JPH0517522A - Alpha-olfein polymer - Google Patents

Abstract

PURPOSE:To obtain an a-olefin polymer having a specific steric structure in which the NMR spectral value is within a constant range by polymerizing alpha-olefin in the presence of a catalyst composed of a specific transition metallic component and an organometallic compound for polymerization. CONSTITUTION:An alpha-olefin polymer is obtained by polmerizing a >=13Calpha-olefin such as propylene or 1-butene in the presence of a catalyst composed of (A) a transition metallic compound composed of Ti, Zr, Hf, Nb and/or Ta and (B) an organometallic compound such as triethylaluminum for polymerizing the alpha-olefin. The aforementioned alpha-olefin polymer satisfies 1.6<Tbetagamma/Talphagamma<6 or 1.6<Talphabeta/Talphagamma<6 in a 13C-NMR spectrum and has a specific steric structure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an α-olefin polymer, and more particularly to an α-olefin polymer having a unique steric structure.

[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. (Tβγ + Tαγ) and (Tββ + 2Tβ observed in the ¹³ C-NMR spectrum of polypropylene obtained by using
The intensity ratio of γ + Tαγ) is almost zero. That is, there is almost no inversion, and thus there is almost no heterologous binding. Further, as a catalyst for producing polypropylene, a catalyst system composed of zirconocene or hafnocene and aluminoxane is also known, but in polypropylene obtained by using such a known metallocene catalyst, the ratio is about 0.01 or less. It is known that there is a heterologous bond.

As a result of intensive studies on such a peculiar structure of polypropylene, the present inventors will find out the details later, but the peak intensity ratio derived from Tβγ and Tαγ observed in the ¹³ C-NMR spectrum of the polypropylene. It has been found that the occurrence ratio can be defined for two types of inversion occurrence patterns.

According to such an analysis, the ratio of Tβγ to Tαγ in polypropylene obtained by using the above-mentioned known metallocene catalyst is usually 1.5 or less. Polypropylene is used in various applications depending on its three-dimensional structure. Therefore, providing polypropylene having a unique three-dimensional structure leads to further expansion of applications of polypropylene.

This applies not only to polypropylene but also to other α-olefin polymers.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and it is made of Ti-based, Zr-based, Hf-based and N-based materials.
It is an object of the present invention to provide an α-olefin polymer having a unique three-dimensional structure, which has hitherto not been obtained with a b-based catalyst or a Ta-based catalyst.

[0007]

SUMMARY OF THE INVENTION The α-olefin polymer according to the present invention is
In the presence of an olefin polymerization catalyst composed of at least one transition metal compound selected from Ti, Zr, Hf, Nb and Ta, and an organometallic compound, α having 3 or more carbon atoms is used.
-A polymer obtained by polymerizing an olefin, which is characterized by satisfying the following requirements.

(A) ¹³ C--N of the α-olefin polymer
In the MR spectrum, 1.6 <Tβγ / Tαγ <6
Alternatively, 1.6 <Tαβ / Tαγ <6.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The α-olefin polymer according to the present invention will be specifically described below. The α-olefin polymer according to the present invention comprises Ti, Zr, Hf, Nb and Ta.
It is a polymer obtained by polymerizing an α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst composed of at least one transition metal compound selected from the group consisting of an organometallic compound. As the α-olefin having 3 or more carbon atoms, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-
Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1
-Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1
-Pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. To branched C3-C20 α-olefins; styrene, dimethylstyrenes, allylbenzene,
Aromatic vinyl compounds such as allyltoluenes, vinylnaphthalenes, and allylnaphthalenes, alicyclic vinyl compounds such as vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, and allylnorbornane, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl -1-butene, 6-trimethylsilyl-1-hexene, 8-
Trimethylsilyl-1-octene, 10-Trimethylsilyl-
Silane-based unsaturated compounds such as 1-decene, cyclopentene,
Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene And other cyclic olefins.

