JP2001081123A - Production of olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefinic polymer which has carbonyl groups at the terminals of most polymer terminals, has a narrow mol.wt. distribution, and is useful as a compatibilizing agent and the like by polymeerizing a specific olefinic monomer in the presence of a specific catalyst at a specific temperature and then reacting the obtained polymer with a carbonylating agent. SOLUTION: This method for producing an olefinic polymer having carbonyl groups at the polymer terminals comprises polymerizing a 2 to 20C olefinic monomer such as propylene in the presence of a catalyst at a polymerization temperature of -20 to -100 deg.C and then reacting the obtained olefinic living polymer with a carbonylating agent. The catalyst comprises (A) a zirconium- containing compound having one or more cyclopentadienyl skeletons (for example, biscyclopentadienylzirconium dimethyl), (B) a borane compound of the formula: B(Ph)3 [Ph is (substituted)phenyl] [for example, tris(pentafluorophenyl) boron] or a borate compound of the formula: B-(Ph)4X+ (X+ is a cation), and (C) a titanium-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an olefin polymer having a carbonyl group at a terminal. More specifically, the molecular weight distribution is narrow (however, the total molecular weight distribution may be wide because the previous olefinic living polymer may be a mixture). A process for producing an olefinic polymer having a carbonyl group at a terminal. About.

[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 to 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] 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]

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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, 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] The living polymerization of propylene and 1-hexene is carried out at -50 ° C at [tBuNSiMe ₂ Flu] T.
It has been reported that iMe ₂ occurs as a catalyst (Macromolecules, 31 3184 (1998)).

On the other hand, propylene is used in the presence of a catalyst comprising a β-diketone vanadium chelate and an aluminum compound of the general formula: R ₂ AlX (where R represents a hydrocarbon group having 1 to 8 carbon atoms or a halogen atom). Has been reported to produce a propylene polymer having a carbonyl group at a terminal by polymerizing the polymer at -78 ° C. into a living propylene polymer and reacting the polymer with a carbonylating agent (JP-A-61-151202). No.).

[0013]

However, for example, the aforementioned [(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)
_When living polymerization is carried out using a ₃ catalyst or the above-mentioned bulky aryl group-containing diimine complex of Ni / methylaluminoxane catalyst, there is a problem that both catalysts are complicated, difficult to produce, and have low regularity. In addition, [tBuNSi
[Me ₂ Flu] TiMe ₂ / B (C ₆ F ₅ ) ₃ catalyst,
When producing a syndio-rich living polymer at low temperatures, only a syndio-rich polymer with a low stereoregularity can be produced. I can't get it. There is no example of terminal functionalization.

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, 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 narrower molecular weight distribution or a higher living polymer is desired from the viewpoint that a polymer having a high terminal functionalization rate and a high blocking rate can be obtained.

Further, [tBuNSiMe ₂ Flu] T
When living polymerization is carried out at −50 ° C. using an iMe ₂ catalyst, the yield and molecular weight of the polymer are not sufficient.

Therefore, the above problem is also involved when a living polymer is obtained by the above-mentioned conventional technique and is intended to react with a carbonylating agent to obtain a polymer having a carbonyl group at a terminal.

The present inventors have conducted intensive studies in order to solve the above-mentioned problems of the prior art. As a result, a hafnium or zirconium-containing compound having one or two cyclopentadienyl skeletons, even if substituted, When an olefin-based monomer is polymerized at a low temperature using a catalyst composed of a borane compound or a borate compound having a good phenyl group and optionally a specific alkylaluminum compound, an olefin-based living polymer having a molecular weight distribution of 1.3 or less can be obtained. They have found that they can be manufactured and have already filed an application (Japanese Patent Application No. 11-128732).

However, when using a zirconium-containing compound having one or two cyclopentadienyl skeletons, there is a problem that the polymerization temperature cannot always be increased.

Therefore, the above problem is also involved when a living olefin polymer is produced by the method described in Japanese Patent Application No. 11-128732 to produce a polymer having a carbonyl group at a terminal.

[0020]

According to the present invention, there is provided a method for producing a living polymer using a zirconium-containing compound having one or two cyclopentadienyl skeletons.
The present invention has been made to improve the problem that the polymerization temperature cannot always be increased, and thus the same problem is involved in obtaining a terminal-functionalized polymer using the living polymer. 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) After polymerizing an olefinic monomer having 2 to 20 carbon atoms at a polymerization temperature of -20 to -100 ° C using a catalyst comprising a borate compound represented and a (D) titanium-containing compound,
A method for producing an olefin polymer having a terminal carbonyl group, characterized by reacting the obtained living olefin polymer with a carbonylating agent (claim 1), (A) 1
A zirconium-containing compound having one or two cyclopentadienyl skeletons, (B) (B-1) a general formula (I): B (Ph) ₃ (I) (wherein Ph may be substituted) borane compounds represented by a phenyl group) or (B-2) the general formula ^{(II): B - (Ph} ) represented by ₄ X ⁺ (II) (wherein, Ph is as defined above, X ⁺ is a cation group) (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, an alkoxy group, a trialkylsiloxy group) , A di (trialkylsilyl) amino group or a trialkylsilyl group, n is 0, 1 or 2) using a catalyst comprising an aluminum compound and a titanium-containing compound (D) at a polymerization temperature of -20 to -100 ° C. C2-20 olefins A method for producing an olefin polymer having a carbonyl group at a terminal, characterized by reacting the obtained olefin living polymer with a carbonylating agent after polymerizing the nomer (claim 2), and (D) titanium-containing polymer. The method according to claim 1 or 2, wherein the compound is a titanium-containing compound having one cyclopentadienyl skeleton, and (A) a zirconium-containing compound having one or two cyclopentadienyl skeletons. 4. The method according to claim 1, wherein at least one of the compound and (D) the titanium-containing compound contains an alkyl group (claim 4), wherein the polymerization temperature is -30 to -80 ° C. The production method according to 2, 3 or 4 (Claim 5), wherein the polymerization temperature is -40 to -6.
The method according to claim 1, 2, 3 or 4, wherein the Ph group in the general formula (I) or (II) is 0 to 1 ° C.
A group substituted with 5 fluorine atoms,
The method according to claim 2, 3, 4, 5 or 6, wherein the Ph group in the general formula (I) or (II) is a group substituted with 5 fluorine atoms. The method of claim 2, 3, 4, 5 or 6 (claim 8), wherein n in the general formula (III)
Is 0, n is 0 in the general formula (III), and R is alkyl having 4 to 8 carbon atoms. Claim 2, which is a group
3, 4, 5, 6, 7, or 8 (claim 1).
0), wherein the olefin-based monomer is an α-olefin having 2 to 20 carbon atoms.
The method according to claim 8, 9, or 10 (claim 11), wherein the olefin monomer is an α-olefin having 2 to 10 carbon atoms, claim 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
The method according to claim 1, wherein the olefin monomer is an α-olefin having 3 to 6 carbon atoms.
The method according to claim 4, 5, 6, 7, 8, 9 or 10 (claim 13), and the polymerization is carried out within a range in which the polymer does not precipitate. , 9, 10, 1
The present invention relates to the production method according to claim 1, 12, or 13.

