JPH0680726A - Production of olefin copolymer - Google Patents

Abstract

PURPOSE:To obtain an olefin copolymer having excellent randomness of copolymerization and containing a larger amount of structural units derived from a polyene compound by copolymerizing an olefin with a polyene compound in the presence of a specified olefin polymerization catalyst. CONSTITUTION:An olefin is copolymerized with a polyene compound in the presence of an olefin polymerization catalyst which contains at least one transition metal compound (1) selected from among Ti, Zr, Hf, Nb and Ta compounds or contains a vanadium compound (2) and, when used in the homopolymerization of propylene, can give a polypropylene satisfying the requirements: (a) the intensities of peaks ascribable to Tbetabeta, Tbetagamma and Talphagamma in the <13> C-NMR spectrum of the polyprophlene satisfy the relationship of the formula and (b) the intensity ratio of Tbetagamma to Talphagamma in the above spectrum is 2 or higher when the catalyst contains compound (1) and is 2 or greater when the catalyst contains compound (2).

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
It represents the ratio of the number of times that a 2,1 addition reaction occurs after the addition reaction and another 2,1 addition reaction occurs, and the number of times that a 1,1 addition reaction occurs after that 1,2 addition reaction and then a 1,2 addition reaction occurs. It is a measure.

By the way, the present inventors have found that when propylene is polymerized using a certain catalyst, the resulting polypropylene has Tβγ / Tαγ of 2 or more as described above, and this catalyst is used to produce an olefin. The present invention has been completed by finding that an olefin / diene copolymer obtained by copolymerizing an olefin and a polyene at random can be obtained by copolymerizing a polyene compound.

[0006]

The present invention is excellent in randomness when an olefin and a polyene compound are copolymerized, and
An object of the present invention is to provide a method for producing an olefin copolymer using a unique olefin polymerization catalyst capable of producing an olefin copolymer having many constituent units derived from a polyene compound.

[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. Characterized in that the olefin and the polyene compound are copolymerized 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) In the ¹³ C-NMR spectrum of the polypropylene, the peak intensities derived from Tββ, Tβγ and Tαγ satisfy the following formula (i):

[0009]

[Equation 3]

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

[0011]

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" is sometimes 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 peculiar 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),

[0014]

[Equation 4]

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

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 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 occurs.

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. In other words, it can be said that inversion has hardly occurred.

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
(2,1) addition reaction followed by 2,1 (1,2) addition reaction, and then 1,2 (2,1) addition reaction for the number of times that the 2,1 (1,2) addition reaction continues 2 and 1
Immediately after the (1,2) addition reaction occurs, 1, ((2,2
1) It is considered as a parameter indicating the ratio to the number of times the addition reaction occurs.

In the above, since the peak intensity of Tαβ is theoretically almost the same as Tβγ, the requirement (a) is:

[0024]

[Equation 5]

Also, in the requirement (b), Tαγ of Tβγ
The intensity ratio with respect to can also be evaluated by the intensity ratio of Tαβ to Tαγ. In the present invention, Tαγ of Tβγ
The intensity ratio to is as follows.

When a catalyst containing at least one transition metal compound selected from Ti, Zr, Hf, Nb and Ta is used, it is 2 or more, preferably 4 or more, more preferably 5 or more. Yes, more preferably 6 or more, and particularly preferably 10 or more.

When a catalyst containing a vanadium compound is used, it is 6 or more, preferably 7 or more, more preferably 8 or more, further preferably 9
It is above, and especially preferably is 10 or above.

As described above, in the polypropylene obtained with a zirconocene or hafnocene-based catalyst, Tβγ
The ratio of the intensity of Tαγ to Tαγ is usually 1.5 or less. Therefore, the ratio of 1,2 addition reaction followed by 2,1 addition reaction and then 1,2 addition reaction is 2,1,
It is considered to be higher than the rate at which the addition reaction occurs.

Although there are apparent peaks attributed to Tβγ and Tαβ, the peaks attributed to Tαγ may be hidden by noise and may not be identified. In this case, Tαγ of Tβγ is not recognized. The intensity ratio to or the intensity ratio of Tαβ to Tαγ is considered to be ∞.

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

Such an olefin has 2 carbon atoms.
The above α-olefins can be mentioned. 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, 1-hexadecene, 1-octadecene, 1-eicosene and other straight-chain or branched C2-C20 α-olefins .

Further, as olefins, aromatic vinyl compounds such as styrene, methylstyrene, dimethylstyrene, chlorostyrene, allylbenzene, allyltoluene, vinylnaphthalene, allylnaphthalene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, methylvinyl. C7-C20 alicyclic vinyl compounds such as cyclohexane and allylnorbornane, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8
Examples thereof include silane-based unsaturated compounds such as -trimethylsilyl-1-octene and 10-trimethylsilyl-1-decene.

