JPH0616728A - Method for producing olefin-based copolymer - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] When an α-olefin and a cyclic olefin are copolymerized, an olefin copolymer having excellent randomness and having many structural units derived from the cyclic olefin is obtained. Provided is a method for producing an olefin-based copolymer using a unique olefin polymerization catalyst that can be produced. [Structure] Containing one or more kinds of transition metal compounds selected from Ti, Zr, Hf, Nb and Ta, or containing a vanadium compound and carrying out homopolymerization of propylene, the requirements (a) and (b) ) In the presence of an olefin polymerization catalyst capable of providing a polypropylene satisfying
Copolymerize an olefin and a cyclic olefin. (a) In the ¹³ C-NMR spectrum of the polypropylene, the peak intensities derived from Tββ, Tβγ, and Tαγ satisfy the following formula, (b) The intensity ratio of Tβγ to Tαγ in the ¹³ C-NMR spectrum of the polypropylene is 2 or more.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin copolymer, and more particularly to a method for producing an olefin copolymer using a catalyst for olefin polymerization capable of providing polypropylene having a unique stereostructure. .

[0002]

BACKGROUND OF THE INVENTION As a catalyst for producing an α-olefin polymer such as polypropylene, a titanium-based catalyst composed of a titanium compound and organic aluminum has been conventionally known. Such a known titanium-based catalyst is known. Of (Tβγ + Tαγ) (Tββ + 2Tβ observed in the ¹³ C-NMR spectrum of polypropylene obtained by using
The intensity ratio to (γ + Tαγ) is almost zero. That is, when propylene is polymerized using a conventionally known titanium-based catalyst, almost no inversion occurs, and therefore, there is almost no heterogeneous bond in the obtained polypropylene.

Further, as a catalyst for producing polypropylene, a catalyst system composed of zirconocene or hafnocene and aluminoxane is also known, but with polypropylene obtained by using such a known metallocene catalyst, about 0.01 Heterologous bonds are present in the following proportions. In polypropylene obtained by using such a known metallocene catalyst, the ratio of Tβγ to Tαγ (Tβγ / T
αγ) is 1.5 or less.

Note that Tβγ / Tαγ is, for example, 1, 2
Following the addition reaction, a 2,1 addition reaction occurs
Number of addition reactions and 1,2 addition reactions followed by 2,1
It is a measure of the ratio of the number of times an addition reaction occurs and then the number of 1,2 addition reactions occurs.

The present inventors have found that when propylene is polymerized by using a certain catalyst, the resulting polypropylene has Tβγ / Tαγ of 2 or more as described above, and α- When an olefin is copolymerized with a cyclic olefin such as tetracyclododecene, α containing a large amount of structural units derived from the cyclic olefin
The present invention has been completed by finding that an olefin / cyclic olefin copolymer can be obtained.

[0006]

An object of the present invention is to use a unique olefin polymerization catalyst capable of producing an olefin-based copolymer having a large number of constitutional units derived from a cyclic olefin when an α-olefin and a cyclic olefin are copolymerized. It is intended to provide a method for producing an olefin-based copolymer.

[0007]

SUMMARY OF THE INVENTION A method for producing an olefin copolymer according to the present invention comprises at least one transition metal compound selected from Ti, Zr, Hf, Nb and Ta, or a vanadium compound, and propylene. Represented by the following formula [I] and / or [II] in the presence of an olefin polymerization catalyst capable of providing a polypropylene satisfying the following requirements (a) and (b) when the homopolymerization of A method for producing an olefin-based copolymer, which comprises copolymerizing a cyclic olefin and an α-olefin; (a) In a ¹³ C-NMR spectrum of the polypropylene, peak intensity derived from Tββ, Tβγ, and Tαγ is Satisfies the following formula (i),

[0008]

[Equation 3]

(B) The intensity ratio of Tβγ to Tαγ in the ¹³ C-NMR spectrum of the polypropylene is T
It is 2 or more when a catalyst containing at least one transition metal compound selected from i, Zr, Hf, Nb and Ta is used, and 6 or more when a catalyst containing a vanadium compound is used. .

[0010]

[Chemical 3]

[I] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ And R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are each
R ¹⁵ and R ¹⁶ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. Alternatively, R ¹⁷ and R ¹⁸ may form an alkylidene group).

[0012]

[Chemical 4]

[II] (In the formula [II], p and q are 0 or 1)
The above integers, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon. A carbon atom to which R ⁹ and R ¹⁰ are bonded, and a carbon atom to which R ¹³ is bonded or a carbon atom to which R ¹¹ is bonded, which represent an atom or group selected from the group consisting of a group and an alkoxy group. May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n =
When m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring).

[0014]

DETAILED DESCRIPTION OF THE INVENTION The method for producing an olefin copolymer according to the present invention will be specifically described below.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization. In the method for producing an olefin-based copolymer according to the present invention, the olefin polymerization catalyst used is
It is a catalyst capable of providing polypropylene having a unique three-dimensional structure when homopolymerizing propylene.

Here, the polypropylene having a unique three-dimensional structure means that at least the following requirements (a) and (b) are satisfied. (a) In the ¹³ C-NMR spectrum of the polypropylene, the peak intensities derived from Tββ, Tβγ, and Tαγ satisfy the following formula (i),

[0017]

[Equation 4]

(B) The intensity ratio of Tβγ to Tαγ in the ¹³ C-NMR spectrum of the polypropylene is T
It is 2 or more when a catalyst containing at least one transition metal compound selected from i, Zr, Hf, Nb and Ta is used, and 6 or more when a catalyst containing a vanadium compound is used. .

Requirements for polypropylene according to the present invention
(a) and (b) are calculated based on the ¹³ C nuclear magnetic resonance (NMR) spectrum measured by the following method. That is, the polymer concentration is 10% by weight or less, preferably 5% by weight.
67,20 MHz, 120 ° C. using a mixed solution of 1,2,4-trichlorobenzene / d ₆ -benzene = 9/1 (weight ratio)
Determined by measuring at. As a measuring device,
For example, JEOL-GX270 NMR measuring device manufactured by JEOL Ltd. is used.

