JPH04142309A - Production of alpha-olefin copolymer - Google Patents

Abstract

PURPOSE:To obtain an alpha-olefin copolymer having specified properties by copolymerizing at least two monomers selected from among ethylene, a 3C or higher alpha-olefin and a diene compound in the presence of a specified olefin polymerization catalyst. CONSTITUTION:An olefin polymerization catalyst which, when used in the homopolymerization of propylene, can give a polypropylene wherein the intensity ratio between Tbetagamma and Tbetabeta in the <13>C-NMR spectrum is 0.001 or above, and the intensity ratio between Tbetagamma and Talphagamma or the intensity ratio between Talphabeta and Talphagamma is 2 or above, is prepared. An example of the catalyst is one comprising a compound of a transition metal such as Ti or Hf (e.g. TiCl4) and an organometallic compound (e.g. triethylaluminum). At least two monomers selected from among ethylene, a 3C or higher alpha-olefin (e.g. propylene) and a diene compound (e.g. 1,3-butadiene) are copolymerized in the presence of this catalyst to obtain an alpha-olefin copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing an α-olefin copolymer, and more particularly, to a method for producing an α-olefin copolymer using an olefin polymerization catalyst capable of providing polypropylene having a unique steric structure. -Regarding a method for producing an olefin copolymer.

Technical Background of the Invention Conventionally, titanium-based catalysts consisting of titanium compounds and organic aluminum have been known as catalysts for producing α-olefin polymers, such as polypropylene. Tβγ observed in the C-NMR spectrum of the resulting polypropylene
The intensity ratio of Tββ and Tββ is approximately 0. Also, a catalyst system consisting of zirconocene or hafnocene and aluminoxane is also known as a catalyst for producing polypropylene, and the ratio of Tβa to Tar of polypropylene obtained using such a known catalyst is 1.5 or less. be.

In addition, the ratio of Taβ to Tay of polypropylene obtained by polymerizing propylene using a known vanadium-based catalyst consisting of a vanadium compound and an organoaluminum compound is 1.5 or less.

Polypropylene is used for various purposes depending on its three-dimensional structure, and therefore, providing polypropylene having a three-dimensional structure that did not previously exist will lead to further expansion of the uses of polypropylene.

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

By using such an olefin polymerization catalyst not only for the polymerization of propylene but also for the polymerization or copolymerization of other polymerizable monomers, it is possible to obtain polymers with unique physical properties that did not previously exist. Based on this knowledge, we have completed the present invention.

Purpose of the Invention The present invention has been made in view of the prior art as described above, and is a polypropylene that is obtained using a catalyst for olefin polymerization that provides polypropylene with unique stereoregularity and has unique physical properties. The object of the present invention is to provide a method for producing an α-olefin copolymer having the following properties.

Summary of the Invention The method for producing an α-olefin copolymer according to the present invention satisfies the following requirements (a) when propylene is homopolymerized.
) to (b) in the presence of an olefin polymerization catalyst capable of providing polypropylene, at least two polymerizable monomers selected from the group consisting of ethylene, an α-olefin having 3 or more carbon atoms, and a diene compound. (a) The intensity ratio of Tβγ to Tββ in the 13C-NMR spectrum of the α-olefin polymer is 0.00.
(b) The intensity ratio of Tay to Tay in the 13C-NMR spectrum of the α-olefin polymer is 2 or more, or the intensity ratio of Tαβ to Tay is 2 or more.

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

In the present invention, the term "polymerization" is sometimes used to include not only homopolymerization but also copolymerization.

In the method for producing an α-olefin copolymer according to the present invention, the olefin polymerization catalyst used is a catalyst that can provide polypropylene having a three-dimensional structure that has not been previously obtained when propylene is homopolymerized. .

Here, polypropylene having a conventionally unobtainable steric structure means that it satisfies at least the following requirements (a) to (b).

(a) The intensity ratio of Tβγ to Tββ in the C-NMR spectrum of the α-olefin polymer is 0.001
(b) The intensity ratio of Tβγ to Tay in the 13C-NMR spectrum of the α-olefin polymer is 2 or more, or the intensity ratio of Tαβ to Tay is 2 or more.

Requirements required for the α-olefin polymer according to the present invention (
A) and (b) are calculated based on the measurement results of 13c nuclear magnetic resonance spectra according to the following method.

That is, using a mixed solution with a polymer concentration of 10% by weight or less, preferably 5% by weight, and a weight ratio of 1.24-trichlorobenzene/d,-benzene = 971, 67, 20MHz,
Determined by measuring at 120°C. As a measuring device, for example, JEOL-GX270 manufactured by JEOL Ltd.
An NMR measuring device is used.

Analysis of NMR spectra is based on the proposal of υNdenman Adams (Analysis Ct + emission 43
．． p1245 (1971)).

Next, each requirement will be described using the case of polypropylene resin as an example.

Tay the peak appearing at 30-32 ppm, 28-3
The peaks appearing at 0 ppm were assigned to Tββ.

In addition, the peak appearing at 35 to 38 ppm is T4β, and 38 to 4
The peaks appearing at 0 ppm were assigned to Tαγ.

