JPH08176217A - Catalyst for polymerization of olefin and prodution of alpha-olefin copolymer - Google Patents

Abstract

PURPOSE: To obtain a catalyst which can give an ethylene/α-olefin copolymer having a high α-olefin content and a high molecular weight efficiently by using a combination of specified compounds. CONSTITUTION: This catalyst compsises a titanium amide compound (A) having a titanium-nitrogen bond, a compound (B) which reacts with a transition metal compound to form a stable anion, and an organoaluminum compound (C). Preferably component (A) is a titanium amide compound having at least two titaniumnitrogen bonds. Examples include titanium amide compounds represented by formulas I and II (R<1> to R<4> and R<7> to R<10> are each a 1-20C hydrocarbon group; X is O, S or N having a hydrocarbon group; and R<5> , R<6> , R<11> and R<12> are each a 1-20C hydrocarbon, 1-20C alkoxy, a 1-20C silicon-containing hydrocarbon group, or a halogen). An example of component B is a complex compound composed of an anion composed of boron and a plurality of groups bonded thereto and a cation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel Ziegler catalyst and a process for producing an ethylene-α-olefin copolymer using the catalyst.

[0002]

BACKGROUND OF THE INVENTION Olefin copolymers, especially ethylene-α-olefin copolymers, are used in films, laminates,
It is used in numerous applications such as wire coatings, injection molded products and special molded products. The basic physical properties of the ethylene / α-olefin copolymer are determined by the amount and distribution of the comonomer introduced into the ethylene chain. That is, the number and distribution of short chain branches have a great influence on basic properties such as crystallinity, crystallization rate, spherulite structure and melting point. Consequently, from the viewpoint of practical physical properties, it will affect many aspects such as environmental stress resistance, film strength, flexibility, and moldability. From the above, it is very important to control the number of short chain branches and the distribution thereof in the ethylene-α-olefin copolymer in order to improve practical physical properties.

As a method for producing an olefin copolymer, generally, a so-called Ziegler-Natta catalyst comprising a transition metal compound of Group IV to VI and an organometallic compound of Group I to III of the periodic table is used. Is widely known.

In recent years, a catalyst system composed of a metallocene compound of a transition metal and an aluminoxane has been proposed as a new catalyst system (for example, JP-A-58-19309). These catalysts have been attracting attention in terms of polymerization activity and the like, but they have the drawback of requiring a large amount of aluminoxane. Further, JP-A-5-65308 discloses the result of copolymerization of ethylene-α-olefin in a catalyst system composed of a zirconium compound and aluminoxane, but the copolymerizability of the catalyst system is not always satisfactory. . Further, it has been reported that increasing the α-olefin content in the ethylene-α-olefin copolymer lowers the molecular weight of the copolymer (Makr.
omol. Chem. 193, 823 (1992)),
This is a problem in producing a polymer having a good balance between the α-olefin content and the molecular weight of the copolymer. Further, a method using a catalyst composed of an ionic metallocene catalyst and an alkylaluminum, a reaction product of a halogenated metallocene compound and an organometallic compound, and a catalyst composed of a stable anion has been proposed (JP-A-3-207704, International Publication No. 3-207704). Publication WO92 / 01723). However, all of these methods use expensive zirconium compounds and hafnium compounds, and it is said that they can be used for other inexpensive transition metal compounds, but no specific method or result is shown.

Further, there has been proposed a method for producing a polyolefin by a catalyst system containing a compound that forms an ionic complex by reacting a titanium compound with a transition metal compound and an organoaluminum compound as main components (Japanese Patent Laid-Open No. HEI 5). -23
0133, JP-A-5-331228, and JP-A-6-192330). However, specific examples are those in which an alkoxy group or a cyclopentadienyl ring is used as a ligand, and the copolymerizability thereof is not always satisfactory.

On the other hand, as a method for polymerizing or copolymerizing an olefin using a catalyst system comprising a compound having a titanium-nitrogen bond and an organoaluminum compound, a method comprising using a catalyst system comprising a titanium diphenylamide compound and an organoaluminum compound. (JP0104374, JP-B-42-11646), a method using a catalyst system composed of a titanium amide compound having an aryl substituent and an organic aluminum compound (JP-B-42-22691), and further dimethylamide titanium trichloride. And the like using a catalyst system composed of a titanium amide compound having a lower alkyl group and an organic aluminum compound (J.
of Polym. Sci. Part A-1,241,
6 (1968)) and the like have been proposed. However, even if the copolymerization of ethylene and α-olefin is carried out by using the catalyst system disclosed therein, for example, EP010437
4, Japanese Patent Publication No. 42-11646, Japanese Patent Publication No. 42
-22691, and J. of Polym. S
ci. The methods disclosed in Part A-1, 241, 6 (1968) and the like are still unsatisfactory in catalytic activity and copolymerizability.

