JP2007131749A - METHOD FOR PRODUCING PROPYLENE-alpha-OLEFIN BLOCK COPOLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polypropylene material improving the rigidity, heat resistance and impact resistance in good balance and further improving the impact resistance at low temperatures. <P>SOLUTION: The method for producing the propylene-α-olefin block copolymer is characterized as follows. The three-stage polymerization is carried out in the presence of a metallocene supported type catalyst supported on a fine particulate carrier. In the first stage, a component (1) which is a propylene homopolymer or a copolymer of propylene with an α-olefin and contains ≥95 wt.% of the propylene is produced. In the second stage, a component (2) of a copolymer containing the propylene and 10-30 wt.% of the α-olefin is produced. In the third stage, a component (3) of a copolymer of the propylene and the α-olefin is produced so that the content of the α-olefin is higher than that of the α-olefin in the component (2) by 15-40 wt.%. The content of the component (1) is 5-95 wt.% and the weight ratio of the component (2) and the component (3) is (10:90) to (90:10). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a method for producing a propylene-α-olefin block copolymer. Specifically, by performing three-step sequential polymerization using a metallocene-supported catalyst, rigidity, heat resistance and impact resistance are balanced. The present invention relates to a polymerization method for obtaining a propylene-α-olefin block copolymer, which is well-excellent, has improved impact resistance at low temperatures, and has good powder properties.

Polypropylene, which excels in moldability and various physical properties, is widely used as an industrial resin material, but in order to further improve performance such as flexibility and impact resistance, copolymers with other olefins and olefin resins As a composition, etc., improvement of performance is constantly being studied.
In particular, improvements in impact resistance are required for automotive interior and exterior materials and packaging materials, which are important uses of polypropylene, and packaging materials are also required to improve impact resistance at low temperatures (cold resistance). .

  A composition of propylene and an elastomer component such as a propylene-ethylene random copolymer is well known as a technique for improving the impact resistance of polypropylene. In particular, such a composition obtained by a series of polymerization steps, that is, a copolymer obtained as a composition obtained by producing crystalline polypropylene in the first step and a propylene-ethylene copolymer elastomer in the second step. The coalescence is commonly referred to as a propylene-ethylene block copolymer, and exhibits excellent performance in the balance between rigidity and impact resistance, and thus has been heavily used in many fields including automobile interior and exterior materials.

  Propylene-based copolymers such as propylene-ethylene block copolymers are almost industrially produced using Ziegler-type catalysts, but Ziegler-type catalysts generally have various active points. It is known that the molecular weight distribution and the comonomer composition distribution of the copolymer part are wide. In the case of a propylene-ethylene copolymer having such a wide composition distribution, it can be crystallized in the copolymer. Propylene chains or ethylene chains are present, and these are considered to adversely affect the impact resistance of the block copolymer. Furthermore, it has been pointed out that heat resistance deteriorates as a result of the low ethylene content component and low molecular weight component of the copolymer component being dissolved in the crystalline polypropylene component (see Patent Document 1).

Therefore, many attempts have been made to improve impact resistance by producing propylene-based copolymers such as propylene-ethylene block copolymers with metallocene-based catalysts that have recently been used industrially. In particular, crystalline propylene homopolymers or copolymers with a small amount of ethylene and propylene-ethylene copolymers are produced by two-stage polymerization (see Patent Documents 1 to 4).
The metallocene catalyst is greatly characterized in that the polymerization active sites are uniform, and the molecular weight distribution and comonomer composition distribution are narrower than those of the Ziegler catalyst. Accordingly, a more homogeneous and soft elastomer component (rubber component) is produced, and an improvement in impact resistance is expected, and the compatibility with the crystalline polypropylene component can be controlled, so the above-mentioned problems regarding heat resistance are also improved. it is conceivable that.
However, the narrow distribution of comonomer composition, on the other hand, reduces the affinity of the crystalline polypropylene component and the propylene-ethylene copolymer elastomer component, which adversely affects the particle size and interfacial strength of the elastomer component, A simple block copolymer that uses a metallocene catalyst to produce only two components, crystalline polypropylene and an elastomer component, does not necessarily give a good balance of rigidity, impact resistance, heat resistance, etc. Currently, coalescence cannot be obtained.

  By the way, in order to improve the rigidity, heat resistance and impact resistance of such a propylene-based block copolymer in a well-balanced manner, while maintaining sufficient impact resistance in the copolymer component, at the same time, it is possible to copolymerize with crystalline polypropylene. It is thought that it is necessary to control the compatibility of the coalescence component within an appropriate range. The compatibility problem between this polypropylene component and the copolymer component is the propylene-ethylene block produced with the conventional Ziegler-based catalyst. It has also been found in copolymers, etc., and by adding a compatibilizer component between the polypropylene component and the copolymer part, a method for improving the compatibility and improving the impact resistance is old. (See Patent Documents 5 and 6). In this technique, a polypropylene component, a propylene-ethylene copolymer component and a propylene-ethylene copolymer compatibilizer component are polymerized by three-stage polymerization using a Ziegler catalyst.

  In the three-stage polymerization method using a Ziegler-based catalyst, a number of improved methods for improving impact resistance in propylene-α-olefin copolymers such as propylene-ethylene block copolymers and other applied methods have been disclosed. For example, a three-stage polymerization method is proposed in which three-stage polymerization is performed in the absence of a solvent and the quantity ratio and comonomer ratio of components in each stage are specified to improve the powder properties of polymer particles (Patent Document 7). In order to improve the balance between rigidity and impact resistance, many techniques for polymerizing by specifying the component ratio and comonomer ratio in each stage of the three-stage polymerization have been proposed (Patent Document 8). -10).

  Furthermore, recently, in the same manner as the method using the Ziegler catalyst, a compatibilizer component of propylene-ethylene (or α-olefin) copolymer is formed using a metallocene catalyst, and rigidity and heat resistance are formed. In addition, an attempt has been made to produce a propylene resin composition having an excellent balance of impact resistance by at least three stages of polymerization (see Patent Document 11). In a legal method, a metallocene catalyst is used instead of a Ziegler catalyst to produce a composition, and only a wide range of component ratios and ethylene contents, as well as a wide range of intrinsic viscosities and MFR, are specified. It is difficult to say that a specific production method for a propylene-based resin composition having an excellent balance between property and impact resistance is disclosed.

  Recently, as one of the developments of higher performance or higher functionality in polypropylene materials, frozen food storage packaging materials and industrial materials at low temperatures have a low temperature ( Although there is an increasing demand for improvement in impact resistance (cold resistance) of about −30 ° C., even if the improvement in impact resistance at low temperature is suggested in the above-mentioned Patent Document 3, other physical properties Therefore, it is not always possible to maintain the balance, and improvement of such physical properties is also desired.

  As outlined above, polypropylene materials, which are very important as industrial resin materials, are manufactured using Ziegler-based and metallocene-based catalysts that are extremely versatile and exceptionally useful. In the propylene-based copolymer, the rigidity, heat resistance and impact resistance have not been sufficiently improved in a well-balanced manner, and it cannot be said that the low-temperature impact resistance is sufficiently satisfactory. It should be said that these improvements are still being requested.

JP-A-8-67883 (abstract, claims 1, 3, 4 and paragraphs 0002-0004) JP-A-4-337308 (Abstract) Japanese Patent Laid-Open No. 5-202152 (Abstract) JP-A-6-172414 (Summary) JP-A-57-67611 (Claim 1 of the claims) JP-A-61-152442 (claim (1), page 2, lower right column, lines 1 to 2, page 3, upper right column, lower line, lines 5 to lower left column, line 2 and Example 1) JP-A-7-145218 (Abstract) Japanese Patent Laid-Open No. 6-1000063 (Summary) JP-A-6-306129 (summary) JP-A-8-59953 (Abstract and Claim 2) WO95 / 27741 (Summary, Claim 1 and Lines 1-3 on page 49)

  Against the background of the technical status of polypropylene materials outlined in paragraphs 0002 to 0010, the present invention improves the rigidity, heat resistance and impact resistance in a well-balanced manner, which is industrially demanded for polypropylene materials. In addition, it is an object of the present invention to develop a method for producing a propylene-based resin material that also improves impact resistance at low temperatures.

