JP3409803B2 - Method for producing olefin-based polymer and olefin-based copolymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an olefin polymer and a novel olefin copolymer. More specifically, the present invention improves the heat resistance, transparency and mechanical properties of conventional linear low density polyethylene (L-LDPE) by using a highly active and highly copolymerizable catalyst, and A method for efficiently producing an olefin polymer having a homogeneous composition with improved molding processability, which is a drawback, and a random copolymer of ethylene and / or propylene and a specific branched α-olefin, which is a polyolefin The present invention relates to an olefin-based copolymer having the above properties, which is useful as a system-based engineering resin.

[0002]

2. Description of the Related Art Conventionally, olefin (co) polymers have been widely used as a general-purpose resin in many fields.
As a method for producing this olefin (co) polymer, a method using a catalyst containing a transition metal compound as a main component is known. For example, a copolymer obtained by copolymerizing ethylene and various α-olefins using a catalyst containing the transition metal compound as a main component is marketed as linear low-density polyethylene (L-LDPE). Examples of the α-olefin which is a comonomer component in this L-LDPE include, for example, 1-
Butene, 1-hexene, 1-octene, 4-methyl-1
-Chain or branched α-olefins such as pentene are used. However, the L-LDPE has a problem that the activation energy of the flow in the molten state is small and the moldability is inferior, and the heat resistance, transparency and mechanical properties are not always satisfactory. On the other hand, 3,5,5-trimethyl-1 which is a branched α-olefin
-A crystalline polymer (melting point of 420 ° C or higher) obtained by polymerizing hexene using a Ziegler-Natta type catalyst is disclosed (US Pat. No. 3,010,951). However, although this polymer has excellent heat resistance, it has the drawback of being inferior in moldability. The above 3,
5,5-Trimethyl-1-hexene can be produced by dehydration of 3,5,5-trimethyl-1-hexanol, which can be industrially produced as an isobutylene derivative (US Pat. No. 3,010,951). Also, 3,
An olefin copolymer composed of 5,5-trimethyl-1-hexene units and 1-butene units has been disclosed (Japanese Patent Publication No. 2-24287). This olefin copolymer was isomerized to 3,5-5-trimethyl-1-hexene and 1-butene or 2-butene (in the case of 2-butene, 1-butene was isomerized in the presence of a Ziegler type polymerization catalyst, It is obtained by copolymerizing with. However, in the olefin copolymer, one or two or more melting points are observed during the copolymerization process, and the presence of two or more melting points suggests the presence of an unconnected crystal phase. , Block copolymers or blends of two or more polymers. Further, in the conventional Ziegler type polymerization catalyst, 3,5,5-trimethyl-1-
Copolymerization of hexene with ethylene or propylene is difficult because of different polymerization rates. Further, a polymer of 3-ethyl-1-hexene which is a branched α-olefin is disclosed (JP-A-4-311707). However, although the publication shows the possibility of copolymerization, there is no example of a copolymer of 3-ethyl-1-hexene and a comonomer.

[0003]

Under the circumstances described above, the present invention uses a catalyst having high activity and high copolymerizability to obtain heat resistance, transparency and mechanical properties of conventional L-LDPE. And a method for efficiently producing an olefin-based polymer having a homogeneous composition with improved molding processability, and a novel olefin-based copolymer having the above properties useful as a polyolefin-based engineering resin, etc. It was made for the purpose.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that at least one of specific branched α-olefins is polymerized using a specific catalyst system. Alternatively, by polymerizing at least one of the branched α-olefins and at least one of the α-olefins having 20 or less carbon atoms excluding the branched α-olefin, heat resistance and transparency of the conventional L-LDPE, It was found that an olefin polymer having a homogeneous composition with improved mechanical properties and improved molding processability can be efficiently obtained. Further, it has been found that a random copolymer of ethylene and / or propylene and a specific branched α-olefin has the above-mentioned properties and is useful as a polyolefin-based engineering resin or the like. The present invention has been completed based on such findings. That is, the present invention provides (A) general formulas (I), (II),
(III) or ^{_{(IV) CpM 1 R 1 a}} R 2 b R 3 c ··· (I) Cp 2 M 1 R 1 a R 2 b ··· (II) (Cp-A e -Cp) M 1 R ¹ _a R ² _b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV) [In the formula, M ¹ is titanium, zirconium or hafnium.
Show. Cp is a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon
Indicates a hydrogen group, and in the general formulas (II) and (III), two
Cp may be the same or different from each other
May be R ¹ , R ² , R ³ and R ⁴ are respectively
Independently, a sigma-bonding ligand, a chelating ligand or a ligand.
Is a chair base, and R ¹ , R ² , R ³ and R ⁴ are 2 or more.
The tops may combine with each other to form a ring. A is a covalent bond
Shows the cross-linking by a, b, c and d are each independently
The integer of 0-4 and e show the integer of 0-6. ]]
A transition metal compound , (B) a compound capable of reacting with the transition metal compound or a derivative thereof to form an ionic complex, and
(C) the general formula ^{_{(XI) R 15 r AlQ 3}} -r ··· (XI) ( ^{wherein, R 15} represents an alkyl group having 1 to 10 carbon atoms, Q is water
Elementary atom, C1-C20 alkoxy group, C6-C2
0 represents an aryl group or a halogen atom, r is 1 to 3
From an organoaluminum compound represented by
And (b) polymerizing at least one kind selected from among branched α-olefins having a total carbon number of 7 or more and having at least one alkyl branch having a carbon number of 1 or more in the main chain using the catalyst system Alternatively, the branched type α-of the above (a) component
At least one selected from olefins and (b) at least one selected from α-olefins having 20 or less carbon atoms excluding the branched α-olefin of the component (a). Which has at least one alkyl branch having 5 to 30 mol% of ethylene units and / or propylene units and 1 or more carbon atoms in the main chain, and having 7 to 9 carbon atoms in total in the main chain. Units consisting of 95 to 70 mol% derived from at least one monomer selected from the group α-olefins,
And in a decalin solvent at a temperature of 135 ° C., the reduced viscosity at a concentration of 0.05 g / deciliter is 0.01 to 30 deciliter / g, and when the melting point is shown, only one is shown,
An olefin-based random copolymer having a melting point of 110 to 400 ° C. is provided.