Therefore, in order to solve these problems, the present applicant first (A) formula (R1R2N) 4- (m + n) T.
iXm Yn (wherein R 1 and R 2 are saturated hydrocarbon groups having 8 to 30 carbon atoms, X is halogen, Y is alkoxy group, m
Is a number 1 ≦ m ≦ 3, and n is a number 0 ≦ n ≦ 2 (m +
n) is 1 ≦ (m + n) ≦ 3. ), A method for producing ethylene and α-olefin copolymers by using a liquid catalyst component composed of a titanium amide compound and a catalyst system composed of an organoaluminum compound has been proposed (JP-A-2-77412). . However, in the production method using the catalyst system, the catalytic activity is not sufficient in view of the object of the present application, and the copolymerizability is not yet satisfactory.

[0008]

Under the present circumstances,
The problem to be solved by the present invention, that is, the object of the present invention is to provide a novel catalyst system, and by using such a novel catalyst, ethylene and α-olefin can be efficiently copolymerized to obtain a content of α-olefin. To provide a method for producing a high molecular weight ethylene-α-olefin copolymer.

[0009]

Means for Solving the Problems That is, the present invention provides a titanium amide compound (A) having a titanium-nitrogen bond, a compound (B) which reacts with a transition metal compound to form a stable anion, and an organoaluminum compound (C). And a method for producing an ethylene-α-olefin copolymer using the catalyst.

Hereinafter, the present invention will be described in detail. First, the titanium amide compound (A) referred to in the present invention is a titanium amide compound having a titanium-nitrogen bond, and preferably,
It is a titanium amide compound having two titanium-nitrogen bonds. Specific examples of the titanium amide compound (A) include titanium amide compounds represented by the following general formula [I] or [II].

Embedded image

[Chemical 4] (In the formula, R ^{1 to} R ⁴ and R ^{7 to} R ¹⁰ represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different. X has an oxygen atom, a sulfur atom, and a hydrocarbon group. A nitrogen atom, wherein R ⁵ , R ⁶ , R ¹¹ and R ¹² are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 carbon atom
To 20 silicon-containing hydrocarbon groups or halogen atoms. )

Here, in the titanium amide compound represented by the general formula [I], the hydrocarbon group represented by R ¹ , R ² , R ³ and R ⁴ is a methyl group, an ethyl group, a propyl group, Butyl group, pentyl group, hexyl group, heptyl group,
A hydrocarbon group having 1 to 20 carbon atoms such as an octyl group is exemplified. In addition, among those represented by R ⁵ and R ⁶ , examples of halogen include chlorine, bromine, iodine and the like. Examples of the alkoxy group include alkoxy groups having 1 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group and 2-ethylhexyloxy group. And, as the hydrocarbon group, a methyl group, an ethyl group, a propyl group,
Examples thereof include an alkyl group such as a butyl group, a 2-ethylhexyl group, an octyl group, a decyl group, a dodecyl group, and a cycloalkyl group; an aryl group such as a phenyl group, a tolyl group, and a naphthyl group; and an aralkyl group such as a benzyl group. Furthermore, examples of the silicon-containing hydrocarbon group include a trimethylsilylmethyl group and a ditrimethylsilylmethyl group. .

Specific examples of the titanium amide compound having halogen in R ⁵ and R ⁶ include bis (dimethylamino) titanium dichloride, bis (diethylamino) titanium dichloride, bis (dipropylamino) titanium dichloride and bis (dibutylamino). Examples thereof include titanium dichloride, bis (dihexylamino) titanium dichloride, bis (dicyclohexylamino) titanium dichloride and bis (dioctylamino) titanium dichloride.

Specific examples of the titanium amide compound having benzyl groups in R ⁵ and R ⁶ include bis (di-n-propylamino) dibenzyltitanium, bis (di-isopropylamino) dibenzyltitanium,
Bis (di-n-butylamino) dibenzyltitanium,
Bis (di-iso-butylamino) dibenzyltitanium, bis (di-s-butylamino) dibenzyltitanium, bis (di-tert-butylamino) dibenzyltitanium, bis (di-n-pentylamino) dibenzyl Titanium, bis (di-isopentylamino) dibenzyltitanium, bis (di-2-pentylamino) dibenzyltitanium, bis (di-3-pentylamino) dibenzyltitanium, bis (di-n-hexylamino) di Benzyl titanium, bis (di-2-hexylamino)
Dibenzyltitanium, bis (di-3-hexylamino) dibenzyltitanium, bis (di-isohexylamino) dibenzyltitanium, bis (di-n-heptylamino) dibenzyltitanium, bis (di-2-heptylamino) ) Dibenzyltitanium, bis (di-3-heptylamino) dibenzyltitanium, bis (di-4-heptylamino) dibenzyltitanium, bis (di-isoheptylamino) dibenzyltitanium, bis (di-n)
-Octylamino) dibenzyltitanium, bis (di-
2-octylamino) dibenzyltitanium, bis (di-3-octylamino) dibenzyltitanium, bis (di-4-octylamino) dibenzyltitanium, bis (di-isooctylamino) dibenzyltitanium and the like. . The benzyl group also includes those having a substituent such as an alkyl group or an aryl group.

