JP2002206007A - Production method of olefin block copolymer - Google Patents

Abstract

(57) [Problem] To provide an olefin block copolymer having a small molecular weight distribution (Mw / Mn). SOLUTION: (A) a hafnium or zirconium-containing compound having one or two cyclopentadienyl skeletons, (B) a triphenylboron-based compound or a tetraphenylboron-salt-based compound and optionally a specific mono, di or Using a catalyst composed of a trialkylaluminum-based compound, block copolymerizing an olefin-based monomer having 2 to 20 carbon atoms at a low temperature to obtain a molecular weight distribution (Mw / M
n) produces an olefin-based block copolymer of 1 to 1.3. By mixing the obtained propylene-based block copolymer with a propylene-based (co) polymer other than the propylene-based block copolymer, a propylene-based block copolymer composition that is dispersed very small in some cases is obtained. can get.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin block copolymer and a propylene copolymer comprising the produced propylene block copolymer and a propylene (co) polymer other than the propylene block copolymer. The present invention relates to a system block copolymer composition. More specifically, a method for producing an olefin-based block copolymer having a narrow molecular weight distribution, a propylene-based block copolymer produced and a propylene-based (co) other than the propylene-based block copolymer
The present invention relates to a propylene-based block copolymer composition comprising a polymer.

[0002]

2. Description of the Related Art With respect to living polymerization of olefins,
(Acac) ₃ / R ₂ AlX catalyst (acac is acetylacetonate, R is ethyl group, isobutyl group, X is Cl, B
r) and a molecular weight distribution (Mw / Mn) of 1.0
5-1.4 syndiotactic polypropylene (P
Example of the production of P) ([r] -0.8) (Macromolecules, 12 814)
_{(1979)), Me 2 Si} (2-SiMe 3 -4-tB
_{u-C 5 H 2) 2} Sm (THF) 2 catalyst (Me is methyl,
tBu is a t-butyl group, and THF is tetrahydrofuran.
Using ethylene without a cocatalyst to produce a living polymer of ethylene or 1-hexene (Catalyst, 37 205 (199)
5)), [(2,6- iPr 2 C 6 H 3) N (CH 2) 3 N
_{(2,6-iPr 2 C 6 H} 3)] TiMe 2 / B (C 6 F 5)
_{Using 3} catalyst (iPr is i-propyl group, Me is methyl group), Mw / Mn is 1.1 or less carbon number 6-10 at room temperature.
Of an α-olefin living polymer (J. Am. Chem. Soc.), 118 100
08 (1996)), a bulky aryl group-containing diimine complex of Ni

[0003]

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[0004] A low-concentration 3-1 carbon atom at 0 ° C or lower
8 obtained by living polymerization of α-olefin (Journal of the American Chemical Society,
118 11664 (1996)), 3-coordinated diamide complex of Zr ([NON] ZrMe ₂ complex) / B (C ₆ F ₅ ) ₃
Example of producing an atactic living polymer of 1-hexene having Mw / Mn of 1.1 or less at 0 ° C. using a catalyst (Journal of the American Chemical Society, 119 3830 (1997)), NON] ZrMe ₂ complex:

[0005]

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[TBuNSiMe ₂ Flu] TiMe ₂ /
B (C ₆ F ₅ ) ₃ catalyst (tBu is t-butyl group, Me is methyl group, Flu is

[0007]

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Example of producing a syndio-rich propylene living polymer having a [r] of about 0.65 at low temperature using Polymer Preprint Japan (Polym P)
repr. , Japan. ,) 46 1601 (199
7)) and the like (eg, polymer, 47
Vol., February, pp. 74-77 (1998)).

Also, the reaction formation of a metallocene component (first component) such as a bis (cyclopentadienyl) derivative of titanium, zirconium and hafnium with a second component having a proton-donating cation and a miscible non-coordinating anion. A first living polymer is produced by contacting the first olefin component at −5 to + 10 ° C. with a catalyst, which is a product, and then a second monomer is sequentially added and copolymerized with the first polymer to obtain a molecular weight. An example of producing a multi-block copolymer having a distribution of 1.4 to 1.8 has been reported (Japanese Unexamined Patent Application Publication No. Hei.
503546).

Further, one or more olefinic monomers are polymerized at −5 to + 10 ° C. using a catalyst which is a reaction product of a metal of cyclopentadienyl group 4 / alumoxane or a compatible non-coordinating anion, Molecular weight distribution 1.35-
Examples of the production of block copolymers or tapered copolymers of 4.1 have been reported. Examples of metals forming the cyclopentadienyl group 4 metal include Ti, Z
r, Hf, and the like are described (Tokuhei 9-5015)
No. 0).

In addition, Solvay TiCl ₃ / (C
From the pR) 2TiMe ₂ catalyst, iPP-b-EPR
(Living polymerization with a homogeneous transition metal catalyst, IPC, P50-51, 1999) (JP-A-57-111307).

[0012]

However, for example, in the case of the V (acac) ₃ / R ₂ AlX catalyst, a block copolymer having a highly regular polypropylene block, that is, an isotactic polypropylene block is used. Can not get. [(2,6-iP
_{r 2 C 6 H 3) N} (CH 2) 3 N (2,6-iPr 2 C
₆ H ₃ )] TiMe ₂ / B (C ₆ F ₅ ) ₃ catalyst and the bulky aryl group-containing diimine complex / methylaluminoxane catalyst of Ni are both complex and difficult to produce, and the regularity is low. There is a problem of low. In addition, [t
In the case of producing a syndio-rich living polymer at low temperature using a [BuNSiMe ₂ Flu] TiMe ₂ / B (C ₆ F ₅ ) ₃ catalyst, the stereoregularity is low and the structure of the catalyst is complicated, making it difficult to produce. There's a problem. Solvay
In the case of the TiCl ₃ / (CpR) ₂ TiMe ₂ catalyst, the molecular weight distribution of the resulting polymer is quite broad due to the heterogeneous catalyst.

In the case of using a catalyst which is a reaction product of a metallocene component / a second component having a proton-donating cation and a miscible non-coordinating anion, a metal of a cyclopentadienyl group 4 / alumoxane or a phase In the case of using a catalyst that is a reaction product of a soluble non-coordinating anion, the molecular weight distribution cannot always be reduced, or a high-level living polymer cannot always be obtained. In the field of use, a polymer having a narrow molecular weight distribution or a highly living polymer is desired.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result,
Or a zirconium-containing compound having one or two cyclopentadienyl skeleton, a borane compound or a borate compound having a phenyl group which may be substituted, and optionally a specific alkylaluminum compound, at a low temperature. It has been found that when an olefin-based monomer is polymerized, an olefin-based block copolymer having a molecular weight distribution of 1.3 or less can be produced, and the present invention has been completed.

