (A) of the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also.

When the olefin polymerization is performed using the olefin polymerization catalyst as described above, the component (K) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² , per liter of the reaction volume. It is used in such an amount that it becomes a mole.

Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) and all transition metal atoms (M) in component (K) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (b-2) has a molar ratio [(b-2) / M] of component (b-2) to transition metal atom (M) in component (K) of usually 1 to 10, preferably It is used in such an amount as to be 1-5. Component (b-3) has a molar ratio [(b-3) / M] of aluminum atoms in component (b-3) to all transition metals (M) in component (K) of usually 10 to 10. The amount used is 5000, preferably 20-2000.

Component (D) has a molar ratio [(D) / (b-1)] of usually 0 when component (B) is component (b-1).
. When the component (B) is the component (b-2) in an amount such as 01 to 10, preferably 0.1 to 5, the molar ratio (D) / (b-2)] is usually 0.01. -10, preferably 0.1-5, and when component (B) is component (b-3), the molar ratio [(D) / (b-3)] is usually 0. 01-2,
Preferably it is used in such an amount as to be 0.005-1.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually −50 to
It is +200 degreeC, Preferably it is the range of 0-170 degreeC. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (B) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

  A part of the syndiotactic propylene polymer (A) obtained by the polymerization method described above may be graft-modified with a polar monomer. Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, chlorides. Examples include vinyl, vinyl group-containing organosilicon compounds, carbodiimide compounds, and the like.

As the polar monomer, an unsaturated carboxylic acid or a derivative thereof is particularly preferable. Examples of the unsaturated carboxylic acid or a derivative thereof include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Specific examples of the compound include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocis-bicyclo [2.2.1]).
Unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters and the like. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. These unsaturated carboxylic acids and / or derivatives thereof can be used singly or in combination of two or more. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferred, and maleic acid, nadic acid [trademark] or acid anhydrides thereof are particularly preferably used.

  The modified syndiotactic propylene polymer is obtained by graft polymerization of a polar monomer on the syndiotactic propylene polymer as described above. When the above polar monomer is graft-polymerized to the syndiotactic propylene polymer, the polar monomer is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight with respect to 100 parts by weight of the syndiotactic propylene polymer. Used in an amount of 80 parts by weight. This graft polymerization is usually carried out in the presence of a radical initiator.

As the radical initiator, an organic peroxide or an azo compound can be used.
The radical initiator can be used as it is mixed with the ethylene polymer and the polar monomer, but can also be used after being dissolved in a small amount of an organic solvent. Any organic solvent that can dissolve the radical initiator can be used without particular limitation.

  Further, when the polar monomer is graft-polymerized to the syndiotactic propylene polymer, a reducing substance may be used. When a reducing substance is used, the graft amount of the polar monomer can be improved.

  Graft modification of a syndiotactic propylene polymer with a polar monomer can be performed by a conventionally known method. For example, syndiotactic propylene polymer is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution. , 70 to 200 ° C., preferably 80 to 190 ° C., for 0.5 to 15 hours, preferably 1 to 10 hours.

  Moreover, a syndiotactic propylene polymer can also be manufactured by making a syndiotactic propylene polymer and a polar monomer react using an extruder etc. without a solvent. This reaction is usually preferably performed at a temperature equal to or higher than the melting point of the ethylene polymer, specifically at a temperature of 120 to 250 ° C., usually for 0.5 to 10 minutes.

  The modified amount of the modified syndiotactic propylene polymer thus obtained (the graft amount of the polar monomer) is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight, more preferably 0.2. Desirably, it is 10% by weight.

When the above-mentioned modified syndiotactic propylene polymer is contained in the syndiotactic propylene polymer of the present invention, the adhesiveness and compatibility with other resins are excellent, and the wettability of the molded body surface may be improved. is there.

In addition, by cross-linking the modified syndiotactic propylene polymer, it may be suitably used for a cross-linked electric wire and a cross-linked pipe.
The syndiotactic propylene polymer (A) of the present invention may contain polyethylene, isotactic polypropylene or styrenic elastomer, but may also contain polyethylene, isotactic polypropylene or styrenic elastomer in one embodiment. is there.

Moreover, in order to further improve the moldability of the syndiotactic propylene polymer (A) according to the present invention, that is, to increase the crystallization temperature and increase the crystallization speed, a nucleating agent which is a specific optional component may be included. In this case, for example, the nucleating agent is dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di-). tert-butylphenyl) sodium phosphate, pimelic acid and salts thereof, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, etc., and the amount is not particularly limited, but is 0.1 to 0.1% relative to the propylene polymer composition. There is preferably about 1 part by weight. There is no restriction | limiting in particular in a mixing | blending timing, It can add during superposition | polymerization, after superposition | polymerization, or a shaping | molding process.

