JPH08311136A - Production of block copolymer - Google Patents

Abstract

PURPOSE: To obtain a block copolymer excellent in impact resistance, physical property balance (rigidity, impact resistance and MFR) and appearance of molded products. CONSTITUTION: In the production of a block copolymer comprising 95-10wt.% of following block (i) and 5-90wt.% of following block (ii) is obtained by at least 2-step polymerization of propylene and/(or) ethylene, the polymerization catalyst is prepared by preliminary polymerization treatment where an α-olefin and a polyene are brought into contact with a polymerization catalyst comprising following components A and B, A and C or A, B and C in the absence of hydrogen: Component A: a transition metal compound catalyst component, Component B: an organometallic compound catalyst component containing a metal in group I-III of the periodic table, Component C: a compound forming an ionic complex by reacting with a transition metal compound in the component A, Block (i): a block of a polymer containing 100-90wt.% of propylene and 0-10wt.% of ethylene, block (ii): a block of a polymer containing 0-90wt.% of propylene and 100-10wt.% of ethylene.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to a propylene block having excellent impact resistance, excellent balance of physical properties (balance of rigidity, impact resistance and melt flow rate (MFR)), and a molded body with few flow marks. The present invention relates to a method for producing a copolymer.

[0002]

2. Description of the Related Art Conventionally, various molded products in the field of industrial parts, for example, various parts for home electric appliances such as TV cases, VTR cases, washing machine covers, automobile interior / exterior parts such as bumpers, instrument panels, glove boxes and stereos. As a material for audio products such as cases, propylene-based block copolymers have been put into practical use in large quantities by taking advantage of their excellent mechanical strength, moldability and economic efficiency.

[0003]

However, in recent years, with high performance, high functionality, and large size of the above-mentioned various parts, a high level of mechanical strength balance and appearance are often required. However, as the required performance becomes higher, it has become more and more difficult to provide polypropylene-based materials that can satisfy the required performance.

For example, in order to improve the impact resistance of the propylene-based block copolymer, there is a method of mixing a rubber component by post-addition. According to this method, although the impact resistance is improved, the rigidity is decreased, and the balance of the physical properties after the improvement (balance of rigidity, impact resistance and MFR) is the above-mentioned high level mechanical strength balance. It is hard to say that they are always satisfied. Moreover, this method is considered to be economically disadvantageous.

Further, in JP-A-5-194778, JP-A-5-194793 and JP-A-5-202237, a catalyst is prepolymerized with α-olefin and polyene, and the catalyst is used to produce an olefin. However, these publications seem to aim at improving the melt tension of polyolefins, and in order to achieve the purpose we intended, these publications are not enough. It is believed that there is.

An object of the present invention is to solve the above problems and
An object of the present invention is to provide a method for producing a propylene-based block copolymer having improved impact resistance, an excellent balance of rigidity, impact resistance and MFR, and less flow marks of a molded product.

[0007]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The present invention is characterized in that when a propylene-based block copolymer is produced by polymerization using a catalyst preliminarily polymerized with an α-olefin and a polyene compound under hydrogen-free conditions, This is based on the unexpected fact that not only the property can be improved, but also the balance of rigidity, impact resistance and MFR is excellent and the flow mark of the molded product can be reduced.

Therefore, the method for producing a block copolymer according to the present invention comprises the steps of polymerizing propylene and / or ethylene in at least two stages to obtain the following block (i) 95:
-10% by weight and block (ii) 5 to 90% by weight, wherein the block copolymers are substantially different in the content of propylene and / or ethylene. In the above, the polymerization catalyst used is at least the following prepolymerized catalyst (T).

Prepolymerized catalyst (T): Stereoregular polymerization consisting of the following components (A) and (B), components (A) and (C), or (A), (B) and (C): The catalyst is contacted with an α-olefin and a polyene compound under hydrogen-free conditions to give 0.1 to 1 per 1 g of the component (A).
A prepolymerized catalyst (T) obtained by subjecting to a prepolymerization treatment comprising copolymerization in an amount of 0000 g.

Component (A): Transition metal compound catalyst component.

Component (B): An organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table.

Component (C): A compound which reacts with the transition metal compound contained in the component (A) to form an ionic complex.

Block (i): Propylene content is 100
~ 90 wt%, ethylene content 0 ~ 10 wt%
Is a block composed of a propylene polymer.

Block (ii): Propylene content 0-9
0% by weight, ethylene content of 100 to 10% by weight
Is a block of polymer. <Effect> The propylene-based block copolymer according to the present invention is superior in impact resistance to the conventional propylene-based block copolymer, and has a good balance of physical properties (rigidity, impact resistance and MFR balance) and excellent. It has a molded body appearance. Therefore, the block copolymer according to the present invention is used for various parts of home electric appliances such as TV cases, VTR cases, washing machine covers, automobile interior / exterior parts such as bumpers, instrument panels and glove boxes, and audio products such as stereo cases. It has excellent properties as a part, especially as a material for automobile bumpers. [Detailed Description of the Invention] I. Catalyst The catalyst used in the present invention comprises a specific prepolymerized catalyst (T). Here, "consisting of the prepolymerization-treated catalyst (T)" does not mean that the catalyst consists of only the prepolymerization-treated catalyst (T), but excludes coexistence of other purposeful components. do not do. <Prepolymerization-treated catalyst (T)> The prepolymerization-treated catalyst (T) used in the present invention comprises the following components (A) and (B), components (A) and (C), or (A),
In the presence of the stereoregular polymerization catalyst component consisting of (B) and (C), the α-olefin and the polyene compound are brought into contact with each other under hydrogen-free conditions to give 0.1 to 1 per 1 g of the component (A).
It is obtained by subjecting it to a prepolymerization treatment which comprises copolymerization in an amount of 10,000 g.

Component (A): Transition metal compound catalyst component.

Component (B): An organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table.

Component (C): A compound which reacts with the transition metal compound contained in the component (A) to form an ionic complex.

Here, the "stereoregular polymerization catalyst" means the boiling n- of a polymer obtained by homopolymerizing propylene.
A heptane extraction residue having a weight percentage (I, I) of 90 or more, preferably 93 or more, particularly preferably 95 or more, or 3 measured by NMR of the obtained polymer.
A polymerization catalyst giving a chain [mm] or [rr] of 80% or more, preferably 85% or more, particularly preferably 90% or more. << Component (A): Transition Metal Compound Catalyst Component >> The transition metal compound catalyst component (component A) used for forming the prepolymerized catalyst (T) is preferably Periodic Table IV.
Examples thereof include compounds containing a transition metal selected from the B to VIB groups, particularly preferably compounds containing at least one transition metal selected from Ti, Tr and Hf.

Examples of the transition metal compound catalyst component include all known catalyst components for α-olefin polymerization catalysts as long as they are capable of stereoregular polymerization based on the transition metal compound.

Preferred compounds in the present invention are, for example, the transition metal compound catalyst components [1] to
[3] can be mentioned. [B] Transition metal compound catalyst component [1] Classified into this group in this specification are conventionally known titanium trichloride-based catalyst components.

As such a titanium trichloride-based catalyst component, TiCl ₄ reduced with hydrogen [TiCl 4
₃ (H)], reduced with titanium metal [TiCl
₃ (T)], reduced with aluminum metal [TiC
l 3 _(A)], and those reduced with an organoaluminum compound (e.g., TiCl 3 with diethyl aluminum chloride _reduction) there are many other types, such as. In the present invention, the catalytic activity may differ depending on the type of TiCl ₃ used, and the obtained catalytic performance is not necessarily the same. However, so-called Ziegler catalyst (including Ziegler-Natta catalyst) titanium trichloride is used. All that can be used as the system catalyst component can be used. Therefore, this titanium trichloride-based catalyst component is pure Ti
It does not have to be Cl ₃ , and may be, for example, TiCl ₃ (A) to which 1/3 mol of AlCl ₃ has been added, or an auxiliary component such as an electron donor introduced afterwards, and inevitable. Purposely or purposefully a small amount of unreduced TiCl ₄ or overreduced TiCl ₂ or
It may contain an oxidation product of a reducing agent. [B] Transition metal compound catalyst component [2] The transition metal compound component [2] is a catalyst component containing magnesium, titanium and halogen as essential components.

Such a transition metal compound catalyst component [2]
A known material can be used. For example, JP-A-53
-45688, 54-3894, 54-310.
No. 92, No. 54-39483, No. 54-94591
No. 54-118484 and No. 54-131589.
No. 55, No. 55-75411, No. 55-90510, No. 55-90511, No. 55-127405, No. 55.
-147507, 55-155003, 56-
No. 18609, No. 56-70005, No. 56-720
01, 56-86905, 56-90807.
56-155206, 57-3803, 57-34103, 57-92007, 57-.
121003, 58-5309, 58-531
0, 58-5311, 58-8706, 5
8-27732, 58-32604, 58-3
2605, 58-67703, 58-1172.
06, 58-127708, 58-18370.
No. 8, No. 58-183709, No. 59-149905.
No. 59-149906, etc. are used.

As the magnesium compound used as the magnesium source in the present invention, magnesium halide, dialkoxy magnesium, alkoxy magnesium halide, magnesium oxyhalide, dialkyl magnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, etc. can give. Among these magnesium compounds, magnesium halide is preferable.