That is, the present invention provides (A-1) a hafnium-containing compound having one or two cyclopentadienyl skeletons and (B) (B-1) a general formula (I): B (Ph) ₃ A borane compound represented by (I) (where Ph is a phenyl group which may be substituted) or (B-2) a general formula (II): B ⁻ (Ph) ₄ X ⁺ (II) (wherein Ph is the same as above, and X ⁺ is a cationic group).
Block copolymerization of an olefin monomer having 2 to 20 carbon atoms at 20 to -100 ° C to molecular weight distribution (Mw / Mn)
Is a process for producing an olefin-based block copolymer, wherein a block copolymer having a ratio of 1 to 1.3 is obtained (claim 1),
(A-1) a hafnium-containing compound having one or two cyclopentadienyl skeletons, (B) (B-1) a general formula (I): B (Ph) ₃ (I) (where Ph is A borane compound represented by an optionally substituted phenyl group) or (B-2) a general formula (II): B ⁻ (Ph) ₄ X ⁺ (II) (where Ph is the same as above, and X ⁺ is (C) General formula (III): AlR _3-n Y _n (III) (wherein R is a hydrocarbon group having 4 to 20 carbon atoms, Y is a halogen atom, alkoxy Polymerization temperature of -20 to -10 using a catalyst comprising an aluminum compound represented by the formula: a trialkylsiloxy group, a di (trialkylsilyl) amino group or a trialkylsilyl group, where n is 0, 1 or 2).
An olefin monomer having 2 to 20 carbon atoms is subjected to block copolymerization at 0 ° C. to have a molecular weight distribution (Mw / Mn) of 1 to 1.3.
The method for producing an olefin-based block copolymer (claim 2), wherein the polymerization temperature is -30 to -8.
The method according to claim 1 or 2, wherein the temperature is 0 ° C (claim 3).
The method according to claim 1 or 2, wherein the polymerization temperature is -40 to -80 ° C, (A-2) a zirconium-containing compound having one or two cyclopentadienyl skeletons, and (B). (B-1) a borane compound represented by the general formula (I): B (Ph) ₃ (I) (where Ph is a phenyl group which may be substituted); or (B-2) a general formula (II) _{^{: B - (Ph) 4 X}} + (II) ( wherein, Ph is the same, X ⁺ is a cation group) using a catalyst consisting of a borate compound represented by the polymerization temperature -
The molecular weight distribution (Mw / Mn) is obtained by block copolymerizing an olefin monomer having 2 to 20 carbon atoms at 60 to -100 ° C.
(A-5), a method for producing an olefin-based block copolymer, wherein a polymer having a ratio of 1 to 1.3 is obtained.
A zirconium-containing compound having one or two cyclopentadienyl skeletons, (B) (B-1) a general formula (I): B (Ph) ₃ (I) (wherein Ph is substituted borane compounds represented by a phenyl group) or (B-2) the general formula ^{(II): B - (Ph} ) 4 X + (II) ( wherein, Ph is as defined above, X ⁺ is a cation group) borate compound represented and (C) the general formula _{(III): AlR 3-n} Y n (III) ( wherein, R represents a hydrocarbon group having 4 to 20 carbon atoms, Y is a halogen atom, an alkoxy group, trialkylsiloxy Polymerization temperature of -60 to -10 using a catalyst comprising an aluminum compound represented by the formula: a di (trialkylsilyl) amino group or a trialkylsilyl group, n is 0, 1 or 2)
An olefin monomer having 2 to 20 carbon atoms is subjected to block copolymerization at 0 ° C. to have a molecular weight distribution (Mw / Mn) of 1 to 1.3.
(6) A method for producing an olefin block copolymer, wherein the polymerization temperature is -60 to -8.
The method according to claim 5 or 6, wherein the temperature is 0 ° C (claim 7).
4. The method according to claim 1, wherein the Ph group in the general formula (I) or (II) is a group substituted with 1 to 5 fluorine atoms.
4. The method according to claim 4, 5, 6 or 7, wherein the Ph group in the general formula (I) or (II) is a group substituted with 5 fluorine atoms. 3, 4, 5, 6
Or the production method according to claim 7 (claim 9), the production method according to claim 2, 3, 4, 6, 7, 8, or 9 wherein n in the general formula (III) is 0 (claim 10); N) in III) is 0, and R is an alkyl group having 4 to 8 carbon atoms;
3, 4, 6, 7, 8, or 9 (claim 1).
1) The block copolymer of an olefin monomer having 2 to 20 carbon atoms is a block copolymer using two or more kinds of α-olefins having 2 to 20 carbon atoms.
The method according to 4, 5, 6, 7, 8, 9, 10 or 11 (Claim 12), wherein the block copolymerization of an olefin monomer having 2 to 20 carbon atoms is carried out by converting 2 to 10 carbon atoms of an α-olefin having 2 to 10 carbon atoms. A block copolymer using at least one species,
2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 (Claim 13), wherein the block copolymerization of an olefin monomer having 2 to 20 carbon atoms is performed by using an α having 3 to 6 carbon atoms. -It is a block copolymer using two or more types of olefins, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.
The method according to any one of claims 1 to 3, wherein the polymerization is performed within a range in which the polymer is not precipitated.
5, 6, 7, 8, 9, 10, 11, 12, 13 or 1
4. The method according to claim 4 (claim 15), wherein the molecular weight distribution is 1 to 1.2.
1, 2, 3, 4, 5, 6, 7, 8, 9, 1
0, 11, 12, 13, 14 or 15 (Claim 16) Claims 1, 2, 3, 4, 5, 6, 7, 8,
9, 10, 11, 12, 13, 14, 15 or 16 or a propylene-based block copolymer 1 produced by the method described in the above.
A propylene-based block copolymer composition comprising 99% by weight (hereinafter referred to as%) and 99 to 1% of a propylene-based (co) polymer other than at least one propylene-based block copolymer (claim 17); The diameter of particles of 90% or more of the dispersed phase of the propylene-based block copolymer composition is 4
The propylene block copolymer composition according to claim 17, which has a diameter of not more than 00 nm (claim 18), and a particle diameter of 90% or more of the dispersed phase of the propylene block copolymer composition is 200 nm or less. A propylene block copolymer composition according to claim 17 (claim 19).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (A) (A-1) 1
A hafnium-containing compound having one or two cyclopentadienyl skeletons, or (A-2) a zirconium-containing compound having one or two cyclopentadienyl skeletons, (B) (B-1) a general formula (I) ): A borane compound represented by B (Ph) ₃ (I) (where Ph is a phenyl group which may be substituted) or (B-2) a general formula (II): B ⁻ (Ph) ₄ X ⁺ (II) (wherein Ph is the same as above and X ⁺ is a cationic group) and optionally (C) a general formula (III): AlR _3-n Y _n (III) R is a hydrocarbon group having 4 to 20 carbon atoms, Y is a halogen atom, an alkoxy group, a trialkylsiloxy group, a di (trialkylsilyl) amino group or a trialkylsilyl group, and n is 0, 1 or 2) From aluminum compounds That the catalyst to polymerize the olefin monomers using the olefin block copolymer is manufactured.

As the olefin monomer, α-
Olefins are preferred, and have 2 to 20 carbon atoms, and more preferably 2 to 2 carbon atoms.
10, 2 or more of 2 to 6 are preferably used. There is no particular limitation on how to combine the two or more olefin monomers forming the block copolymer, but as the block copolymer, it is common to combine an elastomer component having different physical properties with a crystalline component or a glass component. It is. Atactic polypropylene, atactic poly α-olefin, ethylene α-olefin copolymer (ethylene propylene copolymer,
Elastomer components such as ethylene butene copolymer, ethylene hexene copolymer, ethylene octene copolymer, and ethylene propylene diene terpolymer);
Polyethylene, ethylene cycloolefin (such as ethylene norbornene), ethylene cyclodiene (such as ethylene ethylidene norbornene), isotactic polypropylene, syndiotactic polypropylene, crystalline α-olefin homopolymer, crystalline α-olefin copolymer, and cycloolefin homopolymer It is preferably a combination with a crystalline component such as polycyclopentene and polynorbornene or a glass component.

Specific examples of the olefin-based monomer include ethylene, propylene, 1-butene, and 3-methyl-
1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl- 1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 4,4-dimethyl-
Linear α-olefins such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene;
1,4-pentadiene, 1,4-hexadiene, 1,5
Chain diene such as hexadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cyclotetradecene, cycloeico Sen, 3-methylcyclopentene, 3-methylcyclohexene, vinylcyclohexane, 1,2-dihydrodicyclopentadiene, dicyclopentadiene, norbornene, 1-methylnorbornene, 5-methylnorbornene, 7-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, norbornadiene, 5,6-dimethylno Bornene, 5,5,6 and cyclic olefins or cyclic dienes such as trimethyl norbornene. These may be used alone,
Two or more kinds may be used in combination. When two or more kinds are used in combination, each monomer may be randomly polymerized or block polymerized. Among the monomers, ethylene, propylene, butene, hexene, octene, cyclopentene, and norbornene are preferable because they are industrially available and inexpensive. In terms of α-olefins, ethylene, propylene, butene,
Hexene and octene are preferred, and ethylene, propylene, butene and hexene are particularly preferred.