  The syndiotactic propylene polymer (A) of the present invention has a weather resistance stabilizer, heat resistance stabilizer, anti-static agent, anti-slip agent, anti-blocking agent, foaming agent, crystallization aid, as long as the object of the invention is not impaired. Additives such as additives, anti-fogging agents, clear nucleating agents, lubricants, pigments, dyes, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, mold release agents, impact modifiers, anti-UV agents May be blended.

  The syndiotactic propylene polymer (A) is prepared by various known methods within the above-described range, for example, a multistage polymerization in a continuous or batch manner using a slurry phase, a solution phase or a gas phase, a Henschel mixer , V-blender, riboblender, tumbler blender, etc., or after mixing, melt-kneaded with a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc., then granulated or pulverized can do.

Molding method and molded product obtained by the method Syndiotactic propylene polymer (A) obtained by the above method, a modified product thereof, or the syndiotactic propylene polymer (A) and the syndiotactic propylene polymer Since a composition with a polymer different from (A) can provide a molded article having excellent moldability and heat resistance, and having a good balance between moldability, heat resistance, transparency, mechanical properties and strength, Although it was difficult to use syndiotactic polypropylene in practice, it can be widely used in polyolefin applications. In particular, syndiotactic propylene polymer (A) can be used in, for example, sheets, unstretched or stretched films, filaments, other It can be used by forming into a molded body of various shapes. In addition, a molded body using the syndiotactic propylene polymer (A) may be any as long as the syndiotactic propylene polymer (A) is contained in a part of the molded body. The tick propylene polymer (A) may be used, and the syndiotactic propylene polymer (A) may be used for the entire molded body. As an example in which the syndiotactic propylene polymer (A) is used in a part of the molded body, a multilayer laminate can be mentioned. Specifically, the multilayer laminate is a laminate in which at least one layer thereof is a layer containing the syndiotactic propylene polymer (A), the multilayer film and sheet, the multilayer container, the multilayer tube, and the water-based paint A multilayer coating film laminate included as a constituent component of

  The syndiotactic propylene polymer (A) of the present invention is extrusion molding, injection molding, inflation molding, extrusion lamination molding, cast molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foaming. It can be molded by a known thermoforming method such as molding or powder slush molding. Furthermore, it can be used for fibers, monofilaments, nonwoven fabrics and the like.

  These molded products include molded products (laminates and the like) including a portion made of the syndiotactic propylene polymer (A) and a portion made of another resin. The syndiotactic propylene polymer (A) may be one that has been crosslinked in the molding process.

  Specific examples of the molded body include known thermoforming such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, foam molding, and powder slush molding. The molded object obtained by a method is mentioned. Hereinafter, the molded body will be described with several examples.

  When the molded product of the present invention is, for example, an extrusion-molded product, the shape and product type are not particularly limited, and examples include a sheet, a film (unstretched), a pipe, a hose, an electric wire coating, a tube, and the like. (Skin material), film, tube, catheter, monofilament (nonwoven fabric) and the like are preferable.

  Syndiotactic propylene polymer (A) obtained by the above method, a modified product thereof, or a composition of the syndiotactic propylene polymer (A) and a polymer different from the syndiotactic propylene polymer (A) The object is transparent, impact resistance, heat resistance, flexibility or rigidity, wear resistance, surface hardness, shrinkage, soundproofing, vibration damping, cutability, high breakdown voltage, radiation resistance, degraling resistance, Since it is excellent in uniform foaming property, rubber elasticity, kink resistance, stretchability, creep properties, adhesiveness, softness-modifying property, transparency-modifying property, etc., it can be suitably used for the following applications.

  In general, food containers, beverage bottles, pipes, food packaging materials, retort containers, medical containers, infusion bags, clothing cases, transparent substrates, transparent sealants, sealants, automotive interior and exterior materials, automotive skin materials, Abrasion-resistant automotive interior and exterior materials, molding materials, automotive sealing materials, building material skin materials, shrink films, wrap films, porous films, laminates, sound insulation materials, vibration damping materials, vibration insulation materials, sound absorption materials, sound insulation materials, foaming Body, foam material, cushion material, masking film, capacitor film, protect film, reflective film, dicing film, laminate (including glass), electric cable, stretched film, shape memory material, laminated glass film, bulletproof material, bulletproof Film for glass, solar cell encapsulant, radiation resistant film, gamma ray resistant film, flow mark modifier, weld Materials, nonwoven fabrics, stretchable nonwoven fabrics, modifiers, adhesives, compatibilizers (graft modification), chipping resistance, chipping resistance modifiers, stretched films, weld modifiers, wrap films, capacitor films, etc. Is mentioned.