  In order to solve the above-mentioned problems, the present inventors have improved the rigidity, heat resistance, and impact resistance in a well-balanced manner in order to solve the above-described problems in view of the above-described background art and the flow of improvement in the prior art. In order to improve impact resistance at low temperatures, the most effective method is to produce a propylene-α-olefin block copolymer by a three-stage polymerization method using the characteristics of a metallocene catalyst. Recognizing that the expected results can be obtained, the polymerization process and polymerization conditions of each polymerization stage in the three-stage polymerization method, the type and usage of the metallocene catalyst, and the ratio of each component in each polymerization stage And comonomer ratio, comonomer types and combinations, and the functions of compatibilizer components and the index (characteristic value) of each component Considering and taking into account in detail, repeated verification and comparison by experiment, about the types and usage of metallocene catalysts, and the amount ratio and comonomer ratio of each component and the types and combinations of comonomer at each polymerization stage Thus, specific conditions for solving the problems of the invention can be found, and the present invention has been created.

The realization of the invention employs, as a basic requirement, a metallocene-supported catalyst supported on a particulate carrier as a metallocene catalyst, and in the first stage of the three-stage polymerization, a propylene homopolymer or propylene is used. A component (1) which is a copolymer of 2 to 20 carbon atoms excluding propylene and containing 95 wt% or more of propylene is produced, and in the second stage, 2 to 2 carbon atoms excluding propylene and propylene are produced. The component (2) of the copolymer containing 10-30 wt% of 20 α-olefins is produced. In the third stage, the α-olefin having 2 to 20 carbon atoms excluding propylene and propylene is converted into 25-70 wt%. The component (3) of the copolymer containing is produced.
The content of component (1) is 5 to 95 wt%, the total content of component (2) and component (3) is 95 to 5 wt%, and the weight ratio of component (2) and component (3) is The content of the α-olefin having 2 to 20 carbon atoms excluding propylene in the component (3) is 10:90 to 90:10, and the content of the α-olefin having 2 to 20 carbon atoms excluding propylene in the component (2). It is required that the content is 15 to 40 wt% higher than the content.
The basic requirements of such an invention configuration are those whose rationality and significance are demonstrated by contrast with each of Examples and Comparative Examples described later.

  In the present invention, as described above, as a basic requirement, (i) a metallocene-supported catalyst supported on a fine particle carrier is employed as a metallocene catalyst, and a propylene-α-olefin block copolymer is obtained by a three-stage polymerization method. (Ii) the amount ratio of each component, comonomer ratio and comonomer type in each polymerization stage are specified, and (iii) the rigidity, heat resistance and impact resistance of the polypropylene material are determined according to their requirements. (Iv) can improve the impact resistance at low temperature (about -30 ° C), and (v) can additionally suppress the adhesion of the polymer particles to improve the particle properties. (Vi) Further, the impact resistance of the produced polymer is synergistically increased by the blending ratio of the component (2) and the component (3). Requirements and their Effects by its bright with such a configuration, not Miidase in the prior art, but new and remarkable.

  As an additional aspect, ethylene is optimal as the α-olefin of each component, and the polymerization is performed in four or more stages as a multistage polymerization instead of the three-stage polymerization, and the component of the α-olefin having 2 to 20 carbon atoms is obtained. In the metallocene-supported catalyst, at least one of the conjugated five-membered ring ligand is bonded to an adjacent substituent on the conjugated five-membered ring ligand and includes two atoms of the conjugated five-membered ring. The transition metal compound which forms the 7-10 membered condensed ring is preferable, and the molecular weight of each component is prescribed | regulated.

  By the way, with respect to the three-stage polymerization method using a metallocene catalyst, which is a basic requirement in the present invention, each patent document described in paragraph 0010 in the above background art and other patent documents of other prior art are scrutinized, Reference 1 (Japanese Patent Laid-Open No. 8-67783) relates to the invention of a propylene-based resin composition by two-stage polymerization using a metallocene-based catalyst. Although it is described that an ethylene copolymer of a three-component compatibilizer) can be added by multistage polymerization, this description is merely given, and three-stage polymerization using a metallocene catalyst is specific. No description or example can be found. This level of description can also be found on page 11, lines 16 to 27 of JP-T-2002-501555.

Patent Document 11 (WO95-27741) specifically describes a propylene-based resin composition containing a compatibilizing agent by a three-stage polymerization using a metallocene-based catalyst and a production method thereof. At least three stages of polymerization in the presence of a system catalyst, having a melting point of 100 ° C. or higher and an MFR (230 ° C., load 2.16 kg) of 0.01 to 1000 g / 10 min. 20 to 90% by weight of the propylene (co) polymer component containing 5 to 75% by weight of propylene / olefin copolymer component containing propylene in excess of 50 mol% and having an intrinsic viscosity in the range of 0.1 to 20 dl / g. And an ethylene / olefin copolymer component containing more than 50 mol% of ethylene and having an intrinsic viscosity in the range of 0.1 to 20 dl / g. , A method for producing a propylene-based resin composition having an MFR of 0.01 to 500 g / 10 min. ”(Summary of claim 1 on pages 97 to 98), and improvement of impact resistance by a compatibilizing agent (Page 49, lines 1 to 3), but the contents of the literature are almost only descriptions of catalyst components and well-known matters, and almost no essential description of the invention can be found.
And as described in the paragraph 0015 and the examples described later, the present invention improves the rigidity, heat resistance and impact resistance of the polypropylene material in a well-balanced manner, and at the same time, impact resistance at low temperatures (about -30 ° C). In addition, the adhesion of the polymer particles can be suppressed and the particle properties can be improved, and the comonomer content and the compounding ratio of the component (2) and the component (3) are specified in detail. Thus, the impact resistance of the produced polymer is synergistically increased, and such effects and features are not described or suggested in Patent Document 11. In addition, the invention of Patent Document 11 is different from the present invention in the copolymer monomer even when viewed from each Example, and each Example other than Example 1 is mainly composed of ethylene and does not use propylene. It is an invention of a method for producing a polymer composition substantially different from the invention.
Therefore, it can be said that the present invention is substantially different from the invention of Patent Document 11 and cannot be obtained from the invention.

  In the above, the background of the creation of the present invention, the specific configuration of the invention, the main features, and the comparison with related prior art, etc. have been described generally, so here is a summary of the overall configuration of the present invention. The present invention is composed of the following unit groups of the invention, and the invention described in [1] is a basic invention, and [2] the following invention adds an additional requirement to the basic invention or forms an embodiment. It is something to do.

[1] Three-stage polymerization is carried out in the presence of a catalyst comprising a metallocene-supported catalyst component supported on a particulate carrier and an organoaluminum compound as an optional component. In the first stage, a propylene homopolymer or A component (1) that is a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms excluding propylene and containing 95 wt% or more of propylene is produced, and in the second stage, the number of carbon atoms excluding propylene and propylene A component (2) of a copolymer containing 10 to 30 wt% of an α-olefin having 2 to 20 is produced, and in the third stage, a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms excluding propylene is produced. The coalescence component (3) is produced so that the α-olefin content is 15 to 40 wt% higher than the α-olefin content of the component (2), and the content of the component (1) The amount is 5 to 95 wt%, the total content of component (2) and component (3) is 95 to 5 wt%, and the weight ratio of component (2) and component (3) is 10:90 to 90: 10. A method for producing a propylene-α-olefin block copolymer,
[2] The method for producing a propylene-α-olefin block copolymer according to [1], wherein the α-olefin of each component is ethylene.
[3] Polymerization in four or more stages is carried out in the presence of a catalyst component comprising a metallocene-supported catalyst supported on a particulate carrier and an organoaluminum compound as an optional component, and an α-olefin having 2 to 20 carbon atoms is polymerized. The method for producing a propylene-α-olefin block copolymer according to [1] or [2], further comprising a component.
[4] In the metallocene-supported catalyst, at least one of the conjugated five-membered ring ligand is bonded to an adjacent substituent on the conjugated five-membered ring ligand, and includes 7 to 10 including two atoms of the conjugated five-membered ring. A method for producing a propylene-α-olefin block copolymer according to any one of [1] to [3], wherein a member condensed ring is formed.
[5] The weight average molecular weight of component (1) is 80,000 to 250,000, the weight average molecular weight of component (2) is 250,000 to 1,200,000, and the weight average of component (3) Any of [1] to [4], wherein the molecular weight is 200,000 to 1,000,000, and the weight average molecular weight of component (2) is not less than the weight average molecular weight of component (3) A process for producing a propylene-α-olefin block copolymer.
[6] The propylene-α-olefin block according to any one of [1] to [5], wherein impact resistance is increased in a synergistic manner depending on the blending ratio of component (2) and component (3) A method for producing a copolymer.