The catalyst comprising the components (A), (B) and, if necessary, the component (C) is a relatively stable catalyst which can be easily produced. Block living copolymer using two or more kinds of α-olefins having 2 to 6 carbon atoms,
In some cases, it serves as a catalyst for stereoregular block living polymerization.

The hafnium-containing compound (A-1) having one or two cyclopentadienyl skeletons or the zirconium-containing compound (A-2) having one or two cyclopentadienyl skeletons (hereinafter, referred to as The compound of Group 4 (A) is also represented by the general formula (IV): CpM ¹ R ¹ R ² R ³ (IV) General formula (V): Cp ₂ M ¹ R ¹ R ² (V) VI): (Cp-Ae-Cp) M ¹ R ¹ R ² (VI) (In the formulas (IV), (V) and (VI), M ¹ is Zr or Hf
An atom, Cp is an optionally substituted cyclopentadienyl skeleton, R ¹ , R ² and R ³ are each a σ-binding ligand, a chelating ligand, and A is a covalent divalent divalent Group,
e is an integer of 1 to 3, and two or more of R ¹ , R ^2, and R ³ in formulas (V) and (VI), two or more of which may be bonded to each other to form a ring, May be the same or different from each other) or a derivative thereof. These may be used alone or in combination of two or more. Of these, compounds having two cyclopentadienyl skeletons and represented by formulas (V) and (VI) are preferred.

Examples of the optionally substituted cyclopentadienyl skeleton include a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group. Group, fluorenyl group, octahydrofluorenyl group, and substituted fluorenyl group. When the cyclopentadienyl skeleton which may be substituted has a substituent, the substituent is preferably a hydrocarbon group having 1 to 20 carbon atoms, for example, an alkyl group.

Examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, Methylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, ethylmethylcyclopentadienyl group, tetraethylcyclopentadienyl group, propylcyclopentadienyl group, propylmethylcyclopentadienyl Group, butylcyclopentadienyl group, butylmethylcyclopentadienyl group, t-butylcyclopentadienyl group, hexylcyclopentadienyl group, cyclohexylcyclopentadienyl group, cyclohexylmethyl Cyclopentadienyl group, benzyl cyclopentadienyl group, diphenyl cyclopentadienyl group, penta (trimethylsilyl) cyclopentadienyl group, trimethylgermyl cyclopentadienyl group,
And a trimethylstannylcyclopentadienyl group, a trifluoromethylcyclopentadienyl group and the like.

Examples of the σ-binding ligand include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group and A hydrocarbon group having 1 to 20 carbon atoms such as -butyl group, neopentyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, norbornyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, phenoxy group Carbon number 1
An alkoxy group having 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a benzyl group, and a diphenylmethyl group;
20 aryl groups, alkylaryl groups or arylalkyl groups; allyl groups, substituted allyl groups; silicon atoms such as trimethylsilyl, phenyldimethylsilyl, triphenylsilyl, tri (dimethylsilyl) silyl, and (trimethylsilyl) methyl groups And the like. When an aluminum compound (C) described later is not used, the hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, an allyl group, a substituted allyl It must contain at least one of a group and a substituent containing a silicon atom.

Examples of the chelating ligand include an acetylacetonato group and a substituted acetylacetonato group.

Examples of the covalent divalent group represented by A in the general formula (VI) include methylene, dimethylmethylene, ethylene, isopropylidene, cyclobutylidene, cyclopentylidene and the like. Groups, cyclohexylidene group, dimethylsilylene group, dimethylgermylene group, dimethylstannylene group, phenyl (methyl) methylene group, phenyl (methyl) silylene group, diphenylmethylene group, diphenylsilylene group and the like. For example, when e is 2, two A and two Cp in two places
Are combined. A need not be the same.

When the bridged dicyclopentadienyl compound represented by the general formula (VI) is a compound having C ₁ symmetry, C ₂ symmetry or C _s symmetry, the living weight having high stereoregularity is high. Coalescence can be obtained.

Specific examples of the Group 4 compound (A) represented by the general formulas (IV) to (VI) include the following. Of these, compounds of group 4 represented by the general formulas (V) and (VI) having two cyclopentadienyl skeletons are preferred.

Examples of the compound represented by the general formula (IV) include (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, and (cyclopentadienyl). ) Trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, cyclopentadienylmethyldichlorozirconium, (methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) )
Triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trimethylzirconium, (trimethylcyclopentadienyl) trimethylzirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) trimethyl zirconium,
(Pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (pentamethyl (Cyclopentadienyl) dimethyl (methoxy) zirconium, (cyclopentadienyl) triethylzirconium, (cyclopentadienyl) tripropylzirconium, (cyclopentadienyl) trineopentylzirconium, (cyclopentadienyl) tri (diphenyl) (Methyl) zirconium, (cyclopentadienyl) dimethylhydridozirconium, (cyclopentadienyl) triethoxyzirconium, (cyclopentadienyl) triiso Lopoxyzirconium, (cyclopentadienyl) triphenoxyzirconium, (cyclopentadienyl) dimethylisopropoxyzirconium, (cyclopentadienyl) diphenylisopropoxyzirconium, (cyclopentadienyl) dimethoxychlorozirconium, (cyclopentadienyl Enyl) methoxydichlorozirconium, (cyclopentadienyl)
Diphenoxychlorozirconium, (cyclopentadienyl) phenoxydichlorozirconium, (cyclopentadienyl) tri (phenyldimethylsilyl) zirconium, (n-butylcyclopentadienyl) dimethyln
-Butoxyzirconium, (benzylcyclopentadienyl) di-m-tolylmethylzirconium, (trifluoromethylcyclopentadienyl) tribenzylzirconium, (diphenylcyclopentadienyl) dinorbornylmethylzirconium, (tetraethylcyclopentadiene (Enyl) tribenzylzirconium, (pentatrimethylsilylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trineopentylzirconium, (pentamethylcyclopentadienyl) methyldichlorozirconium, (pentamethylcyclopentadienyl) ) Triethoxyzirconium,
(Pentamethylcyclopentadienyl) triphenoxyzirconium, (pentamethylcyclopentadienyl)
Methoxydichlorozirconium, (pentamethylcyclopentadienyl) diphenoxychlorozirconium,
(Pentamethylcyclopentadienyl) phenoxydichlorozirconium, (indenyl) trimethylzirconium, (indenyl) tribenzylzirconium, (indenyl) trichlorozirconium, (indenyl) trimethoxyzirconium, (indenyl) triethoxyzirconium and zirconium of these compounds Compounds substituted with hafnium, for example, cyclopentadienyltrimethylhafnium and the like can be mentioned. Among them, cyclopentadienyl group, ethylcyclopentadienyl group, propylcyclopentadienyl group, butylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group Having one ligand selected from a methylindenyl group, a tetrahydroindenyl group, and a fluorenyl group, and three ligands selected from a chlorine atom and a methyl group are industrially available. It is preferable because it is easy to perform.

