JP3433431B2 - Ethylene copolymer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel ethylene copolymer and a method for producing the same. More specifically, the present invention relates to an ethylene-based copolymer having highly improved molding and processing properties and optical properties, and a method for efficiently producing the same.

[0002]

2. Description of the Related Art Conventionally, ethylene-based (co) polymers have been widely used in many fields as general-purpose resins.
It has the following problems, and its improvement has been strongly desired. For example, linear low density polyethylene (L-LD
In PE) and high density polyethylene (HDPE), the activation energy of the flow in the molten state is small, and the moldability is inferior to that of low density polyethylene (LDPE). Particularly, the high molecular weight polymer has poor moldability, It has an inherent problem. In addition, the ethylene-based (co) polymer has a problem of neck-in when forming a sheet or a film,
Further, there is a problem that linear low density polyethylene is inferior in transparency and heat sealability.

As a method for solving such a problem, for example, an olefin-based copolymer having a long-chain branch using an α, ω-diene compound or a cyclic endomethylene-based diene compound has been disclosed (Japanese Patent Laid-Open Publication No. Sho-Sho). 47-34981). However, in this olefin-based copolymer, the diene component is involved in the long-chain branching, and at the same time, a crosslinking reaction occurs concurrently and a gel is generated during film molding, and the melting property is adversely decreased, and the control range is reduced. It has the drawback of being extremely narrow. Further, the copolymerization reactivity is low, and there is a problem that the physical properties are deteriorated due to the formation of a low molecular weight substance.

Further, when the non-conjugated diene compound is copolymerized with the olefin, the polymerization is carried out in two steps so that the content of the non-conjugated diene compound unit in the high molecular weight part is higher than that in the low molecular weight part. A characteristic manufacturing method is disclosed (JP-A-59-56412). However, this method involves introducing long chain branching into the high molecular weight component,
Since the increase in molecular weight due to cross-linking is significant, there is a high possibility that insolubilization and gelation will occur at the same time, and the control range is narrow, and the copolymerization reactivity is low. There is also.

Further, an ethylene / α-olefin / 1,5-hexadiene copolymer using a metallocene / aluminoxane catalyst has been disclosed (Japanese Patent Publication No. 01-501).
555 publication). However, in this copolymer, the molecular weight distribution is narrow, which is disadvantageous for blow molding and film molding, and at the same time, the cyclization reaction of 1,5-hexadiene progresses to form a branch point, which is effective. It has the disadvantage of low monomer concentration.

[0006]

Under these circumstances, the present invention allows the activation energy of the flow of the melt to be arbitrarily controlled, enables high-speed molding, has a low processing cost, and The object of the present invention is to provide an ethylene copolymer having improved transparency and uniformity, and a method for efficiently producing the same.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that ethylene units and specific aromatic diolefin units, or ethylene units and other α-olefin units. An ethylene-based copolymer having a specific property consisting of and a specific aromatic diolefin unit can meet the above purpose, and this ethylene-based copolymer can be efficiently produced by using a specific polymerization catalyst. I found that I could do it. The present invention has been completed based on such findings.

That is, the present invention relates to an ethylene unit and a diolefin unit, or an ethylene unit and an α-containing 3 or more carbon atoms.
In a copolymer comprising an olefin unit and a diolefin unit, (a) the diolefin unit has the general formula (I)

[0009]

[Chemical 2]

(In the formula, R'is a hydrogen atom, a halogen atom,
Or a substituent containing at least one of a carbon atom and a silicon atom, R ″ is a vinyl group, f is an integer of 1 to 4, and f is
When is 2 or more, plural R's may be the same or different. ) Having a branch point derived from a diolefin monomer, (b) having a density (D) of 0.86 to 0.97 g / cm ³ , (c) a differential scanning calorimeter ( The relationship between the crystallization enthalpy (ΔH) and the density (D) observable by DSC satisfies the expression 1417D-1206 ≦ ΔH ≦ 1417D-1161 (where ΔH ≧ 0), (d) Temperature 190 ° C. , A melt index (MI) measured under a load of 2.16 kg is 0.001 to 2000
g / 10 minutes, or in decalin, temperature 135 ° C., concentration 0.
The reduced viscosity measured under the condition of 2 g / deciliter is 0.0.
5 to 20 deciliters / g, (e) containing 0.35 to 3 mol% of diolefin units,
And that the two reaction sites of the diolefin unit include a crosslinked structure reacted with an ethylene unit and / or an α-olefin unit having 3 or more carbon atoms, and (f) the content of the monomer unit other than the ethylene unit is 30.
It is intended to provide an ethylene-based copolymer characterized by being in an amount of not more than wt%.

The ethylene-based copolymer is, for example,
In the presence of a polymerization catalyst containing (A) a transition metal compound and (B) a compound capable of forming a cationic species from the transition metal compound of the component (A) or a derivative thereof, ethylene and the above general formula ( It can be produced by copolymerizing the diolefin represented by I) or ethylene, the α-olefin having 3 or more carbon atoms and the diolefin represented by the general formula (I). The ethylene unit, α-olefin unit and diolefin unit in the present invention refer to repeating units derived from ethylene, α-olefin and diolefin monomers, respectively.