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

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, (A) one or two
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 , (D) a titanium-containing compound and, optionally, (C) a general formula (III): AlR _3-n Y _n (III) (wherein, R is a hydrocarbon group having 4 to 20 carbon atoms, and Y is halogen) An olefin monomer is polymerized using a catalyst comprising an aluminum compound represented by an atom, an alkoxy group, a trialkylsiloxy group, a di (trialkylsilyl) amino group or a trialkylsilyl group, where n is 0, 1 or 2). Olefin type Ring polymer is produced.

As the olefin-based 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 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), (B), (D) and, if necessary, the component (C) is a relatively stable catalyst, and is an olefinic monomer having 2 to 20 carbon atoms, especially propylene. And, in some cases, a catalyst for stereoregular living polymerization.

The zirconium-containing compound (A) having one or two cyclopentadienyl skeletons (hereinafter referred to as “the compound”).
The Zr-containing compound (A) is represented by the general formula (I
V): 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 a Zr atom, Cp
Is an optionally substituted cyclopentadienyl skeleton, R
¹ , R ² and R ³ are σ-binding ligands and chelating ligands, A is a covalent divalent group, and e is 1-3
In general formulas (V) and (VI), two Cp are the same, and R ¹ , R ² and R ³ may be such that two or more of them may be bonded to each other to form a ring. Well,
(Which may be different from each other) or their derivatives are preferably used. 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.

The cyclopentadienyl skeleton which may be substituted includes, in addition to a cyclopentadienyl group and 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.

The substituted cyclopentadienyl group includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl 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 isopropyl group, 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, 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 a methylene group, a dimethylmethylene group, an ethylene group, an isopropylidene group, a cyclobutylidene group, a cyclopentylidene group 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 Zr-containing compound (A) represented by the general formulas (IV) to (VI) include the following. Among them, cyclopentadienyl group, ethylcyclopentadienyl group, propylcyclopentadienyl group, butylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group , Which has both two ligands selected from a methylindenyl group, a tetrahydroindenyl group and a fluorenyl group and two 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 (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 the like.

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 and (trifluoromethylcyclopentadienyl) (cyclopentadienyl) dimethylzirconium.

Examples of the compound represented by the general formula (VI) include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, and ethylene bis (tetrahydroindenyl) dichloro Zirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclopentene Lydene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, dimethylsilylene Screw (2,3,5
-Trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (indenyl) dichlorozirconium,
Methylenebis (cyclopentadienyl) dimethylzirconium, methylenebis (cyclopentadienyl) di (trimethylsilyl) zirconium, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) dimethylzirconium, methylene (cyclopentadienyl) (fluorenyl) ) Dimethyl zirconium, ethylenebis (cyclopentadienyl) dimethyl zirconium,
Ethylene bis (cyclopentadienyl) dibenzyl zirconium, ethylene bis (cyclopentadienyl) dihydride zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methylchlorozirconium, ethylene bis (tetrahydroindenyl) dibenzyl Zirconium, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (octahydrofluorenyl) dihydridozirconium, dimethylsilylenebis (cyclopentadienyl) dineo Pentyl zirconium, dimethylsilylenebis (cyclopentadienyl) dihydride zirconium, dimethylsilylenebis (methylcyclopentadienyl) dichloro Rukoniumu, dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (tetrahydroindenyl)
Dichlorozirconium, dimethylsilylene (cyclopentadienyl) (fluorenyl) dichlorozirconium,
Dimethylsilylene (cyclopentadienyl) (fluorenyl) dihydridozirconium, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) dihydridozirconium, dimethylsilylenebis (3-trimethylsilylcyclopentadienyl) dihydridozirconium, dimethylsilylenebis (Indenyl) dimethyl zirconium, diphenylsilylenebis (indenyl) dichlorozirconium, phenylmethylsilylenebis (indenyl) dichlorozirconium and the like. Among them, C ₁ symmetric, C ₂ symmetric and C _s symmetric
A stereoregular living polymer can be obtained.

