Propylene Polymer, Composition Comprising the Polymer, and Molded Product Obtained Therefrom

Abstract

A propylene polymer which is constituted of 10 to 40 wt % room-temperature n-decane soluble part (Dsol) and 60 to 90 wt % room-temperature n-decane insoluble part (Dinsol), comprises skeletons derived from propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, and satisfies all of the following requirements [1] to [5]. The polymer is characterized by having a high melting point and a high molecular weight and is suitable for use in producing various moldings therefrom. [1] the molecular weight distribution (Mw/Mn) of both Dsol and Dinsol as determined by GPC is 4.0 or less; [2] the melting point (Tm) of Dinsol is 156° C. or more; [3] the sum of the 2,1-bond content and the 1,3-bond content in Dinsol is 0.05 mol % or less; [4] the intrinsic viscosity [η] (dl/g) of Dsol satisfies the relationship 2.2<[η]≦6.0; and [5] the concentration of skeletons derived from the olefin (MX) in Dinsol is 3.0 wt % or less.

Description

TECHNICAL FIELD

The present invention relates to a propylene copolymer, a composition comprising the polymer, and a molded product obtained therefrom.

BACKGROUND ART

Highly crystalline polypropylene obtained by polymerizing propylene with a Ziegler catalyst is used as a material having rigidity and heat resistance as thermoplastic resin in wide applications.

For using the highly crystalline polypropylene in a field requiring impact resistance, a propylene/ethylene block copolymer has been developed for example by continuously polymerizing propylene alone or a mixture of propylene and a small amount of ethylene in a former stage and then continuously copolymerizing propylene with ethylene in a latter stage (in the following description, “propylene/ethylene block copolymer” is referred to sometimes as “block polypropylene”). In the polymerization method using a Ziegler catalyst, however, not only the desired polymer that is a propylene/ethylene copolymer soluble in solvents such as n-decane or p-xylene, but also a propylene/ethylene copolymer, an ethylene homopolymer and a propylene homopolymer insoluble in these solvents, are formed as byproducts in the latter stage of copolymerizing propylene with ethylene. These solvent-insoluble components produced as byproducts in the step of copolymerizing propylene with ethylene are known to cause deterioration in physical properties such as impact resistance of the propylene copolymer.

To reduce the amount of these solvent-insoluble components formed as byproducts, a method of producing block polypropylene by using a metallocene catalyst is actively developed. Japanese Patent Application Laid-Open No. 5-202152 and Japanese Patent Application Laid-Open No. 2003-147035 disclose that a metallocene catalyst can be used for considerably reducing the amount of byproducts, such as propylene/ethylene copolymers insoluble in n-decane or p-xylene, in the latter copolymerization step, thereby improving impact resistance, but the method disclosed therein cannot be said to cope with the balance between impact resistance and rigidity in various industrial fields, and there is demand for further improvements.

The tendency toward diversification and higher level in industrial fields using plastics brings about the advent of application fields not satisfied even with heat resistance and rigidity achieved as excellent performance of the conventional polypropylene. In other words, there are appearing many industrial fields which cannot be dealt with the existing propylene resin only. By way of example, the following two fields are presented: one is directed to retort film and the other to injection molding for automotive material.

In recent years, retort food is rapidly becoming widely used not only at home but also in business field, thus necessitating a packaging material (retort pouch) capable of packaging a large amount of food all together. The retort food is generally stored at ambient temperatures or kept in a refrigerator or a freezer for a prolonged period, and thus the film used in its packaging material needs high heat-sealing strength and resistance to impact at low temperatures in order to prevent breakage at a heat sealed portion of the package. However, a blend film consisting of polypropylene and ethylene/α-olefin copolymer rubber, a polypropylene block copolymer film, or a blend film consisting of a polypropylene block copolymer and ethylene/α-olefin copolymer rubber, which have been used conventionally as a sealant layer of a retort pouch, are hardly said to be excellent in balance among heat resistance, resistance to impact at low temperatures and heat sealing properties out of key performance requirements. In the retort food, the food is packed and sealed and then subjected to retort sterilization treatment in a high-temperature and high-pressure boiler at about 100 to 140° C., so the heat resistance and heat sealing strength of the heat-sealed portion durable to such treatment are also required from the viewpoint of the quality control of food. Sterilization at high temperatures for a short time leads not only to improvement in working efficiency but also to improvement in the food survival rate of the content, and thus further improvements in the allowable temperature limit of propylene resin used as a sealant layer for a retort pouch etc. are demanded in the industrial field.

The propylene resin, for its excellent rigidity, hardness and heat resistance, is used widely in automobile interior applications and automobile exterior applications such as a fender, bumper, side molding, mudguard, mirror cover etc. by injection molding. Depending on use, a polypropylene composition with impact resistance improved by compounding propylene resin with polyethylene or a rubber component, an amorphous or low-crystalline ethylene/propylene copolymer (EPR), an amorphous ethylene/α-olefin copolymer, etc., a polypropylene composition having inorganic fillers such as talc added for compensating for rigidity reduced upon compounding with a rubber component, etc. are also known. In such propylene resin, however, there is demand for further weight saving and thinner wall of a molded product. For obtaining a molded product realizing such performance and simultaneously having sufficient strength, propylene resin with further improvement in the balance between rigidity and impact resistance (that is, excellent in both rigidity and impact resistance) or a propylene resin composition comprising the resin is required.

The present invention was made in view of the related art described above, and the object of the present invention is to provide propylene resin excellent in heat resistance, also excellent in both rigidity and impact resistance, and particularly suitably usable in a film and an injection molded product, a resin composition comprising the resin, and a molded product obtained therefrom.

DISCLOSURE OF INVENTION

The present invention relates to a propylene polymer (A) consisting of 10 to 40 wt % room-temperature n-decane soluble part (D_sol) and 60 to 90 wt % room-temperature n-decane insoluble part (D_insol), comprising skeletons derived from propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, and satisfying all of the following requirements [1] to [5]:

[1] the molecular weight distribution (Mw/Mn) of both D_sol and D_insol as determined by GPC is 4.0 or less;

[2] the melting point (Tm) of D_insol is 156° C. or more;

[3] the sum of the 2,1-bond content and the 1,3-bond content in D_insol is 0.05 mol % or less;

[4] the intrinsic viscosity [η] (dl/g) of D_sol satisfies the relationship 2.2<[η]≦6.0; and

[5] the concentration of skeletons derived from the olefin (MX) in D_insol is 3.0 wt % or less.

In a preferable aspect, the propylene polymer (A) of the present invention is a propylene polymer (A1), which is obtained by carrying out the following two steps (steps 1 and 2) successively:

[Step 1] step wherein propylene (MP), and if necessary at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, are (co)polymerized in the presence of a catalyst containing a metallocene compound, thereby producing a (co)polymer wherein the concentration of room-temperature n-decane soluble part (D_sol) is 0.5 wt % or less, and

[Step 2] step wherein propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins are copolymerized in the presence of a catalyst containing a metallocene compound, thereby producing a copolymer wherein room-temperature n-decane insoluble part (D_insol) is 5.0 wt % or less.

In a preferable aspect, the catalyst for producing the propylene polymer (A) of the present invention is a catalyst comprising a metallocene compound represented by the following general formula [I]: [I] wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³R¹⁴, R¹⁵ and R¹⁶ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group and may be the same or different, and the adjacent groups R¹ to R¹⁶ may be bound to one another to form a ring, provided that R² is not an aryl group; M is the group IV transition metal; Q is selected from the group consisting of a halogen atom, a hydrocarbon group, an anion ligand, and a neutral ligand capable of coordination with a lone pair of electrons; j is an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different.

The present invention relates to a thermoplastic resin composition (B) comprising the propylene polymer (A).

In a preferable aspect, the thermoplastic resin composition (B) is a propylene resin composition (B1) comprising the propylene polymer (A) of the present invention and at least one member selected from a polypropylene resin (P) different from the propylene polymer (A), an elastomer (Q) and an inorganic filler (R).

The present invention relates to an injection-molded product (C1) obtained by molding the propylene polymer (A), a film (D1) obtained by molding the propylene polymer (A), a sheet (E1) obtained by molding the propylene polymer (A), and a blow molded container (F1) obtained by molding the propylene polymer (A).

Further, the present invention relates to an injection molded product (C2) obtained by molding the thermoplastic resin composition (B) or the propylene resin composition (B1), a film (D2) obtained by molding the thermoplastic resin composition (B) or the propylene resin composition (B1), a sheet (E2) obtained by molding the thermoplastic resin composition (B) or the propylene resin composition (B1), and a blow-molded container (F2) obtained by molding the thermoplastic resin composition (B) or the propylene resin composition (B1).

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the best mode for carrying out the invention is described in detail by reference to the propylene polymer (A), the method of producing the propylene polymer (A), the thermoplastic resin composition (B) comprising the propylene polymer, and applications thereof in this order.

Propylene Polymer (A)

The propylene polymer (A) of the present invention is a propylene polymer (A) consisting of 10 to 40 wt %, preferably 10 to 30 wt %, room-temperature n-decane soluble part (D_sol) and 60 to 90 wt %, preferably 70 to 90 wt %, room-temperature n-decane insoluble part (D_insol), provided that the sum of D_sol and D_insol is 100 wt %, comprising skeletons derived from propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, and satisfying all of requirements [1] to [5] described later. In the present invention, the “room-temperature n-decane soluble part” refers to the part of the polypropylene polymer (A) which after dissolved by heating at 145° C. for 30 minutes in n-decane and then cooled to 20° C., remains dissolved in n-decane, as described in detail in the Examples described later. In the following description, the “room-temperature n-decane soluble part” and “room-temperature n-decane insoluble part” are abbreviated sometimes as “n-decane soluble part” and “n-decane insoluble part”, respectively.

The propylene polymer (A) of the present invention is composed of a skeleton derived from propylene (MP) as an essential skeleton and a skeleton derived from at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins. The C4 or more α-olefins (hereinafter referred to sometimes as merely “α-olefins”) are preferably C4 or more α-olefins composed exclusively of carbon atoms and hydrogen atoms, and examples of such α-olefins include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene etc. When the α-olefin is used, it is preferably at least one member selected from 1-butene, 1-hexene and 4-methyl-1-pentene.

[1] the molecular weight distribution (Mw/Mn) of both D_sol and D_insol as determined by GPC is 4.0 or less;

[2] the melting point (Tm) of D_insol is 156° C. or more;

[3] the sum of the 2,1-bond content and the 1,3-bond content in D_insol is 0.05 mol % or less;

[4] the intrinsic viscosity [η](dl/g) of D_sol satisfies the relationship 2.2<[η]≦6.0; and

[5] the concentration of skeletons derived from the olefin (MX) in D_insol is 3.0 wt % or less.

Hereinafter, the requirements [1] to [5] of the propylene polymer (A) of the present invention are described in detail.

Requirement [1]

The molecular-weight distribution (Mw/Mn) of both n-decane soluble part (D_sol) and n-decane insoluble part (D_insol) in the propylene polymer of the present invention, as determined by GPC, is 4.0 or less. The molecular-weight distribution of D_sol is preferably 3.5 or less, more preferably 3.0 or less. The molecular-weight distribution of D_insol is preferably 3.5 or less, more preferably 3.0 or less. Mw is weight-average molecular weight, and Mn is number-average molecular weight.

Requirement [2]

The melting point (Tm) of n-decane insoluble part (D_insol) in the propylene polymer (A) of the present invention is 156° C. or more, preferably 156° C.≦Tm≦167° C., more preferably 158° C.≦Tm≦165° C. A Tm of less than 156° C. is not preferable because rigidity is lowered and the heat resistance of the propylene polymer in the form of a film may not guarantee demand characteristics in some fields.

Requirement [3]

The sum of positionally irregular units based on 2,1-insertion and 1,3-insertion (referred to as “2,1-bond content” and “1,3-bond content” respectively) of propylene monomers in all propylene units in the n-decane insoluble part (D_insol) of the propylene polymer (A) of the present invention, as determined from ¹³C-NMR spectrum, is 0.05 mol % or less, preferably 0.04 mol % or less, still more preferably 0.02 mol % or less. When the sum of the 2,1-bond content and 1,3-bond content in the n-decane insoluble part (D_insol) of the propylene polymer (A1) of the present invention, as determined from ¹³C-NMR spectrum, is higher than 0.05 mol %, the 2,1-bond content and 1,3-bond content in the n-decane soluble part (D_sol) of the propylene polymer (A1) are also increased, and the compositional distribution of the n-decane soluble part (D_sol) is broadened to sometimes lower impact resistance.

Requirement [4]

The intrinsic viscosity [η] (dl/g) of n-decane soluble (D_sol) in the propylene polymer (A) of the present invention usually satisfies the relationship 2.2<[η]≦6.0. Generally, when the intrinsic viscosity [η] of the n-decane soluble part (D_sol) is increased, the characteristics of the propylene polymer (A) are expected to be excellent, but in most of applications intended by the present invention, the propylene polymer satisfying the relationship 2.2<[η]≦5.0, preferably 2.2<[η]≦4.5, is preferably used.

Requirement [5]

The weight concentration of skeletons derived from at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, in n-decane insoluble part (D_insol) of the propylene polymer (A) of the present invention, is usually 3.0 wt % or less, preferably 2.0 wt % or less, more preferably 1.5 wt % or less.

Although the propylene polymer (A) of the present invention can exhibit its properties sufficiently in applications intended by the present invention insofar as the requirements [1] to [5] are satisfied, it is preferable that the following requirements [1′] to [4′] are simultaneously satisfied.

Requirement [1′]

The ratio Mw/Mn of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the component soluble in orthodichlorobenzene at 0° C. is 1.0 to 4.0, preferably 1.0 to 3.5, more preferably 1.0 to 3.0. When the Mw/Mn is greater than 4.0, resistance to low-temperature embrittlement is sometimes deteriorated.

Requirement [2′]

The weight-average molecular weight (Mw) of the component soluble in orthodichlorobenzene at 0° C. is 1.8×10⁵ or more, preferably 2.0×10⁵ or more, more preferably 2.5×10⁵. When the Mw is lower than 1.8×10⁵, impact resistance is sometimes lowered.

Requirement [3′]

The ratio Mw/Mn of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of the component insoluble in orthodichlorobenzene at 90° C. and soluble in orthodichlorobenzene at 135° C. is 1.0 to 4.0, preferably 2.0 to 3.5.