In the ethylene copolymer of the present invention, ethylene and a diolefin, or ethylene, an α-olefin having 3 or more carbon atoms, and a diolefin are used as raw material monomers. As the α-olefin having 3 or more carbon atoms, an aliphatic α-olefin having 3 to 20 carbon atoms, styrene and its derivative are used. Examples of the aliphatic α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1
-Pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
-Examples include eicosene.

Examples of styrene and its derivatives (having a substituent containing carbon, halogen, silicon, etc.) include, for example, styrene, p-methylstyrene, o.
-Methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, pt-
Alkyl styrene such as butyl styrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p
-Halogenated styrene such as -bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, 4-vinylbiphenyl, 3- Examples thereof include vinyl biphenyls such as vinyl biphenyl and 2-vinyl biphenyl. In the present invention, these α-olefins may be used alone,
You may use it in combination of 2 or more type. On the other hand, as the diolefin, general formula (I)

[0014]

[Chemical 3]

An aromatic diolefin represented by the formula (wherein R ', R "and f are the same as above) is used.
Examples of such compounds include p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, di- (p-vinylphenyl) methane, 1,3-bis (p-
Examples thereof include vinylphenyl) propane and 1,5-bis (p-vinylphenyl) pentane. These diolefins may be used alone or in combination of two or more.

To produce the ethylene-based copolymer of the present invention,
As the polymerization catalyst, those containing (A) a transition metal compound and (B) a compound capable of forming a cationic species from the transition metal compound of the component (A) or a derivative thereof as a main component are used. As the transition metal compound of the component (A), a transition metal compound containing a metal belonging to Group 3 to 10 of the periodic table or a lanthanoid series metal can be used. As the transition metal, specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum or the like is preferable, and zirconium, hafnium, titanium, nickel or palladium is particularly preferable. Examples of such a transition metal compound include various compounds, particularly compounds containing a transition metal of Groups 4 and 8 to 10, particularly a transition metal selected from Group 4 of the periodic table, that is, titanium, zirconium or hafnium. A compound containing is preferably used. In particular,
Formula ^{_{CpM 1 R 1 a R 2 b}} R 3 c ··· (II) Cp 2 M 1 R 1 a R 2 b ··· (III) (Cp-A e -Cp) M 1 R 1 a R 2 _The compound represented by _b ... (IV) or the general formula M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (V) or a derivative thereof is preferable.

In the above general formulas (II) to (V), M¹
Is the periodic table of titanium, zirconium or hafnium
Indicates a Group 4 transition metal, 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. R¹, R ², R³And R^FourEach is German
Vertical σ-bonding ligand, chelating ligand, Lewis salt
A ligand such as a group is shown, and as a σ-bonding ligand,
Physically, hydrogen atom, oxygen atom, halogen atom, carbon number 1
~ 20 alkyl groups, C1-20 alkoxy groups,
C6-C20 aryl group, alkylaryl group
Or arylalkyl group, acyloxy group having 1 to 20 carbon atoms
Si group, allyl group, substituted allyl group, substitution containing silicon atom
Groups and the like, and as the chelating ligand,
Acetylacetonate group, Substituted acetylacetonate group
Can be exemplified. A indicates crosslinking by covalent bond.
a, b, c and d are each independently an integer of 0 to 4, and e is
Indicates an integer of 0 to 6. R¹, R², R³And R^FourIs that
Two or more may combine with each other to form a ring. Cp above
Has a substituent, the substituent has 1 to 20 carbon atoms.
Alkyl groups of are preferred. Smell of formula (III) and formula (IV)
Therefore, two Cp's may be the same or different from each other.
It may be

In the above formulas (II) to (IV), the substituted cyclo
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, (II) ~
R in formula (V) 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, chain unsaturated
As hydrocarbons, ethylene; butadiene; 1-pente
Isoprene; Pentadiene; 1-Hexene and this
As a derivative thereof, as a cyclic unsaturated hydrocarbon, benzene;
Ruene; Xylene; Cycloheptatriene; Cyclooctane
Tadiene; Cyclooctatriene; Cyclooctatetra
Examples thereof include ene and derivatives thereof. Also, above
Examples of the covalent cross-linking of A in the formula (IV) include
For example, methylene bridge, dimethylmethylene bridge, ethylene
Cross-linked, 1,1'-cyclohexylene cross-linked, dimethylsilyl
Lene cross-link, dimethyl germylene cross-link, dimethyl stannile
And cross-linking.

Examples of the compound represented by the general formula (II) 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 (III) 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) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethyi) Rucyclopentadienyl) 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 (IV) 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 (V) 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.