The borane compound (A), the titanium-containing compound (D) described later, and the aluminum compound (C) described below, which may be used in some cases, together with the aluminum compound (C) described later, constitute the catalyst used in the present invention. B-
As described above, 1) is 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 group or different groups, but the three groups have a total of 3 It is preferable that the number is included in the number of at least 15 and particularly 15 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 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 group or different groups, but the four groups have a total of 4 fluorine atoms. The number is preferably at least 20 and particularly at least 20, because it is industrially easily available.

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, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, and tetraphenylammonium. 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 preferred.

The Zr-containing compound (A), the boron-containing compound (B) represented by the general formula (I) or (II) and the titanium-containing compound (D), and optionally an aluminum compound constituting the catalyst used in the present invention. (C)
As described above, the general formula (III): AlR _3-n Y _n (III) (where R is a hydrocarbon group having 4 to 20 carbon atoms, Y is a halogen atom, an alkoxy group, a trialkylsiloxy group, a di ( N is an aluminum compound represented by 0, 1 or 2) such as a trialkylsilyl) amino group or 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 represented by R in 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. Among them, an alkyl group having 4 to 8 carbon atoms is preferable from the viewpoint of industrial availability.

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, that is, the number of n is 0, since chain transfer is less likely to occur and a living polymer is easily obtained. Further, three Rs are an alkyl group having 4 to 8 carbon atoms. Preferably it is. 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.

The titanium-containing compound constituting the catalyst used in the present invention together with the Zr-containing compound (A), the boron-containing compound (B) represented by the general formula (I) or (II) and the aluminum compound (C) optionally used. Compound (D) is used to increase the living polymerization temperature.

The titanium-containing compound (D) contains a cyclopentadienyl skeleton, a hydrogen atom, an oxygen atom,
Substituents containing silicon atoms, such as halogen atoms, alkyl groups, substituted alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, allyl groups, substituted allyl groups, and trialkylsilyl groups, and substitutions containing germanium atoms Group, a substituent containing a phosphorus atom, an alkoxy group, an aryloxy group, a thiol group, an arylthio group,
Amino group, alkylamino group, acetylacetonato group,
It is a compound to which one or more groups such as a substituted acetylacetonato group, an acyloxy group and a substituted sulfonato group are bonded.
These groups may be cross-linked to each other. In particular, a compound to which a halogen atom, an alkoxy group, an alkylamino group, an acetylacetonato group, or a substituted acetylacetonato group is bonded is preferable because it is industrially easily available.

It is preferable that the titanium-containing compound (D) is a titanium-containing compound having one cyclopentadienyl skeleton, since the yield is high and the molecular weight tends to be large.

Specific examples of the titanium-containing compound (D) which does not contain a cyclopentadienyl skeleton include:
For example, tetramethyltitanium, tetraneopentyltitanium, tetranorbornyltitanium, dinorbornyldimethyltitanium, tetrabenzyltitanium, tribenzylhydridotitanium, tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetrachlorotitanium, tetrachlorotitanium Titanium, butoxytrichlorotitanium, dimethoxydi (benzhydryl) titanium, butoxytris ((trimethylsilyl) methyl) titanium, diphenoxybis (trimethylsilyl) titanium, (tri-t
-Butylsiloxy) trimethyltitanium, bis (2,
5-di-t-butylphenoxy) dimethyltitanium,
Bis (2,5-di-t-butylphenoxy) dichlorotitanium, bis (2,6-diisopropyl-4-methylphenoxy) dibenzyltitanium, bis (2,4,6
-Trimethylphenoxy) dibenzyl titanium, titanium bis (acetylacetonate), titanium tetra (acetylacetonate), 2,2'-thiobis (4
-Methyl-6-t-butylphenyl) dimethoxycytitanium, 2,2'-thiobis (4-methyl-6-t-butylphenyl) diisopropoxytitanium, tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium, (Me ₂ N) ₂ TiCl _{2 and the} like. Specific examples of the titanium-containing compound having a cyclopentadienyl skeleton include a compound represented by the general formula (IV):
In addition to the examples of (V) and (VI) in which Zr is changed to Ti, biscyclopentadienylchlorotitanium, biscyclopentadienylmethyltitanium, bispentamethylcyclopentadienylchlorotitanium, bispenta A trivalent titanium compound such as methylcyclopentadienylmethyltitanium, or a crosslinked titanium compound having one cyclopentadienyl skeleton, for example, (dimethylsilyl) tetramethylcyclopentadienyl-t-butyl Amidodimethyltitanium, (dimethylsilyl) tetramethylcyclopentadienyl-t-butylamidodiethyltitanium, (dimethylsilyl)-
t-butylcyclopentadienyl-t-butylamidodihydridotitanium, (dimethylsilyl) -t-butylcyclopentadienyl-t-butylamidodiphenyltitanium, (dimethylsilyl) trimethylsilylcyclopentadienyl-t-butylamide Dihydridotitanium, (dimethylsilyl) tetramethylcyclopentadienylphenylamidodimethyltitanium, (dimethylsilyl) tetramethylcyclopentadienylphenylamiditolitolyltitanium, (methylphenylsilyl) tetramethylcyclopentadienyl-t-butyl Amidodihydridotitanium, (methylphenylsilyl) tetramethylcyclopentadienyl-t-butylamidodimethyltitanium, (dimethyldilyl) fluorenyl-cyclohexylamidedi Tiltitanium, (diphenylgermyl) indenyl-t-butylphosphodidihydridotitanium, (methylphenylsilyl) tetramethylcyclopentadienyl-t-butylamidodimethyltitanium, (dimethylsilyl) tetramethylcyclopentadienyl-p -N-butylphenylamidodihydridotitanium, (dimethylsilyl) tetramethylcyclopentadienyl-pn-butylphenylamidodi (trimethylsilyl) titanium, (ethylene) tetramethylcyclopentadienyl-t-butylamidodichlorotitanium , (Ethylene) tetramethylcyclopentadienyl-
t-butylamidodimethyltitanium, (ethylene) tetramethylcyclopentadienyl-t-butylamidodi (methylbenzyl) titanium, (ethylene) tetramethylcyclopentadienylmethylamidodichlorotitanium, (ethylene) tetramethylcyclopentadienylmethyl Amido Dineopentyl Titanium, (Ethylene)
Tetramethylcyclopentadienylmethylamidodi (benzhydryl) titanium, (methylene) tetramethylcyclopentadienylethylamidodichlorotitanium, (methylene) tetramethylcyclopentadienylethylamidodiphenyltitanium, (dibenzylsilyl) tetramethylcyclo Pentadienyl-t-butylamidodibenzyltitanium, (dimethylsilyl) tetramethylcyclopentadienylbenzylamidodichlorotitanium, (dimethylsilyl) tetramethylcyclopentadienylbenzylamidodi (trimethylsilyl) titanium, (dimethylsilyl) tetra Methylcyclopentadienylphenylphosphodidibenzyltitanium,
[TBuNSiMe ₂ Flu] TiMe _{2 and the} like. Among them, cyclopentadienyl group, ethylcyclopentadienyl group, propylcyclopentadienyl group, butylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group , One having one ligand selected from a methylindenyl group, a tetrahydroindenyl group, and a fluorenyl group, and two or three ligands selected from a chlorine atom and a methyl group are industrially used. It is preferable because it is easily available.