The peak observed in the ¹³ C-NMR spectrum is the peak of Lindenman Adams (Analysis Chemist
ry 43 , p1245 (1971)).

In the ¹³ C-NMR spectrum of polypropylene, the peak appearing at 30 to 32 ppm is Tβγ.
The peaks appearing at 28 to 30 ppm were assigned to Tββ. Also, the peak appearing at 35 to 38 ppm is Tαβ
The peaks appearing at 38 to 40 ppm were assigned to Tαγ.

Next, the above requirements (a) and (b) will be described. In the requirement (a), (Tβγ + Tαγ) (Tβ
The intensity ratio for β + 2Tβγ + Tαγ) is generally 1,
The ratio of 2,1 addition reaction following 2 addition reaction,
The rate of 1,2 addition reaction following the 1 addition reaction, that is, the rate of inversion (heterologous bond) is shown.

In the present invention, the intensity ratio of (Tβγ + Tαγ) to (Tββ + 2Tβγ + Tαγ) is 0.
It is 001 or more, preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, and particularly preferably 0.15 or more.

As described above, in polypropylene obtained by a known titanium-based catalyst, the strength ratio of (Tβγ + Tαγ) to (Tββ + 2Tβγ + Tαγ) is usually less than 0.001. That is, there is almost no inversion, and thus there is no heterologous binding.

Next, the above requirement (b) is a parameter first proposed by the present inventors to define the special structure of polypropylene. That is, in requirement (b), Tβγ
The intensity ratio (Tβγ / Tαγ) of Tαγ to
Following the (2,1) addition reaction, the 2,1 (1,2) addition reaction occurs, then the number of 2,1 (1,2) addition reactions, and the 1,2 (2,1) addition reaction. 2,1 (1,2)
It is considered as a parameter indicating the ratio of the number of times that an addition reaction occurs and then the 1,2 (2,1) addition reaction occurs.

In the above, since the peak intensity of Tαβ is theoretically almost the same as Tβγ, (Tβγ + Tαγ) /
The (Tββ + 2Tβγ + Tαγ) value may be
(Tαβ + Tαγ) / (Tββ + 2Tβγ + Tαγ) value or (Tαβ + 2Tαγ + Tβγ) / 2 (Tββ + Tβ
γ + Tαβ + Tαγ) value, and the intensity ratio of Tβγ to Tαγ can be evaluated by the intensity ratio of Tαβ to Tαγ.

In the present invention, the intensity ratio of Tβγ to Tαγ is as follows. When using a catalyst containing at least one transition metal compound selected from Ti, Zr, Hf, Nb and Ta, it is 2 or more, preferably 4 or more, more preferably 5 or more, and further preferably Is 6 or more, and particularly preferably 10 or more.

When a catalyst containing a vanadium compound is used, Tβγ / Tαγ is 6 or more, preferably 7 or more, more preferably 8 or more, further preferably 9 or more, and particularly It is preferably 10 or more.

As described above, in polypropylene obtained by using a zirconocene or hafnocene-based catalyst, Tβγ
The intensity ratio of Tαγ to Tαγ (or the intensity ratio of Tαβ to Tαγ) is usually 1.5 or less.
It is considered that the rate of returning to the 1,2 addition reaction after the 2,1 addition reaction following the 2-addition reaction is higher than the rate of the subsequent 2,1 addition reaction.

It should be noted that while there are apparent peaks attributed to Tβγ and Tαβ, the peaks that should be attributed to Tαγ may be hidden due to noise and cannot be identified. In this case, Tαγ of Tβγ The intensity ratio to or the intensity ratio of Tαβ to Tαγ is considered to be ∞.

In the present invention, α-olefin and cyclic olefin are combined and copolymerized in the presence of an olefin polymerization catalyst capable of producing polypropylene satisfying the above-mentioned unique requirements.

Examples of such α-olefins include α-olefins having 2 or more carbon atoms. Specifically, the following compounds can be mentioned. Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-hexene, 4,4-dimethyl-1-pentene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
Linear or branched C2-C20 α-olefins such as 1-hexadecene, 1-octadecene and 1-eicosene.

Aromatic vinyl compounds such as styrene, methylstyrene, dimethylstyrene, chlorostyrene, allylbenzene, allyltoluene, vinylnaphthalene, allylnaphthalene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, methyl together with α-olefin. C7-C20 alicyclic vinyl compounds such as vinylcyclohexane and allylnorbornane, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilylyl-1 It is also possible to use silane unsaturated compounds such as octene and 10-trimethylsilyl-1-decene.

These α-olefins can be copolymerized alone or in combination of two or more with the following cyclic olefins. Of these, preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
2-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 3-methyl-1-butene and the like having 2 to 10 carbon atoms
[Alpha] -olefin can be mentioned, and particularly preferably, ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like can be mentioned.

Examples of the cyclic olefin used in the present invention include cyclic olefins represented by the following formula [I] or [II].

[0036]

[Chemical 5]

[I] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. Note that q is 0. In this case, the bond defined by q is a single bond, and thus the ring formed here is a 5-membered ring.

In the above formula [I], R ^{1 to} R ¹⁸
R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, as the halogen atom,
For example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned. As the hydrocarbon group, each independently, usually, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms and an aromatic group. Hydrocarbon group can be mentioned, and specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group. As a specific example of the alkyl halide, a group in which at least a part of hydrogen atoms forming the alkyl group as described above is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be used. Can be mentioned. Further, specific examples of the cycloalkyl group include a cyclohexyl group, specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, and these groups include a lower alkyl group. It may have a group.

Further, in the above formula [I], R ¹⁵ and R
¹⁶ and R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸
And R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ may be bonded to each other (cooperate with each other) to form a monocyclic or polycyclic group.

Here, examples of the monocyclic or polycyclic group include:
The groups described below can be mentioned.

[0041]

[Chemical 6]

In the above-exemplified groups, the carbon atoms numbered 1 and 2 are the same as R in the formula [I].
It represents a carbon atom of an alicyclic structure to which a group represented by ^{15 to} R ¹⁸ is bonded.