Intensity ratio of Tay to Tββ or Taβ to Ta
In general, the intensity ratio to g is the rate at which a 2,1 addition reaction occurs following a 1,2 addition reaction that occurs two or more times in succession,
It is considered to be a measure that indicates the rate at which a 1,2 addition reaction occurs following a 21 addition reaction that occurs two or more times in succession. In the present invention, the intensity ratio of Tβγ to Tag is 0.00.
It is 1 or more, preferably 0.05 or more, more preferably 0.10 or more, particularly preferably 0.15 or more.

In addition, the intensity ratio of Ta7 to Tαγ is 2. following the 12-addition reaction. As a measure of the rate at which the 2.1 addition reaction occurs after the 2.1 addition reaction occurs, the intensity ratio of Tag to Tag is calculated as follows. 1 in a row
．． It is thought to be a measure of the rate at which 2-addition reactions occur.

The intensity ratio of Tβγ to Tαγ is 2 or more, preferably 5 or more, particularly preferably 10 or more,
Further, the intensity ratio of Tag to Tα is 2 or more,
It is preferably 4 or more, particularly preferably 5 or more.

In addition, while peaks attributed to Ta2 and Tag clearly exist, there are cases where a peak attributed to Tαγ cannot be identified because it is hidden in noise, or in this case, it is T of Tβa. The intensity ratio to γ or the intensity ratio of Tag to Tαγ is considered a prisoner.

In polypropylene obtained using the above-mentioned known titanium-based catalyst, the strength ratio of Ta2 to Tag is 0.00.
It is less than 1. In addition, for the aforementioned zirconocene and hafnocene catalysts, the intensity ratio of Tβγ to Tαγ is generally less than 1.5, so the 1.2 addition reaction is followed by the 2
, 1 addition reaction, the rate at which the reaction returns to the 1,2 addition reaction is considered to be lower than the rate at which the 2°1 addition reaction occurs. In addition, for polypropylene that is generally obtained using vanadium catalysts, the probability of returning to the 2,1 addition reaction after a 2,1 addition reaction and a 1°2 addition reaction is proportional to the probability of returning to a 1,2 addition reaction. It is considered to be low.

In the present invention, in the presence of an olefin polymerization catalyst capable of producing polypropylene that satisfies the above-mentioned specific requirements, at least two compounds selected from the group consisting of ethylene, an α-olefin having 3 or more carbon atoms, and a diene compound are used. Copolymerization of various polymerizable monomers is carried out.

As the α-olefin having 3 or more carbon atoms, propylene,
1-butene, 1-pentene, 1-hexene, 4-methyl-
Straight chain or branched α-olefins having 3 to 20 carbon atoms such as 1-pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 1-decene, 1-dodecene, styrene Examples include cyclic vinyl compounds having 7 to 20 carbon atoms, styrenes such as methylstyrene, dimethylstyrene, and chlorostyrene, and vinylcycloalkanes such as vinylcyclohexane and methylvinylcyclohexane.

Further, cyclic olefins such as those shown below can also be used.

Tetracyclo[4,4,O,l' 1.17 0] such as vinclo[2,2 1]hept-2-ene derivatives such as Ato; Hexacyclo[6,6,1,1'' such as dodecene derivatives , +10o @
, +4] -4-heptadecene derivative, 027 octacyclo[8,8,0,1,1 8,14 7,1 6,03'' 7]-5 tococene derivative with 5-tococene i.

4-hexadecene and bentashi')O[6,6,1,1'', 027.0
'4] - Tricyclo[4,3,0 125 such as heptacyclo-5-eicosene derivatives such as -4-hexadecene derivatives or heptacyclo-5-heneicosene derivatives] Tricyclo[4,4,0 126 co- such as decene derivatives - 3 Undecene derivatives and pentacyclo[6,5,1 x″, 1.o2·7.01 3]4-pentadecene derivatives.

Nato diene compound.

Pentacyclo [7,4,0,1", 1@2.0' 3] Hebutacyclo [8,7,0,1", 1"0!, such as pentadecene derivatives]
・Nonacyclo[10,9,1,1'・7,1+
2°20, 111 OLI J, IO, g12.21.
Pentacyclo[8,4,0,1'・@, 11. +! , 0
@・l-] -3-Hexadecene derivative: heptacyclo-D-'\no+L, 1--no and heptacyclo[8 147,1 Jl+ It 02.1. Q 1117] nonacyclo[10,10,1,1''', 11 such as heneicosene derivatives
4°21.11@, Il, 0th 01,, I, O
I+・22. QIL! o] -5-hexacosene derivatives and further, among these, preferably propylene, 1-butene, 1
α-olefins having 3 to 8 carbon atoms such as -pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, l-octene, and 3-methyl-1-butene, particularly Preferred is propylene.