In the method for producing an olefin polymer according to the present invention, as a polymerization catalyst, (A) a transition metal compound and (B) a transition metal compound or a derivative thereof can be reacted to form an ionic complex. The thing which has a compound as a main component is used. As the transition metal compound of the component (A),
Although it includes various ones, the general formula ^{_{CpM 1 R 1 a R 2 b}} R 3 c ··· (I) Cp 2 M 1 R 1 a R 2 b ··· (II) (Cp-A e -Cp ) A compound represented by M ¹ R ¹ _a R ² _b ... (III) or a general formula M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV) or a derivative thereof is preferable.

In the above general formulas (I) to (IV), M ¹
Represents a transition metal such as titanium, zirconium, hafnium, vanadium, niobium, and chromium, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group. Group, a cyclic unsaturated hydrocarbon group such as a fluorenyl group or a substituted fluorenyl group, or a chain unsaturated hydrocarbon group. R ¹ , R ² , R ³ and R
Each of ⁴ independently represents a σ-bonding ligand, a chelating ligand, a ligand such as a Lewis base. As the σ-bonding ligand, specifically, a hydrogen atom, an oxygen atom, Halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, carbon number 1 to 2
Examples thereof include an acyloxy group of 0, an allyl group, a substituted allyl group, and a substituent containing a silicon atom, and examples of the chelating ligand include an acetylacetonato group and a substituted acetylacetonato group. A indicates crosslinking by covalent bond. a, b, c and d are each independently 0 to 4
, And e is an integer of 0 to 6. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other.

Substituted cyclohexyl in the above formulas (I) to (III)
Examples of the pentadienyl group include methylcyclopenta
Dienyl group, ethylcyclopentadienyl group; isopro
Pyrcyclopentadienyl group; 1,2-dimethylcyclo
Pentadienyl group; tetramethylcyclopentadienyl
Group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethyl
Cyclopentadienyl group; trimethylsilylcyclopen
Examples thereof include a tadienyl group. In addition, the above (I)
R in formula (IV) ¹~ R^FourFor example,
Fluorine atom, chlorine atom, bromine atom as halogen atom,
Iodine atom, methyl as an alkyl group having 1 to 20 carbon atoms
Group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, octyl group, 2-ethylhexyl group, carbon number
Methoxy group and ethoxy as the alkoxy group of 1 to 20
Group, propoxy group, butoxy group, phenoxy group, carbon number
6 to 20 aryl groups, alkylaryl groups or
Phenyl group, tolyl group, xylyl as reel alkyl group
Group, benzyl group, and acyloxy group having 1 to 20 carbon atoms
The heptadecylcarbonyloxy group and silicon atom.
Trimethylsilyl group as a substituent, (trimethylsilyl group
) Methyl group, dimethyl ether as a Lewis base, di-
Ethers such as ethyl ether and tetrahydrofuran
, Thioethers such as tetrahydrothiophene,
Esters such as tylbenzoate, acetonitrile;
Nitriles such as benzonitrile, trimethylamine;
Triethylamine; tributylamine; N, N-dimethyl
Luaniline; pyridine; 2,2'-bipyridine; phena
Amines such as nitroline, triethylphosphine;
Phosphines such as Liphenylphosphine, ethylene;
Butadiene; 1-Pentene; Isoprene; Pentadie
Chain-unsaturated such as 1-hexene and their derivatives
Hydrocarbons, Benzene; Toluene; Xylene; Cyclohep
Tatriene; Cyclooctadiene; Cyclooctatriene
Such as cyclooctatetraene and derivatives thereof
Examples include cyclic unsaturated hydrocarbons. Also, the above (II
Examples of the covalent cross-linking of A in the formula (I) include
For example, methylene bridge, dimethylmethylene bridge, ethylene bridge
Bridge, 1,1'-cyclohexylene bridge, dimethylsilyle
Crosslinking, dimethylgermylene crosslinking, dimethylstannylene
Examples include crosslinking.