  In the present invention, a metallocene supported catalyst supported on a fine particle carrier is employed as a metallocene catalyst, and a propylene-α-olefin block copolymer is produced by a three-stage polymerization method. The requirements for the new composition that specifies the quantity ratio, comonomer ratio, and type of comonomer improve the balance of rigidity, heat resistance, and impact resistance of the polypropylene material in a well-balanced manner, and at the same time, the resistance at low temperatures (about -30 ° C). The impact property can be improved, and additionally, the adhesion of the polymer particles can be suppressed to improve the particle properties. Further, the polymer produced by the blending ratio of the component (2) and the component (3) The impact resistance is increased synergistically.

  The outline of the present invention and the skeleton of the structure of the invention have been described above. In the following, embodiments of the invention will be described in detail in order to explain each invention group in the present invention in detail.

1. Metallocene catalyst As described above, the propylene-α-olefin block copolymer of the present invention is preferably produced by a metallocene catalyst, but has a higher melting point and excellent heat resistance and rigidity. In order to produce a metallocene copolymer that is industrially easy to handle and inexpensive, [A] a transition metal compound represented by the following general formula [I] and [B] (B -1) From any one or more of organoaluminum oxy compounds, (B-2) compounds capable of reacting with transition metal compounds to form cations, and (B-3) ion-exchangeable layered compounds (including silicates) It is preferable to use a catalyst comprising an activating agent as an essential component and [C] an organoaluminum compound as an optional component, and among them, [A] and (B-3) and optional components as Most preferably use a catalyst comprising a machine aluminum compound.

I. [A] Transition metal compound The transition metal compound mainly used in the present invention is a metallocene complex represented by the following formula.

In the general formula [I], A ¹ and A ² represent conjugated five-membered ring ligands (A ¹ and A ² may be the same or different in the same compound), and A ¹ and A ² The conjugated five-membered ring ligand may have a substituent on carbon not bonded to the binding group Q.

Typical examples of the conjugated five-membered ring ligand include a cyclopentadienyl group. This cyclopentadienyl group may have 4 hydrogen atoms, and as described above, some of the hydrogen atoms may be substituted with substituents. One specific example of the above substituent is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, phenyl group, naphthyl group, butenyl group, butadienyl group, and triphenylcarbyl group.
The hydrocarbon group may be bonded to the cyclopentadienyl group as a monovalent group, and two types may be bonded at the end of the substituent to form a condensed ring. Typical examples of the cyclopentadienyl group having a condensed ring include compounds such as indene, fluorene, and azulene, and derivatives thereof. Among these, indene, azulene and derivatives thereof are more preferable, and among them, azulene is most preferable.
Examples of the substituent other than the hydrocarbon group include hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur. Typical examples thereof include methoxy group, ethoxy group, phenoxy group, furyl group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, carbazolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group. , Dimethoxyboron group, thienyl group and the like.
Examples of other substituents include a halogen atom or a halogen-containing hydrocarbon group. Typical examples thereof include chlorine, bromine, iodine, fluorine, trichloromethyl group, trifluoromethyl group, fluorophenyl group, pentafluorophenyl group and the like.

By the way, the feature of the transition metal compound used in the present invention is that at least one of A ¹ and A ² is bonded to an adjacent substituent on the conjugated five-membered ring ligand and includes two atoms of the five-membered ring. It is in the point which has a 7-10 membered condensed ring. That is, either ^one of A ¹ and A ² can form a 7 to 10 condensed ring including at least two adjacent carbon atoms of a conjugated five-membered ring. The carbon of the condensed ring may be saturated or unsaturated except for two atoms of the conjugated five-membered ring.
For example, the above ligands constituting A ¹ and A ² include hydroazurenyl group, methylhydroazurenyl group, ethylhydroazurenyl group, dimethylhydroazurenyl group, methylethylhydroazurenyl group, methylisopropyl Hydroazurenyl group, methylphenylisopropylhydroazurenyl group, hydrogenated product of various azulenyl groups, bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo- [6.3.0] -undecanyl group, ethyl -Bicyclo- [6.3.0] -undecanyl group, phenyl-bicyclo- [6.3.0] -undecanyl group, methylphenyl-bicyclo- [6.3.0] -undecanyl group, ethylphenyl-bicyclo- [6.3.0] -Undecanyl group, methyldiphenyl-bicyclo- [6.3.0] -undecanyl Methyl-bicyclo- [6.3.0] -undecadienyl group, methylphenyl-bicyclo- [6.3.0] -undecadienyl group, ethylphenyl-bicyclo- [6.3.0] -undecadienyl group, methylisopropyl -Bicyclo- [6.3.0] -undecadienyl group, bicyclo- [7.3.0] -dodecanyl group and derivatives thereof, bicyclo- [7.3.0] -dodecadienyl group and derivatives thereof, bicyclo- [8 .3.0] -tridecanyl group and derivatives thereof, and bicyclo [8.3.0] -tridecadienyl group and derivatives thereof.
Examples of the substituent for each group include the hydrocarbon groups described above, hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur, halogen atoms, or halogen-containing hydrocarbon groups.

Q represents a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position. That is, Q is a divalent linking group and crosslinks A ¹ and A ² .
The type of Q is not particularly limited, and specific examples thereof include (a) a divalent hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, specifically, An unsaturated hydrocarbon group such as an alkylene group, a cycloalkylene group, and an arylene, a haloalkylene group, a halocycloalkylene group, (b) a silylene group or an oligosilylene group, and (c) a carbon number of usually 1 to 20, preferably 1 to A silylene group or an oligosilylene group having 12 hydrocarbon groups or halogenated hydrocarbon groups as a substituent, (d) germylene group, (e) a hydrocarbon group or halogenated hydrocarbon group usually having 1 to 20 carbon atoms. Examples thereof include a germylene group as a substituent.
In these, the silylene group or germylene group which has an alkylene group, a cycloalkylene group, an arylene group, and a hydrocarbon group as a substituent is preferable.
M represents a transition metal atom selected from groups 4 to 6 of the periodic table (short-period type), preferably a group 4 transition metal of titanium, zirconium or hafnium, more preferably zirconium or hafnium. Particularly preferred is hafnium.
X and Y are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a phosphorus-containing hydrocarbon group bonded to M. Or a silicon-containing hydrocarbon group is shown.
Carbon number in each said hydrocarbon group is 1-20 normally, Preferably it is 1-12. Among these, a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamino group, and a diethylamino group are preferable.

As specific examples of the transition metal compound in the present invention, since the block copolymer of the present invention is excellent in rigidity and heat resistance, the following compounds are particularly preferable. In addition, although description of a compound is only designated only with the chemical name, the three-dimensional structure means both the compound with asymmetry and the compound with symmetry as used in the present invention.
(1) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4H-azulenyl}] zirconium, (2) Dichloro [1,1′-dimethylsilylenebis {2-methyl -4- (4-t-butylphenyl) -4H-azurenyl}] hafnium, (3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4H -Azulenyl}] hafnium, (4) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4H-5,6,7,8-tetrahydroazurenyl}] Hafnium, (5) Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] hafnium, (6) Dichloro [1 1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -4H-5,6,7,8-tetrahydroazurenyl}] hafnium, (7) dichloro [1,1′- Dimethylsilylenebis {2-ethyl-4- (3-chloro-4-t-butylphenyl) -4H-azulenyl}] hafnium, (8) Dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-trimethylsilylphenyl) -4H-azurenyl}] hafnium, (9) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-3-methyl-phenyl)- 4H-azulenyl}] hafnium, (10) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-3,5-dichloro-fe) Nil) -4H-azurenyl}] hafnium, (11) dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl}] hafnium, (12) Dichloro [1,1′-silafluorenylbis {2-ethyl-4- (4-trimethylsilyl-3,5-dimethylphenyl) -4H-azurenyl}] hafnium can be exemplified.