The titanium compound serving as the titanium source is represented by the general formula Ti (OR) _4-m X _m (wherein R is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms,
X represents halogen, and m represents a number of 0 ≦ m ≦ 4. ). As a specific example, Ti
Cl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl,
_{Ti (O-iC 3 H 7} ) Cl 3, Ti (O-nC
_{4 H 9) Cl 3, Ti} (O-nC 4 H 9) 2 Cl 2, T
i (OC ₂ H ₅ ) Br ₃ , Ti (OC ₂ H ₅ ) (OC _{4
H 9) 2 Cl, Ti (} O-nC 4 H 9) 3 Cl, Ti
_{(O-C 6 H 5)} Cl 3, Ti (O-iC 4 H 9) 2 C
l ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ).
_{Cl 3, Ti (OC 2 H} 5) 4, Ti (O-nC
_{3 H 7) 4, Ti (} O-nC 4 H 9) 4, Ti (O-i
_{C 4 H 9) 4, Ti} (O-nC 6 H 13) 4, Ti (O-
nC ₈ H ₁₇ ) ₄ , Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄
H ₉ ] ₄ etc.

It is also possible to use a molecular compound obtained by reacting TiX ' ₄ (here, X'represents halogen) with an electron donor described later. As a specific example, TiCl _{4
· CH 3 COC 2 H 5,} TiCl 4 · CH 3 CO 2 C 2
H ₅ , TiCl ₄ · C ₆ H ₅ NO ₂ , TiCl ₄ · CH
₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl
₄・ C ₆ H ₅ COCl, TiCl ₄・ C ₆ H ₅ CO ₂ C
₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ ·
C ₄ H ₄ O and the like.

Among these titanium compounds, preferred are TiCl ₄ , Ti (OEt) ₄ and Ti (OBu).
₄ , Ti (OBu) Cl _{3 and the} like.

The halogen source is usually supplied from the above-mentioned magnesium and / or titanium halogen compounds, but from known halogenating agents such as aluminum halides, silicon halides and phosphorus halides. It can also be supplied. The halogen may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

The transition metal compound catalyst component [2] used in the present invention includes SiCl ₄ , CH ₃ Si, in addition to the above essential components.
Cl _3, silicon compounds such as _{methylhydrogenpolysiloxane, Al (Oi-C 3 H} 7) 3, AlCl 3, A
lBr ₃ , Al (OC ₂ H ₅ ) ₃ , Al (OCH ₃ ) ₂
It is also possible to use other components such as an aluminum compound such as Cl and a boron compound such as B (OC ₆ H ₅ ) ₃ and these are added to the transition metal compound catalyst component [2] as components such as silicon, aluminum and boron. There is no problem in remaining.

Further, this transition metal compound catalyst component [2]
The electron donor can also be used as a so-called internal donor in the case of producing.

As electron donors (internal donors) that can be used in the production of the transition metal compound catalyst component [2], alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids are used. Examples thereof include oxygen-containing electron donors such as ethers, acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol and isopropylbenzyl alcohol, (b) phenol, cresol, xylenol, ethylphenol,
Propylphenol, cumylphenol, nonylphenol, naphthol and other C6 to C25 phenols, which may have an alkyl group, (C) Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and other C3 to C15 phenols Ketones, (d) acetaldehyde, propionaldehyde,
C2-C15 aldehydes such as octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl (f) formate, methyl acetate, ethyl acetate, vinyl acetate, ethyl cellosolve acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propione Ethyl acidate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, ethyl benzoate cellosolve, benzoic acid Propyl, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate,
Organic acid esters having 2 to 20 carbon atoms such as diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc., (f) ethyl silicate, butyl silicate, phenyltriethoxysilane, diphenyldimethoxy Silicone compounds such as silane and tert-butylmethyldimethoxysilane or silicon compounds such as silane, carbon number 2 such as (to) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride and isophthaloyl chloride. To 15 acid halides, (chi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether and other C 2 to 20 ethers,
(I) Acetic acid amide, benzoic acid amide, acid amides such as toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine,
Tribenzylamine, aniline, pyridine, picoline,
Amines such as tetramethylethylenediamine, (R)
Acetonitrile, benzonitrile, nitriles such as tolunitrile _{(Wo) (CH 3) CH (OCH} 3) 2, C
_{H 2 (CH 2 OCH 3)} 2, (i-C 3 H 7) 2 C (C
_{H 2 OCH 3) 2, (} i-C 4 H 9) 2 C (CH 2 OC
_{H 3) 2, (C 6} H 5) C (OCH 3) 3, (C
_{6 H 5) 2 C (OCH} 3) 2, (C 6 H 5) C (OC 2
H _{5) 3,}

[0032]

Embedded image _{CH (OCH 3) 2 CH 2} CH (OCH 3) 2, CH
_{(OC 2 H 5) 2 CH} 2 CH (OC 2 H 5) 2, CH 2
_{(OCH 3) C (i-} C 3 H 7) 2 CH 2 (OC
_{H 3), CH 2 (OCH} 3) C (i-C 4 H 9) 2 CH
Polyethers such as ₂ (OCH ₃ ) can be cited. Two or more of these electron donors can be used. Among these, preferred are organic acid esters, acid halides and silicon compounds, and particularly preferred are ethyl acetate cellosolve, phthalic esters, phthalic halides and organic alkoxysilicons.

The amount of each of the above-mentioned components used may be arbitrary as long as the effects of the present invention are recognized, but in general,
The following range is preferable.

The amount of the titanium compound used is 1 × 10 ^-4 to 1 in molar ratio with respect to the amount of the magnesium compound used.
The range of 000 is good, and the range of 0.01 to 10 is preferable.

When a compound therefor is used as a halogen source, the amount used is a molar ratio with respect to the amount of magnesium used, whether or not the titanium compound and / or the magnesium compound contains halogen. It is preferably in the range of 1 × 10 ^{-2 to} 1000, and more preferably in the range of 0.1 to 100.

The amount of the silicon, aluminum and boron compounds used as the above optional components is 1 × 10 ^{−3 to} 100 in terms of molar ratio with respect to the amount of the above magnesium compound used.
Is preferably in the range of 0.01 to 1, and preferably in the range of 0.01 to 1.

The amount of the electron donor used is preferably in the range of 1 × 10 ⁻³ to 10 and more preferably in the range of 0.01 to 5 with respect to the amount of the magnesium compound used.

The transition metal compound catalyst component [2] is produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source and, if necessary, other components such as an electron donor. .

(A) A method in which a magnesium halide is optionally contacted with an electron donor and a titanium-containing compound.

(B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and magnesium halide, an electron donor and a titanium halogen-containing compound are brought into contact therewith.

(C) A method of bringing a titanium halogen compound and / or a silicon halogen compound into contact with a solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, those represented by the following formula (VI) are suitable.

[0043]

[Chemical 4] (Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, n
Indicates a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.) Of these, methylhydrogenpolysiloxane, 1,
3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7,9-pentamethylcyclopentasiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane and the like are preferable.

(D) A method in which a magnesium compound is dissolved in titanium tetraalkoxide and an electron donor, and a titanium compound is brought into contact with a solid component precipitated by a halogenating agent or a titanium halogen compound.

(E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact therewith as necessary.

(F) A method of bringing a halogenating agent and / or a titanium compound into contact with an alkoxymagnesium compound in the presence or absence of an electron donor.

Such a transition metal compound catalyst component [2]
Is usually -70 to 200 ° C, preferably -50 to 200 ° C.
It is carried out at a temperature of 150 ° C.

Of these, preferred are (a),
(C) and (D), especially (C) and (D). [C] Transition metal compound catalyst component [3] In this specification, the metallocene compound is classified as the transition metal compound catalyst component [3].

Preferred specific examples of the metallocene compound include cyclopentadienyl compounds represented by the following general formula (VII), (VIII) or (IX) or their derivatives or compounds represented by the following general formula (X): These derivatives can be mentioned.

CpMR ¹ _a R ² _b R ³ _c Formula (VII) Cp ² MR ¹ _d R ² _e Formula (VIII) (Cp-A _f -Cp) MR ¹ _d R ² _e Formula (IX) MR ¹ _g R ² _h R ³ _i R ⁴ _j Formula (X) where the symbols have the following meanings.

M represents a transition metal of Group IVB to VIB of the Periodic Table, preferably Ti, Zr or hafnium.

Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a silaindenyl group, a substituted silaindenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group,
An azulenyl group, a substituted azulenyl group, a fluorenyl group or a substituted fluorenyl group is shown. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In formula (VIII) and formula (IX), two C
p may be the same or different from each other. By the symbol "Cp", not only a cyclopentadienyl ring but also a cyclopentadienyl ring-containing condensed ring such as an indenyl group is contained. By virtue of the fact that the enyl ring moiety can be considered as a substituent on the cyclopentadienyl ring, i.e. formed by two substituents attached at their ω-end.

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number. 6-20 aryl group, alkylaryl group or arylalkyl group, C1-C20 acyloxy group, allyl group, substituted allyl group, acetylacetonato group, substituted acetylacetonato group, substituents containing silicon atom, Or carbonyl, oxygen molecule, nitrogen molecule,
A ligand such as a Lewis base, a chain unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon is shown.

A, b and c are integers of 0 to 3 respectively, d and e are integers of 0 to 2 respectively, g, h and i.
And j each represent an integer of 0 to 4. R ¹ ,
Two or more of R ² , R ³ and R ⁴ may combine with each other to form a ring.

A shows a covalent cross-link between Cp's.

F represents the number of atoms in the shortest distance between Cp of the crosslinked chain constituting the bridge A (the phenylene group is considered to be 1 atom), and is an integer of 0 to 6, preferably 1 to 2. f
Since A can be 0, the bridge A is C that does not go through a bridge.
Includes a direct bond between p.

In the above formulas (VII) to (IX), the substituted cyclopentadienyl group, the substituted indenyl group, the substituted silaindenyl group, the substituted tetrahydroindenyl group, the substituted azulenyl group and the substituted fluorenyl group have 1 carbon atoms. to 4 hydrocarbon residue, preferably a _C 1 -C ₂ alkyl group and phenyl group, in particular the _former, C 1 -C ₂ alkyl silyl group, and other. Specific examples of the substituted cyclopentadienyl group include, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Phenyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclo Examples include pentadienyl group.