Examples of the compound represented by the general formula (V) include bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, and bis (cyclopentadienyl). Dienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) chlorohydridozirconium, bis (Methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclyl) Pentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) dineopentyl zirconium, bis (cyclopentadienyl) di-m-tolyl zirconium, bis (cyclopentadienyl) di-p-tolyl zirconium, bis (cyclopentadienyl) bis (diphenylmethyl) Zirconium, bis (cyclopentadienyl) dibromozirconium, bis (cyclopentadienyl) methylchlorozirconium, bis (cyclopentadienyl) ethylchlorozirconium, bis (cyclopentadienyl) cyclohexylchlorozirconium,
Bis (cyclopentadienyl) phenylchlorozirconium, bis (cyclopentadienyl) benzylchlorozirconium, bis (cyclopentadienyl) hydridomethylzirconium, bis (cyclopentadienyl) methoxychlorozirconium, bis (cyclopentadienyl) ) Ethoxychlorozirconium, bis (cyclopentadienyl) (trimethylsilyl) methylzirconium,
Bis (cyclopentadienyl) bis (trimethylsilyl) zirconium, bis (cyclopentadienyl) (triphenylsilyl) methylzirconium, bis (cyclopentadienyl) (tris (dimethylsilyl) silyl)
Methyl zirconium, bis (cyclopentadienyl)
(Trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (methylcyclopentadienyl) diphenylzirconium, bis (ethylcyclopentadienyl) dimethylzirconium, bis (ethylcyclopentadienyl) dichlorozirconium, bis (propylcyclopentadienyl) Dimethyl zirconium, bis (propylcyclopentadienyl) dichlorozirconium, bis (n-butylcyclopentadienyl) dichlorozirconium, bis (t-butylcyclopentadienyl) bis (trimethylsilyl) zirconium, bis (hexylcyclopentadienyl) ) Dichlorozirconium, bis (cyclohexylcyclopentadienyl) dimethylzirconium, bis (dimethylcyclopentadienyl) dimethylzirconium, bis Dimethyl cyclopentadienyl)
Dichlorozirconium, bis (dimethylcyclopentadienyl) ethoxychlorozirconium, bis (ethylmethylcyclopentadienyl) dichlorozirconium, bis (propylmethylcyclopentadienyl) dichlorozirconium, bis (butylmethylcyclopentadienyl) dichlorozirconium , Bis (trimethylcyclopentadienyl) dichlorozirconium, bis (tetramethylcyclopentadienyl) dichlorozirconium, bis (cyclohexylmethylcyclopentadienyl) dibenzylzirconium, bis (trimethylsilylcyclopentadienyl) dimethylzirconium, bis ( Trimethylsilylcyclopentadienyl) dichlorozirconium, bis (trimethylgermylcyclopentadienyl)
Dimethyl zirconium, bis (trimethylgermylcyclopentadienyl) diphenylzirconium, bis (trimethylstannylcyclopentadienyl) dimethylzirconium, bis (trimethylstannylcyclopentadienyl) dibenzylzirconium, bis (trifluoromethylcyclopenta Dienyl) dimethyl zirconium, bis (trifluoromethylcyclopentadienyl)
Dinorbornyl zirconium, bis (indenyl) dibenzyl zirconium, bis (indenyl) dichlorozirconium, bis (indenyl) dibromozirconium,
Bis (tetrahydroindenyl) dichlorozirconium, bis (fluorenyl) dichlorozirconium, (propylcyclopentadienyl) (cyclopentadienyl) dimethylzirconium, (cyclohexylmethylcyclopentadienyl) (cyclopentadienyl) dibenzylzirconium, (Pentatrimethylsilylcyclopentadienyl) (cyclopentadienyl) dimethylzirconium, (trifluoromethylcyclopentadienyl) (cyclopentadienyl) dimethylzirconium, and compounds obtained by substituting zirconium of these compounds with hafnium, such as bis (cyclo (Pentadienyl) dimethylhafnium. Of these,
Cyclopentadienyl group, ethylcyclopentadienyl group, propylcyclopentadienyl group, butylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, methylindenyl group , A tetrahydroindenyl group,
Those having both two ligands selected from a fluorenyl group and two ligands selected from a chlorine atom and a methyl group are preferable from the viewpoint of industrial availability.

As the compound represented by the general formula (VI)
Is, for example, ethylenebis (indenyl) dimethylzyl
Conium, ethylenebis (indenyl) dichlorozirco
, Ethylenebis (tetrahydroindenyl) dim
Tyl zirconium, ethylene bis (tetrahydroindene
Nyl) dichlorozirconium, dimethylsilylenebis
(Cyclopentadienyl) dimethylzirconium,
Tylsilylenebis (cyclopentadienyl) dichlorodi
Ruconium, isopropylidene (cyclopentadienyl
) (9-fluorenyl) dimethyl zirconium, iso
Propylidene (cyclopentadienyl) (9-fluor
Nyl) dichlorozirconium, [phenyl (methyl) meth
Tylene] (9-fluorenyl) (cyclopentadienyl
Le) dimethyl zirconium, diphenylmethylene
Lopentadienyl) (9-fluorenyl) dimethylzyl
Conium, ethylene (9-fluorenyl) (cyclopen
Tadienyl) dimethyl zirconium, cyclohexylide
(9-fluorenyl) (cyclopentadienyl) dimethyl
Tyl zirconium, cyclopentylidene (9-fluor
Nyl) (cyclopentadienyl) dimethyl zirconium
Cyclobutylidene (9-fluorenyl) (cyclope
Antadienyl) dimethylzirconium, dimethylsilyl
(9-fluorenyl) (cyclopentadienyl) dimethyl
Tylzirconium, dimethylsilylenebis (2,3,5
-Trimethylcyclopentadienyl) dimethyl zirconi
Dimethylsilylenebis (2,3,5-trimethyl
Cyclopentadienyl) dichlorozirconium, dimethyl
Rusilylenebis (indenyl) dichlorozirconium,
Methylene bis (cyclopentadienyl) dimethyl zircon
, Methylenebis (cyclopentadienyl) di (t
Limethylsilyl) zirconium, methylene (cyclopen
Tadienyl) (tetramethylcyclopentadienyl) di
Methyl zirconium, methylene (cyclopentadienyl
Le) (fluorenyl) dimethyl zirconium, ethylene
Bis (cyclopentadienyl) dimethyl zirconium,
Ethylenebis (cyclopentadienyl) dibenzyldiyl
Conium, ethylenebis (cyclopentadienyl) dihi
Zirconium hydride, ethylene bis (indenyl) diph
Enyl zirconium, ethylenebis (indenyl) methyl
Ruchlorozirconium, ethylenebis (tetrahydroy
Ndenyl) dibenzylzirconium, isopropylidene
(Cyclopentadienyl) (methylcyclopentadienyl)
Le) dichlorozirconium, isopropylidene (cyclo
Pentadienyl) (octahydrofluorenyl) dihydride
Lid zirconium, dimethylsilylene bis (cyclopen
Tadienyl) dineopentyl zirconium, dimethyl
Rylene bis (cyclopentadienyl) dihydride zircon
And dimethylsilylenebis (methylcyclopentadi
Enyl) dichlorozirconium, dimethylsilylenebis
(Dimethylcyclopentadienyl) dichlorozirconium
Dimethylsilylenebis (tetrahydroindenyl)
Dichlorozirconium, dimethylsilylene (cyclopen
Tadienyl) (fluorenyl) dichlorozirconium,
Dimethylsilylene (cyclopentadienyl) (fluor
Nil) dihydride zirconium, dimethylsilylene
Tylcyclopentadienyl) (fluorenyl) dihydrido
Dozirconium, dimethylsilylenebis (3-trimethyl
Lucylylcyclopentadienyl) dihydridozirconium
Dimethylsilylenebis (indenyl) dimethylsilyl
Conium, diphenylsilylenebis (indenyl) dic
Lorodisilconium, phenylmethylsilylenebis (in
Denenyl) dichlorozirconium and the di-
Examples include compounds in which ruconium is replaced by hafnium
It is. Among them, C₁Symmetry, C_TwoSymmetry, C _sSymmetrical
From which it is possible to obtain a stereoregular living polymer
You. Of these, cyclopentadienyl group, ethyl
Rucyclopentadienyl group, propylcyclopentadie
Nyl group, butylcyclopentadienyl group, tetramethyl
Cyclopentadienyl group, pentamethylcyclopentadi
Enyl, indenyl, methylindenyl, tetra
Two selected from hydroindenyl and fluorenyl groups
And two ligands selected from a chlorine atom and a methyl group
It is said that those having both ligands are industrially available
It is preferred from the point of view.