  When extruding the syndiotactic propylene polymer (A), conventionally known extruders and molding conditions can be employed. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder The molten propylene composition can be formed into a desired shape by extruding from a specific die or the like.

  The stretched film is obtained by stretching an extruded sheet or extruded film (unstretched) as described above by a known stretching method such as a tenter method (longitudinal and transverse stretching or transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method, or the like. Can be obtained.

  The stretching ratio when stretching the sheet or unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 μm by stretching.

Moreover, an inflation film can also be manufactured as a film-shaped molded object. Drawdown is less likely to occur during inflation molding.
Sheets and film molded articles using the syndiotactic propylene polymer (A) are not easily charged, mechanical properties, heat resistance, stretchability, impact resistance, aging resistance, transparency, transparency, gloss, rigidity It is excellent in moisture resistance and gas barrier properties, and can be widely used as a packaging film.

  In this case, the sheet and film molded product using the syndiotactic propylene polymer (A) may be a multilayer molded product, and used as a multilayer laminate containing at least one syndiotactic propylene polymer. It is done.

  The filament molded body can be produced, for example, by extruding a molten syndiotactic propylene polymer (A) through a spinneret. Specifically, a spunbond method or a melt bron method is preferably used. The filament thus obtained may be further stretched. This stretching may be performed to such an extent that at least one uniaxial direction of the filament is molecularly oriented, and it is usually desirable to perform the stretching at a magnification of about 5 to 10 times. The filament made of the syndiotactic propylene polymer (A) is not easily charged and is excellent in transparency, flexibility, heat resistance, impact resistance, and stretchability.

  The injection-molded body can be produced by injection molding the syndiotactic propylene polymer (A) into various shapes using a known condition using a conventionally known injection molding apparatus. The injection molded body using the propylene composition is less charged and has excellent transparency, rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc. It can be widely used for automobile exterior materials, home appliance housings, containers and the like.

  The blow molded article can be produced by blow molding the syndiotactic propylene polymer (A) using a known blow molding apparatus under known conditions. In this case, the blow molded article made of the syndiotactic propylene polymer (A) may be a multilayer molded article, and contains at least one layer of the syndiotactic propylene polymer (A).

  For example, in extrusion blow molding, a syndiotactic propylene polymer (A) is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is held in a mold having a desired shape. A hollow molded body can be manufactured by blowing after-air and mounting the mold at a resin temperature of 130 ° C to 300 ° C. The stretching (blowing) magnification is desirably about 1.5 to 5 times in the lateral direction.

  In injection blow molding, the syndiotactic propylene polymer (A) is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison, and then the parison is held in a mold having a desired shape. A hollow molded body can be manufactured by blowing air and mounting it on a mold at a resin temperature of 120 ° C to 300 ° C. The draw (blow) magnification is desirably 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.5 times in the transverse direction.

A blow molded article using the syndiotactic propylene polymer (A) is excellent in transparency, rigidity or flexibility, heat resistance and impact resistance, and also in moisture resistance.
Examples of the press-molded body include a mold stamping molded body. For example, when a base material and a skin material are press-molded at the same time and the both are integrally formed (mold stamping molding), the base material is a syndiotactic propylene polymer. Can be formed.

  Specific examples of such a mold stamping molded body include automotive interior materials such as door rims, rear package trims, seat back garnishes, and instrument panels.

  A press-molded product using the syndiotactic propylene polymer (A) is hardly charged, and has rigidity or flexibility, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, and wear resistance. Excellent in properties.

  A foamed molded product using the syndiotactic propylene polymer (A) is obtained at a high expansion ratio, has good injection moldability, and has high rigidity and material strength.

  The syndiotactic propylene polymer (A) can produce vacuum molded bodies such as interior skin materials such as automobile instrument panels and door trims. The molded body is hardly charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance, and the like.

  By molding the propylene-based polymer (A) of the present invention, powder slush moldings such as automobile parts, home appliance parts, toys and sundries can be manufactured. The molded body is hardly charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance, and the like.