Specific examples of the substituted indenyl group and the like when the unsubstituted group is a fused cyclopentadienyl ring such as indenyl are the corresponding fused cyclopentadienyl group derivatives of the above-mentioned substituted cyclopendienyl group.

Specific examples of R ^{1 to} R ⁴ include, for example,
(A) Fluorine atom, chlorine atom, bromine atom, iodine atom as halogen atom, (b) methyl group, ethyl group, n-propyl group, iso- as an alkyl group having 1 to 20 carbon atoms
Propyl group, n-butyl group, octyl group, 2-ethylhexyl group, (c) methoxy group, ethoxy group, propoxy group, butoxy group as an alkoxy group having 1 to 20 carbon atoms,
Phenoxy group, (d) aryl group having 6 to 20 carbon atoms, phenyl group as an arylaryl group or arylalkyl group, tolyl group, xylyl group, benzyl group, (e)
Heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms, trimethylsilyl group, (trimethylsilyl) methyl group as a substituent containing (f) silicon atom, and ether such as dimethyl ether, diethyl ether, tetrahydrofuran as a (to) Lewis base. , Thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitril and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2'-piperidine, phenanthroline, etc. Amines, phosphines such as triethylphosphine and triphenylphosphine, and ethylene as a (h) chain unsaturated hydrocarbon, butadiene, 1-pentene, isoprene,
Pentadiene, 1-hexene and their derivatives,
(I) benzene, toluene as a cyclic unsaturated hydrocarbon,
Examples include xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and (nu) derivatives thereof.

Examples of the crosslink of A _{f by} a covalent bond include a methylene crosslink (f = 1) and a dimethylmethylene crosslink (f
= 1), ethylene bridge (f = 2), dimethylsilylene bridge (f = 1), dimethylgermylene bridge (f = 1), dimethylstannylene bridge (f = 1) and the like.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Condensed cyclopentadienyl groups such as cyclopentadienyl group and indenyl group shall be treated as compatible. (I) Compound of formula (VII) (1) (pentamethylcyclopentadienyl) trimethylzirconium, (2) (pentamethylcyclopentadienyl) triphenylzirconium, (3) (pentamethylcyclopentadienyl) tri Benzyl zirconium, (4) (pentamethylcyclopentadienyl) trichlorozirconium, (5) (pentamethylcyclopentadienyl) trimethoxyzirconium, (6) (cyclopentadienyl) trimethylzirconium, (7)
(Cyclopentadienyl) triphenylzirconium,
(8) (Cyclopentadienyl) tribenzyl zirconium, (9) (Cyclopentadienyl) trichlorozirconium, (10) (Cyclopentadienyl) trimethoxyzirconium, (11) (Cyclopentadienyl) dimethyl (methoxy ) Zirconium, (12) (methylcyclopentadienyl) trimethylzirconium, (13) (methylcyclopentadienyl) triphenylzirconium, (14) (methylcyclopentadienyl) tribenzylzirconium, (15) (methylcyclo Pentadienyl) trichlorozirconium, (16) (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(17) (dimethylcyclopentadienyl) trichlorozirconium, (18) (trimethylcyclopentadienyl) trichlorozirconium, (19) (trimethylsilylcyclopentadienyl) trimethylzirconium,
(20) (Tetramethylcyclopentadienyl) trichlorozirconium. (Ii) Compound of formula (VIII) (1) Bis (cyclopentadienyl) dimethylzirconium, (2) Bis (cyclopentadienyl) diphenylzirconium, (3) Bis (cyclopentadienyl) diethylzirconium, (4) ) Bis (cyclopentadienyl) dibenzylzirconium, (5) bis (cyclopentadienyl) dimethoxyzirconium, (6) bis (cyclopentadienyl) dichlorozirconium, (7) bis (cyclopentadienyl) dihydride zirconium,
(8) Bis (cyclopentadienyl) monochloromonohydrido zirconium, (9) Bis (methylcyclopentadienyl) dimethyl zirconium, (10) Bis (methylcyclopentadienyl) dichlorozirconium, (11)
Bis (methylcyclopentadienyl) dibenzylzirconium, (12) bis (pentamethylcyclopentadienyl) dimethylzirconium, (13) bis (pentamethylcyclopentadienyl) dichlorozirconium, (14)
Bis (pentamethylcyclopentadienyl) dibenzylzirconium, (15) bis (pentamethylcyclopentadienyl) chloromethylzirconium, (16) bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (17) (cyclo Pentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium. (Iii) Compound of formula (IX) (1) Methylenebis (indenyl) dichlorozirconium, (2) Ethylenebis (indenyl) dichlorozirconium, (3) Ethylenebis (indenyl) monochloromonohydridozirconium (4) Ethylenebis (indenyl) Chloromethylzirconium, (5) ethylenebis (indenyl) chloromethoxyzirconium, (6) ethylenebis (indenyl)
Diethoxyzirconium, (7) ethylenebis (indenyl) dimethylzirconium, (8) ethylenebis (4,5,6,7-tetrahydroindenyl) dichlorozirconium, (9) ethylenebis (2-methylindenyl) dichlorozirconium , (10) ethylene bis (2
-Ethylindenyl) dichlorozirconium, (11) ethylene (2,4-dimethylcyclopentadienyl)
(3 ', 5'-dimethylcyclopentadienyl) dichlorozirconium, (12) ethylene (2-methyl-4-te
rt-Butylcyclopentadienyl) (3'-tert-butyl-5'-methylcyclopentadienyl) dichlorozirconium, (13) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4 ′, 5′-Trimethylcyclopentadienyl) dichlorozirconium, (14) isopropylidenebis (indenyl) dichlorozirconium, (15) isopropylidenebis (2,4-dimethylcyclopentadienyl) (3 ′, 5′- Dimethylcyclopentadienyl) dichlorozirconium, (16) isopropylidene bis (2-methyl-4-tertbutylcyclopentadienyl) (3'-tertbutyl-5-methylcyclopentadienyl) dichlorozirconium, (17) Isopropylidene (cyclopentadienyl) (fluorenyl) dichlorozirconium, (18) Si Rohekishiriden (2,5
-Dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) dichlorozirconium,
(19) Dimethylsilylenebis (indenyl) dichlorozirconium, (20) Dimethylsilylenebis (4,5,5
6,7-Tetrahydroindenyl) dichlorozirconium, (21) Dimethylsilylenebis (2-methylindenyl) dichlorozirconium, (22) Dimethylsilylenebis (2-methyl-4-phenylindenyl) dichlorozirconium, (23) Dimethyl silylene bis (2,4,4
-Trimethyl-4,5,6,7-tetrahydrosilylindenyl) dichlorozirconium, (24) dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazulenyl) dichlorozirconium, (25) dimethylsilylenebis (2- Methyl-4,5,6,7-tetrahydroindenyl) dichlorozirconium, (26) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-Dimethylcyclopentadienyl) dichlorozirconium, (27) phenylmethylsilylenebis (indenyl) dichlorozirconium, (28) phenylmethylsilylenebis (4,5,6,7-tetrahydroindenyl)
Dichlorozirconium, (29) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ',
5'-dimethylcyclopentadienyl) dichlorozirconium, (30) phenylmethylsilylene (2,3,5-
Trimethylcyclopentadienyl) (2 ', 4', 5 '
-Trimethylcyclopentadienyl) dichlorozirconium, (31) diphenylsilylenebis (indenyl) dichlorozirconium, (32) tetramethyldisilylenebis (indenyl) dichlorozirconium, (33) tetramethyldisilylenebis (3-methylcyclopenta (Dienyl) dichlorozirconium, (34) dicyclohexylsilylenebis (indenyl) dichlorozirconium, (3
5) Dicyclohexylsilylenebis (2-methylindenyl) dichlorozirconium, (36) Dicyclohexylsilylenebis (2,4,7-trimethylindenyl) dichlorozirconium, (37) Dimethylgermanium bis (indenyl) dichlorozirconium, (38) Dimethyl germanium (cyclopentadienyl) (fluorenyl) dichlorozirconium, (39) methylaluminum bis (indenyl) dichlorozirconium, (40) phenylaluminum bis (indenyl) dichlorozirconium, (41) phenylphosphinobis (indenyl) dichlorozirconium , (42) ethyleneboranobis (indenyl) dichlorozirconium, (43) phenylaminobis (indenyl) dichlorozirconium, (44) phenylamino (cyclopentadiene (Enyl) (fluorenyl)
Dichlorozirconium. (Iv) Compound of formula (X) tetrabenzylzirconium, bis (2,5-di-t-
Butylphenoxy) dimethyl zirconium.

It is also possible to use the compounds of the above formulas (VII) to (IX) in which chlorine is replaced by bromine, iodine, hydride, methyl or phenyl.

These compounds may be used alone,
You may use it in combination of 2 or more type. Further, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.
Preferred metallocene compounds in the present invention are zirconium compounds, hafnium compounds and titanium compounds. Further preferred are zirconium compounds and hafnium compounds having at least two cyclopentadienyl skeletons. Particularly preferred compounds are the compounds (20), (21), (22), (23) and (2) above.
4) and (25).

