JP2001026612A - Production of olefinic living polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a living polymer that has a narrow molecular weight distribution and that can be converted to a terminally functionalized polymer or block copolymer by polymerizing an olefin at a specified temperature using a catalyst which comprises a Hf- or Zr-containing compound and a phenyl group-containing borane compound or borate compound. SOLUTION: A 2-20C olefinic monomer is polymerized with the use of a catalyst which comprises a Hf- or Zr-containing compound having one or two cyclopentadienyl skeletons and a borane compound represented by B(Ph)3 (wherein Ph is phenyl which may be substituted) or a borate compound represented by B-(Ph)4X+ (wherein X+ is a cationic group) and in some cases, further comprises an aluminum compound at -20 to -100 deg.C in the case of the use of a Hf-containing compound or at -60 to -100 deg.C in the case of the use of a Zr-containing compound to thereby produce a living polymer having a Mw/Mn of 1-1.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an olefin-based living polymer. More particularly, the present invention relates to a method for producing an olefin-based living polymer which can be converted into a terminal-functionalized polymer having a narrow molecular weight distribution or a block copolymer.

[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]

Embedded image

[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] Z
rMe ₂ complex:

[0005]

Embedded image

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

[0007]

Embedded image

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

[0011]

[SUMMARY OF THE INVENTION However, for example, the _{[(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)
_{3 When the} catalyst or the bulky aryl group-containing diimine complex of Ni / methylaluminoxane catalyst is used,
There is a problem that the catalyst is complicated and difficult to produce, and the regularity is low. In addition, [tBuNSiMe ₂ Flu] TiM
Even when a syndio-rich living polymer is produced at a low temperature using an e ₂ / B (C ₆ F ₅ ) ₃ catalyst, there is a problem that the stereoregularity is low, the structure of the catalyst is complicated, and the production is difficult.

Further, when 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 is used, and a cyclopentadienyl group IVB metal / alumoxane or a miscible In the case of using a catalyst that is a reaction product of a non-coordinating anion of either, it is not always possible to narrow the molecular weight distribution, or it is not always possible to obtain a high-level living polymer, terminal-functionalized polymer, In the field of using a block copolymer or the like, a polymer having a narrow molecular weight distribution or a highly living polymer is desired.

[0013]

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, a living olefin-based polymer 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 relates to (A-1) a hafnium-containing compound having one or two cyclopentadienyl skeletons, and (B) (B-1) a general formula (I): B (Ph) ₃ (I) borane compound represented by (wherein, Ph is a phenyl group which may be substituted) or (B-2) the general formula ^(II): B - (Ph) in ₄ X ⁺ (II) (wherein, Ph is the same as above, and X ⁺ is a cationic group).
An olefin monomer having 2 to 20 carbon atoms is polymerized at 20 to -100 ° C to have a molecular weight distribution (Mw / Mn) of 1 to 1.
3. A method for producing an olefin-based living polymer (claim 1), wherein the polymer of (3) is obtained.
Hafnium-containing compound having two cyclopentadienyl skeletons, (B) (B-1) general formula (I): B (Ph) ₃ (I) (where Ph is a phenyl group which may be substituted) in represented by borane compound 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 by And (C) a 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, an alkoxy group, a trialkylsiloxy group, a di ( Polymerization temperature of -20 to -10 using a catalyst comprising an aluminum compound represented by trialkylsilyl) amino group or trialkylsilyl group, n is 0, 1 or 2).
A method for producing a living olefin polymer, wherein a polymer having a molecular weight distribution (Mw / Mn) of 1 to 1.3 is obtained by polymerizing an olefin monomer having 2 to 20 carbon atoms at 0 ° C. The method according to claim 1 or 2, wherein the polymerization temperature is -30 to -80 ° C (claim 3).
The method according to claim 1 or 2, wherein the temperature is 40 to -80 ° C (claim 4), (A-2) a zirconium-containing compound having one or two cyclopentadienyl skeletons and (B) (B-1). ) general formula (I): B (Ph) 3 (I) ( wherein, Ph is borane compounds represented by a phenyl group) optionally substituted or (B-2) the general formula (II): B ^- ( Ph) ₄ X ⁺ (II) (wherein Ph is the same as above and X ⁺ is a cationic group).
An olefin monomer having 2 to 20 carbon atoms is polymerized at 60 to -100 ° C to have a molecular weight distribution (Mw / Mn) of 1 to 1.
3. A process for producing an olefin-based living polymer (claim 5), wherein the polymer of (3) is obtained.
Zirconium-containing compound having two cyclopentadienyl skeletons, (B) (B-1) General formula (I): B (Ph) ₃ (I) (where Ph is a phenyl group which may be substituted) in represented by borane compound 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 by And (C) a 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, an alkoxy group, a trialkylsiloxy group, a di ( Polymerization temperature of -60 to -10 using a catalyst comprising an aluminum compound represented by trialkylsilyl) amino group or trialkylsilyl group, n is 0, 1 or 2)
A process for producing a living olefin polymer, characterized in that a polymer having a molecular weight distribution (Mw / Mn) of 1 to 1.3 is obtained by polymerizing an olefin monomer having 2 to 20 carbon atoms at 0 ° C. 7. The method according to claim 5, wherein the polymerization temperature is -60 to -80 ° C. (claim 7), and the general formula (I).
Or the method according to claim 1, 2, 3, 4, 5, 6, or 7 wherein the Ph group in (II) is a group substituted with 1 to 5 fluorine atoms. The method according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the Ph group in the formula (I) or (II) is a group substituted with 5 fluorine atoms. The method according to claim 2, 3, 4, 6, 7, 8 or 9, wherein n in the general formula (III) is 0, wherein n in the general formula (III) is 0; R is an alkyl group having 4 to 8 carbon atoms, wherein R is an alkyl group having 4 to 8 carbon atoms.
The method according to 7, 8 or 9 (Claim 11), wherein the olefin-based monomer is an α-olefin having 2 to 20 carbon atoms, Claims 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Or the production method according to claim 11 (claim 12), wherein the olefin monomer is an α-olefin having 2 to 10 carbon atoms.
2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 (claim 13), wherein the olefin monomer is an α-olefin having 3 to 6 carbon atoms. 4,
The method according to 5, 6, 7, 8, 9, 10 or 11 (claim 14), wherein the polymerization is carried out within a range in which the polymer does not precipitate. , 7, 8,
9. The method according to claim 9, 10, 11, 12, 13 or 14 (claim 15), and the molecular weight distribution is 1 to 1.2, 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11,
The production method according to claim 12, 13, 14, or 15 (claim 16).
About.