Requirement [4′]

The skeletons, in D_sol, derived from at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins (MX) contain an ethylene-derived skeleton as an essential component, and the ethylene-derived skeleton is contained in D_sol in an amount of preferably 15 mol % to 90 mol %, more preferably 20 mol % to 70 mol %, still more preferably 25 mol % to 60 mol %. When the concentration of the ethylene-derived skeleton is lower than 15 mol % or higher than 90 mol %, impact resistance may be not sufficiently exhibited.

Method of Producing Propylene Polymer (A)

The method of producing the propylene polymer (A) of the present invention is not particularly limited insofar as the requirements described above are satisfied. According to another finding of the inventors, the n-decane insoluble part (D_insol) constituting the propylene polymer (A) of the present invention is substantially identical with a propylene homopolymer, a propylene random polymer (propylene polymer containing up to 1.5 mol % skeleton derived from ethylene or a C3 or more α-olefin) or a mixture of two or more of the above, while the n-decane soluble part (D_sol) is substantially identical with a propylene/ethylene copolymer, a propylene/α-olefin copolymer, an ethylene/α-olefin copolymer, or a mixture of two or more of the above (“copolymer” includes a random polymer). Accordingly, the propylene polymer (A) of the present invention can be produced mainly by either of the following production methods.

Method A: A method wherein the following two steps (steps 1 and 2) are successively carried out thereby producing the propylene polymer (A) satisfying all of the requirements [1] to [5]. (Hereinafter, this method is referred to as “direct polymerization method”, and the propylene polymer (A) produced by this method is referred to sometimes as propylene polymer (A1).)

[Step 1] Step wherein propylene (MP), and if necessary at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, are (co)polymerized in the presence of a catalyst containing a metallocene compound, thereby producing a (co)polymer wherein the concentration of room-temperature n-decane soluble part (D_sol) is 0.5 wt % or less (hereinafter, this (co)polymer is referred to sometimes as copolymer [a1]).

[Step 2] Step wherein propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins are copolymerized in the presence of a catalyst containing a metallocene compound, thereby producing a copolymer wherein room-temperature n-decane insoluble part (D_insol) is 5.0 wt % or less (hereinafter, this (co)polymer is referred to sometimes as copolymer [a2]).

Method B: A method wherein a (co)polymer (=polymer [a1]) formed in step 1 in Method A and a copolymer (=polymer [a2]) formed in step 2 in Method A are produced separately in the presence of a catalyst containing a metallocene compound and then blended with each other by a physical means. (Hereinafter, this method is referred to as “blending method”, and the propylene polymer (A) produced by this method is referred to sometimes as propylene polymer (A2).)

The metallocene compound-containing catalyst used in common in Methods A and B is specifically a catalyst containing a metallocene compound [m] represented by the following general formula [I]:

In a preferable aspect, the catalyst containing the metallocene compound [m] comprises:

[m] metallocene compound represented by the general formula [I],

[k] at least one kind of compound selected from [k-1] organometallic compound, [k-2] organoaluminum oxy compound, and [k-3] compound reacting with the metallocene compound [m] to form an ion pair, and

[s] particulate catalyst support if necessary.

Hereinafter, the components [m], [k] and [s] constituting the polymerization catalyst according to the present invention are described in detail.

Component [m]

Component [m] is a metallocene compound represented by the general formula [I] above. In the general formula [I], R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group and may be the same or different, and the adjacent groups R¹ to R¹⁶ may be bound to one another to form a ring, provided that R² is not an aryl group. As used herein, the aryl group refers to a substituent having free atomic valence on conjugated sp² carbon in an aromatic hydrocarbon group, and examples include a phenyl group, tolyl group, naphthyl group etc., and do not include a benzyl group, phenethyl group, phenyldimethylsilyl group etc. The hydrocarbon group includes linear hydrocarbon groups such as a methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decanyl group; branched hydrocarbon groups such as an isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group and 1-methyl-1-isopropyl-2-methylpropyl group; cyclic saturated hydrocarbon groups such as a cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, methylcyclohexyl group and methyladamantyl group; cyclic unsaturated hydrocarbon groups such as a phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group and anthracenyl group; cyclic unsaturated hydrocarbon group-substituted saturated hydrocarbon groups such as a benzyl group, cumyl group, 1,1-diphenylethyl group and triphenylmethyl group; and heteroatom-containing hydrocarbon groups such as a methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N,N-dimethylamino group, N-phenylamino group, pyryl group and thienyl group. The silicon-containing group can include a trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group etc. The adjacent substituents R⁹ to R¹⁶ on the fluorenyl group may be bound to one another to form a ring. Such substituted fluorenyl group can include a benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group etc.

In the general formula [I], each of R¹ and R³ is preferably a hydrogen atom. R⁶ and/or R⁷ are/is preferably a hydrogen atom, and each of R⁶ and R⁷ is more preferably a hydrogen atom.

In the general formula [I], R² with which the cyclopentadienyl group is substituted is preferably not an aryl group but a hydrogen atom or a C1 to C20 hydrocarbon group. The C1 to C20 hydrocarbon group can be exemplified by the hydrocarbon groups mentioned above. R² is preferably a hydrocarbon group which is preferably a methyl group, ethyl group, isopropyl group or tert-butyl group, particularly preferably a tert-butyl group.

Each of R⁴ and R⁵ is selected from a hydrogen atom, a C1 to C20 alkyl group and an aryl group, and is preferably a C1 to C20 hydrocarbon group. Each of R⁴ and R⁵ is more preferably selected from a methyl group and a phenyl group, and particularly preferably R⁴ and R⁵ represent the same group.

In the general formula [I], each of R⁹, R¹², R¹³ and R¹⁶ on the fluorene ring is preferably a hydrogen atom.

In the general formula [I], M is a transition metal in the IV group, specifically Ti, Zr, Hf etc. Q is selected from the group consisting of a halogen atom, a hydrocarbon group, an anion ligand, and a neutral ligand capable of coordination with a lone pair of electrons. j is an integer of 1 to 4, and when j is 2 or more, Q may be the same or different. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and examples of the hydrocarbon group include those described above. Examples of the anion ligand include an alkoxy group such as methoxy, tert-butoxy, phenoxy etc., a carboxylate group such as acetate, benzoate etc., a sulfonate group such as mesylate, tosylate etc., an amide group such as dimethyl amide, diisopropyl amide, methyl anilide, diphenyl amide etc. Specific examples of the neutral ligand capable of coordination with a lone pair of electrons include organic phosphorus compounds such as trimethyl phosphine, triethyl phosphine, triphenyl phosphine, diphenyl methyl phosphine etc., and ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane etc. At least one of Qs is preferably a halogen atom or an alkyl group.

Examples of the metallocene compound represented by the general formula [I] in the present invention can include [3-(fluorenyl)(1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,1,3,5-tetramethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3,5-tetramethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1,3,5-tetramethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3,5-tetramethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,1-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,1,3-triethyl-2-methyl 5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3-triethyl-2-methyl 5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1,3-triethyl-2-methyl 5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-triethyl-2-methyl 5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,3-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,3-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,3-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,3-dimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,1,3-trimethyl-5-ethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-ethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-ethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-ethyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,1,3-trimethyl-5-trimethylsilyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-trimethylsilyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-trimethylsilyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-trimethylsilyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1-phenyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1-phenyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1-phenyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1-phenyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1-p-tolyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1-p-tolyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1-p-tolyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1-p-tolyl-3-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,3-diphenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,3-diphenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,3-diphenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,3-diphenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,3-diphenyl-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,3-diphenyl-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,3-diphenyl-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,3-diphenyl-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,3-di(p-tolyl)-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,3-di(p-tolyl)-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,3-di(p-tolyl)-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,3-di(p-tolyl)-1-methyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1-methyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1-methyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1-methyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1-methyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) ]zirconium dichloride, [3-(fluorenyl)(1,1-dimethyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1-dimethyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1-dimethyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1-dimethyl-3-phenyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]hafnium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]hafnium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]hafnium dichloride, [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]hafnium dichloride, [3-(fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]titanium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]titanium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]titanium dichloride, and [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]titanium dichloride, among which particularly preferable compounds include [3-(fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, [3-(3′,6′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride, and [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride. The metallocene compound [m] of the present invention is not limited to the above exemplary compounds, and encompasses all compounds satisfying requirements defined in the claims. The position numbers used in the nomenclature of the above compounds are shown in the following formulae [I′] and [I″] by reference to [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride and [3-(2′,7′-di-tert-butylfluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride.

When the method A or B is used in producing the propylene polymer (A) of the present invention, the metallocene compound is not limited to the metallocene compound [m] represented by the general formula [I]. Specifically, when the method B is used, a (co)polymer corresponding to polymer [a1] can be produced in the presence of a polymerization catalyst containing metallocene compound [m′] disclosed in International Application WO2002/074855 filed by the present applicant, and a copolymer corresponding to polymer [a2] can be produced in the presence of a polymerization catalyst containing metallocene compound [m″] disclosed in International Application WO2004/087775 filed by the present applicant. Specifically, when the method A is used, the propylene polymer of the present invention can be obtained by polymerization in step 1 in the presence of a polymerization catalyst containing the metallocene compound [m′] and then charging a polymerizer in step 2 with a polymerization catalyst containing the metallocene compound [m″]. Actually, in the Examples below, isopropyl (3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride was used as [m′], and diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride was used as [m″]. In the present invention, the type of the metallocene compound-containing catalyst and the method of producing the same are not particularly limited insofar as the requirements [1] to [5], preferably the requirements [1′] to [4′] in addition to the requirements [1] to [5], are satisfied by the propylene polymer of the present invention.

When there are continuous production facilities wherein the steps 1 and 2 can be continuously carried out, a direct polymerization method wherein a catalyst containing the metallocene compound [m] represented by the general formula [I] applicable to both the steps 1 and 2 is used in common in the steps 1 and 2 is preferably used because it is economical and mass-production is feasible. On the other hand, when the above continuous production facilities are not present and simultaneously a desired amount of the propylene polymer (A) of the present invention is not large, a blending method using a catalyst containing a metallocene compound selected suitably from the metallocene compound [m], metallocene compound [m′] and metallocene compound [m″] can be used. These will be determined depending on circumstances inherent in manufacturer and consumer.

The metallocene compound of the present invention can be produced by methods known in the art, and the production method is not particularly limited. For example, a compound represented by the general formula [1] can be produced by the following step. The compound represented by the general formula (1), serving as a precursor of the compound represented by the general formula [I], can be produced by the following reaction scheme 1:

In the reaction scheme 1, R¹ to R⁶ and R⁸ to R¹⁶ are the same as in the general formula [I], R⁷ is a hydrogen atom, and L is an alkali metal or alkaline earth metal salt. In the reaction scheme 1, compounds represented by the formula (1), (2) or (5) may be isomers different only in the positions of double bonds in the cyclopentadienyl ring or may be a mixture thereof. In the reaction scheme 1, only one of such compounds is illustrated.

The compound (5) used in the reaction scheme 1 is obtained by reacting a neutral fluorene compound serving as a precursor with an alkali metal compound or an alkaline earth metal compound. The alkali metal compound includes alkyl alkali metals such as alkyl lithium etc. and other lithium salts, sodium salts or potassium salts, and the alkaline earth metal compound includes dialkyl alkaline earth metals and magnesium salts and calcium salts such as magnesium chloride, magnesium bromide, etc.

The compound (4) in the reaction scheme 1 may be produced from a cyclopentadiene derivative and α,β-unsaturated ketone according to a known method (for example, J. Org. Chem., 1989, 54, 4981-4982) or may be produced by a method shown in the following reaction scheme 2:

In the reaction scheme 2, R¹ to R⁶ and R⁸ have the same meaning as defined in the general formula [I]. In the reaction scheme 2, the reaction can be promoted more efficiently by adding a base. The base used may be a known base. Examples of the base include alkali metals such as sodium, potassium, lithium etc., alkali metal or alkaline earth metal salts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, barium hydroxide, sodium alkoxide, potassium alkoxide, magnesium hydroxide, magnesium alkoxide, potassium hydride, sodium hydride etc., nitrogen-containing bases such as diethyl amine, ammonia, pyrrolidine, piperidine, aniline, methyl aniline, triethyl amine, lithium diisopropyl amide, sodium amide etc., organic alkali metal compounds such as butyl lithium, methyl lithium, phenyl lithium etc., and Grignard reagents such as methyl magnesium chloride, methyl magnesium bromide, phenyl magnesium chloride, etc. For efficient progress of the above reaction, phase-transfer catalysts represented by, for example, crown ethers such as 18-crown-6-ether, 15-crown-5-ether etc., cryptants, quaternary ammonium salts such as tetrabutyl ammonium fluoride, methyl trioctyl ammonium chloride, tricapryl methyl ammonium chloride etc., phosphonium salts such as methyl triphenyl phosphonium bromide, tetrabutyl phosphonium bromide etc., and chain polyethers may be added.

One example of the method of producing the metallocene compound [m] represented by the general formula [I] in the present invention from the precursor compound represented by the general formula (I) is shown below, but the present invention is not limited to the following method. The precursor compound represented by the general formula (I), obtained by the reaction scheme 1, is contacted with an alkali metal, an alkali metal hydride, an alkali metal alkoxide, an organic alkali metal or an organic alkaline earth metal in an organic solvent in the range of −80° C. to 200° C., thereby forming a dialkali metal salt. The organic solvent used in this contact step includes aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane and decalin, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether and cyclopentyl methyl ether, halogenated hydrocarbons such as dichloromethane and chloroform, or a mixed solvent of two or more thereof. The alkali metal used in the reaction includes lithium, sodium, potassium etc.; the alkali metal hydride includes sodium hydride, potassium hydride etc.; the alkali metal alkoxide includes sodium methoxide, potassium ethoxide, sodium ethoxide and potassium tert-butoxide; the organic alkali metal includes methyl lithium, butyl lithium and phenyl lithium; the organic alkaline earth metal includes methyl magnesium halide, butyl magnesium halide, phenyl magnesium halide etc.; and these may be used as a mixture of two or more thereof. Then, the di-alkali metal salt obtained above can be converted into a metallocene compound represented by the general formula [I] by reacting it in an organic solvent with a compound represented by the following general formula (8): MZ_k  (8) wherein M is a metal selected from the group IV in the periodic table, Z may be selected in the same or different combination from a halogen atom, an anion ligand, and a neutral ligand capable of coordination with a lone pair of electrons, and k is an integer of 3 to 6. Preferable examples of the compound represented by the general formula (8) can include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide, tetravalent zirconium fluoride, chloride, bromide and iodide, tetravalent hafnium fluoride, chloride, bromide and iodide, and complexes thereof with ethers such as tetrahydrofuran, diethyl ether, dioxane and 1,2-dimethoxyethane. The organic solvent used can include the same organic solvents as described above. In the above reaction, the dialkali metal salt is charged in an amount of 0.7 to 2.0 equivalents, preferably 0.8 to 1.5 equivalents, more preferably 0.9 to 1.2 equivalents, relative to the compound represented by the general formula (8), and the reaction temperature in the organic solvent is in the range of −80° C. to 200° C., more preferably −75° C. to 120° C. The resulting metallocene compound can be isolated and purified by methods such as extraction, recrystallization, sublimation etc. The metallocene compound of the present invention obtained by such method can be identified by analysis methods such as proton nuclear magnetic resonance spectrum, ¹³C nuclear magnetic resonance spectrum, mass spectrometry and elemental analysis.

