JP2001151828A - Modified ethylene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified ethylene polymer excellent in adhesion to a metal or a polar material without having problems with production in a modifying process by grafting a polar monomer into a specific single ethylene or a specific copolymer of ethylene and an α-olefin. SOLUTION: This modified ethylene polymer is obtained by grafting the polar monomer into the ethylene polymer which is the single ethylene polymer or the copolymer of ethylene and the α-olefin having 3-20 number of carbon atoms and satisfies the following relationships: (A) melt index is 0.3-20 g/10 min at 190 deg.C under 2.16 kg road; (B) density is >=0.920 g/cm3; (C) molecular- weight distribution measured by a gel permeation chromatography is 3-4.5; and (D) the amount of terminal vinyl group in the polymer is <0.005 based on 1,000 carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a modified ethylene polymer obtained by grafting a polar monomer to a specific ethylene polymer. More specifically, by using a specific ethylene polymer, the decrease in the melt viscosity of the modified ethylene polymer during the grafting reaction of the polar monomer in the extruder is small and extremely small. Also, the present invention relates to a modified ethylene polymer having excellent adhesion to metals or polar substances.

[0002]

2. Description of the Related Art At present, polyethylene is used for various purposes due to its excellent properties. However, polyethylene has a problem that it has no polar group in the molecule and has poor affinity for metals and various polar substances. In order to solve this problem, a method of grafting a polar monomer to polyethylene to give a polar group to polyethylene has been widely used.

However, various problems arise when a polar monomer is grafted on polyethylene produced from a conventional Ziegler-Natta catalyst. For example, when a polar monomer is grafted on the polyethylene, there is a problem that the fluidity of the modified ethylene polymer is significantly reduced. In addition, the conventional polyethylene has a large amount of low molecular weight components and a comonomer is inserted into the lower molecular weight components. Therefore, the polar monomer is preferentially grafted to the low molecular weight components. There is a problem that the polar monomer is not grafted, and particularly, a modified product of a low molecular weight component has a problem that it causes burns at the time of extrusion.

Recently, there has been an attempt to apply a polyethylene produced from a metallocene catalyst to a modified graft. Japanese Patent Application Laid-Open No. 9-3138 discloses an ethylene polymer using a metallocene catalyst, but also in this case, the flowability of the polyethylene during grafting is greatly reduced, and it is difficult to control the melt index of the modified product. A large amount of unmelted gel is also generated in the modified ethylene polymer. JP 9
No. 3137 discloses a modified ethylene polymer having a narrow molecular weight distribution using a metallocene catalyst. In this case, since the molecular weight distribution is too narrow, the extrusion load at the time of producing a graft reactant is high, and the resulting modified ethylene polymer is obtained. Polymers also have the problem of causing problems such as melt fracture.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a modified ethylene polymer in which the melt viscosity of the ethylene polymer is less reduced at the time of graft modification, is less noticeable at the time of extrusion, and is excellent in adhesion to metals or polar substances. The purpose is.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that when a specific ethylene polymer is graft-modified with a polar monomer, the melt viscosity of the ethylene polymer at the time of the modification is lowered, and is significantly reduced. It has been found that the modified ethylene polymer obtained has excellent adhesion to metals or polar substances.

That is, according to the present invention, the ethylene polymer is an ethylene homopolymer or an ethylene having 3 to 20 carbon atoms.
(A) a melt index (MI) under a load of 2.16 kg at 190 ° C. of 0.3 to 20 g / 10 min. (B) a density of 0.920 g / cm ³ or more ( C) Gel permeation chromatography (GPC)
(D) a modified ethylene obtained by grafting a polar monomer to an ethylene polymer having a terminal vinyl group content in the polymer of less than 0.005 per 1000 carbon atoms It is a polymer.

Hereinafter, the present invention will be described in detail. The specific ethylene polymer used in the present invention is ethylene homopolymer, or ethylene and α having 3 to 20 carbon atoms, preferably 4 to 20 carbon atoms.
-Copolymers with olefins. Α having 3 to 20 carbon atoms
-As olefins, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-
Methylpentene-1, octene-1, decene-1, tetradecene-1, hexadecene-1, octadecene-1,
Eikosen-1 or the like can be used. Further, vinyl compounds such as vinylcyclohexane or styrene and derivatives thereof can also be used. In particular, butene-1, hexene-
1, octene-1 is preferred.

[0009] insertion amount of these α- olefins density ethylene polymer 0.92 g / cm ³ or more, an amount preferably comprised in the range of ^{0.925g / cm 3 ~0.96g / cm 3} . The density here is measured by a density gradient tube after heat-treating the strand obtained at the time of the melt index measurement at 120 ° C. for 1 hour and further cooling it at room temperature for 1 hour. When the density is less than 0.92 g / cm ³ , the molecular weight distribution of the ethylene polymer becomes narrow, the extrusion load at the time of modification increases, and a large amount of blemishes occurs during extrusion due to an increase in the low melting point component due to the low density. The resulting modified ethylene polymer also tends to generate melt fracture and the like.

The melt index of the ethylene homopolymer or the copolymer of ethylene and α-olefin at 190 ° C. under a load of 2.16 kg is 0.3 to 0.3.
20 g / 10 min, preferably 0.8 to 10 g / 10 min,
More preferably, the range is 1 to 5 g / 10 minutes. If the melt index is less than 0.3 g / 10 minutes, the extrusion load at the time of grafting becomes high, and extrusion is difficult. 20g
If the time exceeds / 10 minutes, the adhesion of the modified ethylene polymer becomes poor.

