JP4875954B2 - Propylene-based copolymer, method for producing the same, and molded product - Google Patents

Description

  The present invention relates to a propylene-based copolymer having a specific molecular structure and phase structure, a method for producing the same, and a molded body having a specific structure formed by molding the same, and more specifically, used as a molding material and a molded body. Propylene-based copolymer that exhibits a very good stiffness-impact resistance balance, has good heat resistance, has a particularly good balance between impact strength and heat resistance at low temperatures, and has excellent impact whitening properties The present invention relates to a production method thereof and a molded body comprising the same.

Crystalline polypropylene is widely used in various molding fields because of its excellent mechanical properties and chemical resistance. However, when a propylene homopolymer is used as crystalline polypropylene, rigidity is increased but impact resistance is insufficient. Therefore, impact resistance is improved by a method of adding an elastomer such as ethylene-propylene rubber to a propylene homopolymer or a method of producing a so-called block copolymer by copolymerizing ethylene and propylene after the homopolymerization of propylene. It has been done to improve.
Although improvement of physical properties by these methods can be realized to a considerable extent, further improvement in rigidity-impact resistance balance is desired. In addition to these characteristics, improvement in heat resistance, improvement in impact strength at low temperatures, and improvement in whitening resistance are strongly desired.

On the other hand, it is known that isotactic polypropylene can be obtained by polymerizing propylene using a metallocene catalyst different from the conventional Ziegler type catalyst system. It is also known to produce a propylene-based copolymer (so-called propylene-ethylene block copolymer) by homopolymerizing propylene and subsequently copolymerizing ethylene and propylene using the same catalyst. For example, Patent Documents 1 to 5 describe examples thereof. Patent Documents 6 to 11 describe examples of propylene-ethylene block copolymers having good rigidity and impact properties.
Although the rigidity and impact resistance have been further improved by the invention described in the above-mentioned patent document, in order to apply more generally to the field of propylene-ethylene block copolymers, the rigidity and resistance to resistance are further increased. In addition to improving impact properties, improvements are also required in terms of heat resistance, moldability, and low temperature impact strength. Furthermore, when an impact is applied to a molded body made of these materials and materials, whitening due to frequent occurrence of crazes and voids is remarkable, and the improvement thereof is also an important issue.

  These conventionally known propylene copolymers (propylene-ethylene block copolymers) have a so-called sea-island structure in which an ethylene-propylene copolymer component is dispersed as a dispersed phase in a crystalline polypropylene component forming a continuous phase. It is common. In a propylene-based copolymer (propylene-ethylene block copolymer) having a sea-island structure, crazing is induced at the interface between the sea (polypropylene phase) and the island (ethylene-propylene copolymer phase) when an impact is applied. Absorbs impact energy efficiently, resulting in an improved balance between stiffness and impact resistance. Such a sea-island structure can be confirmed by observing a sample section prepared after staining with ruthenium tetroxide with a transmission electron microscope. That is, since crystalline polypropylene is not dyed by ruthenium tetroxide, a white transmission electron microscope image is obtained, and an ethylene-propylene copolymer component is dyed to give a black image. An electron microscopic image in which a black ethylene-propylene copolymer is dispersed in a polypropylene matrix is obtained. Furthermore, if the same observation is performed after the impact is applied, it is possible to observe the formation of crazes from the sea island interface.

  In general, in a polymer blend system composed of two types of polymer components A and B that are not compatible, the phase structure changes according to the structure of A and B and the blend ratio, and is roughly divided into three types of phase structures (A is a continuous phase). And B is a sea-island structure in which a dispersed phase is formed, conversely, A is a dispersed phase, B is an inverted sea-island structure in which a continuous phase is formed, and A and B are both co-continuous structures in which a continuous phase is formed). It has been known. Among these, the co-continuous structure has different physical properties from the structure in which only one component becomes a continuous phase, such as the sea-island structure or the reverse sea-island structure, because A and B having different properties form a continuous phase. In the polyphenylene sulfide / polycarbonate system (for example, see Patent Document 12) and polyalkyl methacrylate / polycarbonate system (for example, see Patent Document 13), the physical properties are improved by taking a co-continuous structure. It has been reported.

On the other hand, for a so-called propylene-ethylene block copolymer or a blend of crystalline polypropylene and ethylene-propylene copolymer, for example, in Patent Document 14, 70 parts by weight of propylene ethylene block copolymer and 30 parts by weight of ethylene propylene rubber are added. It has been shown that a composition obtained by melt-kneading with a screw extruder exhibits a co-continuous structure, and its rigidity and low-temperature impact resistance are improved. However, the phase structure of such a composition is not necessarily stable. However, further improvements in rigidity, heat resistance, and whitening resistance are required.
Further, Patent Document 15 includes a blend composition containing a crystalline first polymer component and a crystallizable second polymer component, and both the first and second polymer components contain stereotactic propylene having the same tacticity. Although disclosed and described as exhibiting a co-continuous structure, this composition is intended to increase elastic recovery and to increase compatibility between the first and second polymer components. The structures of both components are in a limited range, and as a result, the rigidity and heat resistance are extremely low.

  As described above, studies on the properties of propylene-ethylene block copolymers (propylene-based copolymers) exhibiting a co-continuous structure are still not sufficient. The co-continuous structure referred to here is not a layered structure having a specific orientation or direction, which is found in the vicinity of the surface of an injection molded product or in a part of a stretched film, but a crystalline polypropylene component and ethylene- This refers to a structure in which propylene copolymer components form a continuous phase together and exist in an intricate manner. For example, a continuous layered structure as shown in FIG. 1 on page 7 of Patent Document 16 is not regarded as a co-continuous structure in the present invention (see FIGS. 1 to 3, FIG. 1: a co-continuous structure, FIG. 2: a layered structure). Structure, Fig. 3: Sea-island structure).

In addition, the performance of the conventionally known propylene-ethylene block copolymer has been improved to some extent in impact resistance, but has never reached a satisfactory level, and further includes heat resistance and impact whitening resistance. In addition, there is a strong demand for improvement in terms of overall physical property balance. Furthermore, regarding low-temperature impact strength, not only Charpy impact strength and Izod impact strength, which are usually used for evaluation, but also “surface” impact strength represented by DuPont impact strength, especially “surface” impact strength at low temperatures, is strongly improved. Desired.
For this reason, in the propylene-ethylene block copolymer obtained by the conventional method, further improvement in rigidity-impact resistance balance, moldability, heat resistance, “surface” impact strength at low temperature, and whitening resistance can be improved. It was an issue. Moreover, in the propylene-ethylene block copolymer, an example in which physical properties are improved by taking a co-continuous structure has not been known.
JP 04-337308 A Japanese Patent Laid-Open No. 06-287257 Japanese Patent Laid-Open No. 05-202152 Japanese Patent Laid-Open No. 06-206921 Japanese Patent Laid-Open No. 10-219047 Japanese Patent Laid-Open No. 11-228648 JP-A-11-240929 JP-A-11-349649 JP-A-11-349650 Japanese Patent Laid-Open No. 2003-247035 JP 2003-206325 A JP 2000-248179 A JP 2001-207010 A Japanese Patent Laid-Open No. 06-021177 Japanese translation of PCT publication No. 2002-519497 Japanese Patent Laid-Open No. 06-313048

  In view of the above problems, the object of the present invention is to exhibit a very good balance between rigidity and impact resistance when used as a molding material and a molded body, and has good heat resistance, particularly impact strength at low temperatures. Another object is to provide a propylene-based copolymer having an excellent balance between heat resistance and impact whitening resistance, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a propylene-based copolymer having a specific molecular structure and a specific phase structure has extremely good rigidity when used as a molding material. -It has a balance of impact resistance, and it has been found that it has both high heat resistance and extremely excellent "surface" impact strength and impact whitening characteristics at low temperatures, and based on these findings, the present invention has been completed. .

That is, according to the first invention of the present invention, the first step (I) for producing a crystalline propylene polymer component (PP) and an ethylene-propylene copolymer component using an olefin polymerization catalyst containing a metallocene compound. A propylene-based copolymer is provided which is obtained by the subsequent step (II) for producing (EP) and satisfies the following (i) to (v).
(I) MFR (test conditions: 230 ° C., 2.16 kg load) is 0.1 to 300 g / 10 min.
(Ii) The proportion of the p-xylene soluble portion at 23 ° C. is 45 to 60% by weight of the entire copolymer.
(Iii) The ethylene content of the portion soluble in p-xylene at 23 ° C. is 40 to 65% by weight.
(Iv) The propylene content of the portion insoluble in p-xylene at 23 ° C. is 98% by weight or more.
(V) In the form observed with a transmission electron microscope, the (PP) portion and the (EP) portion are intertwined with each other to form a continuous phase.

Further, according to the second invention of the present invention, in the first invention, the intrinsic viscosity [η] _{CXS of the} part soluble in p-xylene at 23 ° C. obtained at 135 ° C. using decalin as a solvent and 23 ° C. _Provided is a propylene-based copolymer characterized in that the intrinsic viscosity [η] _CXIS ratio ([η] _CXS / [η] _CXIS ) of the portion insoluble in p-xylene is 0.75 to 2.00 Is done.