Examples of diene compounds include 1.3-butadiene, 1,3pentadiene, 1.4-pentadiene, 1.3-hexanoene, 1,4-hexadiene, ■, 5-hexadiene,
4-methyl-1,4-hexadiene, 5-methyl = 1.4
-hexadiene, 6-methyl 1,6-octadiene, 7
-Methyl-16=octadiene, 6-ethyl-1,6-
Octadiene, 6-broby-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-1,6
-nonadiene, 6-methyl-1,6-decadiene, 7-
Methyl-1,6-decadiene, 6-methyl-1,6 undecadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene,
Diene compounds having 4 to 20 carbon atoms such as ethylidenenorbornene, vinylnorbornene and dicyclopentadiene can be mentioned, and among these, preferably 1,
4-hexadiene, 1.5-'\xadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, ethylidenenorbornene, vinylnorbornene carbon number 5 such as
~12 diene compounds may be mentioned.

Among the above combinations of at least two polymerizable monomers selected from the group consisting of ethylene, α-olefins having 3 or more carbon atoms, and diene compounds, particularly preferred combinations include ethylene and propylene, ethylene and Butene-1, ethylene and pentene-11 Propylene and butene-1, ethylene and tetracyclododecene, ethylene and propylene and ethylidenenorbornene, ethylene and propylene and vinylnorbornene, ethylene and 1.5-hexadienehexene-1 and 4 Combinations such as -methylpentene-1 hexene=1, 4-methylpentene-1 and 7-methyl-16-octadiene can be mentioned.

When copolymerizing ethylene and propylene, the proportion of structural units derived from ethylene in the resulting copolymer is 10 to 90 mol%, preferably 30 to 85 mol%, particularly preferably 40 to 80 mol%. It is preferable that it exists in

Furthermore, when copolymerizing ethylene and butene-1, the content of structural units derived from ethylene in the resulting copolymer is 10 to 97 mol%, preferably 50 to 96 mol%.
, particularly preferably in a proportion of 70 to 95 mol %.

Also, when copolymerizing ethylene and pentene-1,
In the resulting copolymer, it is preferable that the structural unit derived from ethylene is present in a proportion of 10 to 95 mol%, preferably 40 to 90 mol%, particularly preferably 50 to 85 mol%.

In addition, when copolymerizing propylene and butene-1,
In the resulting copolymer, the structural unit derived from propylene is preferably present in a proportion of 10 to 90 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%.

In addition, in the copolymer obtained by copolymerization of ethylene, propylene, and a diene compound, the content of structural units derived from ethylene is 10 to 90 mol%, preferably 30 to 90 mol%.
85 mol%, particularly preferably 60 to 80 mol%, structural units derived from propylene, 10 to 90 mol%, preferably 15 to 70 mol%, particularly preferably 20 to 40 mol%, derived from diene compounds Constituent units are 1 to 50
mol%, preferably 3 to 30 mol%, particularly preferably 5
~15 mol%.

Furthermore, when copolymerizing ethylene and tetracyclododecene, the content of structural units derived from ethylene in the resulting copolymer is 10 to 90 mol%, preferably 30 to 90 mol%.
It is 80 mol%, particularly preferably 50 to 75 mol%.

In the method for producing an α-olefin copolymer according to the present invention, the above copolymer is produced using an olefin polymerization catalyst capable of producing polypropylene having the above-mentioned unique steric structure. Let's do it.

Examples of such olefin polymerization catalysts include:
Examples include catalysts for olefin polymerization comprising at least one transition metal compound selected from Ti, V, Zr, Hf, Nb, and Ta and an organometallic compound.

A particularly preferable example of the above catalyst for olefin polymerization is an olefin polymerization catalyst (hereinafter referred to as "catalyst 1") comprising a solid catalyst in which a non-metallocene transition metal compound is supported on a solid carrier and an organometallic compound. It is sometimes abbreviated as.

), an olefin polymerization catalyst (hereinafter sometimes abbreviated as "catalyst 2") comprising a metallocene compound and an organometallic compound.

Hereinafter, the above catalysts 1 and 2 will be explained, and the α-olefin polymer according to the present invention is not limited to the α-olefin polymer produced using the above catalyst 1 or 2, but also the α-olefin polymer produced using other catalyst systems. - Also includes olefin polymers.

Specifically, the non-metallocene transition metal compound used in the preparation of catalyst 1 is, for example, 4 represented by the following formula.
titanium compounds with high valence.

T r (OR), X 4 □ R is a hydrocarbon group,
4, Ti(OCR3)C13, Ti(OC2H5)C13, T1(On-C4Hs)C13, 'ri(OC2H-B r3, Ti(○-130C4H9)B r3 Trihalogenated alkoxytitaniums such as T l(OCH3)2C12, Ti(OC2H6)2C12, T1(On-C4)(9)2C12, Ti(OC2
H5) Dihalogenated dialkoxytitanium such as 2B r2, Ti(OCH3)3C1.

Ti(OC2H5)3Cl.

Monohalogenated trialkoxytitanium such as Ti(On-C4HG)3Cl, Ti(OC2Hs)zBr, Ti(OCH2)4, Ti(OC2H6)4, Tl(On C4Hl)4, Ti( Examples include tetraalkoxytitanium such as ○-1so-C4Hl)4 and Ti(0-2-ethylhexyl)4.

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

Catalyst 1 consists of a solid catalyst in which the above-mentioned non-metallocene-based foreign metal compound is supported on the following carrier compound, and an organometallic compound.