Specific examples of the titanium amide compound having a silicon-containing hydrocarbon group in R ⁵ and R ⁶ include bis (dipropylamino) di [(trimethylsilyl) methyl] titanium and bis (dibutylamino) di [(trimethylsilyl). ) Methyl] titanium, bis (dipentylamino)
Examples include di [(trimethylsilyl) methyl] titanium, bis (dihexylamino) di [(trimethylsilyl) methyl] titanium, bis (dioctylamino) di [(trimethylsilyl) methyl] titanium, and the like.

Next, in the titanium amide compound represented by the general formula [II], R ^{7 to} R ¹⁰ are R ^{1 to} R ⁴ used in the titanium amide compound represented by the above general formula [I].
What is illustrated by can be illustrated as it is. Also R ¹¹ and R
Examples of the group represented by ¹² include those exemplified as R ⁵ and R ⁶ used in the titanium amide compound represented by the general formula [I], and preferably a hydrocarbon group having 1 to 20 carbon atoms. It may be present, but it is more preferable to have an aromatic ring. Further, X is an oxygen atom, a sulfur atom, and a nitrogen atom having a hydrocarbon group.

Specific examples of such compounds include 2,
2'-oxobis (N-methylanilino) titanium dichloride, 2,2'-oxobis (N-ethylanilino) titanium dichloride, 2,2'-oxobis [N
-(N-propyl) anilino] titanium dichloride,
2,2'-oxobis (N-isopropylanilino) titanium dichloride, 2,2'-oxobis (Nn-
Butylanilino) titanium dichloride, 2,2′-oxobis (N-2-butylanilino) titanium dichloride, 2,2′-oxobis (N-isobutylanilino) titanium dichloride, 2,2′-oxobis (N
-T-butylanilino) titanium dichloride, 2,
2′-oxobis (N-pentylanilino) titanium dichloride, 2,2′-oxobis (N-hexylanilino) titanium dichloride, 2,2′-oxobis (N-octylanilino) titanium dichloride, 2,
2'-thiobis (N-methylanilino) titanium dichloride, 2,2'-thiobis (N-ethylanilino) titanium dichloride, 2,2'-thiobis [N- (n-
Propyl) anilino] titanium dichloride, 2,2 '
-Thiobis (N-isopropylanilino) titanium dichloride, 2,2'-thiobis (N-n-butylanilino) titanium dichloride, 2,2'-thiobis (N-
2-Butylanilino) titanium dichloride, 2,2 '
-Thiobis (N-isobutylanilino) titanium dichloride, 2,2'-thiobis (Nt-butylanilino) titanium dichloride, 2,2'-thiobis (N-
Pentylanilino) titanium dichloride, 2,2'-
Thiobis (N-hexylanilino) titanium dichloride, 2,2'-thiobis (N-octylanilino) titanium dichloride, 2,2'-oxobis (N-methylanilino) dibenzyltitanium, 2,2'-oxobis (N -Ethylanilino) dibenzyltitanium, 2,
2'-oxobis [N- (n-propyl) anilino] dibenzyltitanium, 2,2'-oxobis (N-isopropylanilino) dibenzyltitanium, 2,2'-
Oxobis (N-n-butylanilino) dibenzyltitanium, 2,2'-oxobis (N-2-butylanilino) dibenzyltitanium, 2,2'-oxobis (N
-Isobutylanilino) dibenzyltitanium, 2,
2′-oxobis (Nt-butylanilino) dibenzyltitanium, 2,2′-oxobis (N-pentylanilino) dibenzyltitanium, 2,2′-oxobis (N-hexylanilino) dibenzyltitanium, 2 ，
2'-oxobis (N-octylanilino) dibenzyltitanium, 2,2'-thiobis (N-methylanilino) dibenzyltitanium, 2,2'-thiobis (N-
Ethylanilino) dibenzyltitanium, 2,2′-thiobis [N- (n-propyl) anilino] dibenzyltitanium, 2,2′-thiobis (N-isopropylanilino) dibenzyltitanium, 2,2′-thiobis ( N
-N-butylanilino) dibenzyltitanium, 2,
2'-thiobis (N-2-butylanilino) dibenzyltitanium, 2,2'-thiobis (N-isobutylanilino) dibenzyltitanium, 2,2'-thiobis (N
-T-butylanilino) dibenzyltitanium, 2,
2'-thiobis (N-pentylanilino) dibenzyltitanium, 2,2'-thiobis (N-hexylanilino) dibenzyltitanium, 2,2'-thiobis (N-
Octylanilino) dibenzyltitanium, 2,2'-
(Methylamino) bis (N-methylanilino) dibenzyltitanium, 2,2 '-(methylamino) bis (N-
Ethylanilino) dibenzyltitanium, 2,2'-
(Methylamino) bis [N- (n-propyl) anilino] dibenzyltitanium, 2,2 '-(methylamino) bis (N-isopropylanilino) dibenzyltitanium, 2,2'-(methylamino) bis (N-n-butylanilino) dibenzyltitanium, 2,2 '-(methylamino) bis (N-2-butylanilino) dibenzyltitanium, 2,2'-(methylamino) bis (N-