Examples of the compound represented by the general formula (I) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl). Tribenzylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadiene (Enyl) tribenzylzirconium, (cyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconi , (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and the like, Among these, compounds in which zirconium is replaced with titanium or hafnium are mentioned.

Examples of the compound represented by the general formula (II) include bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis ( Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethane Cyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (penta Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
(Pentamethylcyclopentadienyl) dichlorozirconium and the like, as well as compounds in which zirconium is replaced with titanium or hafnium.

Examples of the compound represented by the general formula (III) include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl).
Dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) Dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopentadienyl) (9 -Fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexalidene (9-fluorenyl ) (Cyclopentadienyl) dimethylzirconium, cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) ) (Cyclopentadienyl) dimethyl zirconium, dimethylsilylene bis (2,3,5
-Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, etc. Alternatively, a compound can be given by substituting with hafnium.

Further, examples of the compound represented by the general formula (IV) include tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t -Butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate), and the like, and compounds in which zirconium is replaced with titanium or hafnium. Specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium. , Dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentadienyl vanadium dichloride, dicyclopentadienylmethyl vanadium and the like.

Specific examples of the chromium compound include tetramethyl chromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl) chromium, hydrido tricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclo Examples include pentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like. further,
As the component (A), in the above general formula (III), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group) is a periodic table. A Group 4 transition metal compound having a multicoordinating compound bonded to each other through an element selected from Group 14 above as a ligand can be preferably used. Examples of such compounds include those represented by the general formula (V)

[0013]

[Chemical 1]

The compounds represented by
be able to. Y in the general formula (V)¹Is carbon, Kei
Element, germanium or tin atom, R^Five _t-C_FiveH_4-tOver
And R^Five _u-C_FiveH_4-uAre each substituted cyclopentadiene
The nyl group, t and u represent an integer of 1 to 4. Where R^Five
Are hydrogen atoms, silyl groups or hydrocarbon groups,
It may be one or different. Also, at least one piece
The other cyclopentadienyl group is Y¹Is bound to
R on at least one carbon next to the carbon^FiveExists.
R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group of formula 6 to 20, an alkylaryl group or
Indicates an arylalkyl group. M²Is titanium, zirconium
Or a hafnium atom, X¹Is a hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or aryl group of
It shows a alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
¹R may be the same or different from each other, and R⁶Also
They may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above general formula (V) include a methylcyclopentadienyl group; an ethylcyclopentadienyl group; an isopropylcyclopentadienyl group; a 1,2-dimethylcyclopentadienyl group. Group; 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X ¹ include F, Cl, Br, I as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms, 2-ethylhexyl group, methoxy group as an alkoxy group having 1 to 20 carbon atoms,
Examples of the ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group include phenyl group, tolyl group, xylyl group and benzyl group. Specific examples of R ⁶ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group and a benzyl group.

Specific examples of the compound represented by the general formula (V) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (2,3,5-trimethyl). Examples thereof include cyclopentadienyl) titanium dichloride and dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride. Furthermore, general formula (VI)

[0017]

[Chemical 2]

It also includes compounds represented by: The general formula
In the compound of (VI), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl group, fluorenyl group or substituted fluorescein
Cyclic unsaturated hydrocarbon group such as nyl group or chain unsaturated carbonization
Indicates a hydrogen group. M³Is titanium, zirconium or hafni
X represents a um atom²Is hydrogen atom, halogen atom, carbon
C1-C20 alkyl group, C6-C20 aryl
Group, alkylaryl group or arylalkyl group, or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is Si
R⁷ ₂, CR⁷ ₂, SiR⁷ ₂SiR⁷ ₂, CR⁷ ₂CR⁷ ₂, CR
⁷ ₂CR⁷ ₂CR⁷ ₂, CR⁷= CR⁷, CR⁷ ₂SiR⁷ ₂Or
GeR⁷ ₂Indicates Y ²Is -N (R⁸)-, -O-, -S-
Or -P (R⁸) -Indicates. R above⁷Is a hydrogen atom or 2
Alkyl, aryl, silyl having up to 0 non-hydrogen atoms
And alkyl halides, aryl halides and
R is a group selected from these combinations,⁸Has 1 to 1 carbon atoms
An alkyl group having 10 or an aryl group having 6 to 10 carbon atoms
Yes, or one or more R⁷And up to 30
May form a fused ring system of non-hydrogen atoms. w is 1 or
2 is shown.