The polymerization of olefin-based monomers includes not only homopolymerization but also copolymerization of olefin-based monomers.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (A) (A-1) 1
Hafnium-containing compound having one or two cyclopentadienyl skeletons or (A-2) zirconium-containing compound having one or two cyclopentadienyl skeletons, (B) (B-1) a compound represented by the 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) (where Ph is the same as above, 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) Aluminum compound Olefin living polymer is prepared by polymerizing an olefin monomer with a catalyst.

As the olefin monomer, those having 2 to 20, more preferably 2 to 10, especially 3 to 6 carbon atoms are used, and α-olefins are preferred.

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 propylene, butene and hexene are particularly preferred.

The catalyst comprising the components (A) to (B) and, if necessary, the component (C) is a relatively stable catalyst which can be easily produced, and is an olefin monomer having 2 to 20 carbon atoms, especially It is a catalyst for propylene living polymerization, and in some cases, stereoregular 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 group IVB compound (A) is represented by the following general formula (IV): CpM ¹ R ¹ R ² R ³ (IV) General formula (V): Cp ₂ M ¹ R ¹ R ² (V) General formula (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 IVA compound (A) represented by the general formulas (IV) to (VI) include the following. Among these, represented by general formulas (V) and (VI) having two cyclopentadienyl skeletons
Group IVB compounds 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 group and fluorenyl group
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 group IVB compound (A) and the optionally used aluminum compound (C) which will be described later is as described above. 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 IVB compound (A) and the boron-containing compound (B) represented by the general formula (I) or (II) is described above. As shown in 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 contained 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; 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 IVB 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 / Mn) is from 1 to 1 by polymerizing an olefin-based monomer at -60 to -100 ° C, further at -60 to -80 ° C.
3. Further, an olefin-based living polymer of 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 polymer. 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.

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. is a ² G.

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 living polymer having a molecular weight distribution of 1.3 or less, more preferably 1.2 or less, especially 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 living polymer.

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, but 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 precipitates during the polymerization, and the molecular weight is reduced. The distribution tends to spread. The polymer is difficult to precipitate during polymerization and has a narrow molecular weight distribution. The molecular weight is preferably 3000 or less, preferably 2000 or less, more preferably 1000 or less, and most preferably 5 or less.
00 or less. Since it is a polymer, its molecular weight is usually 10
0 or more. In order to make crystallization or precipitation difficult during polymerization, it is also preferable to copolymerize these monomers.