One or both of the dichlorides forming the X and Y moieties in the compound as described above are a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an isobutyl group, a phenyl group, a fluorophenyl group, a benzyl group, Examples also include compounds substituted for a methoxy group, a dimethylamino group, a diethylamino group, and the like. In addition, compounds in which the central metal of the compound exemplified above is replaced with zirconium, hafnium, titanium, zirconium, tantalum, niobium, vanadium, tungsten, molybdenum, or the like can also be exemplified.
Among these, a group 4 transition metal compound of zirconium, titanium, and hafnium is preferable, and hafnium is particularly preferable among them.
These [A] components may be used in combination of two or more. In addition, the [A] component may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

B. [B] Cocatalyst (activator component)
In the present invention, the component [B] includes (B-1) an organoaluminum oxy compound, (B-2) a compound capable of reacting with a transition metal compound to form a cation, and (B-3) an ion-exchange layered compound ( Activating agents comprising any one or more of silicates) are used.

In the present invention, the (B-1) organoaluminum oxy compound specifically includes compounds represented by the following general formulas.


In the above general formula, R ¹ represents a hydrogen atom or a hydrocarbon group, preferably having from 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 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.
Among the general formulas, the compounds represented by the first and second formulas are compounds also referred to as aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.
The compound represented by the third general formula is 10: 1 to 1 type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ² B (OH) ₂ . It can be obtained by a 1: 1 (molar ratio) reaction.
In the general formula, R ¹ and R ² represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

In the present invention, as a compound capable of reacting with the transition metal compound (B-2) to form a cation, an ionic property capable of reacting with the component [A] to convert the component [A] into a cation. A compound or Lewis acid is used. As such an ionic compound, a cation such as a carbonium cation or an ammonium cation and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, or tris (pentafluorophenyl) boron are used. Examples include complexed products.
Examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halide 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 component [A] and convert component [A] into a cation.
The reaction product of the above components [A] and (B-1) or the reaction product of components [A] and (B-2) should be used as a catalyst supported on a particulate carrier such as silica. Is most preferred.

In the present invention, (B-3) an ion-exchange layered compound (including silicate) is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force. Ions can be exchanged. Examples of the ion-exchangeable layered compound include ion crystalline compounds having a layered crystal structure such as a hexagonal close-packed packing type, an antimony type, a CdCl ₂ type, and a CdI ₂ type.
Specific examples of the ion-exchange layered compound having such a crystal structure include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H. _{2 O, α-Ti (HPO} 4) 2, α-Ti (HAsO 4) 2 · H 2 O, α-Sn (HPO 4) 2 · H 2 O, y-Zr (HPO 4) 2, y-Ti Examples thereof include crystalline acidic salts of polyvalent metals such as (HPO ₄ ) ₂ and y-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. A synthetic product may be used for these, and the mineral produced naturally may be used. Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Smectites such as stone, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, sea chlorite, etc., attapulgite, sepiolite, pygorskite, bentonite , Kibushi clay, gyrome clay, hysingelite, pyrophyllite, chlorite and the like. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Of these specific examples, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, serpentine groups such as chrysotile, lizardite and antigolite, montmorillonite, sauconite and beidellite. , Smectites of nontronite, saponite, hectorite, etc., vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, chlorophyll, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, Preferably, smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hector Ito, synthetic saponite, synthetic taeniolite.
These ion-exchangeable layered compounds may be used as they are, but are acid-treated with hydrochloric acid, nitric acid, sulfuric acid and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , MgSO ₄ , ZnSO ₄ , Ti (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) _{3 and the} like are preferably subjected to salt treatment. In addition, shape control such as pulverization and granulation may be performed, and granulation is preferable in order to obtain a block copolymer having excellent particle properties. The above components are usually used after being dehydrated and dried.

C. [C] Organoaluminum Compound An example of an organoaluminum compound used as the [C] component of the present invention is represented by the following formula AlR _m X _3-m (wherein R is a hydrocarbon group having 1 to 20 carbon atoms. , X is hydrogen, halogen, alkoxy group, aryloxy group, m is a number of 0 <m ≦ 3), specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum Alternatively, halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride and diethylaluminum ethoxide. In addition, aluminoxane such as methylaluminoxane can also be used.
Of these, trialkylaluminum is particularly preferred. These [C] components may be used in combination of two or more. In addition, a [C] component may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

D. Contact and Support The above [A] component, [B] component, and [C] component are brought into contact with each other to form a catalyst, but the contact method is not particularly limited. This contact may be performed not only during catalyst preparation but also during prepolymerization with olefins or during polymerization of olefins. A polymer such as polyethylene or polypropylene and a solid of an inorganic oxide such as silica or alumina may be allowed to coexist or contact with each other when the catalyst components are contacted or after contact.
The contact may be performed in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene. The contact temperature is between −20 ° C. and the solvent boiling point, and particularly preferably between room temperature and the solvent boiling point.

E. Use amount of catalyst component The use amount of each component of the catalyst is, for example, 0.0001 to 10 mmol, preferably 0.001 to 5 mmol of [A] component per 1 g of component (B-3), and 0 of [C] component. 0.001 to 10,000 mmol, preferably 0.01 to 100 mmol. Moreover, the atomic ratio of the transition metal in the [A] component and the aluminum in the [C] component is 1: 0.01 to 1,000,000, preferably 0.1 to 100,000. The catalyst thus obtained may be used without washing as it is, or may be used after washing.
You may use it combining a [C] component newly as needed. The amount of the [C] component used at this time is selected so that the atomic ratio of aluminum in the [C] component to the transition metal in the [A] component is 1: 0 to 10,000.

F. Prepolymerization Prior to polymerization, olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and styrene are preliminarily prepared. A polymerized polymer and washed as necessary can be used as a catalyst. This prepolymerization may be performed in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene.

2. Regarding the three-stage polymerization method [1] Basic constitution The method for producing the propylene-α-olefin block copolymer of the present invention comprises a metallocene-supported catalyst component supported on a fine particle carrier and organic aluminum as an optional component. A three-stage polymerization is carried out in the presence of a catalyst comprising a compound.
In the first stage, a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms excluding propylene and containing 95 wt% or more of propylene is produced, and the second stage Produces a copolymer component (2) containing 10 to 30 wt% of an α-olefin having 2 to 20 carbon atoms excluding propylene and propylene, and in the third stage, the number of carbon atoms excluding propylene and propylene is 2 Component (3) of ˜20 α-olefin copolymer is produced such that the α-olefin content is 15-40 wt% higher than the α-olefin content of component (2).
And content of a component (1) is 5-95 wt%, content of a component (2) and a component (3) is 95-5 wt%, and the weight ratio of a component (2) and a component (3) is 10:90 to 90:10.
Ethylene is preferably used as the α-olefin of each component from the viewpoints of productivity and economy.

As the polymerization process, a slurry method, a bulk method, a gas phase method, a solution method and the like can be arbitrarily used. Among them, the first stage polymerization is performed by the bulk method or the gas phase method, and the second stage polymerization is performed. Most preferably, the polymerization and the third stage polymerization are both carried out by a gas phase method. As the polymerization method, either a batch polymerization method or a continuous polymerization method can be employed.
The molecular weight of the polymer in each stage can be controlled by supplying a molecular weight regulator, polymerization temperature, polymerization pressure, and the like. Hydrogen is preferred as the molecular weight regulator. Hydrogen is appropriately selected in consideration of the desired molecular weight of the polymer to be produced, MFR, and the like. For example, 0.001 to 20 mol% is used as the gas phase hydrogen concentration.
Moreover, about each component ratio manufactured in the 1st stage to the 3rd stage, it can adjust by controlling the manufacturing amount ratio of each component.