Further, as the component (A), in the general formula (IV), two substituted or unsubstituted conjugated cyclopentadienyl groups (provided that at least one is a substituted cyclopentadienyl group). A group 4 transition compound having a multicoordinating compound, which is bonded to each other via an element selected from group 14 of the periodic table, as a ligand can be preferably used. Examples of such a compound include general formula (VI)

[0024]

[Chemical 4]

Examples of the compound represented by
You can Y in the general formula (VI)¹Is carbon
Ion, germanium or tin atom, R^Five _t-C_FiveH_4-t
And R^Five _u-C_FiveH_4-uAre each substituted cyclopentadi
The enyl group, t and u represent an integer of 1 to 4. Where R
^FiveAre hydrogen atoms, silyl groups or hydrocarbon groups, and
It may be the same or different. Also, at least
One cyclopentadienyl group contains Y¹Is bound to
R on at least one carbon next to the carbon^FiveExists
It R⁶Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or
C6-C20 aryl group, alkylaryl group
Represents an arylalkyl group. M²Is titanium, zirco
X represents a hydrogen atom or halo.
Gen atom, alkyl group having 1 to 20 carbon atoms, 6 to 2 carbon atoms
0 aryl group, alkylaryl group or aryl
An alkyl group or an alkoxy group having 1 to 20 carbon atoms is shown.
X¹R may be the same or different from each other, and R⁶
May be the same as or different from each other.

Examples of the substituted cyclopentadienyl group in the general formula (VI) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 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 methyl group, ethyl group, phenyl group, tolyl group, xylyl group, and benzyl group. Examples of the compound of the general formula (VI) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, and compounds in which this zirconium is replaced with titanium or hafnium. Furthermore, the general formula (VII)

[0027]

[Chemical 5]

It also includes compounds represented by: The general formula
In the compound of (VII), 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
Alkyl, aryl, silane with up to 20 non-hydrogen atoms
Ryl, halogenated alkyl, halogenated aryl groups and
R is a group selected from those combinations,⁸Is the carbon number
1-10 alkyl or 6-10 carbon aryl
A group or one or more R⁷And 30
Up to a non-hydrogen atom fused ring system may be formed. w is 1
Or 2 is shown.

The transition metal compound containing a transition metal of Groups 5 to 10 is not particularly limited, and specific examples of the chromium compound include tetramethylchromium, tetra (t-butoxy) chromium, and bis (cyclopentadiene). Enyl) chrome,
Hydride tricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyl tris (triphenylphosphonate) chromium, tris (allyl)
Examples include chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like.

Specific examples of the manganese compound include trica
Lubonyl (cyclopentadienyl) manganese, pentaca
Rubonyl methyl manganese, bis (cyclopentadiene
Le) manganese, manganese bis (acetylacetonate)
And so on. Specific examples of nickel compounds include
Dicarbonyl bis (triphenylphosphine) nickel
Le, dibromobis (triphenylphosphine) nickel
Dinitrogen bis [bis (tricyclohexylphosphine
Nickel), chlorohydridobis (tricyclohexyl)
Sylphosphine) nickel, chloro (phenyl) bis
(Triphenylphosphine) nickel, dimethylbis
(Trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel
Le, bis (cyclopentadienyl) nickel, bis (me
Cylcyclopentadienyl) nickel, bis (pentame
Cylcyclopentadienyl) nickel, allyl (cyclo
Pentadienyl) nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroboric acid
Salt, bis (cyclooctadiene) nickel, nickel bi
Sacetylacetonate, allyl nickel chloride,
Tetrakis (triphenylphosphine) nickel, chloride
Nickel, formula (C₆H_Five) Ni [OC (C₆H_Five) CH = P (C
₆H_Five)₂] [P (C₆H_Five)₃], (C₆H_Five) Ni [OC
(C₆H_Five) C (SO₃Na) = P (C₆H_Five)₂] [P
(C ₆H_Five)₃] And the like.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanate) palladium, and palladium bis (acetylacetonate). ), Dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5-cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetra Fluoroborate, (acetylacetonato) (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium tetrafluoroborate, etc. It is. In the polymerization catalyst used in the present invention, the transition metal compound of the component (A) may be used alone or in combination of two or more kinds.

On the other hand, in the polymerization catalyst, the compound used as the component (B) and capable of forming a cation species from the transition metal compound of the component (A) or a derivative thereof is (B-1) A compound which reacts with the transition metal compound of the component (A) to form an ionic complex, and (B-
2) Aluminoxane etc. can be illustrated.