The molecular weight distribution (Mw / Mn) of the ethylene alone or a copolymer of ethylene and an α-olefin used in the present invention is 3 to 4.5, preferably 3 to 4. The molecular weight distribution is 150-C, ALC manufactured by Waters.
/ GPC, column: AT-80 manufactured by Shodex
7S and TSK-gelGMH-H6 manufactured by Tosoh Corporation were used in series, and 10 ppm of Irganox 1010 was used as a solvent.
Using trichlorobenzene containing (trade name), 14
Measure at 0 ° C. A standard curve is prepared using commercially available monodisperse polystyrene as a standard substance. If the molecular weight distribution is less than the above range, the extrusion load during denaturation increases,
The resulting modified ethylene polymer also tends to cause melt fracture.

When the molecular weight distribution exceeds the above range, the adhesiveness of the resulting modified ethylene polymer is reduced, and a large amount of pits are generated even at the time of graft modification. As one measure of the occurrence of the above-mentioned blemishes, the melting characteristics of the ethylene polymer are small in the following cases. In other words, this is the case where the fluidity index (FI) and the melt index (MI) defined by the shear rate when the shear stress at 190 ° C. reaches 2.4 × 10 ⁵ Pa satisfy the relationship of FI <75 × MI. . In the FI measurement, using a Capillograph 1C manufactured by Toyo Seiki Seisaku-sho, capillary L8mm, D2.0mm, 190 ° C
Then, the shear rate (sec ^-1 ) at which the shear rate reaches 2.4 × 10 ⁵ Pa is measured while changing the shear rate.

Further, the terminal vinyl group in the specific ethylene polymer used in the present invention has a content of 0.1 per 1000 carbon atoms.
Less than 005. If the amount of the terminal vinyl group exceeds the above range, the melt viscosity of the ethylene polymer is greatly reduced by the reaction in the extruder at the time of graft modification, and it is difficult to control the melt index of the modified ethylene polymer. Further, there is a problem that a high molecular component is generated in the modified ethylene polymer and a large amount of unmelted gel is generated.
The amount of terminal vinyl groups is determined by preparing a hot pressed sheet having a thickness of about 0.5 mm, and measuring the absorbance (A ₉₁₀ ) at ₉₁₀ cm ^-1 by infrared resonance absorption method (IR). Here, ρ is the density (g / cm ³ ), and t is the thickness (mm) of the film. Amount of terminal vinyl groups (month / 1000 carbons) = 0.114 × A ₉₁₀ / ρ
× t

Next, a method for producing an ethylene homopolymer or an ethylene / α-olefin copolymer having the characteristics (A) to (D) will be described. Ethylene homopolymers and copolymers used in the present invention include, for example, (A) a carrier substance, (A) an organoaluminum compound, (C) a transition metal compound having a cyclic η-binding anion ligand, and (D) a cyclic η. Using a supported catalyst adjusted from an activator capable of forming a complex exhibiting catalytic activity by reacting with a transition metal compound having a binding anion ligand, ethylene is homopolymerized, or ethylene and carbon number It is obtained by copolymerizing 3 to 20 α-olefins.

The carrier substance (A) may be either an organic carrier or an inorganic carrier. The organic carrier is preferably (1) an α-olefin having 2 to 10 carbon atoms (co)
Polymers, for example, polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, propylene-butene-1 copolymer, propylene-divinyl Benzene copolymers, (2) aromatic unsaturated hydrocarbon polymers, for example, polystyrene, styrene-divinylbenzene copolymer, and (3) polar group-containing polymers, for example, polyacrylates, polymethacrylates, Examples thereof include polyacrylonitrile, polyvinyl chloride, polyamide, and polycarbonate.

As the inorganic carrier, (4) an inorganic oxide such as SiO ₂ , Al ₂ O ₂ , MgO, TiO ₂ , B ₂ O ₃ ,
CaO, ZnO, BaO, ThO, SiO ₂ -MgO,
_{SiO 2 -Al 2 O 3, SiO} 2 -MgO, SiO 2 -V 2 O
_5, etc., (5) an inorganic halogen compound, for example, MgCl
₂ , AlCl ₃ , MnCl _2, etc. (6) Inorganic carbonates, sulfates, nitrates such as Na ₂ CO ₃ , K ₂ CO ₃
, CaCO ₃ , MgCO ₃ , Al ₂ (SO ₄ ) ₃ , B
(7) hydroxides such as aSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , for example, Mg (OH) ₂ , Al (OH) ₃ , Ca (O
H) _{2 and the} like. The most preferred support material is silica.

The particle size of the carrier is arbitrary, but is generally 1
3,000 μm, preferably 5-2000 μm, more preferably 10-1000 μm. The carrier material is optionally treated with (a) an organoaluminum compound. Examples of preferred organoaluminum compounds include alkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride Alkyl aluminum hydrides such as ethyl aluminum dichloride, diethyl aluminum hydride, diisobutyl aluminum hydride, aluminum alkoxides such as diethyl aluminum ethoxide, dimethyl aluminum trimethyl siloxide, dimethyl aluminum phenoxide, methyl alumoxane, ethyl aluminum oxane, isobutyl aluminum San include alumoxane such as methyl isobutyl alumoxane. Of these, trialkylaluminum, aluminum alkoxide and the like are preferable. Most preferred are trimethylaluminum, triethylaluminum and triisobutylaluminum.

The supported catalyst of the present invention comprises (c) a transition metal compound having a cyclic η-bonding anion ligand (hereinafter sometimes simply referred to as “transition metal compound” in the present invention).
including. The transition metal compound of the present invention can be represented, for example, by the following general formula (1).

[0019]

Embedded image In the formula, M is a transition metal belonging to Group 4 of the long period type periodic table having an oxidation number of +2, +3 or +4 having one or more ligands L and an η ⁵ bond.