The produced living polymer was evaluated generally by (a) that the molecular weight distribution of the formed polymer was extremely narrow (close to monodisperse), and (b) that the polymer yield number average molecular weight was increased as the time was increased. (Mn) is proportionally increased and the molecular weight distribution is not broadened.

The living polymer is contacted with a reagent having an appropriate reactivity such as carbon monoxide, thereby
It can be a so-called terminal-functionalized polymer having no group IVB transition metal at the molecular terminal. In the case of converting into a block copolymer, the block copolymer can be obtained in high yield by contacting with an appropriate different monomer and performing multi-stage polymerization.

[0059]

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.

Examples 1-2 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.
04 mmol and 83 mmol of propylene were added, and the mixture was polymerized for 3 hours in Example 1 and 12 hours in Example 2. Thereafter, the mixture was poured into 1,000 ml of hydrochloric methanol to terminate the polymerization, thereby precipitating a polymer. The precipitate is separated by filtration,
The polymer was obtained by vacuum drying.

The yield (Yield) of the polymer was 89 mg in Example 1 and 291 mg in Example 2. The number average molecular weight (Mn) and the molecular weight distribution (Mw (weight average molecular weight) / Mn) measured by GPC were 9400 and 1.06 in Example 1, and 2 in Example 2.
7300 and 1.15.

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

FIG. 1 shows the relationship between time and the number average molecular weight and the relationship between time and yield.

FIG. 1 shows that time and the number average molecular weight are proportional. Also, it can be seen that both the time and the yield are proportional. These results also show that the polymerization is living polymerization.

Comparative Example 1 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 -50 ° C. Biscyclopentadienyl zirconium dimethyl 0.04m
mol, tris (pentafluorophenyl) boron 0.
04 mmol and 83 mmol of propylene were added, and in the case of Comparative Example 1, polymerization was carried out 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 1110
mg. Number average molecular weight (M
n) and the molecular weight distribution (Mw / Mn) were 46300 and 1.55.

As described above, only a polymer having a wide molecular weight distribution was obtained, indicating that the polymerization did not necessarily proceed in a living manner.

Examples 3 to 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
Example 3 was added with 4 mmol and 83 mmol of propylene.
3 hours, Example 4 15 hours, Example 5
In the case of, polymerization was carried out for 24 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 (Yield) of the polymer was 88 mg in Example 3, 460 mg in Example 4, and 650 mg in Example 5. Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) measured by GPC
Are 6000 and 1.08 in the case of Example 3, and Example 4
23200 and 1.04 in the case of, 34 in the case of the fifth embodiment
300 and 1.05.

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

FIG. 2 shows the relationship between time and number average molecular weight and the relationship between time and yield.

FIG. 2 shows that time and the number average molecular weight are proportional. Also, it can be seen that both the time and the yield are proportional. These results also show that the polymerization is living polymerization.

Examples 6 and 7 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. Biscyclopentadienyl zirconium dichloride 0.0
4 mmol, tris (pentafluorophenyl) boron 0.04 mmol, and propylene 83 mmol were added, and the mixture was polymerized for 6 hours in Example 6 and 12 hours in Example 7. 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 (Yield) of the polymer was 2.0 mg in Example 6 and 10 mg in Example 7. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) measured by GPC were 1100 in Example 6.
And 1.20, 3900 and 1.2 for Example 7
It was 3.

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

FIG. 3 shows the relationship between the time and the number average molecular weight and the relationship between the time and the yield. From FIG. 3, it can be seen that the time and the number average molecular weight are proportional to the presence of the induction period. Also, it can be seen that both the time and the yield are proportional. These results also show that the polymerization is living polymerization.

Examples 8 to 10 11.0 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, tris (pentafluorophenyl) boron 0.04 mmol, and 1-hexene 83 mmol were added, and the mixture was polymerized for 5 hours in Example 8, 12 hours in Example 9, and 14 hours in Example 10. 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 (Yield) of the polymer was 10 mg in Example 8, 21 mg in Example 9, and Example 1.
In the case of 0, it was 28 mg. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) measured by GPC are
2300 and 1.27 in Example 8, 4300 and 1.22 in Example 9, 5400 in Example 10
And 1.29.

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

FIG. 4 shows the relationship between time and number average molecular weight and the relationship between time and yield.