As the compound of the component (B-1), any compound can be used as long as it can react with the transition metal compound of the component (A) to form an ionic complex. A compound composed of an anion in which a plurality of groups are bound to an element, particularly a coordination complex compound composed of a cation and an anion in which a plurality of groups are bound to an element, can be preferably used. As a compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the general formula ([L ¹ -R ⁹ ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² ·· Z ⁿ ] ^{(nm) -} ) _Q・ ・ ・ (VIII) or ([L ² ] ^{k +} ) _p ([M ⁵ Z ¹ Z ² ·· Z ⁿ ] ^(nm)- ) _q・ ・ ・ (IX) (where L ² is M ⁶ , R ¹⁰ R ¹¹ M ⁷ , R ¹² ₃ C or R ¹³ M ⁷ ) [In the formula, L ¹ is a Lewis base, M ⁴ and M ⁵ are groups 5, 6 and 7 of the periodic table, respectively. , 8-10 groups, 11 groups, 12
An element selected from Group 13, 13, 14 and 15 groups, preferably an element selected from Group 13, 14 and 15 groups, M
⁶ and M ⁷ are the 3rd, 4th, 5th, and 6th groups of the periodic table, respectively.
An element selected from Group 7, Group 7, 8-10, Group 1, 11, Group 2, 12 and Group 17, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, and an alkoxy group having 1 to 20 carbon atoms, respectively. Group, aryloxy group having 6 to 20 carbon atoms, 1 to carbon atoms
20 alkyl group, C 6-20 aryl group, alkylaryl group, arylalkyl group, C 1-20
Represents a halogen-substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group or a halogen atom,
¹ to Z ⁿ may form a ring of two or more thereof with each other. 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 cyclopenta group. Dienyl group, indenyl group or fluorenyl group, R ¹² has 1 carbon atom
To 20 alkyl groups, aryl groups, alkylaryl groups or arylalkyl groups. R ¹³ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. m is the valence of M ⁴ and M ⁵ , and is an integer of 1 to 7, and n is 2
8 is an integer, k is an ionic valence of [L ¹ -R ⁹ ], [L ² ] and is an integer of 1 to 7, p is an integer of 1 or more, q = (p × k) /
(Nm). ] It is a compound represented by these.

Specific examples of the Lewis base represented by L ¹ are ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, N. , N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
-Amines such as dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, dioxane, thioethers such as diethylthioether and tetrahydrothiophene, ethylbenzoate And the like.

As specific examples of M ⁴ and M ⁵ ,
B, Al, Si, P, As, Sb, etc., preferably B or P, M ⁶ are exemplified by Li, Na, Ag, C.
Specific examples of M ⁷ , such as u, Br, and I, include Mn and F.
e, Co, Ni, Zn, etc. may be mentioned. Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group as a dialkylamino group; a diethylamino group, a methoxy group, an ethoxy group, an n-butoxy group, and a carbon number of 6 to 20 as an alkoxy group having 1 to 20 carbon atoms. Phenoxy group as an aryloxy group; 2,6-dimethylphenoxy group; naphthyloxy group, methyl group as an alkyl group having 1 to 20 carbon atoms;
Ethyl group; n-propyl group; isopropyl group; n-butyl group; n-octyl group; 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms; phenyl group as an alkylaryl group or arylalkyl group; p-tolyl group Benzyl group; 4-t-butylphenyl group; 2,6-dimethylphenyl group; 3,5-dimethylphenyl group; 2,4-
Dimethylphenyl group; 2,3-dimethylphenyl group; p-fluorophenyl group as halogen-substituted hydrocarbon group having 1 to 20 carbon atoms; 3,5-difluorophenyl group; pentachlorophenyl group; 3,4,5-trifluoro group Phenyl group; pentafluorophenyl group; 3,5-di (trifluoromethyl) phenyl group, F, C as halogen atom
1, Br, I, pentamethylantimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group,
Examples thereof include diphenylarsine group, dicyclohexylantimony group, and diphenylboron group. Specific examples of R ⁹ and R ¹² include the same as those mentioned above.
Specific examples of the substituted cyclopentadienyl group for R ¹⁰ and R ¹¹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. To be Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups is an integer of 1 to 5.