L is a cyclic η-bonding anion ligand, and each independently represents a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, or an octahydrofluorene group. A hydrocarbon group containing up to 20 non-hydrogen atoms, a halogen, a halogen-substituted hydrocarbon group, an aminohydrocarbyl group, a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylphosphino group, a silyl group. , An aminosilyl group, a hydrocarbyloxysilyl group, and a halosilyl group, each independently having 1 to 8 substituents, and two hydrocarbyl groups each having L containing up to 20 non-hydrogen atoms. Diyl, halohydrocarbadiyl, hydrocarbyleneoxy, hydrocarby N'amino, siladiyl, Haroshirajiiru, may be linked by a divalent substituent of aminosilane or the like.

X is each independently a monovalent anionic σ-bonded ligand having up to 60 non-hydrogen atoms, a divalent anionic σ-bonded ligand bonded to M divalently, Or a divalent anionic σ-bonded ligand that binds to M and L with a valence of one each. X ′ is a neutral Lewis base coordinating compound selected from phosphine, ether, amine, olefin, and / or conjugated diene, each independently having 4 to 40 carbon atoms.

Further, 1 is an integer of 1 or 2. p is an integer of 0, 1 or 2, and X is a monovalent anionic σ-binding ligand or a divalent anionic σ-binding coordination binding to M and L with a valence of one each. P is at least l less than the formal oxidation number of M, and p is l + 1 or more than the formal oxidation number of M when X is a divalent anionic σ-bonded ligand that bonds divalently to M. Few. Q is 0, 1 or 2. As the transition metal compound, the case where l = 1 in the above general formula (1) is preferable. For example, a preferred example of the transition metal compound is represented by the following general formula (2).

[0023]

Embedded image

In the formula, M is the formal oxidation number +2, +3 or +4
Of titanium, zirconium and hafnium. R ^{3 is} independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a complex group thereof, each of which can have up to 20 non-hydrogen atoms; ^{The three} may be combined to form a divalent derivative such as hydrocarbadiyl, siladiyl, or germadiyl to form a ring.

X ″ is each independently a halogen, a hydrocarbon group,
A hydrocarbyloxy group, a hydrocarbylamino group, or a silyl group, each having up to 20 non-hydrogen atoms, and two X ″ s represent a neutral conjugated diene or divalent derivative having 5 to 30 carbon atoms. Y is -O-, -S-, -NR ^* -, -PR ^* -, and Z is S
iR ^* ₂ , CR ^* ₂ SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR
^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ , wherein R ^* is each independently an alkyl or aryl group having 1 to 12 carbon atoms. N is an integer of 1 to 3. Further, more preferred examples of the transition metal compound are represented by the following general formulas (3) and (4).

[0026]

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[0027]

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In the formula, each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a combination thereof, and each can have up to 20 non-hydrogen atoms. M is titanium, zirconium or hafnium. Z, Y, X and X ^* are the same as defined above. p is 0, 1 or 2;
Q is 0 or 1.

However, when p is 2 and q is 0, the oxidation number of M is +4, and X is a halogen, a hydrocarbon group, a hydrocarbyloxy group, a dihydrocarbylamide group, a dihydrocarbyl sulfide group, a hydrocarbyl sulfide group. ,
There are silyl groups or composite groups thereof, having up to 20 non-hydrogen atoms. When p is 1 and q is 0, the oxidation number of M is +3 and X is an allyl group, a 2- (N, N-dimethylaminomethyl) phenyl group or a 2- (N, N-
A stabilized anionic ligand selected from dimethyl) -aminobenzyl group, or a derivative of M having an oxidation number of +4 and X being a divalent conjugated diene, or both M and X being metallocyclopentene Forming a group.

When p is 0 and q is 1, the oxidation number of M is +2 and X 'is a neutral conjugated or non-conjugated diene, optionally substituted with one or more hydrocarbon groups. And X ′ may contain up to 40 carbon atoms, and M ′
And a π-type complex. Further, in the present invention,
The most preferred examples of the transition metal compound are represented by the following general formulas (5) and (6).

[0031]

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[0032]

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In the formula, each R ³ is independently hydrogen or an alkyl group having 1 to 6 carbon atoms. Further, M is titanium, Y is -O -, - S -, - NR * -, - PR * - a and, Z is _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2
CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂
Wherein R ^* is each independently hydrogen, or a hydrocarbon group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, a halogenated aryl group or a composite group thereof, and R ^* is up to 20. It can have a non-hydrogen atoms, or may be made with two R ^* How or Z ^* cyclic I R ^* and is coupled with in R ^* and Y medium, medium Z ^* optionally .

P is 0, 1 or 2, and q is 0 or 1. However, when p is 2 and q is 0, the oxidation number of M is +
And X is each independently a methyl or benzyl group. When p is 1 and q is 0, the oxidation number of M is +3.
And X is 2- (N, N-dimethyl) aminobenzyl, or the oxidation number of M is +4 and X is 2-butene-1,4-diyl. Also, if p is 0 and q
Is 1, the oxidation number of M is +2 and X ′ is 1,4-
Diphenyl-1,3-butadiene or 1,3-pentadiene. The diene is an example of an asymmetric diene that forms a metal complex, and is actually a mixture of geometric isomers.

Further, the metallocene catalyst of the present invention comprises:
(D) an activator capable of forming a complex exhibiting catalytic activity by reacting with a transition metal compound (hereinafter sometimes simply referred to as “activator” in the present invention). Usually, in a metallocene-based catalyst, a complex formed by a transition metal compound and the above-described activator exhibits high olefin polymerization activity as a catalytically active species. In the present invention, examples of the activator include a compound defined by the following general formula (7).

