JPH11106429A - Modified ethylene polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified ethylene polymer excellent in mechanical physical properties and molding processability, not containing a gel in the product, high in shear rate, low in viscosity, large in melt tension and thereby capable of being suitably used for injection blow molding. SOLUTION: This modified ethylene polymer is obtained by reacting ethylene homopolymer or a copolymer of ethylene with a 3-20C α-olefin with an oxygen- nitrogen mixture gas having an oxygen concentration of 1-30 vol.% and/or a radical generator having a half life of 1 min at 150-220 deg.C at a temperature of >=185 deg.C. The ethylene homopolymer or copolymer has (A) a melt index of 0.1-100 g/10 min under a load of 2.16 kg at 190 deg.C, (B) a GPC mol.wt. distribution of 3-7, (C) >=0.02 vinyl group/1000 carbon atoms at the molecular end of the polymer, and (D) <=0.02 vinylidene group/1000 carbon atoms at the molecular end of the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene polymer modified with an oxygen and / or a radical generator using a specific ethylene polymer and a method for producing the same. More specifically, an ethylene homopolymer having a specific molecular weight distribution and a terminal double bond amount, an ethylene homopolymer modified with a specific concentration of oxygen and / or a specific radical generator using a copolymer, and a copolymer, Regarding its manufacturing method.

[0002]

2. Description of the Related Art Currently, ethylene polymers polymerized by a Ziegler polymerization catalyst are widely used. However, when this ethylene polymer is used alone, the melt moldability and mechanical properties are not satisfactory. Thus, melt moldability has been improved by blending two or more ethylene polymers having different molecular weights. However, the ethylene polymer composition obtained by this method is not particularly satisfactory in terms of impact strength. On the other hand, as a method for improving the melt moldability of an ethylene polymer without using the blending method, there is a method of inserting a long-chain branch into a molecule. As a method for inserting the long-chain branch, a method of polymerizing ethylene in the presence of a special catalyst, or a method of subjecting an ethylene polymer to a small amount of a crosslinking reaction by an appropriate method after polymerization to insert a long-chain branch, etc. is there.

As an attempt to insert a long-chain branch by this crosslinking technique, Japanese Patent Application Laid-Open No. 52-82964 discloses an attempt to improve moldability by adding a radical generator to polyethylene.
Japanese Patent Application Laid-Open No. 1-271403 discloses a technique for modifying linear low-density polyethylene with a radical generator. However, when a polyethylene polymerized by a Ziegler polymerization catalyst is used, there is a problem that the resulting modified ethylene polymer has many gels. It is presumed that the reason for this is that polyethylene polymerized by the Ziegler polymerization catalyst originally had many double bonds at the molecular terminals, and the double bonds were involved in crosslinking to produce ultrahigh molecular weight polyethylene.

In recent years, an attempt has been made to produce an ethylene polymer having improved mechanical properties by using a catalyst prepared from a metallocene compound and an aluminoxane.
-19309, 60-35006, 60-3500
7, No. 61-130314, No. 61-221208, No. 62-121709, and No. 62-121711. However, the ethylene polymers obtained by these processes have a rather narrow molecular weight distribution, and therefore have poor moldability. When these ethylene polymers are modified with oxygen and / or radical generators, satisfactory moldability cannot be obtained unless cross-linking is performed under extremely severe conditions, and under such conditions, a large amount of gel is contained in the ethylene polymer. Occurs.

Further, a constrained geometry addition catalyst (Japanese Patent Laid-Open Publication No.
No. 3088), attempts have been made to produce an ethylene polymer satisfying both moldability and mechanical properties by keeping the molecular weight distribution narrow and inserting long-chain branches into the molecule. It is not satisfactory in terms of gender. Since these ethylene polymers are formed by a solution polymerization method at a high temperature, they have a large number of double bonds at the molecular terminals, and a large amount of gel is generated when a modification method using oxygen or / and a radical generator is used. Produces a point.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a modified ethylene polymer which is excellent in moldability and mechanical properties and has no gel.

[0007]

As a result of intensive studies, the present inventors have found a modified ethylene polymer which is excellent in moldability, processability and mechanical properties and has no gel, and a process for producing the same. The present invention is characterized by satisfying each of the following conditions (A) to (D): ethylene homopolymer or copolymer modified with a specific concentration of oxygen and / or a specific radical generator. It relates to coalescence and its manufacturing method.

That is, (A) 2.1 at 190 ° C.
Melt index under 6kg load is 0.1-100g
/ 10 min, (B) the molecular weight distribution measured by gel permeation chromatography is 3 to 7, and (C) the vinyl group present at the molecular end of the polymer has 0.02 (gas / 1).
(D) an ethylene homopolymer or C3 having a vinylidene group present at the molecular terminal of the polymer of not more than 0.02 (pcs / 1000 carbons).
From 20 to α-olefin, a mixed gas of oxygen and nitrogen having an oxygen concentration of 1 to 30% by volume and / or
Alternatively, the decomposition temperature for making the half life 1 minute is 150 to 22.
The present invention relates to a modified ethylene polymer obtained by reacting a radical generator at 0 ° C. with a temperature of 185 ° C. or higher and a method for producing the modified ethylene polymer.