Among the compounds of the above general formulas (VIII) and (IX), those in which M ⁴ and M ⁵ are boron are preferable. Among the compounds of the general formulas (VIII) and (IX), the following compounds can be used particularly preferably. For example, as the compound of the general formula (VIII), triphenylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate,
Tetraphenylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate,
Benzyltri (n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate,
Methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, benzylmethylsulfonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro (Phenyl) borate tri (n-butyl) ammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetrabutylammonium, tetrakis (pentafluorophenyl) borate tetraethylammonium, tetrakis (pentafluorophenyl) borate [Methyltri (n-butyl) ammonium], tetrakis (pentafluorophenyl) ) Borate [benzyltri (n-butyl) ammonium], tetrakis (pentafluorophenyl) borate methyldiphenylammonium, tetrakis (pentafluorophenyl) borate methyltriphenylammonium, tetrakis (pentafluorophenyl) borate dimethyldiphenylammonium, tetrakis (pentafluoro) Phenyl) anilinium borate, tetrakis (pentafluorophenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyl tetrakis (pentafluorophenylmethyl) borate (p- Bromoanilinium), pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate ( N-benzylpyridinium),
Tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-) Benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrafelphosphonium tetrakis (pentafluorophenyl) borate, dimethylanili tetrakis (3,5-ditrifluoromethylphenyl) borate Nium, tris (pentafluorophenyl)
Dimethylanilinium (p-trifluoromethyltetrafluorophenyl) borate, triethylammonium tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) ) Pyridinium borate, tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (N-methylpyridinium), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate (o-cyano-) N-methylpyridinium), tris (pentafluorophenyl)
(P-Trifluoromethyltetrafluorophenyl) borate (p-cyano-N-benzylpyridinium), tris (pentafluorophenyl) (p-trifluoromethyltetrafluorophenyl) borate triphenylphosphonium, tris (pentafluorophenyl) ( 2, 3, 5,
Dimethylanilinium 6-tetrafluoropyridinyl) borate, tris (pentafluorophenyl) (2,3,3
5,6-Tetrafluoropyridinyl) borate triethylammonium, tris (pentafluorophenyl) (2,
3,5,6-Tetrafluoropyridinyl) pyridinium borate, tris (pentafluorophenyl) (2,3,3
5,6-Tetrafluoropyridinyl) boric acid (N-methylpyridinium), tris (pentafluorophenyl)
(2,3,5,6-tetrafluoropyridinyl) boric acid (o-cyano-N-methylpyridinium), tris (pentafluorophenyl) (2,3,5,6-tetrafluoropyridinyl) boric acid ( p-cyano-N-benzylpyridinium), tris (pentafluorophenyl) (2,
3,5,6-Tetrafluoropyridinyl) borate triphenylphosphonium, tris (pentafluorophenyl)
Dimethylanilinium (phenyl) borate, Tris (pentafluorophenyl) [3,5-di (trifluoromethyl) phenyl] dimethylanilinium borate, Tris (pentafluorophenyl) (4-trifluoromethylphenyl) dimethylanilinium borate , Dimethylanilinium triphenyl (pentafluorophenyl) borate, trimethylammonium hexafluoroarsenate, and the like.

On the other hand, examples of the compound of the general formula (IX) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) ferrocenium borate, tetrakis (Pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) borate acetylferrocenium, tetrakis (pentafluorophenyl) borate Formylferrocenium, tetrakis (pentafluorophenyl) borate cyanoferrocenium, tetrakis (pentafluorophenyl) borate silver, tetrakis (pentafluorophenyl) borate triti , Lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetrakis (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetrakis ( Pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate and the like can be mentioned. Examples of compounds other than the general formulas (VIII) and (IX) include tris (pentafluorophenyl) boric acid and tris [3,5-di (trifluoromethyl)
Phenyl] boric acid, triphenylboric acid, etc. can also be used.

The component (B-1), 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. Good. On the other hand, as the aluminoxane as the component (B-2), a compound represented by the general formula (X)

[0039]

[Chemical 6]

[Wherein R ¹⁴ is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group, s is a degree of polymerization, and usually 3 It is an integer of -50, preferably 7-40. ] Chain aluminoxane represented by, and the general formula (XI)

[0041]

[Chemical 7]

[In the formula, R ¹⁴ and s are the same as defined above. ] The cyclic aluminoxane represented by these can be mentioned. Among the compounds represented by the general formulas (X) and (XI), aluminoxane having a degree of polymerization of 7 or more is preferable. When the aluminoxane having a degree of polymerization of 7 or more or a mixture thereof is used, high activity can be obtained. Further, a modified aluminoxane which is insoluble in a general solvent obtained by modifying the aluminoxane represented by the general formulas (X) and (XI) with a compound having active hydrogen such as water can also be preferably used.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other. The means therefor is not particularly limited, and the reaction may be carried out according to a known method. For example, an organoaluminum compound is dissolved in an organic solvent, a method of bringing it into contact with water, a method of initially adding an organoaluminum compound during polymerization, and a method of adding water later, water of crystallization contained in a metal salt, There are a method of reacting water adsorbed on 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. These aluminoxanes may be used alone or in combination of two or more.

In the present invention, as the catalyst component (B), only the component (B-1) may be used, or (B-
The component (2) may be used alone, or the component (B-1) and the component (B-2) may be used in combination. In the polymerization catalyst used in the present invention, if desired, as the component (C),
Formula ^{_{(XII) R 14 r AlQ 3}} -r ··· (XII) ( wherein, R ¹⁴ is as defined above, Q is a hydrogen atom,
It represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is a number of 1 to 3. ) An organoaluminum compound represented by In particular, when a compound which reacts with the transition metal compound of the component (A) shown as the component (B-1) to form an ionic complex is used as the component (B), the organoaluminum compound (C) is used in combination. It is possible to obtain higher activity. The general formula (XII)
Specific examples of the compound represented by, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride,
Methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned.

Next, in the present invention, the above (A),
At least one of (B) and the (C) catalyst component used as desired can be used by supporting it on a suitable carrier. The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and organic carriers can be used, but an inorganic oxide carrier or another inorganic carrier is particularly preferable. As the inorganic oxide carrier,
Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, Zn
Examples include O, BaO, ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite, and glass fiber. Among these, especially SiO ₂ , A
1 ₂ O ₃ is preferred. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like. On the other hand, as inorganic carriers other than the above, MgCl ₂ , Mg (O
Examples thereof include magnesium compounds such as C ₂ H ₅ ) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ¹⁵ _X X ³ _y . Here, R ¹⁵ has 1 carbon atom
To an alkyl group having 20 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ³ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, and x represents 0 to 2 or y.
Is 0 to 2.