[0036]

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Here, in the formula, [LH] ^{d +} is a proton-donating Bronsted acid, and L is a neutral Lewis base. In the formula, [MmQp] ^d- is a compatible non-coordinating anion, M is a metal or metalloid selected from Groups 5 to 15 of the periodic table, and Q is each independently hydride or dialkyl. It is an amide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, a substituted hydrocarbon group having up to 20 carbon atoms, and Q as the halide is one or less. In addition, m is an integer of 1 to 7, p is an integer of 2 to 14, d is an integer of 1 to 7, and p−
m = d. In the present invention, more preferred examples of the activator are compounds defined by the following general formula (8).

[0038]

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In the formula, [LH] ⁺ is a proton-donating Bronsted acid, and L is a neutral Lewis base. In the formula, [MmQn (Gq (TH) r) z] ^d-
Is a compatible non-coordinating anion, and M is
A metal or a metalloid selected from Group 15 to Group 15, wherein Q is independently a hydride, a dialkylamide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, a substituted hydrocarbon group having up to 20 carbon atoms; The number of halides Q is one or less.

G is a polyvalent hydrocarbon group having a valence of r + 1 bonded to M and T, and T is O, S, NR or PR, wherein R is a hydrocarbyl or trihydrocarbylsilyl group. , A trihydrocarbylgermanium group, or hydrogen. M is an integer of 1 to 7, n is an integer of 0 to 7, q is an integer of 0 or 1, r is an integer of 1 to 3, z is an integer of 1 to 8, And d is an integer from 1 to 7, and n + z−m = d
It is.

Further preferred examples of the activator are represented by the following general formula (9).

[0042]

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Here, in the formula, [LH] ⁺ is a proton-donating Bronsted acid, and L is a neutral Lewis base. In the formula, [BQ ₃ Q ^* ] ^- is a compatible non-coordinating anion, B is a boron element, Q is a pentafluorophenyl group, and Q ^* is one OH group as a substituent. A substituted aryl group having 6 to 20 carbon atoms.

Specific examples of the compatible non-coordinating anion of the present invention include, for example, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl)
Borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl ) Borate, tris (3,5-dimethylphenyl) (hydroxyphenyl)
Borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (Pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4'-hydroxyphenyl) phenyl) borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate And most preferably tris (pentafluorophenyl) (hydroxyphenyl) borate.

Examples of other preferred compatible non-coordinating anions include the above exemplified borates wherein the hydroxy group is NH
Borates replaced with R groups. here,
R is preferably a methyl group, an ethyl group or tert-
It is a butyl group.

Specific examples of the proton-providing Bronsted acid include, for example, triethylammonium,
Tripropyl ammonium, tri (n-butyl) ammonium, trimethyl ammonium, tributyl ammonium and tri (n-octyl) ammonium, diethyl methyl ammonium, dibutyl methyl ammonium, dibutyl ethyl ammonium, dihexyl methyl ammonium, dioctyl methyl ammonium, didecyl methyl ammonium Trialkyl group-substituted ammonium cations such as, didodecylmethylammonium, ditetradecylmethylammonium, dihexadecylmethylammonium, dioctadecylmethylammonium, diicosylmethylammonium, bis (hydrogenated tallowalkyl) methylammonium, etc. And N, N-dimethylanilinium, N, N-diethylanilinium,
N, N-2,4,6-pentamethylanilinium, N,
N, N- such as N-dimethylbenzylanilinium
Dialkylanilinium cations are also suitable. Further, dialkylammonium cations such as di- (i-propyl) ammonium, dicyclohexylammonium and the like are also suitable, and triphenylphosphonium,
Triarylphosphonium cations such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and the like, or dimethylsulfonium, diethylfluphonium or diphenylsulfonium are also suitable. Are also preferably triphenylcarbonium ion, diphenylcarbonium ion, cycloheptatrinium, indenium and the like. In the present invention, an organometallic oxy compound having a unit represented by the following formula (10) can be used as an activator.

[0047]

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Here, M ² is a group 13 to 1 of the periodic table.
A metal or metalloid of group V, R is independently a hydrocarbon group having 1 to 12 carbon atoms or a substituted hydrocarbon group, n is a valence of metal M ² , and m is an integer of 2 or more . Preferred examples of the activator of the present invention include, for example, the following formula (1)
An organoaluminum oxy compound containing the unit represented by 1).

[0049]

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Here, R is an alkyl group having 1 to 8 carbon atoms, and m is an integer of 2 to 60. The most preferred example of the activator of the present invention is, for example, methylalumoxane containing a unit represented by the following formula (12).

[0051]

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Here, m is an integer of 2 to 60. The catalyst used in the present invention includes component (a) a carrier material, component (a) an organoaluminum compound, component (c) a transition metal compound having a cyclic η-binding anion ligand, and component (d) the cyclic η-binding anion. It can be obtained by supporting an activator capable of forming a complex exhibiting catalytic activity by reacting with a transition metal compound having a ligand, and the method of supporting component (a) to component (d) is optional. In general, there is a method in which the components (a), (c) and (d) are dissolved in an inert solvent in which each can be dissolved, mixed with the component (a), and then the solvent is distilled off. In addition, component (a), component (c)
And dissolving the component (d) in an inert solvent, and then adding the component (a) in an amount that does not cause precipitation of a solid, and concentrating the solid to keep the entire amount of the next concentrated liquid in the particles. (A) First, the component (a) and the component (d) are supported,
Next, a method of supporting the component (c), a method of successively supporting the component (a), the component (d), and the component (c) on the component (a) are exemplified. The component (c) and the component (d) of the present invention are generally liquid or solid.