The metallocene compound as described above is
It can also be used by supporting it on a carrier by bringing it into contact with a particulate carrier compound. As the carrier compound, SiO ₂ , Al
₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, TiO
Inorganic support compounds such as ₂ , ZnO, SnO ₂ and BaO,
Resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. These carrier compounds may be used in combination of two or more. Of these, SiO ₂ , Al ₂ O ₃ , MgO,
Polypropylene is preferably used, and particularly preferably,
Porous SiO ₂ , Al ₂ O ₃ , MgO, and polypropylene can be used. << Component (B): Organometallic Compound Catalyst Component >> Organometallic compound catalyst component (component) containing a metal selected from Group I to Group III of the periodic table used for forming the prepolymerized catalyst (T) A) covers all known compounds used as so-called cocatalysts in combination with transition metal compound catalyst components.

Specifically, such a compound is, for example, an organoaluminum compound, a complex alkyl compound of a Group I metal and aluminum, an organometallic compound of a Group II metal, or an alumoxane.

As such an organic aluminum compound, the organic group has 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms.
Known organoaluminum compounds having at least one hydrocarbon group of 5 can be used. Specific preferred examples of the organoaluminum compound include (a) trialkylaluminum, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) alkylaluminum halide, For example, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, etc., (C) dialkyl aluminum hydride, for example, diethyl aluminum hydride, diisobutyl aluminum hydride, etc.
(D) Alkyl aluminum alkoxides such as diethyl aluminum ethoxide, diethyl aluminum butoxide, diethyl aluminum phenoxide, and diethyl aluminum trimethylsiloxide can be mentioned.

A preferred specific example of the complex alkyl compound of a Group I metal and aluminum is LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) can be given ₄ or the like.

Preferred specific examples of the organometallic compound of Group II metal include diethyl zinc, di-n-butyl zinc, dibutyl magnesium, butyl ethyl magnesium, butyl magnesium bromide and the like.

These compounds can be used in combination of two or more kinds.

The following compounds can be used as the alumoxane. Alumoxane is a product obtained by reacting one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane, etc. obtained from one type of trialkylaluminum, and methylethylalumoxane, methylbutyl obtained from two types of trialkylaluminum and water. Alumoxane, methyl isobutyl alumoxane, etc. are illustrated. It is possible to use a plurality of these alumoxanes in combination, and it is also possible to use in combination with other alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride.
It is also possible to use two types of alumoxane or alumoxane modified by reacting one type of alumoxane with another organoaluminum compound. Among these, preferred are methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, and mixtures of these alumoxane and trialkylaluminum. More preferred are methylalumoxane and methylisobutylalumoxane. Particularly preferred is methyl isobutyl alumoxane.

These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified. (A) A method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether, (b) a salt hydrate having a trialkylaluminum and water of crystallization, such as copper sulfate or aluminum sulfate. Method of reacting with hydrate, (c) Method of reacting trialkylaluminum with water impregnated in silica gel, etc. (d) Mixing trimethylaluminum and triisobutylaluminum, and mixing with toluene, benzene, ether, etc. A method of directly reacting with water using an organic solvent, (e) a method of mixing trimethylaluminum and triisobutylaluminum and heating and reacting with a salt hydrate having water of crystallization, for example, copper sulfate or aluminum sulfate hydrate. , (F) Impregnated with water into silica gel, triisobutylaluminum After treatment, a method of adding treated with trimethylaluminum, method (g) synthesized in methylalumoxane and isobutyl alumoxane known methods, these two components are mixed predetermined amounts, reacted under heating.

The above organometallic compound catalyst components may be used alone or in combination. Alternatively, the metallocene compound may be supported on the above-mentioned carrier compound for use. As the organometallic compound catalyst component, in the case of the transition metal compound catalyst component [1] or [2], an organoaluminum compound, a complex alkyl compound of a Group I metal and aluminum, or an organometal of a Group II metal A compound is preferable, and in the case of the transition metal compound catalyst component [3], an organoaluminum compound and / or alumoxane is preferable.

In addition to the above organometallic compound catalyst component, the following components can be used, if necessary, during the prepolymerization treatment. In the case of the transition metal compound catalyst component [1] or [2], the electron donor that can be used when preparing the transition metal compound catalyst component [2] can be used in combination. << Component (C) >> The component (C) is a compound that reacts with the transition metal compound contained in the component (A) to form an ionic complex. This component (C) may be used in combination with a compound that reacts with the metallocene compound contained therein to form an ionic complex, particularly when the component (A) is the transition metal compound catalyst component [3]. preferable. Such compounds include ionic compounds formed from ion pairs of cations and anions. This ionic compound can be represented by the following formula (V).

[Q] ^{s +} [Y] ^s- Formula (V) Here, Q is a cation component of the ionic compound, and preferably, for example, carbonium cation, tropylium cation, ammonium cation, oxonium cation, Examples thereof include a sulfonium cation and a phosphonium cation. Particularly preferred specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, tetrabutylammonium, N, N-dimethylanilinium, tripropylammonium, tricyclohexylammonium, tetraphenylphosphonium and tetraphenylcarbonium. Examples thereof include methylphosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium and pyrylium.

Y is an anion component of an ionic compound, and preferably includes, for example, a boron compound anion, an aluminum compound anion, a gallium compound anion, a phosphorus compound anion, an arsenic compound anion, an organic antimony compound anion and the like. As preferred specific examples, tetraphenylboron, tetrakis (pentafluorophenyl) boron, tetraphenylaluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium, tetrakis (pentafluorophenyl) gallium, hexafluorophosphorus, hexafluoroarsenic And hexafluoroantimony.

S represents an integer of 1, 2 or 3.

Of the above anion components which are Y, the boron compound anion is preferable. Specific preferred examples of the ionic compound containing the boron compound anion include the following boron compounds.

Triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetrakis (pentafluorophenyl) Triethylammonium borate, tetrakis (pentafluorophenyl) borate tri (n-butyl) ammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate-N, N-
Examples thereof include dimethylanilinium, tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetraphenylborate, and triphenylsulfonium tetrakis (pentafluorophenyl) borate.

In the case of the transition metal compound component [1] or [2], when the electron donor is used in combination, the amount of the electron donor is 0.01 to 0.01 per gram atom of the transition metal in the transition metal compound catalyst component. 50 mol, preferably 0.05-30
It is used in an amount of 1 mole, more preferably 0.1 to 10 moles.

In the case of the transition metal compound component [3], when a compound which reacts with the metallocene compound to form an ionic complex is used in combination, this compound is added to the transition metal compound catalyst component in an amount of 0. 01 to 100 mol, preferably 0.5 to 10 mol, more preferably 1
~ 5 moles can be used. << Preliminary Polymerization >> One of the olefins used in the preliminary polymerization treatment is α-olefin. Examples of such α-olefins include α-olefins having 2 to 20 carbon atoms, particularly 2 to 10 carbon atoms.
-Olefins are preferred. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1
-Heptene, 1-octene, 1-decene, 3-methyl-
1-butene, 4-methyl-1-pentene and the like can be mentioned, with ethylene, propylene and 1-butene being preferred, and ethylene and propylene being especially preferred. Two or more kinds of these α-olefins may be mixed and used.

Other olefins used in the prepolymerization process are polyene compounds. Such polyene compounds are typically selected from the group represented by the following general formulas (I) to (IV) having at least two polymerizable olefinic double bonds. Here, the “polymerizable olefinic double bond” means an olefinic double bond that can be polymerized by a catalyst described later.

[0082]

Embedded image

[0083]

[Chemical 6] (In the formula, p, q, r, u and x are each independently
0 or a positive integer, t, v, w and y are each independently 0 or 1, z is a positive integer,
R ^{1 to} R ⁴⁸ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{37 to} R ⁴⁰ are bonded to each other to form a monocyclic or polycyclic ring. And the monocyclic or polycyclic ring may have a double bond, and R ^{37 to} R ³⁸ and / or R ^{39 to} R ⁴⁰ may form an alkylidene group. Good. However, the compound represented by the formula (III) is
At least one having a structural unit represented by CH = CH _2, the compound represented by formula (IV), having at least two structural units represented by -CH = CH _2. In general, the compounds of the general formulas (I) to (IV) are preferably different depending on the catalyst used in the production. Although the catalyst used in the present invention will be described later, three types of catalyst systems, that is, (1) titanium trichloride catalyst system, (2) catalyst system containing magnesium, titanium and halogen as essential components, and (3) metallocene catalyst. For the system, when using the above catalyst systems (1) and (2),
When the compounds represented by the above general formulas (I) and (IV) use the above catalyst system (3), the above general formula (I),
The compounds represented by (II), (III) and (IV), particularly (I) and (II), are preferably used. (I) Compound of General Formula (I) In the above general formula (I), p, q and r are each independently 0 or a positive integer, preferably 1 ≦.
p + q + r ≦ 26, particularly preferably 4 ≦ p + q + r ≦ 1
It is a number that satisfies 6. This polyene compound has a main chain (R ^{1 to} R ⁴ = H) having 5 to 30 carbon atoms, preferably 8 carbon atoms.
What is -20 is preferable. R ^{1 to} R ⁴ each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, each independently, usually, an alkyl group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms.
In the present invention, a cycloalkyl group and an aromatic hydrocarbon group (phenyl or naphthyl group, or a lower alkyl-substituted product thereof) are preferable. Also, an aromatic group such as a benzyl group via a lower alkylene group, particularly a methylene group, is also used in the present invention. Aromatic groups are included in the category), and specific examples of the alkyl group include a methyl group,
Examples thereof include an ethyl group, an isopropyl group, an isobutyl group and an amyl group. Specific examples of the cycloalkyl group include a cyclohexyl group, a cyclopropyl group, a cyclobutyl group and a cyclopentyl group, and an aromatic hydrocarbon. Examples of the group include a phenyl group, a benzyl group, a naphthalene group, and the like, or derivatives thereof.