As the organic carrier, polystyrene,
Examples thereof include polymers such as polyethylene, polypropylene, substituted polystyrene and polyarylate, starch and carbon. Here, the properties of the carrier used vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² /
g, preferably 50 to 500 m ² / g, the pore volume is usually
It is 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained from the volume of nitrogen gas adsorbed according to the BET method (Journal of American Chemical Society, No. 60).
Vol., Page 309 (1983)). Further, the carrier is usually 150 to 1000 ° C., preferably 200.
It is desirable to use by firing at ~ 800 ° C. The method of loading on the carrier is not particularly limited, and a conventionally used method can be used.

Next, the use ratio of each catalyst component in the present invention will be described. When (1) (A) component and (B-1) component are used as the catalyst component, (A) component /
The component (B-1) has a molar ratio of 1 / 0.1 to 1/100, preferably 1 / 0.5 to 1/10, and more preferably 1/1 to 1 /.
It is desirable to use both components so as to be in the range of 5.
(2) When the component (A), the component (B-1) and the component (C) are used, the molar ratio of the component (A) / the component (B-1) is the same as the case (1). However, the molar ratio of component (A) / component (C) is 1/2000 to 1/1, preferably 1/10.
It is desirable to be in the range of 00 to 1/5, more preferably 1/500 to 1/10. Moreover, when using (3) (A) component and (B-2) component, (A) component / (B
-2) It is desirable to use both components so that the component molar ratio is in the range of 1/20 to 1/10000, preferably 1/100 to 1/2000. (4) (A) component and (B-
When the 2) component and the (C) component are used, the molar ratio of the (A) component / (B-2) component is the same as that of the above (3), but the (A) component / (C) component is used. The molar ratio is 1 / 2000-
It is preferably 1/1, preferably 1/1000 to 1/5, more preferably 1/500 to 1/10.

The ethylene-based polymer of the present invention comprises ethylene and a diolefin represented by the general formula (I) or ethylene and α-olefin and the general formula (I) in the presence of the above-mentioned polymerization catalyst.
It is obtained by copolymerizing with a diolefin represented by Ratio of the monomer component and the catalyst component is a monomer component / (A) catalyst component molar ratio, typically 10 ^7/10
/ 1, preferably chosen to be 10 ^{5/10 2/1.} The polymerization pressure is usually normal pressure to 30 kg / c.
The polymerization temperature is preferably selected within the range of m ² · G, and is preferably as high as possible without impairing the catalytic activity.
C, preferably -50 to 200 C, more preferably 10
It is selected in the range of 180 ° C. The density of the ethylene copolymer of the present invention thus obtained is 0.86 to 0.97 g.
The range is / cm ³ . This density can be controlled in the above range, that is, in a wide range from ultra-low density polyethylene to high-density polyethylene, by the content of α-olefin units such as butene-1 and octene-1 and the branch density.

Further, the copolymer of the present invention has a crystallization exothermic peak which can be observed by a differential scanning calorimeter (DSC) when the temperature of the molten resin is lowered, that is, a crystallization enthalpy (Δ
H) and the density (D) must satisfy the expression 1417D-1220 ≦ ΔH ≦ 1417D-1150, preferably 1417D-1214 ≦ ΔH ≦ 1417D-1156, more preferably 1417D-1206 ≦ ΔH ≦ 1417D-1161. Is. This enthalpy of crystallization decreases with increasing α-olefin unit content and can be varied with branching density. The crystallization enthalpy is 1 for sheets pressed at 190 ° C.
After melting at 50 ° C for 5 minutes, -5 at a rate of 10 ° C / minute
This is a value calculated by measuring the exothermic peak of crystallization observed when the temperature was lowered to 0 ° C. by a differential scanning calorimeter and calculating from the area of the crystallization peak.

The copolymer of the present invention has a temperature of 190 ° C. and a load.
Melt index (M
I) is 0.001 to 2000 g / 10 minutes, preferably 0.0
05-1500g / 10 minutes, more preferably 0.01-1
The reduced viscosity is in the range of 200 g / 10 minutes or in decalin at a temperature of 135 ° C. and a concentration of 0.2 g / deciliter, and is 0.05 to 20 deciliter / g, preferably 0.08 to 18 deciliter / g, more preferably 0.1
It should be in the range of -15 deciliters / g. If the MI is less than 0.001 g / 10 minutes, the moldability is poor, and if it exceeds 2000 g / 10 minutes, the wax-like mechanical properties are deteriorated. Further, the copolymer of the present invention has a diolefin unit content in the range of 0.001 to 3 mol% and includes a structure in which at least two of the diolefin units have reacted (a crosslinked structure exists). is necessary. If the diolefin unit content is less than 0.001 mol%, a sufficient branched structure cannot be formed, and if it exceeds 3 mol%, the copolymer tends to gel. Furthermore, the content of monomer units other than ethylene units, that is, the total content of α-olefin units and diolefin units is 30.
It needs to be less than or equal to wt%. When the content of α-olefin unit is increased, the density and enthalpy of crystallization (ΔH) are generally lowered, and the transparency is improved, while when the content of diolefin unit is increased, activation of melt flow described later is activated. Energy (Ea) increases. Therefore, the density, transparency, ΔH and Ea of the copolymer can be controlled by appropriately selecting the contents of the α-olefin unit and the diolefin unit within the above range.