Preferably, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-
Examples thereof include olefins having 3 to 8 carbon atoms such as 1-pentene, 1-octene and 3-methyl-1-butene, and propylene is particularly preferable.

The α-olefin polymer according to the present invention satisfies the requirement (a). The requirement (a) is that the intensity ratio of Tβγ to Tαγ is 1.6 to 6, or the intensity ratio of Tαβ to Tαγ is 1.6 to 6.

The requirement (a) required for the α-olefin polymer according to the present invention is calculated based on the measurement result of ¹³ C nuclear magnetic resonance spectrum according to the following method. That is, a polymer concentration of 10% by weight or less, preferably 5% by weight of 1,2,
It is determined by using a mixed solution of 4-trichlorobenzene / d ₆ -benzene = 9/1 weight ratio and measuring at 67.20MHz, 120 ° C. As a measuring device, for example, JE manufactured by JEOL Ltd.
An OL-GX270 NMR measuring device is used.

The analysis of the NMR spectrum was conducted by Linden Mann Adams (Analysis Chemistry 43 , p1245 (197
1)) was basically assigned. Next, regarding each requirement, the case of polypropylene will be described as an example.

The peak appearing at 30 to 32 ppm is represented by Tβγ and 35
The peak appearing at ˜38 ppm was assigned to Tαβ, and the peak appearing at 38-40 ppm was assigned to Tαγ.

This requirement (a) is a parameter proposed by the present inventors to define the special structure of the α-olefin polymer. Intensity ratio of Tβγ to Tαγ (Tβ
γ / Tαγ) is 2, (2,1) addition reaction followed by 2,
After the 1 (1,2) addition reaction has taken place,
The number of 1 (1,2) addition reactions and 1,2 (2,2
1) It is considered as a parameter indicating the ratio of the number of times the 1,2 (2,1) addition reaction occurs after the 2,1 (1,2) addition reaction following the addition reaction.

Further, in the present invention, Tαγ of Tβγ
It is desirable that the intensity ratio of Tαβ to Tαγ or the intensity ratio of Tαβ to Tαγ is 1.6 to 6, preferably 2 to 6, and particularly preferably 4 to 6.

It should be noted that while there are apparent peaks attributed to Tβγ and Tαβ, peaks that should be attributed to Tαγ may be hidden by 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 ∞.

The peak intensity of Tαβ is theoretically Tβγ
Is almost the same value as Tαβ / Tαγ value and Tβγ / Tα
The γ value is the same value. In known zirconocene and hafnocene-based catalysts, the strength ratio of Tβγ to Tαγ is generally
1.5 or less, so that 1,2 addition reaction is followed by 2,
It is considered that the rate of returning to the 1,2 addition reaction again after the 1 addition reaction occurs is higher than the rate of the 2,1 addition reaction. Also, for polypropylene generally obtained with a vanadium-based catalyst, the ratio of returning to the 2,1 addition reaction after the 1,1 addition reaction following the 2,1 addition reaction is
It is considered to be higher than the rate of returning to the 1,2 addition reaction.

Further, one of the α-olefin polymers according to the present invention
The intrinsic viscosity [η] of all polymers measured in decalin at 35 ° C. is 0.001-30 dl / g, preferably 0.01-10 d
1 / g, particularly preferably 0.05 to 5 dl / g.
The same applies especially when the α-olefin polymer is polypropylene.

The isotactic index (II) represented by the boiling heptane extraction residue of the α-olefin polymer according to the present invention is not particularly limited, but preferably 40
% Or less, more preferably 25 to 0%. The same applies especially when the α-olefin polymer is polypropylene.

The molecular weight distribution of the α-olefin polymer according to the present invention is 2 or more, preferably 3 or more, more preferably 4 or more, particularly preferably 4 or more in the value of Mw / Mn measured by GPC. Is 5 or more. G
The measurement of PC was carried out using a mixed polystyrene gel column (10 ⁶ -10 ³ Å
pore size) using, for example, Water Associates model ALC / GPC 150C.
It can be carried out at 135 ° C. using dichlorobenzene as a solvent.