Such carrier compounds include Al1203.5i0
2, B 20 a, Mgo, CaO,, T i
02, Zn0Z n 02.5nOx, BaO1Th
O and resins such as styrene-divinylbenzene copolymer and MgCfMg(OH'h, MgCO5, Mg
E t ) 2, Mg stearate, and the like. Among these hitting compounds, SiO
2. AI! 20Mg0. Examples of organometallic compounds used in the preparation of catalyst 1 include Zn0, ZnO□, etc. Organometallic compounds of metals from Groups 1 to 2 of the periodic table [
Compounds are used, specifically, the following compounds are used.

(1) R□Al (OR2). H, XQ (wherein R1 and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a norogen atom, O<m≦3, n is O≦n3, p is 0≦p<3, q
is a number such that 0≦q<3, and m + n + p
+ q = 3).

(2) M'A IR'.

(In the formula, Ml is Li or Na, and R1 is the same as above.) A complex alkylated product of a Group (1) metal and aluminum, represented by the formula:

(3) R'R"M" (wherein, R1 and R2 are the same as above. M2 is M
A dialkyl compound of Group 1 or Group 2 represented by Zn or Cd).

As the organoaluminum compound belonging to the above (1), the following compounds can be exemplified.

General formula R1, A1 (OR2)! -yo (in the formula, R1 and R2 are the same as above. m is preferably 1.5≦m≦3
), General formula R', A LX 3-1 (In the formula, R1 is the same as above. X is halogen, m is preferably 0<m<3), General formula R', A IH3 -m (wherein, R1 is the same as above. m is preferably 2≦m<3
), general formula R1 yoA, l (OR”), ,X.

(In the formula, R1 and R2 are the same as above. X is halogen,
0<m≦3.0≦n<3.0≦q<3, m+n+q”3
Examples include compounds represented by

More specifically, aluminum compounds belonging to (1) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum such as diethylaluminum ethoxide and dibutylaluminum butoxide. Alkoxide; Alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R'2. sA l (OR2). Partially alkoxylated alkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, etc., with an average composition represented by Alkylaluminum sesquihalides such as amide; dialkylaluminum hydrides such as partially halogenated alkylaluminum diethylaluminum hydride, dibutylaluminum hydride, etc. ; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, probylaluminum dihydride; Particularly alkoxylated and halogenated alkyl aluminums can be mentioned.

Compounds similar to (1) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2H,) 2At○Al (
C2H5)2, (C4H,)2AIOAl (C,H8
)2, (C2H6)2AINAl (C2H5)22H
In addition to 5 and the like, aluminoxanes such as methylaluminoxane can be mentioned.

Examples of compounds belonging to the above (2) include LiAl (C2H5)4 and LiAl (C7H15)4.

Among these, organoaluminum compounds are preferably used, and halogen-containing alkyl aluminums are particularly preferably used.

An electron donor may be added to the catalyst 1 made of such an organometallic compound, the above-mentioned transition metal compound, and a carrier compound, if necessary.

As the electron donor added to the catalyst l as necessary,
Specifically, the following compounds may be mentioned.

Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine; Pyrroles such as pyrrole, methylpyrrole, dimethylpyrrole; Virolin; Pyrrolidine; Indole; Pyridine , methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridine chloride, and other pyridines; piperidines, quinolines, isoquinolines, and other nitrogen-containing cyclic compounds; tetrahydrofuran , 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalan, tetrahydropyran, pyran, ditedropyran and other cyclic oxygenated compounds methanol, ethanol, propatool, Alcohols having 1 to 18 carbon atoms, such as pentanol, hexanol, octatool, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylhensyl alcohol; Phenols having 6 to 20 carbon atoms that may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone Ketones having 3 to 15 carbon atoms such as , acetylacetone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and 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, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-maleate
Butyl, diisobutyl methylmalonate, diethyl cyclohexenecarboxylate di-n-hexylnadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, Organic acid esters having 2 to 30 carbon atoms such as δ-valerolactone, coumarin, phthalide, and ethyl carbonate; Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, and anisyl chloride; Methyl ether , ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether, ethers having 2 to 2 carbon atoms such as epoxy-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-pincrow [2,2
, 1]-hebutane, diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-2-isopropyl-1,3-dimethoxycyclohexane, etc. Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; nitriles such as acetonitrile, benzonitrile, and tolnitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride; and the like.

In addition, as an electron donor, the following general formula [I a]
Organosilicon compounds represented by can also be used.

R,,5i(OR') 4-n ・[I
a] [wherein R and R' are hydrocarbon groups, and ocn<4] As the organosilicon compound represented by the above general formula [I a], specifically, trimethyl Methoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-
Butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bismetyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis p -Tolyljethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane Methoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane Silane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(
β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

Furthermore, as an electron donor, the following general formula [I[a
] It is also possible to use an organosilicon compound represented by the following.

StR'R2, (OR") 3-m ...[I[
a] [In the formula, R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, and R3 is a hydrocarbon group. Yes, m is O≦m≦2. In the above formula [I[a], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
Examples of 1 include, in addition to the cyclopentyl group, cyclopentyl groups having an alkyl group such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group.