[0043]

[Chemical 7]

[II] In the formula [II], p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2.

R ^{1 to} R ¹⁹ are each independently an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group. Represents Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or are alkylene groups having 1 to 3 carbon atoms. It may be bound via. That is, when the above two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ or the groups represented by R ¹⁰ and R ¹¹ cooperate with each other. Methylene group (-CH _2- ), ethylene group (-CH
₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _2- ) forms an alkylene group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. In this case, examples of the monocyclic or polycyclic aromatic ring include R ¹⁵ and R when n = m = 0.
Mention may be made of the groups described below in which ¹² further forms an aromatic ring.

[0047]

[Chemical 8]

In the above formula, q has the same meaning as in formula [II]. In the formula [II], the halogen atom has the same meaning as the halogen atom in the above formula [I]. In addition, the aliphatic hydrocarbon group herein has 1 to 1 carbon atoms.
It is an alkyl group having 20 or a halogenated alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and a halogenated alkyl group. As a specific example, a group in which at least a part of hydrogen atoms forming the above alkyl group are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be given. Further, specific examples of the alicyclic hydrocarbon group include a cyclohexyl group, and specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. May have a lower alkyl group.

Examples of the cyclic olefins represented by the formulas [I] and [II] include bicyclo [2,2,1] hept-2-ene derivative, tetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] -3-Dodecene derivative, hexacyclo [6,6,1,1 ^3.6 , 1 ^10.13 , 0
^2.7, 0 ^9.14] -4 Heputadensen derivatives, octacyclo [8,8,0,1 ^2.9, 1 ^{4.7, 1 11.18,} 1 ^13.16, 0 ^3.8, 0
^12.17 ] -5-dococene derivative, pentacyclo [6,6,1,1
^3.6, 0 ^2.7, 0 ^9.14] -4-hexadecene derivative, heptacyclo-5-eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4,3,0,1 ^2.5] -3-decene derivatives , Tricyclo [4,3,0,1 ^2.5 ] -3-undecene derivative, pentacyclo [6,5,1,1 ^3.6 , 0 ^2.7 ,
0 ^9.13] -4-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo 7,4,0,1 ^2.5, 1
^9.12, 0 ^8.13 3-pentadecene derivatives, pentacyclo [8,7,0,1,3,6,1 ^{10.17, 1 12.15,} 0 ^2.7, 0
^11.16 ] -4-Eicosene derivative, nonacyclo [10,9,
1,1 ^4.7 , 1 ^13.20 , 1 ^15.18 , 0 ^3.8 , 0 ^2.10 ,
0 ^12.21 , 0 ^14.19 ] -5-Pentacocene derivative, pentacyclo [8,4,0,1 ^2.3 , 1 ^9.12 , 0 ^8.13 ] -3-Hexadecene derivative, pentacyclo [8,8,0,1 ^4.7 , 1 ^11.18 , 1
^13.16 , 0 ^3.8 , 0 ^12.17 ] -5- Heneicosene derivative,
Nonashikuro [10,10,1,1 ^{5.8, 1 14.21,} 1 ^16.19, 0
^2.11 , 0 ^4.9 , 0 ^13.22 , 0 ^15.20 ] -5-hexacocene derivative, bicyclo [2,2,1] hept-2-ene derivative, 1,4-methano-1,4,4a, 9a-Tetrahydrofluorene derivative, 1,4-
Examples thereof include methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative and cyclopentadiene-acenaphthylene adduct.

Specific examples of such cyclic olefins are shown below.

[0051]

[Chemical 9]

[0052]

[Chemical 10]

[0053]

[Chemical 11]

[0054]

[Chemical 12]

[0055]

[Chemical 13]

[0056]

[Chemical 14]

[0057]

[Chemical 15]

[0058]

[Chemical 16]

[0059]

[Chemical 17]

[0060]

[Chemical 18]

[0061]

[Chemical 19]

[0062]

[Chemical 20]

[0063]

[Chemical 21]

[0064]

[Chemical formula 22]

[0065]

[Chemical formula 23]

[0066]

[Chemical formula 24]

The cyclic olefin represented by the above formula [I] or [II] can be produced by a Diels-Alder reaction between cyclopentadiene and the corresponding olefin.

The above-mentioned cyclic olefins represented by the formulas [I] and [II] can be copolymerized alone or in combination of two or more kinds with the above-mentioned α-olefin. Of these, preferably,

[0069]

[Chemical 25]

Bicycloheptene, such as

[0071]

[Chemical formula 26]

Methylbicycloheptene, such as

[0073]

[Chemical 27]

Tetracyclododecene, such as

[0075]

[Chemical 28]

Methyltetracyclododecene, such as

[0077]

[Chemical 29]

Dimethyltetracyclododecene, such as

[0079]

[Chemical 30]

Methyltricyclodecene, such as

[0081]

[Chemical 31]

Pentacyclopentadecene such as

[0083]

[Chemical 32]

Hexacycloheptadecene, such as

[0085]

[Chemical 33]

Mention may be made of phenylbicycloheptene such as In the present invention, when copolymerizing the above α-olefin and cyclic olefin, preferred combinations include ethylene and tetracyclododecene, propylene and tetracyclododecene, butene and tetracyclododecene, and ethylene and penta. Examples include combinations of cyclopentadecene, propylene and pentacyclopentadecene, ethylene and bicycloheptene, propylene and bicycloheptene, ethylene, propylene and tetracyclododecene.

In the present invention, when the α-olefin and the cyclic olefin are copolymerized, 0.01-99 mol, preferably 0.1-90 mol of the cyclic olefin is usually added to 1 mol of the α-olefin. It is more preferable to use it in a ratio of 0.5 to 80 mol.

In the present invention, a polyene compound may be copolymerized within a range not impairing the object of the invention. Such polyene compounds include butadiene, isoprene and 1,3-
Butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,
3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl- 1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-
1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl- Fats such as 1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene Group diene compounds, vinylcyclohexene, vinyl norbornene, ethylidene norbornene,
Examples thereof include alicyclic polyene compounds such as dicyclopentadiene, cyclooctadiene and 2,5-norbornadiene, and aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene.