When the metallocene compounds [m] to [m″] in the present invention are used as a polymerization catalyst component, the catalyst component is composed of the metallocene compound [m] and at least one kind of compound [k] selected from an organoaluminum oxy compound [k-1], a compound [k-2] reacting with the metallocene compound [m] to form an ion pair, and an organoaluminum compound [k-3] (for simplification, [m], [m′] and [m″] are referred to collectively as [m]).

Hereinafter, the respective components are specifically described.

[k-1] Organoaluminum Oxy Compound

As the organoaluminum oxy compound [k-1] in the present invention, conventionally known aluminoxane can be used as it is. Specific examples include compounds represented by the general formula [II]:

and/or the general formula [III]: wherein R is a C1 to C10 hydrocarbon group, and n is an integer of 2 or more. Particularly, methyl aluminoxane wherein R is a methyl group and n is 3 or more, preferably 10 or more, is utilized. Certain amount of organoaluminum compound may be mixed in these aluminoxanes. A characteristic feature of the polymerization method of the present invention is that benzene-insoluble organoaluminum oxy compounds as illustrated in Japanese Patent Application Laid-Open No. 2-78687 can be used. Organoaluminum oxy compounds described in Japanese Patent Application Laid-Open No. 2-167305 and aluminoxane having two or more alkyl groups described in Japanese Patent Application Laid-Open No. 2-24701 and Japanese Patent Application Laid-Open No. 3-103407 can also be suitably used. The “benzene-insoluble” organoaluminum oxy compound used in the polymerization method of the present invention refers to a compound insoluble or sparingly soluble in benzene, wherein the Al component thereof dissolved in benzene at 60° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less, in terms of Al atom.

The organoaluminum oxy compound used in the present invention can also include modified methyl aminosiloxane represented by the following [IV]: wherein R represents a C1 to C10 hydrocarbon group, and m and n each represent an integer of 2 or more.

This modified methyl aluminoxane is prepared by using trimethyl aluminum and alkyl aluminum other than trimethyl aluminum. Such compound [IV] is generally called MMAO. MMAO can be prepared by methods mentioned by U.S. Pat. No. 4,960,878 and U.S. Pat. No. 5,041,584. The compound wherein R is an isobutyl group, prepared by using trimethyl aluminum and triisobutyl aluminum, is commercially produced under the name “MMAO” or “TMAO” by Tosoh Finechem Corporation etc. Such MMAO is conveniently used when the polymerization method of the present invention is carried out in the form of solution polymerization described below because this compound is an aluminoxane which has been improved in solubility in various solvents and in storage stability, and unlike the compounds [II] and [III] insoluble or sparingly soluble in benzene, is characterized by being dissolved in an aliphatic hydrocarbon and an alicyclic hydrocarbon.

The organoaluminum oxy compound used in the polymerization method of the present invention can also include boron-containing organoaluminum oxy compounds represented by the following general formula [V]: wherein R^c represents a C1 to C10 hydrocarbon group; R^ds may be the same or different and each represent a hydrogen atom, a halogen atom or a C1 to C10 hydrocarbon group. [k-2] Compound Reacting with the Crosslinked Metallocene Compound [m] to Form an Ion Pair

The compound [k-2] which reacts with the metallocene compound [m] to form an ion pair (hereinafter referred to sometimes as “ionic compound”) includes Lewis acid, ionic compounds, borane compounds and carborane compounds described in Japanese Patent Application National Publication (Laid-Open) Nos. 1-501950 and 1-502036, Japanese Patent Application Laid-Open No. 3-179005, Japanese Patent Application Laid-Open No. 3-179006, Japanese Patent Application Laid-Open No. 3-207703, Japanese Patent Application Laid-Open No. 3-207704 and U.S. Pat. No. 5,321,106. Further, heteropoly compounds and isopoly compounds can also be mentioned.

The ionic compounds used preferably in the present invention are compounds represented by the following general formula [VI]: wherein R^e+ includes H⁺, a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal, and R^f to Rⁱ may be the same or different and each represent an organic group, preferably an aryl group.

Specific examples of the carbenium cation can include tri-substituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, tris(dimethylphenyl)carbenium cation, etc.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation and triisobutylammonium cation, N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation, and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

R^e+ is preferably a carbenium cation, ammonium cation or the like, particularly preferably triphenylcarbenium cation, N,N-dimethylanilinium cation or N,N-diethylanilinium cation.

Specific examples of the carbenium salt can include triphenyl carbenium tetraphenyl borate, triphenyl carbenium tetrakis(pentafluorophenyl)borate, triphenyl carbenium tetrakis(3,5-difluoromethylphenyl)borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate, etc.

The ammonium salt can include a trialkyl-substituted ammonium salt, N,N-dialkyl anilinium salt, dialkyl ammonium salt etc.

Specific examples of the trialkyl-substituted ammonium salt can include triethyl ammoniumtetraphenyl borate, tripropyl ammoniumtetraphenylborate, tri(n-butyl)ammoniumtetraphenyl borate, trimethyl ammonium tetrakis (p-tolyl)borate, trimethyl ammonium tetrakis(o-tolyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethyl ammonium tetrakis(pentafluorophenyl)borate, tripropyl ammonium tetrakis(pentafluorophenyl)borate, tripropyl ammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium tetrakis(o-tolyl)borate, dioctadecyl methyl ammoniumtetraphenyl borate, dioctadecyl methyl ammonium tetrakis(p-tolyl)borate, dioctadecyl methyl ammonium tetrakis(o-tolyl)borate, dioctadecyl methyl ammonium tetrakis(pentafluorophenyl)borate, dioctadecyl methyl ammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecyl methyl ammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethyl ammonium tetrakis (4-trifluoromethylphenyl)borate, dioctadecyl methyl ammonium tetrakis(3,5-ditrifluoromethylphenyl)borate, dioctadecyl methyl ammonium, etc.

Specific examples of the N,N-dialkylanilinium salt can include N,N-dimethylanilinium tetraphenyl borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium tetraphenyl borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-2,4,6-pentamethylanilinium tetraphenyl borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, etc.

Specific examples of the dialkylammonium salt can include (1-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenyl borate, etc.

In addition, ionic compounds disclosed by the present applicant (Japanese Patent Application Laid-Open No. 2004-51676) can also be used without limitation.

The ionic compounds (b-2) described above can be used as a mixture of two or more thereof.

[k-3] Organoaluminum Compound

The organoaluminum compound [k-3] constituting the polymerization catalyst can include, for example, an organoaluminum compound represented by the general formula [VII] below and a complex alkylated compound consisting of the group I metal and aluminum, represented by the general formula [VIII] below. R^a_mAl(OR^b)_nH_pX_q  [VII] wherein R^a and R^b may be the same or different and each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number of 0<m≦3, n is a number of 0<n≦3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3.

Specific examples of such compounds include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum and trioctylaluminum; tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydride such as diisopropylaluminum hydride and diisobutylaluminum hydride; alkenylaluminum such as isoprenylaluminum represented by the general formula (i-C₄H₉)_xAl_y(C₅H₁₀)_z (wherein x, y and z are positive number, and z≦2x); alkylaluminum alkoxide such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminum having an average composition represented by R^a_2.5Al(OR^b)_0.5 (wherein R^a and R^b have the same meanings as defined in the general formula [VII] above) or the like; alkylaluminum aryloxide such as diethylaluminum phenoxide and diethylaluminum (2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halide such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; alkylaluminum sesquihalide such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride; dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminum such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminumbutoxychloride, and ethylaluminum ethoxybromide. M^aAlR^a₄  [VIII] wherein M² represents Li, Na or K, and R^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

Examples of such compounds include LiAl(C₂H₅)₄, LiAl(C₇H₁₅)₄ etc.

Alternatively, compounds similar to the compound represented by the general formula [VIII] may also be used, and examples thereof include organoaluminum compounds in which two or more aluminum compounds are bound to each other via a nitrogen atom. Specific examples of such compounds include (C₂H₅)₂AlN(C₂H₅)Al(C₂H₅)₂.

From the viewpoint of polymerization performance and availability, trimethyl aluminum, triethyl aluminum and triisobutyl aluminum are preferably used as the organoaluminum compound [k-3].

In the polymerization method of the present invention, the olefin polymerization catalyst described above may be used after being supported on particulate support [s]. Particularly in bulk polymerization using a supported catalyst used in the Examples shown later, the catalyst is utilized preferably in a form supported on the particulate catalyst support [s].

The catalyst support [s] is an inorganic or organic compound in the form of granular or microparticulate solid. The inorganic compound is preferably a porous oxide, inorganic halide, clay, clay mineral, or ion-exchangeable layered compound.

Specific examples of the porous oxide used include SiO₂, Al₂O₃, MgO, ZrO, TiO₂, B₂O₃, CaO, ZnO, BaO and ThO₂ or complexes or mixtures containing them, for example natural or synthetic zeolite, SiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr₂O₃ and SiO₂—TiO₂—MgO. Among these, those based on SiO₂ and/or Al₂O₃ are preferable.

The above inorganic oxide may contain a small amount of carbonates, sulfates, nitrates and oxide components such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂ (SO₄)₃, BaSO₄, KNO₃, Mg (NO₃)₂, Al(NO₃)₃, Na₂O, K₂O, Li₂O etc.

As the inorganic halide, MgCl₂, MgBr₂, MnCl₂, MnBr₂ etc. are used. The inorganic halide may be used as it is or may be used after milling with a ball mill, a vibration mill or the like. Fine particles of the inorganic halide obtained by dissolving the inorganic halide in a solvent such as alcohol and then precipitating it with a precipitator can also be used.

The clay is composed usually of clay mineral as a major component. The ion-exchangeable layered compound is a compound having a crystal structure wherein faces constituted by ionic bonding etc. are layered in parallel by weak bonding force, and ions contained therein are exchangeable with one another. A majority of clay minerals are ion-exchangeable layered compounds. These clays, clay minerals and ion-exchangeable layered compounds are not limited to natural products, and artificially synthesized products can also be used.

The clays, clay minerals or ion-exchangeable layered compounds can be exemplified by clays, clay minerals, and ionic crystalline compounds having a layered crystal structure of hexagonal close packing type, antimony type, CdCl₂ type or CdI₂ type.

Such clays and clay mineral include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, mica group, montmorilonite group, vermiculite, chlorite group, palygorskite, kaolinite, nacrite, dickite, halochite etc., and the ion-exchangeable layered compounds include crystalline acidic salts of multivalent metals, such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂, α-Zr(KPO₄)₂.3H₂O, α-Ti(HPO₄)₂, α-Ti(HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O, γ-Zr(HPO₄)₂, γ-Ti(HPO₄)₂, γ-Ti(NH₄PO₄)₂.H₂O etc.

Such clays, clay minerals or ion-exchangeable layered compounds are those wherein the volume of voids having a radius of 20 Å or more is preferably at least 0.1 cc/g, more preferably 0.3 to 5 cc/g, as determined by porosimetry. The void volume is measured in the radius range of 20 to 3×10⁴ Å by porosimetry using a mercury porosimeter.

When a material wherein the volume of voids having a radius of 20 Å or more is less than 0.1 cc/g is used as a catalyst support, high polymerization activity tends to be hardly obtained.

The clays and clay minerals are preferably subjected to chemical treatment.

As chemical treatment, any treatment such as surface treatment for removing impurities adhering to a surface and treatment for giving an influence to a crystal structure of clay can be used. Specifically, the chemical treatment includes acid treatment, alkali treatment, salt treatment, organic material treatment etc. The acid treatment brings about not only removal of impurities from a surface, but also an increase in surface area by eluting cations such as Al, Fe, Mg etc. in a crystal structure. The alkali treatment brings about a change in a clay structure by destroying a crystal structure of clay.

By the salt treatment or organic substance treatment, a surface area and a distance between layers can be changed by forming an ion complex, a molecular complex, an organic derivative etc.

The ion-exchangeable layered compound may be a layered compound in such a state that the distance between layers is increased by exchanging exchangeable ions between the layers with other larger bulky ions by utilizing its ion exchangeability.

Such bulky ions play a role as a pillar for supporting the layered structure, and is usually called a pillar. Such introduction of other substances into between layers in the layered compound is called intercalation. A guest compound subjected to intercalation includes cationic inorganic compounds such as TiCl₄ and ZrCl₄, metal alkoxides such as Ti(OR)₄, Zr(OR)₄, PO(OR)₃ and B(OR)₃ (wherein R is a hydrocarbon group or the like), and metal hydroxide ions such as [Al₁₃O₄(OH)₂₄]⁷⁺, [Zr₄(OH)₁₄]²⁺ and [Fe₃O(OCOCH₃)₆]⁺. These compounds are used alone or as a mixture of two or more thereof. For intercalation of these compounds, polymeric products obtained by hydrolyzing metal alkoxides such as Si(OR)₄, Al(OR)₃ and Ge(OR)₄ (wherein R is a hydrocarbon group or the like) or colloidal inorganic compounds such as SiO₂ can be coexistent. The pillar includes oxides formed by thermal dehydration after intercalation of the metal hydroxide ions into between layers.

The clays, clay minerals and ion-exchangeable layered compounds may be used as such, or may be used after treatment by a ball mill, sifting etc. These materials may be used after addition and adsorption of new water or after thermal dehydration treatment. These materials may be used alone or as a mixture of two or more thereof.