Further, in formula [IIa], R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, An alkyl group such as a hexyl group, or a cyclopentyl group and a cyclopentyl group having an alkyl group as exemplified as R1 can be similarly mentioned.

Further, in formula [IIa], R3 is a hydrocarbon group, and examples of R3 include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethyl Examples include monoalkoxysilanes such as methoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

Next, a method for preparing a catalyst 1 consisting of the above-mentioned carrier compound, a non-metallocene transition metal compound supported on the carrier compound, and an organometallic compound will be described.

The non-metallocene transition metal compound can be supported on the carrier compound by simply contacting it, by mixing it under heating, or by contacting the carrier compound with an organometallic compound, an electron donor, a halogenating agent, etc. in advance. Examples include a method in which the non-metallocene transition metal compound is supported on a carrier compound after treatment.

Further, the non-metallocene transition metal compound supported on a carrier thus obtained can be brought into contact with an organometallic compound prior to polymerization. In this case, it is preferable to contact at a temperature range of 0 to -200°C, preferably -40 to -90°C.

The amount of the non-metallocene transition metal compound supported per gram of the carrier compound is generally from 0.01 to 100 mmol, preferably from 0.01 to 100 mmol. 1 to 50 mmol of O, particularly preferably 0.05 to 20 mmol.

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

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 catalyst 1 as described above.

Polymerization of α-olefin using Catalyst 1 is usually carried out in gas phase or solution polymerization, or in a slurry state.

When using a reaction method of polymerization, slurry polymerization, or solution polymerization, an inert hydrocarbon can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can be used.

Specifically, the inert hydrocarbon medium used in this case includes aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, cyclopentane, cyclohexane, methylcyclopentane, etc. Examples include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and contact substances thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

In the polymerization system, catalyst 1 is usually used in an amount of about 0.001 to 50 mmol, preferably about 0.01 to 10 mmol, calculated as transition metal atoms per polymerization volume lβ. The organometallic compound is used in an amount such that the metal atoms contained in the organometallic compound are usually about 1 to 1000 moles, preferably about 2 to 200 moles, per 1 mole of transition metal atoms in the polymerization system. It will be done.

If hydrogen is used during polymerization, the molecular weight of the resulting polymer can be adjusted, and a polymer with a high melt flow rate can be obtained.

The polymerization temperature of olefin is usually about -50 to 200°C.
1 preferably about 20 to 100°C, and the pressure is usually normal pressure to 100 kg/cd, preferably about 2 to 50 kg/d
is set to Polymerization can be carried out in any of the batch, semi-continuous and continuous methods.

Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In such a polymerization system, it is preferable that the catalyst 1 is difficult to form clusters when the solid catalyst supported on a carrier of the non-metallocene transition metal compound comes into contact with the organometallic compound. In addition, for example, in the case of a titanium-based catalyst component, the term "hard to form clusters" refers to the ratio of T13+ to the total Ti measured by ESR, that is, T i '' (E
SR)/T 1 (total) and T i ”(ESR)/T after adsorbing pyridine vapor to the catalyst component.
The evaluation can be made based on the ratio of the value of i (total) to 3 months to 3 months, preferably 1 to 2 months.

For example, ESR measurement can be carried out using a Varian E-12 type E
The measurement is carried out using an SR measuring device in a quartz tube with an inner diameter of 3 mm at room temperature and a modulation frequency of 100 K) Iz. At this time, MnO doped with 1,1-diphenyl-2-vicrylhydrazine (DPPH) and divalent Mn ions was used as a reference material for quantifying trivalent titanium atoms and determining g value.
are used respectively.

In the conventional catalyst system, it has been confirmed that a large amount of clusters are formed in the polymerization system, or in the catalyst system using Catalyst 1 as described above, clusters are not formed or are formed. There are very few if any. This kind of catalyst system that is difficult to form is α-
When olefins are polymerized, the reason is not clear.
An α-olefin polymer having a unique three-dimensional structure can be obtained.

Incidentally, the catalyst 1 may be subjected to a preliminary polymerization treatment prior to polymerization.

Next, an olefin polymerization catalyst (catalyst 2) comprising a metallocene compound and an organometallic compound will be explained.

The metallocene compound used in the preparation of catalyst 2 is as follows: M.L.

(In the formula, M is a transition metal selected from the group consisting of Ti, ■, Zr, Hf, Nb, and Ta, L is a ligand that coordinates to the transition metal, and at least one L is a cycloalkaline A ligand having a dihenyl skeleton, other than a ligand having a cycloalkagenyl skeleton, has 1 to 12 carbon atoms.
is a hydrocarbon group, alkoxy group, aryloxy group, halogen or hydrogen, and X is the valence of the transition metal. )
Metallocene compounds represented by:

Examples of the ligand having a cycloalkagenyl skeleton include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a t-butylcyclopentagenyl group, a dimethylcyclopentagenyl group, indenyl group, 4, 5. Examples include '6,7-titrahydroindenyl group.

The ligands other than those having a cycloalkagenyl skeleton are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen, or hydrogen.