In the method for producing an olefin-based copolymer according to the present invention, the above-mentioned copolymerization of α-olefin and cyclic olefin can be carried out to produce polypropylene having a unique stereostructure as described above. It is carried out in the presence of a polymerization catalyst.

Examples of such olefin polymerization catalysts include Ti, V, Zr, Hf, Nb and Ta.
Examples thereof include olefin polymerization catalysts composed of at least one transition metal compound selected from the group consisting of organic metal compounds.

As a particularly preferred example of the above-mentioned olefin polymerization catalyst, an olefin polymerization catalyst comprising a solid catalyst in which a nonmetallocene transition metal compound is supported on a solid support and an organometallic compound (hereinafter, referred to as " And a catalyst for olefin polymerization composed of a metallocene compound and an organometallic compound (hereinafter, sometimes abbreviated as "catalyst 2").

Specific examples of the nonmetallocene-based transition metal compound used for preparing the catalyst 1 include tetravalent titanium compounds represented by the following formula. Ti (OR) _g X _{4 -g} R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4. As such a compound, specifically, TiCl ₄ , Ti
Tetrahalogenated titanium such as Br ₄ and TiI ₄ , Ti (O
CH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) C
Trihalogenated alkoxytitanium such as l ₃ , Ti (OC ₂ H ₅ ) Br ₃ and Ti (O-iso-C ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) _{2
Cl 2, Ti (OC 2 H} 5) 2 Cl 2, Ti (On-C 4 H 9) 2 Cl
₂ , dihalogenated dialkoxy titanium such as Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl,
Monohalogenated trialkoxy titanium such as Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ) ₄ , T
i (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄ H
₉ ) ₄ and tetraalkoxy titanium such as Ti (O-2-ethylhexyl) ₄ can be exemplified.

A compound in which the titanium atom of the titanium compound is replaced with zirconium or hafnium can be used as well, and a niobium compound or tantalum compound similar to the titanium compound can be used as well.

Further, as the vanadium compound, a compound in which a titanium atom of the above titanium compound is replaced by a vanadium atom, and a compound represented by the formula VO (OR) _a X _b or the formula V
Examples thereof include compounds represented by (OR) _c X _d .

However, in the above formula, R is a hydrocarbon group, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3,
It has a relationship of 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 3 ≦ c + d ≦ 4. Examples of this vanadium compound include VOCl ₃ ,
VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (O-n-C ₄ H ₉ ) C
l ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOC
l ₂ , VO (O-n-C ₄ H ₉ ) ₃ , VCl ₃・ 2 (OC ₈ H ₁₇
Examples thereof include vanadium compounds such as OH). These vanadium compounds can be used alone or in combination.

Further, the nonmetallocene type transition metal compound as described above may be used by being brought into contact with an electron donor described later in advance. The catalyst 1 is composed of a solid catalyst obtained by supporting a nonmetallocene-based transition metal compound as described above on a carrier compound as described below, and an organometallic compound.

Examples of such carrier compounds include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Zn
Resins such as O, ZnO ₂ , SnO ₂ , BaO, ThO and styrene-divinylbenzene copolymer, MgCl ₂ , Mg (O
H) ₂ , MgCO ₃ , Mg (OEt) ₂ , and magnesium stearate. Among these carrier compounds,
Preferably, SiO ₂ , Al ₂ O ₃ , MgO, ZnO, ZnO _{2 and the} like can be mentioned.

As the organometallic compound used for preparing the catalyst 1, organometallic compounds of Group I to Group III metals of the periodic table are used, and specifically, the following compounds are used. (1) R ¹ _m Al (OR ² ) _n H _p X _q (wherein R ¹ and R ² are usually 1 to 15 carbon atoms,
It is preferably a hydrocarbon group containing 1 to 4 groups, which may be the same or different from each other. X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number 0 ≦ q <3, and m + n + p + q = 3
Is an organoaluminum compound. _{^{(2) M 1 AlR 1 4}} ( wherein, M ¹ is Li, Na, a K, R ¹ is as defined above) alkylated complex of Group I metal and aluminum represented by. (3) R ¹ R ² M ² (wherein R ¹ and R ² are the same as above. M ² is M
g, Zn or Cd), a dialkyl compound of Group II or Group III.

Examples of the organoaluminum compound belonging to (1) above include the following compounds. Formula _{^{R 1 m Al (OR 2)}} ( wherein, R ¹ and R ² are the same .m said is preferably a number of _{1.5 ≦ m ≦ 3) 3-} m, the general formula R ¹ _m AlX _3-m (in the formula, R ¹ is the same as above. X is halogen, m is preferably 0 <m <3), general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above) .M is preferably 2 ≦ m <3
R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X is a halogen,
0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q =
3) can be mentioned.

Specific examples of the aluminum compound belonging to (1) include trialkylaluminums such as triethylaluminum, tributylaluminum and triisobutylaluminum, trialkenylaluminums such as triisoprenylaluminum, diethylaluminum ethoxide and dibutyl. Dialkyl aluminum alkoxides such as aluminum butoxide, ethyl aluminum sesquiethoxide, alkyl aluminum sesquialkoxides such as butyl aluminum sesquibutoxide, partially alkoxylated having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5, etc. Alkyl aluminum; Dialkyl alkyl chlorides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide Minium halides; alkyl aluminum sesquichlorides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc. Alkyl aluminum, diethyl aluminum hydride, dialkyl aluminum hydride such as dibutyl aluminum hydride, ethyl aluminum dihydride, other partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as propyl aluminum dihydride, ethyl aluminum ethoxy chloride, Butyl aluminum butoxycyclolide, ethyl aluminum Mention may be made of partially alkoxylated and halogenated alkylaluminiums such as umethoxybromide.

Examples of the compound similar to (1) include an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such a compound include (C ₂ H ₅ ) ₂ AlOAl
(C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ ,
(C ₂ H ₅₎ etc. ₂ AlN (C ₂ H ₅₎ Al (C ₂ H _{5) 2,} can further include aluminoxanes such as methyl aluminoxane.