When ion-exchangeable layered silicate is used, not only the function thereof as a catalyst support but also its ion-exchanging property and layered structure can be utilized to reduce the amount of the used organic aluminum oxy compound such as alkyl aluminoxane. The ion-exchangeable layered silicate is produced mainly as a main component of clay mineral, but is not limited to natural products and may be artificial synthetic compounds. Specific examples of clays, clay minerals and ion-exchangeable layered silicates can include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, taeniolite, synthetic mica, synthetic hectorite etc.

The organic compound includes granular or microparticulate solids having a particle diameter in the range of 5 to 300 μm. Specific examples include (co)polymers formed from C2 to C14 α-olefins such as ethylene, propylene, 1-butene and 4-methyl-1-pentene as major components, (co)polymers formed from vinyl cyclohexane and styrene as major components, and polymers or modified products thereof having polar functional group obtained by copolymerizing or graft-polymerizing polar monomers such as acrylic acid, acrylates, maleic anhydrides etc. with the copolymer or above polymers. These particulate supports can be used alone or as a mixture of two or more thereof.

If necessary, the olefin polymerization catalyst according to the present invention can also contain a specific organic compound component [q]. In the present invention, the organic compound component [q] is used as necessary for the purpose of improving polymerization performance and physical properties of the polymer formed. Such organic compounds include alcohols, phenolic compounds, carboxylic acid, phosphorous compounds and sulfonates.

In polymerization, the usage and addition order of the components [m], [k] and [s] constituting the polymerization catalyst are arbitrarily selected and can be exemplified by the following method. (The following exemplary method involves feeding the catalyst components into a single polymerizer. A method of feeding the catalyst components into two or more polymerizers arranged in series, such as a method used in a direct polymerization method, is in accordance with a method of feeding into a single polymerizer.)

(1) Method of adding the component [m] alone to a polymerizer

(2) Method of adding the components [m] and [k] in an arbitrary order to a polymerizer

(3) Method of adding a catalyst component comprising the component [m] supported by support [s], and the component [k], in an arbitrary order to a polymerizer

(4) Method of adding a catalyst component comprising the component [k] supported by support [s], and the component [m], in an arbitrary order to a polymerizer

(5) Method of adding a catalyst component comprising the components [m] and [k] supported by support [s] to a polymerizer

In each of the methods (2) to (5), at least two of the catalyst components may be previously contacted with each other. In the methods (4) and (5) using the supported component [k], unsupported components [k] may be added if necessary in an arbitrary order. In this case, the components [k] may be the same or different. Olefins may be previously polymerized in the solid catalyst component having the component [m] supported by the component [s] or the solid catalyst component having the components [m] and [k] supported by the component [s]. The olefins used in preliminary polymerization can be arbitrarily in the form of a single C2 to C6 olefin or a mixture of C2 to C6 olefins, and usually ethylene is preferably used. The amount of the olefins preliminarily polymerized varies depending on the olefin species, but is usually 0.01 to 100 g, preferably 0.05 to 50 g, per g of the solid catalyst component. A catalyst component may be further carried on the preliminarily polymerized solid catalyst component. (In the following description, “preliminary polymerization” is referred to as “pre-polymerization”, and “preliminarily polymerized solid catalyst component” is referred to sometimes as “pre-polymerization catalyst”.)

In the present invention, propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins are polymerized or copolymerized thereby giving the propylene polymer [A] of the present invention.

The polymerization in the present invention can be carried out by liquid-phase polymerization such as solution polymerization or suspension polymerization or by gaseous-phase polymerization. Examples of inert hydrocarbon solvents used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene dichloride, chlorobenzene and dichloromethane, or mixtures thereof. Bulk polymerization using liquefied olefin itself as solvent can also be used.

When the polymerization catalyst described above is used in polymerization, the component (A) is used usually in an amount of 10⁻⁹ to 10⁻² mole, preferably 10⁻⁸ to 10⁻³ mole, per L of the reaction volume. The component [k-1] is used in such an amount that the molar ratio of the component [k-1] to the total transition metal atom (M) in the component [m] ([k-1]/M) is usually 0.01 to 5,000, preferably 0.05 to 2,000. The component [k-2] is used in such an amount that the molar ratio of the aluminum atom in the component [k-2] to the total transition metal (M) in the component [m] ([k-2]/M) is usually 10 to 5,000, preferably 20 to 2,000. The component [k-3] is used in such an amount that the molar ratio of the component [k-3] to the transition metal atom (M) in the component [m] ([k-3]/M) is usually 1 to 3,000, preferably 1 to 500. The component [q] is used in such an amount that when the component [k] is the component [k-1], the molar ratio ([q]/[k-1]) is usually 0.01 to 10, preferably 0.1 to 5; when the component [k] is the component [k-2], the molar ratio ([q]/[k-2]) is usually 0.01 to 2, preferably 0.005 to 1; and when the component [k] is the component [k-3], the molar ratio ([q]/[k-3]) is usually 0.01 to 10, preferably 0.1 to 5.

The polymerization temperature with the polymerization catalyst is usually in the range of −50° C. to +200° C., preferably 0 to 170° C. The polymerization pressure is usually normal pressures to 10 MPa gauge pressure, preferably normal pressures to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any methods in a batch, semi-continuous or continuous system. The polymerization reaction can be carried out in two or more stages different in reaction conditions. In the “direct polymerization method” described above, a multistage polymerization method wherein polymerizers different in reaction conditions are connected in series is preferably adopted. The molecular weight of the obtained propylene polymer can be regulated by allowing hydrogen molecules to be present in the polymerization system or by changing the polymerization temperature. Further, the molecular weight can be regulated by changing the amount of the component [k] used. When hydrogen molecules are added, the amount thereof is appropriately about 0.001 to 100 NL per kg of the formed propylene polymer.

The propylene polymer [A] of the present invention is composed of a skeleton derived from propylene (MP) as an essential skeleton and a skeleton derived from at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins. Among the C4 or more α-olefins, “preferable α-olefins” are as previously illustrated, but when the propylene polymer [A] of the present invention is used in a field where the adhesion thereof to metal or polar resin is required, in a field where high-dimensional transparency is required, or in a field where carbon-carbon double bonds are desired to remain in a polymer molecule, it is possible to mention, in addition to the previously described “preferable α-olefins” as the olefin source, C3 to C30, preferably C3 to C20, cyclic olefins, for example cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polar monomers, for example α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, and metal salts thereof such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt, aluminum salt etc.; α,β-unsaturated carboxylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate etc.; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprinate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate etc.; and unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate etc. Further, the polymerization can also proceed in the reaction system in the coexistence of aromatic vinyl compounds such as vinyl cyclohexane, diene or polyene, for example styrene and mono- or polyalkyl styrene such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o,p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene etc.; functional group-containing styrene derivatives such as methoxy styrene, ethoxy styrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinyl benzene etc.; 3-phenylpropylene, 4-phenylpropylene, a-methyl styrene etc.; α,β-nonconjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene etc.; nonconjugated dienes such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene etc.; conjugated dienes such as butadiene, isoprene etc.; nonconjugated trienes such as 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, 5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND), 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene and 4-ethylidene-1,7-undecadiene; and conjugated trienes such as 1,3,5-hexatriene (the above olefins which, depending on applications, are used in combination with propylene and “preferable α-olefins” are referred to sometimes as “arbitrary olefins).

When the arbitrary olefins are also used in the polymerization reaction according to the present invention, the used amount thereof is usually within the range of 0.001 to 20 mol %, preferably 0.001 to 10 mol %, based on the total olefins fed.

The propylene polymer (A) of the present invention, when viewed from the substance, is composed of n-decane insoluble part (D_insol) and n-decane soluble part (D_sol), and when viewed from the production method, is composed of a (co)polymer (=polymer [a1]) corresponding substantially to n-decane insoluble part (D_insol) and a copolymer (=polymer [a2]) corresponding substantially to n-decane soluble part (D_sol), as described above. Hereinafter, the methods of producing these respective components are described in detail by reference to the process of producing them.

In the methods A and B, the olefin used in production of the polymer [a1] is propylene (MP) and if necessary at least one kind of olefin (MX) selected from ethylene and the C4 or more α-olefins. When at least one kind of olefin (MX) selected from ethylene and the C4 or more α-olefins is used in addition to propylene, the amount of MX used in polymerization reaction is 0.0003 to 0.04 mole, preferably 0.0003 to 0.02 mole, more preferably 0.0003 to 0.012 mole, per mole of propylene (MP). A preferable aspect of the olefin source is propylene (MP) and if necessary at least one kind of olefin selected from ethylene and the C4 or more α-olefins, more preferably propylene (MP) and if necessary ethylene. A particularly preferable aspect in the intended use of the invention is propylene (MP) alone. By the method described above, the polymer [a2] wherein room-temperature n-decane soluble part (D_sol) is 0.5 wt % or less, preferably 0.4 wt % or less, can be obtained.

In the methods A and B, the olefin used in production of the polymer [a2] is propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins. The amount of MX used in the polymerization reaction is 0.12 to 9.0 moles, preferably 0.20 to 7.5 moles, more preferably 0.28 to 6.0 moles, per mole of propylene (MP) used. A preferable aspect of the olefin source is propylene (MP) and ethylene. By the method described above, the polymer [a2] wherein room-temperature n-decane insoluble part (D_insol) is 5.0 wt % or less, preferably 4.0 wt % or less, can be obtained.

In the method B, the polymers [a1] and [a2] are polymerized separately in the same polymerizer or different polymerizers, if necessary followed by known post-treatment steps such as a catalyst inactivation treatment step, a catalyst residue eliminating step and a drying step, and the resulting two polymers are blended by a physical means. The blending ratio of the respective polymers to be blended, in terms of (weight of [a1])/(weight of [a2]), is usually 60/40 to 90/10, preferably 70/30 to 90/10. The physical blend comprises a combination of different kinds of polymers, which is attributable to specific interaction of the polymers. The physical blending method can include, for example, a melt blending method. The melt blending method is a method wherein the polymers are kneaded mechanically while they are plasticized by heating with a mixing roll, a Banbury mixer, a single- or twin-screw extruder or the like. The melting conditions for blending in the method B in the present invention are not particularly limited insofar as the two polymers [a1] and [a2] are made sufficiently compatible with each other to such an extent that the performance is not inhibited in applications intended by the present invention, and for example, a method of melt-kneading at 180 to 250° C. in a twin-screw extruder can be mentioned.

The amounts of the polymers produced in the steps 1 and 2 in the method A are described in the following example. In this example, the propylene polymer is produced by continuously conducting the two steps, that is, (1) a step of producing a propylene homopolymer (=step 1) and a step of producing a propylene/α-olefin copolymer (=step 2). The following example is 3-stage polymerization wherein the first step is carried out in 2 stages and the second step is carried out in 1 stage. That is, it is preferable that the propylene homopolymer is produced in the first stage at a polymerization temperature of 0 to 100° C. at a polymerization pressure of normal pressure to 5 MPa gauge pressure and then produced in the second stage at a polymerization temperature of 0 to 100° C. at a polymerization pressure of normal pressure to 5 MPa gauge pressure such that the content thereof in the resulting polypropylene resin becomes 90 to 60 wt % in total of the first and second stages, and the propylene/α-olefin copolymer is produced in the third stage at a polymerization temperature of 0 to 100° C. at a polymerization pressure of normal pressure to 5 MPa gauge pressure such that the content of the finally obtained propylene polymer becomes 10 to 40 wt %. As illustrated in the above example, the step 1 or 2 in the method B in the present invention may be composed of two or more polymerization stages. After the polymerization is finished, the propylene polymer is obtained as powder by carrying out known post-treatment steps such as a catalyst inactivation treatment step, a catalyst residue eliminating step and a drying step. The propylene polymer produced as described above is blended if necessary with various additives such as an antioxidant, an UV absorber, an antistatic agent, a nucleating agent, a lubricant, a flame-retardant, an anti-blocking agent, a colorant, inorganic or organic fillers, and various kinds of synthetic resin, then melt-kneaded and pelletized into pellets to be subjected to production of various molded products.

Thermoplastic Resin Composition (B) Comprising the Propylene Polymer (A)

The thermoplastic resin composition (B) of the present invention is a resin composition comprising the propylene polymer (A) of the present invention and at least one component selected from propylene resin (P), elastomer (Q) and inorganic filler (R). The propylene resin (P) in the present invention refers to a propylene homopolymer different from the propylene polymer (A) of the present invention or to a propylene/ethylene copolymer, a propylene/α-olefin copolymer, a propylene/ethylene block copolymer, a propylene/α-olefin block copolymer, etc. The α-olefin used herein can be exemplified by the same α-olefin as used in producing the propylene polymer of the present invention. The type of the catalyst for producing the propylene resin (P) is not particularly limited and a Ziegler-Natta catalyst may be used insofar as the melting point (Tm) of the resulting propylene polymer (P) is 150 to 170° C., preferably 155 to 167° C. and the melt flow rate (MFR: ASTM D1238, 230° C., loading 2.16 kg) of the resulting polymer (P) is 0.3 to 200 g/10 min., preferably 2 to 150 g/10 min., more preferably 10 to 100 g/10 min.

The elastomer (Q) includes an ethylene/α-olefin random copolymer, an ethylene/α-olefin/nonconjugated polyene random copolymer, a hydrogenated block copolymer, other elastic polymers and a mixture thereof. The fillers (R) include talc, clay, calcium carbonate, mica, silicates, carbonates and glass fiber each having an average particle diameter of 1 to 5 μm.

The compounding ratio of the respective components constituting the thermoplastic resin composition (B) of the present invention is determined according to the intended use of the thermoplastic resin composition (B) and is not determined unambiguously, but the percentage of the propylene polymer (A) in the thermoplastic resin composition (B) is preferably at least 10 wt % to exhibit the effect of the propylene polymer (A) of the present invention.

In a preferable aspect, the thermoplastic resin composition (B) of the present invention is a propylene resin composition (B1) comprising 20 to 98 wt % propylene polymer (A), 1 to 40 wt % elastomer (Q) and 1 to 40 wt % inorganic filler (R), provided that the total amount of the components (A), (Q) and (R) is 100 wt %. Hereinafter, the elastomer (Q) and the inorganic filler (R) among the components constituting the propylene resin composition (B1) are described in this order.

Elastomer (Q)

The elastomer (Q) includes an ethylene/α-olefin random copolymer (Q-a), an ethylene/α-olefin/nonconjugated polyene random copolymer (Q-b), a hydrogenated block copolymer (Q-c), other elastic polymers and a mixture thereof.

From the viewpoint of impact strength and rigidity, the content of the elastomer (Q) is 1 to 40 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight.