In the present invention, the components (a), (c) and (d)
Is sometimes diluted with an inert solvent before loading. As the inert solvent used for this purpose, for example,
Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethyl chloride, chlorobenzene, and dichloromethane, and mixtures thereof. Can be. Such an inert hydrocarbon solvent is desirably used after removing impurities such as water, oxygen, and sulfur using a desiccant, an adsorbent, or the like.

Component (a) per 1 gram of carrier material, component (a) organoaluminum compound is 1 × 1 in terms of Al atom.
0-5 to 1 × 10 -1 mol, preferably 1 × 10 -4
The transition metal compound having a cyclic η-bonding anion ligand of component (c) is 1 × 10 −7 mol to 1 × 10 −3 mol, preferably 5 × 10 −7 mol to 5 × 10 −2 mol. × 10-4 mol, component (d) The activator capable of forming a complex exhibiting catalytic activity by reacting with the transition metal compound having the cyclic η-binding anion ligand is 1 × 10−7 mol to 1 × 10-4 mol. X 10-3 mol, preferably in the range of 5 x 10-7 mol to 5 x 10-4 mol. The amount of each component used and the method of loading are determined by activity, economy, powder characteristics, scale in the reactor, and the like. The obtained supported catalyst is an organoaluminum compound not supported on a carrier,
For the purpose of removing the borate compound and the titanium compound, washing can be performed by a method such as decantation or filtration using an inert hydrocarbon solvent.

The above series of operations such as dissolution, contact, and washing are performed as follows.
It is recommended to perform at a temperature in the range of −30 ° C. to 150 ° C. selected for each unit operation. A more preferable range of such a temperature is 0 ° C or higher and 100 ° C or lower. A series of operations for obtaining the supported catalyst is preferably performed in a dry inert atmosphere. The supported catalyst used in the present invention can be stored in a slurry state dispersed in an inert hydrocarbon solvent, or can be dried and stored in a solid state.

For the polymerization of ethylene alone or a copolymer of ethylene and an α-olefin, known polymerization methods such as a slurry polymerization method and a gas phase polymerization method can be used. When the polymerization is carried out in the present invention, the polymerization pressure is generally 0.1 to 10
MPa, preferably from 0.3 to 3 MPa, and the polymerization temperature is from 20 ° C to 115 ° C, preferably from 50 ° C to 90 ° C. In order to achieve the object of the present invention, a slurry polymerization method is particularly preferred. When the slurry polymerization method is used in the present invention, the upper limit of the temperature is a temperature at which the produced ethylene homopolymer or copolymer can substantially maintain a slurry state. Alternatively, the molecular weight distribution of the copolymer becomes less than 3.

As the solvent used in the slurry polymerization method, the inert hydrocarbon solvent described above in the present invention is preferable.
In particular, isobutane, isopentane, heptane, hexane, octane and the like are preferred. The comonomer that can be used in the present invention is an α-olefin represented by the following general formula.

H ₂ C ＝ CHR ² (wherein R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms;
It is branched or cyclic. ) Such comonomers include, for example, propylene,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane , And styrene, wherein the cyclic olefin having 3 to 20 carbon atoms is, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,
Tetracyclododecene, and 2-methyl-1.4,5.
8-Dimethano-1,2,3,4,4a, 5,8,8a-
A linear, branched or cyclic diene having 4 to 20 carbon atoms selected from the group consisting of octahydronaphthalenes is, for example, 1,3-butadiene, 1,4-pentadiene,
It is selected from the group consisting of 5-hexadiene, 1,4-hexadiene, and cyclohexadiene. In the present invention, propylene, 1-butene, 1-pentene, 1
-Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene and the like are preferred.

The supported catalyst used in the present invention is capable of polymerizing ethylene or ethylene and α-olefin by itself. However, in order to prevent poisoning of the solvent and the reaction system, an organoaluminum compound is used as an additional component. It is also possible to use them together. Examples of preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diethylaluminummonochloride,
Alkyl aluminum hydrides such as diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, dimethylaluminum trimethylsiloxide, dimethylaluminum phenoxide, etc. And alumoxanes such as xane, ethylaluminoxane, isobutylaluminoxane and methylisobutylalumoxane. Of these, trialkylaluminum, aluminum alkoxide and the like are preferable. Most preferably trimethylaluminum,
Triethyl aluminum and triisobutyl aluminum.

The polar monomers used in the present invention include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, a vinyl ester compound, and an unsaturated carboxylic acid. And at least one monomer selected from derivatives thereof.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxy-propyl (meth) acrylate. , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, trimerolpropane (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono ( (Meth) acrylates such as (meth) acrylate and 2- (6-hydroxyhexanoyloxy) ethyl acrylate;
0-undecene-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2
-(Meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol and the like.

Examples of the amino group-containing ethylenically unsaturated compound include alkyl ethyl acrylate or methacrylic acid such as aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate. Ester derivatives; vinylamine derivatives such as N-vinylethylamine and N-acetylvinylamine; allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide and N, N-dimethylaminopropylacryloyl Allylamine derivatives such as amides; acrylamide derivatives such as acrylamide and N-methylacrylamide; aminostyrenes such as P-aminostyrene; 6-aminohexylsuccinimide, aminoethyl Click acid imide and the like.