The formula (I) is

[0085]

[Chemical 7] It means that there are p, q and r structural units, respectively, and does not mean that these structural units exist continuously. Then, these structural units can take any constitutional order, but in the formula (I), it is preferable to take the constitutional order so as to have a non-conjugated structure.

Preferred specific examples of such polyene include 1,6-heptadiene, 1,7-octadiene,
1,8-nonadiene, 1,9-decadiene, 1,10-
Undecadiene, 1,13-tetradecadiene, 1,1
5-hexadecadiene, 4-methyl-1,9-decadiene, 4,4-dimethyl-1,9-decadiene, 1,5
9-decatriene, 5-allyl-1,9-decadiene and the like can be mentioned. (Ii) Compound of General Formula (II) In the general formula (II), t is 0 or 1, and preferably 0. Further, u is 0 or a positive integer, preferably 0 to 3. And v is 0 or 1
Is. R ^{5 to} R ²⁰ are each independently a hydrogen atom,
It represents an atom or a group selected from the group consisting of a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, as the hydrocarbon group, each independently, usually, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group (phenyl or naphthyl group, or these The lower alkyl-substituted product of is also preferred.
An aromatic group through a lower alkylene group, especially a methylene group,
For example, a benzyl group is also included in the category of an aromatic group in the present invention), and specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and an amyl group. Specific examples of the cycloalkyl group include a cyclohexyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group, and the aromatic hydrocarbon group includes
Examples thereof include phenyl group, benzyl group, naphthalene group and the like, or derivatives thereof.

Specifically, for example, (1) bicyclo [2,2,1] hept-2,5-diene derivative, (2)
Tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3,8
-Dodecadiene derivative, (3) hexacyclo [6,6,6]
1,1 ^3,6, 1 ^{10, 13,} 0 ^2,7, 0 ^9,14] 4,11
A heptadecadiene derivative etc. can be mentioned. The following are preferred specific examples of such compounds.

[0088]

[Table 1] And so on. (iii) Compound of General Formula (III) In the above general formula, w is 0 or 1, and preferably 0. Further, x is 0 or a positive integer, preferably 0 to 3. And y is 0 or 1.
R ^{21 to} R ⁴⁰ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the hydrocarbon group, each independently, usually, an alkyl group or an alkenyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group (phenyl or naphthyl group,
Alternatively, these lower alkyl-substituted products are preferable. Further, lower alkylene groups, particularly aromatic groups through a methylene group, such as benzyl group, are also included in the category of aromatic groups in the present invention). Specific examples of the alkyl group can include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and an allyl group, and specific examples of the alkenyl group can include a vinyl group, a propenyl group, a butenyl group, and a heptenyl group. Group, an octenyl group, and the like. Specific examples of the cycloalkyl group include a cyclohexyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group,
As the aromatic hydrocarbon group, a phenyl group, a benzyl group,
A naphthalene group etc. or these derivatives can be mentioned.

Further, R ^{37 to} R ⁴⁰ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond. Examples of such monocycles or polycycles include the following. These rings may have a substituent such as a lower alkyl group such as a methyl group or a lower alkoxy group.

[0090]

Embedded image In addition, in the above formula, the carbon atoms denoted by 1 and 2 are carbon atoms of an alicyclic structure to which the groups represented by R ^{37 to} R ⁴⁰ are bonded.

Further, R ³⁷ and R ³⁸ and / or R ³⁹ and R ⁴⁰ may form an alkylidene group.
Such an alkylidene group usually has 2 to 4 carbon atoms.
The alkylidene group can be mentioned, and specific examples thereof include an ethylidene group, a propylidene group, an isopropylidene group and an isobutylidene group.

However, the compound represented by the formula (III) is
It has at least one structural unit represented by CH = CH ₂ .

Specifically, for example, (1) 5-vinylbicyclo [2,2,1] hept-2-
Ene derivative (2) 5-allylbicyclo [2,2,1] hept-2-
Ene derivative (3) 8-vinyltetracyclo [4,4,0,1 ^2,5 ,
1 ^7,10 ] -3-dodecene derivative (4) 8-allyltetracyclo [4,4,0,1 ^2,5 ,
1 ^7,10 ] -3-dodecene derivative and the like can be mentioned. The following are preferred specific examples of such compounds.

[0094]

[Table 2] (Iv) Compound of General Formula (IV) In the above general formula, z is a positive integer, preferably 1 to 10, particularly preferably 1 to 7. R ^{41 to} R ⁴⁶
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a base atom, a bromine atom and an iodine atom. Moreover, as a carbon atom, the C1-6 alkyl group or an alkenyl group, a C3-6 cycloalkyl group, and an aromatic hydrocarbon group can be mentioned each independently. Specific examples of these groups include those similar to R ^{21 to} R ⁴⁰ in the compound of the general formula (III).

However, the compound represented by the formula (IV) is -C
The structural unit represented by H = CH ₂ having at least two.

Specific examples thereof include (i) divinylcyclohexane derivative (ii) diallylcyclohexane derivative (iii) vinylallylcyclohexane derivative (iv) divinylcyclooctane derivative (v) diallylcyclooctane derivative and the like. The following are preferred specific examples of such compounds.

1,4-divinylcyclohexane, 1,3
-Divinylcyclohexane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1,
Examples thereof include 5-divinylcyclooctane and 1,5-diallylcyclooctane.

Among the polyene compounds represented by the above general formulas (I) to (IV), 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 1,5,9 -Decatriene, bicyclo [2,2,
1] hept-2-ene (norbornadiene), tetracyclo [4,4,0,1 ^2.5, 1 ^7,10] -3,8-dodecadiene are particularly preferred.

However, even a polyene compound is a compound in which a part of the olefinic double bond exists inside and its polymerizability is practically negligible as compared with the terminal double bond, for example, a diene compound. But having one or both olefinic double bonds inside, ie, diene compounds having less than two polymerizable olefinic double bonds in the molecule, eg 1,4-hexadiene, 5- Polyene compounds such as methyl-1,4-hexadiene and 7-methyl-1,6-octadiene have no effect in the present invention (see Comparative Example 6).

In carrying out the prepolymerization treatment, the above α-
The combination of olefin and polyene compound is ethylene /
1,7-octadiene, ethylene / 1,9-decadiene, ethylene / 1,13-tetradecadiene, ethylene / 1,5,9-decatriene, ethylene / norbornadiene, propylene / 1,7-octadiene, propylene / 1. 9-decadiene, propylene / 1,13-tetradecadiene, propylene / 1,5,9-decatriene,
Propylene / norbornadiene, butene / 1,9-decadiene, butene / 1,13-tetradecadiene, 4-methyl-1-pentene / 1,9-decadiene, 3-methyl-1-butene / 1,9-decadiene, propylene / tetracyclo [4,4,0,1 ^2.5, 1 ^7.0] -3,8-dodecadiene and the like are preferable. Among these, ethylene /
A combination of polyene compound and propylene / polyene compound is particularly preferred.

After the prepolymerization, the composition ratio of the α-olefin and the structural unit derived from the polyene compound is such that the constitutional unit derived from the α-olefin is usually 99.9 to 50 mol%, preferably 99.8. ˜70 mol%, and particularly preferably 99.5 to 85 mol%. α-
If the olefin content exceeds 99.9 mol%, the effect of the present invention is extremely low, and if it is less than 50 mol%, the prepolymerized catalyst produced swells and is difficult to handle.

The composition ratio of α-olefin and polyene as described above can be calculated by measuring the amounts of α-olefin and polyene consumed during the prepolymerization treatment. Specifically, for example, it can be calculated by calculation from the amount of α-olefin and polyene supplied to the polymerization vessel and the amount of α-olefin and polyene remaining in the polymerization vessel measured by gas chromatography.

The number of moles of the α-olefin and polyene charged in the prepolymerization treatment may be such that the composition of the copolymer produced in the prepolymerization treatment is as described above. For example, 1 mole of the α-olefin. On the other hand, polyene is 0.
It is used in an amount of 01 to 50 mol, preferably 0.05 to 25 mol.

The prepolymerization treatment with this specific monomer can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. The liquid phase polymerization method can be carried out in the presence of an inert solvent described later.

Specific examples of the above-mentioned inert solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane,
Examples thereof include alicyclic hydrocarbons such as methylcyclohexane, and mixtures thereof.

When the catalyst containing the above-mentioned components (A) and (B) as the main components is subjected to the prepolymerization treatment, each component is treated with a transition metal atom (Tr) in the component (A) and a component in the component (B). The atomic ratio (Me / Tr) to the metal atom (Me) is usually 0.01 to 10,000, preferably 0.1 to 5,000.
It can be used in an amount of 0, particularly preferably 1 to 1,000. When the catalyst is mainly composed of the components (A) and (C), the component (C) is usually added in an amount of 0.01 to 100 mol, preferably 1 to 100 mol, per gram atom of the transition metal in the component (A). Is 0.5 to 10 mol, particularly preferably 1 to
Used in an amount of 5 mol. Even when the components (A), (B) and (C) are the main components, the quantitative ratio relationship between the components (A) and (B) and the components (A) and (C) is the above quantitative ratio. Is preferred.

The proportion of the transition metal compound catalyst component used in the prepolymerization treatment is 10 ⁻⁵ to 10 gram atom, preferably 10 ⁻⁴ , in terms of the amount of transition metal atom per liter of the polymerization volume.
~ 1 gram atom.

The prepolymerization treatment temperature is usually from -20 to +10.
0 ° C., preferably −20 to + 80 ° C., particularly preferably −
It is in the range of 10 to + 50 ° C. Further, hydrogen is not used during the prepolymerization treatment. When hydrogen is used, the impact resistance improving effect is reduced.