Compounds belonging to the above (2) include LiAl
_{(C 2 H 5) 4,} LiAl (C 7 H 15) 4 and the like.

Of these, organoaluminum compounds are preferably used, and halogen-containing alkylaluminum is particularly preferably used. An electron donor may be added to the catalyst 1 composed of such an organometallic compound and the above-mentioned transition metal compound and carrier compound, if necessary.

Specific examples of the electron donor added to the catalyst 1 as required include the following compounds. Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine and tribenzylamine, pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole, pyrroline, pyrrolidine, indole and pyridine. Nitrogen-containing cyclic compounds such as methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridine chloride, piperidine, quinoline, isoquinoline, etc., tetrahydrofuran ,
1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran,
Pyran, cyclic oxygenated compounds such as ditedropyran, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, C1-C18 alcohols such as isopropylbenzyl alcohol, phenol, cresol, xylenol,
C6-C20 phenols which may have a lower alkyl group such as ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol, acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, acetylacetone and benzoquinone C2-C15 ketones, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other C2-C15 aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, Octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, cyclo Ethyl xanthate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl Ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexylcarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate , 2-diethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate having 2 to 2 carbon atoms
C2 to C15 acid halides such as 30 organic acid esters, acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether epoxy- C2-C20 ethers such as p-menthane, 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-isobutyl-1,3-dimethoxypropane, 2,2
-Isopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl-1,3-dimethoxypropane,
2,2-isopentyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane,
2-Cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo-2,2,1-heptane, diphenyldimethoxy Silane, isopropyl-t-
Butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane and other diethers, acetic acid amide, benzoic acid amide, toluic acid amide and other acid amides And nitriles such as acetonitrile, benzonitrile and tolunitrile, and acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

As the electron donor, an organosilicon compound represented by the following general formula [Ia] can be used. R _n Si (OR ′) _4-n ... [Ia] (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula [Ia] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butyl. Methyldimethoxysilane,
t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane , Screw p-
Tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltrisilane Ethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy Silane, vinyl tris (β-methoxyethoxysilane),
Vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

Further, as the electron donor, an organosilicon compound represented by the following general formula [IIa] can be used. SiR ¹ R ² _m (OR ³ ) _3-m ... [IIa] (In the formula, R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is an alkyl group, a cyclopentyl group or a cyclopentyl group having an alkyl group. R ³ is a hydrocarbon group, and m is 0 ≦ m ≦ 2. In the above formula [IIa], R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group. In addition, as R ¹ , other than the cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, 2,3-
A cyclopentyl group having an alkyl group such as a dimethylcyclopentyl group can be mentioned.

In the formula [IIa], R ² is any one of an alkyl group, a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is
For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a hexyl group, or a cyclopentyl group exemplified as R ¹ and a cyclopentyl group having an alkyl group can be similarly mentioned.

In the formula [IIa], R ³ is a hydrocarbon group, and examples of R ³ include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.

Specific examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane. Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, di Cyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyl Ethyl silane, mono-alkoxysilanes such as cyclopentyl dimethylethoxysilane, and the like.

Next, a method for preparing the catalyst 1 comprising the above carrier compound, the nonmetallocene-based transition metal compound supported on the carrier compound, and the organometallic compound will be described.

The nonmetallocene transition metal compound is supported on the carrier compound by a simple contact method, a method of mixing under heating, a carrier compound in advance, an organometallic compound, an electron donor or a halogenating agent. A method of supporting the nonmetallocene-based transition metal compound on the carrier compound after the contact treatment with the above-mentioned substances can be mentioned.

The carrier-supported nonmetallocene-based transition metal compound thus obtained can be contact-treated with an organometallic compound prior to polymerization. In that case 0-200
It is preferable to contact in the temperature range of ℃, preferably -40 to -90 ℃.

The amount of the nonmetallocene transition metal compound supported on 1 gram of the carrier compound is generally 0.01.
˜100 mmol, preferably 0.01 to 50 mmol, particularly preferably 0.05 to 20 mmol.

In the catalyst 1 as described above, the nonmetallocene transition metal compound and the organometallic compound have an atomic ratio (transition metal atom / metal atom contained in the organometallic compound) of 1
It is contained in an amount ratio of ˜1000, preferably 1 to 200. The amount of the electron donor used, which is added as desired, is not particularly limited, but is 0.1 to 1 mol of the transition metal atom.
It is desirable that the amount is 100 mol, preferably about 1 to 10 mol.

In the present invention, an α-olefin and a cyclic olefin are copolymerized in the presence of the catalyst 1 as described above to obtain an olefin copolymer. The α-olefin copolymerization using the catalyst 1 is usually carried out in a gas phase, solution polymerization, or a slurry state.

When the polymerization takes the reaction form of slurry polymerization or solution polymerization, an inert hydrocarbon can be used as the reaction solvent, or an olefin which is liquid at the reaction temperature can be used.

Specific examples of the inert hydrocarbon medium used at this time include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons, cyclopentane, cyclohexane, methyl. Examples thereof include alicyclic hydrocarbons such as cyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and contact products thereof. Of these inert hydrocarbon media, it is particularly preferred to use aliphatic hydrocarbons.

In the polymerization system, the catalyst 1 is usually about 0.
It is used in an amount of 001 to 50 mmol, preferably about 0.01 to 10 mmol. Further, the organometallic compound is used in an amount such that the metal atom contained in the organometallic compound is usually about 1 to 1000 mol, preferably about 2 to 200 mol, relative to 1 mol of the transition metal atom in the polymerization system. To be

If hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. The polymerization temperature of olefin is
Usually about -50 to 200 ° C, preferably about 20 to 100 ° C.
The temperature is usually set to normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . The polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In such a polymerization system, the catalyst 1
It is preferable that the carrier-supported solid catalyst of the non-metallocene transition metal compound is difficult to form clusters in contact with the organometallic compound. Note that it is difficult to form clusters, for example, in the case of a titanium-based catalyst component, the ratio of Ti ³⁺ to total Ti measured by ESR, that is, Ti
³⁺ (ESR) / Ti and the value of (total), the ratio of the value of Ti ³⁺ after adsorbed pyridine vapors to the catalyst component (ESR) / Ti (total) is 0.2 to 1, preferably Can be evaluated by being 0.5 to 1.