Next, the method for producing the α-olefin polymer according to the present invention will be described. The olefin polymerization catalyst used for producing the α-olefin polymer according to the present invention,
It is composed of at least one transition metal compound selected from Ti, Zr, Hf, Nb and Ta, and an organometallic compound.

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").

The catalysts 1 and 2 will be described below. The α-olefin polymer according to the present invention is the same as the catalyst 1 described above.
Alternatively, it includes not only the α-olefin polymer produced by using 2, but also the α-olefin polymer produced by another catalyst system included in the above-mentioned catalyst category.

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 compounds, specifically, TiCl ₄ , TiBr ₄ ,
Tetrahalogenated titanium such as TiI ₄ , Ti (OCH ₃ ).
Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ ,
Trihalogenated alkoxytitanium such as 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 , T
i (OC ₂ H ₅ ) ₂ Br ₂ and other dihalogenated dialkoxy titanium, Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (On
_{-C 4 H 9) 3 Cl,} Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br, Ti (OCH 3) 4} , Ti (OC 2
_{H 5) 4, Ti (On} -C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4,
Examples thereof include tetraalkoxy titanium such as Ti (O-2-ethylhexyl) ₄ .

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.

The metallocene-based transition metal compound as described above may be used after being brought into contact with an electron donor as 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 copolymers, MgCl ₂ , Mg (O
H) ₂ , MgCO ₃ , Mg (OEt) ₂ , and magnesium stearate. Among these carrier compounds,
Preferable examples include SiO ₂ , Al ₂ O ₃ , MgO, ZnO and ZnO ₂ .

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 hydrocarbon groups containing usually 1 to 15, preferably 1 to 4 carbon atoms, and these are X may represent 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. General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably a number of 1.5 ≦ m ≦ 3), 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. Dialkylaluminum alkoxides such as aluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, partially alkoxylated alkyls having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 Aluminum; Dialkyl aluminum such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide Alkyl aluminum sesquihalide such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated such as ethyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Alkyl aluminum; dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminium dihydrides such as ethylaluminum dihydride, propylaluminium dihydride; partially alkoxylated and partially aluminum aluminum ethoxy chlorides, butyl aluminum butoxycyclolides, ethyl aluminum ethoxy bromides Mention may be made of halogenated alkylaluminums.

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 compounds include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (C ₄ H ₉ ) ₂ AlO.
Al (C ₄ H ₉ ) ₂ ,

[0033]

[Chemical 1]

In addition to the above, aluminoxane such as methylaluminoxane can be used. (2) above
Examples of the compounds belonging to the category include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

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 necessary 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; pyridine, methylpyridine,
Pyridines such as ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine and pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,
Cyclic oxygenated compounds such as 4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and ditedropyran; methanol, ethanol, propanol, pentanol, Hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; even if it has a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol Good C6-20 phenols; acetone, methyl ethyl ketone, methyl isobutyl ketone,
Acetophenone, benzophenone, acetylacetone,
C3-C15 ketones such as benzoquinone; C2-C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; 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, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate Propyl acid, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, anise Methyl, n-butyl maleate, diisobutyl methylmalonate, din-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di2-phthalate C2-C2 such as ethylhexyl, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethyl carbonate
30 organic acid esters; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and other acid halides having 2 to 15 carbon atoms; 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-
Diethers such as butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide Nitriles such as acetonitrile, benzonitrile and tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride are used.

Further, as the electron donor, an organosilicon compound represented by the following general formula [Ia] can be used. R _n Si (OR ') in _4-n ... [Ia] [wherein, R and R' is a hydrocarbon group, 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. Is a group selected from the group consisting of, 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, and R ¹ is, in addition to the cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 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-mentioned 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 may be supported on the carrier compound by a simple contact method, a method of mixing with heating, or 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-based transition metal compound thus obtained can be contact-treated with an organometallic compound prior to polymerization.