The prepolymerized catalyst (T) thus obtained is generally 0.1 to 10,000 g, preferably 0.1%, per 1 g of the above component (A).
5-8,000 grams, particularly preferably 1-5,000
Gram of prepolymerized polymer, but when the catalyst is based on components (A) and (B), preferably 0.5 to 500 grams, especially preferred, per gram of component (A). 1 to 200 grams per gram of component (A), if the catalyst is based on components (A) and (C) or components (A), (B) and (C), It is customary to contain prepolymerized polymers in amounts of preferably 50 to 8,000 grams, particularly preferably 100 to 5,000 grams.

In the present invention, prior to the above-mentioned prepolymerization treatment, the transition metal compound catalyst components [1] to [3] are mixed with α-
It can also be subjected to a preliminary prepolymerization which comprises contacting and polymerizing an olefin. The α-olefin at that time is preferably an α-olefin having 2 to 20 carbon atoms. More preferably ethylene or propylene is used, especially propylene. Such preliminary prepolymerization can be carried out by a known method and is usually carried out in the coexistence of an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table. Yes, the transition metal compound catalyst component [1] to [3] is 0.
It is common to polymerize 1 to 7,000 grams of α-olefin.

As described above, when the catalyst is subjected to preliminary prepolymerization with α-olefin prior to the prepolymerization treatment of the present invention, specifically, for example, the particle shape such as particle size distribution and particle size distribution is excellent. A prepolymerized catalyst is obtained. II. Block Copolymer The block copolymer according to the present invention is composed of block (i) and block (ii). The block (i) is made of propylene (and ethylene), and the block (ii) is made of ethylene (and propylene). In the above, "consisting of" includes the purposed blocks or components other than the listed blocks, namely (i) and (ii), or the listed components, namely propylene and ethylene (details below). It means to go. Therefore, the block copolymer according to the present invention also includes those in which blocks or components other than the above components are present in each block or between each block. Also, therefore,
"Polymerizing propylene and / or ethylene ..." does not mean to polymerize only both of the monomers listed above, but also includes polymerizing a purposeful copolymerizable monomer. Is. However, it is preferable that the content of the third monomer is up to 10% by weight of the block copolymer.

The block copolymer according to the present invention comprises the propylene polymer (i) in an amount of usually 95 to 10% by weight, preferably 90 to 30% by weight, particularly preferably 85 to 50% by weight, The copolymer (ii) is used in an amount of usually 5 to 90% by weight, preferably 10 to 70% by weight, particularly preferably 15
˜50% by weight.

In addition, the block copolymer according to the present invention is
The melt flow rate (MFR) measured based on ASTM D-1238 is usually 3,000 g / 10 minutes or less, preferably 0.01 to 1,000 g / 10 minutes, and particularly preferably 0.05 to 100 g / 10 minutes. The range is typically in the range of.

<Block (i)> The block (i) has a propylene content of 100 to 90% by weight, preferably 10%.
0-93% by weight, particularly preferably 100-95% by weight,
And a block of a propylene polymer having an ethylene content of 0 to 10% by weight, preferably 0 to 7% by weight, particularly preferably 0 to 5% by weight.

As described above, the block (i) in the present invention can contain components other than propylene and ethylene. A typical example of such a component other than propylene and / or ethylene is a compound copolymerizable with propylene and / or ethylene, preferably (a) an α-olefin having 4 to 20 carbon atoms, specifically, Is 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-
Decene, 1-tetradecene, 1-octadecene, etc.
(B) Aromatic vinyl compounds, specifically styrenes such as styrene and dimethylstyrene, allylbenzenes such as allylbenzene and allyltoluene, vinylnaphthalenes and allylnaphthalenes, and (c) aliphatic vinyl compounds, such as Specific examples include (d) cyclic olefins such as vinylcyclohexanes, vinylcyclopentanes, vinylcycloheptanes and allylnorbornane, specifically, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene and tetracyclodone. Decene, 2-methyl-1,4,5,8-dimethano-1,2,3,4a,
(Fo) silane-based unsaturated compounds such as 5,8,8a-octahydronaphthalene, specifically, allyltrimethylsilane, ayltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, Examples thereof include (f) polyene compounds used in the prepolymerization treatment such as 8-trimethylsilyl-1-octene and 10-trimethylsilyl-1-decene. Here, "...", for example, "styrenes", means a side chain and / or a nucleus or a ring-substituted or unsubstituted body. In this case, the substituent is preferably, for example, a lower alkyl group (especially one having 1 to 4 carbon atoms), a lower alkoxy group, a trifluoromethyl group or a halogen atom, particularly a lower alkyl group.

These may be used alone or in combination. Of these, 1-butene, 3-methyl-1
-Butene, 3-methyl-1-pentene, 4-methyl-1
-Pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene and the like are preferably used. Particularly preferred is 1-
Butene, 3-methyl-1-butene and 4-methyl-1
-Pentene etc. are mentioned.

When these components such as α-olefin other than propylene and ethylene are used in combination, the content thereof is optional as long as the effects of the present invention are not impaired, but up to 10% by weight (block (i) standard) ).

The propylene polymer (i) may have a predominantly isotactic structure or a syndioctactic structure.

<Block (ii)> The block (ii) has a propylene content of 0 to 90% by weight, preferably 0 to 85.
% By weight, particularly preferably 0 to 80% by weight and the ethylene content is 100 to 10% by weight, preferably 100 to 1
It is a block composed of a copolymer of 5% by weight, particularly preferably 100 to 20% by weight, and the block (i) and the propylene and / or ethylene content are different in the same block copolymer.

The block (ii) also contains a small amount of a copolymerizable olefin other than ethylene and propylene, such as those described above for the block (i), or a polyene compound used in the prepolymerization treatment, as long as the effect of the present invention is not impaired. (For example, up to 10% by weight (based on the block (ii))) may be copolymerized. Examples of such α-olefins include α-olefins having 4 to 20 carbon atoms, preferably 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene. 4-methyl-1-pentene and the like can be mentioned. As the polyene compound, those exemplified in the section of prepolymerization can be mentioned.

The composition ratio of propylene and ethylene can be calculated, for example, by measuring the amounts of propylene and ethylene consumed during the polymerization. Specifically, it can be calculated from the amount of propylene and ethylene supplied into the polymerization vessel and the amounts of propylene and ethylene remaining in the polymerization vessel measured by gas chromatography.

III. Use of Catalyst / Production of Block Copolymer The method for producing a block copolymer according to the present invention comprises at least the blocks (i) and (ii) in the presence of a catalyst comprising at least the prepolymerized catalyst (T). It is produced in a two-step process. When the prepolymerized catalyst containing the above components (A) and (B) as the main components is used, each component is composed of the transition metal atom (Tr) in the component (A) and the metal in the component (B). Atom (M
The atomic ratio (Me / Tr) to e) is usually 0.1 to 5
It can be used in an amount of 50,000, preferably 1 to 10,000, particularly preferably 2 to 5,000. When the prepolymerized catalyst is mainly composed of the components (A) and (C), the component (C) is usually added in an amount of 0.01 to about 1 gram atom of the transition metal in the component (A). 100
Mol, preferably 0.5 to 10 mol, particularly preferably 1
Used in an amount of ~ 5 mol. Component (A), component (B),
Even in the case where (C) and (C) are the main components, it is preferable to use the above-mentioned amount ratios for the component (A) and (B) and the component (A) and (C).

The prepolymerized catalyst (T) has a polymerization ability by itself, but the components (B) and / or components which are the same as or different from those used in the preparation of the stereoregular catalyst to be subjected to the prepolymerization treatment. It can be used in the presence of a combination with (C), or an electron donor can be used in combination as a so-called external donor. This is the reason that the catalyst is defined as "consisting of at least the prepolymerized catalyst (T)" in the present invention.

The ratio of the component (A) used for the polymerization is
Usually, 10 ^-7 to 1 in terms of the transition metal atom in the component (A).
0 ^-1 gram atom / liter, preferably 10 ^-6 to 10
^-The range is ² grams atom / liter.

Polymerization methods include bulk polymerization, solution polymerization,
Either method such as suspension polymerization or gas phase polymerization may be used. Further, a batch method or a continuous method may be used. When using a polymerization solvent, specifically, hexane, an aliphatic hydrocarbon such as heptane, an aromatic hydrocarbon such as benzene, toluene and xylene, an alicyclic hydrocarbon such as cyclohexane and methylcyclohexane, or a mixture thereof. Etc. can be used. Further, a monomer such as α-olefin may be used as a solvent.

The polymerization condition of the block copolymer is usually -4.
At a polymerization temperature of 0 to 250 ° C., preferably −30 to 150 ° C., more preferably −20 to 120 ° C., usually atmospheric pressure to
10 kg / cm ² G, preferably 1 to 50 kg / cm ²
G, under the polymerization pressure.

In the present invention, the polymerization is carried out in two steps: a step of mainly producing the block (i) and a step of mainly producing the block (ii). Either step may be performed first, but it is preferable to perform the step that mainly generates the block (i) first. In either method, it is important to carry out the latter-stage polymerization by coexisting the polymer produced in the former stage.

In addition, when producing the block copolymer, the above-mentioned electron donor that can be used in the prepolymerization treatment can be used if necessary. These electron donors are present in the prepolymerization catalyst (T) at 0.
It can be used in the range of 001 to 10 mol, preferably 0.01 to 5 mol.

Transition metal compound catalyst components [1] to [3] 1
The block copolymer yield per gram is usually 0.1 to
2,000 kg, preferably 0.5-1,000 kg,
Range. The yield of the block copolymer per 1 g of the prepolymerized polymer is 5 g or more, preferably 10 g or more, and particularly preferably 20 g or more.