  According to a third aspect of the present invention, there is provided a molded body obtained by molding the propylene-based copolymer according to the first or second aspect, in a form observed with a transmission electron microscope (PP ) Part and (EP) part are intertwined with each other to provide a co-continuous structure in which a continuous phase is formed.

On the other hand, according to the fourth aspect of the present invention, in the presence of an olefin polymerization catalyst obtained by contacting the following components (A), (B), (C), a crystalline propylene polymer component (PP): A process for producing a propylene-based copolymer by the former stage process (I) for producing an ethylene-propylene copolymer component (EP) and the latter stage process (II) for producing an ethylene-propylene copolymer component (EP), comprising the following (i) to (v): A method for producing a propylene-based copolymer is provided.
(A): A transition metal compound represented by the following general formula [1].

(In the formula [1], A and A ′ represent a conjugated five-membered ring ligand, Q represents a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and M represents Represents a metal atom selected from groups 4 to 6 in the periodic table, and X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. A and A ′ may be the same or different from each other in the same compound.)
(B): A solid component containing one or more selected from the following (b-1) to (b-4).
(B-1) A particulate carrier on which an aluminum oxy compound is supported (b-2) An ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation is supported. Fine particle carrier (b-3) Solid acid fine particles (b-4) Ion exchange layered silicate (C): Organoaluminum compound.
(I) MFR (test conditions: 230 ° C., 2.16 kg load) is 0.1 to 300 g / 10 min.
(Ii) The proportion of the p-xylene soluble portion at 23 ° C. is 45 to 60% by weight of the entire copolymer.
(Iii) The ethylene content of the portion soluble in p-xylene at 23 ° C. is 40 to 65% by weight.
(Iv) The propylene content of the portion insoluble in p-xylene at 23 ° C. is 98% by weight or more.
(V) In the form observed with a transmission electron microscope, the (PP) portion and the (EP) portion are intertwined with each other to form a continuous phase.

Since the propylene-based copolymer of the present invention has a specific molecular structure and a specific phase structure (co-continuous structure), when used as a molding material, it exhibits a very good balance between rigidity and impact resistance. In addition, the heat resistance is good, and particularly, there is a remarkable effect that the balance between impact strength and heat resistance at low temperature is excellent, and the impact whitening property is excellent.
Moreover, according to the method for producing a propylene-based copolymer of the present invention, the above-mentioned propylene-based copolymer having excellent performance can be produced with high productivity and efficiency.

  The propylene-based copolymer of the present invention is obtained using an olefin polymerization catalyst containing a metallocene compound, and includes a crystalline propylene polymer (hereinafter also referred to as PP) and an ethylene-propylene copolymer (hereinafter also referred to as EP). It is characterized by satisfying the following (i) to (v).

(I) MFR (test conditions: 230 ° C., 2.16 kg load) is 0.1 to 300 g / 10 min.
When the MFR is less than 0.1 g / 10 min, the fluidity is lowered and the rigidity is also lowered. On the other hand, when the MFR exceeds 300 g / 10 minutes, the impact strength decreases. Moreover, within this range, it is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 70 g / 10 minutes, and particularly preferably 2 to 50 g / 10 minutes.

(Ii) The proportion of the p-xylene soluble portion at 23 ° C. is 45 to 60% by weight of the entire copolymer.
The proportion of the portion soluble in p-xylene at 23 ° C. (hereinafter also referred to as CXS portion) is extremely important for obtaining the target phase structure. If the ratio of the CXS part deviates from this range, it becomes difficult to obtain the target co-continuous phase structure or the stability of the phase structure is lowered, and it becomes difficult to achieve a high balance of physical properties. Deteriorating the appearance. That is, when the CXS portion ratio is less than 45%, even if the continuity of the phase composed of the EP component is maintained, the proportion of EP existing as dispersed particles increases at the same time, and the structural stability of the EP continuous phase portion. As a result, impact strength decreases and impact whitening resistance deteriorates. On the other hand, if the proportion of the CXS portion exceeds 60%, the continuity of the PP phase is impaired, and the rigidity and heat resistance are remarkably increased. In addition, due to the interruption of continuity, the PP phase shear yield does not occur sufficiently, and the degree of improvement in impact resistance reaches a peak or decreases. Further, within this range, it is preferably 45 to 58% by weight, more preferably 46 to 57% by weight, and particularly preferably 46 to 56% by weight.

In the present invention, the proportion of the portion soluble in p-xylene at 23 ° C. (CXS portion) and the proportion of the portion insoluble in p-xylene at 23 ° C. (hereinafter also referred to as CXIS portion) are determined by the following methods. The
After 1 g of a propylene-based copolymer sample was completely dissolved in 200 ml of p-xylene at a temperature of 120 ° C. or higher (a temperature sufficient to completely dissolve the sample), the sample solution was placed in a thermostatic chamber at 23 ° C. A part that precipitates when left for more than an hour (insoluble part = CXIS part) and a part that is dissolved without precipitation (soluble part = CXS part). Can be separated and recovered. These are weighed to determine the weight of the CXS part and the CXIS part.
CXS part ratio (% by weight) = CXS part weight ÷ (CXS part weight + CXIS part weight) × 100,
Ratio of CXIS portion (% by weight) = weight of CXIS portion ÷ (weight of CXS portion + weight of CXIS portion) × 100.

(Iii) The ethylene content of the part soluble in p-xylene at 23 ° C. (CXS part) is 40 to 65% by weight.
If the ethylene content of the CXS portion is less than 40% by weight, the glass transition temperature of EP may increase, resulting in a decrease in impact strength at low temperatures. On the other hand, if it exceeds 65% by weight, the affinity between EP and PP is impaired. As a result, peeling tends to occur at the interface between PP and EP, resulting in a decrease in impact strength, particularly a surface impact strength at low temperatures, and a decrease in impact whitening characteristics. Within this range, it is preferably 42 to 63% by weight, more preferably 43 to 60% by weight, still more preferably 44 to 60% by weight, and particularly preferably 45 to 58% by weight. Here, the ethylene content of the CXS portion can be determined by a known method using ¹³ C-NMR or IR for the CXS portion recovered by the above-described method.

(Iv) The propylene content of the part insoluble in p-xylene at 23 ° C. (CXIS part) is 98% by weight or more.
When the propylene content of the CXIS part is less than 98% by weight, the rigidity and heat resistance are lowered, or the impact resistance and impact whitening characteristics at low temperatures are deteriorated. That is, in the preceding crystalline propylene polymer production step (I), when copolymerizing ethylene or an α-olefin other than propylene as a comonomer, the propylene content of the CXIS portion is 98% by weight or more. The amount of comonomer to be copolymerized needs to be kept small, and if it deviates from this range, the crystallinity of the PP portion is excessively lowered, and the rigidity and heat resistance are impaired.
On the other hand, even if a propylene homopolymer is produced without introducing a comonomer in the former stage, when a known Ziegler catalyst is used, in the latter stage ethylene-propylene copolymerization step (II), ethylene or propylene is chained. As a result, it becomes impossible to adjust the propylene content of the CXIS part to 98% by weight or more as a result of being generated in a block form and becoming insoluble in p-xylene at 23 ° C. Impact resistance and impact resistance at low temperatures Since whitening characteristics are deteriorated, it is essential to use a highly uniform metallocene catalyst in order to obtain a copolymer that simultaneously satisfies the requirements (i) to (iv).
The propylene content of the CXIS portion can be determined by a known method using ¹³ C-NMR or IR for the CXIS portion recovered by the above-described method.

(V) In the form observed with a transmission electron microscope, the (PP) portion and the (EP) portion together form a continuous phase, and form a co-continuous structure that is intertwined with each other.
The propylene-based copolymer of the present invention has a so-called co-continuous structure in which both PP and EP portions form a continuous phase and are interlaced with each other, and the size of the constituent unit of this co-continuous structure is sufficiently large. As a result of being fine and stable, craze formation at the interface between PP and EP is suppressed, shear yielding of both PP and EP components is induced, and even if impact is applied, it is effective with little or no whitening. To absorb impact energy.
In particular, as compared with a normal sea-island structure propylene-based copolymer in which PP forms a continuous phase and EP forms a dispersed phase, the amount of craze formation is extremely small while the amount of shear yield increases, resulting in impact whitening resistance. And significantly improve impact resistance, especially "surface" impact properties at low temperatures. On the other hand, in a so-called reverse sea-island structure propylene-based copolymer in which EP forms a continuous phase and PP forms a dispersed phase, crease formation is suppressed to some extent, and although whitening resistance is improved, PP forms a continuous phase. As a result, the rigidity and heat resistance are remarkably lowered, and the shear yield of PP is hardly induced, and the degree of improvement in impact resistance is low.
In the copolymer of the present invention, PP and EP together form a continuous phase and are present in an intricate manner. As a result, these physical properties are extremely balanced. Furthermore, the copolymer of the present invention exhibits a particularly good balance of physical properties because the size of the basic structural unit of the co-continuous structure is sufficiently small and thermally stable.