In the copolymer of the present invention, the activation energy (Ea) of melt flow is preferably in the range of 6 to 12 kcal / mol. Regarding the activation energy (Ea) of the melt flow, the high pressure low density polyethylene is
Compared to linear polyethylene produced using a Ziegler catalyst, it has a large Ea and is excellent in processing characteristics such as blow molding. Therefore, Ea is an extremely important index because processing characteristics can be imparted from injection molding to blow molding to film molding by controlling Ea arbitrarily. The activation energy (Ea) can be calculated as follows. That is, the measurement temperature 1
Frequency dependence of dynamic viscoelasticity at 50 ° C, 170 ° C, 190 ° C, 210 ° C and 230 ° C (10 ^-2 to 10 ² rod
/ Sec), 170 ° C. as the reference temperature, and G ′ at each temperature using the temperature-time conversion rule,
The activation energy (Ea) is calculated by the Arrhenius equation from the shift factor of G ″ and the reciprocal of absolute temperature.

[0052]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Example 1 (1) Preparation of methylaluminoxane 200 ml of toluene, 17.7 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, which was replaced with argon. 24 ml (250 mmol) was added, and the reaction was carried out at 40 ° C. for 8 hours. afterwards,
From the solution obtained by removing the solid components, toluene was further distilled off under reduced pressure to obtain a catalyst product (methylaluminoxane) 6.
7 g was obtained. The molecular weight of this product measured by the freezing point depression method was 610. Moreover, when a high magnetic field component measured by ¹ H-NMR measurement, that is, a proton nuclear magnetic resonance spectrum in a toluene solution at room temperature is observed (Al—CH ₃ ).
The methyl proton signal due to binding is found in the range of 1.0-0.5 ppm based on tetramethylsilane. The proton signal of tetramethylsilane is (0pp
Since m) is in the observation region based on the methyl proton based on the Al—CH ₃ bond, the methyl proton signal based on the Al—CH ₃ was measured with reference to 2.35 ppm of the methyl proton signal of toluene in the tetramethylsilane standard. , High magnetic field components (ie, -0.1 to -0.5
ppm) and other magnetic field components (ie 1.0 to -0.1 pp)
m) and the high magnetic field component was 43% of the whole.

(2) Manufacture of copolymer In a pressure-resistant autoclave made of stainless steel of 1 liter, 400 ml of toluene, 140 ml of octene-140, divinylbenzene (mixture of m and p bodies, content: 55w).
t%) 30 mmol, triisobutylaluminum 0.5
Mmol, 3 mmol of methylaluminoxane prepared in (1) above, and 2 micromoles of dicyclopentadienylzirconium dichloride (Cp ₂ ZrCl ₂ ) were added, and
The temperature was raised to 0 ° C. Add ethylene pressure of 7 kg / cm ²
It was pressurized with G and copolymerized for 30 minutes under constant conditions. After completion of the reaction, the reaction mixture was deactivated with methanol and the polymer was recovered. The yield after drying was 65 g. MI (190 of this copolymer
℃, 2.16kg) is 5.6g / 10 minutes, and the infrared absorption spectrum shows that the absorption derived from the benzene ring derived from divinylbenzene at 1600cm ^-1 is 1630cm.
Absorption of vinyl group was observed at ^-1 . The divinylbenzene unit content calculated from the absorption derived from the aromatic ring of the divinylbenzene residue by the ultraviolet absorption spectrum method was 0.4 mol%, which was 1630 cm in the infrared absorption spectrum.
^The amount of unreacted vinyl groups determined from ^-1 was about 0.28 mol%. Further, the octene-1 unit content determined by ¹ H-NMR measurement was 1.8 mol%.

Next, as a device, DS7 manufactured by Perkin Elmer
The crystallization enthalpy (ΔH) was measured by the following method using a differential scanning calorimeter. That is, after a sheet pressed at 190 ° C. is melted at 150 ° C. for 5 minutes, 10
The exothermic peak of crystallization observed when the temperature was lowered to -50 ° C at a rate of ° C / min was measured. As a result, the crystallization enthalpy (ΔH) was 122 J / g. The film density of this product was 0.922 g / cm ³ . Further, the activation energy (Ea) of the melt flow was measured according to the following method using RMS E-605 manufactured by Rheometrics as an apparatus. That is, the measurement temperature 150
Frequency dependence of dynamic viscoelasticity at 10 ° C, 170 ° C, 190 ° C, 210 ° C, 230 ° C (10 ^-2 to 10 ² rod / s
ec) is measured, 170 ° C is set as a reference temperature, the activation energy (Ea) is calculated by the Arrhenius equation from the shift factors of G'and G "at each temperature and the reciprocal of the absolute temperature using the temperature-time conversion rule. As a result, Ea was 8.5 kcal / mol.