The borane compound (B-1) of the component (B) constituting the catalyst used in the present invention together with the compound of the group 4 (A) and the optionally used aluminum compound (C) described later is the same as that described above. Thus, a borane compound represented by the general formula (I): B (Ph) ₃ (I) (wherein Ph is a phenyl group which may be substituted), and a borate compound (B-
2) the general formula ^{(II): B - (Ph} ) 4 X + (II) ( wherein, Ph is as defined above, X ⁺ is a borate compound represented by cationic groups). These may be used in combination.

The phenyl group which may be substituted in the general formula (I) includes, for example, a phenyl group and 1 to 5 of 5 hydrogen atoms contained in the phenyl group are other groups such as a fluorine atom. An alkyl group having 1 to 20 carbon atoms, a group substituted with an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom, specifically, a monofluorophenyl group,
Examples include a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a fluoromethylphenyl group, a di (trifluoromethyl) phenyl group, a tolyl group, and a dimethylphenyl group. Among these, a group in which 1 to 5 of the 5 hydrogen atoms contained in the phenyl group are substituted with a fluorine atom, particularly a group in which all 5 hydrogen atoms are substituted with a fluorine atom. However, it is preferable in view of industrial availability.

The three optionally substituted phenyl groups contained in the general formula (I) may be the same or different, but the three groups have a total of 3 fluorine atoms. It is preferable to include at least 15 pieces, especially 15 pieces from the viewpoint of industrial availability.

Specific examples of the borane compound (B-1) include, for example, triphenylboron, tris (2-fluorophenyl) boron, tris (3-fluorophenyl)
Boron, tris (4-fluorophenyl) boron, tris (2,3-difluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (2
3,5-trifluorophenyl) boron, tris (2,
3,4,6-tetrafluorophenyl) boron, tris (pentafluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tri (3,5-di (trifluoromethyl) phenyl) boron, tris (p- Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The optionally substituted phenyl group in the general formula (II) is the same as that in the general formula (I).
Description is omitted.

The four optionally substituted phenyl groups contained in the general formula (II) may be the same or different, but the four groups have a total of 4 fluorine atoms. The number is preferably at least 20 and more preferably at least 20 in terms of industrial availability.

On the other hand, as the cationic group X ⁺ contained in the general formula (II), for example, triethylammonium, tri (n-butyl) ammonium, trimethylammonium, tetraethylammonium, methyltri (n)
-Butyl) ammonium, benzyltri (n-butyl)
Ammonium, dimethyldiphenylammonium, methyltriphenylammonium, trimethylanilinium, methylpyridinium, benzylpyridinium, methyl (2-cyanopyridinium), trimethylsulfonium, benzyldimethylsulfonium, triphenylammonium, tetrabutylammonium, methyldiphenylammonium, anilinium, Methylanilinium,
Dimethylanilinium, dimethyl (m-nitroanilinium), dimethyl (p-bromoanilinium), pyridinium, p-cyanopyridinium, N-methylpyridinium, N-benzylpyridinium, o-cyano-N-methylpyridinium, p- Examples include cyano-N-methylpyridinium, p-cyano-N-benzylpyridinium, tetraphenylphosphonium, triphenylphosphonium, trityl and the like.

Specific examples of the borate compound (B-2) represented by the general formula (II) include, for example, tetraphenylborate triethylammonium, tetraphenylborate tri (n-butyl) ammonium, tetraphenylborate trimethylammonium, tetraphenylborate Borate tetraethylammonium, tetraphenylboratemethyltri (n-butyl) ammonium, tetraphenylboratebenzyltri (n-butyl) ammonium, tetraphenylboratedimethyldiphenylammonium, tetraphenylboratemethyltriphenylammonium, tetraphenylboratetrimethylanilinium, Tetraphenylborate methylpyridinium,
Tetraphenylborate benzylpyridinium, tetraphenylboratemethyl (2-cyanopyridinium),
Compounds having a tetraphenylborate ion such as tetraphenylborate trimethylsulfonium, tetraphenylboratebenzyldimethylsulfonium, and tetraphenylborate trityl; tetrakis (pentafluorophenyl) borate triethylammonium; tetrakis (pentafluorophenyl) borate tri (n-
Butyl) ammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetrabutylammonium, tetrakis (pentafluorophenyl) borate (tetraethylammonium), tetrakis (pentafluorophenyl) borate (methyltri (n- Butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate methyldiphenylammonium, tetrakis (pentafluorophenyl) borate methyltriphenylammonium, tetrakis (pentafluorophenyl) ) Borate dimethyldiphenylammonium, tetrakis (pentafluorophene) Le) borate anilinium tetrakis (pentafluorophenyl) borate-methyl anilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (pentafluorophenyl) volleys Totori methyl anilinium tetrakis (pentafluorophenyl) borate dimethyl (m-
Nitroanilinium), tetrakis (pentafluorophenyl) borate dimethyl (p-bromoanilinium), tetrakis (pentafluorophenyl) boratepyridinium, tetrakis (pentafluorophenyl)
Borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N-benzylpyridinium), tetrakis (pentafluorophenyl) borate (o-cyano-N- Methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium, Tetrakis (pentafluorophenyl) borate benzyldimethylsulfonium, tetrakis (pentafluorophenyl) borate tetraphenylphosphonium, tetrakis (pen Fluorophenyl) borate trityl, tetrakis (3,5-ditrifluoromethylphenyl) borate dimethyl tetrakis (fluorine atom-containing phenyl such as anilinium) a compound having a borate ion, and the like. Of these, tetrakis (pentafluorophenyl) boratetrityl is particularly preferred.

The aluminum compound (C) constituting the catalyst optionally used in the present invention together with the group 4 compound (A) and the boron-containing compound (B) represented by the general formula (I) or (II) is described above. Like the general formula (II
I): AlR _3-n Y _n (III) (wherein, R is a hydrocarbon group having 4 to 20 carbon atoms, Y is a halogen atom, an alkoxy group, a trialkylsiloxy group, a di (trialkylsilyl) amino group or N is an aluminum compound represented by 0, 1 or 2) such as a trialkylsilyl group. The aluminum compound (C) is a so-called scavenger (impurity scavenger) and may not be used when the system contains no impurities.
By using the compound, a living polymer can be obtained more stably than when not used.

Specific examples of the hydrocarbon group having 4 to 20 carbon atoms, R, which is included in the general formula (III) include, for example, n-
Butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, isohexyl, octyl, 2-ethylhexyl, decyl, cyclohexyl, cyclooctyl, phenyl and the like.

The number of R contained in the general formula (III) is 1 to 3
When the number of carbon atoms is from 4 to 20, chain transfer is less likely to occur and a living polymer is easily obtained. Also, R
Is preferably three. When the number of R contained in the general formula (III) is two or more, they may be the same group or different groups.

The number of Y is from 0 to 2, and specific examples of Y include halogen atoms such as chlorine, bromine and iodine;
1 carbon atom such as methoxy, ethoxy, phenoxy, etc.
To 20 alkoxy groups, trialkylsiloxy groups (alkyl groups having 1 to 20 carbon atoms), di (trialkylsilyl)
Examples thereof include an amino group (alkyl group having 1 to 20 carbon atoms) and a trialkylsilyl group (alkyl group having 1 to 20 carbon atoms). When the number of Y in the general formula (III) is 2, they may be the same group or different groups.