  The bicontinuous structure can be confirmed by a transmission electron microscope. A propylene-based copolymer is press-molded to prepare a sheet having a thickness of 2 mm, and the central portion (a portion having a depth of 1 mm from the surface) of the cross section is dyed with ruthenium tetroxide, and then 0.1 μm with an ultramicrotome. Cut into slices of thickness and observe the phase structure with a transmission electron microscope. When observed in a visual field of 20 μm × 20 μm, a white PP phase that is not dyed with ruthenium tetroxide and an EP phase that is dyed and appears black form a continuous phase. When it is determined that it has a co-continuous structure and either the white PP phase or the black (EP) phase has lost continuity (when it has a so-called sea-island structure or layered structure) It is determined that the co-continuous structure is not taken (see FIGS. 1 to 3).

  Furthermore, another preferred embodiment of the present invention is a propylene-based copolymer that satisfies the requirement (vi) in addition to the requirements (i) to (v).

(Vi) Ratio of intrinsic viscosity [η] _{CXS of} a portion soluble in p-xylene at 23 ° C. obtained at 135 ° C. using decalin as a solvent to intrinsic viscosity [η] _CXIS of a portion insoluble in p-xylene at 23 ° C. ([Η] _CXS / [η] _CXIS ) is 0.75 to 2.00. That is, 0.75 ≦ [η] _CXS / [η] _CXIS ≦ 2.00.
[Η] _CXS / [η] _CXIS has a strong influence on the phase structure of propylene-based copolymer and its size and stability. When [η] _CXS / [η] _CXIS is adjusted to the above range, an extremely stable and fine co-continuous structure can be formed, and the effect of improving impact resistance is particularly strong. [Η] _CXS / [η] _CXIS is preferably 0.80 to 1.80, more preferably 0.80 to 1.50, and most preferably 0.80 to 1.20.
In the present invention, the intrinsic viscosity of the CXS part and the CXIS part was determined by using decalin as a solvent and an Ubbelohde viscosity tube at 135 ° C for the components insoluble and soluble in para-xylene at 23 ° C recovered according to the method described above. It is measured by a known method (see JIS K7367).

Furthermore, another aspect of the present invention is a molded article obtained by molding a propylene-based copolymer that satisfies the requirements (i) to (v) or (i) to (vi), wherein (vii) In the form observed with a transmission electron microscope, the PP part and the EP part form a continuous phase, and form a co-continuous structure in which they are interlaced with each other.
The phase structure of a molded product produced from a propylene-based copolymer is a known method in which a small specimen cut out from a molded sample is stained with ruthenium tetroxide, and then an ultrathin section is cut out with a microtome and observed with a transmission electron microscope. (For example, H. Sano et al., Polymer, 27, 1497, 1986).

  Another aspect of the present invention provides a propylene copolymer that produces a propylene copolymer that satisfies the above requirements (i) to (v) or (i) to (vi) in the presence of a specific catalyst. Propylene-based copolymer satisfying the above requirements (i) to (v) or (i) to (vi), which is used for forming a molded product satisfying the requirement (vii) This is a method for producing a propylene-based copolymer produced in the presence of a catalyst.

Furthermore, the melting point of the propylene-based copolymer of the present invention is preferably 153 to 165 ° C, more preferably 155 to 163 ° C, particularly preferably 156 to 162 ° C, most preferably, in view of high rigidity and heat resistance. 157-161 ° C.
Here, the melting point of the propylene-based copolymer is a peak melting temperature in the melting curve of the copolymer measured by DSC, and when a plurality of melting peaks occur, the melting temperature of the peak on the highest temperature side Defined. The melting point of the propylene-based copolymer is governed by the melting point of the crystalline propylene part (PP part). The PP part is a propylene homopolymer or a propylene content of 98% by weight or more. It is a copolymer with an α-olefin excluding ˜20 propylene. Examples of the α-olefin excluding propylene having 2 to 20 carbon atoms in the case of the copolymer described above include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc. And / or 1-butene is preferred, and ethylene is most preferably used among them.

[Production of propylene-based copolymer]
The method for producing the propylene-based copolymer according to the present invention is not particularly limited as long as it provides a propylene-based copolymer satisfying the above physical properties. Among them, the propylene-based copolymer of the present invention is produced. A suitable catalyst system for this is a metallocene catalyst. For example, an olefin polymerization catalyst obtained by contacting the following components A, B, and C as shown below can be used.

Component (A): Transition metal compound represented by the following general formula [1].

Here, in the formula [1], A and A ′ represent a conjugated five-membered ring ligand, Q represents a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, M represents a metal atom selected from groups 4 to 6 in the periodic table, and X and Y are a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. Indicates. A and A ′ may be the same or different from each other in the same compound.
Among the transition metal compounds represented by the general formula [1], the component (A) defined below is preferable.

[Preferred component (A)]
The transition metal compound component (A) is represented by the following general formula (Ia).

The transition metal compound according to the present invention includes a five-membered ring ligand having substituents R ¹ , R ² and R ³ and a five-membered ring ligand having substituents R ⁴ , R ⁵ and R ⁶ . In terms of relative position via Q, it includes compound (a) that is asymmetric with respect to the plane containing M, X, and Y and compound (b) that is symmetric. However, in order to produce an α-olefin polymer having a high molecular weight and a high melting point, the above compound (a), that is, two five-membered rings facing each other across a plane containing M, X and Y are sandwiched. It is preferred to use compounds whose ligands are not mirror images of entities with respect to the plane.

In General Formula (Ia), R ¹ , R ² , R ⁴ , and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 12 carbon atoms, or A halogenated hydrocarbon group having 1 to 12 carbon atoms is shown.

  Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n -In addition to alkyl groups such as hexyl, cyclopropyl, cyclopentyl, and cyclohexyl, and alkenyl groups such as vinyl, propenyl, and cyclohexenyl, phenyl groups, naphthyl groups, and the like can be given.

  Specific examples of the silicon-containing hydrocarbon group having 1 to 12 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl. It is done.

  In the halogenated hydrocarbon group having 1 to 12 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2, 1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, o-, m-, p-fluorophenyl, o-, m-, p-chlorophenyl, o -, M-, p-bromophenyl, 2,4-, 3,5-, 2,6-, 2,5-difluorophenyl, 2,4-, 3,5-, 2,6-, 2,5 -Dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pen Such as chlorophenyl and the like.

In these, as R < ¹ > and R < ⁴ >, C1-C6 hydrocarbon groups, such as methyl, ethyl, propyl, butyl, and phenyl, are preferable, and a hydrogen atom is preferable as R < ² > and R < ⁵ >.
In general formula (Ia), R ³ and R ⁶ each independently represents a saturated or unsaturated divalent hydrocarbon having 3 to 10 carbon atoms that forms a condensed ring with respect to the five-membered ring to which R ³ and R ⁶ are bonded. Indicates a group.
Therefore, the condensed ring is a 5- to 12-membered ring. Provided that at least one of the carbon atoms of ^{R 3} and ^{R 6} are 5-10, to form a condensed ring composed of 7- to 10-membered ring derived from ^{R 3} or ^{R 6.} At this time, both of the condensed rings are preferably 7 to 10-membered rings.

Specific examples of R ³ and R ⁶ include divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene, -Pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene , Divalent unsaturated hydrocarbon groups such as 2,5-hexadienylene and 1,3,5-hexatrienylene.
Of these, a pentamethylene group, a 1,3-pentadienylene group, a 1,4-pentadienylene group or a 1,3,5-hexatrienylene group is preferable, and a pentamethylene group, a 1,3-pentadienylene group or a 1,4-pentaethylene group is preferable. A pentadienylene group is more preferable, and a 1,3-pentadienylene group or a 1,4-pentadienylene group is particularly preferable.

As a more preferable example, in the general formula (Ia), R ⁷ and R ⁸ are each independently an aryl group having 6 to 20 carbon atoms, a halogen having 6 to 20 carbon atoms or a halogenated hydrocarbon-substituted aryl group. Show.
Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl group, methylphenyl group, dimethylphenyl group, mesityl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, i-propylphenyl group, dii -Propylphenyl group, tri-i-propylphenyl group, n-butylphenyl group, di-n-butylphenyl group, tri-n-butylphenyl group, t-butylphenyl group, di-t-butylphenyl group, tri-t-butylphenyl Group, biphenylyl group, p-terphenyl group, m-terphenyl group, naphthyl group, anthryl group, phenanthryl group and other aryl groups.
Among these, t-butylphenyl group, biphenylyl group, p-terphenyl group, naphthyl group, anthryl group, and phenanthryl group are particularly preferable.

In the halogen having 6 to 20 carbon atoms or the halogenated hydrocarbon-substituted aryl group, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen or halogenated hydrocarbon-substituted aryl group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specifically, fluorophenyl group, (trifluoromethyl) phenyl group, methylfluorophenyl group, fluorodimethylphenyl group, (fluoromethyl) methylphenyl group, ethylfluorophenyl group, diethylfluorophenyl group, triethylfluorophenyl group, Fluoro i-propylphenyl group, fluorodi i-propylphenyl group, (fluoro i-propyl) i-propylphenyl group, fluorotri i-propylphenyl group, n-butylfluorophenyl group, di-n-butylfluorophenyl group, Fluorobutyl) butylphenyl group, tri-n-butylfluorophenyl group, t-butylfluorophenyl group, di-t-butylfluorophenyl group, tri-t-butylfluorophenyl group, fluorobiphenylyl group, fluoro p-terphenyl Fluoro m- terphenyl group, fluoro naphthyl group, fluoro anthryl group, etc. fluoro phenanthryl group.
As the halogenated hydrocarbon group, the fluorinated product is preferably a fluorinated hydrocarbon-substituted aryl group, and the chlorinated product is preferably a chlorinated hydrocarbon-substituted aryl group, such as a t-butylfluorophenyl group, a fluorobiphenylyl group, a fluoro p-tell. Phenyl group, fluoronaphthyl group, fluoroanthryl group, fluorophenanthryl group, t-butylchlorophenyl group, chlorobiphenylyl group, chloro p-terphenyl group, chloronaphthyl group, chloroanthryl group, chlorophenanthryl group Is particularly preferred.