[2] First Stage In the production method of the present invention, in the first stage polymerization, a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms excluding propylene is used. The component (1) containing 95 wt% or more is produced, and the polymerization is preferably carried out by bulk polymerization or gas phase polymerization, particularly preferably gas phase polymerization.
The polymerization temperature at that time is 50 to 150 ° C., preferably 50 to 100 ° C., most preferably 60 to 90 ° C., and the polymerization pressure is 0.5 to 10 MPaG, preferably 1 to 5 MPaG. is there.
When the content of propylene in the component (1) is less than 95 wt%, the rigidity of the block copolymer is lowered, which is not preferable. The propylene content is preferably 95 wt% or more, and most preferably a propylene homopolymer.
From the viewpoint of the balance between the rigidity and impact resistance of the block copolymer, the content of the component (1) in the copolymer in the entire propylene-ethylene copolymer needs to be 5 to 95 wt%, Preferably it is 30-93 wt%, Most preferably, it is the range of 40-90 wt%.

[3] Second Stage In the second stage polymerization, a component (2) of a copolymer containing 10 to 30 wt% of an α-olefin having 2 to 20 carbon atoms excluding propylene and propylene is produced. Is carried out by gas phase polymerization.
The polymerization temperature at that time is 55 to 150 ° C., preferably 55 to 100 ° C., most preferably 55 to 90 ° C., and the polymerization pressure is 0.5 to 5 MPaG, preferably 0.5 to 3 MPaG.
The component (2) having a relatively low α-olefin content is a component that acts as a compatibilizer component between the component (1) and the component (3), and is a component that contributes to an improvement in impact resistance of the block copolymer. . Therefore, if the α-olefin content is too low, the affinity with the third component is inferior, and if it is too high, the affinity with the first component is inferior, so it is necessary to be in the range of 10 to 30 wt%, preferably 10 to 26 wt%, most preferably 15 to 26 wt%. At this time, when a plurality of types of α-olefins are used, the total amount of the content of each type of α-olefin is within the above range.

[4] Third Stage In the third stage polymerization, a component (3) of a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms excluding propylene is produced. It is necessary that the α-olefin content of 3) is 15 to 40 wt% higher than the α-olefin content (10 to 30 wt%) of the component (2) polymerized in the second stage, and the component (3) The content of α-olefin is 25 to 70 wt%.
The polymerization is carried out by gas phase polymerization, and the polymerization temperature at that time is 55 to 150 ° C., preferably 55 to 100 ° C., most preferably 55 to 90 ° C., and the polymerization pressure is 0.5 -5 MPaG, preferably 0.5-3 MPaG.
The component (3) having a relatively high α-olefin content is a component necessary for imparting low-temperature impact resistance (cold resistance) to the block copolymer. Therefore, if the α-olefin content is too low or too high, the glass transition temperature of the component (3) itself becomes high, or the compatibility between the components (2) and (3) deteriorates, so that the component (2) And the difference in the α-olefin content of component (3) must be 15 to 40 wt%, preferably 16 to 35 wt%, more preferably 18 to 30 wt%.
At this time, when a plurality of types of α-olefins are used, the total amount of the content of each type of α-olefin is within the above range.
The amount ratio of component (2) to component (3) is 10:90 to 90:10, preferably 10:90 to 50:50, and most preferably 10:90 to 34:66. If it is out of this range, the balance between impact resistance and cold resistance is inferior.

[5] Multi-stage polymerization The three-stage polymerization can be expanded to a multi-stage polymerization having 4 or more stages to further contain an α-olefin component having 2 to 20 carbon atoms. Thereby, you may manufacture an additional component in the range of the content of 10 wt% or less with respect to the whole block copolymer. For example, in the fourth and subsequent stages, a copolymer of propylene-α-olefin (range of 2 to 20 carbon atoms excluding propylene) having an α-olefin content of 78 mol% or more, or ethylene and carbon number 3 Examples include producing a copolymer of -20 α-olefin and homopolymerizing an α-olefin having 2 to 20 carbon atoms excluding propylene.

[6] Molecular weight The weight average molecular weight (Mw) of component (1) is 80,000 to 250,000, the weight average molecular weight of component (2) is 250,000 to 1,200,000, and component (3 ) Is preferably 200,000 to 1,000,000, and the weight average molecular weight of component (2) is preferably greater than or equal to the weight average molecular weight of component (3). More preferably, component (2) is 270,000 to 1,000,000, component (3) is 220,000 to 900,000, more preferably component (2) is 300,000 to 900,000, component ( 3) is in the range of 250,000 to 800,000. If the molecular weight is lower than these, the impact resistance and rigidity are inferior.
Moreover, it is preferable from a viewpoint of impact resistance that the weight average molecular weight of a component (2) is more than the weight average molecular weight of a component (3). Although it is not clear about this reason, since a component (2) plays the role which reinforces the interface of a component (1) and a component (3) as a compatibilizing agent component, the one with higher molecular weight and component (1) This is probably because more entanglements are formed between the components (3), and the strength of the interface can be further increased.
The range of the weight average molecular weight of the component (1) is preferably lower than that of the component (3) from the viewpoint of providing the block copolymer with fluidity required at the time of molding. Is 250,000 or less. Moreover, since it will embrittle if molecular weight is too low, it is preferable that it is 60,000 or more. A more preferable range is 250,000 to 70,000, and a further preferable range is 200,000 to 80,000.
In the present invention, the weight average molecular weight is measured by gel permeation chromatography (GPC), and is obtained by measuring at a temperature of 140 ° C. using orthodichlorobenzene as a solvent. Conversion to molecular weight is performed by conversion using a standard polystyrene sample.

[7] Other features In each stage, the propylene-α-olefin block copolymer of the present invention is characterized in that it is produced at industrially extremely advantageous production conditions, that is, at a relatively high polymerization temperature. This is also very advantageous from an industrial point of view.
According to the method for producing a propylene-α-olefin block copolymer of the present invention, a polymer having an excellent powder property can be obtained due to the use of a specific metallocene catalyst, and the production is extremely high. It is possible to produce a block copolymer that is efficient and has a good balance between high rigidity, heat resistance and impact resistance, particularly impact resistance at low temperatures.
Another feature of the production method of the present invention is that the impact resistance is increased in a synergistic manner depending on the blending ratio of the component (2) and the component (3).

3. Other Special Notes [1] Determination of Index of Each Component The index of α-olefin content and molecular weight of each component when produced by multistage polymerization of three or more stages can be determined by the following procedure.
For example, in the case of three-stage polymerization in which the components (1) to (3) are polymerized in this order, the polymerization to the component (3) is performed at the end of the polymerization of the component (1) and the polymerization to the component (2). Each sample was measured for the polymerization amount, α-olefin content and molecular weight, and calculated according to the following formulas (1) and (2).
The amount of polymerization can be determined by disconnecting the reactor from the polymerization system at the end of each stage and directly measuring the amount of polymer in the reactor as it is. Alternatively, there is a method of obtaining the polymerization amount by separately polymerizing only the component (1) and two-stage polymerization of the component (1) and the component (2) under the same conditions as the multistage polymerization. In the case of four or more stages of polymerization, it can be calculated by extending these equations.
Mw (1 + 2) = (W1 × Mw1 + W2 × Mw2) / (W1 + W2) (1)
Mw (T) = (W1 + W2) × Mw (1 + 2) + W3 × Mw3 (2)
[C] (1 + 2) = {W1 × [C] 1 + W2 × [C] 2} / (W1 + W2) (3)
[C] (T) = (W1 + W2) × [C] (1 + 2) + W3 × [C] 3 (4)
Here, Mw1, Mw2, and Mw3 are the weight average molecular weights of the component (1), the component (2), and the component (3), respectively. Mw (1 + 2) is the weight average molecular weight of the sample polymerized up to component (2), Mw (T) is the weight average molecular weight of the sample polymerized up to component (3). Can be evaluated. Similarly, [C] 1, [C] 2, and [C] 3 are comonomer contents of the respective components. [C] (1 + 2) is the α-olefin content of the sample polymerized up to component (2), and [C] (T) is the α-olefin content of the sample polymerized up to component (3), The extracted sample can be evaluated by ¹³ C-NMR or IR measurement. W1, W2, and W3 are weight fractions of the respective components.