Moreover, as a molded object of this invention, the laminated body which has at least one layer which consists of a syndiotactic propylene polymer (A) can be mentioned.
The propylene polymer (A) of the present invention is particularly suitable for extrusion molded articles (films, sheets, etc.), inflation molded articles, injection molded articles, blow molded articles, and fibers, and is extruded from the viewpoint of transparency and heat resistance. It is particularly suitable for molded bodies, inflation molded bodies, injection molded bodies, and blow molded bodies.

  The propylene polymer (A) of the present invention is suitable for a container or a nonwoven fabric, for example. Examples of the container include a food container such as a frozen storage container and a retort pouch, and a bottle container. Moreover, a medical container, an infusion bag, etc. can be illustrated.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the examples, each physical property was measured as follows.

Intrinsic viscosity [η]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of polymer powder, pellets or resin mass is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η _sp is measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).

[Η] = lim (η _sp / C) (C → 0)
n-decane soluble part amount Add 5 ml sample of syndiotactic propylene polymer to 200 ml of n-decane
It was dissolved by heating for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (n-decane insoluble part) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate was filtered off from acetone and then dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following equation.

n-decane soluble part amount (wt%) = [precipitate weight / sample weight] × 100
Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as an antioxidant, moving at 1.0 ml / min, sample concentration 15 mg / 10 mL, sample injection volume 500 micro A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

Ethylene, propylene, α-olefin content in the polymer Quantification of ethylene, propylene, α-olefin content was measured as follows using a JNM GX-500 NMR measuring apparatus manufactured by JEOL Ltd. A 0.35 g sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. This solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is charged into an NMR tube having an inner diameter of 10 mm, and ¹³ C-NMR measurement is performed at 120 ° C. The number of integration is 10,000 times or more. The composition of ethylene, propylene and α-olefin was quantified by the obtained 13C-NMR spectrum.

Melting point (Tm), heat of fusion (ΔH)
Using a DSCPyris 1 or DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20
ml / min), a sample of about 5 mg was heated to 200 ° C. and held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 5 minutes, the melting point was calculated from the peak of the crystal melting peak when the temperature was raised to 200 ° C. at 10 ° C./min, and the heat of fusion was calculated from the integrated value of the peaks.

Note that in the propylene-based polymer described in an embodiment of the present invention, the case where two peaks were observed, the low-temperature side peak Tm _1, the high temperature side peak to the case of the Tm _2, the Tm _2, present claim 1 It is assumed that Tm is defined in requirement [2].

Semi-isothermal crystallization time (t _1/2 )
About 5mg of sample is packed in a special aluminum pan, heated from 30 ° C to 200 ° C at 320 ° C / min using DSCPyris 1 or DSC7 manufactured by PerkinElmer, and held at 200 ° C for 5 minutes, then isothermal crystal from 200 ° C A half crystallization time (t _1/2 ) was obtained from the DSC curve obtained by lowering the crystallization temperature to 110 ° C. at 320 ° C./min and maintaining the temperature at each isothermal crystallization temperature. Here, the half crystallization time (t _1/2 ) was determined by assuming that the isothermal crystallization process start time (time when the isothermal crystallization temperature was reached from 200 ° C.) t = 0. The composition of the present invention is t _1/2 as described above.
For example, when crystallization is not performed at a certain isothermal crystallization temperature, for example, 110 ° C., several measurements are performed at an isothermal crystallization temperature of 110 ° C. or less for convenience, and the extrapolated value is half The crystallization time (t _1/2 ) was determined.

MFR
Based on JIS K-6721, it measured with the load of 2.16kgf at 230 degreeC.
Method for producing various measurement press sheets A 10 MPa pressure sheet was formed using a hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 200 ° C. In the case of 0.5 to 3 mm thick sheet (spacer shape; 240 x 240 x 2 mm thick plate 80 x 80 x 0.5 to 3 mm, 4 pieces), the remaining heat is about 5-7 minutes and 10MP
After pressurizing with a for 1 to 2 minutes, a measurement sample was prepared by compressing at 10 MPa using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set at 20 ° C. and cooling for about 5 minutes. A 5 mm thick brass plate was used as the hot plate. The samples prepared by the above method were used for various physical property evaluation samples.

From a press sheet having a tensile modulus of elasticity of 1 mm, punched with a JIS No. 3 dumbbell order bell in accordance with JIS K6301, and used as an evaluation sample. The sample was measured at 23 ° C. with a span interval of 30 mm and a tensile speed of 30 mm / min.

Izod impact strength In accordance with ASTM D-256, a test piece of 12.7 mm (width) x 3.2 mm (thickness) x 64 mm (length) was punched from a 3 mm thick press sheet, and a notch for machining was added. , Measured at 0 ° C.