In general formula (Ia), m and n each independently represent an integer of 0 to 20, with 1 to 5 being particularly preferred. When m and / or n is an integer of 2 or more, the plurality of groups R ⁷ (R ⁸ ) may be the same as or different from each other. When m and / or n is 2 or more, R ⁷ or R ⁸ may be connected to each other to form a new ring structure. The bonding position of R ⁷ and R ⁸ to R ³ and R ⁶ is not particularly limited, but is preferably a carbon adjacent to each 5-membered ring (α-position carbon).

  In general formula (Ia), Q is a divalent hydrocarbon group having 1 to 20 carbon atoms and a silylene group optionally having a hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings. , Either an oligosilylene group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure.

Specific examples of Q include methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, and 1,4-cyclohexane. Alkylene groups such as xylene; arylalkylene groups such as (methyl) (phenyl) methylene and diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, Alkylsilylene groups such as di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene, methyl (tolyl) silylene; arylsilylene groups such as diphenylsilylene; alkyl oligosilylenes such as tetramethyldisilylene Group; germylene group; the above divalent carbon Alkylgermylene alkylene group silicon silylene groups and substituted germanium having from 1 to 20 hydrocarbon group; (alkyl) (aryl) germylene group; an aryl gel Mi alkylene group can be exemplified.
In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, an alkylsilylene group, an (alkyl) (aryl) silylene group or Arylsilylene groups are particularly preferred.

  In general formula (Ia), X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. A silicon-containing hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

  Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n -Alkyl groups such as hexyl, cyclopropyl, cyclopentyl, cyclohexyl, and methylcyclohexyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; and arylalkenyl groups such as trans-styryl; Examples include aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl.

  Specific examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy and butoxy, allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, phenylmethoxy And oxygen-containing heterocyclic groups such as arylalkoxy groups such as naphthylmethoxy and furyl groups.

  Specific examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include alkylamino groups such as methylamino, dimethylamino, ethylamino and diethylamino, arylamino groups such as phenylamino and diphenylamino, (methyl) ( (Alkyl) (aryl) amino groups such as phenyl) amino, and nitrogen-containing heterocyclic groups such as pyrazolyl and indolyl.

In the halogenated hydrocarbon group having 1 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated hydrocarbon group is a compound in which, when the halogen atom is, for example, a fluorine atom, the fluorine atom is substituted at an arbitrary position of the hydrocarbon group.
Specifically, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1 , 1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, o-, m-, p-fluorophenyl, o-, m-, p-chlorophenyl, o-, m-, p-bromophenyl, 2,4-, 3,5-, 2,6-, 2,5-difluorophenyl 2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophen 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1-naphthyl, heptachloro-1-naphthyl, o- , M-, p-trifluoromethylphenyl, o-, m-, p-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,5-bis (trifluoromethyl) phenyl, 2,4-, 3,5-, 2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloro Examples thereof include a methyl naphthyl group and a 2,4-bis (trifluoromethyl) naphthyl group.

Specific examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl, dialkyl such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, and dimethyltolylsilylmethyl. (Alkyl) (aryl) silylmethyl group and the like can be mentioned.
X and Y are preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or carbon. A nitrogen-containing hydrocarbon group having a number of 1 to 20 is more preferable, and a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a benzyl group, a dimethylamino group or a diethylamino group is particularly preferable.

Specifically, among the above compounds,
(1) dimethylsilylene bis (2-ethyl-4-tertbutylphenyl-indenyl) zirconium chloride,
(2) dimethylsilylene bis (2-methyl-4-tertbutylphenyl-indenyl) zirconium chloride,
(3) Dimethylsilylene (2-methyl-4-tertbutylphenyl-indenyl) (2-isopropyl-4-tertbutylphenyl-indenyl) zirconium chloride,
(4) Dimethylsilylene bis (2-isopropyl-4-naphthyl-indenyl) zirconium dichloride,
(5) dimethylsilylenebis (2-methyl-4-tert-butylcyclopentadienyl) hafnium dichloride,
(6) Dimethylsilylenebis (2-ethyl-4- (4-tertbutyl-3-chlorophenyl) -4H-azurenyl) zirconium dichloride,
(7) Dimethylsilylenebis (2-ethyl-4-phenyl-4H-azurenyl) hafnium dichloride,
(8) Dimethylsilylenebis (2-ethyl-4-naphthyl-4H-azurenyl) hafnium dichloride,
(9) Dimethylsilylenebis (2-ethyl-4-biphenyl-4H-azurenyl) hafnium dichloride,
(10) Dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl) hafnium dichloride,
(11) Dimethylsilylenebis (2-ethyl-4- (4-chloro-2-naphthyl-4H-azurenyl)) hafnium dichloride,
(12) Dimethylsilylenebis (2-ethyl-4- (4-chloro-2-tetrahydronaphthyl-4H-tetrahydroazurenyl)) hafnium dichloride,
(13) Dimethylsilylenebis (2-ethyl-4- (3-chloro-4-tertiarybutyl-phenyl-4H-azurenyl)) hafnium dichloride,
Etc.

  Among these, azulenyl-containing and hafnium-centered metal compounds are particularly preferable, and dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl) hafnium dichloride, dimethylsilylenebis (2-ethyl-) 4- (4-chloro-2-naphthyl-4H-azurenyl)) hafnium dichloride, dimethylsilylenebis (2-ethyl-4- (3-chloro-4-tertiarybutyl-phenyl-4H-azurenyl)) hafnium dichloride, Etc.

Moreover, what replaced the chlorine of the above-mentioned compound by bromine, iodine, hydride, methyl, phenyl, etc. can be used.
Further, in the present invention, a compound in which the central metal of the zirconium compound exemplified above is replaced with titanium, hafnium, niobium, molybdenum, tungsten, or the like can also be used as the component (A).

  Among these, preferred are a zirconium compound, a hafnium compound, and a titanium compound. More preferred are zirconium compounds and hafnium compounds. These components (A) may be used in combination of two or more. Further, component (A) may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

[Component (B)]
In the present invention, the component (B) is preferably a component selected from the following (b-1) to (b-4).
(B-1) a particulate carrier carrying an aluminum oxy compound,
(B-2) an ionic compound capable of reacting with component (A) to convert component (A) into a cation or a particulate carrier carrying a Lewis acid,
(B-3) solid acid fine particles,
(B-4) Ion exchange layered silicate.

(B-1) A particulate carrier carrying an aluminum oxy compound First, the aluminum oxy compound will be described (the particulate carrier will be described later).
Carriers in which an aluminum oxy compound is supported on a metal oxide such as silica are known. For example, JP-A 61-108610, JP-A 63-280703, JP-A 63-51405, JP-A 63-63. -61010, JP-A-63-248803, JP-A-3-709, JP-A-4-100808, JP-A-4-7306, JP-A-7-188253, JP-A-7-278220, etc. There is a description.
Specific examples of the aluminum oxy compound include compounds represented by the following general formula [2], [3] or [4].

In each of the above general formulas, R ¹ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Moreover, several R < ¹ > may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30.

  The compounds represented by the general formula [2] and the general formula [3] are compounds also called alumoxanes. Among these, methylalumoxane or methylisobutylalumoxane is preferable. The above-mentioned alumoxane can be used in combination within a group and between groups. And said alumoxane can be prepared on well-known various conditions.

The compound represented by the general formula [4] is 10: 1 to 1: 1 type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the following general formula [5]. It can be obtained by a reaction of 1 (molar ratio).
In general formula [5], R ⁵ represents a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
General formula [5]: R ⁵ B (OH) ₂

(B-2) An ionic compound capable of reacting with component (A) to convert component (A) into a cation or a particulate carrier carrying a Lewis acid. Reacting with component (A), component (A) Examples of ionic compounds capable of converting cation to cation include cations such as carbonium cation and ammonium cation, triphenyl boron, tris (3,5-difluorophenyl) boron, tris (pentafluorophenyl) boron, etc. And a complex of the organic boron compound with a cation.

Examples of Lewis acids that can convert the component (A) into cations include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified. In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with a component (A) and can convert a component (A) into a cation.
Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one. The fine particle carrier will be described later.
Examples of a method using a catalyst in which a cationic metallocene compound reacted with a non-coordinating boron compound is supported on an inorganic metal compound such as silica are disclosed in JP-A-3-234709, JP-A-5-247128, Kaihei 5-239138, JP-A-5-148316, JP-A-5-148316, JP-A-3-234709, JP-A-5-155926, JP-A-5-502906, JP-A-8-113604, etc. Is disclosed.

(B-3) Solid acid Examples of the solid acid include solid acids such as alumina and silica-alumina.