[2] Additives The propylene-α-olefin block copolymer of the present invention impairs the functions of the present invention in order to enhance the performance of the copolymer of the present invention or to impart other performance. Additives can be blended within a range that does not exist.
As this additional component, a nucleating agent widely used as a compounding agent for polyolefin resin, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a neutralizer, a light stabilizer, an ultraviolet absorber, a lubricant Various additives such as antistatic agents, metal deactivators, peroxides, antibacterial agents, antifungal agents, fluorescent whitening agents, and coloring agents can be added. In addition, a rubber material can be added to further improve the impact resistance.
The amount of these additives is generally 0.0001 to 3% by weight, preferably 0.001 to 1% by weight, based on 100% by weight of the composition. Further, various rubbers for improving impact resistance are generally added in an amount of 1 to 50% by weight based on 100% by weight of the composition.

  In order to describe the present invention more specifically, preferred examples and comparative examples corresponding thereto are described below. By contrasting each example and each comparative example, the rationality and significance of the requirements of the configuration of the present invention are demonstrated, and further, the superiority of the present invention over the prior art is clarified.

The measurement methods of various physical properties, the production methods of propylene-α-olefin block copolymers, the evaluation methods thereof and the like in the following Examples and Comparative Examples are as follows.
1) GPC
Apparatus: GPC manufactured by Waters (ALC / GPC 150C) Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK Mobile phase solvent: o-dichlorobenzene (ODCB) Measurement temperature: 140 ° C. Flow rate: 1.0 ml / min Injection amount: 0.2 ml Sample preparation: ODCB (sample) Prepare a 1 mg / mL solution using 0.5 mg / mL BHT) and dissolve at 140 ° C. for approximately 1 hour. Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. Standard polystyrenes used are the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical values are used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ α = 0.7
PP: K = 1.03 × 10 ⁻⁴ α = 0.78

2) DSC
Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./min, and further melt at a rate of temperature increase of 10 ° C./min. The melting peak temperature at that time was Tm (unit: ° C)

3) Determination of ethylene content and butene content The average ethylene content in the copolymer was measured using an infrared spectrophotometer. The measurement conditions are shown below. Apparatus: Shimadzu FTIR-8300 Resolution: 4.0 cm ⁻¹ Measurement range: 4,000 to 400 cm ⁻¹ Preparation of sample: Polymer powder or pellet is adjusted to a film having a thickness of 500 μm by a heating and pressing press (temperature 190 ° C. Data processing (ethylene content): i) Using 760,700 cm ⁻¹ as a base point, calculate the absorbance peak area in that range. (Corresponds to ethylene content) ii) Calculate peak area / sample thickness. iii) A calibration curve is prepared using a sample whose ethylene content has been quantified in advance by NMR, and the ethylene content is quantified by the formula [ethylene content∝peak area / sample thickness]. Data processing (butene content): i) a 776,755Cm ^-1 as a base point, determine the absorbance of peaks detected in a range of 767 ± ^{3 cm -1.} (Corresponds to butene content) ii) Calculate absorbance / sample thickness. iii) A calibration curve is prepared using a sample whose butene content has been quantified in advance by NMR, and the butene content is quantified by the formula [butene content∝peak area / sample thickness].

4) Flexural properties Flexural modulus: The flexural modulus of the obtained composition was evaluated under the following conditions. Standard number: Compliant with JIS K-7171 (ISO178) Testing machine: Precision universal testing machine Autograph AG-20kNG (manufactured by Shimadzu Corporation) Test specimen sampling direction: Flow direction Test specimen shape: Thickness 4 mm Width 10 mm Length 80 mm Test How to make a piece: Injection molding (see paragraph 0075 for injection molding) Condition adjustment: Leave in a temperature-controlled room at room temperature 23 ° C and humidity 50% for more than 24 hours Test room: Room temperature 23 ° C and humidity 50% Constant temperature chambers Number of test pieces: 5 Distance between fulcrums: 32.0 mm Test speed: 1.0 mm / min

5) Impact strength The impact resistance of the block copolymer was evaluated by a Charpy impact test. Standard number: Compliant with JIS K-7111 (ISO 179 / 1eA) Tester: Toyo Seiki Co., Ltd. Fully automatic Charpy impact tester (with thermostatic bath) Test piece shape: Single notch test piece Thickness 4 mm Width 10 mm Length 80 mm Notch shape: Type A notch (notch radius 0.25 mm) Impact speed: 2.9 m / s Nominal pendulum energy: 4J Test piece preparation method: Cutting a notch into an injection-molded test piece (ISO 2818 compliant) Condition adjustment: Room temperature 24 hours or more in a temperature-controlled room adjusted to 23 ° C./humidity 50% Test room: Temperature-controlled room temperature adjusted to 23 ° C./humidity 50% Number of test pieces: n = 5 Test temperature: 23 ° C. 0 ° C.-30 ° C. In the case of 0 and −30 ° C., the test was performed after adjusting the condition for 40 min or more in a state where the thermostatic bath was within ± 1 ° C. of the test temperature) Evaluation item: Absorbed energy

6) Heat resistance Heat resistance was evaluated by heat distortion temperature (HDT). HDT was measured flat-wise under the condition of 0.45 MPa in accordance with JIS K7191-1 using an injection molded piece. However, as a test piece condition adjustment before measurement, after injection molding, an operation of annealing at 100 ° C. for 30 minutes and cooling to room temperature is performed.

[Production Example 1]
1) Preparation of catalyst component [A] Synthesis of (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl}] hafnium (racemic) -Synthesis of 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 resulting yellow precipitate at 0 ° C. N-methylimidazole (50 μl) and dimethyldichlorosilane (1.4 ml, 11.4 mmol) were added, and the mixture was warmed to room temperature and 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, and the solvent was distilled off under reduced pressure. Dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenyl) -1 , 4-dihydroazulene} was obtained (8.3 g).
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 distilled off under reduced pressure from the resulting slurry solution, 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.

Purification of 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 from this solution 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.
1H-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 (m, 16H, arom).

2) Adjustment of catalyst component [B] (a) Chemical treatment 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 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 a commercially available granulated montmorillonite (manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 28.0 μm) is 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. The slurry was filtered under reduced pressure using a device in which an aspirator was connected to Nutsche and a suction bottle. The cake was collected, and 5.0 L of pure water was added to reslurry and filtered. 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. .
(B) Chemically treated montmorillonite treated with organoaluminum 10.0 g of chemically treated montmorillonite obtained in (a) above was weighed into a flask having an internal volume of 1 L, 64.6 ml of heptane, and 35.4 ml (25 mmol) of heptane solution of triisobutylaluminum. And stirred at room temperature for 1 hour. Thereafter, it was washed with heptane, and finally the amount of slurry was adjusted to 100 ml.

3) Prepolymerization with propylene 2.13 ml (1,504 μmol) of a triisobutylaluminum heptane solution was added to the triisobutylaluminum-treated montmorillonite heptane slurry prepared in (b) of (2) above for 10 minutes at room temperature. Stir.
In another flask (volume: 200 ml), (r) -dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl)-synthesized in (1) above] 4H-azurenyl}] hafnium (299 μmol) was added with toluene (60 ml) to form a slurry, which was then added to the 1 L flask and stirred at room temperature for 60 minutes.
The toluene slurry of the complex was analyzed and the dissolved component and insoluble component of the complex were determined. The dissolved component of the complex was 60 μmol, the insoluble component was 239 μmol, and the dissolved component was 6 μmol / g-carrier for montmorillonite. there were.
Next, 340 ml of heptane was further added to the montmorillonite heptane slurry, and the mixture was introduced into a stirring autoclave having an internal volume of 1 L and stirred for 60 minutes. When the temperature in the autoclave was stabilized at 40 ° C., a toluene slurry of the complex was added, and then propylene was supplied at a constant rate of 238.1 mmol / hr (10 g / hr) for 120 minutes. After completion of the propylene supply, the temperature was raised to 50 ° C. and maintained for 2 hours, after which the remaining gas was purged and the prepolymerized catalyst slurry was recovered from the autoclave. The total time required for the prepolymerization was 4 hours. The recovered prepolymerized catalyst slurry was allowed to stand, and the supernatant liquid was extracted. To the remaining solid, 8.5 ml (6.0 mmol) of a heptane solution of triisobutylaluminum was added at room temperature, stirred at room temperature for 10 minutes, and then dried under reduced pressure to recover 31.8 g of a solid catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.09.