Examples of the epoxy group-containing ethylenically unsaturated compound include glycidyl acrylate, glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, and maleic acid. Mono and diglycidyl esters, mono and diglycidyl esters of tetrahydrophthalic acid, mono and diglycidyl esters of itaconic acid, mono and diglycidyl esters of butenetricarboxylic acid, mono and diglycidyl esters of citraconic acid, endo-cis-bicyclo [ 2.2.1] Mono and diglycidyl esters of hept-5-ene 2,3-dicarboxylic acid (trade name nadic acid), hept-5-ene-2-methyl-2,3-dicarboxylic acid (trade name) : Mono- and diglycidyl esters of methyl nadic acid), mono- and alkyl glycidyl esters of dicarboxylic acids such as mono- and glycidyl esters of allyl succinic acid, alkyl glycidyl ether of p-styrene carboxylic acid, allyl glycidyl ether,
2-methylallyl glycidyl ether, styrene-P-
Glycidyl ether, 3,4-epoxy 3-methyl-1
-Butene, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-
Examples thereof include 1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, and vinylcyclohexene monoxide.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, 4-vinylpyridine and 2-vinylpyridine. Vinylpyridine, 5-ethyl-2-vinylpyridine, 2-
Methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinone, 3-vinylisoquinone, N-
Vinyl carbazole, N-vinyl pyrrolidone and the like.

Examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and anhydrides thereof. Or derivatives thereof. Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl rallylate, vinyl stearate, vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate, and the like. Is mentioned.

The modified ethylene polymer of the present invention is prepared by extruding a specific ethylene polymer and a polar monomer using an extruder or the like.
The kneading reaction is carried out in the presence of a known organic peroxide. The reaction temperature is in the range of 120 to 300 ° C, and the reaction time is 0.5
A range of 10 to 10 minutes is preferred. The graft amount of the polar monomer is 0.01 to 100 parts by weight of the ethylene polymer.
10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.08 to 3 parts by weight. When the graft amount is less than the above range, the adhesion of the modified ethylene polymer is insufficient, and when the amount exceeds this amount,
Eyes are formed and continuous production of the modified ethylene polymer is difficult.

The obtained modified ethylene polymer is a known phenol stabilizer, an organic phosphite stabilizer, an organic thioether stabilizer, a stabilizer such as a metal of higher fatty acid, a pigment, a weathering agent, a dye, a nucleating agent. , A lubricant such as calcium stearate, an inorganic filler or reinforcing material such as carbon black, talc and glass fiber, a compounding agent added to a polyolefin such as a flame retardant or a neutron blocking agent within a range not detracting from the object of the present invention. Can be added.

Examples of the phenolic stabilizer include 2,6-di-t-butyl-4-methylphenol, 2,6-di-cyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, , 6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl -6-t-butylphenol, 2-t-
Butyl-2-ethyl-6-t-octylphenol, 2
-Isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate )
Methane, 2,2, -methylenebis (4-methyl-6-t
-Butylphenol), 4,4, -butylidenebis (3
-Methyl-6-t-butylphenol), 4,4, -thiobis (3-methyl-6-t-butylphenol),
2,2, -thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzyl Benzene, 1,3,5-tris (2-methyl-4-hydroxy-5-t-butylphenol) methane, tetrakis (methylene (3,5-di-butyl-4-)
Hydroxyphenyl) propionate) methane, β-
(3,5-Di-t-butyl-4-hydroxylphenol) propionic acid alkyl ester, 2,2, -oxamidobis (ethyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, tetrakis (methylene (2,4-di-t-butyl-4-hydroxyl) propionate), n-octadecyl-3- (4,
-Hydroxy-3,5-di-tert-butylphenyl) propionate, 2,6-di-tert-butyl-p-cresol, 2,4,6-tris (3,, 5, di-tert-butyl-)
4, -Hydroxybenzylthiono-1,3,5-triazine, 2,2-methylenebis (4-methyl-6-t-
Butylphenol), 4,4, -methylenebis (2,6
-Di-t-butylphenol), 2,2, -methylenebis (6- (1-methylcyclohexyl) -p-cresol), bis (3,5-bis (4-hydroxy-3-t-
Butylphenyl) butyric acid) glycol ester, 4,4, -butylidenebis (6-t-butyl-m-
Cresol), 1,1,3-tris (2-methyl-4-
(Hydroxy-5-t-butylphenyl) butane, 1,
3,5-tris (2,6-dimethyl-3-hydroxy-
4-t-butylbenzyl) isocyanurate, 1,3
5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,
3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate, 1,3,5-tris ((3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl) isocyanurate,
2-octylthio-4,6-di (4-hydroxy-3,
5-di-t-butyl) phenoxy-1,3,5-triazine, 4,4, -thiobis (6-t-butyl-m-cresol) and the like.

As the organic phosphite-based stabilizer, trioctyl phosphite, trilauryl phosphite,
Tridecyl phosphite, octyl diphosphite,
Tris (2,4-di-t-butylphenyl) phosphite, triphenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl)- 1,1,3-Tris (2-
Methyl-5-t-butyl-4-hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4,4,
-Butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono or dinonylphenyl) phosphite, hydrogenated-
4,4, -isopropylidene diphenol polyphosphide, bis (octylphenyl) bis (4,4, -butylidenebis (3-methyl-6-t-butylphenol)) 1,6-hexaneol diphosphide, phenyl- 4,4, -isopropylidene diphenol pentaerythritol diphosphide, bis (2,4-di-t-
Butylphenyl) pentaerythritol diphosphide, bis (2,6-di-t-butyl-4methylphenyl) pentaerythritol diphosphide, tri ((4,4, -isopropylidenebis (2-t-butylphenol)) Phosphide, di (nonylphenyl) pentaerythritol diphosphide, tris (1,3-
Di-stearoyloxyisopropyl) phosphite,
4,4, -isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphide, 9,10
-Di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t
-Butylphenyl) -4,4, -biphenylenediphosphide and the like.