Here, the particulate carrier in (b-1) and (b-2) described above will be described.
The elemental composition and compound composition of the particulate carrier according to the present invention are not particularly limited. For example, a particulate carrier made of an inorganic or organic compound can be exemplified.
Examples of the inorganic carrier include silica, alumina, silica / alumina magnesium chloride, activated carbon, inorganic silicate, and the like. Alternatively, a mixture thereof may be used.
Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated hydrocarbons such as styrene and divinylbenzene. Examples thereof include a porous polymer fine particle carrier made of a polymer or the like. Alternatively, a mixture thereof may be used.
These fine particle carriers usually have an average particle diameter of 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm.

(B-4) Ion-exchangeable layered silicate In the present invention, the ion-exchangeable layered silicate used as a raw material (hereinafter simply abbreviated as “silicate”) has a surface composed of ionic bonds or the like with bonding force. It refers to a silicate compound having a crystal structure stacked in parallel and having exchangeable ions. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. But you can.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.
The silicate used as a raw material in the present invention is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

(Chemical treatment)
Although the silicate used by this invention can be used as it is, without performing a process especially, it is preferable to give a chemical process. Here, the chemical treatment may be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Specifically, known acid treatment, alkali treatment, salt treatment, organic matter treatment, etc. disclosed in JP-A-5-301917, JP-A-7-224106, JP-A-8-127613 and the like can be used.

Among the components (B) described above, (b-4) ion-exchange layered silicate is particularly preferable.
In the catalyst for olefin polymerization according to the present invention, (b-1) a particulate carrier carrying an aluminum oxy compound, (b-2) reacting with component (A) to convert component (A) into a cation. Possible ionic compound or fine particle carrier carrying Lewis acid, (b-3) solid acid fine particle, or (b-4) ion exchange layered silicate fine particle, each used alone as component (B) In addition, these four components can be used in appropriate combination.

[Component (C)]
Component (C) is an organoaluminum compound, and as the organoaluminum compound used as component (C) in the present invention, a compound represented by the general formula: AlR ⁹ _p R ¹⁰ _q X _{3- (p + q)} is suitable. .
In this formula, R ⁹ and R ¹⁰ represent a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. p and q are each an integer of 0 to 3, and p + q is an integer of 1 to 3.
R ⁹ and R ¹⁰ are preferably an alkyl group, and X is chlorine when it is halogen, and when it is an alkoxy group, the alkoxy group having 1 to 8 carbon atoms is an amino group. A C1-C8 amino group is preferable.

Therefore, specific examples of preferable compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethyl Examples include aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride, diethylmethylaluminum, diethylpropylaluminum, and ethylmethylaluminum chloride.
Of these, trialkylaluminum with p = 3 and dialkylaluminum hydride with p = 2 and q = 0 are preferable. More preferably, p = 3 and R ⁹ is a trialkylaluminum having 1 to 8 carbon atoms.

[Catalyst formation and prepolymerization]
The catalyst according to the present invention can be formed by bringing the above-mentioned components into contact in the (preliminary) polymerization tank, simultaneously or continuously, at once, or multiple times. As these contact methods, various known methods can be used.
Moreover, the usage-amount of component (A), (B) and (C) used by this invention is arbitrary, A various well-known method can be utilized.

The catalyst according to the present invention is preferably subjected to a prepolymerization treatment consisting of a small amount of polymerization by bringing an olefin into contact therewith. Although the olefin to be used is not particularly limited, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, and the like can be used. It can be illustrated. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. In addition, the prepolymerization amount is preferably 0.01 to 100, more preferably 0.1 to 50 in the weight ratio of the prepolymerized polymer to the component (B). Moreover, a component (C) can also be added or added at the time of prepolymerization.
A method of coexisting a polymer such as polyethylene or polypropylene and a solid of an inorganic oxide such as silica or titania at the time of contacting or after the contact of the above components is also possible.

[polymerization]
Previous Step (I): (Propylene Polymer (PP) Production Method)
The propylene polymer (PP) is produced by using propylene alone or a propylene / α-olefin mixture in the presence of an organoaluminum compound as described above for the catalyst component (A), component (B), and as necessary. It is a step of producing a crystalline homopolymer of propylene or a propylene / α-olefin copolymer containing less than 2% by weight of an α-olefin by contacting with a metallocene catalyst comprising (C). In the present invention, the α-olefin includes ethylene.
In this step, polypropylene or a copolymer of propylene and α-olefin is formed in one or more stages so as to correspond to 40 to 55% by weight, preferably 42 to 52% by weight of the total polymerization amount.

The polymerization temperature in the method for producing propylene polymer (PP) is about 30 to 120 ° C, preferably about 50 to 80 ° C. The polymerization pressure is about 1 to 40 kg / cm ² .

  In this propylene polymer (PP) production method, it is preferable to use a molecular weight regulator so that the final polymer has an appropriate fluidity, and hydrogen is preferred as the molecular weight regulator.

Post-stage process (II): (Ethylene-propylene copolymer (EP) production method)
The method for producing an ethylene-propylene copolymer (EP) has an ethylene content of 40 to 65% by weight, preferably 42 to 63% by weight, more preferably 43 to 60% by weight, still more preferably 44 to 60% by weight, Particularly preferred is a step of producing an ethylene-propylene copolymer of 45 to 58% by weight.
In this step, an amount corresponding to 45 to 60% by weight, preferably 45 to 58% by weight, more preferably 46 to 57% by weight, and particularly preferably 46 to 56% by weight of the total polymerization amount is formed.

  In the ethylene-propylene copolymer (EP) production method, it is preferable that an electron-donating compound such as an active hydrogen-containing compound, a nitrogen-containing compound, or an oxygen-containing compound is present.

The polymerization temperature in the latter polymerization step is about 30 to 120 ° C, preferably about 50 to 80 ° C. The polymerization pressure is about 1 to 40 kg / cm ² , preferably 1 to 30 kg / cm ² .

In the crystalline propylene polymer (PP) production method, a molecular weight modifier may or may not be used depending on the purpose. That is, when it is desired to increase the impact resistance of the final polymer, it is preferable to carry out this step in the substantial absence of a molecular weight modifier.
The post-stage polymerization step (II) may be multi-stage polymerization as in the pre-stage polymerization step (I).

The propylene-based copolymer of the present invention thus obtained is an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a colorant, an inorganic or organic substance as necessary. After blending various additives such as fillers and various synthetic resins, the mixture can be used as a molding material as pellets cut into granules after heating and melt-kneading using a melt-kneader.
These pellet-shaped molding materials are molded by various known polypropylene molding methods, such as injection molding, extrusion molding, foam molding, hollow molding, and various industrial injection molded parts, various containers, unstretched films. Various molded products such as a uniaxially stretched film, a biaxially stretched film, a sheet, a pipe, and a fiber can be produced.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples without departing from the gist thereof.
The following catalyst synthesis step and polymerization step were all performed under a purified nitrogen atmosphere. The solvent used was dehydrated with molecular sieve MS-4A.

Hereafter, the measuring method and apparatus of each physical property value in this invention are shown below.
(1) MFR (melt mass flow rate)
Apparatus: Melt indexer manufactured by Takara Co., Ltd. Measuring method: Test conditions of JIS K7210 “Plastics—Testing methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics”: 230 ° C., 2.16 kg load Measured according to

(2) Proportion of parts soluble and insoluble in p-xylene at 23 ° C. According to the method described above, the amount of the part soluble in p-xylene at 23 ° C. (CXIS part) and the insoluble part (CXIS part) Was determined as a ratio (% by weight) of the CXS portion in the entire propylene copolymer.

(3) Ethylene content of the portion soluble in p-xylene at 23 ° C. The CXS portion recovered according to the above-mentioned method is press-molded into a film having a thickness of 100 μm, its infrared absorption spectrum is measured, and a new edition polymer analysis handbook (The Kinokuniya bookstore, Japan Analytical Chemistry Society polymer analysis study round-table edition, 1995) It calculated | required according to 616 page type | formulas (2.3.9).

(4) Propylene content of the part insoluble in p-xylene at 23 ° C. The CXIS part recovered according to the above-mentioned method is press-molded into a film having a thickness of 500 μm, its infrared absorption spectrum is measured, Published by Kinokuniya, edited by Japan Society for Analytical Chemistry, Polymer Analysis Research Meeting, 1995) Obtain the ethylene content of the CXIS part according to 616 page formula (2.3.8) and subtract this value from 100%. Asked.

(5) Phase structure confirmation by transmission electron microscope The propylene-based copolymer was press-molded into a sheet having a thickness of 2 mm, and the form was observed from the surface at a depth of 1 mm (central thickness). When the phase structure of the molded body was observed, the shape of the central portion of the thickness was similarly observed for the molded body.
H. According to the description of Sano et al. (Polymer, 27, 1497, 1986), ruthenium tetroxide staining was performed, and an ultrathin section prepared with an ultramicrotome was observed with a transmission electron microscope, and a field area of 20 μm × 20 μm was observed. Among them, the case where the PP phase and the EP phase are both continuous and have a complicated structure is determined to be co-continuous, and the case where the EP phase does not form a continuous phase is a sea-island structure (PP is a continuous phase, EP Is a dispersed phase), and the case where the PP phase does not form a continuous phase was determined to be an inverted sea island structure (PP is a dispersed phase, EP is a continuous phase).
For samples with a co-continuous structure, heat treatment was performed by leaving the samples to stand in a nitrogen atmosphere at 200 ° C. for 24 hours to accelerate the phase structure change, and after cooling to room temperature, staining and sectioning were similarly performed and transmitted. Observe with a scanning electron microscope to see if a co-continuous structure is maintained,
○: It has almost the same co-continuous structure as before heat treatment,
Δ: A co-continuous structure is maintained, but an increase in the basic size is observed.
×: co-continuous structure is not retained,
A three-stage evaluation was conducted.