The amount of the nonmetallocene-based transition metal compound supported per gram of the carrier compound is generally 0.01-10.
It is 0 mmol, preferably 0.01 to 50 mmol, and 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 a quantity ratio of ˜1000, preferably 1 to 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 1 to 10 mol per mol of the transition metal atom.

The α-olefin polymer according to the present invention can be obtained by polymerizing an α-olefin having 3 or more carbon atoms such as propylene in the presence of the above catalyst 1.

Polymerization of α-olefin using the catalyst 1 is usually carried out in a gas phase, solution polymerization or slurry state. When the polymerization takes a reaction form of slurry polymerization or solution polymerization, an inert hydrocarbon can be used as a reaction solvent, or an olefin which is liquid at the reaction temperature can be used.

Specific examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; 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 0.000 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. 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, based on 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, it is about -50 to 200 ° C, preferably about 20 to 100 ° C, and the pressure is usually normal pressure to 100 kg / cm ² , preferably about 2 to 2.
It is set to 50 kg / cm ² . Polymerization is batch type, semi-continuous type,
It can be carried out by any of the continuous methods. 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+ (ESR) / Ti (} total) after adsorbing the pyridine vapor to the catalyst component 0.1, preferably Can be evaluated by being 0.2 to 1, particularly preferably 0.5 to 1.

The ESR is measured, for example, by the Varian E-12 type.
Using an ESR measuring device, it is performed in a quartz tube with an inner diameter of 3 mm at room temperature at a modulation frequency of 100 KHz. At this time, 1,1-diphenyl-2-picrylhydrazine (DPPH) and 2 were used as reference substances for the determination of the trivalent titanium atom and the determination of the g value.
MnO doped with valent Mn ions is used, respectively.

In the conventional catalyst system, it was confirmed that a large amount of clusters were formed in the polymerization system. However, in the catalyst system using the catalyst 1 as described above, whether clusters are formed or not, Or, if formed, it is very small. When the α-olefin is polymerized with a catalyst system in which such clusters are difficult to form, an α-olefin polymer having a peculiar three-dimensional structure is obtained, although the reason is not clear.

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, Zr, Hf, Nb and Ta, and L is coordinated with the transition metal). At least one L is a ligand having a cycloalkadienyl skeleton, and L 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, 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, 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 ).

The metallocene compound has the formula R ² _k R ³ _l R
⁴ _m R ⁵ _n 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 two cycloalkadienyl skeletons Is bound through lower alkylene such as ethylene and propylene, and R ⁴ and R ⁵ are groups having a cycloalkadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, 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) 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-tetrahydro-1-indenyl) dimethyltitanium, ethylenebis (4,5,6,7-tetrahydro-1-) Indenyl) methyltitanium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydro-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.

Further, in the metallocene compound as described above, a compound in which titanium is replaced with zirconium or hafnium can be used. Further, a niobium compound or a tantalum compound similar to the above titanium-based metallocene compound can be similarly used. The metallocene compound as described above may be used after being brought into contact with an electron donor in advance.

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, but among them, aluminoxane is preferably 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, if desired, is not particularly limited, but with respect to 1 mol of the transition metal atom,
It is desired to be 0.1 to 100 mol, preferably about 1 to 10 mol.

As a method of preparing the catalyst 2, a method of supporting on a carrier as exemplified in the catalyst 1 can be mentioned as a preferable example. The α-olefin polymer according to the present invention is obtained by polymerizing an α-olefin having 3 or more carbon atoms such as propylene 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 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 0.001 to 0.001 in terms of transition metal atoms per liter of polymerization volume.
It is used in an amount of 50 mmol, preferably about 0.01-10 mmol. 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, based on 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, it is set to about 20 to 200 ° C, preferably about 50 to 100 ° C. 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.

The α-olefin polymer obtained by using the catalyst 1 or 2 as described above has the peculiar three-dimensional structure as described above. The α-olefin polymer according to the present invention, which has such a unique three-dimensional structure, is expected to be used as an elastomer because it is superior in transparency and elongation at break as compared with the conventional α-olefin polymer.