Softening temperature by TMA measurement In accordance with JIS K7196, using a test piece with a thickness of 1 mm, a pressure of ² Kgf / cm ² is applied to a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min. temperature(
° C).

Preparation method of internal haze measurement sample
In the case of a 1 mmt press sheet, a test sample was prepared in accordance with the above-described manufacturing methods of various measurement press sheets. In the case of a 2 mmt injection piece, it was molded under the conditions of a resin temperature of 200 ° C., an injection pressure of 1000 kgf / cm ² , and a mold temperature of 40 ° C. using an injection molding machine IS-55 manufactured by Toshiba Corporation. A square plate test piece having a thickness of 2 mm, a length of 120 mm, and a width of 130 mm was prepared.

Internal haze (%)
Using a 1 mm thick press sheet as a test piece, measurement was performed with a digital turbidity meter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.

Evaluation of Injection Molding Using a Toshiba 55-ton injection molding machine, the resin temperature was 200 ° C., the mold temperature was 40 ° C., and the rejection time was 20 seconds (condition 1) and 1 second (condition 1). The moldability is 5 times injection molding, peeling from the mold by the piercing pin and continuous operation is possible; ○, peeling from the mold is not possible even once; Δ, peeling from the mold No continuous operation was possible;

[Catalyst synthesis example]
Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride was produced by the method described in Synthesis Example 3 of JP-A No. 2004-189668.

Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride was prepared as follows.
(I) Synthesis of 2,7-dibromo-3,6-ditert-butyl-fluorene A method described in Bull. Chem. Soc. Jpn., 59, 97 (1986) in a 300 mL three-necked flask under a nitrogen atmosphere. Then, 15.22 g (54.7 mmol) of 3,6-ditert-butyl-fluorene synthesized according to the above and 170 mL of propylene carbonate were added and stirred. To this solution, 20.52 g (115 mmol) of N-bromosuccinimide was added, and the mixture was heated and stirred at 80 ° C. for 5 hours. Thereafter, the reaction solution was allowed to cool naturally, and the reaction solution was added to 800 mL of water. After stirring at room temperature for 15 minutes, the precipitated solid was filtered off. The resulting solid was washed 5 times with 10 mL of ethanol. Thereafter, a mixed solution of n-hexane and a small amount of dichloromethane was added to the solid, heated to 60 ° C., dissolved, and allowed to stand at −20 ° C. overnight. The precipitated crystals were washed 3 times with 5 mL of hexane to obtain the desired product (yield 21.16 g, yield 76%). The object was identified by ¹ H-NMR and FD-MS spectra.

¹ H NMR (270 MHz, CDCl ₃ , TMS): δ1.60 (s, tBu (Flu), 18H), 3.75 (s, Flu-9H, 2H), 7.73 (s, Flu, 2H), 7.81 (s , Flu, 2H).
MS (FD): M / z 436 (M ⁺ ).
(Ii) Synthesis of 2,7-diphenyl-3,6-ditert-butyl-fluorene In a 300 mL three-necked flask under a nitrogen atmosphere, 2,7-dibromo-3,6-ditert-butyl-fluorene 8.15 g ( 18.7 mmol) and Pd (PPh ₃ ) 1.08 g (0.93 mmol) were added 120 mL of dehydrated 1,2-dimethoxyethane and stirred at room temperature for 20 minutes. To this solution was added a solution of phenylboric acid (5.01 g, 41.1 mmol) in ethanol (20 mL) and stirred at room temperature for 20 minutes, and then 2.0 mol / L sodium carbonate aqueous solution (37.4 mL, 74.8 mmol) was added. Thereafter, the mixture was heated to reflux for 18 hours, allowed to cool naturally, and then quenched with dilute hydrochloric acid in an ice bath. Ether was added to extract the soluble part, and the organic layer was washed twice with saturated aqueous sodium hydrogen carbonate solution, twice with water and twice with saturated brine, and then dried over magnesium sulfate. Thereafter, the solvent was distilled off, and the resulting solid was separated by column chromatography to obtain the desired product (yield 4.36 g, yield 54%). The object was identified by ¹ H-NMR and FD-MS spectra.