Isobutylanilino) dibenzyltitanium, 2,2 '
-(Methylamino) bis (Nt-butylanilino) dibenzyltitanium, 2,2 '-(methylamino) bis (N-pentylanilino) dibenzyltitanium, 2,
2 '-(methylamino) bis (N-hexylanilino)
Dibenzyltitanium, 2,2 '-(methylamino) bis (N-octylanilino) dibenzyltitanium,
2,2 '-(ethylamino) bis (N-methylanilino) dibenzyltitanium, 2,2'-(ethylamino) bis (N-ethylanilino) dibenzyltitanium, 2,2 '-(ethylamino) bis [N -(N-Propyl) anilino] dibenzyltitanium, 2,2'-
(Ethylamino) bis (N-isopropylanilino) dibenzyltitanium, 2,2 ′-(ethylamino) bis (Nn-butylanilino) dibenzyltitanium,
2,2 '-(ethylamino) bis (N-2-butylanilino) dibenzyltitanium, 2,2'-(ethylamino) bis (N-isobutylanilino) dibenzyltitanium, 2,2 '-(ethylamino ) Bis (Nt-butylanilino) dibenzyltitanium, 2,2 ′-(ethylamino) bis (N-pentylanilino) dibenzyltitanium, 2,2 ′-(ethylamino) bis (N-hexylanilino) ) Dibenzyltitanium, 2,2 '-(ethylamino) bis (N-octylanilino) dibenzyltitanium, 2,2'-(propylamino) bis (N-
Methylanilino) dibenzyltitanium, 2,2'-
(Propylamino) bis (N-ethylanilino) dibenzyltitanium, 2,2 '-(propylamino) bis [N- (n-propyl) anilino] dibenzyltitanium, 2,2'-(propylamino) bis (N -Isopropylanilino) dibenzyltitanium, 2,2 '-(propylamino) bis (Nn-butylanilino) dibenzyltitanium, 2,2'-(propylamino) bis (N-2-butylanilino) dibenzyltitanium ,
2,2 ′-(Propylamino) bis (N-isobutylanilino) dibenzyltitanium, 2,2 ′-(Propylamino) bis (Nt-butylanilino) dibenzyltitanium, 2,2 ′-(Propylamino ) Bis (N-pentylanilino) dibenzyltitanium, 2,2'-
(Propylamino) bis (N-hexylanilino) dibenzyltitanium, 2,2 ′-(propylamino) bis (N-octylanilino) dibenzyltitanium, 2
2 '-(butylamino) bis (N-methylanilino) dibenzyltitanium, 2,2'-(butylamino) bis (N-ethylanilino) dibenzyltitanium, 2,
2 '-(Butylamino) bis [N- (n-propyl) anilino] dibenzyltitanium, 2,2'-(butylamino) bis (N-isopropylanilino) dibenzyltitanium, 2,2 '-(butyl Amino) bis (N-n-
Butylanilino) dibenzyltitanium, 2,2'-
(Butylamino) bis (N-2-butylanilino) dibenzyltitanium, 2,2 ′-(butylamino) bis (N-isobutylanilino) dibenzyltitanium,
2,2 '-(Butylamino) bis (Nt-butylanilino) dibenzyltitanium, 2,2'-(butylamino) bis (N-pentylanilino) dibenzyltitanium, 2,2 '-(butylamino) ) Bis (N-hexylanilino) dibenzyltitanium, 2,2 ′-(butylamino) bis (N-octylanilino) dibenzyltitanium, 2,2 ′-(octylamino) bis (N-methylanilino) di Benzyl titanium, 2,2 ′-(octylamino) bis (N-ethylanilino) dibenzyltitanium, 2,2 ′-(octylamino) bis [N- (n
-Propyl) anilino] dibenzyltitanium, 2,
2 '-(octylamino) bis (N-isopropylanilino) dibenzyltitanium, 2,2'-(octylamino) bis (Nn-butylanilino) dibenzyltitanium, 2,2 '-(octylamino) bis (N-2-
Butylanilino) dibenzyltitanium, 2,2'-
(Octylamino) bis (N-isobutylanilino) dibenzyltitanium, 2,2 ′-(octylamino) bis (Nt-butylanilino) dibenzyltitanium,
2,2 '-(octylamino) bis (N-pentylanilino) dibenzyltitanium, 2,2'-(octylamino) bis (N-hexylanilino) dibenzyltitanium, 2,2 '-(octylamino ) Bis (N-octylanilino) dibenzyltitanium, 2,2 '-(phenylamino) bis (N-methylanilino) dibenzyltitanium, 2,2'-(phenylamino) bis (N-ethylanilino) dibenzyltitanium , 2,2 '-(phenylamino) bis [N- (n-propyl) anilino]
Dibenzyl titanium, 2,2 '-(phenylamino)
Bis (N-isopropylanilino) dibenzyltitanium, 2,2 '-(phenylamino) bis (Nn-butylanilino) dibenzyltitanium, 2,2'-(phenylamino) bis (N-2-butylanilino) Dibenzyl titanium, 2,2 '-(phenylamino) bis (N
-Isobutylanilino) dibenzyltitanium, 2,
2 ′-(phenylamino) bis (Nt-butylanilino) dibenzyltitanium, 2,2 ′-(phenylamino) bis (N-pentylanilino) dibenzyltitanium, 2,2 ′-(phenylamino) bis (N-hexylanilino) dibenzyltitanium, 2,2 ′-(phenylamino) bis (N-octylanilino) dibenzyltitanium, 2,2′-oxobis (N-methylanilino) bis (trimethylsilylmethyl) titanium, Two
2′-oxobis (N-ethylanilino) bis (trimethylsilylmethyl) titanium, 2,2′-oxobis [N- (n-propyl) anilino] bis (trimethylsilylmethyl) titanium, and the like.