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

At least one of the compound (A) and the compound (D) used at this time is a compound containing an alkyl group (preferably a methyl group), because a living polymer is easily obtained. preferable.

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) may be used in a ratio of 1 / 0.1 to 1/100 by mole of the compound (A) / compound (B) in the production of 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 used unnecessarily, which is uneconomical.

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

The compound (A) / compound (D) may be used in a molar ratio of compound (A) / compound (D) of 1 / 0.5 to 1 / 1.5, more preferably 1 / 0.5 to 1 / 0.5. .75-1
/1.25 is (A), (D) and (B) are 1:
A ratio of 1: 1 is preferred in that it facilitates interaction and facilitates living polymerization. If the ratio of compound (D) to compound (A) is too small or too large, (A), (D), and (B) are less likely to interact at a ratio of 1: 1: 1.

The conditions for mixing and reacting compound (A), compound (B), compound (D) and optionally compound (C) are as follows: -100 ° C. to room temperature, and
It is carried out by reacting in a solvent such as a polymerization solvent described below under an inert gas atmosphere at 100 to -20 ° C,
It is preferable because 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 below.

In the presence of the catalyst thus prepared,
-20 to -100C, furthermore, -30 to -80C, particularly -40 to -60C, particularly -40C or lower -60C
By polymerizing the olefin-based monomer at a temperature higher than the above, an olefin-based living polymer having a molecular weight distribution (Mw / Mn) of 1 to 1.3, or even 1 to 1.2 (the living polymer may be a mixture) Therefore, the total molecular weight may exceed 1.3). 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 will be low.

The amount of the catalyst to be used is such that the molar ratio of the olefin monomer / catalyst (to be the amount of the compound (B)) is 10 to 10 ⁹ , more preferably 100 to 10 ⁷ , especially 100 to 10 ⁷ .
Preferably 0 to 10 ^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; 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 preferred 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 further, 500 to 2000
Olefin-based living polymer having a molecular weight distribution of 1.3 or less, particularly 1.2 or less. May exceed 1.3). 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.

When the polymer does not precipitate during the polymerization, the molecular weight is 500 to 2,000,000, more preferably 1000 to 2,000,000.
1,000,000, in particular, 2,000 to 500,000 is preferable, and this condition is usually satisfied. 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 precipitates during the polymerization, the molecular weight distribution is widened, and the yield and the molecular weight tend not to increase linearly with time. If the polymer is likely to precipitate during polymerization,
As a molecular weight that makes it difficult to precipitate a polymer, narrows the molecular weight distribution, and easily increases the yield and molecular weight linearly with time, the molecular weight is 3000 or less, preferably 2000 or less, more preferably 1000 or less, and most preferably 500 or less. It is. Since it is a polymer, the molecular weight is usually 100 or more. In order to make crystallization or precipitation difficult during polymerization, it is also preferable to copolymerize these monomers.

The evaluation of the produced living polymer is generally based on the increase of the polymer yield and the number average molecular weight (M
n) is proportionally increased and the molecular weight distribution is not broadened. In addition, when a mixture of living polymers is obtained, or when a polymer precipitates during polymerization, the above-mentioned evaluation may not be applied. In this case, for example, the obtained bimodal GPC curve may be approximated by two Gaussian curves, and the peak may be separated and evaluated.

The living polymer is reacted with a carbonylating agent having an appropriate reactivity such as carbon monoxide to form a polymer having a carbonyl group at the terminal without a Zr-containing group at the molecular terminal. Can be. Also, by performing multi-stage polymerization by contacting with an appropriate heterogeneous monomer to convert it into a block copolymer in high yield, it is further reacted with a carbonylating agent to form a polymer having a carbonyl group at a terminal. Can be.

The living polymer is a polymer having a narrow molecular weight distribution and close to monodisperse (however, it may be a mixture of living polymers. In this case, the total molecular weight distribution is, for example, 1.51). However, the molecular weight distribution can be increased to 1.3 or less as in Reference Example 1 if separated into individual living polymers.
It is considered to be a polymer close to a monodispersion of 2 or less. In addition, a polymer may precipitate during polymerization to broaden the molecular weight distribution. In this case, too, a living polymer is obtained.) Since a catalyst is bonded to, a carbonyl group can be introduced into almost all polymer chain terminals by reaction with a carbonylating agent.