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group; aryl groups include phenyl group, tolyl group, etc.; aralkyl groups include benzyl group, Examples include a neophyll group.

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

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

For example, when the valence of the transition metal is 4, the metallocene compound containing a ligand having a cycloalkagenyl skeleton used in the present invention has the following formulas: R2, R'', R' , Rs, M (wherein M is a transition metal selected from the group consisting of Ti, ■, Zr, and Hf, R2 is a group having a cycloalkagenyl skeleton, and R3, R4, and R5 are cycloalkagenyl groups having a base structure, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups,
aryloxy group, /SS rosin group or hydrogen, k
is an integer greater than or equal to 1, and k+1+m+n=4).

The metallocene compound has the above formula % and at least two of R5, namely R2 and R3, are groups having a cycloalkagenyl skeleton, and these two groups having a cycloalkagenyl skeleton are lower alkylenes such as ethylene, are bonded via propylene etc., and R4 and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cycloalkyl group, an aryl group,
It may be an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or hydrogen.

Hereinafter, specific examples of metallocene compounds containing a ligand having a cycloalkagenyl skeleton in which M is titanium will be exemplified.

Bis(cyclopentagenyl) titanium monochloride monohydride, Bis(cyclopentagenyl) titanium monopromide monohydride, Bis(cyclopentagenyl) methyl titanium hydride, Bis(cyclopentagenyl) ethyl titanium hydride, Bis (cyclopentagenyl) phenyl titanium hydride, bis(cyclopentagenyl) benzyl titanium hydride, bis(cyclopentagenyl) neopentyl titanium hydride, bis(methylcyclopentagenyl) titanium monochloride hydride, bis(indenyl) Titanium monochloride monohydride, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium dibromide, bis(cyclopentagenyl) methyltitanium monochloride, bis(cyclopentagenyl) ethyl titanium monochloride Chloride, Bis(cyclopentagenyl)cyclohexyltitanium monochloride, Bis(cyclopentagenyl)phenyltitanium monochloride, His(cyclopentagenyl)penciltitanium monochloride, Bis(methylcyclopentagenyl)titanium dichloride, Bis (t-Butylcyclopentagenyl)titanium dichloride, bis(indenyl)titanium dichloride, bis(indenyl)titanium dipromide, bis(cyclopentagenyl)titanium dimethyl, his(cyclopentajenyl)titanium diphenyl, bis(cyclo pentagenyl) titanium dibenzyl, bis(cyclopentagenyl) titanium methoxychloride, his(cyclopentagenyl) titanium ethoxychloride, bis(methylcyclopentagenyl) titanium ethoxychloride, bis(cyclopentagenyl) titanium Phenoxy chloride, bis(fluorenyl) titanium dichloride.

Further, M includes at least two or more ligands having a cycloalkagenyl skeleton in which M is titanium, and the at least two ligands having a cycloalkagenyl skeleton are bonded via a lower alkylene group. Specific examples of metallocene compounds are listed below.

Ethylenebis(indenyl)dimethyltitanium, ethylenebis(indenyl)diethyltitanium, ethylenebis(indenyl)diphenyltitanium, ethylenebis(indenyl)methyltitanium, ethylenebis(indenyl)ethyltitanium monochloride, ethylenebis(indenyl)methyltitanium mono Promide, Ethylenebis(indenyl)titanium dimethyldo, Ethylenebis(indenyl)titanium dimethyldo, Ethylenebis(indenyl)titanium methoxy monochloride, Ethylenebis(indenyl)titanium ethoxymonochloride, Ethylenebis(indenyl)titanium phenoxymonochloride , Ethylenebis(cyclopentagenyl)titanium dichloride, Propylenebis(cyclopentagenyl)titanium dichloride, Ethylenebis(t-butylcyclopentagenyl)titanium monochloride, Ethylenebis(4,5,6,7-telodihydro) -1-indenyl)dimethyltitanium, ethylenebis(4,5,6,7-telodihydro-1-indenyl)methyltitanium monochloride, ethylenebis(4,5,6,7-telodihydro-1-indenyl)
Titanium dichloride, Ethylenebis(4,5,6,7-terolahydro-indenyl)titanium dipromide, 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.

Further, specific examples of metallocene compounds containing one ligand having a cycloalkagenyl skeleton of M or titanium will be given.