These α-olefins can be copolymerized with the polyene compound alone or in combination of two or more kinds. Of these, preferably, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl
Examples thereof include α-olefins having 2 to 10 carbon atoms such as -1-pentene, 3-methyl-1-pentene, 1-octene and 3-methyl-1-butene, and particularly preferably ethylene, propylene, 1- Butene, 1-pentene, 1-hexene, 4-methyl-1-
Mention may be made of pentene and 3-methyl-1-butene.

The polyene compound has 4 to 4 carbon atoms.
There may be mentioned 20 diene compounds, specifically,
Conjugated diene compounds such as butadiene and isoprene, 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 non-conjugated diene compounds, vinyl cyclohexene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, cyclooctadiene, 2,
5-norbornadiene, 1,4-divinylcyclohexane, 1,
3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5 -Diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-
Isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane,

[0035]

[Chemical 1]

[0036]

[Chemical 2]

[0037]

[Chemical 3]

[0038]

[Chemical 4]

Examples thereof include cyclic polyene compounds such as, and aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene.

These polyene compounds can be used alone or in combination of two or more.

Of these, preferably 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4 -Hexadiene, 7-methyl-1,6-octadiene, ethylidene norbornene, vinyl norbornene, etc., having 5 to 12 carbon atoms
The diene compound can be mentioned.

In the present invention, when copolymerizing the above-mentioned olefin and polyene compound, a preferable combination is ethylene and ethylidene norbornene,
Ethylene and propylene and ethylidene norbornene, ethylene and propylene and vinyl norbornene, ethylene and 1,
5-hexadiene, ethylene and 1,7-octadiene, ethylene and 1,9-decadiene, propylene and 1,9-decadiene, propylene and ethylidene norbornene, hexene-1 and 4-methyl-1-pentene and 7-methyl-1. A combination of 6,6-octadiene and the like can be mentioned.

In the present invention, when copolymerizing an olefin and a polyene compound, the polyene compound is usually used in an amount of 0.01 to 99 mol, preferably 0.1 to 90 mol, and more preferably 0 to 1 mol of the olefin. .5-8
It is desirable to use it at a ratio of 0 mol.

Further, to the extent that the object of the present invention is not impaired,
A cyclic olefin may be copolymerized.

In the method for producing an olefin copolymer according to the present invention, the above-mentioned copolymer is produced by using an olefin polymerization catalyst capable of producing a polypropylene having a unique three-dimensional structure as described above. Do it.

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.

Further, a compound in which the titanium atom of the above titanium compound is replaced by zirconium or hafnium can also be used, and a niobium compound or tantalum compound similar to the above titanium compound can also be used.

Further, examples of the vanadium compound include compounds obtained by replacing the titanium atom of the titanium compound with a vanadium atom, and compounds represented by the formula VO (OR) _a X _b or the formula VO (OR) _c X _d. it can. (However, in the above formula, R is a hydrocarbon group, and 0 ≦ a ≦ 3, 0 ≦ b
≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦
c + d ≦ 4. ) Examples of such vanadium compounds, VOCl _{3,
VO (OC 2 H 5) Cl} 2, VO (OC 2 H 5) 2 Cl 2, VO
_{(O-iso-C 3 H} 7) Cl 2, VO (O-n-C 4 H 9) Cl 2, V
O (OC ₂ H ₅ ) ₃ , VOBr ₂ , VOCl ₂ , VO (O-n-
_{C 4 H 9) 3, VCl} 3 · 2 (OC 8 H 17 OH) can be exemplified vanadium compounds such as.

The nonmetallocene-based 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 metals of groups I to III 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 the above (1) 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.

As a compound similar to (1), an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can be mentioned. 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
Examples of the organosilicon compound represented by the general formula [Ia] include trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyl Diethoxysilane, bis
o-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, 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, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyl Triacetoxysilane, 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. Yes, R ¹
Examples of the cyclopentyl group include a cyclopentyl group having an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, and a 2,3-dimethylcyclopentyl group.

In the formula [IIa], R ² is either 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-based 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, 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 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-based transition metal compound supported per 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 having 2 or more carbon atoms is 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

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 -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, for example, by using 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 in 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 methoxy group, ethoxy group and butoxy group, and examples of the aryloxy group include 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 bonded 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) methyl titanium monochloride, bis (cyclopentadienyl) ethyl titanium monochloride, bis (cyclopentadienyl) cyclohexyl titanium monochloride,
Bis (cyclopentadienyl) phenyltitanium monochloride, bis (cyclopentadienyl) benzyltitanium 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) thi Um phenoxy cycloalkyl chloride, bis (fluorenyl) titanium dichloride.