The ESR is measured by using, for example, a Varian E-12 type ESR measuring device in a quartz tube having an inner diameter of 3 mm at room temperature and a modulation frequency of 100 KHz. At this time, 1,1-diphenyl-2-picrylhydrazine (D was used as a reference substance for the determination of the trivalent titanium atom and the determination of the g value.
PPH) and MnO doped with divalent Mn ions are used, respectively.

In the conventional catalyst system, it has been confirmed that a large amount of clusters are formed in the polymerization system, but it is considered that the above catalyst 1 does not form clusters or clusters are formed. Very few. When the α-olefin copolymerization is carried out in such a catalyst system that hardly forms clusters, the reason is not clear,
An olefin-based copolymer having a unique three-dimensional structure is obtained.

The catalyst 1 may be preliminarily polymerized prior to the polymerization. Next, the olefin polymerization catalyst (catalyst 2) composed of a metallocene compound and an organometallic compound will be described.

The metallocene compound used for the preparation of catalyst 2 includes ML _x (wherein M is a transition metal selected from the group consisting of Ti, V, Zr, Hf, Nb and Ta, and L is a transition metal). Coordinating ligand, at least one L is a ligand having a cycloalkadienyl skeleton, and L other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon having 1 to 12 carbon atoms. Group, an alkoxy group, an aryloxy group, halogen or hydrogen, and x is a valence of a transition metal.).

Examples of the ligand having a cycloalkadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, t-butylcyclopentadienyl group, dimethylcyclopentadienyl group. Examples thereof include enyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group and the like.

The ligand other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, halogen or hydrogen.
Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. Specifically, the alkyl group includes a methyl group, an ethyl group and a propyl group. , Isopropyl group, butyl group and the like, as the cycloalkyl group, a cyclopentyl group, a cyclohexyl group, and the like, as the aryl group, a phenyl group, a tolyl group and the like, and as the aralkyl group, a benzyl group, Examples include neophyll groups.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group, and examples of the aryloxy group include a phenoxy group.

Halogen includes fluorine, chlorine, bromine,
Examples thereof include iodine. Such a metallocene compound containing a ligand having a cycloalkadienyl skeleton used in the present invention can be more specifically represented by the formula R ² _k R ³ _l R when the transition metal has a valence of 4. ⁴ _m R ⁵ _n M (wherein M is a transition metal selected from the group consisting of Ti, V, Zr and Hf, R ² is a group having a cycloalkadienyl skeleton, and R ³ , R ⁴ and R ⁵ is a group having a cycloalkadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom or hydrogen, k is an integer of 1 or more, and k + l + m + n = 4. Is indicated). The metallocene compound has the formula R ² _k R ³ _l R ⁴ _m R ⁵ _n
In M, at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups having a cycloalkadienyl skeleton, and these groups having two cycloalkadienyl skeletons are lower. R ⁴ and R ⁵ are linked via alkylene such as ethylene and propylene, and R ⁴ and R ⁵ are groups having a cycloalkadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups,
It may be an aryloxy group, a halogen atom or hydrogen.

Specific examples of the metallocene compound containing a ligand having a cycloalkadienyl skeleton in which M is titanium will be shown below. Bis (cyclopentadienyl) titanium monochloride monohydride, bis (cyclopentadienyl) titanium monobromide monohydride, bis (cyclopentadienyl) methyltitanium hydride, bis (cyclopentadienyl) ethyltitanium hydride, bis ( Cyclopentadienyl) phenyltitanium hydride, bis (cyclopentadienyl) benzyltitanium hydride, bis (cyclopentadienyl) neopentyltitanium hydride, bis (methylcyclopentadienyl) titanium monochloride hydride, bis (indenyl) titanium Monochloride monohydride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bi (Cyclopentadienyl) methyltitanium monochloride, bis (cyclopentadienyl) ethyltitanium monochloride, bis (cyclopentadienyl) cyclohexyltitanium monochloride, bis (cyclopentadienyl) phenyltitanium monochloride, bis (cyclo Pentadienyl) benzyl titanium monochloride,
Bis (methylcyclopentadienyl) titanium dichloride, bis (t-butylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) titanium dibromide, bis (cyclopentadienyl) titanium dimethyl, bis (Cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) titanium dibenzyl, bis (cyclopentadienyl) titanium methoxy chloride, bis (cyclopentadienyl) titanium ethoxy chloride, bis (methylcyclopentadienyl) Titanium ethoxy chloride, bis (cyclopentadienyl)
Titanium phenoxycyclolide, bis (fluorenyl)
Titanium dichloride.

Further, at least two ligands having a cycloalkadienyl skeleton in which M is titanium are contained, and the ligand having at least two cycloalkadienyl skeletons is bonded via a lower alkylene group. Specific examples of the bound metallocene compound will be illustrated.

Ethylenebis (indenyl) dimethyltitanium, ethylenebis (indenyl) diethyltitanium, ethylenebis (indenyl) diphenyltitanium, ethylenebis (indenyl) methyltitanium, ethylenebis (indenyl) ethyltitanium monochloride, ethylenebis (indenyl). Methyltitanium monobromide, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dibromide, ethylenebis (indenyl) titanium methoxymonochloride, ethylenebis (indenyl) titaniumethoxymonochloride, ethylenebis (indenyl) titaniumphenoxymono Chloride, ethylene bis (cyclopentadienyl) titanium dichloride, propylene bis (cyclopenta Enyl) titanium dichloride,
Ethylenebis (t-butylcyclopentadienyl) titanium monochloride, ethylenebis (4,5,6,7-telorahydro-1-indenyl) dimethyltitanium, ethylenebis (4,5,6,7-telorahydro-1- Indenyl) methyltitanium monochloride, ethylenebis (4,5,6,7-telorahydro-1-indenyl) titanium dichloride, ethylenebis (4,5,6,7-telorahydro-1-indenyl) titanium dibromide, ethylenebis (4-methyl-1-indenyl)
Titanium dichloride, ethylenebis (5-methyl-1-indenyl) titanium dichloride, ethylenebis (6-methyl-1-indenyl) titanium dichloride, ethylenebis (7-methyl-1-indenyl) titanium dichloride, ethylenebis (5- Methoxy-1-indenyl) titanium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) titanium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) titanium dichloride, ethylenebis (4,7-dimethoxy-) 1-Indenyl) titanium dichloride.