(6) Intrinsic Viscosity Measurement of CXS Part and CXIS Part For each of the CXS part and the CXIS part recovered by the above-described method, using an Ubbelohde viscosity tube at 135 ° C. using decalin as a solvent, “plastic-capillary viscosity” Measured in accordance with “How to determine viscosity of diluted polymer solution using meter”.

(7) Measurement of melting point A DSC7 differential scanning calorimeter manufactured by Perkin Elmer was used. A 5 mg sample punched out from a 0.2 mm thick press sheet was inserted into the sample pan and set in the apparatus. The temperature was raised from room temperature to 230 ° C. under the condition of 10 ° C./min. After holding at this temperature for 10 minutes, The temperature was lowered to 40 ° C. at a rate of −10 ° C./min, held at this temperature for 3 minutes, and then taken as the melting peak temperature when the temperature was raised at a rate of temperature increase of 10 ° C./min.

(8) Flexural modulus (FM) (unit: Mpa)
The measurement was performed at 23 ° C. in accordance with JIS K7203 “Bending test method of hard plastic”.
The dimension of the molded product was 90 × 10 × 3 mm.

(9) Deflection temperature under load (HDT, unit: ° C)
The measurement was performed under the condition of 4.6 kgf / cm ² load in accordance with JIS K7207 “Testing method for deflection temperature under load of hard plastic”.

(10) Charpy impact strength Using a fully automatic Charpy impact tester (with a thermostatic bath) manufactured by Toyo Seiki, measurement was performed under the following conditions.
Standard number: Compliant with “Plastic-Charpy impact strength test method” of JIS K7111 (ISO 179 / 1eA) Shape of test piece: Test piece with single notch, thickness 4 mm, width 10 mm, length 80 mm
Notch shape: Type A notch (notch radius 0.25mm)
Impact speed: 2.9 m / s
Nominal pendulum energy: 4J
Test piece preparation method: Notch cut into injection molded test piece (ISO 2818 compliant)
Condition adjustment: 24h or more in a constant temperature room adjusted to room temperature 23 ° C and humidity 50%

(11) DuPont impact strength 25 pieces of flat test pieces of 70 × 70 × 1 mm are preliminarily 24 hours or longer in 99% isopropyl alcohol-modified alcohol (manufactured by Imazu Pharmaceutical Co., Ltd.) at −20 ° C. cooled with a refrigerator. After cooling, take out the test piece, and on the striker cradle of the DuPont impact tester described in JIS K5600-5-3 (striker cradle inner diameter 3/2 inch, striker tip R1 / 4 inch) The weight was immediately dropped from a 50 cm high place.
At this time, if no crack is observed in the flat test piece, the drop location is raised by 5 cm, and if the test piece is broken or a crack is observed, it is lowered by 5 cm and replaced with a new test piece. An impact test was performed.
Thus, when a crack was not observed, the impact test was repeated 25 times in total by raising the height by 5 cm from the previous time, and when cracking or cracking was observed, by lowering the height by 5 cm from the previous time.
In addition, the weight of the weight to drop was suitably selected in the range of 500g-2kg. The DuPont impact strength is a value obtained by calculating the 50% fracture height of the test piece according to JIS K7211 “Test method for falling weight impact of hard plastic” from the measurement results of 25 times, and multiplying that value by the weight load (kg • cm).

(12) Evaluation of impact whitening resistance In the DuPont impact test of (11) above, by visually judging a test piece that did not break by dropping a weight from a 50% fracture height,
○: Whitening is not noticeable,
Δ: Remarkable whitening is observed,
×: Extremely whitening occurs
A three-stage evaluation was conducted.

[Manufacture of catalyst]
(Catalyst production example 1)
(1) Synthesis of dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl}] hafnium:
(A) synthesis of racemic / meso mixtures;
To a mixed solution of 4-trimethylsilyl-3,5-dichlorophenyl bromide (2.98 g, 10 mmol) in hexane (50 mL) and diisopropyl ether (10 mL) at -70 ° C., a pentane solution of t-butyllithium (13.4 mL, 19 .9 mmol, 1.48 M) was added dropwise, and the mixture was stirred at −10 ° C. for 1 hour.
To this was added 2-ethylazulene (1.48 g, 9.5 mmol, 0.95 eq.), And the mixture was warmed to room temperature and stirred for about 1 hour. Tetrahydrofuran (20 mL) and N-methylimidazole (20 μL) were added thereto, cooled to 0 ° C., and then a solution of silafluorenyl dichloride (1.18 g, 4.7 mmol, 0.47 eq.) In THF (5 mL). The mixture was heated to room temperature and stirred for 2 hours.
Then, after adding water and liquid-separating, the organic layer was dried with magnesium sulfate and the solvent was distilled off under reduced pressure to obtain a crude product (4.72 g).
The crude product was purified by silica gel column chromatography [Kanto Chemical Silica Gel 60N, hexane, hexane: dichloromethane = 10: 1], and pure silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5 -Dichlorophenyl) 1,4-dihydroazulene} (1.73 g, 1.87 mmol, 40% yield).

Next, the ligand obtained above was dissolved in diethyl ether (10 mL), and a hexane solution (2.37 mL, 3.74 mmol, 1.58 M) of n-butyllithium was added dropwise at 0 ° C., and gradually to room temperature. The temperature was raised and the mixture was further stirred for 2 hours. Toluene (80 mL) was further added, and the mixture was cooled to −60 ° C., hafnium tetrachloride (599 mg, 1.87 mmol) was added, the temperature was raised to room temperature over about 30 minutes, and the mixture was further stirred for 30 minutes.
After the solvent was distilled off, extraction with diethyl ether (20 mL) was performed twice to remove a component containing lithium chloride as an insoluble matter, and a crude product containing a racemate of the target complex as a soluble matter was obtained.

(B) purification of the racemate;
The solvent of the crude product obtained above was distilled off, washed with hexane (20 mL) three times, and further washed with diethyl ether (20 mL) three times to obtain almost pure dichloro [1,1′-sila. A racemic form (440 mg) of fluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl}] hafnium was obtained.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.46 (s, 18H, TMS), 1.01 (t, 6H, 2-CH ₂ CH ₃ ), 2.7-2.8 (m, 2H, 2 _{-CHHCH 3), 3.0-3.1 (m,} 2H, 2-CHHCH 3), 5.02 (d, 2H, 4-H), 5.8-6.2 (m, 6H), 6 .15 (s, 2H), 7.17 (s, 4H, arom), 7.30 (d, 2H), 7.46 (t, 2H), 7.59 (t, 2H), 8.02 ( d, 2H), 8.31 (d, 2H).

(2) Chemical treatment of ion-exchangeable layered silicate 500 g of ion-exchanged water was added to a 5 L separable flask equipped with a stirring blade and a reflux device, and 249 g (5.93 mol) of lithium hydroxide monohydrate was further added. And stir.
Separately, 581 g (5.93 mol) of sulfuric acid is diluted with 500 g of ion-exchanged water and added dropwise to the lithium hydroxide aqueous solution using a dropping funnel. At this time, a part of the sulfuric acid is consumed in the neutralization reaction to form a lithium sulfate salt in the system, and when the sulfuric acid becomes excessive, it becomes an acidic solution.
Further, 350 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 28.0 μm) was added and stirred.
Thereafter, the temperature is raised to 108 ° C. over 30 minutes and maintained for 150 minutes. Then, it cooled to 50 degreeC over 1 hour. This slurry was filtered under reduced pressure using an apparatus in which an aspirator was connected to Nutsche and a suction bottle.
The cake was collected, 5.0 L of pure water was added to reslurry, and filtration was performed. This operation was repeated four more times. All filtrations were completed in less than a few minutes. The pH of the final washing liquid (filtrate) was 5.
The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. As a result, 275 g of a chemically treated product was obtained.
As a result of compositional analysis by fluorescent X-ray, the molar ratio of the constituent elements to silicon as the main component was Al / Si = 0.21, Mg / Si = 0.046, and Fe / Si = 0.022. .

(3) Preparation of catalyst / preliminary polymerization Montmorillonite chemically treated in (2) above was dried under reduced pressure at 200 ° C for 4 hours. Further, 200 g of the dried chemically treated montmorillonite was introduced into an autoclave having an internal volume of 10 L, and 1160 ml of heptane and 840 ml (0.5 mol) of a heptane solution of triethylaluminum (0.6 mmol / ml) were added over 30 min. Stir at 1 ° C. for 1 hour.
Thereafter, the slurry was settled down and 1300 ml of the supernatant was extracted, washed twice with 2600 ml of heptane, and finally adjusted by adding heptane so that the total amount of heptane became 1200 ml.