The ethylene/α-olefin random copolymer (Q-a) is a random copolymer rubber consisting of ethylene and a C3 to C20 α-olefin. The C3 to C20 α-olefin includes the same α-olefin as used in production of the propylene polymer (A) of the present invention described above. In the ethylene/α-olefin random copolymer (Q-a), the molar ratio of the ethylene-derived skeleton to the α-olefin-derived skeleton (ethylene-derived skeleton/α-olefin-derived skeleton) is desirably 95/5 to 15/85, preferably 80/20 to 25/75. The MFR of the ethylene/α-olefin random copolymer (Q-a) at 230° C. under a loading of 2.16 kg is desirably at least 0.1 g/10 minutes, preferably 0.5 to 10 g/10 minutes.

The ethylene/α-olefin/nonconjugated polyene random copolymer (Q-b) is a random copolymer rubber consisting of ethylene, a C3 to C20 α-olefin and a nonconjugated polyene. The C3 to C20 α-olefin includes the same as described above. The nonconjugated polyene includes acyclic dienes such as 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and norbornadiene; linear nonconjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene and 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene. Among those described above, 1,4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene are preferably used. In the ethylene/α-olefin/nonconjugated polyene random copolymer (Q-b), the molar ratio of the ethylene-derived skeleton, the α-olefin-derived skeleton and the nonconjugated polyene-derived skeleton (ethylene-derived skeleton/α-olefin-derived skeleton/nonconjugated polyene-derived skeleton) is desirably 94.9/5/0.1 to 30/45/25, preferably 89.5/10/0.5 to 40/40/20. The MFR of the ethylene/α-olefin/nonconjugated polyene random copolymer (Q-b) at 230° C. under a loading of 2.16 kg is desirably at least 0.05 g/10 minutes, preferably 0.1 to 10 g/10 minutes. Specific examples of the ethylene/α-olefin/nonconjugated polyene random copolymer (Q-b) include an ethylene/propylene/diene ternary copolymer (EPDM) etc.

The hydrogenated block copolymer (Q-c) is a hydrogenated product of a block copolymer having a block represented by the following formula (a) or (b) and the amount of hydrogen added is 90 mol % or more, preferably 95 mol % or more: X(YX)_n  (a) (XY)_n  (b)

A monovinyl-substituted aromatic hydrocarbon constituting the polymer block represented by X in the formula (a) or (b) includes styrene and styrene derivatives such as α-methyl styrene, p-methyl styrene, chlorostyrene, lower alkyl-substituted styrene, vinyl naphthalene etc. These can be used alone or as a mixture of two or more thereof. The conjugated diene constituting a polymer block represented by Y in the formula (a) or (b) includes butadiene, isoprene, chloroprene etc. These can be used alone or in combination with two or more thereof. n is an integer of 1 to 5, preferably 1 or 2. Specific examples of the hydrogenated block copolymer (Q-c) include a styrene/ethylene/butane/styrene block copolymer (SEBS), a styrene/ethylene/propylene/styrene block copolymer (SEPS) and a styrene/ethylene/propylene block copolymer (SEP). The block copolymer before hydrogenation can be produced by a method of block copolymerization in the presence of a lithium catalyst or a Ziegler catalyst in an inert solvent. The production method is described in detail in, for example, Japanese Published Examined Application No. 40-23798. The hydrogenation treatment can be carried out in the presence of a known hydrogenation catalyst in an inert solvent. The method is described in detail in, for example, Japanese Published Examined Application No. 42-8704, Japanese Published Examined Application No. 43-6636 and Japanese Published Examined Application No. 46-20814. When butadiene is used as the conjugated diene monomer, the proportion of 1,2-bond in the polybutadiene block is desirably 20 to 80 wt %, preferably 30 to 60 wt %. As the hydrogenated block copolymer (Q-c), a commercially available product can also be used. Specific examples include Clayton G1657 (registered trademark) (manufactured by Shell Chemicals Limited), Septone 2004 (registered trademark) (manufactured by Kuraray Co., Ltd.), Toughtec H1052 (registered trademark) (manufactured by Asahi Kasei Corporation) etc. The elastomers (Q) can be used alone or in combination of two or more thereof.

Inorganic Filler (R)

The inorganic filler (R) includes talc, clay, calcium carbonate, mica, silicates, carbonates, glass fiber etc. Among these, talc and calcium carbonate are preferable, and talc is particularly preferable. The average particle diameter of talc is desirably in the range of 1 to 5 μm, preferably 1 to 3 μm. The fillers can be used alone or as a mixture of two or more thereof. The content of the inorganic filler (R) is 1 to 40 wt %, preferably 3 to 30 wt %, more preferably 5 to 25 wt %.

The propylene resin composition (B) of the present invention may further contain the propylene polymer (P) in an amount of 30 wt % or less, preferably 25 wt % or less, based on the propylene resin composition (B1).

The thermoplastic resin composition (B) obtained in the manner as described above, preferably the propylene resin composition (B1), is blended if necessary with various additives such as an antioxidant, an UV absorber, an antistatic agent, a nucleating agent, a lubricant, a flame-retardant, an anti-blocking agent, a colorant, inorganic or organic fillers, and various kinds of synthetic resin, then melt-kneaded and pelletized into pellets to be subjected to production of various molded products.

Use of Propylene Copolymer (A) and Resin Composition (B)

The propylene polymer (A) of the present invention satisfies the requirements [1] to [5] described above and can thus be used in production of various molded products. Specifically, the molded products include an injection-molded product (C1) obtained by molding the propylene polymer (A), a film (D1) obtained by molding the propylene polymer (A), a sheet (E1) obtained by molding the propylene polymer (A) and a blow-molded container (F1) obtained by molding the propylene polymer (A), and these various molded products are within the scope of the claims of the present invention. When the propylene polymer (A) of the present invention is applied for use in film, particularly for use as a material for film or sheet constituting a retort pouch, the performance of the propylene polymer (A) can be exhibited sufficiently. Specifically, when the propylene polymer (A) of the present invention is formed into a film by a molding method such as casting molding, the film shows excellent properties such as 1) excellent transparency, 2) high Young's modulus at high temperatures (for example at 60° C.), 3) excellent impact at low temperatures (for example at −10° C.), and 4) high heat-sealing strength. The film showing such properties are useful as a sealant of a laminate film for high retort and can be expected to contribute to considerable development of retort pouch industry in the future. However, applications of the propylene polymer (A) of the present invention are not limited to the retort film and can be used widely in fields requiring at least one performance among the above-mentioned 1) to 4).

On the other hand, the thermoplastic resin composition (B) and the propylene resin composition (B1) in the present invention, when utilized mainly in application to injection molding and particularly used in the field of automotive material, can be expected to contribute to tremendous development of the field of automotive material in the future because they contain the propylene polymer (A) of the present invention and the specific elastomer (Q) in a specific ratio and thus their product is excellent in tensile elongation, hardness and brittle temperature and also excellent in balance among these physical properties. The “automotive material” refers specifically to automobile interior parts such as door trim, instrument panel etc. and automotive elements for example automotive exterior parts such as bumper, mudguard etc.

The propylene polymer (B) and the thermoplastic resin composition of the present invention are also used preferably in blow-molded containers. Such blow-molded containers are molded products excellent in outward appearance such as surface gloss etc. and excellent in mechanical strength and are thus used preferably not only in solid-detergent containers but also in containers for liquid detergent and face lotion and containers for food and drinking water.

EFFECT OF THE INVENTION

The propylene polymer (A) of the present invention is a polymer consisting of n-decane insoluble part (D_insol) having a high melting point, that is, a propylene homopolymer part, and n-decane soluble part (D_sol) having high intrinsic viscosity [η], that is, a copolymer part consisting essentially of a propylene-derived skeleton, and which satisfies the above requirements [1] to [5], and thus when molded into various molded products, shows performance not present in the conventional material in respect of (1) heat resistance, (2) transparency, (3) impact strength, (4) elastic modulus (Young's modulus, flexural modulus), and (5) adhesion. Specifically, the propylene polymer (A) maintains the same performance as achieved by the conventional material in respect of the specified items among (1) to (5) and further exhibits significant improvements in other specific items. As a matter of course, the various molded products described above generally have required performance inherent in the type of the molded products. Under such condition, an invention of a material improving only specific performance at the sacrifice of a certain performance (that is, at the cost of a certain performance, thus resulting in deterioration in the performance) cannot be said to contribute to industrial development, and an invention attempting at partial improvement of specific performance while maintaining the whole performance, such as the present invention, can contribute truly to industrial development.

Hereinafter, the present invention is described specifically by reference to the Examples, but the present invention is not limited by such examples. The analysis methods used in the present invention are as follows:

[m1] Amount of Room-Temperature N-decane Soluble Part (D_sol)

5 g of the final product (that is, the propylene polymer of the present invention) was added to 200 ml n-decane and then dissolved by heating at 145° C. for 30 minutes. This sample was cooled over about 3 hours to 20° C. and left for 30 minutes. Thereafter, a precipitate (referred to hereinafter as n-decane insoluble part (D_insol)) was separated by filtration. The filtrate was introduced into acetone in an amount about 3 times that of the filtrate, whereby the component dissolved in n-decane was precipitated. Precipitate (A) was separated by filtration from the acetone and then dried. When the filtrate was concentrated into dryness, no residues were recognized. The amount of n-decane soluble part was determined according to the following equation: Amount of n-decane soluble part(wt %)=[weight of precipitate(A)/weight of the sample]×100 [m2] Measurement of Mw/Mn [Weight-Average Molecular Weight (Mw)/Number-Average Molecular Weight (Mn)]

Using GPC-150C Plus manufactured by Waters Corporation, Mw/Mn was determined in the following manner. As columns for separation, TSK gel GMH6-HT and TSK gel GMH6-HTL were used, and their column sizes were 7.5 mm in inner diameter and 600 mm in length respectively, and the column temperature was 140° C., and o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) was used as the mobile phase and transferred at 1.0 ml/min. with 0.025 wt % BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant. The concentration of a sample was 0.1 wt %, and the volume of the sample injected was 500 μL, and a differential refractometer was used as the detector. Standard polystyrene having a molecular weight of Mw<1,000 and Mw>4×10⁶ was a product of Tosoh Corporation, and standard polystyrene having a molecular weight of 1,000≦Mw≦4×10⁶ was a product of Pressure Chemical Company, to determine PP-equivalent molecular weight by an universal calibration method. The Mark-Houwink coefficients of PS and PP used were values described in a literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976).

[m3] Melting Point (Tm)

Melting point was measured by using a differential scanning calorimeter (DSC, manufactured by PerkinElmer, Inc.). An endothermic peak in the third step was defined as melting point (Tm).

(Measurement Conditions)

First step: Temperature rising at 10° C./min to 240° C. and keeping 240° C. for 10 minutes.

Second step: Temperature falling at 10° C./min to 60° C.

Third step: Temperature rising at 10° C./min to 240° C.

[m4] Measurement of 2,1-Bond Content and 1,3-Bond Content

A sample, 20 to 30 mg, was dissolved in 0.6 ml mixed solvent of 1,2,4-trichlorobenzene/deuterated benzene (2:1) and then subjected to carbon nuclear magnetic resonance analysis (¹³C-NMR). The following partial structures containing positionally irregular units based on 2,1-insertion and 1,3-insertion are represented by the following (i) and (ii):

The monomer formed by 2,1-insertion forms a positionally irregular unit represented by the above partial structure (i) in a polymer chain. The frequency of insertion of 2,1-propylene monomer, based on insertion of every propylene, was calculated according to the following equation. Proportion (%) of positionally irregular unit based on 2,1-insertion={0.5×[area of methyl group(16.5-17.5 ppm)]/[ΣICH₃+(Iαδ+Iβγ)/4]}×100

In this equation, ΣICH₃ represents the area of every methyl group. Iαδ and Iβδ each represent the area of αδ peak (resonating in the vicinity of 37.1 ppm) and the area of βγ peak (resonating in the vicinity of 27.3 ppm), respectively. Designation of these methylene peaks were in accordance with a method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781).

Similarly, the frequency of insertion of 1,3-propylene monomer represented by the partial structure (ii), based on insertion of every propylene, was calculated according to the following equation: Proportion(%) of positionally irregular unit based on 1,3-insertion=[(Iαδ+Iβγ)/4]/[ΣICH₃+(Iαδ+Iβγ)/4]×100 [m5] Intrinsic Viscosity [η]

Intrinsic viscosity was measured at 135° C. in a decalin solvent. About 20 g sample was dissolved in 15 ml decalin and measured for its specific viscosity η_sp in an oil bath at 135° C. This decalin solution was diluted with additional 5 ml decalin solvent and then measured for its specific viscosity η_sp in the same manner as above. This diluting procedure was repeated further twice, and the value of η_sp/C upon extrapolation of concentration (C) to 0 was determined as the intrinsic viscosity. [η]=lim(η_sp/C)(C→0) [m6] Content of Ethylene-Derived Skeleton

For measurement of the concentration of ethylene-derived skeletons in D_insol and D_sol, 20 to 30 mg sample was dissolved in 0.6 ml mixed solvent of 1,2,4-trichlorobenzene/deuterated benzene (2:1) and then subjected to carbon nuclear magnetic resonance analysis (¹³C-NMR). Propylene, ethylene and α-olefin were quantified by diad chain distribution. For example, in the case of propylene-ethylene copolymer, PP=S_αα, EP=S_αγ+S_αβ, and EE=½(S_βδ+S_δδ)+¼S_γδ were used to determine the content of ethylene-derived skeletons by the following equations (Eq-1) and (Eq-2): Propylene(mol %)=(PP+½EP)×100/[(PP+½EP)+(½EP+EE) Ethylene(mol %)=(½EP+EE)×100/[(PP+½EP)+(½EP+EE)

In the Examples, the amount of ethylene and α-olefin in D_insol was shown in terms of wt %.

[m7] MFR (Melt Flow Rate)

MFR was measured according to ASTM D1238 (230° C., loading 2.16 kg).

[m8] Tensile Test of Injection-Molded Product (Breaking Elongation)

The tensile test was carried out according to ASTM D638.

<Measurement Conditions>

Test specimen: Dumbbell ASTM-1, 19 mm (width)×3.2 mm (thickness)×165 mm (length)

Stress rate: 50 mm/min

Span distance: 115 mm

[m9] Flexural Modulus of Injection-Molded Product

Flexural modulus (FM) was measured under the following conditions according to ASTM D790.