Specific examples of the metallocene compound containing one ligand having a cycloalkadienyl skeleton in which M is titanium will be given below. Cyclopentadienyltitanium trichloride, Cyclopentadienyltitanium tribromide, Cyclopentadienylmethyltitanium dichloride, Cyclopentadienylethyltitanium dichloride, Cyclopentadienylphenyltitanium dichloride, Cyclopentadienylbenzyltitanium dichloride, Cyclopenta Dienyl neopentyl titanium dichloride, methylcyclopentadienyl titanium dichloride hydride, indenyl titanium dichloride monohydride, cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl diethyl titanium monochloride, cyclopentadienyl dicyclohexyl titanium monochloride, Cyclopentadienyldiphenyltitanium monochloride, Si Ropentadienyldibenzyltitanium monochloride, methylcyclopentadienyltitanium trichloride, t-butylcyclopentadienyltitanium trichloride, indenyltitanium trichloride, indenyltitanium tribromide, cyclopentadienyltitanium trimethyl, cyclo Pentadienyltitanium triphenyl, cyclopentadienyltitanium tribenzyl, cyclopentadienyltitanium methoxydichloride, cyclopentadienyltitanium ethoxydichloride, methylcyclopentadienyltitanium ethoxydichloride, cyclopentadienyltitaniumphenoxydichloride, fluore Nyltitanium trichloride, cyclopentadienylmethyltitanium dibromide, cyclopentadienylethyi Rutitanium dibromide, cyclopentadienyl phenyl titanium dibromide, cyclopentadienyl benzyl titanium dibromide, cyclopentadienyl neopentyl titanium dibromide, methyl cyclopentadienyl titanium dibromide hydride, indenyl titanium dibromide monohydride , Cyclopentadienyldimethyltitanium monobromide, cyclopentadienyldiethyltitanium monobromide, cyclopentadienyldicyclohexyltitanium monobromide, cyclopentadienyldiphenyltitanium monobromide, cyclopentadienyldibenzyltitanium monobromide, methylcyclopenta Dienyl titanium tribromide, t-butylcyclopentadienyl titanium tribromide, indene Le titanium tribromide, cyclopentadienyl titanium trimethyl, cyclopentadienyl titanium triphenyl,
Cyclopentadienyltitanium tribenzyl, cyclopentadienyltitanium methoxydibromide, cyclopentadienyltitanium ethoxydibromide, methylcyclopentadienyltitanium ethoxydibromide,
Cyclopentadienyl titanium phenoxy dibromide, fluorenyl titanium tribromide.

In the metallocene compound as described above, a compound in which titanium is replaced with zirconium or hafnium can be used. Further, a vanadium compound, a niobium compound or a tantalum compound similar to the above titanium metallocene compound can be similarly used.

Particularly, as the vanadocene compound, the following compounds can be exemplified. Biscyclopentadienyldichlorovanadium, biscyclopentadienyldibromovanadium, biscyclopentadienyltrichlorovanadium, biscyclopentadienyltribromovanadium, biscyclopentadienyldichlorooxovanadium, biscyclopentadienyldibromooxovanadium , Biscyclopentadienyldioxovanadium, biscyclopentadienylchlorovanadium, biscyclopentadienylbromovanadium, biscyclopentadienyliodovanadium, biscyclopentadienylchlorooxovanadium, biscyclopentadienylbromooxo Vanadium, ethylenebisindenyldichlorovanadium, ethylenebisindenyldibromovanadium, ethylenebisindenylchlorooxova Indium, ethylenebis indenyl bromo oxovanadium, dimethylsilylene bis (cyclopentadienyl) dichloro vanadium, dimethyl silylene biscyclopentadienyl chloro oxovanadium.

As the organometallic compound used for preparing the catalyst 2, the same compounds as the organometallic compounds used for preparing the catalyst 1 described above can be exemplified, but among them, aluminoxane is used. preferable. If desired, the above-mentioned electron donor can be added.

In the catalyst 2 as described above, the metallocene compound and the organometallic compound have an atomic ratio (transition metal atom contained in the metallocene compound / metal atom contained in the organometallic compound) of 1 to 1000, preferably 2 to Included in a quantity ratio of 200. The amount of the electron donor to be added as desired is not particularly limited, but is preferably 0.1 to 100 mol, preferably about 1 to 10 mol per 1 mol of the transition metal atom.

As a method for preparing the catalyst 2, a method of supporting on a carrier as exemplified in the catalyst 1 can be mentioned as a preferable example. In the present invention, an α-olefin and a cyclic olefin are copolymerized in the presence of the catalyst 2 as described above to obtain an olefin-based copolymer.

The polymerization of α-olefin using the catalyst 2 usually takes the form of solution polymerization or solution polymerization. As the reaction solvent during the polymerization, an inert hydrocarbon can be used, or an olefin which is liquid at the reaction temperature can be used.

The inert hydrocarbon medium used in this case may be the same as the above-mentioned inert hydrocarbon medium. In the polymerization system, the catalyst 2 is usually about 0.000 in terms of transition metal atoms per liter of polymerization volume.
It is used in an amount of 1 to 50 mmol, preferably about 0.01 to 10 mmol. Further, the organometallic compound is used in an amount such that the metal atom contained in the organometallic compound is usually about 1 to 1000 mol, preferably about 2 to 200 mol, relative to 1 mol of the transition metal atom in the polymerization system. To be

When hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. The polymerization temperature of olefin is
Usually about 20 to 200 ° C, preferably about 50 to 100 ° C
Is set to. The polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further polymerization,
It is also possible to carry out the reaction in two or more steps by changing the reaction conditions.