Examples of the organic thioether-based stabilizer include dialkylthiopropionates such as dilauryl, dimyristyl and distearyl, and butyl, octyl, and the like.
Esters of polyhydric alcohols of alkylthiopropionic acids such as laurilu, stearyl-, etc. (eg glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (eg, pentaerythitol tetralaurylthiopropionate) Is mentioned. More specifically, dilauryl thiopropionate, dimyristyl thiopropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutyrate and the like can be mentioned.

Examples of unsaturated carboxylic acids and derivatives thereof include alkaline earth earths such as magnesium, calcium, barium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, caprylic acid, arachidic acid, palmitic acid and behenic acid. Metal salts, cadmium salts, zinc salts, lead salts, sodium salts, potassium salts, lithium salts and the like are used. Magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate calcium oleate, barium stearate, barium laurate, barium laurate, magnesium, zinc stearate, zinc calcium oleate, zinc stearate, zinc laurate, Lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, calcium 12-hydroxystearate and the like.

[0072]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below with reference to examples and the like, but these do not limit the scope of the present invention. (1) Melt flow index; ASTM D-1238
Is a value measured at 190 ° C. under a load of 2.16 kg. (2) Molecular weight distribution: Waters was measured by Waters
150-C, ALC / GPC, Sh-column
Odex AT-807S and Tosoh TSK-ge
Using lGMH-H6 in series, measurement was made at 140 ° C. using trichlorobenzene containing 10 ppm of Irganox 1010 (trade name) as a solvent. A calibration curve was prepared using commercially available monodisperse polystyrene as a standard substance.

(3) Flow index (FI): Capillograph 1C manufactured by Toyo Seiki Seisaku-sho, capillary L8 mm, D2.
Using 0 mm at 190 ° C., changing the shear rate to 2.4 × 1
Shear speed when reaching 0 ⁵ Pa (sec ^-1 ) (FI)
Is measured. (4) Terminal vinyl group content: The amount of terminal vinyl groups is determined by preparing a hot pressed sheet having a thickness of about 0.5 mm, and measuring the absorbance (A ₉₁₀ ) at ₉₁₀ cm ^-1 by infrared resonance absorption method (IR). Where ρ is the density (g / cm ³ ) and t is the film thickness (m
m). Amount of terminal vinyl groups (month / 1000 carbons) = 0.114 × A ₉₁₀ / ρ
× t

(5) Evaluation of adhesion of modified ethylene polymer: The modified ethylene polymer was pressed into a 200 mm × 200 mm × 0.2 mm by press molding.
It was molded to 5 mm. The obtained sheet and a sufficiently dried polyamide (nylon 66) sheet of the same size
C., pressure 1 MPa, bonding time 10 seconds. The obtained sheet was measured for 180 degree peel strength according to the JIS-K6854 method. (6) Graft amount of maleic anhydride: after dissolving the modified ethylene polymer in boiling water xylene,
Double the amount of acetone was added to precipitate the polymer, and the modified ethylene polymer was recovered. This modified ethylene polymer was hot-pressed to a thickness of about 0.5 mm, and 1850 by infrared resonance absorption method.
The absorbance (A ₁₈₅₀ ) out of cm ^-1 was measured, and the graft amount of maleic anhydride was determined by the following formula. Graft amount (%) of maleic anhydride = 1.06 × A ₁₈₅₀
/ tt (mm) is the film thickness.

[0075]

Example 1 Preparation of Ethylene Polymer 6.2 g (8.8 mmol) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was added to 4 l of toluene, and 90
It stirred at 30 degreeC for 30 minutes. Next, 40 ml of a 1 mol / l toluene solution of trihexyl aluminum was added to the solution, and the mixture was stirred at 90 ° C. for 1 minute. Separately, silica P-10 (trade name, manufactured by Fuji Silysia Ltd., Japan) was treated with a nitrogen stream at 500 ° C. for 3 hours, and the treated silica was stirred in 1.7 l of toluene. The toluene solution of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate and trihexylaluminum was added to the silica slurry solution, and the mixture was added for 3 hours.
Stirred at ° C.

Next, 206 ml of a 1 mol / l toluene solution of trihexyl aluminum was added, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the supernatant was decanted five times using toluene at 90 ° C. to remove excess trihexyl aluminum. 0.218 mol / l dark purple titanium (N-1,1-dimethylethyl) dimethyl (1- (1,2,3,4,5, -eta) -2,3
4,5-tetramethyl-2,4-cyclopentadiene-
1-yl) silanaminato) ((2-) N)-(η ⁴ −
ISOPARTME (1,3-pentadiene) (E, USA
xxon Chemical Co., Ltd.) solution (20 ml) was added to the above mixture.
After stirring for an hour, a green supported catalyst was obtained.

A part of the obtained supported catalyst was put into a 1.5-liter reactor together with 0.8 liter of dehydrated and deoxygenated hexane.
The temperature inside the container was set to 75 ° C., and the mixed gas ratio of ethylene, 1-butene and hydrogen was adjusted, and the total pressure was set to 0.8 MPa. By replenishing the mixed gas of the above composition, the total pressure is maintained at 0.8MPa.
Polymerization was carried out for an hour to obtain an ethylene polymer shown in Table 1.