FIG. 4 shows that time and the number average molecular weight are proportional. Also, it can be seen that both the time and the yield are proportional. These results also show that the polymerization is living polymerization.

FIG. 5 shows the ¹³ C-NMR signal of the polymer obtained in Example 10. As shown in FIG. 5, the signal of each carbon is almost single, and it can be understood that the polymer is a polymer having high stereoregularity.

Examples 11 to 12 14.4 ml of dry toluene and 0.8 mmol of tri (isobutyl) aluminum were added to a sufficiently dried 100 ml autoclave, and the mixture was cooled to -78 ° C. Biscyclopentadienyl zirconium dimethyl 0.04mm
ol, tris (pentafluorophenyl) boron 0.0
Example 1 was added with 4 mmol and 83 mmol of propylene.
In the case of 1, polymerization was carried out for 3 hours, and in the case of Example 12, polymerization was carried out for 12 hours. The polymerization was stopped by pouring into 1000 ml of hydrochloric methanol, and a polymer was precipitated. The precipitate was separated by filtration and dried under vacuum to obtain a polymer.

The yield (Yield) of the polymer was 30 mg in Example 11 and 150 mg in Example 12. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) measured by GPC were 27 in Example 11
00 and 1.23, and 10300 and 1.04 in Example 12.

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

FIG. 6 shows the relationship between time and the number average molecular weight and the relationship between time and yield.

FIG. 6 shows that time and the number average molecular weight are proportional. Also, it can be seen that both the time and the yield are proportional. These results also show that the polymerization is living polymerization.

Examples 13 and 14 14.4 ml of dry toluene and 0.4 mmol of tris (pentafluorophenyl) boron were added to a fully dried 100 ml autoclave, and the mixture was cooled to -78 ° C. 0.04 mmol of biscyclopentadienyl zirconium dimethyl and 83 mmol of propylene were added, and the mixture was polymerized for 6 hours in Example 13 and for 24 hours in Example 14. The polymerization was stopped by pouring into 1000 ml of hydrochloric methanol, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer (Yield) was 24.0 mg in Example 13 and 110 mg in Example 14.
Met. According to GPC, the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were 19
00, 1.16, 9200, 1.11 in Example 14
Met.

FIG. 7 shows the relationship between time and number average molecular weight, and the relationship between time and yield.

FIG. 7 shows that time and the number average molecular weight are proportional. Also, it can be seen that both the time and the yield are proportional. These results also show that the polymerization is living polymerization.

Examples 15 to 16 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)
0.04 mmol of boron and 83 mmol of propylene were added, and 6 hours in Example 15 and 1 in Example 16.
The polymerization was carried out for one hour. After that, hydrochloric acid methanol 100
The mixture was poured into 0 ml to stop the polymerization, and a polymer was precipitated.
The precipitate was separated by filtration and dried under vacuum to obtain a polymer.

The yield (Yield) of the polymer was 1600 mg in Example 15, and 2920 m in Example 16.
g. Number average molecular weight (M
n) and molecular weight distribution (Mw (weight average molecular weight) / M
n) is 60000 and 1.10 for Example 15,
In the case of Example 16, they were 104000 and 1.10.

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

FIG. 8 shows the relationship between time and the number average molecular weight and the relationship between time and yield.

FIG. 8 shows that time and the number average molecular weight are proportional. Also, it can be seen that both the time and the yield are proportional. These results also show that the polymerization is living polymerization.

[0097]

According to the present invention, an olefin monomer having 2 to 20 carbon atoms is polymerized at a low temperature using a catalyst comprising a compound (A), a compound (B) and optionally a compound (C). A polyolefin-based living polymer having a molecular weight distribution of 1.3 or less can be produced.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Examples 1 and 2, and the reaction time.

FIG. 2 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Examples 3 to 5, and the reaction time.

FIG. 3 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Examples 6 and 7, and the reaction time.

FIG. 4 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Examples 8 to 10 and the reaction time.

FIG. 5 is a view showing a ¹³ C-NMR signal of a polymer obtained in Example 10.

FIG. 6 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Examples 11 to 12, and the reaction time.

FIG. 7 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Examples 13 and 14, and the reaction time.