Cyclopentadienyl titanium trichloride, cyclopentadienyl titanium trichloride, cyclopentadienyl methyl titanium dichloride, cyclopentadienyl ethyl titanium dichloride, cyclopentadienyl phenyl titanium dichloride, cyclopentadienyl benzyl Titanium dichloride, cyclopentagenyl neobentyl titanium dichloride, methylcyclopentagenyl titanium dichloride hydride, indenyl titanium dichloride monohydride, cyclopentagenyl dimethyl titanium monochloride, cyclopentagenyl diethyl titanium monochloride, cyclopentagenyl titanium dichloride cyclohexyl titanium monochloride, cyclopentadienyl diphenyl titanium monochloride, cyclopentajenyl dibenzyl titanium monochloride, methylcyclopentajenyl titanium trichloride, t-butylcyclopentadienyl titanium trichloride, indenyl titanium trichloride, Indenyl titanium tripromide, Cyclopentajenyl titanium trimethyl, Cyclopentajenyl titanium triphenyl cyclopentajenyl titanium tribenzyl cyclopentajenyl titanium methoxycyclolide, Cyclopentajenyl titanium ethoxy dichloride, Methyl cyclopentadienyl titanium Ethoxy dichloride, cyclopentadienyl titanium phenoxy cyclolide, fluorenyl titanium trichloride, cyclopentadienyl methyl titanium dibromide, cyclopentadienyl ethyl titanium dibromide, cyclopentadienyl phenyl titanium dibromide, cyclopenta Dienylbenzyl titanium dibromide, cyclopentadienyl neopentyl titanium dipromide, methyl cyclopentadienyl titanium dichloride hydride, indenyl titanium dichloride monohydride, cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl diethyl titanium mono Chloride, cyclopentadienyldicyclohexyltitanium monochloride, cyclopentadienyldiphenyltitanium monobromide, cyclopentadienyldibenzyltitanium monochloride, methylcyclopentadienyltitanium tripromide, t-butylcyclohexyltitanium tripromide , indenyltitanium tripromide, cyclopentadienyltitanium trimethyl, cyclopentadienyltitanium triphenylcyclopentadienyltitanium tribenzylcyclobentajenyltitanium methoxydifuromide, cyclopentadienyltitanium ethoxydipromide, methylcyclopenta Genyl titanium ethoxydibromide, cyclopentadienyl titanium phenoxydibromide
Fluorenyl titanium tripromide.

Furthermore, in the above metallocene compounds, compounds in which titanium is replaced with zirconium or hafnium can also be used. Further, niobium compounds or tantalum compounds similar to the above-mentioned titanium-based metallocene compounds can also be used.

Examples of the organometallic compound used in the preparation of Catalyst 2 include the same compounds as those used in the preparation of Catalyst 1 described above, and among them, it is preferable to use aluminoxanes. Further, the above-mentioned electron donor can be added if desired.

In the above catalyst 2, 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 200. included in the ratio. There is no particular restriction on the amount of the electron donor added as desired, or 0.1 to 1 mole of transition metal atom.
It is desirable that the amount is about 1 to 100 mol, preferably about 1 to 10 mol.

As a method for preparing catalyst 2, a method of supporting it on a carrier as exemplified for catalyst 1 can be cited as a preferable example.

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 catalyst 2 as described above.

Polymerization of α-olefin using catalyst 2 usually takes the form of solution polymerization or solution polymerization.

As a reaction solvent during polymerization, an inert hydrocarbon can be used, or an olefin that is liquid at the reaction temperature can be used.

Examples of the inert hydrocarbon medium used in this case include those similar to the above-mentioned inert hydrocarbon medium.

In the polymerization system, the catalyst 2 is usually used in an amount of about 0,00 to 50 mmol, preferably about 0.01 to 10 mmol, calculated as transition metal atoms per 11 polymerization volumes. The organometallic compound is used in an amount such that the metal atoms contained in the organometallic compound are usually about 1 to 1000 moles, preferably about 2 to 200 moles, per 1 mole of transition metal atoms in the polymerization system. It will be done.

If hydrogen is used during polymerization, the molecular weight of the resulting polymer can be adjusted, and a polymer with a high melt flow rate can be obtained.

Also, two or more types of α-olefin copolymers having 3 or more carbon atoms, copolymers of α-olefins having 3 or more carbon atoms and ethylene, copolymers of α-olefins having 3 or more carbon atoms and diene, Alternatively, the present invention also includes a copolymer of an α-olefin having 3 or more carbon atoms, ethylene, and a diene.

Note that the above dienes include butadiene, 1.4
-hexadiene, 5-ethylidene-2-norbornene, etc. are used.

The polymerization temperature of olefin is usually about 20 to 200°C1
Preferably it is set at about 50 to 100°C.

Polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The α-olefin polymer obtained using Catalyst I or 2 as described above has the unique three-dimensional structure described above.

The α-olefin copolymer obtained by the present invention will be specifically explained below.

The resulting copolymer has excellent transparency and elongation at break, so it can be expected to be used as an elastomer and optoelectronic material, and because of its narrow composition distribution, the low molecular weight product is also expected to be used as a lubricating oil. can.

In particular, in the case of the resulting copolymer or ethylene-propylene copolymer, it is expected that it will be used as a material for improving impact resistance, etc., and if it is a low molecular weight product, it can be used as a lubricating oil.

Furthermore, when the resulting copolymer is an ethylene/butene-1 copolymer, it can be expected to be used as an improving material for imparting impact resistance and transparency.

In addition, ethylene-tetracyclododecene copolymers are expected to provide optoelectronic materials with excellent transparency.

As described in detail, according to the present invention, it is possible to provide an α-olefin copolymer having unique physical properties that did not previously exist, and the use of α-olefin copolymers has been expanded. It will expand further.