Next, the metallocene complex synthesized in (1) above, dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl, was synthesized in a 2 L flask. }] After adding 6 mol of hafnium and 516 ml of heptane and stirring well, 84 ml (11.8 g) of a heptane solution of triisobutylaluminum (140 mg / ml) was added at room temperature and stirred for 60 minutes.
Subsequently, the above solution was introduced into the montmorillonite slurry previously prepared in the autoclave, stirred for 60 minutes, and further heptane was introduced until the total volume reached 5 L, and the temperature was maintained at 30 ° C.
Propylene was introduced there at a constant speed of 100 g / hr at 40 ° C. for 4 hours and then maintained at 50 ° C. for 2 hours.
The prepolymerized catalyst slurry was collected with a siphon, and after removing the supernatant, it was dried at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.

(Catalyst production example 2)
(1) Synthesis of dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl]} hafnium:
(A) synthesis of racemic / meso mixtures;
2-Fluoro-4-bromobiphenyl (6.35 g, 25.3 mmol) was dissolved in a mixed solvent of diethyl ether (50 mL) and hexane (50 mL), and a pentane solution of t-butyllithium (33 mL, 50.6 mmol, 1. 54N) was added dropwise at -78 ° C. The mixture was stirred at −10 ° C. for 2 hours, 2-ethylazulene (3.55 g, 22.8 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. Hexane (30 mL × 2) was added and the supernatant was decanted.
Hexane (30 mL) and tetrahydrofuran (40 mL) were added to the obtained yellow precipitate at 0 ° C. N-methylimidazole (50 μL) and dimethyldichlorosilane (1.4 mL, 11.4 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. After this, dilute hydrochloric acid was added and the layers were separated, and then the organic phase was dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -1, A crude product (8.3 g) of 4-dihydroazulene) was obtained.

Next, the crude product obtained above was dissolved in diethyl ether (30 mL), and a hexane solution of n-butyllithium (14.9 mL, 22.8 mmol, 1.53N) was added dropwise at -70 ° C. The mixture was warmed and stirred overnight at room temperature. Furthermore, toluene (200 mL) was added, and the mixture was cooled to −70 ° C., hafnium tetrachloride (3.6 g, 11.4 mmol) was added, the temperature was gradually raised, and the mixture was stirred at room temperature for 4 hours.
Most of the solvent was removed from the resulting slurry solution under reduced pressure, diethyl ether (50 mL) was added, and the resulting slurry was filtered. After washing with diethyl ether (5 mL × 2), ethanol (15 mL × 2), hexane (10 mL × 2), dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenyl) ) -4H-azulenyl]} hafnium racemic meso mixture (4.53 g, 42% yield) was obtained.

(B) purification of the racemate;
The racemic / meso mixture (4.5 g) obtained above was suspended in dichloromethane (35 mL), and irradiated with light using a high-pressure mercury lamp (100 W) for 1 hour. The solvent was distilled off from this solution under reduced pressure. Toluene (25 mL) and dichloromethane (11 mL) were added to the obtained solid and heated to 60 ° C. to obtain a homogeneous solution. When dichloromethane was distilled off under reduced pressure, crystals were precipitated and filtered. After washing with hexane (5 mL × 2) and drying under reduced pressure, a racemate (1.79 g, 37%) was obtained.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.02 (s, 6H, SiMe ₂ ), 1.08 (t, J = 8 Hz, 6H, CH ₃ CH ₂ ), 2.54 (sept, J = 8 Hz, _{2H, CH 3 CH 2),} 2.70 (sept, J = 8Hz, 2H, CH 3 CH 2), 5.07 (brs, 2H, 4-H), 5.85-6.10 (m, 8H ), 6.83 (d, J = 12 Hz, 2H), 7.30-7.6 (s, 16H, arom).

(2) Preparation of catalyst / preliminary polymerization To the metallocene complex, dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl] synthesized in (1) above. ]} Except for using 6 mol of hafnium, the same operation as in (3) Preparation of catalyst / preliminary polymerization in Catalyst Production Example 1 was performed. By this operation, a prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.

(Catalyst production example 3)
(1) Granulation of fine particles (first stage granulation step)
Distilled water (2850 ml) and commercially available montmorillonite (Mizusawa Chemical Benclay SL) (150 g) were gradually added to a 4.5 liter metal container, stirred for several hours, and then homogenized using polytron for 10 minutes. .
When the average particle size was measured, it was 0.63 μm for the montmorillonite water slurry. This slurry was subjected to spray granulation using a spray granulator (LT-8) manufactured by Okawara Chemical Corporation. The physical properties and operating conditions of the slurry are as follows.
Slurry physical properties: pH = 9.6, slurry viscosity = 3500 CP;
Operating conditions: atomizer rotation speed 30000 rpm, liquid supply amount = 0.7 L / h, inlet temperature = 200 ° C., outlet temperature = 140 ° C., cyclone differential pressure = 80 mmH ₂ O
As a result, 90 g of granulated fine particles were recovered. The average particle size was 10.1 μm. The shape was spherical.

(2) Acid treatment To a glass flask equipped with a 1.0 liter stirring blade, 510 ml of distilled water and then 150 g of concentrated sulfuric acid (96%) were slowly added, and 80 g of the fine particles granulated above were dispersed. And heat-treated at 90 ° C. for 2 hours. After cooling, the slurry was filtered under reduced pressure to recover the cake. Distilled water was added to the cake in an amount of 0.5 to 0.6 liter, and the slurry was reslurried and then filtered. This washing operation was repeated 4 times.
The collected cake was dried at 110 ° C. overnight. The weight after drying was 67.5 g.

(3) Re-granulation The acid-treated fine particles 50 g thus obtained were gradually added to 150 ml of distilled water and stirred. This slurry was subjected to spray granulation using a spray granulator (LT-8) manufactured by Okawara Chemical Corporation. The physical properties and operating conditions of the slurry are as follows.
Slurry physical properties: pH = 5.7, slurry viscosity = 150 CP;
Operating conditions: atomizer rotation speed 10000 rpm, supply amount = 0.7 L / h, inlet temperature = 130 ° C., outlet temperature = 110 ° C., cyclone differential pressure = 80 mmH ₂ O
As a result, 45 g of granulated particles were recovered. The average particle size was 69.3 μm. The shape was spherical, although the surface was rough. When the shape was measured, the number of particles having an M / L of 0.8 or more and 1.0 or less was 92%. The crushing strength was 3.6 MPa.

(4) Preparation of catalyst The granulated product of the ion-exchange layered silicate was dried at 200 ° C. under reduced pressure for 2 hours. 10 g of the granulated particles obtained by the above operations (1) to (3) were introduced into a glass reactor equipped with a stirring blade having an internal volume of 1 liter, and a heptane solution (25 mmol) of normal heptane and triisobutylaluminum was added. It was added and stirred at room temperature. After 1 hour, the slurry was thoroughly washed with heptane to prepare a slurry of 100 ml.
Next, (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-] synthesized in advance according to the method described in JP-A-11-240909 is used. Azulenyl}] hafnium To 0.30 mmol, 43 ml of mixed toluene was added and stirred for 1 hour or longer. Then, a mixture of 1.5 mmol of triisobutylaluminum (heptane solution, 2.13 ml) was allowed to react at room temperature for 1 hour. In addition to the granulated particle slurry, the mixture was stirred for 1 hour.

  Subsequently, 105 ml of mixed heptane was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with nitrogen, and maintained at 40 ° C. The previously prepared granulated particle / complex slurry was introduced there. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 2 hours, the propylene feed was stopped and maintained for another 2 hours. The prepolymerized catalyst slurry was recovered with a siphon, and about 100 ml of the supernatant was removed, followed by drying at 40 ° C. under reduced pressure. By this operation, a prepolymerized catalyst containing 2.1 g of polypropylene per 1 g of catalyst was obtained.

(Catalyst production example 4)
Purified kerosene 1050 ml, anhydrous MgCl ₂ 15 g, dry ethanol 36.3 g and trade name Emazole 320 (manufactured by Kao Atlas Co., Ltd.) 4.5 g were placed in a nitrogen-substituted SUS autoclave, and the mixture was stirred. The temperature was raised, and the mixture was stirred at 120 rpm at 800 rpm for 30 minutes. While stirring the molten mixture at a high speed, the solution was transferred to a 3 liter flask with stirring, which was filled with 1.5 liters of purified kerosene cooled to −10 ° C., using a Teflon (registered trademark) tube having an inner diameter of 5 mm. . The product was sufficiently washed with hexane after filtration to obtain a simple substance. After 15 g of the simple substance was suspended in 300 ml of titanium tetrachloride at room temperature, 2.6 ml of diisobutyl phthalate was added, and the temperature of the mixture was raised to 120 ° C. After stirring and mixing at a temperature of 120 ° C. for 2 hours, the solid was filtered and suspended again in 300 ml of titanium tetrachloride. The suspension solution was stirred and mixed at 130 ° C. for 2 hours. After filtering the solid material, it was sufficiently washed with purified hexane to obtain a titanium-containing solid catalyst component.
After replacing the stainless steel reactor with inclined blades with an inner volume of 15 L with nitrogen gas, “Kristol-52” manufactured by Esso Oil Co., Ltd. having a kinematic viscosity at 40 ° C. of 7.3 centistokes as a saturated hydrocarbon solvent. 8.3 liters, 525 mmol of triethylaluminum, 80 mmol of diisopropyldimethoxysilane, 700 g of the titanium-containing solid catalyst component obtained above were added at room temperature, then heated to 40 ° C., and reacted for 7 hours at a propylene partial pressure of 0.15 MPa. To obtain a prepolymerized catalyst (reaction of 3.0 g of propylene per 1 g of the titanium-containing solid catalyst component).