As a method for synthesizing such a titanium amide compound, for example, Japanese Patent Publication Nos. 41-5397 and 42/42.
-11646, H.I. Burger et. a
l. , J. et al. of Organomet. Chem. 10
8 (1976), 69-84, H.M. Burger et
al. , J. et al. of Organomet. Che
m. , 20 (1969), 129-139 H .; Bur
ger, Z. Anorg. allg. Chem. , 36
The method described in 5,243-254 ('91) and the like can be used.

The titanium amide compound represented by the general formula [I] can be obtained by, for example, (i) the general formula R
¹³ R ¹⁴ NH (provided that R ¹³ and R ¹⁴ represent a hydrocarbon group having 1 to 30 carbon atoms and may be the same or different).
And a secondary amine compound represented by (ii) R ¹⁵ M ¹ (wherein R ¹⁵ is a hydrocarbon group having 1 to 30 carbon atoms, M ¹ is L
i represents an alkali metal such as K. ) Is reacted with an alkyl alkali metal to synthesize an alkali metal amide compound. Then, (iii) general formula tiz ¹ ₄ (provided that, Z ¹ represents chlorine, bromine, halogens iodine and the like,
Preferably Z ¹ is chlorine. ) Is reacted with a double molar amount of the alkali metal amide compound, and (iv) the general formula R ¹⁶ CH ₂ MgZ ² (wherein Z ² is halogen such as chlorine, bromine or iodine). And preferably Z ² is chlorine). In the above reaction (iii) with titanium tetrahalide, two or more kinds of the alkali metal amide compound (ii) may be used at the same time.

Examples of the method for synthesizing the titanium amide compound represented by the general formula [II] include D. C. Bradley
et al. J. Chem. Soc. (196
0), 3857. E. FIG. Benzing et al. C
hem. The methods described in Ber, 94 (1961), 2263 and the like can be used in combination.