Example 2 (1) Preparation of tri-n-butylammonium tetrakis (pentafluorophenyl) borate Pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) and boron trichloride 45 Reaction with millimolar in hexane gave 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) boron as a white solid. Next, 16 mmol of lithium tetrakis (pentafluorophenyl) boron and 16 mmol of tri-n-butylammonium hydrochloride were reacted in water to give trin-butylammonium tetrakis (pentafluorophenyl) borate as a white solid (12.8 mmol). I was able to get it.

(2) Preparation of copolymer Tetrakis (pentafluorophenyl) boric acid prepared in the above (1) by using 1.3 mmol of triisobutylaluminum in Example 1- (2) and changing to methylaluminoxane. Copolymerization was performed in the same manner as in Example 1- (2) except that 6 μmol of tri-n-butylammonium was used. Further, the copolymer was evaluated in the same manner as in Example 1- (2). As a result, the yield of the copolymer after drying was 53 g, and MI (190 ° C, 2.16 kg) was 0.1 g / 10.
The octene-1 unit content was 0.8 mol% and the divinylbenzene unit content was 0.35 mol%. Furthermore, the density is 0.917 g / cm ³ , the enthalpy of crystallization (Δ
H) is 114 J / g, and the activation energy of melt flow (E
a) was 7.5 kcal / mol.

[0057]

EFFECTS OF THE INVENTION According to the present invention, an ethylene-based copolymer in which the activation energy of flow of a melt can be arbitrarily controlled, high-speed molding is possible, processing cost is low, and transparency and uniformity are improved. Is obtained. As a result, high-performance VLDPE with highly improved molding processing characteristics and optical properties
(Ultra low density polyethylene), L-LDPE, HDPE, etc. can be easily obtained.

Continuation of the front page (56) Reference JP 62-241908 (JP, A) JP 5-295034 (JP, A) JP 5-194665 (JP, A) JP 3267298 (JP, B2) (JP) 58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 6/00-246/00 C08F 4/60-4/70

Claims (3)

(57) [Claims] 1. A copolymer comprising an ethylene unit and a diolefin unit, or an ethylene unit and an α-olefin unit having 3 or more carbon atoms and a diolefin unit, wherein (a) the diolefin unit has the general formula (I ) [Chemical 1] (In the formula, R ′ is a hydrogen atom, a halogen atom, or a substituent containing at least one of a carbon atom and a silicon atom, R ″.
Is a vinyl group, f is an integer of 1 to 4, and when f is 2 or more, a plurality of R's may be the same or different. ) Having a branch point derived from a diolefin monomer, (b) having a density (D) of 0.86 to 0.97 g / cm ³ , (c) a differential scanning calorimeter ( The relationship between the crystallization enthalpy (ΔH) and the density (D) observable by DSC satisfies the expression 1417D-1206 ≦ ΔH ≦ 1417D-1161 (where ΔH ≧ 0), (d) Temperature 190 ° C. , A melt index (MI) measured under a load of 2.16 kg is 0.001 to 2000
g / 10 minutes, or in decalin, temperature 135 ° C., concentration 0.
The reduced viscosity measured under the condition of 2 g / deciliter is 0.0.
5 to 20 deciliters / g, (e) containing 0.35 to 3 mol% of diolefin units,
And that the two reaction sites of the diolefin unit include a crosslinked structure reacted with an ethylene unit and / or an α-olefin unit having 3 or more carbon atoms, and (f) the content of the monomer unit other than the ethylene unit is 30.
An ethylene-based copolymer, characterized in that it is contained by weight or less. 2. The ethylene-based copolymer according to claim 1, wherein the activation energy (Ea) of melt flow is 6 to 12 kcal / mol. Wherein (A) the general formula _{^{CpM 1 R 1 a R 2 b}} R 3 c ··· (II) Cp 2 M 1 R 1 a R 2 b ··· (III) (Cp-A e -Cp ) M ¹ R ¹ _a R ² _b ··· (IV) or the general formula M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (V) (wherein, M ¹ is Group 4 of the periodic table) Represents a transition metal, Cp represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group, R ¹ , R ² , R ³ and R ⁴ are each independently a σ-bonding ligand or a chelating agent Represents a ligand or a Lewis base, A
Indicates covalent crosslinking. a, b, c, and d each independently represent an integer of 0 to 4, and e represents an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When the above Cp has a substituent,
The substituent is an alkyl group having 1 to 20 carbon atoms. In the presence of a polymerization catalyst mainly composed of a transition metal compound represented by the formula (B) and a compound capable of forming a cationic species from the transition metal compound of the component (A) or a derivative thereof, ethylene and the above general formula The diolefin represented by (I), or ethylene, the α-olefin having 3 or more carbon atoms, and the diolefin represented by the general formula (I) are copolymerized with each other. A method for producing an ethylene-based copolymer.