Specific examples of the compound represented by the above general formula (VI) include (tertiary butylamide) (tetramethyl-
η ⁵ -Cyclopentadienyl) -1,2-ethanediylzirconium dichloride; (tertiary butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediyl titanium dichloride; (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediyl zirconium dichloride; (methylamido) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl titanium dichloride; (ethylamido) (tetramethyl- [eta] ⁵ -cyclopentadienyl)-
Methylene titanium dichloride; (tertiary butylamide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium dichloride; (tertiary butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl; (benzylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium dichloride; (phenylphosphide) dimethyl (tetramethyl- [eta] ⁵ -cyclopentadienyl) silane zirconium dibenzyl and the like. These transition metal compounds may be used alone or in combination of two or more.

In the polymerization catalyst, a compound capable of reacting with the transition metal compound or its derivative to form an ionic complex is used as the component (B). As the component (B), an ionic compound which reacts with the transition metal compound of the component (B-1) (A) to form an ionic complex,
Examples thereof include (B-2) aluminoxane and (B-3) Lewis acid.

As the component (B-1), any ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex can be used. General formula (VII), (VIII) ([L ¹ -R ⁹ ] ^{k +} ) _p ([Z] ^- ) _q ... (VII) ([L ² ] ^{k +} ) _p ([Z] ^- ) _q ···・ (VIII) (However, L ² is M ⁵ , R ¹⁰ R ¹¹ M ⁶ , R ¹² ₃ C or R
¹³ M ⁶ . ) [(VII), (VIII) In the formula, L ¹ is a Lewis base, [Z] ⁻
Is a non-coordinating anion [Z ^{1] -} and [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element ^{[M 4 A 1 A 2 ···} A n] ^- (wherein, M ⁴ is periodic table 5-15 group element, preferably periodic table 13
Group 15 elements are shown. A ^{1 to} A ⁿ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 2 to carbon atoms.
40 dialkylamino group, C1-20 alkoxy group, C6-20 aryl group, C6-20 aryloxy group, C7-40 alkylaryl group, C7-40 Arylalkyl group, carbon number 1
20 shows a halogen-substituted hydrocarbon group, a C1-C20 acyloxy group, an organic metalloid group, or a C2-C20 hetero atom-containing hydrocarbon group. 2 of A ^{1 to} A ⁿ
One or more may form a ring. n is [(central metal M
The valence of ⁴ ) +1]. ), [Z ^{2] -} is
The logarithm of the reciprocal of the acid dissociation constant (pKa) is -10 or less, and represents a conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid, or a conjugate base generally defined as a super strong acid. Also, a Lewis base may be coordinated. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹⁰ and R ¹¹ respectively represent a cyclopentadienyl group and a substituted group. A cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹² is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ¹³ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is the ion valence of [L ¹ -R ⁹ ] and [L ² ] and is 1
˜3, p is an integer of 1 or more, and q = (k × p). M ⁵ contains an element of Groups 1 to 11, 11 to 13 and ¹⁷ of the Periodic Table, and M ⁶ represents an element of Groups 7 to 12 of the Periodic Table. ] What is represented by these can be used conveniently.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, amines such as p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile. Specific examples of R ⁹ include hydrogen, methyl group, ethyl group, benzyl group, trityl group and the like, and specific examples of R ¹⁰ and R ¹¹ include cyclopentadienyl group and methylcyclopentadienyl group. An ethylcyclopentadienyl group,
Examples thereof include a pentamethylcyclopentadienyl group. Specific examples of R ¹² include phenyl group, p-tolyl group, p-methoxyphenyl group, and the like, and specific examples of R ¹³ include tetraphenylporphyrin, phthalocyanine, allyl, methallyl, and the like. . Further, as a specific example of M ⁵ , Li, N
a, K, Ag, Cu, Br, I, I _{3 and the} like, and specific examples of M ⁶ include Mn, Fe, Co and N.
Examples thereof include i and Zn.