100 parts by weight of the obtained ethylene polymer, 0.1 part by weight of maleic anhydride, and 2,2 as an organic peroxide
5-dimethyl-2,5-di- (t-butylperoxy)
Hexane (0.01 parts by weight) was added, and the mixture was melt-kneaded at 190 ° C. with a coaxial twin screw extruder (D45 mm, L / D30) to extrude the modified ethylene polymer at a rate of 50 kg / hour. Was observed.
Table 1 shows the adhesive strength of the modified ethylene polymer. Further, the obtained modified ethylene polymer was formed into a film on an inflation film, and the unmelted gel was measured. The number of gels having a diameter of 0.2 mm or more per 1 g film was counted.

[0079]

Examples 2 to 4 The ethylene polymers of Examples 2 to 4 shown in Table 1 were produced according to the production method of Example 1. The obtained ethylene polymer has no problem in the graft modification step,
The adhesiveness was also excellent.

[0080]

Comparative Examples 1 to 3 The ethylene polymers of Comparative Examples 1 to 3 shown in Table 1 were produced according to the production method of Example 1. Comparative Example 1 has a low melt index of the modified ethylene polymer.
Extrusion load was high, causing melt fracture of the strands. Comparative Example 2 has a high melt index,
Therefore, the adhesiveness is not satisfactory. In Comparative Example 3, the density of the ethylene polymer was low, the molecular weight distribution was narrow, the extrusion load was high, and the strand also caused melt fracture. In addition, the low melting point component in the ethylene polymer was increased, and eyes were generated during denaturation.

[0081]

Comparative Example 4 Ethylene Polymer Using Ziegler Catalyst The ethylene copolymer of Comparative Example 4 described in Table 1 was prepared using a Ziegler catalyst prepared from magnesium chloride hexahydrate, 2-ethylhexanol, and titanium chloride, which are well known. The polymer was polymerized. At the time of denaturation, the melt index was greatly reduced, the extrusion load was increased, and the strands also violently caused melt fracture. Moreover, since the obtained modified ethylene polymer contains a large amount of low molecular weight components, the adhesiveness is insufficient. The amount of terminal vinyl groups was large, and a large amount of unmelted gel was generated in the modified ethylene polymer.

[0082]

Comparative Example 5 Zirconocene-Catalyzed Ethylene Copolymer Silica (Grand 952, trade name, manufactured by Fuji Devison) in a 200 ml flask sufficiently dried with nitrogen.
g and toluene (40 ml) were added and cooled to -40 ° C.
30 ml of a toluene solution of methylalumoxane (MMAO-3 manufactured by Tosoh Akzo Co., Ltd.) was added and reacted for 1 hour. Thereafter, the reaction was carried out at 0 ° C. for 1 hour, further at 80 ° C. for 3 hours, and cooled to 20 ° C. after completion of the reaction. Thus, a silica carrier supporting methylalumoxane was obtained. Next, 2.5 ml / l of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride was added to 1 μm in terms of zirconium.
ol, and triisobutylaluminum (1.0 mo
(l / l) 0.12 mmol was added to synthesize a catalyst.

The resulting suspension was deaerated and deoxygenated, and the inside thereof was vacuum-degassed together with 0.8 l of hexane and placed in a 1.5 l reactor purged with nitrogen. The temperature in the vessel was set to 75 ° C., and the amount of a mixed gas of ethylene, 1-butene and hydrogen was adjusted to adjust the total pressure to 0.8 MPa. By supplying the mixed gas, polymerization was carried out for 2 hours while maintaining the total pressure at 0.8 MPa to obtain an ethylene polymer shown in Table 1. In the modification step, the molecular weight distribution of the ethylene polymer was narrow, so that the extrusion load was high and the melt flow index was greatly reduced. In addition, the melt fracture was caused in a saw-tooth shape of the extruded strand. Further, in the modified ethylene polymer, a large amount of gel was generated due to a large amount of terminal vinyl groups.

[0084]

[Table 1]

[0085]

EFFECTS OF THE INVENTION The specific ethylene of the present invention or the ethylene polymer obtained by modifying ethylene and an α-olefin with a polar monomer is capable of high-speed extrusion with little decrease in the melt index at the time of modification and with little noticeable. . The resulting modified ethylene polymer has excellent adhesiveness.

Claims (4)

[Claims] 1. The ethylene polymer is an ethylene homopolymer,
Or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and (A) a melt index (MI) at 190 ° C. under a load of 2.16 kg of 0.3 to 20 g / 10 minutes (B) Density of 0.920 g / cm ³ or more (C) Gel permeation chromatography (GPC)
(D) a modified ethylene obtained by grafting a polar monomer to an ethylene polymer having a terminal vinyl group content in the polymer of less than 0.005 per 1000 carbon atoms Polymer. 2. An ethylene homopolymer of the ethylene polymer or a copolymer of ethylene and an α-olefin, wherein (a) a carrier substance, (a) an organoaluminum compound,
(C) a transition metal compound having a cyclic η-binding anion ligand; and (iv) an activity capable of forming a complex exhibiting catalytic activity by reacting with the transition metal compound having the cyclic η-binding anion ligand. The modified ethylene polymer according to claim 1, wherein an ethylene homopolymer or a copolymer of ethylene and an α-olefin obtained using a supported catalyst adjusted from an agent is used. 3. Shear stress at 190 ° C. 2.4 × 10
A fluidity index (FI) defined by a shear rate (sec ^-1 ) when the pressure reaches ⁵ Pa and a melt index (MI) are characterized by using an ethylene polymer satisfying a relationship of FI <75 × MI. Then, the modified ethylene polymer according to claim 1 or 2. 4. A polar monomer comprising a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, a vinyl ester compound, an unsaturated carboxylic acid and derivatives thereof. At least one monomer selected from the group consisting of ethylene polymer 1
The modified ethylene polymer according to any one of claims 1 to 3, wherein the amount is in the range of 0.01 to 10% by weight based on 00 parts by weight.