<Measurement Conditions>

Test specimen: 12.7 mm (width)×6.4 mm (thickness)×127 mm (length)

Stress rate: 2.8 mm/min

Bend span: 100 mm

[m10] Izod Impact Strength (IZ) of Injection-Molded Product

Izod impact strength (IZ) was measured under the following conditions according to ASTM D256.

<Measurement Conditions>

Temperature: 23° C., −30° C.

Test specimen: 12.7 mm (width)×6.4 mm (thickness)×64 mm (length)

A notch was machined.

[m11] Rockwell Hardness of Injection-Molded Product

Rockwell hardness was measured under the following conditions according to ASTM D2240.

<Measurement Conditions>

Test specimen: Dumbbell ASTM-1

19 mm (width)×3.2 mm (thickness)×165 mm (length)

Measurement site: Dumbbell gate side

[m12] Brittle Temperature of Injection-Molded Product at Low Temperatures

Brittle temperature at low temperatures was measured according to ASTM D746.

[m13] Young's Modulus of Film

The Young's modulus of film was measured according to JIS K6781.

<Measurement Conditions>

Temperature: 23° C., 60° C.

Stress rate: 200 mm/min

Distance between chucks: 80 mm

[M14] Impact Test of Film

A film 5 cm×5 cm was used as a sample and measured for its surface impact strength at a predetermined temperature with an impact tester (in a system of pushing up a hammer).

<Measurement Conditions>

Temperature: 0° C., −10° C.

Hammer: top 1 inch, loading 3.0 J

[m15] Haze of Film

Measured according to ASTM D-1003.

[m16] Heat Sealing Properties of Film (Minimum Heat Sealing Temperature)

A film of 5 mm in width was used as a sample and sealed for a sealing time of 1 second at a pressure of 0.2 MPa. Both the ends of the sealed film were drawn at 300 mm/min. to determine the maximum peel strength. An upper part of a seal bar was set at a specified temperature of 170° C., and a lower part was set at 70° C.

[m17] Cross-Chromatographic Fractionation Measurement (CFC)

The analysis of component soluble in o-dichlorobenzene at each temperature was carried out by cross-chromatographic fractionation measurement (CFC). In CFC, an apparatus shown below, equipped with a temperature rising elution fractionation (TREF) part wherein compositional fractionation is carried out and a GPC part wherein molecular-weight fractionation is carried out, was used in measurement under the following conditions to determine the amount of the component soluble at each temperature.

Measurement apparatus: CFC T-150A, manufactured by Mitsubishi Petrochemical Co., Ltd.

Columns: Shodex AT-806MS (3 columns)

Eluent: o-Dichlorobenzene

Flow rate: 1.0 ml/min

Sample concentration: 0.3 wt %/vol % (containing 0.1% BHT)

Injection volume: 0.5 ml

Solubility: Completely dissolved

Detector: Infrared absorption detection method, 3.42 p (2924 cm⁻¹), NaCl plate

Elution temperature: 0 to 135° C., 28 fractions

0, 10, 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 94, 97, 100, 103, 106, 109, 112, 115, 118, 121, 124, 127, 135 (° C.)

The measurement was specifically carried out as follows: The sample was dissolved by heating at 145° C. for 2 hours, then kept at 135° C., cooled to 0° C. at 10° C./hr, and kept at 0° C. for 60 minutes, to coat the sample. The capacity of the temperature rising elution column was 0.83 ml, and the capacity of the pipe was 0.07 ml. The detector was an infrared spectrograph MIRAN 1A CVF (CaF₂ cell) manufactured by FOXBORO, and infrared light at 3.42 μm (2924 cm⁻¹) was detected in an absorbance mode for a response time of 10 seconds. The sample was fractionated into 25 to 40 fractions at elution temperatures of 0° C. to 135° C. The temperature is indicated in integer, and for example, an elution fraction at 94° C. refers to a component eluted at a temperature between 91 and 94° C. A component not coated even at 0° C. and fractions eluted at the respective temperatures were measured for their molecular weight, and polypropylene-equivalent molecular weights were determined by using a universal calibration curve. The SEC temperature is 135° C., the internal standard injection volume is 0.5 ml, the injection position is 3.0 ml, and the data sampling time is 0.50 second. Data sampling was carried out with an analysis program “CFC Data Processing (Version 1.50)” attached to the apparatus.

Details of the Examples are shown below. Small-letter alphabet “a” indicated after Example (and Comparative Example) Number means that the Example (and Comparative Example) are related to the propylene based resin composition of the present invention; alphabet “b” means that the Example (and Comparative Example) are related to an injection-molded product of the propylene polymer of the present invention; alphabet “c” means that the Example (and Comparative Example) are related to the thermoplastic resin composition or propylene polymer of the present invention; and alphabet “d” means that the Example (and Comparative Example) are related to the film of the present invention.

EXAMPLE 1a

(1) Production of Solid Catalyst Support

300 g SiO₂ (manufactured by Dokai Kagakusha) was introduced into a 1-L side-arm flask and then 800 ml toluene was added to form slurry. Then, the slurry was transferred to a 5-L four-neck flask, and 260 ml toluene was added. 2,830 ml solution of methyl aluminoxane (hereinafter abbreviated as MAO) in toluene (10 wt % solution manufactured by Albemarle Corporation) was introduced. The mixture was stirred at room temperature for 30 minutes. The mixture was heated over 1 hour to 110° C. and reacted for 4 hours. After the reaction was finished, the mixture was cooled to room temperature. After cooling, the supernatant toluene was removed and substituted with fresh toluene until the degree of substitution became 95%. (The term “degree of substitution” in the present invention refers to the degree of substitution of solvent; for example, when 9 L toluene is removed from 10 L toluene and 9 L heptane is added thereto to give 10 L, “the degree of substitution thereof” is defined as 90%.)

(2) Production of Solid Catalyst (Supporting of the Metal Catalyst Component on a Catalyst Support)

2.0 g of [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride was weighed out in a 5-L four-neck flask in a glove box. The flask was put outside, and 0.46 L toluene and 1.4 L of the MAO/SiO₂/toluene slurry prepared in the above (1) were added thereto under nitrogen and stirred for 30 minutes for supporting. 99% of the toluene in the resulting [3-(1′,1′,4′,4′,7′,7′,10′,10′-octamethyloctahydrodibenzo[b,h]fluorenyl)(1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)]zirconium dichloride/MAO/SiO₂/toluene slurry was substituted with n-heptane to give slurry in a final volume of 4.5 L. This operation was carried out at room temperature.

(3) Production of Pre-Polymerization Catalyst

202 g of the solid catalyst component prepared in the above (2), 103 ml triethyl aluminum and 100 L heptane were introduced into an autoclave with an inner volume of 200 L equipped with a stirrer, and while the internal temperature was kept at a temperature of 15 to 20° C., 2020 g ethylene was introduced and the mixture was reacted for 180 minutes under stirring. After the polymerization was finished, solid components were precipitated, and removal of the supernatant and washing with heptane were carried out twice. The resulting pre-polymerization catalyst was suspended again in refined heptane such that the concentration of the solid catalyst component became 2 g/L. This pre-polymerization catalyst contained 10 g polyethylene per g of the solid catalyst component.

(4) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in the above (3) as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 54° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.06 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-a). The property values thereof after vacuum drying at 80° C. are shown in Table 1. The weight-average molecular weight (Mw) of the propylene polymer (I-a) soluble in o-dichlorobenzene at 0° C. was 2.9×10⁵, the ratio (Mw/Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) was 2.3, the ratio (Mw/Mn) of the weight-average molecular weight (Mw) thereof insoluble in o-dichlorobenzene at 90° C. and soluble in o-dichlorobenzene at 135° C. to the number-average molecular weight (Mn) thereof was 2.2, and the content of the ethylene-derived skeleton of the propylene polymer (I-a) in D_insol was 1.0 mol %.

EXAMPLE 2a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 51° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.07 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-b). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

EXAMPLE 3a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 47° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.07 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-b). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

EXAMPLE 4a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 51° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.04 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-d). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

EXAMPLE 5a

A polymer was obtained in the same manner as in Example la except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 47° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.07 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-e). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 1a

(1) Production of Solid Catalyst Support

300 g SiO₂ (manufactured by Dokai Kagakusha) was introduced into a 1-L side-arm flask and then 800 ml toluene was added to form slurry. Then, the slurry was transferred to a 5-L four-neck flask, and 260 ml toluene was added. 2,830 ml of MAO/toluene solution (10 wt % solution manufactured by Albemarle Corporation) was introduced. The mixture was stirred at room temperature for 30 minutes. The mixture was heated over 1 hour to 110° C. and reacted for 4 hours. After the reaction was finished, the mixture was cooled to room temperature. After cooling, the supernatant toluene was removed and substituted with fresh toluene until the degree of substitution became 95%.

(2) Production of Solid Catalyst

Supporting of the Metal Catalyst Component on a Catalyst Support

2.0 g of diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di tert-butylfluorenyl)zirconium dichloride was weighed out in a 5-L four-neck flask in a glove box. The flask was put outside, and 0.46 L toluene and 1.4 L of the MAO/SiO₂/toluene slurry prepared in the above (1) were added thereto under nitrogen and stirred for 30 minutes for supporting. 99% of the toluene in the resulting diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di tert-butylfluorenyl)zirconium dichloride/MAO/SiO₂/toluene slurry was substituted with n-heptane to give slurry in a final volume of 4.5 L. This operation was carried out at room temperature.

(3) Production of Pre-Polymerization Catalyst

202 g of the solid catalyst component prepared in the above (2), 109 ml triethyl aluminum and 100 L heptane were introduced into an autoclave with an inner volume of 200 L equipped with a stirrer, and while the internal temperature was kept at a temperature of 15 to 20° C., 2,020 g ethylene was introduced and the mixture was reacted for 180 minutes under stirring. After the polymerization was finished, solid components were precipitated, and removal of the supernatant and washing with heptane were carried out twice. The resulting pre-polymerization catalyst was suspended again in refined heptane such that the concentration of the solid catalyst component became 2 g/L. This pre-polymerization catalyst contained 10 g polyethylene per g of the solid catalyst component.

(4) Main Polymerization

40 kg/hour propylene, 4 NL/hour hydrogen, 2.0 g/hour catalyst slurry produced in (3) as the solid catalyst component and 4 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 47° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.06 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-f). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 2a

A polymer was obtained in the same manner as in Comparative Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 4 NL/hour hydrogen, 2.0 g/hour catalyst slurry produced in (3) as the solid catalyst component and 4 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 46° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.06 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-g). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 3a

(1) Production of Solid Titanium Catalyst Component

952 g magnesium chloride anhydride, 4,420 ml decane and 3,906 g 2-ethylhexyl alcohol were heated at 130° C. for 2 hours to form a uniform solution. 213 g phthalic anhydride was added to this solution and dissolved by further stirring at 130° C. for 1 hour. The uniform solution thus obtained was cooled to 23° C., and 750 ml of this uniform solution was added dropwise over 1 hour to 2,000 ml titanium tetrachloride kept at −20° C. After dropwise addition, the temperature of the resulting mixture was increased over 4 hours to 110° C., and when the temperature reached 110° C., 52.2 g diisobutyl phthalate (DIBP) was added and then the mixture was kept at the same temperature under stirring for 2 hours. Then, the solid part was collected by filtration while in a hot state, and this solid part was suspended again in 2,750 ml titanium tetrachloride and heated again at 110° C. for 2 hours. After heating was finished, the solid part was collected again by filtration while in a hot state and then washed with decane at 110° C. and hexane until the titanium compound became undetectable in the wash.

Although the solid titanium catalyst component prepared as described above was stored as hexane slurry, a part thereof was dried and examined for its catalyst composition. The solid titanium catalyst component contained 2 wt % titanium, 57 wt % chlorine, 21 wt % magnesium and 20 wt % DIBP.

(2) Production of Pre-Polymerization Catalyst

56 g of the solid catalyst component, 20.7 ml triethyl aluminum, 7.0 ml 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, and 80 L heptane were introduced into an autoclave with an inner volume of 200 L equipped with a stirrer, and while the internal temperature was kept at a temperature of 5° C., 560 g propylene was introduced and the mixture was reacted for 60 minutes under stirring. After the polymerization was finished, solid components were precipitated, and removal of the supernatant and washing with heptane were carried out twice. The resulting pre-polymerization catalyst was suspended again in refined heptane such that the concentration of the solid titanium catalyst component became 0.7 g/L. This pre-polymerization catalyst contained 10 g polypropylene per g of the solid titanium catalyst component.

(3) Main Polymerization

30 kg/hour propylene, 220 NL/hour hydrogen, 0.3 g/hour catalyst slurry as the solid catalyst component, 3.3 ml/hour triethylaluminum and 1.1 ml/hour dicyclopentyl dimethoxysilane were continuously supplied to a circular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the circular reactor was 70° C., and the pressure was 3.6 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 100 L equipped with a stirrer and further polymerized. The polymerizer was fed with 15 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 9.0 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.4 MPa/G.

The resulting slurry was transferred to an inserted tube with a capacity of 2.4 L (“inserted tube” in the present invention refers to a metering tube for metering a predetermined amount of slurry in order to transfer the slurry), and the slurry was gasified and then subjected to gas-solid separation. The resulting polypropylene homopolymer powder was sent to a 480-L gaseous phase polymerizer and then subjected to ethylene/propylene block copolymerization. Propylene, ethylene and hydrogen were fed continuously such that the gas composition in the gaseous phase polymerizer became ethylene/(ethylene+propylene)=0.32 (molar ratio), and hydrogen/(ethylene+propylene)=0.08 (molar ratio). The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 0.9 MPa/G. The property values of the resulting propylene polymer (I-h) after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 4a

A polymer was obtained in the same manner as in Comparative Example 3a except that the polymerization method was changed as follows:

(1) Main Polymerization

30 kg/hour propylene, 220 NL/hour hydrogen, 0.3 g/hour catalyst slurry as the solid catalyst component, 3.3 ml/hour triethyl aluminum and 1.1 ml/hour dicyclopentyl dimethoxy silane were continuously supplied to a circular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the circular reactor was 70° C., and the pressure was 3.6 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 100 L equipped with a stirrer and further polymerized. The polymerizer was fed with 15 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 9.0 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.4 MPa/G.

The resulting slurry was transferred to an inserted tube with a capacity of 2.4 L, and the slurry was gasified and then subjected to gas-solid separation. The resulting polypropylene homopolymer powder was sent to a 480-L gaseous phase polymerizer and then subjected to ethylene/propylene block copolymerization. Propylene, ethylene and hydrogen were fed continuously such that the gas composition in the gaseous phase polymerizer became ethylene/(ethylene+propylene)=0.32 (molar ratio), and hydrogen/(ethylene+propylene)=0.08 (molar ratio). The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 1.3 MPa/G.