[Z ¹ ] ^- , that is, [M ⁴ A ¹ A
² ... A ⁿ ], specific examples of M ⁴ include B and A.
1, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. As specific examples of A ¹ and A ^{2 to} A ⁿ , dimethylamino group, diethylamino group and the like as dialkylamino group, methoxy group, ethoxy group, n-butoxy group as alkoxy group or aryloxy group,
As a hydrocarbon group such as phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Fluorine, chlorine, bromine, etc. as halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group. Iodine, p-fluorophenyl group as a hydrocarbon group containing a hetero atom, 3,5
-Difluorophenyl group, pentachlorophenyl group,
3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as organic metalloid group pentamethylantimony group, trimethylsilyl group, trimethyl Examples thereof include germyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or Bronsted the slashed.nsted acid and Lewis acid combination conjugate base [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO ₃₎ ^-, bis (trifluoromethanesulfonyl ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , chlorosulfonate anion (ClS
O ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As)
F ₅ ) ⁻ , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{−, and the} like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows.
Triphenyl ammonium borate, tri-n-butyl ammonium tetraphenyl borate, trimethyl ammonium tetraphenyl borate, tetraethyl ammonium tetraphenyl borate, methyl (tri-n-butyl) ammonium tetraphenyl borate, benzyl tetraphenyl borate (tri-n- Butyl) ammonium, dimethyl diphenyl ammonium tetraphenyl borate, triphenyl (methyl) ammonium tetraphenyl borate, trimethylanilinium tetraphenyl borate, methyl pyridinium tetraphenyl borate, benzyl pyridinium tetraphenyl borate, methyl tetraphenyl borate (2-cyanopyridinium) , Trikis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) borate tetraethylammonium, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenyl borate, tetraphenyl porphyrin manganese tetraphenyl borate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate theoraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

The component (B-1), which is an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, may be used alone or in combination of two or more. You may use. On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (IX)

[0027]

[Chemical 3]

(In the formula, R ¹⁴ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
Hydrocarbon groups such as arylalkyl groups, s indicates the degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40).
A chain aluminoxane represented by the general formula (X)

[0029]

[Chemical 4]

(In the formula, R ¹⁴ and s are the same as the above.), And the cyclic aluminoxane shown can be mentioned. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.

Further, the Lewis acid as the component (B-3) is not particularly limited and may be an organic compound or a solid inorganic compound. A boron compound or an aluminum compound is preferably used as the organic compound, and a magnesium compound or an aluminum compound is preferably used as the inorganic compound.
Examples of the aluminum compound include bis (2,6-
Di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1-bi-2-naphthoxy) aluminum methyl and the like, magnesium compounds such as magnesium chloride and diethoxy magnesium, and aluminum compounds such as aluminum oxide. , Aluminum chloride, and the like, as the boron compound, for example, triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron. ,
Trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, Tris (3,5-difluoro) boron, Tris [3,3
5-bis (trifluoromethyl) phenyl) boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron,
Examples thereof include di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron and n-butyldifluoroboron. These Lewis acids may be used alone or in combination of two or more.

(A) in the polymerization catalyst used in the present invention
When the compound (B-1) is used as the component (B), the catalyst component and the component (B) are preferably used in a molar ratio of 10: 1 to 1: 100, more preferably 2 : 1 to 1:10, more preferably 1: 1 to 1: 5, and when the compound (B-2) is used, the molar ratio is preferably 1:20 to 1: 10000. The range of 1: 100 to 1: 2000 is desirable. Furthermore, when the compound (B-3) is used, the molar ratio is preferably 10: 1 to 1: 2000, more preferably 5: 1 to 1: 1000, and further preferably 2: 1 to 1: 5.
A range of 00 is desirable. The polymerization catalyst is the above-mentioned (A)
The component and the component (B) may be contained as the main components, and the component (A), the component (B) and the component (C) may be contained.
It may contain an organoaluminum compound as a main component. Here, the organoaluminum compound as the component (C) is represented by the general formula (XI) R ¹⁵ _r AlQ _3-r (XI) (wherein, R ¹⁵ is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Is an aryl group or a halogen atom, and r is an integer of 1 to 3).