When the α-olefin and the cyclic olefin are copolymerized by the above-mentioned method for producing an olefinic copolymer, the structural unit derived from the cyclic olefin in the resulting copolymer is usually 1 to 80. %, Preferably 5 to 50 mol%, particularly preferably 10 to 45 mol%.

The olefinic copolymer obtained in the present invention may contain a structural unit derived from the above-mentioned polyene compound within the range not impairing the characteristics of the copolymer.

Conventionally, an olefin having a bulky structure such as a cyclic olefin has a lower reaction rate than an α-olefin when it is copolymerized with an α-olefin, and a copolymer having a desired composition. Was difficult to obtain.

As described above, according to the method for producing an olefin-based copolymer of the present invention, especially when an α-olefin and a cyclic olefin are copolymerized, the constitutional unit derived from the cyclic olefin is higher than in the conventional case. An olefin-based copolymer can be obtained.

The olefin copolymer having a high constitutional unit derived from such a cyclic olefin has a high glass transition temperature and thus is excellent in thermal deformability, and has a low crystallinity, and thus is a molded article having good transparency. Can be formed.

[0146]

As described above, according to the present invention, when an α-olefin and a cyclic olefin are copolymerized, an olefin copolymer having a large number of structural units derived from the cyclic olefin is provided. This makes it possible to further expand the uses of the olefin-based copolymer.

[0147]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0148]

Example 1 [Preparation of catalyst] 5 g of silica gel (F952 manufactured by Fuji Devison Co., Ltd.) calcined at 800 ° C. for 3 hours contained 2 mmol of cyclopentadienyl titanium trichloride CpTiCl _3.
It was put into a heptane solution of ml and mixed at 100 ° C. for 3 hours. The solid part was collected by filtration, washed several times with heptane, and then the solid part was dried under reduced pressure at 60 ° C. for 3 hours to obtain CpTiC.
An l ₃ / SiO ₂ catalyst was obtained.

The Ti content was 1.3% by weight. To measure the three-dimensional structure of the polymer obtained from the catalyst, the following polymerization was carried out.

25 ml of heptane was added to a reactor having an internal volume of 100 ml.
And 0.3 mol of propylene were charged, and then 1 mmol of methylaluminoxane (manufactured by Toyo Stoufer) in terms of aluminum atom and the above-mentioned CpTiCl ₃ / SiO.
Add 0.05 mmol of ₂ catalyst in terms of Ti atom to 40
Polymerization was carried out at 0 ° C for 2 hours. Polymerization was stopped by adding 10% hydrochloric acid methanol solution.

The polymer obtained was extracted with boiling o-dichlorobenzene for 10 hours in order to separate it from the SiO ₂ carrier. [Analysis] ¹³ C-NMR of the polymer is JEOL GX
-270, it measured at 67.20MHz and 120 degreeC. The sample for NMR measurement was a solution of a mixing bait with a 1,2,4-trichlorobenzene / d ₆ -benzene = 9/1 weight ratio, and the polymer concentration was 10% by weight or less.

The measurement results are shown in Table 1. [Copolymerization] Toluene 47 was placed in a reactor having an internal volume of 1 liter.
After charging 5.3 ml and 14.7 ml of tetracyclododecene, 10 mmol of methylaluminoxane (manufactured by Toyo Stopher) in terms of aluminum atom and the CpTiCl ₃ / SiO ₂ catalyst of 0.5 in terms of Ti atom. Mmol addition (catalyst synthesis carried out on a 10-fold scale), 40 ° C.
Then, ethylene was fed to the liquid phase part of the polymerization vessel at a rate of 10 liters / hour and nitrogen at a rate of 40 liters / hour for 1 hour for copolymerization.

The polymerization was stopped by adding a 10% hydrochloric acid methanol solution. The polymer obtained was extracted with boiling o-dichlorobenzene for 10 hours in order to separate it from the SiO ₂ carrier, and then the extract was put into methanol to precipitate the polymer, which was filtered and dried under reduced pressure. A polymer was obtained.

The ethylene composition of the obtained copolymer was 56.
It was 2 mol%.

[0155]

Example 2 Copolymerization was carried out in the same manner as in Example 1 except that propylene was fed at a rate of 50 liters / hour instead of ethylene and nitrogen was not fed to obtain a copolymer.

The propylene composition of the obtained polymer was 5
It was 8.2 mol%.

[0157]

[Table 1]

Claims (2)

[Claims] 1. When at least one transition metal compound selected from Ti, Zr, HF, Nb and Ta is contained and homopolymerization of propylene is carried out, the following requirements (a) and (b) are satisfied. In the presence of an olefin polymerization catalyst capable of providing polypropylene, a cyclic olefin represented by the following formula [I] and / or [II] and an α-olefin are copolymerized, and an olefin-based copolymerization (A) In the ¹³ C-NMR spectrum of the polypropylene, the peak intensities derived from Tββ, Tβγ, and Tαγ satisfy the following formula (i), and (b) The intensity ratio of Tβγ to Tαγ in the ¹³ C-NMR spectrum of the polypropylene is 2 or more; ... [I] (In the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a And R ^b are each independently
Represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ may combine with each other to form a monocyclic or polycyclic group, and The ring or polycyclic group may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group). [Chemical 2] ... [II] (In the formula [II], p and q are 0 or 1
The above integers, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon. A carbon atom to which R ⁹ and R ¹⁰ are bonded, and a carbon atom to which R ¹³ is bonded or a carbon atom to which R ¹¹ is bonded, which represent an atom or group selected from the group consisting of a group and an alkoxy group. May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n =
When m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring). 2. The following requirements (a) and (b) when a homopolymerization of propylene is carried out containing a vanadium compound.
An olefin characterized by copolymerizing a cyclic olefin represented by the above formula [I] and / or [II] with an α-olefin in the presence of an olefin polymerization catalyst capable of providing a polypropylene satisfying (A) In the ¹³ C-NMR spectrum of the polypropylene, the peak intensities derived from Tββ, Tβγ and Tαγ satisfy the following formula (i), and (b) The intensity ratio of Tβγ to Tαγ in the ¹³ C-NMR spectrum of the polypropylene is 6 or more.