¹ H NMR (270 MHz, CDCl ₃ , TMS): δ1.29 (s, tBu (Flu), 18H), 3.78 (s, Flu-9H, 2H), 7.16 (s, Flu, 2H), 7.34 (br , PhFlu, 10H), 7.97 (s, Flu, 2H).
MS (FD): M / z 430 (M ⁺ ).
(Iii) Synthesis of 6,6-dibenzofulvene Under a nitrogen atmosphere, 8.0 g (121 mmol) of cyclopentadiene and 100 mL of dehydrated tetrahydrofuran were added to a 500 mL three-necked flask and stirred. The mixed solution was cooled in an ice bath, and 80 mL (125.6 mmol) of a hexane solution of n-butyllithium having a concentration of 1.57 mol / L was added. Thereafter, the mixture was stirred at room temperature for 3 hours, and the resulting white slurry was cooled in an ice bath, and then a solution of 25.0 g (118 mmol) of 1,3-diphenyl-2-propanone in 50 mL of dehydrated tetrahydrofuran was added. The mixture was then stirred at room temperature for 12 hours, and the resulting yellow solution was quenched with a saturated aqueous ammonium chloride solution. Soluble components were extracted by adding 100 mL of n-hexane, and the organic phase was washed with water and saturated brine and then dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by column chromatography to obtain the desired product as a yellow solid (yield 3.7 g, yield 12%). The target product was identified by ¹ H-NMR.

¹ H NMR (270 MHz, CDCl ₃ , TMS): δ3.69 (s, PhCH _2, 4H), 6.60-6.72 (m, Cp, 4H), 7.13-7.32 (m, PhCH ₂ , 10H).
(Iv) Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-)
Synthesis of tert-butylfluorene) Under nitrogen atmosphere, 2,70-diphenyl-3,6-ditert-butylfluorene (1.60 g, 3.71 mmol) was added with dehydrated tetrahydrofuran (mL) and stirred. The solution was cooled in an ice bath, and 2.65 mL (4.13 mmol) of a 1.56 mol / L n-butyllithium hexane solution was added. Stir at room temperature for 2 hours. The obtained red solution was cooled to −78 ° C. with a dry ice-methanol bath, and a solution of 6,6-dibenzofulvene 1.06 g (4.10 mmol) in tetrahydrofuran 20 mL was added dropwise over 20 minutes. Thereafter, the mixture was stirred for 18 hours while gradually warming to room temperature. To the resulting black-red solution, 60 mL of 1N hydrochloric acid was added to terminate the reaction. Diethyl ether (80 mL) was added to carry out liquid separation, and a soluble part was extracted. The organic layer was washed twice with a saturated aqueous sodium hydrogen carbonate solution, twice with water, once with saturated brine, and dried over magnesium sulfate. The solvent was distilled off and the residue was purified by silica gel chromatography to obtain the desired product as a white yellow powder (yield 0.59 g, yield 23%).
The object was identified by ¹ H-NMR and FD-MS spectra.

¹ H NMR (270 MHz, CDCl ₃ , TMS): δ1.25 (s, tBu (Flu), 18H), 2.66 (br, CpH, 1H), 3.22 (br, CH ₂ Ph, 4H), 4.41 (br , Flu-9H, 1H), 5.85-6.51 (m, Cp, 4H), 6.82-7.40 (m, Ph (Flu) and CH ₂ Ph and Flu, 22H), 7.67 (s, Flu, 2H).
MS (FD): M / z 688 (M ⁺ ).
(V) Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-)
Synthesis of tert-butylfluorenyl) zirconium dichloride In a nitrogen atmosphere, add 100 mL Schlenk tube to dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) 0.59 g ( 0.855 mmol) and 40 mL of dehydrated diethyl ether were added and stirred. The mixed slurry solution was cooled in an ice bath, 1.21 mL (1.88 mmol) of a hexane solution of n-butyllithium having a concentration of 1.56 mol / L was added, and the mixture was stirred for 45 hours while gradually warming to room temperature. This red reaction solution was -78 in a dry ice / methanol bath.
After cooling to 0 ° C., 0.200 g (0.858 mmol) of zirconium tetrachloride was added. Thereafter, the mixture was stirred for 42 hours while gradually warming to room temperature to obtain a red-orange suspension. After the solvent was distilled off under reduced pressure, it was dissolved in n-hexane under nitrogen, washed with n-hexane through a glass filter packed with celite, and the orange powder not dissolved in n-hexane was extracted with dichloromethane. The solvent in the dichloromethane-dissolved part was distilled off, washed with diethyl ether / cold n-pentane, and dried to obtain the desired product as an orange powder (yield 515 mg, yield 71%). The object was identified by ¹ H-NMR and FD-MS spectra.