Specific examples of the compound represented by the general formula (XI) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride and dimethyl. Aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The (A) catalyst component and (C) catalyst component are preferably used in a molar ratio of 1: 1 to 1: 200.
The range of 0, more preferably 1: 5 to 1: 1000, and further preferably 1:10 to 1: 500 is desirable. By using the (C) catalyst component, the polymerization activity per transition metal can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the method of the present invention, a small amount of catalyst components is used.
Use at least one supported on an appropriate inorganic carrier or organic substance
You can As the inorganic carrier, for example, SiO₂，
Al ₂O₃, MgO, ZrO₂, TiO₂, Fe
₂O₃, B₂O₃, CaO, ZnO, BaO, ThO₂
And mixtures of these, such as silica-alumina and zeoli.
G, ferrite, sepiolite, fiberglass
But also MgCl₂And Mg (OC₂H_Five)₂Such as
Examples thereof include magnesium compounds. On the other hand, organic carrier
For example, polystyrene, polyethylene, polyp
Heavy materials such as ropylene, substituted polystyrene and polyarylate
Examples include coalescing, starch, and carbon. these
Among the carriers, especially MgCl₂, Mg (OC₂H_Five)₂，
SiO₂, Al₂O ₃Etc. are suitable. In addition,
The average particle size is 1 to 300 μm, preferably 10 to 200 μm
m, more preferably 20-100 μm
Yes. In the method of the present invention, in the presence of the above polymerization catalyst
In addition, (a) there are few alkyl branches having 1 or more carbon atoms in the main chain.
Branched α-olefins having at least one and having a total carbon number of 7 or more
Of at least one selected from the
Is it a branched α-olefin of component (a) above?
At least one selected from (b) the branch of the (a) component
Α-olefins with 20 or less carbon atoms excluding α-olefins
Of at least one selected from the
A vinyl polymer is produced.

Examples of the branched α-olefin of the above-mentioned (a) monomer component include, for example, 3,5,5-trimethyl-1-hexene, 3-ethyl-1-hexene and 4,4-dimethyl-1-hexene. , 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene,
Examples thereof include 3-phenyl-1-butene, 3,4-dimethyl-1-pentene, 4,6-dimethyl-1-heptene, and among these, 3,5,5-trimethyl-1-hexene, 3 -Ethyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene and 3,4-dimethyl-1-pentene are preferred. These branched α-olefins may be used alone or in combination of two or more. On the other hand, as the α-olefin as the monomer component (b), for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-octadecene, 1-eicosene, and the like, among them, ethylene, propylene, 1-butene and 1-hexene are preferable, and further ethylene, propylene and 1-butene are preferable,
Ethylene and propylene are particularly preferable. These α
-The olefins may be used alone or in combination of two or more. Regarding the polymerization conditions in the method of the present invention, the monomer component and the catalyst component are used in such a ratio that the monomer component / (A) catalyst component molar ratio is usually 10 ⁷ / 1-1.
0/1, preferably chosen to be 10 ^{5/10 2/1.} The polymerization pressure is usually normal pressure to 30 kg /
cm ² G, the polymerization temperature is preferably as high as possible without impairing the catalytic activity, and usually −100 to 300.
C, preferably -50 to 200 C, more preferably 10
It is selected in the range of 180 ° C. The polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method or a suspension polymerization method may be used, but a slurry polymerization method or a gas phase polymerization method. Is particularly preferable.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, fats such as pentane, hexane, heptane and octane. Group hydrocarbons, halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent. Depending on the polymerization method, it can be carried out without a solvent. Examples of the method for adjusting the molecular weight of the polymer include selection of the type and amount of each catalyst component, the polymerization temperature, and the like.

In the method of the present invention, as the branched α-olefin of the above-mentioned (a) monomer component, for example, 3, 5, 5
In the case of producing an olefin-based random copolymer by copolymerizing -trimethyl-1-hexene with the α-olefin of the (b) monomer component, α of the (b) monomer component is used.
In an olefin-based copolymer, 3,
By incorporating 5,5-trimethyl-1-hexene unit in an amount of about 1 to 30 mol%, conventional α-olefin L-
Heat resistance is improved compared to LDPE. Also, 3, 5, 5-
In the copolymer mainly composed of trimethyl-1-hexene, the molding processability is remarkably improved by containing about 5 to 30 mol% of the unit derived from the α-olefin of the (b) monomer component. Further, a copolymer having an intermediate composition may not show a melting point in a differential scanning calorimeter (DSC) and may have better transparency. The olefin-based copolymer obtained by the method of the present invention,
Concentration measured in decalin solvent at 135 ℃ 0.05g
/ Reduced viscosity in deciliters (η _sp / c) is 0.01-3
0 deciliter / g, preferably 0.05 to 25 deciliter / g, more preferably 0.1 to 20 deciliter / g
It is desirable to be in the range of. If the reduced viscosity is less than 0.01 deciliter / g, the mechanical strength is poor, and if it exceeds 30 deciliter / g, the molding processability is deteriorated, which is not preferable. Further, the above-mentioned olefin-based copolymer obtained by the method of the present invention shows only one when it has a melting point, regardless of the usual composition, and the composition is extremely homogeneous. When the melting point is indicated, the melting point is usually 110-40.
It is in the range of 0 ° C. The melting point mentioned here is a value measured by the following method. That is, the differential scanning calorimeter (D
The maximum peak position of the melting peak observed when the olefin polymer is melted at a temperature higher than its melting point in (SC) and then the temperature is lowered to 30 ° C. at 20 ° C./min Is the melting point.