Specific examples of the aluminum compound (C) include, for example, tri (n-butyl) aluminum, triisobutylaluminum, trisec-butylaluminum, tri (t-butyl) aluminum, tripentylaluminum, triisopentylaluminum, Trineopentyl aluminum, tri (4-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, trihexylaluminum, triisohexylaluminum, tri (n-octyl) aluminum, tri2
Trialkyl aluminum such as ethylhexyl aluminum and tridecyl aluminum; tricyclic alkyl aluminum such as tricyclopentyl aluminum, tricyclohexyl aluminum and tricyclooctyl aluminum; triphenyl aluminum, tri p-tolyl aluminum, tri m-tolyl aluminum and tri p Triaromatic aluminums such as ethylphenylaluminum and tribenzylaluminum; dialkylaluminum halides such as di (n-butyl) aluminum chloride, diisobutylaluminum chloride, di (t-butyl) aluminum chloride and dioctylaluminum iodide; diisobutylaluminum methoxy , Diisobutylaluminum ethoxide, dioctylaluminum methoxide Dialkylaluminum alkoxides such as sid, dioctylaluminum ethoxide and di-n-butylaluminum phenoxide; alkylaluminum dihalides such as n-butylaluminum dichloride, isobutylaluminum dichloride and octylaluminum dichloride; alkylaluminum sesquichlorides such as n-butylaluminum sesquichloride halides; diisobutylaluminum trimethylsilyl oxide _{((iso-Bu) 2 AlOSiMe} 3), diisobutyl aluminum triethylsilyl oxide ((IS
o-Bu) ₂ AlOSiEt ₃ ), diisobutylaluminum di (trimethylsilyl) amine ((iso-Bu)
₂ AlN (SiMe _{3) 2,} and diisobutyl trimethylsilyl aluminum _{((iso-Bu) 2 AlSiMe} 3) and the like. Of these, trioctyl aluminum and triisobutyl aluminum are preferred because they are industrially available and inexpensive.

Group 4 compound (A) used in the present invention
(Hereinafter, also referred to as compound (A)), a boron-containing compound (B) (hereinafter, also referred to as compound (B)) and optionally used aluminum compound (C) (hereinafter, also referred to as compound (C)). The catalyst can be obtained by mixing the compound (A), the compound (B) and optionally the compound (C) at a predetermined ratio, and reacting them.

The obtained catalyst may be used as it is,
It may be separated and washed before use. It is preferable to produce a catalyst in a polymerization system and use it as it is because it is simple.

The compound (A) and the compound (B) are used in a ratio of 1 / 0.1 to 1/100 in terms of the molar ratio of the compound (A) / the compound (B) in producing the catalyst. 1
/ 1 to 1/5 is preferred from the viewpoint that the target catalyst can be efficiently obtained. If the ratio is too high, the production rate of the catalyst tends to be low. Conversely, if the ratio is too low, the compound (B) is excessively contained, which is uneconomical.

The compound (A) / compound (C) may be used in a molar ratio of compound (A) / compound (C) of from 1/0 to 1/1000, and more preferably from 1/10 to 1/500.
Is preferred from the viewpoint of trapping when impurities are present in the system. If the ratio of the compound (C) to the compound (A) is too small, it is difficult to trap the impurities in the system, and if the ratio is too large, it is difficult to remove the product derived from the compound (C) from the polymer.

The conditions for mixing and reacting the compound (A), the compound (B) and optionally the compound (C) are as follows: -100 ° C. to room temperature, more preferably -100 ° C. to -20 ° C.
It is preferable to carry out the reaction in an inert gas atmosphere in a solvent such as a polymerization solvent described below, since it is easy to shift from the reaction process to the polymerization process.

Specific examples of preferred catalysts used in the present invention include, for example, catalysts described in Examples described later.

In the presence of the catalyst thus prepared,
When the hafnium-containing compound (A-1) is used,
−20 to −100 ° C., further −30 to −80 ° C., particularly −40 to −80 ° C., and a zirconium-containing compound (A-
When 2) is used, the molecular weight distribution (Mw / M) is obtained by block copolymerization using two or more types of olefin monomers at -60 to -100 ° C, further at -60 to -80 ° C.
An olefin-based living block copolymer having n) of 1 to 1.3, and further 1 to 1.2 can be produced. If the temperature is too high, the chain transfer reaction cannot be ignored, and it is difficult to obtain a living block copolymer. If the temperature is too low, the living polymerization rate tends to decrease.

The amount of the catalyst used is such that the molar ratio of the olefin monomer / catalyst (the smaller amount of the compound (A) or the compound (B)) is 10 to 10 ⁹ , and more preferably 100 to 10 ^7. , particularly preferably in the 1,000 to ^5. If the molar ratio is too small, only a polymer having a small molecular weight will be obtained. If the molar ratio is too large, the yield of the polymer relative to the monomer tends to be low.

When a polymerization solvent is used, the catalyst may be added to the polymerization solvent in advance, or may be added later to the polymerization system.

Examples of the polymerization solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; and aliphatic hydrocarbons such as pentane, hexane, heptane and octane. Hydrocarbons; halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Also, α-
Monomers such as olefins, 2-substituted olefins, 3-substituted olefins, 4-substituted olefins and the like may be used as the solvent.

The other polymerization conditions are not particularly limited, and those skilled in the art can appropriately select preferable conditions. The polymerization time is usually 10 minutes to 100 hours, and the reaction pressure is normal pressure to 100 kg / cm ^2. G (about 9.8 × 10 ^{4 to} 9.8 ×
10 ⁶ Pa).

The block copolymer includes a diblock copolymer, a triblock copolymer, a multiblock copolymer, and a tapered block copolymer.

A typical method for producing the block copolymer is a method in which one or more first monomers are added and polymerized, and then one or more second monomers are added and polymerized. It is. Between the polymerizations, the first monomer may be removed by evacuation under reduced pressure or purging with a dry inert gas. In addition, for example, when the reactivity of one monomer is higher than the other and the relative amount of one monomer is smaller than the other, a tapered block copolymer of both random copolymers and one homopolymer becomes can get.

Before termination of the polymerization, the polymer may be coupled using a coupling agent such as terephthalic acid dichloride.

As described above, the number average molecular weight by GPC is 100 to 2,000,000, and more preferably 500 to 2,000.
An olefin block copolymer having a molecular weight distribution of 000, especially 1,000 to 1,000,000, particularly 2,000 to 500,000 and a molecular weight distribution of 1.3 or less, further 1.2 or less, particularly 1.1 or less is produced. In addition, the number average molecular weight and the molecular weight distribution are values obtained by removing the polymerization catalyst by post-treating the block copolymer.

In general, the polymer does not precipitate during the polymerization,
The molecular weight in this case is from 500 to 2,000,000, more preferably from 1000 to 1,000,000, especially from 2000 to 500
000 is preferable. However, in the case of homopolymerization of ethylene, propylene (during stereoregular polymerization), cyclic olefin, or the like, the polymer may be easily crystallized. In such a case, the polymer is precipitated during the polymerization, and the molecular weight is reduced. The distribution may spread. As the molecular weight in which the polymer hardly precipitates during the polymerization and the molecular weight distribution is narrow, a molecular weight of 3000 or less, preferably 2000 or less, more preferably 1000 or less, and particularly preferably 500 or less is mentioned. Because it is a polymer,
The molecular weight is usually 200 or more. In order to make crystallization or precipitation difficult during polymerization, when using the above-mentioned monomer in which the polymer is easily crystallized or precipitated, it is also preferable to carry out copolymerization.

The block copolymer is contacted with a reagent having an appropriate reactivity such as carbon monoxide,
A so-called terminal-functionalized block copolymer having no Group 4 transition metal at the molecular terminal can be obtained.

The propylene-based block copolymer having a polypropylene segment of the block copolymer may be provided with at least one propylene-based (co) polymer other than the propylene-based block copolymer (copolymerized with propylene). By mixing a possible monomer, preferably ethylene, it is possible to obtain a propylene-based block copolymer composition. The propylene-based block copolymer composition can be obtained by melt-kneading a propylene-based block copolymer and at least one propylene-based (co) polymer other than the propylene-based block copolymer. It is preferable from the viewpoint of reducing the size.