4) Polymerization Polymerization comprising the following first to third steps was carried out to produce a polypropylene resin composition.
(Polymerization in the first step)
After fully replacing the inside of the autoclave with a stirrer with a volume of 3 L with propylene, 2.76 ml (2.02 mmol) of a heptane solution of triisobutylaluminum was added, and 700 ml of hydrogen and then 1500 ml of liquid propylene were introduced. The temperature was raised to 65 ° C. The prepolymerized catalyst obtained in the above 3) was slurried in heptane, and 40 mg (amount of net solid catalyst excluding prepolymerized polymer) was injected as a solid catalyst to initiate polymerization. The tank temperature was maintained at 65 ° C. After 1 hour from the introduction of the catalyst, the residual monomer was purged, and a part of the produced polymer was sampled and measured after drying for 30 minutes under a nitrogen stream at 90 ° C. As a result, the amount extracted was 15 g.
(Polymerization in the second step)
In parallel, a mixed gas of 72.5 vol% propylene, 27.5 vol% ethylene, 0.02 vol% hydrogen was prepared at 80 ° C in a mixed gas tank of propylene and ethylene (autoclave with a stirrer). After the stirring of the polymerization tank was resumed and the inside of the polymerization tank was adjusted to a gas composition of propylene 43 vol% and ethylene 57 vol%, the previously prepared mixed gas was supplied so that the polymerization tank pressure was 1.5 MPa gauge pressure, Vapor phase copolymerization of propylene / ethylene was performed at 65 ° C. for 5 minutes. Thereafter, the residual monomer was purged, and a part of the produced polymer was sampled and measured after drying for 30 minutes under a nitrogen stream at 90 ° C. As a result, the amount extracted was 15 g.
(Polymerization in the third step)
In parallel, a mixed gas of propylene 44.99 vol%, ethylene 54.98 vol%, and hydrogen 0.03 vol% was prepared at 80 ° C in a propylene and ethylene mixed gas tank (autoclave with a stirrer). After the stirring of the polymerization tank is resumed and the inside of the polymerization tank is adjusted to a gas composition of 24 vol% propylene and 76 vol% ethylene, the previously prepared mixed gas is supplied so that the pressure in the polymerization tank becomes 2.0 MPa gauge pressure. Then, propylene / ethylene vapor phase copolymerization was carried out at 80 ° C. for 20 minutes. The polymer recovered after the polymerization was dried for 30 minutes under a nitrogen stream at 90 ° C.
The polymerization conditions are summarized in Table 1. Table 1 shows the results of extracting a small amount of sample at each stage of the polymerization and measuring the comonomer content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 2]
The gas composition in the polymerization tank in the second step is 43 vol% propylene and 57 vol% in ethylene, the gas composition in the polymerization tank in the third step is 24 vol% in propylene and 76 vol% in ethylene, and other polymerization conditions are as shown in Table 1. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Further, Table 1 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 3]
The gas composition in the polymerization tank in the second step is 54 vol% propylene and 46 vol% in ethylene, the gas composition in the polymerization tank in the third step is 29 vol% in propylene and 71 vol% in ethylene, and other polymerization conditions are as shown in Table 1. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Further, Table 1 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 4]
The gas composition in the polymerization tank in the second step is 37 vol% propylene and 63 vol% in ethylene, the gas composition in the polymerization tank in the third step is 16 vol% in propylene and 84 vol% in ethylene, and other polymerization conditions are as shown in Table 1. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Further, Table 1 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 5]
The gas composition in the polymerization tank in the second step is 43 vol% propylene and 57 vol% in ethylene, the gas composition in the polymerization tank in the third step is 24 vol% in propylene and 76 vol% in ethylene, and other polymerization conditions are as shown in Table 1. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Further, Table 1 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 6]
The gas composition in the polymerization tank in the second step is 43 vol% propylene and 57 vol% in ethylene, the gas composition in the polymerization tank in the third step is 24 vol% in propylene and 76 vol% in ethylene, and other polymerization conditions are as shown in Table 1. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Further, Table 1 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 7]
The gas composition in the polymerization tank in the second step is 43 vol% propylene and 57 vol% in ethylene, the gas composition in the polymerization tank in the third step is 24 vol% in propylene and 76 vol% in ethylene, and other polymerization conditions are as shown in Table 1. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Further, Table 1 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 8]
The gas composition in the polymerization tank in the second step is 52.1 vol% propylene, 46.0 vol% ethylene, and 1.9 vol% in butene, and the gas composition in the polymerization tank in the third step is 34.5 vol% propylene and 64.0 vol% ethylene. A block copolymer was produced in the same manner as in Production Example 1 except that butene was changed to 1.45 vol% and other polymerization conditions were changed as shown in Table 1. However, in this production example, butene was introduced at the ratio shown in Table 1 during the second and third polymerizations to produce a terpolymer. Table 1 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the comonomer content and molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 2.

[Production Example 9]
A block copolymer was produced by two-stage polymerization. The same as in Production Example 1, except that the gas composition in the polymerization tank in the second step was changed to propylene 24 vol%, ethylene 76 vol%, and other polymerization conditions were as described in Table 3 and the polymerization was terminated in two stages. Manufactured. Table 3 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 4.

[Production Example 10]
The gas composition in the polymerization tank in the second step is 33 vol% propylene and 67 vol% in ethylene, the gas composition in the polymerization tank in the third step is 10 vol% in propylene and 90 vol% in ethylene, and other polymerization conditions are as shown in Table 3. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Table 3 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 4.

[Production Example 11]
The gas composition in the polymerization tank in the second step is 29 vol% propylene and 71 vol% in ethylene, the gas composition in the polymerization tank in the third step is 16 vol% in propylene and 84 vol% in ethylene, and other polymerization conditions are as shown in Table 3. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Table 3 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 4.

[Production Example 12]
The gas composition in the polymerization tank in the second step is 43 vol% propylene and 57 vol% in ethylene, the gas composition in the polymerization tank in the third step is 30 vol% in propylene and 70 vol% in ethylene, and other polymerization conditions are as shown in Table 3. A block copolymer was produced in the same manner as in Production Example 1 except for the change. Table 3 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 4.

[Production Example 13] Three-stage polymerization with Ziegler catalyst (Preparation of solid catalyst component)
2,000 ml of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly purged with nitrogen, and then 2.6 mol of MgCl ₂ and 5.2 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. And reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 320 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.
Next, 4,000 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 1.46 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 2.62 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.15 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 11.4 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid component (A1) was obtained by washing with n-heptane. The titanium content of this solid component was 2.0 wt%.
Next, 200 ml of n-heptane purified in the same manner as above was introduced into a sufficiently nitrogen-substituted flask, 4 g of the solid component (A1) synthesized above was introduced, 0.035 mol of SiCl ₄ was introduced, and 90 ° C. The reaction was performed for 2 hours. After completion of the reaction, further _{(CH 2 = CH) Si (} CH 3) 3 0.006mol, (t-C 4 H 9) (CH 3) Si (OCH 3) 2 0.003mol and _Al (C _{2 H} 5) ₃ 0.016 mol was sequentially introduced and contacted at 30 ° C. for 2 hours. After completion of the contact, the solid catalyst component (A) mainly composed of magnesium chloride was obtained by thoroughly washing with n-heptane. When a part was sampled and analyzed, the titanium content of the sample was 1.8 wt%. (The above catalyst preparation was carried out by the method described in Example 1 of JP-A-11-80235.)
(Preparation of prepolymerization catalyst)
Purified n-heptane was introduced into the solid catalyst component (A) to adjust the concentration of the solid catalyst component (A) to 20 g / L. After cooling the slurry to 15 ° C., _Al a _{(C 2} H _{5) 3} of n- heptane diluent 0.5g was added as _{Al (C 2} H _{5) 3,} was fed slowly propylene 9g. After the supply of propylene was completed, the reaction was further continued for 10 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. Thereafter, vacuum drying was performed to obtain a prepolymerized catalyst (B). This prepolymerized catalyst (B) contained 2.0 g of polypropylene per 1 g of the solid catalyst component (A).