¹ H NMR (270 MHz, CDCl ₃ , TMS): δ1.30 (s, tBu (Flu), 18H), 3.82 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 3.93 (d, J = 15.5 Hz, CH ₂ Ph, 2H), 5.80 (t, J = 2.6 Hz, Cp, 2H), 6.25 (t, J = 2.6 Hz, Cp, 2H), 6.97-7.34 (m, Ph (Flu) and CH ₂ Ph, 20H), 7.37 (s, Flu, 2H), 8.32
(s, Flu, 2H).
MS (FD): M / z 848 (M ⁺ ).
Diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) 2,7-
Di-tert-butylfluorenyl zirconium dichloride was produced by the method described in Example 3c of WO 2004/087775.

[Polymerization Example 1]
(Synthesis of syndiotactic propylene polymer (A-1))
To a reaction vessel having an internal volume of 3 m ³ , which was sufficiently purged with nitrogen, was charged 1000 L of n-heptane, and 610 mL (0.93 mol) of a toluene solution of methylaluminoxane (Al = 1.53 mol / l) was added dropwise at room temperature. On the other hand, a magnetic stirrer was placed in a 5 L branch flask which had been sufficiently purged with nitrogen. To this was added 610 mL (0.93 mol) of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), then dibenzylmethylene ( Cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride 1.30
A toluene solution of g (1.86 mmol) was added and stirred for 20 minutes. This solution was added to the reaction vessel, and then 3200 NL of hydrogen was supplied at 19 Nm ³ / h over 10 minutes. Thereafter, polymerization was started while supplying propylene at 65 kg / h and hydrogen at a gas phase concentration of 53 mol% in the reaction vessel. Propylene is continuously supplied in an amount of 65 kg / h while maintaining a gas phase concentration of 53 mol% in a hydrogen reaction tank, polymerization is performed at 25 ° C. for 4 hours, and then a small amount of diethylene glycol monoisopropyl ether is added to perform polymerization. Stopped. The obtained polymer was washed with heptane 1.8 m ³ and dried under reduced pressure at 80 ° C. for 15 hours.
g was obtained. The polymerization activity is 13.4 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer is 1.90 dl / g, Tm ₁ = 152 ° C., Tm ₂ = 159 ° C., rrrr fraction = 94%.

[Polymerization Example 2]
(Synthesis of syndiotactic propylene polymer (A-2))
To a glass autoclave with a capacity of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 liters / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branched flask with sufficient nitrogen substitution, 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), and then dibenzylmethylene (cyclopentadiene). Enil) (2,
Toluene solution of 7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride (5.0 μmol) was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. for 10 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 6.95 g of polymer was obtained. The polymerization activity is 7.58 kg-PP / mmol-Zr · hr, and [η] of the obtained polymer is 2.54 dl / g, Tm ₁ = 157 ° C., Tm ₂ = 162 ° C., rrrr fraction = 95%.

[Polymerization Example 3]
(Synthesis of syndiotactic propylene polymer (A-3))
1.0 L of heptane was charged into a 2.0 L SUS autoclave which had been thoroughly dried and purged with nitrogen, and then purged by introducing propylene gas to 0.3 MPaG while stirring. This was repeated three times. On the other hand, a magnetic stirrer was placed in a branch flask having an internal volume of 50 ml sufficiently purged with nitrogen, and 1.80 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l) was added thereto, and then dibenzylmethylene (cyclopentadiene). 1.8 μmol of a toluene solution of (enyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) zirconium dichloride was added and stirred for 15 minutes. This solution was added to heptane of an SUS autoclave in which propylene was circulated to initiate polymerization. Propylene gas was continuously supplied to an internal pressure of 0.2 MPaG, and 6
After 0 minutes of polymerization, a small amount of methanol was added to stop the polymerization. The polymer was recovered from the heptane slurry by filtration and dried under reduced pressure at 80 ° C. for 6 hours. As a result, 75.4 g of polymer was obtained. The polymerization activity was 42.0 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer was 2.4 dl / g, Tm = 161 ° C., and the rrrr fraction was 97%.