The propylene-based (co) polymer other than the propylene-based block copolymer has a composition close to the segment components of the propylene-based block copolymer, that is, at least 80 mol%, preferably at least 90 mol%. Propylene units are preferred in that the dispersed phase becomes smaller.

The diameter (particle diameter) of the particles of the dispersed phase is T
It can be measured by EM photograph observation or the like. As a preferred particle size of the dispersed phase, 90% or more of the particles are 400
nm or less is preferable from the viewpoint of transparency.
nm or less, and more preferably 100 nm or less.

The composition may contain, if necessary, a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent,
Various additives such as a lubricant, a flame retardant, an antiblocking agent, a coloring agent, and a filler can be compounded.

[0065]

Next, the production method of the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 A dry toluene (14.4 ml) and tri (n-octyl) aluminum (0.8 mmol) were added to a sufficiently dried 100 ml autoclave, and the mixture was cooled to -78 ° C. Biscyclopentadienyl zirconium dimethyl 0.04m
mol, tris (pentafluorophenyl) boron 0.
After adding 04 mmol and 83 mmol of propylene and polymerizing for 14 hours, the pressure was slightly reduced and 20.5 mmol of ethylene was added and polymerized for 3 hours. Thereafter, the mixture was poured into 1,000 ml of hydrochloric methanol to terminate the polymerization, thereby precipitating a polymer. The precipitate was separated by filtration and dried under vacuum to obtain a polymer.

The yield of the polymer (Yield) was 540 mg.
Met. Number average molecular weight (M
n) was 71,000, and the molecular weight distribution (Mw (weight average molecular weight) / Mn) was as narrow as 1.16. According to room temperature ¹³ C-NMR, not only polypropylene but also
A signal derived from the ethylene propylene copolymer was observed.

As described above, a block copolymer having a narrow molecular weight distribution was obtained.

Example 2 14.4 ml of dry toluene and 0.8 mmol of tri (n-octyl) aluminum were added to a sufficiently dried 100 ml autoclave, and the mixture was cooled to -78 ° C. Bispentamethylcyclopentadienyl hafnium dimethyl 0.04 mmol, tris (pentafluorophenyl)
After adding 0.04 mmol of boron and 83 mmol of propylene and polymerizing for 2 hours, the pressure was slightly reduced to 10.3 m for ethylene.
mol was added and polymerized for 1 hour. Thereafter, the mixture was poured into 1,000 ml of hydrochloric methanol to terminate the polymerization, thereby precipitating a polymer. The precipitate was separated by filtration and dried under vacuum to obtain a polymer.

The polymer yield (Yield) was 1520 m
g. The number average molecular weight (Mn) measured by room temperature GPC was 90000, and the molecular weight distribution (Mw (weight average molecular weight) / Mn) was as narrow as 1.30.

As described above, a block copolymer having a narrow molecular weight distribution was obtained.

Example 3 14.4 ml of dry toluene and 0.8 mmol of tri (n-octyl) aluminum were added to a sufficiently dried 100 ml autoclave, and the mixture was cooled to -78 ° C. ra
c-ethylenebisindenyl zirconium dimethyl
04 mmol, 0.04 mmol of tris (pentafluorophenyl) boron, 20.5 mmol of ethylene, and 83 mmol of propylene were added and polymerized for 8 hours. Thereafter, the mixture was poured into 1,000 ml of hydrochloric methanol to terminate the polymerization, thereby precipitating a polymer. The precipitate was separated by filtration and dried under vacuum to obtain a polymer.

The polymer yield (Yield) was 252 mg.
Met. Number average molecular weight (M
n) was 10,000 and the molecular weight distribution (Mw (weight average molecular weight) / Mn) was as narrow as 1.30. The obtained polymer was soluble in hexane, and according to room temperature ¹³ C-NMR of the hexane-soluble portion, signals derived from not only the ethylene propylene copolymer but also isotactic polypropylene were observed.

As described above, a block copolymer having a narrow molecular weight distribution was obtained.

Example 4 14.4 ml of dry toluene and 0.8 mmol of tri (n-octyl) aluminum were added to a well-dried 100 ml autoclave, and the mixture was cooled to -50 ° C. Biscyclopentadienyl hafnium dimethyl 0.04mm
ol, tris (pentafluorophenyl) boron 0.0
4 mmol and 83 mmol of propylene were added, and the mixture was polymerized for 24 hours, and further added with 20.5 mmol of ethylene, and polymerized for 6 hours. Thereafter, the mixture was poured into 1,000 ml of hydrochloric methanol to terminate the polymerization, thereby precipitating a polymer. The precipitate was separated by filtration and dried under vacuum to obtain a polymer.

The polymer yield (Yield) was 1430 m
g. The number average molecular weight (Mn) measured by room temperature GPC was 69000, and the molecular weight distribution (Mw (weight average molecular weight) / Mn) was as narrow as 1.07. According to room temperature ¹³ C-NMR, signals derived from not only polypropylene but also ethylene propylene copolymer were observed.

As described above, a block copolymer having a narrow molecular weight distribution was obtained.

Example 5 14.4 ml of dry toluene and 0.8 mmol of tri (n-octyl) aluminum were added to a fully dried 100 ml autoclave, and the mixture was cooled to -50 ° C. Biscyclopentadienyl hafnium dimethyl 0.04mm
ol, tris (pentafluorophenyl) boron 0.0
4 mmol, 83 mmol of propylene were added for 24 hours, and 20.5 mmol of ethylene was further added for 3 hours.
Again, 20.5 mmol of ethylene was added and polymerized for 3 hours. Thereafter, the mixture was poured into 1,000 ml of hydrochloric methanol to terminate the polymerization, thereby precipitating a polymer. The precipitate was separated by filtration and dried under vacuum to obtain a polymer.

The polymer yield (Yield) was 2190 m
g. The number average molecular weight (Mn) measured by room temperature GPC was 155000, and the molecular weight distribution (Mw (weight average molecular weight) / Mn) was as narrow as 1.07. According to room temperature ¹³ C-NMR, signals derived from not only polypropylene but also ethylene propylene copolymer were observed.

As described above, a block copolymer having a narrow molecular weight distribution was obtained.

Example 6 1.4 g of the block copolymer obtained in Example 4 and 1.4 g of Homo PP (Mn52000, Mw / Mn5.1) were obtained from Custom Scientific Instruments Inc., CSI Max.
Using a mixing extruder extruder, the mixture was melt-kneaded at 200 ° C. and 100 revolutions to obtain a strand. After pelletizing the obtained strand, it was melt-kneaded at 200 ° C. and 50 rpm again to obtain a strand. The obtained trend is T
Observation with an EM photograph (magnification: 50000) revealed that the block copolymer had at least 90% of the particle size of the dispersed phase dispersed at 200 nm or less (see FIG. 1).

[0082]

According to the present invention, an olefin monomer having 2 to 20 carbon atoms is block-copolymerized at a low temperature by using a catalyst comprising a compound (A), a compound (B) and optionally a compound (C). Thereby, a polyolefin-based block copolymer having a molecular weight distribution of 1.3 or less can be produced. These block copolymers can be used as various additives, impact modifiers, compatibilizers, elastomers, adhesives, various molded articles, and foams.

[Brief description of the drawings]

FIG. 1 is a view showing a screen (photograph) obtained by observing a strand obtained in Example 6 with a TEM photograph (magnification: 50,000).