In the carbonylation of the living polymer, the living polymerization is stopped by contacting the polymer with a carbonylating agent, and at the same time, the carbonylation proceeds to introduce a carbonyl group at the terminal of the polymer chain. Achieved. In some cases, the molecular weight distribution of the obtained polymer having a carbonyl terminal is broadened, for the reason that the living polymerization is stopped, that is, the carbonylation does not proceed simultaneously.

Examples of the carbonylating agent used include carbon monoxide and carbon dioxide. These may be used alone or diluted with an inert gas or liquid medium.

The reaction is carried out at normal pressure to under pressure, at room temperature to -100.
° C, furthermore, -20 to -100 ° C, especially -30 to-
It is preferably performed at a temperature of 80 ° C. for 5 minutes to 50 hours.

The carbonylation means that C is present in the molecule.
= O means to introduce a bond.

The olefin polymer having a carbonyl group at the terminal after the completion of the carbonylation reaction is precipitated and recovered by adding an alcohol such as methanol or ethanol to the reaction system. Note that an acid such as hydrochloric acid may be added together.

In this way, the carbonyl group was introduced at the terminal of almost all polymer chains, and the number average molecular weight was 100 to 2,000,000, more preferably 500 to 2,000.
000, especially 1000 to 1,000,000, especially 2000 to 500,000, and a molecular weight distribution of 2 or less, further 1.5 or less, especially 1.3 or less, especially 1.2 or less.
The following monodisperse olefin polymer can be produced.

[0078]

EXAMPLES Next, the production method of the present invention will be described more specifically based on Reference Examples, Comparative Reference Examples and Examples, but the present invention is not limited to these Examples.

Reference Examples 1 to 3 Into a sufficiently dried 100 ml autoclave, 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a cosolvent, 0.8 ml of tri (n-octyl) aluminum.
mmol was added and cooled to -50 ° C. [TBuNS
iMe ₂ Flu] TiMe ₂ 0.04 mmol, tris (pentafluorophenyl) boron 0.04 mmol,
0.04 mmol of biscyclopentadienyl zirconium hydride chloride and 83 mmol of propylene were added,
Polymerization was performed for 2 hours in Reference Example 1, 4 hours in Reference Example 2, and 9 hours in Reference Example 3. After the polymerization, the mixture was poured into 1000 ml of hydrochloric methanol to terminate the polymerization, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer was 1 in the case of Reference Example 1.
3.3 mg, 21.6 mg in the case of Reference Example 2, Reference Example 3
Was 90.4 mg.

The GPC curve shows bimodality, and when the peaks are separated, the number average molecular weight (Mn) and the molecular weight distribution (Mw)
/ Mn) is 5900/1300 in Reference Example 1,
1.12 / 1.14, 9700/22 in the case of Reference Example 2
00, 1.14 / 1.07, 1980 for Reference Example 3
0/3900 and 1.25 / 1.09.

According to ¹³ C-NMR, the polymer of Reference Example 3 was a polymer having a dyad of m / r = 0.38 / 0.62. The zirconium-derived polymer of Comparative Reference Example 1 described below has a dyad of m / r = 0.62 / 0.38, and the titanium-derived polymer of Comparative Reference Example 3 described later has a m / r = 0.24. /0.76, the polymer of Reference Example 3 has a zirconium-derived polymer 37% and a titanium-derived polymer 63
% Of the mixture was calculated.

From the comparison of Mn in Reference Examples 1 to 3 and Comparative Reference Examples 1 to 3 described below, the polymer derived from zirconium is a polymer on the high molecular weight side, and the polymer derived from titanium is a polymer on the low molecular weight side. I understood that.

The number average molecular weight and the yield were plotted against time (FIG. 1).
Both polymers were found to be living polymers, as they increased linearly with time with yield.

COMPARATIVE REFERENCE EXAMPLES 1-2 In a 100 ml sufficiently dried autoclave, 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a cosolvent, 0.8 ml of tri (n-octyl) aluminum were added.
mmol was added and cooled to -50 ° C. Tris (pentafluorophenyl) boron 0.04 mmol, biscyclopentadienyl zirconium hydride chloride 0.
04 mmol and 83 mmol of propylene were added and polymerized for 4 hours in the case of Comparative Reference Example 1 and 8 hours in the case of Comparative Reference Example 2. After the polymerization, the mixture was poured into 1000 ml of hydrochloric methanol to terminate the polymerization, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer was 1270 mg in Comparative Reference Example 1 and 2500 mg in Comparative Reference Example 2.

According to GPC, number average molecular weight (Mn),
The molecular weight distribution (Mw / Mn) was 2 in Comparative Example 1.
48000, 1.73, 2400 in the case of Comparative Reference Example 2.
00 and 2.0.

According to ¹³ C-NMR, an iso-rich polymer (Comparative Reference Example 1: m / r = 0.62 / 0.38)
Met.

Comparative Reference Example 3 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a co-solvent, 0.8 ml of tri (n-octyl) aluminum were placed in a 100 ml sufficiently dried autoclave.
mmol was added and cooled to -50 ° C. [TBuNS
iMe ₂ Flu] TiMe ₂ 0.04 mmol, tris (pentafluorophenyl) boron 0.04 mmol,
83 mmol of propylene was added and polymerized for 4 hours. After the polymerization, the mixture was poured into 1000 ml of hydrochloric methanol to terminate the polymerization, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer was 14.3 mg.

According to GPC, number average molecular weight (Mn),
The molecular weight distribution (Mw / Mn) was 2200, 1.15. It has been reported that living polymers are produced under these conditions.