The property values of the resulting propylene polymer (I-i) after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 5a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 0.9 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.24 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.24 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.24 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 51° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.3 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-j). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

REFERENCE EXAMPLE 1

(1) Production of Solid Catalyst Support

300 g SiO₂ (manufactured by Dokai Kagakusha) was introduced into a 1-L side-arm flask and then 800 ml toluene was added to form slurry. Then, the slurry was transferred to a5-L four-neck flask, and 260 ml toluene was added. 2,830 ml of MAO/toluene solution (10 wt % solution manufactured by Albemarle) was introduced. The mixture was stirred at room temperature for 30 minutes. The mixture was heated over 1 hour to 110° C. and reacted for 4 hours. After the reaction was finished, the mixture was cooled to room temperature. After cooling, the supernatant toluene was removed and substituted with fresh toluene until the degree of substitution became 95%.

(2) Production of Solid Catalyst

Supporting of the Metal Catalyst Component on a Catalyst Support

2.0 g of isopropyl(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di tert-butylfluorenyl)zirconium dichloride was weighed out in a 5-L four-neck flask in a glove box. The flask was put outside, and 0.46 L toluene and 1.4 L of the MAO/SiO₂/toluene slurry prepared in the above (1) were added thereto under nitrogen and stirred for 30 minutes for supporting. 99% of the toluene in the resulting isopropyl(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di tert-butylfluorenyl)zirconium dichloride/MAO/SiO₂/toluene slurry was substituted with n-heptane to give slurry in a final volume of 4.5 L. This operation was carried out at room temperature.

(3) Production of Pre-Polymerization Catalyst

202 g of the solid catalyst component prepared in the above (2), 109 ml triethyl aluminum and 100 L heptane were introduced into an autoclave with an inner volume of 200 L equipped with a stirrer, and while the internal temperature was kept at a temperature of 15 to 20° C., 2020 g ethylene was introduced and the mixture was reacted for 180 minutes under stirring. After the polymerization was finished, solid components were precipitated, and removal of the supernatant and washing with heptane were carried out twice. The resulting pre-polymerization catalyst was suspended again in refined heptane such that the concentration of the solid catalyst component became 2 g/L. This pre-polymerization catalyst contained 10 g polyethylene per g of the solid catalyst component.

(4) Main Polymerization

40 kg/hour propylene, 4 NL/hour hydrogen, 1.6 g/hour catalyst slurry produced in the above (3) as the solid catalyst component and 4 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.4 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.4 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.4 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.4 mol %. The polymerization was carried out at a polymerization temperature of 66° C. at a polymerization pressure of 2.9 MPa/G.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene homopolymer. The property values of the resulting propylene homopolymer (II-a) after vacuum drying at 80° C. are shown in Table 1.

REFERENCE EXAMPLE 2

A polymer was obtained in the same manner as in Comparative Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

An SUS autoclave with an internal capacity of 30 L at 10° C. sufficiently flushed with nitrogen was charged with 9 kg liquid propylene and charged with ethylene at a partial pressure of 0.8 MPa. The material was heated to 45° C. under sufficient stirring, and a mixed solution of 0.6 g/heptane, 300 ml, and 0.5 ml triethyl aluminum was pressed as the solid catalyst component from a catalyst pot into the autoclave. The polymerization was carried out at 60° C. for 20 minutes and then terminated by adding methanol. After the polymerization was terminated, the propylene was purged, then the atmosphere was replaced sufficiently by nitrogen, and the polymer (III-a) was separated. The property values of the resulting polymer (III-a) after vacuum drying at 80° C. are shown in Table 1.

EXAMPLE 6a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 54° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.08 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-k). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

EXAMPLE 7a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 51° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.08 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-l). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

EXAMPLE 8a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 47° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.07 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-m). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 6a

A polymer was obtained in the same manner as in Comparative Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 4 NL/hour hydrogen, 2.0 g/hour catalyst slurry produced in (3) in Comparative Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.2 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 47° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.06 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-n). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 7a

A polymer was obtained in the same manner as in Comparative Example 3a except that the polymerization method was changed as follows:

(1) Main Polymerization

30 kg/hour propylene, 220 NL/hour hydrogen, 0.3 g/hour catalyst slurry as the solid catalyst component, 3.3 ml/hour triethyl aluminum and 1.1 ml/hour dicyclopentyl dimethoxy silane were continuously supplied to a circular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the circular reactor was 70° C., and the pressure was 3.6 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 100 L equipped with a stirrer and further polymerized. The polymerizer was fed with 15 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 9.0 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.4 MPa/G.

The resulting slurry was transferred to an inserted tube with a capacity of 2.4 L, and the slurry was gasified and then subjected to gas-solid separation. The resulting polypropylene homopolymer powder was sent to a 480-L gaseous phase polymerizer and then subjected to ethylene/propylene block copolymerization. Propylene, ethylene and hydrogen were fed continuously such that the gas composition in the gaseous phase polymerizer became ethylene/(ethylene+propylene)=0.32 (molar ratio), and hydrogen/(ethylene+propylene)=0.08 (molar ratio). The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 0.5 MPa/G.

The property values of the resulting propylene polymer (I-o) after vacuum drying at 80° C. are shown in Table 1.

EXAMPLE 9a

A polymer was obtained in the same manner as in Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 5 NL/hour hydrogen, 1.0 g/hour catalyst slurry produced in (3) in Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.1 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.1 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.1 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 51° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.08 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-p). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 8a

A polymer was obtained in the same manner as in Comparative Example 1a except that the polymerization method was changed as follows:

(1) Main Polymerization

40 kg/hour propylene, 4 NL/hour hydrogen, 2.0 g/hour catalyst slurry produced in (3) in Comparative Example 1a as the solid catalyst component and 4.0 ml/hour triethyl aluminum were continuously supplied to a tubular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the tubular reactor was 30° C., and the pressure was 3.2 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 1,000 L equipped with a stirrer and further polymerized. The polymerizer was fed with 45 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.08 mol %. The polymerization was carried out at a polymerization temperature of 72° C. at a pressure of 3.1 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.08 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and further polymerized. The polymerizer was fed with 10 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.08 mol %. The polymerization was carried out at a polymerization temperature of 68° C. at a pressure of 3.0 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 500 L equipped with a stirrer and copolymerized. The polymerizer was fed at a polymerization temperature of 51° C. at a polymerization pressure of 2.9 MPa/G with 10 kg/hour propylene and with ethylene and hydrogen such that the concentration of hydrogen in the gaseous phase became 0.07 mol %.

The resulting slurry was gasified and then subjected to gas-solid separation to give a propylene polymer (I-q). The property values thereof after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 9a

(1) Production of Solid Titanium Catalyst Component

952 g magnesium chloride anhydride, 4,420 ml decane and 3,906 g 2-ethylhexyl alcohol were heated at 130° C. for 2 hours to form a uniform solution. 213 g phthalic anhydride was added to this solution and dissolved by further stirring at 130° C. for 1 hour. The uniform solution thus obtained was cooled to 23° C., and 750 ml of this uniform solution was added dropwise over 1 hour to 2,000 ml titanium tetrachloride kept at −20° C. After dropwise addition, the temperature of the resulting mixture was increased over 4 hours to 110° C., and when the temperature reached 110° C., 52.2 g diisobutyl phthalate (DIBP) was added and then the mixture was kept at the same temperature under stirring for 2 hours. Then, the solid part was collected by filtration while in a hot state, and this solid part was suspended again in 2,750 ml titanium tetrachloride and heated again at 110° C. for 2 hours. After heating was finished, the solid part was collected again by filtration while in a hot state and then washed with decane at 110° C. and hexane until the titanium compound became undetectable in the wash.

Although the solid titanium catalyst component prepared as described above was stored as hexane slurry, a part thereof was dried and examined for its catalyst composition. The solid titanium catalyst component contained 2 wt % titanium, 57 wt % chlorine, 21 wt % magnesium and 20 wt % DIBP.

(2) Production of Pre-Polymerization Catalyst

56 g of the solid catalyst component, 9.6 ml triethyl aluminum, and 80 L heptane were introduced into an autoclave with an inner volume of 200 L equipped with a stirrer, and while the internal temperature was kept at a temperature of 5° C., 560 g propylene was introduced and the mixture was reacted for 60 minutes under stirring. After the polymerization was finished, solid components were precipitated, and removal of the supernatant and washing with heptane were carried out twice. The resulting pre-polymerization catalyst was suspended again in refined heptane such that the concentration of the transition metal catalyst component became 0.7 g/L. This pre-polymerization catalyst contained 10 g polypropylene per g of the transition metal catalyst component.

(3) Main Polymerization

30 kg/hour propylene, 15 NL/hour hydrogen, 0.25 g/hour catalyst slurry as the solid catalyst component, 2.9 ml/hour triethyl aluminum and 0.8 ml/hour cyclohexyl methyl dimethoxy silane were continuously supplied to a circular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the circular reactor was 70° C., and the pressure was 3.6 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 100 L equipped with a stirrer and further polymerized. The polymerizer was fed with 15 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.9 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.2 MPa/G.

The resulting slurry was transferred to an inserted tube with a capacity of 2.4 L, and the slurry was gasified and then subjected to gas-solid separation. The resulting polypropylene homopolymer powder was sent to a 480-L gaseous phase polymerizer and then subjected to ethylene/propylene block copolymerization. Propylene, ethylene and hydrogen were fed continuously such that the gas composition in the gaseous phase polymerizer became ethylene/(ethylene+propylene)=0.22 (molar ratio), and hydrogen/(ethylene+propylene)=0.04 (molar ratio). The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 1.0 MPa/G.

The property values of the resulting propylene polymer (I-r) after vacuum drying at 80° C. are shown in Table 1.

COMPARATIVE EXAMPLE 10a

A polymer was obtained in the same manner as in Comparative Example 9a except that the polymerization method was changed as follows:

(1) Main Polymerization

30 kg/hour propylene, 15 NL/hour hydrogen, 0.25 g/hour catalyst slurry as the solid catalyst component, 2.9 ml/hour triethyl aluminum, and 0.8 ml/hour cyclohexylmethyl dimethoxy silane were continuously supplied to a circular polymerizer with an inner volume of 58 L and polymerized in the polymerizer filled up in the absence of a gaseous phase. The temperature of the circular reactor was 70° C., and the pressure was 3.6 MPa/G.

The resulting slurry was sent to a vessel polymerizer with an inner volume of 100 L equipped with a stirrer and further polymerized. The polymerizer was fed with 15 kg/hour propylene and with hydrogen such that the concentration of hydrogen in the gaseous phase became 0.9 mol %. The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 3.2 MPa/G.

The resulting slurry was transferred to an inserted tube with a capacity of 2.4 L, and the slurry was gasified and then subjected to gas-solid separation. The resulting polypropylene homopolymer powder was sent to a 480-L gaseous phase polymerizer and then subjected to ethylene/propylene block copolymerization. Propylene, ethylene and hydrogen were fed continuously such that the gas composition in the gaseous phase polymerizer became ethylene/(ethylene+propylene)=0.31 (molar ratio), and hydrogen/(ethylene+propylene)=0.04 (molar ratio). The polymerization was carried out at a polymerization temperature of 70° C. at a pressure of 1.1 MPa/G.

The property values of the resulting propylene polymer (I-s) after vacuum drying at 80° C. are shown in Table 1.

	TABLE 1
	Dinsol	Dsol
	Propylene	MFR	AmountNote 1)	Tm	Mw/Mn	[1,3 + 2,1]Note 2)	[C2]Note 3)	AmountNote 1)	[η]	Mw/Mn	[C2]Note 4)
	polymer	g/10 min	wt %	° C.	—	mol %	wt %	wt %	dl/g	—	mol %
Example	I-a	38	80	156	2.1	<0.02	0.7	20	2.5	2.1	30
1a
Example	I-b	37	80	156	2.1	<0.02	0.7	20	2.4	2.2	35
2a
Example	I-c	38	80	156	2.1	<0.02	0.8	20	2.4	2.2	42
3a
Example	I-d	33	80	156	2.1	<0.02	0.8	20	3.0	2.2	35
4a
Example	I-e	23	71	156	2.0	<0.02	0.9	29	2.4	2.1	41
5a
Comparative	I-f	39	80	147	2.0	0.1	0.8	20	2.4	2.1	42
Example
1a
Comp.	I-g	24	71	147	2.0	0.1	0.8	29	2.4	2.1	43
Example
2a
Comp.	I-h	39	81	160	5.2	<0.02	2.7	19	2.3	4.8	41
Example
3a
Comp.	I-i	22	70	160	5.2	<0.02	2.7	30	2.3	4.8	42
Example
4a
Comp.	I-j	66	80	156	2.1	<0.02	0.7	20	1.5	2.2	35
Example
5a
Example	I-k	64	90	156	2.1	<0.02	0.3	10	2.3	2.1	30
6a
Example	I-l	62	90	156	2.1	<0.02	0.4	10	2.3	2.2	35
7a
Example	I-m	60	90	156	2.1	<0.02	0.4	10	2.4	2.2	42
8a
Comp.	I-n	60	90	147	2.2	0.1	0.4	10	2.4	2.1	42
Example
6a
Comp.	I-o	63	89	160	5.3	<0.02	1.4	11	2.3	4.9	41
Example
7a
Example	I-p	4.6	80	156	2.2	<0.02	0.6	20	2.3	2	34
9a
Comp.	I-q	5.0	80	147	2.1	0.1	0.7	20	2.3	2.1	34
Example
8a
Comp.	I-r	4.5	81	160	6.5	<0.02	3.7	19	2..2	5.5	34
Example
9a
Comp.	I-s	4.8	79	160	6.4	<0.02	4.0	21	2.3	5.8	42
Example
10a
Reference	II-a	—	>99.5	158	2.2	<0.02	<0.1	<0.5	—	—	—
Example 1
Reference	III-a	—	<0.1	—	—	—	—	>99.9	2.5	2.1	35
Example 2
Note 1)Percentage (wt %) in propylene polymer
Note 2)Total amount (mol %) of 2,1-bond and 1,3-bond in Dinsol
Note 3)Concentration (wt %) of ethylene-derived skeleton in Dinsol
Note 4)Concentration (wt %) of ethylene-derived skeleton in Dsol

EXAMPLE 1b

0.1 part by weight of a heat stabilizer IRGANOX1010 (registered trademark) (Ciba Geigy), 0.1 part by weight of a heat stabilizer IRGAFOS168 (registered trademark) (Ciba Geigy) and 0.1 part by weight of calcium stearate were mixed, in a tumbler, with 100 parts by weight of the propylene polymer (I-a) produced in Example 1a and then melt-kneaded in a twin-screw extruder to prepare a pellet-shaped polypropylene resin composition which was then formed into an ASTM test specimen by an injection molding machine. The mechanical physical properties of the molded product are shown in Table 2.