 ────────────────────────────────────────────────── ─── Continued on the front page (71) Applicant 000229117 Nippon Zeon Co., Ltd. 2-6-1 Marunouchi, Chiyoda-ku, Tokyo (71) Applicant 000000941 Kanebuchi Chemical Industry Co., Ltd. 3-2-2 Nakanoshima, Kita-ku, Osaka-shi, Osaka No. 4 (72) Inventor Michihiko Asai 1-1 Higashi 1-1, Tsukuba City, Ibaraki Pref. Ministry of Economy, Trade and Industry, National Institute of Advanced Industrial Science and Technology (72) Inventor Yasumi Suzuki 1-1 Higashi 1-1, Tsukuba City, Ibaraki Pref. (72) Inventor: Satoshi Miyazawa 1-1, Higashi Tsukuba, Ibaraki Pref., Japan Ministry of Economy, Trade and Industry (72) Inventor: Kenji Tsuchihara, Tsukuba, Higashi, Ibaraki 1-1 Institute of Materials Science and Technology, National Institute of Advanced Industrial Science and Technology (72) Inventor Hideaki Hagiwara 1-1, Higashi, Tsukuba, Castle, Japan Within the National Institute of Advanced Industrial Science and Technology, Ministry of Economy, Trade and Industry (72) Inventor Masahide Murata 2-315-504 Suido, Bunkyo-ku, Tokyo (72) Inventor Hiroyuki Ozaki Ibaraki No. 4-6-202 Onogawa, Tsukuba-shi (72) Inventor Masanao Kawabe 2-2-2203 Takezono, Tsukuba-shi, Ibaraki (72) Inventor Toshio Kase 5-2-2 Matsushiro, Tsukuba-shi, Ibaraki (72) Inventor Juan Te-ban 2-238 Umezono, Tsukuba-shi, Ibaraki Yokota Residence Building No.3 (72) Inventor Jin Jiju 8916-12 Takayamacho, Ikoma-city, Nara Takayama Science Plaza Room 407 (72) Inventor Yoshifumi Fukui Tsukuba, Ibaraki Ichinomiya 4-chome 6-3-507 F-term (reference) 4J002 BP00W BP00X BP02W BP02X 4J028 AA01A AB00A AC01A AC27A AC28A BA00A BA02B BB00A BB01B BC12B BC13B BC18B EA02 EB02 EB04 EB04 EB05 EB04 EB05 EB04 EB05 EB05 AC01 AC27 AC28 AD00 BA00A BA02B BB00A BB01B BC12B BC13B BC18B EA02 EB02 EB04 EB05 EB10 EB17 EB18 ED01 ED02 ED03 ED04 ED05 FA10 GA06

Claims (19)

[Claims] (A-1) a hafnium-containing compound having one or two cyclopentadienyl skeletons; and (B) (B-1) a general formula (I): B (Ph) ₃ (I) ( In the formula, Ph is a borane compound represented by an optionally substituted phenyl group) or (B-2) a general formula (II): B ⁻ (Ph) ₄ X ⁺ (II) (wherein Ph is as defined above) (X ⁺ is a cationic group) using a catalyst comprising a borate compound represented by the following formula:
Block copolymerization of an olefin monomer having 2 to 20 carbon atoms at 20 to -100 ° C to molecular weight distribution (Mw / Mn)
Is obtained from 1 to 1.3. (A-1) a hafnium-containing compound having one or two cyclopentadienyl skeletons; (B) (B-1) a general formula (I): B (Ph) ₃ (I) ( In the formula, Ph is a borane compound represented by an optionally substituted phenyl group) or (B-2) a general formula (II): B ⁻ (Ph) ₄ X ⁺ (II) (wherein Ph is as defined above) the same, X ⁺ is a borate compound and represented by the cationic group) (C) the general formula _{(III): AlR 3-n} Y n (III) ( wherein, R represents a hydrocarbon group having 4 to 20 carbon atoms, Y Is a polymerization temperature of −20 using a catalyst comprising an aluminum compound represented by a halogen atom, an alkoxy group, a trialkylsiloxy group, a di (trialkylsilyl) amino group or a trialkylsilyl group, and n is 0, 1 or 2). -10
An olefin monomer having 2 to 20 carbon atoms is subjected to block copolymerization at 0 ° C. to have a molecular weight distribution (Mw / Mn) of 1 to 1.3.
A process for producing an olefin-based block copolymer, characterized by obtaining a polymer of the formula (1). 3. The process according to claim 1, wherein the polymerization temperature is -30 to -80.degree. 4. The process according to claim 1, wherein the polymerization temperature is from -40 to -80.degree. 5. (A-2) a zirconium-containing compound having one or two cyclopentadienyl skeletons and (B) (B-1) a general formula (I): B (Ph) ₃ (I) ( In the formula, Ph is a borane compound represented by an optionally substituted phenyl group) or (B-2) a general formula (II): B ⁻ (Ph) ₄ X ⁺ (II) (wherein Ph is (X ⁺ is a cationic group) using a catalyst comprising a borate compound represented by the following formula:
The molecular weight distribution (Mw / Mn) is obtained by block copolymerizing an olefin monomer having 2 to 20 carbon atoms at 60 to -100 ° C.
A process for producing an olefin-based block copolymer, wherein a polymer having a ratio of 1 to 1.3 is obtained. 6. (A-2) a zirconium-containing compound having one or two cyclopentadienyl skeletons, (B) (B-1) a general formula (I): B (Ph) ₃ (I) ( In the formula, Ph is a borane compound represented by an optionally substituted phenyl group) or (B-2) a general formula (II): B ⁻ (Ph) ₄ X ⁺ (II) (wherein Ph is as defined above) the same, X ⁺ is a borate compound and represented by the cationic group) (C) the general formula _{(III): AlR 3-n} Y n (III) ( wherein, R represents a hydrocarbon group having 4 to 20 carbon atoms, Y Is a polymerization temperature of -60 to 60 ° C. using a catalyst comprising an aluminum compound represented by a halogen atom, an alkoxy group, a trialkylsiloxy group, a di (trialkylsilyl) amino group or a trialkylsilyl group, and n is 0, 1 or 2). -10
An olefin monomer having 2 to 20 carbon atoms is subjected to block copolymerization at 0 ° C. to have a molecular weight distribution (Mw / Mn) of 1 to 1.3.
A process for producing an olefin-based block copolymer, characterized by obtaining a polymer of the formula (1). 7. The process according to claim 5, wherein the polymerization temperature is -60 to -80.degree. 8. The compound according to claim 1, wherein the Ph group in the general formula (I) or (II) is a group substituted with 1 to 5 fluorine atoms. The manufacturing method described. 9. The method according to claim 1, wherein the Ph group in the general formula (I) or (II) is a group substituted with 5 fluorine atoms. Manufacturing method. 10. The process according to claim 2, wherein n in formula (III) is 0. 11. In the formula (III), n is 0, and R
Is an alkyl group having 4 to 8 carbon atoms.
6. The production method according to 6, 7, 8 or 9. 12. The block copolymer of an olefin monomer having 2 to 20 carbon atoms is a block copolymer using two or more α-olefins having 2 to 20 carbon atoms.
2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. 13. The block copolymer of an olefin monomer having 2 to 20 carbon atoms is a block copolymer using two or more α-olefins having 2 to 10 carbon atoms.
2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. 14. The block copolymer of an olefin monomer having 2 to 20 carbon atoms is a block copolymer using two or more α-olefins having 2 to 6 carbon atoms.
2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. 15. The method according to claim 1, wherein the polymerization is carried out in such a range that the polymer does not precipitate.
7. The method according to 7, 8, 9, 10, 11, 12, 13 or 14. 16. The method of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 1 having a molecular weight distribution of 1 to 1.2.
The production method according to 2, 13, 14 or 15. 17. The method of claim 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, or 1
6. A propylene-based (co) polymer other than the above-mentioned propylene-based block copolymer and 1 to 99% by weight of a propylene-based block copolymer produced by the production method according to 6.
A propylene-based block copolymer composition comprising 9 to 1% by weight. 18. The propylene-based block copolymer composition according to claim 17, wherein 90% or more of the particles in the dispersed phase of the propylene-based block copolymer composition have a diameter of 400 nm or less. 19. The propylene block copolymer composition according to claim 17, wherein 90% or more of the particles in the dispersed phase of the propylene block copolymer composition have a diameter of 200 nm or less.