Next, the olefin-based copolymer of the present invention will be described. The olefin-based copolymer of the present invention is a branched type having a total carbon number of 7 to 9 having at least one alkyl branch having 1 to 99.9 mol% of ethylene units and / or propylene units and 1 or more carbon atoms in the main chain. Units derived from at least one monomer selected from α-olefins 99 to
It is a random copolymer composed of 0.1 mol%. The branched α-olefin having a total of 7 to 9 carbon atoms having at least one alkyl branch having 1 or more carbon atoms in the main chain,
For example, 3,5,5-trimethyl-1-hexene, 3-ethyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 3,4dimethyl-1-pentene, etc. Can be preferably mentioned. These may be used alone or in combination of two or more. Further, this olefin-based copolymer has a reduced viscosity (η _sp / c) of 0.01 to 30 deciliter / g at a concentration of 0.05 g / deciliter measured in a decalin solvent at a temperature of 135 ° C., preferably 0.03. It is in the range of 05 to 25 deciliter / g, more preferably 0.1 to 20 deciliter / g. If the reduced viscosity is less than 0.01 deciliter / g, the mechanical strength will be poor, and if it exceeds 30 deciliter / g, the moldability will be deteriorated. In addition, the melting peak in differential scanning calorimetry measurement is usually 1 or 0, and has a homogeneous composition. The method for producing the olefin-based copolymer of the present invention is not particularly limited, and any method may be used as long as a copolymer satisfying the above conditions is obtained, but it is advantageous to apply the method of the present invention. is there. The olefin-based copolymer of the present invention is excellent in heat resistance, transparency, and mechanical properties, has good moldability, and is useful as a polyolefin-based engineering resin.

[0039]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Preparation Example 1 Production of dimethylanilinium tetrakis (pentafluorophenyl) borate Pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) was reacted with 45 mmol of boron trichloride in hexane. To give tris (pentafluorophenyl) boron as a white solid. 41 mmol of this tris (pentafluorophenyl) boron was reacted with 41 mmol of pentafluorophenyllithium to obtain lithium tetrakis (pentafluorophenyl) boric acid as a white solid. Then, by reacting 16 mmol of lithium tetrakis (pentafluorophenyl) borate with 16 mmol of dimethylaniline hydrochloride in water, dimethylanilinium tetrakis (pentafluorophenyl) borate [[PhMe ₂ NH] [B (C ₆ F ₅ ) ₄ ]] as a white solid was obtained. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the product was the desired product.

Preparation Example 2 Preparation of Methylaluminoxane 200 ml of toluene, 17.8 g (71 mmol) of copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) and trimethylaluminum were placed in a glass container having an inner volume of 500 ml and purged with argon. 24 ml (250
(Mmol) and added, and reacted at 40 ° C. for 8 hours. Then, toluene was distilled off under reduced pressure from the solution obtained by removing the solid component to obtain 6.7 g of a catalyst product (methylaluminoxane). The molecular weight of this product measured by the freezing point depression method was 610. Also, JP-A-62-32
A high magnetic field component measured by ¹ H-NMR measurement based on Japanese Patent No. 5391, that is, when its proton nuclear magnetic resonance spectrum is observed in a toluene solution at room temperature, a methyl proton signal based on an “Al—CH ₃ ” bond is a tetramethylsilane standard. It is found in the range of 1.0 to -0.5 ppm.
Since the proton signal of tetramethylsilane (0 ppm) is in the observation area of the methyl proton based on the "Al-CH _3" bonds, the "Al-CH _3" methyl proton signal based on the binding of toluene in tetramethylsilane reference Methyl proton signal 2.35ppm
The high magnetic field component (i.e., -0.1 to -0.
5 ppm) and other magnetic field components (ie 1.0 to -0.1 ppm)
When divided into and, the high magnetic field component was 43% of the whole.

Example 1 340 ml of toluene, 254 mmol of 3,5,5-trimethyl-1-hexene, 1 mmol of triisobutylaluminum, 1 mmol of tetrakis (prepared in Preparation Example 1 in a 1 liter pressure-resistant autoclave at room temperature under a nitrogen atmosphere. 1 μmol of dimethylarinium pentafluorophenyl) borate and 1 μmol of ethylenebisindenylzirconium dichloride were added and the temperature was raised rapidly up to 80 ° C., and ethylene was continuously supplied at a partial pressure of 8 kg / cm ² G for 1 hour. Polymerization was carried out. After completion of the polymerization, unreacted ethylene was removed by depressurization, the copolymer was collected by filtration and dried to obtain 37.2 g of a white solid. By NMR measurement, the content of 3,5,5-trimethyl-1-hexene unit in the copolymer was 1.5 mol%, and the melting point measured by DSC was 1
It was 23.5 ° C. It can be said that a random copolymer is formed because it is lower than the melting point of ordinary high-density polyethylene. The reduced viscosity (η _sp / c) at a concentration of 0.05 g / deciliter measured at 135 ° C. in a decalin solvent was 1.27 deciliter / g.