<Melt-Kneading Conditions>

Same-direction-twin-screw kneader: Product Number NR2-36, manufactured by Nakatani Kikai

Kneading temperature: 190° C.

Number of revolution of screw: 200 rpm

Number of revolution of feeder: 400 rpm

<Conditions for Injection Molding of ASTM Test Specimen>

Injection molding machine: Product Number IS100, manufactured by Toshiba Machine Co., Ltd.

Cylinder temperature: 190° C.

Die temperature: 40° C.

EXAMPLE 2b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-b) produced in Example 2a. The mechanical physical properties of the molded product are shown in Table 2.

EXAMPLE 3b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-c) produced in Example 3a. The mechanical physical properties of the molded product are shown in Table 2.

EXAMPLE 4b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-d) produced in Example 4a. The mechanical physical properties of the molded product are shown in Table 2.

EXAMPLE 5b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-e) produced in Example 5a. The mechanical physical properties of the molded product are shown in Table 2.

COMPARATIVE EXAMPLE 1b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-f) produced in Comparative Example 1a. The mechanical physical properties of the molded product are shown in Table 2.

COMPARATIVE EXAMPLE 2b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-g) produced in Comparative Example 2a. The mechanical physical properties of the molded product are shown in Table 2.

COMPARATIVE EXAMPLE 3b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-h) produced in Comparative Example 3a. The mechanical physical properties of the molded product are shown in Table 2.

COMPARATIVE EXAMPLE 4b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-i) produced in Comparative Example 4a. The mechanical physical properties of the molded product are shown in Table 2.

COMPARATIVE EXAMPLE 5b

An ASTM test specimen was prepared by melt-kneading in the same manner as in Example 1b except that the propylene polymer (I-a) was changed into the propylene polymer (I-j) produced in Comparative Example 5a. The mechanical physical properties of the molded product are shown in Table 2.

EXAMPLE 6b

0.1 part by weight of a heat stabilizer IRGANOX1010 (registered trademark) (Ciba Geigy), 0.1 part by weight of a heat stabilizer IRGAFOS168 (registered trademark) (Ciba Geigy) and 0.1 part by weight of calcium stearate were mixed, in a tumbler, with 100 parts by weight of a combination consisting of 80 parts by weight of the propylene homopolymer (II-a) produced in Reference Example 1 and 20 parts by weight of the propylene/ethylene random copolymer rubber (III-a) produced in Reference Example 2 and then melt-kneaded in a twin-screw extruder to prepare a pellet-shaped polypropylene resin composition which was then formed into an ASTM test specimen by an injection molding machine. The mechanical physical properties of the molded product are shown in Table 2.

<Melt-Kneading Conditions>

Same-direction-twin-screw kneader: Product Number NR2-36, manufactured by Nakatani Kikai

Kneading temperature: 190° C.

Number of revolution of screw: 200 rpm

Number of revolution of feeder: 400 rpm

<Conditions for Injection Molding of ASTM Test Specimen>

Injection molding machine: Product Number IS100, manufactured by Toshiba Machine Co., Ltd.

Cylinder temperature: 190° C.

Die temperature: 40° C.

	TABLE 2
	Mechanical physical properties
					Izod impact
		MFR	breaking	flexural	strength
	Propylene	g/10	elongation	modulus	(23° C.)
	polymer	min	%	MPa	J/m
Example 1b	I-a	38	350	1080	490
Example 2b	I-b	37	210	1100	130
Example 3b	I-c	38	100	1120	80
Example 4b	I-d	33	150	1130	110
Example 5b	I-e	23	>300	790	640
Example 6b	II-a/III-a	35	220	1110	145
Comparative	I-f	39	110	840	75
Example
1b
Comparative	I-g	24	>300	670	610
Example
2b
Comparative	I-h	39	95	1110	70
Example
3b
Comparative	I-i	22	>300	760	600
Example
4b
Comparative	I-j	66	40	1050	40
Example
5b

EXAMPLE 1c

0.1 part by weight of a heat stabilizer IRGANOX1010 (registered trademark) (Ciba Geigy), 0.1 part by weight of a heat stabilizer IRGAFOS168 (registered trademark) (Ciba Geigy) and 0.1 part by weight of calcium stearate were mixed, in a tumbler, with 100 parts by weight of a combination consisting of 60 parts by weight of the propylene polymer (I-k) produced in Example 6a, 20 parts by weight of an ethylene/octane copolymer rubber (IV-a) (Engage 8842 (registered trademark) manufactured by DuPont Dow Elastomer) and 20 parts by weight of talc (High Filler #5000PJ (registered trademark) manufactured by Matsumura Sangyo) and then melt-kneaded in a twin-screw extruder to prepare a pellet-shaped polypropylene resin composition which was then formed into an ASTM test specimen by an injection molding machine. The mechanical physical properties of the molded product are shown in Table 3.

<Melt-Kneading Conditions>

Same-direction-twin-screw kneader: Product Number NR2-36, manufactured by Nakatani Kikai

Kneading temperature: 190° C.

Number of revolution of screw: 200 rpm

Number of revolution of feeder: 400 rpm

<Conditions for Injection Molding of ASTM Test Specimen>

Injection molding machine: Product Number IS100, manufactured by Toshiba Machine Co., Ltd.

Cylinder temperature: 190° C.

Die temperature: 40° C.

EXAMPLE 2c

A test specimen was prepared in the same manner as in Example 1c except that 60 parts by weight of the propylene polymer (I-k) were changed into 60 parts by weight of the propylene polymer (I-l) produced in Example 7a. The mechanical physical properties of the resulting molded product are shown in Table 3.

EXAMPLE 3c

A test specimen was prepared in the same manner as in Example 1c except that 60 parts by weight of the propylene polymer (I-k) were changed into 60 parts by weight of the propylene polymer (I-m) produced in Example 8a. The mechanical physical properties of the resulting molded product are shown in Table 3.

COMPARATIVE EXAMPLE 1c

A test specimen was prepared in the same manner as in Example 1c except that 60 parts by weight of the propylene polymer (I-k) were changed into 60 parts by weight of the propylene polymer (I-n) produced in Comparative Example 6a. The mechanical physical properties of the resulting molded product are shown in Table 3.

COMPARATIVE EXAMPLE 2c

A test specimen was prepared in the same manner as in Example 1c except that 60 parts by weight of the propylene polymer (I-k) were changed into 60 parts by weight of the propylene polymer (I-o) produced in Comparative Example 7a. The mechanical physical properties of the resulting molded product are shown in Table 3.

COMPARATIVE EXAMPLE 3c

0.1 part by weight of a heat stabilizer IRGANOX1010 (registered trademark) (Ciba Geigy), 0.1 part by weight of a heat stabilizer IRGAFOS168 (registered trademark) (Ciba Geigy) and 0.1 part by weight of calcium stearate were mixed, in a tumbler, with 100 parts by weight of a combination consisting of 57 parts by weight of the propylene polymer (I-o) produced in Comparative Example 7a, 23 parts by weight of an ethylene/octane copolymer rubber (IV-a) (Engage 8842 (registered trademark) manufactured by DuPont Dow Elastomer) and 20 parts by weight of talc (High Filler #5000PJ (registered trademark) manufactured by Matsumura Sangyo) and then melt-kneaded in a twin-screw extruder in the same manner as in Example 7 to prepare a pellet-shaped polypropylene resin composition which was then formed into an ASTM test specimen by an injection molding machine. The mechanical physical properties of the molded product are shown in Table 3.

TABLE 3
			Example	Example	Example	Comparative	Comparative	Comparative
			1c	2c	3c	Example 1c	Example 2c	Example 3c
Propylene polymer (I-k)	60
Propylene polymer (I-l)		60
Propylene polymer (I-m)			60
Propylene polymer (I-n)				60
Propylene polymer (I-o)					60	57
Ethylene/octane	20	20	20	20	20	23
copolymer rubber (IV-a)
Talc (V)	20	20	20	20	20	20
Article	MFR	g/10 min	29	30	28	28	30	26
	breaking	%	270	280	260	250	90	320
	elongation
	flexural	MPa	1930	1920	1940	1800	2150	1890
	modulus
	Rockwell	R	61	56	53	49	55	45
	hardness
	low-temperature	° C.	−23	−28	−35	−32	−22	−28
	brittle
	temperature

EXAMPLE 1d

0.1 part by weight of a heat stabilizer IRGANOX1010 (registered trademark) (Ciba Geigy), 0.1 part by weight of a heat stabilizer IRGAFOS168 (registered trademark) (Ciba Geigy) and 0.1 part by weight of calcium stearate were mixed, in a tumbler, with 100 parts by weight of the propylene polymer (I-p) produced in Example 9a and then melt-kneaded in a twin-screw extruder to prepare a pellet-shaped polypropylene resin composition which was then formed into a cast film by a T-die extruder [Product Number GT-25A, manufactured by Plastic Kogaku Kenkyusho]. The mechanical physical properties of the cast film are shown in Table 4.

<Melt-Kneading Conditions>

Same-direction-twin-screw kneader: Product Number NR2-36, manufactured by Nakatani Kikai

Kneading temperature: 210° C.

Number of revolution of screw: 200 rpm

Number of revolution of feeder: 400 rpm

<Film Molding>

25 mmΦ T-die extruder: Product Number GT-25A, manufactured by Plastic Kogaku Kenkyusho

Extrusion temperature: 230° C.

Chill roll temperature: 30° C.

Take-over speed: 4.0 m/min

Film thickness: 70 μm

COMPARATIVE EXAMPLE 1d

A film was prepared in the same manner as in Example 1d except that 100 parts by weight of the propylene polymer (I-p) were changed into 100 parts by weight of the propylene polymer (I-q) produced in Comparative Example 8a. The physical properties of the resulting film are shown in Table 4.

COMPARATIVE EXAMPLE 2d

A film was prepared in the same manner as in Example 1d except that 100 parts by weight of the propylene polymer (I-p) were changed into 100 parts by weight of the propylene polymer (I-r) produced in Comparative Example 8a. The physical properties of the resulting film are shown in Table 4.

COMPARATIVE EXAMPLE 3d

A film was prepared in the same manner as in Example 1d except that 100 parts by weight of the propylene polymer (I-p) were changed into 100 parts by weight of the propylene polymer (I-s) produced in Comparative Example 8a. The physical properties of the resulting film are shown in Table 4.

	TABLE 4
		Comparative	Comparative	Comparative
	Example	Example	Example	Example
	1d	1d	2d	3d
Propylene polymer	I-p	I-q	I-r	I-s
Product	Young's	MPa	820	770	740	760
(70 μm	modulus
cast	(MD) at
film)	23° C.
	Young's	MPa	320	250	210	230
	modulus
	(MD) at
	60° C.
	Impact	J/m	33	31	39	37
	strength
	at 0° C.
	Impact	J/m	28	16	14	15
	strength
	at −10° C.
	HAZE	%	9.0	8.7	12.0	14.5
	heat	N/15 mm	9.8	19.4	5.0	5.5
	sealing
	strength
	at 170° C.

INDUSTRIAL APPLICABILITY

The propylene polymer of the present invention is characterized in that its n-decane insoluble part (D_insol) has a high melting point and its decane soluble part (D_sol) has a high molecular weight and narrow compositional distribution, and the propylene polymer is excellent in rigidity and impact resistance for use in injection molding and excellent in heat resistance, transparency, impact resistance and heat sealing properties for use in film. Accordingly, the propylene polymer of the present invention can be used suitably in automobile applications such as bumper, instrument panel, etc. and for applications to various molded products such as high retort film for packaging food, blow-molded container etc.

Claims

1. A propylene polymer consisting of 10 to 40 wt % room-temperature n-decane soluble part (Dsol) and 60 to 90 wt % room-temperature n-decane insoluble part (Dinsol), comprising skeletons derived from propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, and satisfying all of the following requirements [1] to [5]: [1] the molecular weight distribution (Mw/Mn) of both Dsol and Dinsol as determined by GPC is 4.0 or less; [2] the melting point (Tm) of Dinsol is 156° C. or more; [3] the sum of the 2,1-bond content and the 1,3-bond content in Dinsol is 0.05 mol % or less; [4] the intrinsic viscosity [η] (dl/g) of Dsol satisfies the relationship 2.2<[η]≦6.0; and [5] the concentration of skeletons derived from the olefin (MX) in Dinsol is 3.0 wt % or less.

2. The propylene polymer according to claim 1, which is obtained by carrying out the following two steps 1 and 2 successively: [Step 1] step wherein propylene (MP), and if necessary at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins, are polymerized in the presence of a catalyst containing a metallocene compound, thereby producing a polymer wherein the concentration of room-temperature n-decane soluble part (Dsol) is 0.5 wt % or less, and [Step 2] step wherein propylene (MP) and at least one kind of olefin (MX) selected from ethylene and C4 or more α-olefins are copolymerized in the presence of a catalyst containing a metallocene compound, thereby producing a copolymer wherein room-temperature n-decane insoluble part (Dinsol) is 5.0 wt % or less.

3. The propylene polymer according to claim 2, wherein the metallocene compound is represented by the following general formula [I]:

4. A thermoplastic resin composition comprising the propylene polymer according to any of claims 1 to 3.

5. A propylene resin composition comprising the propylene polymer according to any of claims 1 to 3 and at least one member selected from a polypropylene resin (P), an elastomer (Q) and an inorganic filler (R).

6. An injection-molded product obtained by molding the propylene polymer according to any of claims 1 to 3.

7. A film obtained by molding the propylene polymer according to any of claims 1 to 3.

8. A sheet obtained by molding the propylene polymer according to any of claims 1 to 3.

9. A blow-molded container obtained by molding the propylene polymer according to any of claims 1 to 3.

10. An injection-molded product obtained by molding the resin composition according to claim 4.

11. A film obtained by molding the resin composition according to claim 4.

12. A sheet obtained by molding the resin composition according to claim 4.

13. A blow molded container obtained by molding the resin composition according to claim 4.