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Preparation of catalyst] 3 g of silica gel (F952 manufactured by Fuji Davison) calcined at 800°C for 3 hours was put into a 20-hbutane solution containing 20 mmol of titanium tetrachloride, and mixed at room temperature for 3 hours. did. The solid portion was collected by filtration, washed several times with heptane, and then dried at 60°C under reduced pressure for 3 hours.
An i Ci4/S i O2 catalyst was obtained.

The Ti content was 2.2% by weight.

[Catalyst Pretreatment] 10 r of heptane solution containing 0.2 mmol of triisobutylaluminum! While cooling Ll to -78°C, T
After adding 0.1 mmol of 1Cf+/SiO□ catalyst in terms of Ti atoms, the mixture was washed with heptane to obtain a triisobutylaluminum-treated catalyst.

[Polymerization] After charging 25 mol of heptane and 0.3 mol of propylene into a reactor with an internal volume of 100 ml, 0.2 mmol of triisobutylaluminum and the above T 1CI! 4/S
Adding 0.1 mmol of i○2 catalyst in terms of Ti atom,
Copolymerization was carried out at 40°C for 1 hour. The copolymerization was stopped by adding 10% hydrochloric acid in methanol.

In order to separate the obtained polymer from the SiO□ support, extraction was performed with boiling 0-dichlorobenzene for 10 hours.

[Analysis Core isotactic index (II) was determined by extraction with boiling hebutane for 10 hours. 13C-NMR of the polymer was measured using JEOLGX-270 at 67.20 MHz and 120°C. N.M.
The sample for R measurement was a solution of a mixed solvent of 1,2.4 to trichlorobenzene/d6-benzene at a weight ratio of 9/1, and the polymer concentration was 10% by weight or less.

The measurement results are shown in Table 1.

[Copolymerization volume II! After charging 500 rIL of toluene into the reactor, the pre-treated catalyst (catalyst synthesis and catalyst treatment was carried out at 1
0.5 mmol (conducted on a scale of 0.0 times) was added in terms of Ti atoms, and propylene was fed to the liquid phase of the polymerization vessel at a rate of 601/hour for 2 hours at 40°C to carry out copolymerization. Polymerization was stopped by adding 10% hydrochloric acid in methanol.

In order to separate the obtained polymer from the SiO2 support, extraction was performed with boiling 0-dichlorobenzene for 10 hours.

When the ethylene content in the obtained copolymer was examined, it was found to be 58
It was mol%.

Example 2 [Preparation of catalyst] 5 g of silica gel (F952 manufactured by Fuji Davison) calcined at 800°C for 3 hours was mixed with 20rnI! containing 2 mmol of cyclopentadienyl titanium trichloride. of heptane solution and mixed at 100°C for 3 hours. The solid part was collected by filtration, washed several times with heptane, and then heated at 60°.
CpT1cj2z/SiO2 was dried for 3 hours under reduced pressure.
I got a catalyst.

The Ti content was 1.3% by weight.

[Polymerization] After charging 25 rnJ of heptane and 0.3 mol of propylene into a reactor with an internal volume of 100 mJ, 1 mmol of methylaluminoxane (manufactured by Toyo Stouffer Co., Ltd.) in terms of aluminum atoms and the cp'ricISiOx catalyst were added to Ti. Added 0.05 mmol in terms of atoms, 40°
Copolymerization was carried out at C for 2 hours. The copolymerization was stopped by adding 10% hydrochloric acid in methanol.

In order to separate the obtained polymer from the SiO□ support, extraction was performed with boiling 0-dichlorobenzene for 10 hours.

[Analysis] The same analysis as in Example 1 was conducted.

The measurement results are shown in Table 1.

[Copolymerization volume: 1! ! 500 ml of toluene and 1
．． After charging 20d of octadiene, 10 mmol of methylaluminoxane (manufactured by Toyo Stouffer Co., Ltd.) in terms of aluminum atoms and the above CpTiCI23/5i were added.
02 catalyst was added at 5 mmol in terms of T1 atom (the catalyst synthesis was carried out on a 10-fold scale), and propylene was added at 4°C.
Copolymerization was carried out by feeding ethylene into the liquid phase of the polymerization vessel at a rate of 0.01/hour and 601/hour for 2 hours.

Polymerization was stopped by adding 10% hydrochloric acid in methanol.

In order to separate the obtained polymer from the S i O 2 carrier, extraction was carried out with boiling 0-dichlorobenzene for 10 hours.

The iodine value in the obtained copolymer was measured and found to be 7.

Claims (1)

[Claims] (1) In the presence of an olefin polymerization catalyst that can provide polypropylene that satisfies the following requirements (a) to (b) when homopolymerizing propylene, ethylene, an α-olefin having 3 or more carbon atoms, and A method for producing an α-olefin copolymer, which comprises copolymerizing at least two polymerizable monomers selected from the group consisting of diene compounds. (a) The intensity ratio of Tβγ to Tββ in the ^1^3C-NMR spectrum of the α-olefin polymer is 0.
001 or more, and (b) the intensity ratio of Tβγ to Tαγ in the ^1^3C-NMR spectrum of the α-olefin polymer is 2 or more, or the intensity ratio of Tαβ to Tαγ is 2 or more.
That's all.