(Production of propylene ethylene block copolymer)
Polymerization in the first step After the autoclave with an internal volume of 3 L having a stirring and temperature control device was sufficiently substituted with propylene, 4.82 mmol of triethylaluminum was diluted with n-heptane and then added, followed by 8,000 ml of hydrogen, followed by liquid propylene 750 g was introduced and the temperature was raised to 65 ° C. to maintain the temperature. The above prepolymerized catalyst (B) was slurried with n-heptane, and 6.4 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. Polymerization was continued for 60 minutes while maintaining the temperature in the tank at 65 ° C. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen. A part of the produced polymer was sampled and sufficiently dried and used for analysis.
Second Step Polymerization Separately, a mixed gas used in the second step was prepared using an autoclave with an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 80 ° C., and the mixed gas composition was ethylene 15.56 vol%, propylene 77.77 vol%, and hydrogen 6.67 vol%. After a part of the polymer was sampled in the first step, this mixed gas was supplied to a 3 L autoclave to start polymerization in the second step. The polymerization was continued for 20 minutes at a polymerization temperature of 80 ° C. and a pressure of 2.0 MPaG. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen. A part of the produced polymer was sampled and sufficiently dried and used for analysis.
Polymerization in the third step Separately, a mixed gas used in the third step was prepared using an autoclave having an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 80 ° C., and the mixed gas composition was ethylene 34.05 vol%, propylene 56.75 vol%, and hydrogen 9.20 vol%. After a part of the polymer was sampled in the second step, this mixed gas was supplied to a 3 L autoclave to start the polymerization in the third step. The polymerization was continued for 60 minutes at a polymerization temperature of 80 ° C. and a pressure of 2.0 MPaG. Thereafter, 10 ml of ethanol was introduced to terminate the polymerization. The recovered polymer was sufficiently dried in an oven.
Table 3 shows the results of extracting a small amount of sample at each stage of polymerization and measuring the ethylene content and the molecular weight. The index of each component of the polymer calculated from this result is summarized in Table 4.

[Example 1]
The following antioxidant and neutralizer were added to the polymer powder obtained in Production Example 1 and mixed thoroughly with stirring.
[Additive formulation] Antioxidant: Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane 500 ppm Tris (2,4-di-t-butylphenyl) ) Phosphite 500ppm
Neutralizer: Calcium stearate 500ppm
The physical properties of the product granulated and molded under the following conditions were evaluated. The granulation conditions and molding conditions are shown below.
[Granulation] Extruder: KZW-15-45MG twin screw extruder manufactured by Technobel Co., Ltd. Screw: 15 mm in diameter L / D = 45 Extruder set temperature: (from under the hopper) 40, 80, 160, 200, 200, 200 (die ℃) Screw rotation speed: 400 rpm Discharge amount: Adjusted to about 1.5 kg / h with a screw feeder Die: 3 mm diameter Strand die Number of holes 2 [molding] The obtained raw material pellets were injection molded under the following conditions, A flat specimen for physical property evaluation was obtained.
Standard number: JIS K-7152 (ISO 294-1) reference Molding machine: EC20P injection molding machine manufactured by Toshiba Machine Co., Ltd. Molding machine set temperature: 80, 210, 210, 200, 200 ° C. Mold temperature: 40 ℃ Injection speed: 52 mm / s (screw speed) Holding pressure: 30 MPa Holding time: 8 seconds Mold shape: flat plate (thickness 4 mm, width 10 mm, length 80 mm) Take two physical properties using the obtained molded piece Table 5 shows the evaluation results.

[Examples 2 to 8]
The same procedure as in Example 1 was performed except that the resins used were Production Examples 2 to 8, respectively. The results are shown in Table 5.
[Comparative Examples 1-5]
The same procedure as in Example 1 was performed except that the resins used were those in Production Examples 9 to 13, respectively. The results are shown in Table 6.

[Consideration by contrast between Example and Comparative Example]
Considering each of the above Examples and Comparative Examples in comparison, the flexural elasticity, which is an index of rigidity, is obtained in each Example obtained by a manufacturing method that satisfies each rule in the specific three-stage polymerization method of the present invention. It is clear that the balance between the rate and the impact resistance at each temperature is excellent. Further, in each example, impact resistance at low temperature (−30 ° C.) is improved, and the heat resistance is balanced with other physical properties. Each example of the present invention is a Ziegler catalyst. Compared with the comparative example 5 by, the heat resistance of rigidity matching is superior.
In Comparative Example 1, since the component (3) is not contained in the two-stage polymerization method, the impact strength at each temperature and the low temperature impact resistance are inferior. In Comparative Example 2, the component (3) ethylene is inferior. In the comparative example 3, the ethylene content of the component (2) is too higher than the definition of the present invention, and in each case, the impact resistance at each temperature and the low temperature impact resistance are inferior. In Comparative Example 4, the difference between the ethylene contents of the components (2) and (3) is too small, resulting in poor low-temperature impact resistance. Since Comparative Example 5 is a three-stage polymerization with a conventional Ziegler catalyst, at each temperature, Is inferior in impact strength and low-temperature impact resistance and has low heat resistance.
From the results and discussions of the examples and comparative examples described above, the rationality and significance of the requirements of the configuration of the present invention are demonstrated, and the superiority of the present invention over the prior art is also clarified. ing.

Claims (6)

Three-stage polymerization is carried out in the presence of a catalyst comprising a metallocene-supported catalyst component supported on a fine particle carrier and an organoaluminum compound as an optional component. In the first stage, propylene homopolymer or propylene and propylene In the second stage, a component (1) containing 95 wt% or more of propylene is produced, which is a copolymer with an α-olefin having 2 to 20 carbon atoms excluding propylene, and in the second stage, 2 to 20 carbon atoms excluding propylene and propylene. The component (2) of the copolymer containing 10 to 30 wt% of the α-olefin is produced, and in the third stage, the component of the copolymer of propylene and the α-olefin having 2 to 20 carbon atoms excluding propylene is prepared. (3) is produced so that the α-olefin content is 15 to 40 wt% higher than the α-olefin content of component (2), and the content of component (1) is 5 ~ 95 wt%, the total content of component (2) and component (3) is 95-5 wt%, and the weight ratio of component (2) and component (3) is 10:90 to 90:10 A process for producing a propylene-α-olefin block copolymer. The method for producing a propylene-α-olefin block copolymer according to claim 1, wherein the α-olefin of each component is ethylene. Polymerization in four or more stages is carried out in the presence of a catalyst component comprising a metallocene-supported catalyst supported on a fine particle carrier and an organoaluminum compound as an optional component, and an α-olefin component having 2 to 20 carbon atoms is further added. The method for producing a propylene-α-olefin block copolymer according to claim 1 or 2, wherein the propylene-α-olefin block copolymer is contained. In the metallocene-supported catalyst, at least one of the conjugated five-membered ring ligand is bonded to the adjacent substituent on the conjugated five-membered ring ligand, and the condensed 7 to 10 member including two atoms of the conjugated five-membered ring. The method for producing a propylene-α-olefin block copolymer according to any one of claims 1 to 3, wherein a ring is formed. The weight average molecular weight of component (1) is 80,000 to 250,000, the weight average molecular weight of component (2) is 250,000 to 1,200,000, and the weight average molecular weight of component (3) is 200. The weight average molecular weight of the component (2) is not less than the weight average molecular weight of the component (3), and the weight average molecular weight of the component (2) is not less than 1,000,000,000. For producing a prepared propylene-α-olefin block copolymer. The propylene-α-olefin block according to any one of claims 1 to 5, wherein the impact resistance is increased in a synergistic manner depending on the mixing ratio of the component (2) and the component (3). A method for producing a copolymer.