Further, at least two ligands having a cycloalkadienyl skeleton in which M is titanium are contained, and the ligands having at least two cycloalkadienyl skeletons are 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) titanium ethoxymonochloride, 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,
Cyclopentadienyldicyclohexyltitanium monochloride, cyclopentadienyldiphenyltitanium monochloride, cyclopentadienyldibenzyltitanium monochloride, methylcyclopentadienyltitanium trichloride, t-butylcyclopentadienyltitanium trichloride, indenyl Titanium trichloride, indenyl titanium tribromide, cyclopentadienyl titanium trimethyl, cyclopentadienyl titanium triphenyl, cyclopentadienyl titanium tribenzyl, cyclopentadienyl titanium methoxydichloride, cyclopentadienyl titanium ethoxydichloride, methyl Cyclopentadienyl titanium ethoxy dichloride, Cyclopentadienyl titanium phenoxydi Lolide, fluorenyl titanium trichloride, cyclopentadienyl methyl titanium dibromide, cyclopentadienyl ethyl titanium dibromide, cyclopentadienyl phenyl titanium dibromide, cyclopentadienyl benzyl titanium dibromide, cyclopentadienyl neo Pentyl titanium dibromide, methylcyclopentadienyl titanium dibromide hydride, indenyl titanium dibromide monohydride, cyclopentadienyl dimethyl titanium monobromide, cyclopentadienyl diethyl titanium monobromide, cyclopentadienyl dicyclohexyl titanium monobromide, Cyclopentadienyldiphenyltitanium monobromide, cyclopentadienyldibenzyltitanium monobromide Lromide, methylcyclopentadienyl titanium tribromide, t-butyl cyclopentadienyl titanium tribromide, indenyl titanium tribromide, cyclopentadienyl titanium trimethyl, cyclopentadienyl titanium triphenyl, cyclopentadienyl titanium tribenzyl , Cyclopentadienyltitanium methoxydibromide, cyclopentadienyltitanium ethoxydibromide, methylcyclopentadienyltitanium ethoxydibromide, cyclopentadienyltitaniumphenoxydibromide, fluorenyltitanium tribromide.

In the metallocene compound as described above, a compound in which titanium is replaced by 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, biscyclopentadienylbromooxovanadium, ethylenebisindenyldichlorovanadium, ethylenebisindenyldibromovanadium, ethylenebisindenylchlorooxovanadium, ethylenebisindenylbromooxovanadium, dimethylsilylene Biscyclopentadienyl dichlorovanadium, dimethylsilylene biscyclopentadienyl chlorooxo vanadium, etc.

As a method for preparing the catalyst 2, a method of loading on a carrier as exemplified in the catalyst 1 can be mentioned as a preferable example. Examples of the organometallic compound used for preparing the catalyst 2 include the same compounds as the organometallic compounds used for preparing the catalyst 1 described above,
Of these, it is preferable to use aluminoxanes.
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.

In the present invention, an olefin-based copolymer is obtained by copolymerizing an α-olefin having 2 or more carbon atoms in the presence of the catalyst 2 as described above. The polymerization of α-olefin using the catalyst 2 usually takes the form of solution polymerization or solution polymerization.

As the reaction solvent for the polymerization, an inert hydrocarbon may be used, or an olefin which is liquid at the reaction temperature may be used. Examples of the inert hydrocarbon medium used at this time include the same as the above-mentioned inert hydrocarbon medium.

In the polymerization system, the catalyst 2 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

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 olefin and the polyene compound are copolymerized by the above-mentioned method for producing an olefin-based copolymer, the constitutional unit derived from the olefin in the obtained copolymer is usually 1 to 99.9 mol. %, Preferably 10 to 99 mol%, more preferably 30 to 97 mol%, particularly preferably 50 to 97 mol%, and the structural unit derived from the polyene compound is usually 0.1 to 99 mol%, preferably 1 to 99 mol%. 90 mol%, more preferably 3 to 70 mol%, and particularly preferably 3 to 50 mol%.

When a cyclic diene compound is used as a polyene compound and copolymerized with an olefin, the structural unit derived from the olefin is usually 1 in the resulting copolymer.
0 to 99.9 mol%, preferably 40 to 99 mol%, more preferably 50 to 97 mol%, particularly preferably 50.
˜95 mol%.