For 100 parts by weight of the syndiotactic polypropylene polymer obtained in [Polymerization Example 1], 0.1 part by weight of Tris (2,4-di-tert-buthylphenyl) phosphite as a secondary antioxidant, Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy-, 2,2-bis [[3- [3,5-bis (1,1-dimethylethyl) -4- 0.1 parts by weight of hydroxyphenyl] -1-oxopropoxy] methyl] -1,3-propandiyl ester and 0.1 parts by weight of calcium stearate as a neutralizing agent are blended. Thereafter, a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd. was used at a preset temperature of 200 ° C., and a resin charge amount of 40 g (apparatus batch volume = 60 cm ³ ), 5
After melt-kneading at 0 rpm for 5 minutes, the sample was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Furthermore, the same amount of the above-mentioned additives is blended with the polymer, and a set temperature is set by using a double-screw extruder BT-30 (30 mmφ, L / D = 46, rotating in the same direction, four knee zones) manufactured by Plavo. It was granulated at 230 ° C, resin extrusion rate 50g / min, 200rpm, and used for injection molding evaluation test. The results are shown in Table 3.
Compared to the comparative example, it is excellent in moldability and heat resistance, and further in balance between transparency, mechanical properties and strength.

The same amount of the additive described in Example 1 is blended with 100 parts by weight of the syndiotactic polypropylene polymer obtained in [Polymerization Example 2]. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge amount of 40 g (device batch volume = 60 cm ³ ), 50 rpm, melt for 5 minutes, and then taken out 20 It was made into a sheet with a cooling press set at 0 ° C., and cut into an appropriate size to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Compared to the comparative example, it is excellent in moldability and heat resistance, and further in balance between transparency, mechanical properties and strength.

The same amount of the additive as described in Example 1 is blended with 100 parts by weight of the syndiotactic polypropylene polymer (A-3) obtained in [Polymerization Example 3]. Thereafter, using a lab plast mill (biaxial batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 200 ° C., a resin charge amount of 40 g (device batch volume = 60 cm ³ ), 50 rpm, melt for 5 minutes, and then taken out 20
It was made into a sheet with a cooling press set at 0 ° C., and cut into an appropriate size to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. Table 2 shows the results of various physical properties. Compared to the comparative example, it is excellent in moldability and heat resistance, and further in balance between transparency, mechanical properties and strength.

[Comparative Example 1]
A press sheet was prepared using TOTAL polypropylene 1471 pellets, and the physical properties were measured. Table 2 shows the results of various physical properties. The pellet was used for an injection molding evaluation test. The results are shown in Table 3. Compared to the examples, the moldability and heat resistance are inferior, and the balance between mechanical properties and strength is also inferior.

[Comparative Example 2]
A press sheet was prepared using polypropylene F327 pellets manufactured by Prime Polymer Co., Ltd., and the physical properties were measured. Table 2 shows the results of various physical properties. The pellet was used for an injection molding evaluation test. The results are shown in Table 3. Compared to the examples, it is inferior in heat resistance and inferior in the balance of transparency, mechanical properties and strength.

  The syntactic propylene polymer of the present invention is syndiotactic propylene having excellent moldability and improved crystallization speed and crystallization temperature as compared with existing polymers. In addition, since a molded product obtained from the polymer is excellent in balance of heat resistance, transparency, rigidity, strength, and the like, various new uses that could not be applied to isotactic polypropylene are expected.

FIG. 7 is a graph plotting the relationship between a specific isothermal crystallization temperature (T _iso ) and a half crystallization time (t _1/2 ) at the temperature for the syndiotactic propylene polymers described in the examples and comparative examples of the present invention. is there. The portion surrounded by the thick line indicates the region of the parameter inequality (Eq-1) defined in the requirement [3] of claim 1 of the present application.

Claims (3)

Comprising 90 mol% to 100 mol% of a structural unit derived from propylene and 0 mol% to 10 mol% of a structural unit derived from one or more selected from ethylene and an α-olefin having 4 to 20 carbon atoms (provided that the structural unit Is a propylene polymer that satisfies all the following requirements [1] to [3].
[1] The syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more.
[2] The melting point (Tm) determined by a differential scanning calorimeter (DSC) is 156 to 162 ° C. , and the heat of fusion (ΔH) is 55 mJ / mg or more.
[3] When isothermal crystallization temperature obtained with a differential scanning calorimeter is T _iso , and the half crystallization time at the isothermal crystallization temperature T _iso is t _1/2 , a range of 110 ≦ T _iso ≦ 150 (° C.) Satisfies the following formula (Eq-2).

  The propylene-based polymer according to claim 1, wherein the amount of the n-decane soluble part is 1% by weight or less. The propylene polymer according to claim 1 or 2, wherein the following requirements [a] to [d] are simultaneously satisfied.
[a] The tensile elastic modulus is in the range of 500 to 2000 MPa.
[b] The tensile strength at break is 20 MPa or more.
[c] The internal haze value of a 1 mm thick press sheet is 50% or less.
[d] The needle penetration temperature is 145 ° C. or higher.

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