FIG. 8 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Examples 15 and 16, and the reaction time.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Michihiko Asai 1-1, Higashi, Tsukuba, Ibaraki Pref. Institute of Industrial Science and Technology (72) Inventor Yasumi Suzuki 1-1, Higashi, Tsukuba, Ibaraki Pref. Inside the Institute of Industrial Technology (72) Inventor: Satoshi Miyazawa 1-1, Higashi 1-1, Tsukuba, Ibaraki Prefecture Inside of the Institute of Materials Science and Technology, Institute of Industrial Technology (72) Inventor Kenji Tsuchihara 1-1, Higashi 1-1, Tsukuba, Ibaraki, Japan In-house (72) Inventor Masahide Murata 2-315-504, Suido 2-chome, Bunkyo-ku, Tokyo (72) Inventor Hiroyuki Ozaki 4-6-202 Onogawa, Tsukuba, Ibaraki Prefecture (72) Inventor Masanori Kawabe Tsukuba, Ibaraki Takezono 2-6-2-203 (72) Inventor Toshio Kase 5-2-2 Matsushiro, Tsukuba, Ibaraki Prefecture (72) Inventor Jin Jiju (72) Inventor Hideaki Hagiwara 2-6-14 Amakubo, Tsukuba, Ibaraki Prefecture 203-2, Sakurai Heights 203 (72) Inventor, Yoshifumi Fukui 4-63-3 Ninomiya, Tsukuba City, Ibaraki Prefecture 507 No. F-term (reference) 4J028 AA01A AB00A AC01A AC28A BA00A BA01B BA02B BB00A BB00B BB01B BC12B BC13B BC16B BC17B BC18B BC24B BC28B BC29B EB01 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB15 EB16 EB18 GA01 GA06 4J100 AA02P AA03P AA04P AA07P AA08P AA09P AA15P AA16P AA17P AA18P AA19P AA21P CA01 CA27 DA01 DA04 FA10 FA19

Claims (16)

[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:
An olefin monomer having 2 to 20 carbon atoms is polymerized at 20 to -100 ° C to have a molecular weight distribution (Mw / Mn) of 1 to 1.
3. A process for producing an olefin-based living polymer, which comprises obtaining the polymer of item 3. 2. (A-1) a hafnium-containing compound having one or two cyclopentadienyl skeletons, (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 as defined above, X ⁺ cation group) borate compound represented by and (C) the 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, an alkoxy group, a trialkylsiloxy group, a di (trialkylsilyl) amino group or a trialkylsilyl group, n is 0, Polymerization temperature of -20 to -10 using a catalyst comprising an aluminum compound represented by 1 or 2)
A method for producing a living olefin polymer, comprising polymerizing an olefin monomer having 2 to 20 carbon atoms at 0 ° C to obtain a polymer having a molecular weight distribution (Mw / Mn) of 1 to 1.3. 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 as defined above) (X ⁺ is a cationic group) using a catalyst comprising a borate compound represented by the following formula:
An olefin monomer having 2 to 20 carbon atoms is polymerized at 60 to -100 ° C to have a molecular weight distribution (Mw / Mn) of 1 to 1.
3. A process for producing an olefin-based living polymer, which comprises obtaining the polymer of item 3. (A-2) a zirconium-containing compound having one or two cyclopentadienyl skeletons,
(B) (B-1) a borane compound represented by the general formula (I): B (Ph) ₃ (I) (wherein Ph is a phenyl group which may be substituted) or (B-2) a general formula ^{(II): B - (Ph} ) 4 X + (II) ( wherein, Ph is as defined above, X ⁺ is a cation group) borate compound represented by and (C) the 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, an alkoxy group, a trialkylsiloxy group, a di (trialkylsilyl) amino group or a trialkylsilyl group, n Is a polymerization temperature of -60 to -10 using a catalyst comprising an aluminum compound represented by 0, 1 or 2).
A process for producing an olefin-based living polymer, comprising polymerizing an olefin-based monomer having 2 to 20 carbon atoms at 0 ° C to obtain a polymer having a molecular weight distribution (Mw / Mn) of 1 to 1.3. 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 general 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. An olefin-based monomer having 2 to 2 carbon atoms.
0, α-olefin of claim 1, 2, 3, 4, 5,
The production method according to 6, 7, 8, 9, 10 or 11. 13. An olefin-based monomer having 2 to 1 carbon atoms.
0, α-olefin of claim 1, 2, 3, 4, 5,
The production method according to 6, 7, 8, 9, 10 or 11. 14. An olefin monomer having 3 to 6 carbon atoms.
1, 2, 3, 4, 5,
6. The method according to 6, 7, 8, 9, 10 or 11. 15. The method according to claim 1, wherein the polymerization is carried out within a range where 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.