[Example 1]
(Polymerization process 1)
After introducing 400 mg of triisobutylaluminum, 180 Nml of hydrogen, and 750 g of propylene into a well-dried 3 L autoclave, the temperature in the polymerization tank was maintained at 65 ° C. while stirring, and the prepolymerized catalyst obtained in Catalyst Production Example 1 was used as a solid catalyst. 75 mg was injected as a component, and bulk polymerization was started. After 5 minutes, unreacted monomer was purged, and then the inside of the polymerization tank was replaced with nitrogen. Next, a part (15 g) of the polymerization product was extracted from the polymerization tank, and MFR was measured.

(Polymerization process 2)
Further, while maintaining the temperature in the polymerization tank at 80 ° C. and the pressure at 2.0 MPaG, a gas mixture having a hydrogen concentration of 0.01 mol%, an ethylene concentration of 74 mol%, and a propylene balance was continuously circulated in the polymerization tank. Phase polymerization was performed. After 240 minutes, 10 ml of ethanol was injected into the polymerization tank to stop the polymerization. The flow of the mixed gas was stopped, unreacted monomers in the polymerization tank were purged, and further replaced with nitrogen. The polymerization tank was opened and the propylene copolymer powder was recovered.

(Analysis and observation of polymer)
MFR, melting point, ratio of CXS part, ethylene content of CXS part, propylene content of CXIS part, intrinsic viscosity of each part of CXS, CXIS of the obtained propylene copolymer were measured.
Moreover, this copolymer was press-molded into a 10 mm × 5 mm × 2 mm sheet, and a 1 mm portion from the sheet surface was observed with a transmission electron microscope. Further, this sheet was left to stand at 200 ° C. for 24 hours in a nitrogen atmosphere, and then cooled, and similarly, a 1 mm portion from the surface was observed with a transmission electron microscope.

IRGANOX1010 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, IRGAFOS168 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, calcium stearate 0.05 as a blending component with respect to the propylene-based copolymer % By weight was kneaded and granulated with a single screw extruder to obtain a propylene-based copolymer in the form of pellets.
The obtained copolymer pellets were introduced into an injection molding machine heated at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C., and a test piece was molded by injection molding. For the injection-molded piece that is the obtained molded body, the bending elastic modulus, Charpy impact strength, deflection temperature under load, and DuPont impact strength are measured by the above-described method, the degree of whitening is determined, and the phase structure is observed with a transmission electron microscope. Went.
The powders obtained in the following examples were subjected to the same analysis, and the same pelletization treatment was performed for the same physical property measurement and observation.

[Examples 2 to 9]
Although the same operation as Example 1 was performed, the conditions of each process followed Table 1.

[Comparative Examples 1 to 11]
Although the same operation as Example 1 was performed, the conditions of each process followed Table 2.

[Comparative Example 12]
After replacing the stainless steel reactor with inclined blades having an internal volume of 50 L with nitrogen gas, 9 kg of liquefied propylene and 3.5 mol of hydrogen were added. Further, 56.3 mmol of triethylaluminum and 5.6 mmol of diisopropyldimethoxysilane were injected into the reactor with nitrogen gas and heated to 40 ° C. When the temperature in the reactor reached 40 ° C, 45 ml of the prepolymerized catalyst prepared in Catalyst Production Example 4 was added and heated to 65 ° C. After polymerization for 60 minutes at a polymerization temperature of 65 ° C. and a pressure of 2.85 MPaG, unreacted liquefied propylene was purged from the reactor and released to atmospheric pressure.
Subsequently, after 0.6 mmol of hydrogen was added, copolymerization of ethylene and propylene was carried out by gas phase polymerization. The reaction conditions were a temperature of 60 ° C., a pressure of 0.69 MPa, a polymerization time of 60 minutes, and the gas composition of the gas phase was an ethylene / propylene molar ratio = 0.40. After completion of the reaction, the unreacted mixed gas was purged and released to atmospheric pressure. The obtained polymer powder was substituted with nitrogen gas to sufficiently remove unreacted monomers.

The results of Examples 1 to 9 and Comparative Examples 1 to 12 are shown in Tables 3 and 4.

  As is clear from Tables 3 and 4, the propylene copolymer having a co-continuous structure obtained by the present invention has an excellent rigidity-impact resistance balance, high heat resistance, and extremely excellent low temperature. Has both surface impact strength and impact whitening resistance. On the other hand, propylene-based copolymers (Comparative Examples 1, 7, 11, and 12) whose phase structure is a sea-island structure are inferior in rigidity-impact resistance balance and do not have impact whitening resistance. Further, the propylene copolymer having a reverse sea-island structure (Comparative Example 2) is extremely inferior in rigidity and heat resistance. Propylene copolymers that do not satisfy the composition of the present invention even if they have a co-continuous structure (Comparative Examples 3 to 6, 8 to 10) have a rigidity-impact resistance balance, heat resistance, surface impact strength, and impact resistance. Either of the whitening properties is inferior.

  Since the propylene copolymer of the present invention has a co-continuous structure, it has an excellent rigidity-impact resistance balance, high heat resistance, extremely excellent surface impact strength at low temperature, and impact whitening resistance. Therefore, in various molding fields, such as various industrial injection molded parts, various containers, unstretched films, uniaxially stretched films, biaxially stretched films, sheets, pipes, fibers, etc. Can be used. In addition, the method for producing a propylene-based copolymer of the present invention has high productivity and high industrial applicability.

It is a figure explaining the co-continuous structure which concerns on the propylene-type copolymer of this invention. It is a figure explaining the layered structure concerning the conventional propylene-ethylene copolymer (reprinted from FIG. 1 of patent document 16). It is a figure explaining the sea-island structure based on the conventional propylene-ethylene copolymer (reprinted from FIG. 2 of patent document 16).

Explanation of symbols

1 Propylene-ethylene copolymer 2 Crystalline propylene polymerization part

Claims (4)

Using a catalyst for olefin polymerization containing a metallocene compound, it is obtained by a first step (I) for producing a crystalline propylene polymer component (PP) and a second step (II) for producing an ethylene-propylene copolymer component (EP). And
A propylene-based copolymer satisfying the following (i) to (v).
(I) MFR (test conditions: 230 ° C., 2.16 kg load) is 0.1 to 300 g / 10 min.
(Ii) The proportion of the p-xylene soluble portion at 23 ° C. is 45 to 60% by weight of the entire copolymer.
(Iii) The ethylene content of the portion soluble in p-xylene at 23 ° C. is 40 to 65% by weight.
(Iv) The propylene content of the portion insoluble in p-xylene at 23 ° C. is 98% by weight or more.
(V) In the form observed with a transmission electron microscope, the (PP) portion and the (EP) portion are intertwined with each other to form a continuous phase. Ratio of intrinsic viscosity [η] _{CXS of} a portion soluble in p-xylene at 23 ° C. obtained at 135 ° C. using decalin as a solvent and intrinsic viscosity [η] _CXIS of a portion insoluble in p-xylene at 23 ° C. ([η ] _CXS / [(eta)] _CXIS ) is 0.75-2.00, The propylene-type copolymer of Claim 1 characterized by the above-mentioned.   A molded product obtained by molding the propylene-based copolymer according to claim 1 or 2, wherein the (PP) portion and the (EP) portion are intricately interlinked in a form observed by a transmission electron microscope. And a co-continuous structure forming a continuous phase. In the presence of an olefin polymerization catalyst obtained by contacting the following components (A), (B), and (C), the preceding step (I) for producing the crystalline propylene polymer component (PP) and the ethylene-propylene copolymer A method for producing a propylene-based copolymer by a subsequent step (II) for producing a polymer component (EP),
The manufacturing method of the propylene-type copolymer characterized by satisfy | filling following (i)-(v).
(A): A transition metal compound represented by the following general formula [1].

(In the formula [1], A and A ′ represent a conjugated five-membered ring ligand, Q represents a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and M represents Represents a metal atom selected from groups 4 to 6 in the periodic table, and X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. A and A ′ may be the same or different from each other in the same compound.)
(B): A solid component containing one or more selected from the following (b-1) to (b-4).
(B-1) A particulate carrier on which an aluminum oxy compound is supported (b-2) An ionic compound or Lewis acid capable of reacting with component (A) to convert component (A) into a cation is supported. Fine particle carrier (b-3) Solid acid fine particles (b-4) Ion exchange layered silicate (C): Organoaluminum compound.
(I) MFR (test conditions: 230 ° C., 2.16 kg load) is 0.1 to 300 g / 10 min.
(Ii) The proportion of the p-xylene soluble portion at 23 ° C. is 45 to 60% by weight of the entire copolymer.
(Iii) The ethylene content of the portion soluble in p-xylene at 23 ° C. is 40 to 65% by weight.
(Iv) The propylene content of the portion insoluble in p-xylene at 23 ° C. is 98% by weight or more.
(V) In the form observed with a transmission electron microscope, the (PP) portion and the (EP) portion are intertwined with each other to form a continuous phase.

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