The titanium amide compound represented by the general formula [II] can be obtained by, for example, (i) the general formula R ¹⁷ according to these methods.
NHR ¹⁸ XR ¹⁹ NHR ²⁰ (wherein R ^{17 to} R ²⁰ represent a hydrocarbon group having 1 to 30 carbon atoms and may be the same or different. X is a nitrogen atom having an oxygen atom, a sulfur atom and a hydrocarbon group) And a secondary amine compound represented by
i) a titanium amide compound represented by (R ²¹ R ²² N) ₄ Ti (wherein R ²¹ and R ²² represent a hydrocarbon group having 1 to 30 carbon atoms and may be the same or different). After the reaction, (iii) the general formula TiZ ³ ₄ (wherein Z ³ represents a halogen atom such as chlorine, bromine or iodine, preferably Z
³ is a chlorine atom. ), And further (iv) R ²³ CH ₂ MgZ ⁴ (wherein Z ⁴ represents a halogen atom such as chlorine, bromine or iodine, preferably Z ⁴ is a chlorine atom). It can be synthesized by reacting with.

Further, as an example of the compound (B) which reacts with the transition metal compound used in the present invention to form an ionic complex, a complex compound composed of an anion in which a plurality of groups are bound to boron and a cation is mentioned. be able to.
Specific examples of such complex compounds include triethylammonium tetraphenylborate, dimethylanilinium tetraphenylborate, trimethylsulfonium triethylammonium tetraphenylborate, triethylammonium tetra (pentafluorophenyl) borate, and tetra (pentafluorophenyl) dimethylanilinium. Trimethylsulfonium tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate,
Ferrocenium tetraphenylborate, ferrocenium tetra (pentafluorophenyl) borate, tetraphenylborate (tetraphenylporphyrin manganese), lithium tetraphenylborate, sodium tetraphenylborate, potassium tetraphenylborate, magnesium tetraphenylborate, tetra (pentafluorophenyl) Examples thereof include lithium borate, sodium tetra (pentafluorophenyl) borate, potassium tetra (pentafluorophenyl) borate, magnesium tetra (pentafluorophenyl) borate, and their ether complexes and tetrahydrofuran complexes.

Next, in the present invention, organoaluminization
The compound (C) may be a known organoaluminum compound.
Wear. Examples of the organic aluminum compound include those represented by the general formula
R^{twenty four} _aAlZ^Five _3-aThe organoaluminum compound represented by
It is preferably used.

R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms,
It is preferably a hydrocarbon group having 1 to 10 carbon atoms. Z ⁵ is a hydrogen atom and / or an alkoxy group having 1 to 20 carbon atoms. Also, a is a number 0 <a ≦ 3. General formula R ²⁴ _a
Specific examples of the organoaluminum compound (C) represented by AlZ ⁵ _3-a include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like trialkylaluminums. , Dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride,
Dialkyl aluminum hydrides such as dioctyl aluminum hydride and didecyl aluminum hydride, methoxymethyl aluminum hydride, methoxyethyl aluminum hydride, methoxyisobutyl aluminum hydride, ethoxyhexyl aluminum hydride, ethoxyoctyl aluminum hydride, and alkoxyalkyl aluminum hydrides such as ethoxydecyl aluminum hydride, Dimethyl aluminum methoxide, methyl aluminum dimethoxide, diethyl aluminum methoxide,
Ethyl aluminum dimethoxide, diisobutyl aluminum methoxide, isobutyl aluminum dimethoxide, dihexyl aluminum methoxide, hexyl aluminum dimethoxide, dimethyl aluminum ethoxide, methyl aluminum diethoxide, diethyl aluminum ethoxide, ethyl aluminum diethoxide,
Examples thereof include alkylaluminum alkoxides such as diisobutylaluminum ethoxide and isobutylaluminum diethoxide.

The component (C) can be used in a wide range such as 1 to 10,000 mol per 1 mol of titanium atom of the component (A), but is preferably 1 to 1,000 mol, more preferably 1 to 500 mol. Used in the molar range.

In the present invention, a catalyst comprising a combination of (1), (A) component, (B) component and (C) component may be used as the polymerization catalyst, or (2), (A).
A reaction product obtained by previously contacting the component, the component (B) and the component (C) may be used.

Regarding the amount of each catalyst component used in the above method (1), the component (A) is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and the component (B) is 0.1. 0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter, and the component (C) is in the range of 0.01 to 500 mmol / liter, preferably 0.05 to 100 mmol / liter in terms of Al atom. And the component (B) component / (A) component molar ratio is 0.01 to 100, preferably 0.5 to 10 and the component (C) component / (A) component molar ratio is 0.1 to 2000, preferably 5 to It is desirable to use each component so that it is in the range of 1000.

On the other hand, in the method (2), the components (A), (B) and (C) are brought into contact with each other in an inert solvent in an inert gas atmosphere.
The component (A) is 0.01 to 100 mmol / liter,
It is preferable to use each component so that the component (B) is in the range of 0.01 to 100 mmol / liter and the component (C) is in the range of 0.1 to 1000 mmol / liter in terms of Al atom.