The olefin-based copolymer obtained in the present invention may contain a structural unit derived from a cyclic olefin as described above within a range that does not impair the characteristics of the copolymer.

Conventionally, a polyene compound having a bulky structure such as a cyclic polyene compound has a low reaction rate as compared with an olefin when it is copolymerized with an olefin, and a copolymer having a desired composition is obtained. Was difficult.

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

The olefinic copolymer having a high constitutional unit derived from such a cyclic polyene compound has a high glass transition point and can form a molded product excellent in heat resistance. Further, when the olefin-based copolymer obtained in the present invention is obtained by copolymerizing an olefin and an aliphatic polyene compound, the copolymer is excellent in randomness and a molded article excellent in elongation at break. Can be formed. Such an olefin-based copolymer can be used for applications such as an elastomer and a material for improving impact resistance.

[0102]

As described above, according to the present invention, by copolymerizing an olefin and a polyene compound in the presence of a specific catalyst for olefin polymerization, excellent randomness can be obtained and a derivative derived from the polyene compound can be obtained. It becomes possible to provide an olefin-based copolymer having a large number of constituent units, and the use of the olefin-based copolymer can be further expanded.

[0103]

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

[0104]

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. In order to investigate the three-dimensional structure of polypropylene obtained using the catalyst obtained as described above, 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 mixed solvent of 1,2,4-trichlorobenzene / d ₆ -benzene = 9/1 weight ratio, and the polymer concentration was 10 weight% or less.

The measurement results are shown in Table 1. [Copolymerization] Toluene 500 in a reactor with an internal volume of 1 liter
ml and 1,7-octadiene (20 ml) were added, and then 10 mmol of methylaluminoxane (manufactured by Toyo Stoffer) in terms of aluminum atom and the above CpTiCl ₃ / S.
An iO ₂ catalyst (catalyst synthesis was carried out on a 10-fold scale) was added in an amount of 0.5 mmol in terms of Ti atom, and propylene was added at 60 liters / hour and ethylene at 40 liters / hour at 40 ° C.
The liquid phase part of the polymerization vessel was fed at a rate of time for 2 hours to carry out copolymerization. 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. It was 7 when the iodine value in the obtained copolymer was measured.

[0110]

Example 2 [Copolymerization] Toluene 47 was placed in a reactor having an internal volume of 1 liter.
7.4 ml and 5-ethylidene-2-norbornene 22.6
After charging 1 ml, 10 mmol of methylaluminoxane (manufactured by Toyo Stoufer) in terms of aluminum atom and 0.5 mmol of CpTiCl ₃ / SiO ₂ catalyst in terms of Ti atom were added (catalyst synthesis was 10 times (Implemented on a scale)
10 liter / hour of ethylene and 4 nitrogen at 40 ° C
Copolymerization was carried out by feeding the liquid phase part of the polymerization vessel at a rate of 0 liter / hour for 1 hour.

Polymerization was stopped by adding a 10% hydrochloric acid methanol solution. The polymer obtained was extracted with boiling o-dichlorobenzene for 10 hours to separate it from the SiO ₂ carrier, and then the extract was poured into methanol to precipitate the polymer, which was filtered and dried under reduced pressure to obtain a co-polymer. Got united.

IR measurement of the obtained copolymer gave 1
Strong absorption due to double bond at 680 cm ^-1 , 970c
m ^-1 , 1025 cm ^-1 , 1070 cm ^-1 and 1200 cm ^-1
Strong cyclic methylene-based absorption was observed.

[0113]

Example 3 [Copolymerization] Copolymerization was carried out in the same manner as in Example 2 except that propylene was fed at a rate of 50 liters / hour instead of ethylene and nitrogen was not supplied.

As a result of IR measurement of the obtained copolymer, 1
Strong absorption due to double bond at 680 cm ^-1 , 970c
m ^-1 , 1025 cm ^-1 , 1070 cm ^-1 and 1200 cm ^-1
A strong absorption based on cyclic methylene was observed.

[0115]

[Table 1]

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08F 236/00 MPK 8416-4J

Claims (2)

[Claims] 1. When at least one kind of 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. A method for producing an olefin-based copolymer, which comprises copolymerizing an olefin and a polyene compound in the presence of an olefin polymerization catalyst capable of providing polypropylene; (a) in a 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. 2. The following requirements (a) and (b) when a homopolymerization of propylene is carried out containing a vanadium compound.
A method for producing an olefin-based copolymer, which comprises copolymerizing an olefin and a polyene compound in the presence of a catalyst for olefin polymerization capable of providing a polypropylene satisfying the following: (a) ¹³ C-NMR of the polypropylene In the spectrum, 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.