Further, in the block copolymer according to the present invention, if necessary, a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, an antiblocking agent, a lubricant, a nucleating agent, a pigment, a dye,
Inorganic or organic fillers may be added for practical use.

[0131]

The following examples serve to illustrate the invention in more detail. Therefore, the present invention is not limited to the following examples unless it exceeds the gist.

The evaluation method performed here is as follows. (B) Flexural modulus It was measured according to JIS-K7203. Measurement temperature is 2
It is 3 ° C. (B) Izod impact strength It was measured according to JIS-K7110. (C) 230 ° C / 2.1 based on MFR ASTM D-1238
It was measured under a load of 6 kg. (D) Flow mark 40 × 250 prepared under the molding conditions shown in Example 1 below.
The flow marks generated on the × 2 mm flat plate were evaluated in four grades.

A: No generation B: Almost no reaction C: No reaction D: No reaction [Example 1] <Preliminary polymerization treatment of transition metal compound catalyst component [1]> Purification into an autoclave with an internal volume of 1 liter replaced with nitrogen -
Add 500 ml of heptane, 1 g of diethylaluminum chloride at 20 ° C., and 10 parts of titanium trichloride manufactured by Toho Titanium Co., Ltd. as a transition metal compound catalyst component [1].
After charging 40 ml of g, 1,9-decadiene, when 60 liters of gaseous ethylene was supplied, the supply of ethylene was stopped.

After completion of the prepolymerization, the catalyst was transferred to a nitrogen-substituted 2 liter glass flask and washed with 500 ml of purified n-heptane 5 times to obtain a prepolymerized catalyst (T) -1. 1 per 1g of titanium trichloride
0.1 g of polymer had formed. In this polymer, the constitutional unit derived from 1,9-decadiene was 8.0.
It was found from analysis that it contained mol%.

<Polymerization> Purified n-heptane (48 liters) was placed in an autoclave having an internal volume of 100 liters, which had been replaced with nitrogen, and diethyl aluminum chloride (40 ml) was added at 70 ° C.
g, 7.6 g of the above-mentioned prepolymerized catalyst (T) -1 in terms of titanium trichloride and 50 liters of hydrogen were charged, and then propylene was adjusted to 7 kg / cm ² G at a total pressure.
The block (i) was polymerized at 0 ° C. for 100 minutes. Propylene and hydrogen were purged until the total pressure became 0 kg / cm ² G, the autoclave temperature was lowered to 60 ° C., and then a mixed gas of propylene / ethylene = 2/1 (weight ratio) was injected to bring the total pressure to 2 kg. / Cm ² G, 100 at 60 ℃
The block (ii) was polymerized for a period of time. As a result, 1
9.1 kg of block copolymer was obtained.

<Molding> Block Copolymer 100 Obtained
Parts by weight, tetrakis- [methylene-3- (3 ', 5'-
Di-t-butyl-4'-hydroxyphenyl) propionate] methane 0.05 part by weight, 2,6-di-t-butyl-4-methylphenol 0.1 part by weight, calcium stearate 0.05 part by weight, tri 0.1 part by weight of aluminum p-t-butylbenzoate was mixed and melted at a temperature of 220 ° C. by a 50 mm single screw extruder to obtain pellets.
Injection molding machine M40A-S manufactured by Meiki Seisakusho
Using J, cylinder temperature 230 ℃, mold temperature 40 ℃,
A test piece for measuring flexural modulus and Izod impact strength was injection molded under the conditions of an injection pressure of 137 kg / cm ² , an injection time of 4 seconds and a cooling time of 25 seconds. Also, under the same conditions, 4
A 0 × 250 × 2 mm flat plate was molded.

The flexural modulus measured at 23 ° C., the Izod impact strength measured at −20 ° C. and the flow mark evaluation results are shown in Table 3.

[Comparative Example 1] An experiment was conducted in the same manner as in Example 1 except that titanium trichloride not subjected to the prepolymerization treatment was used in place of the catalyst (T) subjected to the prepolymerization treatment in Example 1. I went. As a result, 19.1 kg of a block copolymer was obtained. The evaluation results are as shown in Table 3.

From the above comparative examples, it is understood that the prepolymerization treatment with 1,9-decadiene and ethylene improves the rigidity, impact resistance and MFR balance, and the flow mark.

Comparative Example 2 An experiment was conducted in the same manner as in Example 1 except that 200 ml of hydrogen was fed into the autoclave during the prepolymerization treatment. However, after the prepolymerization treatment, 9.8 per gram of titanium trichloride in the prepolymerized catalyst (T) -1.
Grams of polymer had formed. It was found by analysis that this polymer contained 8.0% by weight of a structural unit derived from 1,9-decadiene. As a result,
18.9 kg of a block copolymer was obtained. The evaluation results are as shown in Table 3.

From this comparative example, it is understood that the improvement effect is low when the prepolymerization treatment is carried out in the presence of hydrogen.

[Example 2] <Preparation of transition metal compound catalyst component [2]> 200 ml of deoxygenated n-heptane was introduced into a flask sufficiently replaced with nitrogen, and then 0.4 mol of MgCl ₂ and Ti were added.
_{(O-nC 4 H 9)} 4 was 0.8 mol introduction, 2 at 95 ° C.
Allowed to react for hours. After the reaction was completed, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The solid component formed was washed with n-heptane.

Next, 50 ml of n-heptane purified in the same manner as above was introduced into a flask which had been sufficiently replaced with nitrogen, and the solid component synthesized above was converted to 0.2 in terms of Mg atom.
4 mol was introduced. Then, 25 ml of n-heptane was mixed with 0.4 mol of SiCl ₄ and introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, it was washed with n-heptane. Then, 25 ml of n-heptane was mixed with 0.024 mol of phthalic acid chloride and introduced into the flask at 70 ° C./30 minutes,
The reaction was carried out at 90 ° C for 1 hour.

After completion of the reaction, it was washed with n-heptane. Then, 20 ml of SiCl ₄ was introduced and reacted at 80 ° C. for 6 hours. After the reaction was completed, it was thoroughly washed with n-heptane. The titanium content of this component was 1.21% by weight.

Purified n was prepared in a flask in which nitrogen was sufficiently replaced.
Introducing 50 ml of heptane, then introducing 7 g of the component obtained above, then (CH ₃ ) ₃ CSi
2.5 ml of (CH ₃ ) (OCH ₃ ) ₂ was introduced, followed by 0.73 ml of TiCl _{4 and} 4.0 g of triethylaluminum, respectively.
Contact was performed at 30 ° C. for 2 hours. After completion of the contact, the mixture was thoroughly washed with n-heptane to obtain a transition metal compound catalyst component [2]. The titanium content in this component was 3.64% by weight.

<Preliminary Prepolymerization> 400 ml of dehydrated and deoxygenated n-heptane was introduced into a stirring autoclave having an internal volume of 1.5 liter which was sufficiently replaced with nitrogen, and after cooling the system to 15 ° C., 0.65 g of n-butyllithium and 6.5 g of the above transition metal compound catalyst component [2] were introduced, and propylene was fed at 13 g / Hr for 0.5 hours to carry out a prepolymerization treatment with propylene. 10 after the propylene field ends
Residual pressure polymerization was performed for minutes. After completion, it was washed twice with n-heptane. As a result, 0.92 g of polypropylene was prepolymerized per 1 g of the transition metal compound catalyst component [2].

<Preliminary Polymerization Treatment of Transition Metal Compound Catalyst Component [2] After Preliminary Prepolymerization with Ethylene and 1,7-Octadiene> 500 ml of purified n-heptane was placed in an autoclave having an internal volume of 1 liter and purged with nitrogen. At 20 ° C., 0.5 g of triethylaluminum, 12 g of the transition metal compound catalyst component [2] obtained through the above preliminary prepolymerization, and 3 g of 1,7-octadiene.
After charging 2 ml, ethylene was supplied to the autoclave. During the polymerization reaction, the autoclave was kept at 20 ° C., and when 65 liters of gaseous ethylene was supplied, the supply of ethylene was stopped.

After the completion of the prepolymerization treatment, the catalyst was transferred to a nitrogen-substituted 2 liter glass flask and washed with 500 ml of purified n-heptane 5 times to obtain a prepolymerization treated catalyst (T) -2. The prepolymerized catalyst (T) -2 contained 16.9 g of the polymer per gram of the transition metal compound catalyst component [2].
It was found by analysis that this polymer contained 7.0% by weight of a constitutional unit derived from 1,7-octadiene.

<Polymerization> In Example 1, 8 g of triethylaluminum was used in place of diethylaluminum chloride, and the prepolymerized catalyst (T)-
40 grams of prepolymerized catalyst (T) -2 was used instead of 1, and the polymerization temperature and polymerization time of blocks (i) and (ii) were 75 ° C. for 75 minutes and 70 ° C. for 8 minutes, respectively.
An experiment was conducted in the same manner as in Example 1 except that the amount of hydrogen was changed to 0 minutes and the amount of hydrogen was changed to 40 liters. As a result, 18.9 kg of a block copolymer was obtained. The evaluation results are as shown in Table 3.

[Comparative Example 3] In Example 2, in place of the prepolymerized catalyst (T) -2, 5.6 g (transition) of the transition metal compound catalyst component [2] preliminarily prepolymerized. The experiment was conducted in the same manner as in Example 2 except that the amount of the metal compound catalyst component was the same as that in Example 2). As a result, 18.6 kg of a block copolymer was obtained. The evaluation results are as shown in Table 3.

According to this comparative example, when the transition metal compound catalyst component [2] was used as the component (A), 1,7-
When prepolymerization treatment with octadiene and ethylene,
It can be seen that the stiffness, impact resistance and MFR balance, and flow mark are improved.