As a method for supplying each catalyst component to the polymerization tank, there are no particular conditions to be restricted except that the catalyst components are supplied in an inert gas such as nitrogen or argon in a water-free state. The polymerization in the present invention is 0 to 200 ° C, preferably 20 ° C to 10 ° C.
The temperature and the pressure at 0 ° C. are 0 to 100 kg / cm ² , preferably 0 to 50 kg / cm ² , and the polymerization method may be either batch type or continuous type.

In the polymerization by the solution method using the catalyst system of the present invention, the solution is generally selected from hexane, cyclohexane, heptane, kerosene components, hydrocarbon solvents such as toluene and the like.

The α-olefin used in the present invention is an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Examples thereof include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, vinylcyclohexane and the like. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the polymer.

[0031]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The properties of the polymers in the examples were measured by the following methods. (1) The α-olefin content was measured with ethylene and α using an infrared spectrophotometer (manufactured by JASCO Corporation) JASCO-302.
-Determined by characteristic absorption of olefin. (2) The intrinsic viscosity [η] is measured using an Ubbelohde viscometer,
It was measured in a tetralin solution at 135 ° C.

Example 1 (1) Synthesis of Titanium Amide Compound After replacing a 300 ml flask equipped with a stirrer, a dropping funnel and a thermometer with argon, octylamine 9.07 was prepared.
ml (30 mmol) and hexane 150 ml were charged. Next, n-butyllithium 1 diluted with hexane
9.4 ml (30 mmol) was added dropwise from the dropping funnel over 30 minutes while maintaining the temperature of the solution in the flask at 5 ° C, and after completion of the reaction, the reaction was carried out at 5 ° C for 3 hours. Next, 1.65 ml (15 mmol) of TiCl ₄ diluted with hexane was dropped from the dropping funnel into the mixed solution obtained in the above reaction over 30 minutes while maintaining the temperature at 5 ° C.
After reacting for 3 hours, the solid is removed, and the solvent is removed by drying under reduced pressure to obtain a compositional formula [(C ₈ H ₁₇ ) ₂ N] ₂ Ti.
Titanium amide compound (A-1) represented by Cl ₂ .
55 g was obtained. 1 equipped with stirrer, dropping funnel, thermometer
After replacing a 00 ml flask with argon, 0.36 g of the above titanium amide compound (A-1) and 20 ml of toluene
Was charged. Next, add 1.45 ml (1.45 mmol) of a diethyl ether solution of benzyl Grignard reagent to -7.
It was added dropwise at 8 ° C over 3 minutes. After stirring at -78 ° C for 15 minutes, the mixture is stirred at room temperature for 30 minutes. After removing the solid, the solvent was removed by drying under reduced pressure to obtain a compositional formula [(C ₈ H ₁₇ ) ₂ N] ₂ Ti.
0.40 g of a titanium amide compound (A-2) represented by [CH ₂ (C ₆ H ₅ )] ₂ was obtained.

(2) Polymerization of ethylene and α-olefin An autoclave equipped with a stirrer and having an internal volume of 400 ml was vacuum dried and replaced with argon, and then toluene 92 was used as a solvent.
20 ml of butene-1 as an α-olefin was charged and the reactor was heated to 60 ° C. After the temperature was raised, ethylene pressure was adjusted to 6 kg / cm ² and hydrogen pressure was adjusted to 1 kg / cm ² for feeding, and after the system was stabilized, triisobutylaluminum (TIBA) 0. 5 mmol was added, and then 0.01 mmo of the catalyst component (A-2) prepared in (1) above.
l, and then (Ph ₃ C) [B (C ₆ F ₅ ) ₄ ].
0.02 mmol was added. Polymerization was performed for 1 hour while controlling the temperature at 60 ° C. to obtain a copolymer. The results are shown in Table 1. The degree of methyl branching of the obtained copolymer is high,
That is, the α-olefin content was high and the intrinsic viscosity was high, that is, the molecular weight was high.