[0074]

As described above, according to the present invention, an α-olefin polymer having a unique three-dimensional structure, which has not been obtained by the conventional Ti-based, Zr-based, Hf-based, Nb-based, and Ta-based catalysts. Can be provided, and the applications of the α-olefin polymer can be further expanded.

[0075]

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

[0076]

Example 1 [Preparation of catalyst] 3 g of silica gel (F952 manufactured by Fuji Devison Co., Ltd.) calcined at 800 ° C. for 3 hours was put into a 20 ml heptane solution containing 20 mmol of titanium tetrachloride and mixed at room temperature for 3 hours. did. 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,
A TiCl ₄ / SiO ₂ catalyst was obtained.

The Ti content was 2.2% by weight. [Polymerization] Purified hexane 5 in a reactor with an internal volume of 1 liter
After charging 00 ml, 2 mmol of triethylaluminum and 0.5 mmol of the above TiCl ₄ / SiO ₂ catalyst in terms of Ti atom were added in a propylene atmosphere at 40 ° C. (catalyst synthesis was carried out on a 10-fold scale). Polymerization was carried out by feeding propylene at a rate of 150 liters / hour to the liquid phase part of the polymerization vessel at 2 ° C for 2 hours.

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, dried under reduced pressure and dried. Got united. [Analysis] ¹³ C-NMR of the polymer is JEOL GX
-270, it measured at 67.20MHz and 120 degreeC. NM
The R measurement sample 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 Tβγ / Tαγ value was 4.5.

[0080]

[Comparative Example 1] [Catalyst preparation] 200 ml glass flask equipped with a stirrer
Add 50 ml of tetrahydrofuran (THF) to the rusco,
5.43 g of 1,2-bis (1-indenyl) ethane (Et
(Ind) ₂) Was charged and cooled to -20 ° C. Next
26.3 ml of n-butyllithium kept at -20 ° C at
(1.6M hexane solution) was added dropwise over 30 minutes.
Furthermore, it stirred at -20 degreeC for 1 hour. By the above process,
Et (Ind)₂The dilithium salt of

Then, another 200 ml glass flask was charged with 60 ml of THF and cooled to -20 ° C. To the THF in this flask was slowly added 4.9 g of ZrCl ₄ . After the addition was completed, the temperature was raised to 60 ° C, and at this temperature 1
Stir for hours to dissolve ZrCl ₄ . The dilithium salt prepared above was added dropwise to the ZrCl ₄ / THF solution over 30 minutes, and the reaction was carried out at 60 ° C. for 1 hour. The reaction solution was then cooled to room temperature with stirring for 24 hours. THF was distilled off, and the residue was washed with methanol to obtain ethylenebis (indenyl) zirconium dichloride. [Coupling] A stainless reactor having an internal volume of 2 liter equipped with a stirrer was charged with 500 ml of toluene, 250 ml of propylene and 10 mmol of methylaluminoxane in terms of Al source at room temperature. 1 × 10 ⁻³ mmol of ethylenebis (indenyl) zirconium dichloride was added, and the temperature was raised to 50 ° C. to initiate polymerization. After reacting for 1 hour,
The reaction was stopped by adding a small amount of methanol. All products were poured into a large amount of methanol. The obtained powdery polymer was collected by filtration and vacuum dried at 80 ° C. for 12 hours.

The Tβγ / Tαγ value was 1.0.

Claims (2)

[Claims] 1. An α-olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst comprising at least one transition metal compound selected from Ti, Zr, Hf, Nb and Ta and an organometallic compound. An α-olefin polymer which is a polymer obtained by polymerization and which satisfies the following requirements: (a) In the ¹³ C-NMR spectrum of the α-olefin polymer, 1.6 <Tβγ / Tαγ <6 or 1.6
<Tαβ / Tαγ <6. 2. An α-olefin according to claim 1, wherein the α-olefin having 3 or more carbon atoms is propylene.
Olefin polymer.