According to ¹³ C-NMR, it was a syndio-rich polymer (m / r = 0.24 / 0.76).

REFERENCE EXAMPLES 4-5 In a well-dried 100 ml autoclave, 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a cosolvent, and 0.8 ml of tri (n-octyl) aluminum were used.
mmol was added and cooled to -50 ° C. [TBuNS
iMe ₂ Flu] TiMe ₂ 0.04 mmol, tris (pentafluorophenyl) boron 0.04 mmol,
0.04 mmol of biscyclopentadienyl zirconium dichloride and 83 mmol of propylene were added, and the mixture was polymerized for 4 hours in Reference Example 4 and 12 hours in Reference Example 5. After the polymerization, the mixture was poured into 1000 ml of hydrochloric methanol to terminate the polymerization, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer was 6 in Reference Example 4.
2.3 mg and 187 mg in Reference Example 5.

The GPC curve shows unimodality, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 2600 and 1.28 in Reference Example 4, 9900 in Reference Example 5,
It was 1.30.

According to ¹³ C-NMR, the polymer of Reference Example 4 was a polymer having a dyad of m / r = 0.555 / 0.445. Similarly, the polymer of Reference Example 4 was calculated to be a mixture of 83% zirconium-derived polymer and 27% titanium-derived polymer.

When the number average molecular weight and the yield were plotted against time (FIG. 2), these polymers were living polymers because both the number average molecular weight and the yield increased linearly with time. I understand.

COMPARATIVE REFERENCE EXAMPLES 4-5 In a well-dried 100 ml autoclave, 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a co-solvent, 0.8 ml of tri (n-octyl) aluminum
mmol was added and cooled to -50 ° C. Tris (pentafluorophenyl) boron 0.04 mmol, biscyclopentadienyl zirconium dichloride 0.04 mmol
mmol and 83 mmol of propylene were added, and the mixture was polymerized for 4 hours in the case of Comparative Reference Example 4 and 8 hours in the case of Comparative Reference Example 5. After the polymerization, the mixture was poured into 1000 ml of hydrochloric methanol to terminate the polymerization, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer was 3290 mg in Comparative Reference Example 4 and 3300 mg in Comparative Reference Example 5.

According to GPC, number average molecular weight (Mn),
The molecular weight distribution (Mw / Mn) was 2 in Comparative Example 4.
8200, 1.87, 2800 for Comparative Reference Example 5
0 and 2.0.

Reference Examples 6 to 7 Polymers were obtained in the same manner as in Reference Examples 4 and 5, except that biscyclopentadienyl zirconium dichloride was changed to biscyclopentadienyl zirconium dimethyl.

The respective polymerization times were 4 hours and 7.5
Time, yield 193 mg and 434 mg, Mn 12
900 and 20900, and Mw / Mn were 1.51 and 1.41.

According to ¹³ C-NMR, the polymer of Reference Example 6 was a polymer having a dyad of m / r = 0.58 / 0.42. Similarly, the polymer of Reference Example 6 was calculated to be a mixture of 90% zirconium-derived polymer and 10% titanium-derived polymer.

When the number average molecular weight and the yield were plotted against time (FIG. 3), these polymers were living polymers because both the number average molecular weight and the yield increased linearly with time. I understand.

Comparative Reference Examples 6 to 7 Polymers were obtained in the same manner as in Comparative Reference Examples 4 and 5, except that biscyclopentadienyl zirconium dichloride was replaced with biscyclopentadienyl zirconium dimethyl.

The polymerization time was 4 hours and 8 hours, the yield was 273 mg and 422 mg, and Mn was 112 hours.
00 and 12500, and Mw / Mn were 1.55 and 1.69.

Reference Examples 8 to 10 In a well-dried 100 ml autoclave, 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a cosolvent, 0.8 ml of tri (n-octyl) aluminum were added.
mmol was added and cooled to -50 ° C. Pentamethylcyclopentadienyl titanium trichloride 0.0
4 mmol, tris (pentafluorophenyl) boron 0.04 mmol, biscyclopentadienyl zirconium dimethyl 0.04 mmol, propylene 83 mmol
1 was added, and the mixture was polymerized for 7 hours in Reference Example 8, 15 hours in Reference Example 9, and 26 hours in Reference Example 10. After the polymerization, the mixture was poured into 1000 ml of hydrochloric methanol to terminate the polymerization, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer was 9 in Reference Example 8.
5.4 mg, 273 mg in the case of Reference Example 9, and Reference Example 10
Was 526 mg.

According to GPC, the number average molecular weight (Mn),
The molecular weight distribution (Mw / Mn) was 370 in Reference Example 8.
0, 1.29, 8400, 1.38 in Reference Example 9,
In the case of Reference Example 10, they were 17,600 and 1.41.

When the number average molecular weight and the yield were plotted against time (FIG. 4), these polymers were living polymers because both the number average molecular weight and the yield increased linearly with time. I understand.

The molecular weight distributions were determined according to Comparative Reference Examples 6, 7,
It is narrower than 8, 9 but slightly wider than 1.3. This is presumed to be a mixture of living polymers as in Reference Examples 1 to 7.

Comparative Reference Examples 8 to 9 In a well-dried 100 ml autoclave, 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a cosolvent, and 0.8 ml of tri (n-octyl) aluminum were added.
mmol was added and cooled to -50 ° C. Pentamethylcyclopentadienyl titanium trichloride 0.0
4 mmol, 0.04 mmol of tris (pentafluorophenyl) boron, and 83 mmol of propylene were added.
Polymerized for hours. After polymerization, hydrochloric acid methanol 1000m
The mixture was poured into 1 to stop the polymerization, and the precipitate was separated by filtration and dried in vacuo to obtain a polymer.