Example 2 (1) Synthesis of Titanium Amide Compound After replacing a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer with argon, 2.00 g of N, N-dimethylanilinoether and tetrakisdimethylamide were used. 1.97 g of titanium and 30 ml of toluene were charged. 80
After stirring at ℃ for 1 hour, after reacting at room temperature for 5 hours,
The solvent was removed by vacuum drying to obtain the product. Subsequently, a 1 L flask equipped with a stirrer and a thermometer was purged with argon, and the obtained product was transferred into toluene 300 m.
1 was added and cooled to -78 ° C. After replacing another 200 ml flask with argon, titanium titanium tetrachloride 0.9
6 ml and 50 ml of toluene were charged and cooled to -78 ° C. This titanium titanium tetrachloride toluene solution was transferred to the solution of the above 1 L flask with a canister and stirred overnight,
The temperature was gradually raised to room temperature. The supernatant was removed, the precipitate was washed with 60 ml of toluene, and dried under reduced pressure to obtain 2.1 g of a titanium amide compound (A-3) represented by the composition formula [O (C ₁₄ H ₁₄ N ₂ )] TiCl _2. Obtained. After replacing a 100 ml flask equipped with a stirrer and a thermometer with argon, 0.12 g of the titanium amide compound (A-3) and 10 ml of toluene were charged, and the mixture was cooled to -78 ° C. Next, a solution of benzyl Grignard reagent in diethyl ether 10.84
ml (0.84 mmol) was added. The reaction was carried out at −78 ° C. for 15 minutes, and then at room temperature for 30 minutes. After removing the produced solid, the solvent was removed by drying under reduced pressure, and the composition formula [O (C ₁₄ H ₁₄ N ₂ )] Ti [CH ₂ (C
₆ H ₅ )] _{2 The} titanium amide compound (A-4)
0.13 g was obtained.

(2) Polymerization of ethylene and α-olefin An autoclave equipped with a stirrer and having an internal volume of 400 ml was vacuum dried and replaced with argon, and then toluene 92 was used as a solvent.
20 ml of butene-1 as an α-olefin was charged and the reactor was heated to 60 ° C. After the temperature was raised, ethylene pressure was adjusted to 6 kg / cm ² and hydrogen pressure was adjusted to 1 kg / cm ² for feeding, and after the system was stabilized, triisobutylaluminum (TIBA) 0. 5 mmol was charged, and then 0.01 mmo of the catalyst component (A-4) prepared in (1) above.
l, and then (Ph ₃ C) [B (C ₆ F ₅ ) ₄ ].
0.02 mmol was added. Polymerization was performed for 1 hour while controlling the temperature at 60 ° C. to obtain a copolymer. The results are shown in Table 1. The degree of methyl branching of the obtained copolymer is high,
Moreover, the intrinsic viscosity was also high.

Example 3 In the ethylene-α-olefin copolymerization in Example 2, 0.5 mmol of trihexylaluminum (THA) manufactured by Tosoh Akzo Co., Ltd. was used as an organoaluminum compound.
Polymerization was performed in the same manner as in Example 2 except that was used. The results are shown in Table 1. The copolymers obtained in the same manner as in Examples 1 and 2 had a high degree of methyl branching and a high intrinsic viscosity.

Example 4 In the ethylene-α-olefin copolymerization in Example 2, 0.01 mm of (A-3) as a titanium amide compound was used.
Polymerization was performed in the same manner as in Example 2 except that ol was used. The results are shown in Table 1. The copolymers obtained in the same manner as in Examples 1, 2 and 3 had a high degree of methyl branching and a high intrinsic viscosity.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 2 except that 0.7 μmol of biscyclopentadienyl zirconium dichloride was used in place of the titanium amide compound in the ethylene-α-olefin copolymerization. The results are shown in Table 1. Unlike the previous examples, the degree of methyl branching of the copolymer is low, ie α
-Low olefin content and low intrinsic viscosity, i.e. low molecular weight.

[0039]

[Table 1]

[0040]

INDUSTRIAL APPLICABILITY With the catalyst system of the present invention, it is possible to efficiently produce a high molecular weight ethylene-α-olefin copolymer having a high α-olefin content in the copolymerization of ethylene and α-olefin. Become.

[Brief description of drawings]

FIG. 1 is a flow chart diagram to assist in understanding the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Imai 5-1 Anesaki Kaigan, Ichihara City, Chiba Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. An olefin polymerization comprising a titanium amide compound (A) having a titanium-nitrogen bond, a compound (B) which reacts with a transition metal compound to form a stable anion, and an organoaluminum compound (C). catalyst. 2. The catalyst for olefin polymerization according to claim 1, wherein the titanium amide compound (A) is a titanium amide compound represented by the following general formula [I] or [II]. Embedded image Embedded image (In the formula, R ^{1 to} R ⁴ and R ^{7 to} R ¹⁰ represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different. X has an oxygen atom, a sulfur atom, and a hydrocarbon group. A nitrogen atom, wherein R ⁵ , R ⁶ , R ¹¹ and R ¹² are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 carbon atom
To 20 silicon-containing hydrocarbon groups or halogen atoms. ) 3. A method for producing an ethylene-α-olefin copolymer, which comprises polymerizing ethylene and an α-olefin using the olefin polymerization catalyst according to claim 1 or 2.