[Comparative Example 4] In Example 2, except that 1,7-octadiene was not used in the prepolymerization treatment and the amount of hydrogen in the block (i) production was 36 liters. The experiment was conducted in the same manner as in 2.
However, after the prepolymerization treatment, the prepolymerized catalyst (T)-
In 1 of the transition metal compound catalyst component [2], 13.8 g of the polymer was produced in No. 2. As a result,
18.7 kg of a block copolymer was obtained. The evaluation results are as shown in Table 3.

From this comparative example, it is understood that the prepolymerization treatment using only ethylene has no improvement effect.

Comparative Example 5 An experiment was conducted in the same manner as in Example 2 except that 200 ml of hydrogen was fed into the autoclave during the prepolymerization treatment. However, after the prepolymerization treatment, 17.4 g of the polymer was formed in 1 g of the transition metal compound catalyst component [2] in the prepolymerized catalyst (T) -2.
It was found by analysis that this polymer contained 6.7% by weight of a structural unit derived from 1,7-octadiene. As a result, the block copolymer was 19.2 kg.
Obtained. The evaluation results are as shown in Table 4.

From this comparative example, it is understood that the improvement effect is low when the prepolymerization treatment is carried out in the presence of hydrogen.

[Comparative Example 6] In Example 2, 1,7-
An experiment was conducted in the same manner as in Example 2 except that 36 ml of 7-methyl-1,6-octadiene was used instead of octadiene. However, after the prepolymerization treatment, 15.9 g of the polymer was produced per 1 gram of the transition metal compound catalyst component [2] in the catalyst (T) -2 having undergone the prepolymerization treatment. In this polymer, 7-methyl-1,6-
20.1% by weight of structural units derived from octadiene
It was found to be included by analysis. As a result, 18.8 kg of an olefin polymer was obtained. The evaluation results are as shown in Table 4.

This comparative example shows that the diene having less than two polymerizable olefinic double bonds in one molecule has no improvement effect.

Example 3 An experiment was conducted in the same manner as in Example 2 except that 95 g of propylene was used instead of ethylene in the prepolymerization treatment. However, after the prepolymerization treatment, 15.0 g of the polymer was formed per 1 gram of the transition metal compound catalyst component [2] in the prepolymerized catalyst (T) -2. It was found by analysis that this polymer contained 11.3 mol% of constitutional units derived from 1,7-octadiene. As a result, the block copolymer was 19.2 kg.
Obtained. The evaluation results are as shown in Table 4.

Example 4 <Preliminary Polymerization Treatment of Transition Metal Compound Catalyst Component [3]> Purification in an autoclave having an internal volume of 1 liter and being purged with nitrogen n-
Add 500 ml of heptane and add 10 g of methyl alumoxane manufactured by Tosoh Akzo at 20 ° C. and then 8.2 mg of dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) dichlorozirconium. The autoclave was allowed to stir for 30 minutes at 20 ° C. Next, after charging 8 ml of 1,7-octadiene, ethylene was supplied to the autoclave. During the polymerization reaction, the autoclave was kept at 20 ° C., and when 20 liters of ethylene was supplied, the supply of ethylene was stopped.

After the preliminary completion, 3.7 g of the polymer was produced in 1 mg of the zirconium compound in the prepolymerized catalyst (T) -3 obtained.
It was found by analysis that this polymer contained 5.8 mol% of structural units derived from 1,7-octadiene.

<Polymerization> 48 liters of purified toluene was placed in an autoclave having an internal volume of 100 liters, which had been purged with nitrogen, and 1 part of methylalumoxane manufactured by Toso Akzo Co., Ltd. was added at 40 ° C.
8 grams, 72 of the prepolymerized catalyst (T) -3
After loading milligram, propylene is 5kg / cm ² G
Polymerization of the block (i) preparation was carried out for 75 minutes while continuously feeding so as to maintain Then, after purging the unreacted propylene, the propylene was continuously added to 900
Polymerization for the preparation of block (ii) was carried out at 40 ° C. for 60 minutes while continuously feeding ethylene at a rate of 400 grams / hour. Then, the supply of propylene and ethylene was stopped, unreacted propylene and ethylene were purged, and a methanol-hydrochloric acid solution was injected to terminate the polymerization. As a result, 5.5 kg of a block copolymer was obtained. The evaluation results are as shown in Table 4.

[Comparative Example 7] In Example 4, instead of the prepolymerized catalyst (T) -3, dimethylsilylenebis (2-methyl-4,5,5) not prepolymerized.
An experiment was conducted in the same manner as in Example 4 except that 15 mg of 6,7-tetrahydroindenyl) dichlorozirconium was used, and the block copolymer was found to be 5.
8 kg was obtained. The evaluation results are as shown in Table 4.

According to this comparative example, even when the transition metal compound catalyst component [3] was used as the component (A), 1,7-
When prepolymerization treatment with octadiene and ethylene,
It can be seen that the stiffness, impact resistance and MFR balance, and flow mark are improved.

Example 5 An experiment was conducted in the same manner as in Example 4, except that 6 ml of norbornadiene was charged in place of 1,7-octadiene as the polyene compound in the prepolymerization treatment. However, in the obtained prepolymerized catalyst (T) -4, 3.4 g of the polymer was produced per 1 mg of the transition metal compound catalyst component. It was found by analysis that this polymer contained 6.3 mol% of a constitutional unit derived from norbornadiene. As a result of the polymerization, 5.3 kg of an olefin polymer was obtained. The evaluation results are as shown in Table 4.

[0165]

[Table 3]

[0166]

[Table 4]

[0167]

EFFECTS OF THE INVENTION The propylene block copolymer according to the present invention is superior in impact resistance to conventional propylene block copolymers and has a good balance of physical properties (stiffness, impact resistance and MFR balance). And has an excellent molded body appearance, and therefore a TV case, a VT
Various characteristics of home appliances such as R cases and washing machine covers, automobile interior and exterior parts such as bumpers, instrument panels, glove boxes, acoustic product parts such as stereo cases, and especially excellent properties as materials for automobile bumpers. What is possessed is as described above in the section "Outline of the Invention".

Claims (8)

[Claims] 1. Propylene and / or ethylene are polymerized in at least two steps to obtain block (i) 95-
In a method for producing a block copolymer comprising 10% by weight and 5 to 90% by weight of block (ii), provided that the blocks have substantially different contents of propylene and / or ethylene. The method for producing a block copolymer, wherein the polymerization catalyst to be used comprises at least the following prepolymerized catalyst (T). Prepolymerized catalyst (T): the following components (A) and (B), components (A) and (C), or (A),
The stereoregular polymerization catalyst comprising (B) and (C) is contacted with an α-olefin and a polyene compound under hydrogen-free conditions to give 0.1 to 10,000 per 1 g of component (A).
A prepolymerized catalyst (T) obtained by subjecting to a prepolymerization treatment comprising copolymerization in an amount of g. Component (A): Transition metal compound catalyst component. Component (B): An organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table. Component (C): A compound which reacts with the transition metal compound contained in the component (A) to form an ionic complex. Block (i): Propylene content is 100 to 90% by weight
And a block consisting of a propylene polymer having an ethylene content of 0 to 10% by weight. Block (ii): A block made of a polymer having a propylene content of 0 to 90% by weight and an ethylene content of 100 to 10% by weight. 2. A polyene compound having the following general formulas (I) to (IV):
The method for producing a block copolymer according to claim 1, which is selected from the group represented by: Embedded image Embedded image (In the formula, p, q, r, u and x are each independently
0 or a positive integer, t, v, w and y are each independently 0 or 1, z is a positive integer,
R ^{1 to} R ⁴⁸ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{37 to} R ⁴⁰ are bonded to each other to form a monocycle or a polycycle. And the monocyclic or polycyclic ring may have a double bond, and R ^{37 to} R ³⁸
And / or R ^{39 to} R ⁴⁰ may each form an alkylden group. However, compounds of formula (III) has at least one structural unit represented by -C = CH _2, the compound of formula (IV) is a structural unit represented by -C = CH ₂ Have at least two. ) 3. The component (A) is selected from the group consisting of [1] titanium trichloride-based catalyst component, [2] catalyst component containing magnesium, titanium and halogen as essential components, and [3] metallocene compound. The method for producing the block copolymer according to claim 1. 4. The component (B) is an organoaluminum compound,
Complex alkyl compound of Group I metal and aluminum, Group II
The method for producing a block copolymer according to claim 1, which is selected from the group consisting of organometallic compounds of group metals and alumoxane. 5. The method for producing a block copolymer according to claim 1, wherein the component (C) is an ionic compound represented by the following formula (V). [Q] ^{s +} [Y] ^s- Formula (V) (wherein Q is a cation component of an ionic compound, and is a carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation or phosphonium cation. And Y
Is an anion component of an ionic compound, which is a boron compound anion, an aluminum compound anion, a gallium compound anion, a phosphorus compound anion, an arsenic compound anion or an organic antimony compound anion, and s
Represents an integer of 1, 2 or 3. ) 6. The prepolymerized catalyst (T) consists essentially of an α-olefin having 2 to 20 carbon atoms in the presence of the component (B) and / or the component (C) before the prepolymerization treatment. The method for producing a block copolymer according to any one of claims 1 to 5, which has been subjected to preliminary prepolymerization which comprises polymerizing the olefin by contacting with the olefin. 7. The olefin used in the preliminary prepolymerization is
The method for producing a block copolymer according to claim 6, which is propylene. 8. Polymerization of blocks (i) and (ii) is carried out with pre-polymerized catalyst (T) and component (B) according to claim 1.
The block copolymer according to any one of claims 1 to 7, which is carried out in the presence of a combination of the compound represented by the formula (1) and / or the compound represented by the component (C) in claim 1. Manufacturing method.