The yield of the polymer was 36.1 mg in Comparative Reference Example 8 and 70.0 mg in Comparative Reference Example 9.

According to GPC, number average molecular weight (Mn),
The molecular weight distribution (Mw / Mn) was 3 in Comparative Example 8.
400, 1.54, 3400 in the case of Comparative Reference Example 9,
2.04.

Reference Examples 11 to 13 In a well-dried 100 ml autoclave, 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a cosolvent, 0.8 ml of tri (n-octyl) aluminum were used.
mmol was added and cooled to -50 ° C. Pentamethylcyclopentadienyl titanium trimethyl 0.04m
mol, tris (pentafluorophenyl) boron 0.
04 mmol, [(Ph ₂ C) CpFlu] ZrCl ₂
0.04 mmol and 83 mmol of propylene were added, and the mixture was polymerized for 6 hours in Reference Example 11, 12 hours in Reference Example 12, and 18 hours in Reference Example 13. After polymerization,
The polymerization was stopped by pouring the mixture into 1000 ml of hydrochloric methanol, the precipitate was separated by filtration, and the toluene-insoluble matter was separated and dried under vacuum to obtain a polymer. Because of the toluene-insoluble content, the present polymer is represented by [(Ph ₂ C) CpFlu] Z
It is considered a highly crystalline polymer derived from rCl ₂ .

The yield of the polymer was 5.3 mg in Reference Example 11, 8.0 mg in Reference Example 12, and 8.0 mg in Reference Example 1.
In the case of No. 3, it was 11.1 mg.

According to GPC, number average molecular weight (Mn),
The molecular weight distribution (Mw / Mn) was 98 in Reference Example 11.
00, 1.37, and 14,000, 1.
53 and Reference Example 13 had 17100 and 1.58, respectively. It is considered that the reason why the molecular weight distribution is wide is that the highly crystalline polymer is precipitated during the polymerization and the system becomes non-uniform.

When the number average molecular weight and the yield were plotted against time (FIG. 5), the zirconium-derived polymer was found to be a living polymer because both the number average molecular weight and the yield increased with time. all right. It is believed that the increase is not linear because the highly crystalline polymer precipitates during polymerization and the system becomes non-uniform.

Example 1 To a well-dried 100 ml autoclave, 14.4 ml of dry toluene and 0.8 mmol of tri (n-octyl) aluminum were added, and cooled to -50 ° C. 0.04 mmol of pentamethylcyclopentadienyltitanium trichloride, 0.04 mmol of tris (pentafluorophenyl) boron, 0.04 mmol of biscyclopentadienylzirconium dimethyl, and 83 mmol of propylene were added, and polymerized for 5 hours. Five hours later,
Carbon monoxide was supplied to the autoclave to increase the pressure to 30 atm, and the reaction was carried out at -78 ° C for 4 hours. After completion of the reaction, carbon monoxide gas was purged, the polymerization was stopped by pouring into 1000 ml of hydrochloric methanol, and the precipitate was washed with methanol, separated by filtration, and dried under vacuum to obtain a polymer. The yield of the polymer (Yield) was 28.8 mg.

According to high-temperature GPC, the number average molecular weight (Mn _PP ) and molecular weight distribution (Mw / Mn) in terms of PP were 256
0 and 1.25. When the IR spectrum of the obtained polymer was measured, 173 due to the carbonyl group was found.
An absorption spectrum at 4 cm ^-1 was observed, and it was confirmed that a carbonyl group was introduced into the polymer. In addition,
According to ¹ H-NMR, a signal derived from the aldehyde group was detected at around 9.6 to 9.7 ppm, indicating that the aldehyde group was present at the polymer terminal. The number of carbonyl groups introduced into each polymer chain molecule is calculated by the formula: [CO] = (41/440) · (A _{C = O} / A ₁₄₆₀ ) · (M
n _PP / 42) where 41 is 1460 cm due to polypropylene
Molar extinction coefficient of ^-1, 440 molar absorption coefficient due to the carbonyl group, A C _{= O} absorption intensity of the carbonyl group, A ₁₄₆₀
Is the absorption intensity of 1460 cm ^-1 , Mn _PP is the number average molecular weight in terms of PP, and 42 is the molecular weight of propylene. The molecule was found to contain a carbonyl group.

Example 2 9 ml of dry toluene, 7 ml of dry 2-methyl-1-pentene as a cosolvent, and 0.8 ml of tri (n-octyl) aluminum were placed in a sufficiently dried 100 ml autoclave.
mmol was added and cooled to -50 ° C. Pentamethylcyclopentadienyl titanium trimethyl 0.04m
mol, tris (pentafluorophenyl) boron 0.
04 mmol, [(Ph ₂ C) CpFlu] ZrCl ₂
0.04 mmol and 83 mmol of propylene were added, and 6
Polymerized for hours. Six hours later, carbon monoxide was supplied to the autoclave and pressurized to 30 atm.
For 4 hours. After the completion of the reaction, carbon monoxide gas was purged, the polymerization was stopped by pouring into 1000 ml of hydrochloric methanol, and the precipitate was washed with methanol, separated by filtration, further separated into toluene-insoluble components, washed again with methanol, and dried under vacuum. Thus, a polymer was obtained. Polymer yield (Yiel
d) was 3.3 mg. The resulting polymer is
[(Ph ₂ C) CpFlu] A highly crystalline polymer derived from ZrCl ₂ .