Examples 2 to 4 Copolymers were produced in the same manner as in Example 1 except that the polymerization conditions were changed as shown in Table 1.
In Examples 3 and 4, 5 mmol of methylaluminoxane obtained in Preparation Example 2 was used instead of dimethylanilinium tetrakis (pentafluorophenyl) borate. The results are shown in Table 1.

[0043]

[Table 1]

Note 1) TM1H: 3,5,5-trimethyl-1-hexene 2) 3E1H: 3-Ethyl-1-hexene Comparative Examples 1 and 2 Titanium trichloride 1 with the monomer charging composition of Examples 1 and 3 Copolymerization was carried out using 3 mmol of triethylaluminum and 3 mmol of triethylaluminum as catalyst components. DSC of the obtained polymer
As a result of the measurement, the melting point was 136 ° C. in all cases, which was in agreement with the melting point of the high-density polyethylene.

Example 5 1.985 mol of 3,5,5-trimethyl-1-hexene was made into a toluene solution having a total amount of 500 ml, and homopolymerization was carried out at 80 ° C. in the catalyst system of Example 1 without adding ethylene.
I went on time. Then, add hydrochloric acid-methanol to stop the polymerization, decalcify the catalyst, thoroughly wash the produced polymer with methanol, and then dry under reduced pressure to obtain a white powder polymer.
174.2 g (yield 75%) was obtained.

[0046]

According to the method of the present invention, the conventional L-LD is used.
It is possible to improve the heat resistance, transparency, and mechanical properties of PE, and efficiently produce an olefin polymer having a homogeneous composition with improved moldability. The olefin-based copolymer of the present invention is a random copolymer of ethylene and / or propylene and a branched α-olefin having a total carbon number of 7 to 9, and has the above-mentioned characteristics, and is a polyolefin-based engineering product. It is useful as a resin.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-17522 (JP, A) JP-A-4-311707 (JP, A) JP-A-5-331232 (JP, A) JP-B-2- 24287 (JP, B2) Special Table HEI 7-505912 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (2)

(57) [Claims] 1. (A) General formula (I), (II), (III)
Or ^{_{(IV) CpM 1 R 1 a}} R 2 b R 3 c ··· (I) Cp 2 M 1 R 1 a R 2 b ··· (II) (Cp-A e -Cp) M 1 R 1 a R ² _b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV) [In the formula, M ¹ is titanium, zirconium or hafnium.
Show. Cp is a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon
Indicates a hydrogen group, and in the general formulas (II) and (III), two
Cp may be the same or different from each other
May be R ¹ , R ² , R ³ and R ⁴ are respectively
Independently, a sigma-bonding ligand, a chelating ligand or a ligand.
Is a chair base, and R ¹ , R ² , R ³ and R ⁴ are 2 or more.
The tops may combine with each other to form a ring. A is a covalent bond
Shows the cross-linking by a, b, c and d are each independently
The integer of 0-4 and e show the integer of 0-6. ]]
A transition metal compound , (B) a compound capable of reacting with the transition metal compound or a derivative thereof to form an ionic complex, and
(C) the general formula ^{_{(XI) R 15 r AlQ 3}} -r ··· (XI) ( ^{wherein, R 15} represents an alkyl group having 1 to 10 carbon atoms, Q is water
Elementary atom, C1-C20 alkoxy group, C6-C2
0 represents an aryl group or a halogen atom, r is 1 to 3
From an organoaluminum compound represented by
And (b) polymerizing at least one selected from branched α-olefins having a total of 7 or more carbon atoms having at least one alkyl branch having 1 or more carbon atoms in the main chain, using the catalyst system Alternatively, the branched type α-of the above (a) component
At least one selected from olefins and (b) at least one selected from α-olefins having 20 or less carbon atoms excluding the branched α-olefin of the component (a). A method for producing an olefin polymer. 2. Ethylene units and / or propylene units
Units derived from at least one monomer selected from branched α-olefins having 5 to 30 mol% and a total of 7 to 9 carbon atoms and at least one alkyl branch having 1 or more carbon atoms in the main chain. It consists of a 9 5-70 mol%, and the temperature 13
During 5 ° C. in decalin, reduced viscosity at 0.05 g / dl concentration Ah at 0.01 to 30 dl / g
When the melting point is shown, only one is shown and the melting point is 1
An olefin-based random copolymer, which is in the range of 10 to 400 ° C.