According to the high-temperature GPC, the number average molecular weight (Mn _PP ) and the molecular weight distribution (Mw / Mn) in terms of PP were 860.
0 and 1.49. When the IR spectrum of the obtained polymer was measured, 173 due to the carbonyl group was found.
An absorption spectrum at 1 cm ^-1 was observed, and it was confirmed that a carbonyl group was introduced into the polymer. Also,
When the number of carbonyl groups introduced into each polymer chain molecule was calculated in the same manner as in Example 1, the value of [CO] was 1.04, and about 1 molecule per polymer chain molecule was obtained. Was found to contain the carbonyl group of

[0123]

According to the present invention, the use of a catalyst comprising a compound (A), a compound (B), a compound (D) and a compound (C) which is optionally used allows the use of a catalyst having a carbon number of 2 at a higher temperature than before. ~ 20 olefinic monomers can be polymerized to produce an olefinic living polymer,
Further, by reacting the obtained olefin-based living polymer with a carbonylating agent, it is possible to produce an olefin-based polymer in which most of the polymer chains are carbonylated. Such polymers can be used as compatibilizers, surface improvers, viscosity index improvers, drag reducers, and the like.

[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 Reference Examples 1 to 3 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 Reference Examples 4 and 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 Reference 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 Reference Examples 8 to 10 and the reaction time.

FIG. 5 is a graph showing the relationship between the yield and the number average molecular weight of the living polymers produced in Reference Examples 11 to 13 and the reaction time.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takeshi Shiono 4259 Nagatsuta-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Inside the Institute of Natural Resources and Chemical Research, Tokyo Institute of Technology (72) Michihiko Asai 1-1 1-1 Higashi, Tsukuba, Ibaraki Pref. Within the Institute of Industrial Technology (72) Inventor Yasuzou Suzuki 1-1, Higashi 1-1, Tsukuba, Ibaraki Prefecture Inside of the Institute of Materials Science and Technology, Institute of Industrial Science and Technology (72) Inventor Tetsu Miyazawa 1-1, Higashi 1-1, Tsukuba, Ibaraki Prefecture, Research Institute for Materials Engineering, Industrial Science and Technology In-house (72) Inventor Kenji Tsuchihara 1-1 East Higashi, Tsukuba, Ibaraki Pref.Institute of Materials Science and Technology, National Institute of Industrial Science (72) Inventor Masahide Murata 2-15-504, Suido 2-chome, Bunkyo-ku, Tokyo (72) Inventor Hiroyuki Ozaki 4-6-202 Onogawa Tsukuba, Ibaraki Prefecture (72) Inventor Masanao Kawabe 2-6-1203 Takezono Tsukuba City, Ibaraki Prefecture No. (72) Inventor Toshio Kase 5-2-2 Matsushiro, Tsukuba-shi, Ibaraki Prefecture (72) Inventor Jin Jiju 2-2-7 Otateno, Kanazawa-shi, Ishikawa (72) Inventor Hideaki Hagiwara 2 Akubo, Tsukuba-shi, Ibaraki -6-14 Sakurai Heights 203 (72) Inventor Yoshifumi Fukui 4-63 Ninomiya 4-chome, Tsukuba City, Ibaraki Prefecture F-term (reference) 4J028 AA02A AB01A AC06A AC07A AC08A AC09A AC10A AC28A BA01B BA02B BC13B BC15B BC16B BC17B BC18B BC19B BC24B BC29B EB02 EB04 EB05 EB07 EB10 EB16 EB17 EB18 EC01 EC02 FA02 GA01 GA06 GA15 4J100 AA02P AA03P AA04P AA07P AA09P AA15P AA16P AA17P AA18P AA19P AA20P AARP AR13 AR01 AR11 AR01 AR04P HB35 JA15

Claims (14)

[Claims] (A) 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) (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 and (D) a titanium-containing compound represented by the polymerization temperature - After polymerizing an olefin monomer having 2 to 20 carbon atoms at 20 to -100 ° C,
A method for producing an olefin polymer having a carbonyl group at a terminal, comprising reacting the obtained living olefin polymer with a carbonylating agent. (A) 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) (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 ⁺ is a cation group) borate compound represented by, (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, The olefin obtained by polymerizing an olefin monomer having 2 to 20 carbon atoms at a polymerization temperature of -20 to -100 ° C using a catalyst comprising an aluminum compound represented by 1 or 2) and a titanium-containing compound (D). -Based living polymer for carbonylation Preparation of olefin polymer having a carbonyl group at the end which comprises reacting. 3. The method according to claim 1, wherein (D) the titanium-containing compound is a titanium-containing compound having one cyclopentadienyl skeleton. 4. The method according to claim 1, wherein at least one of (A) a zirconium-containing compound having one or two cyclopentadienyl skeletons and (D) a titanium-containing compound contains an alkyl group. Recipe. 5. The process according to claim 1, wherein the polymerization temperature is -30 to -80 ° C. 6. The process according to claim 1, wherein the polymerization temperature is from -40 to -60 ° C. 7. 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. Manufacturing method. 8. The process according to claim 1, wherein the Ph group in the general formula (I) or (II) is a group substituted by five fluorine atoms. 9. The method according to claim 2, wherein n in the general formula (III) is 0. 10. In the general formula (III), n is 0, and R
Is an alkyl group having 4 to 8 carbon atoms.
The production method according to 5, 6, 7 or 8. 11. An olefin monomer having 2 to 2 carbon atoms.
0, α-olefin of claim 1, 2, 3, 4, 5,
The method according to 6, 7, 8, 9 or 10. 12. An olefin monomer having 2 to 1 carbon atoms.
0, α-olefin of claim 1, 2, 3, 4, 5,
The method according to 6, 7, 8, 9 or 10. 13. The olefin monomer having 3 to 6 carbon atoms.
1, 2, 3, 4, 5,
The method according to 6, 7, 8, 9 or 10. 14. The method of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, wherein the polymerization is carried out within a range in which the polymer does not precipitate.
The production method according to 11, 12, or 13.