Hereinafter, the present invention will be described in detail. The ethylene polymer used in the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 4 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, butene-1, pentene-1,3-methylbutene-1, hexene-1,4-methylpentene-1, octene-1, decene-1, tetradecene-1, hexadecene-1, octadecene-1, eicocene-1. Etc. can be used. Further, vinyl compounds such as vinylcyclohexane or styrene and derivatives thereof can also be used. If necessary, a ternary random polymer containing a small amount of a non-conjugated polyene such as 1,5-hexadiene and 1,7-octadiene may be used. These α
-The insertion amount of olefin is 0.9 when the density of ethylene copolymer is 0.9.
15 g / cm ³ or more, preferably 0.925 g / cm ³
It is preferable to use the above range. The density here refers to the strand obtained during melt index measurement,
Heat treatment was performed at 100 ° C. for 1 hour, and after cooling at room temperature for 1 hour, measurement was performed using a density gradient tube.

In particular, when a low-density ethylene copolymer is used, the ratio of α-olefin dyads in the ethylene copolymer increases. In the dyad, the main chain structure is formed by connecting carbons of -methine-methylene-methine-methylene-. When the modification method of the present invention is used by using an ethylene copolymer having many dyads in which the methine group is continuously or inserted into the ethylene polymer main chain through one methylene group, the modified ethylene polymer contains It has been found by the present inventors that a large amount of gel is generated. Therefore, in order to obtain a modified ethylene polymer having no gel, the amount of dyad (hereinafter referred to as (XX)) in which the α-olefin is continuously inserted in the ethylene copolymer as a raw material, and ethylene is continuously inserted. Diad amount (hereinafter referred to as (EE)
), The amount of dyad into which ethylene and α-olefin were continuously inserted (hereinafter referred to as (EX)) was determined by nuclear magnetic resonance analysis, and D = 4 (XX) × (EE) / (E
X) It is calculated by ² , and its D value is preferably 1.3 or less, more preferably 1.1 or less. The larger the value is, the higher the ratio of (XX) is.

The ethylene or copolymer used in the present invention has a melt index of 0.1 to 100 g / 10 min.
Preferably it is in the range of 0.2 to 50 g / 10 min, more preferably 0.5 to 30 g / 10 min. When an ethylene homopolymer or copolymer having a melt index of less than 0.1 g / 10 minutes is used, it is difficult to mold the modified ethylene polymer itself alone. On the other hand, the melt index is 1
If it exceeds 00 g / 10 minutes, the strength of the molded article of the modified ethylene polymer will decrease. The melt index is A
2.16 at 190 ° C. according to STM-D1238
It was measured with a kg load.

The molecular weight distribution of the ethylene homopolymer or copolymer used in the present invention is 3 to 7, preferably 3.5 to 6.5 as measured by gel permeation chromatography. In the case of using an ethylene homopolymer or copolymer having a molecular weight distribution of less than 3, it is necessary to react with oxygen and / or a radical generator under severe conditions in order to obtain a modified ethylene polymer having sufficient moldability. As a result, a large amount of gel is generated in the modified ethylene polymer. On the other hand, when an ethylene homopolymer or copolymer having a molecular weight distribution of more than 7 is used, the mechanical properties of the modified ethylene polymer are reduced, and the high molecular weight component reacts with oxygen and / or a radical generator, and As a result, a large amount of ultrahigh molecular weight gel is generated. The measuring apparatus used for the gel permeation chromatography was 150-C manufactured by Waters.
ALC / GPC, Column: AT manufactured by Shodex
-807S and TSK-gelGMH-H6 manufactured by Tosoh Corporation
Were used in series, and measured at 140 ° C. using trichlorobenzene as a solvent.

In the present invention, in order to satisfy the above-mentioned molecular weight distribution, a method of polymerizing an ethylene homopolymer or a copolymer in a slurry state using a specific catalyst is used. The amount of the double bond existing at the molecular end of the homo- or copolymer of ethylene used in the present invention, that is, the amount of the vinyl group and the vinylidene group is 0.02 (pieces / 1000 carbons) or less. Preferably 0.015 (pcs / 1000
Carbons). A terminal vinyl group in the present invention,
The vinylidene group has the following structure. Terminal vinyl group R—CH ＝ CH ₂ Terminal vinylidene group R—CR ₁ ＣＨCH ₂ (where R is an ethylene polymer chain, R ₁ is a hydrocarbon group having 1 or more carbon atoms, and may be a polymer chain. good)

When an ethylene homopolymer or copolymer having a large content of terminal double bonds is used, a large amount of gel is formed in the modified ethylene polymer. Press films were prepared for quantitative determination of vinyl groups and vinylidene groups, and infrared absorption spectra (I
R) is measured using an apparatus of FT-IR-5300A manufactured by JASCO Corporation. Vinyl group 910cm ^-1, vinylidene groups is calculated from the following equation from the absorbance of the peak of ^878cm-1. Vinyl group (pcs / 1000 carbons) = 0.98 × ΔA
₉₁₀ / t vinylidene group (pcs / 1000 carbons) = 0.91 × △
A ₈₈₇ / t where ΔA is the absorbance and t is the film thickness (mm).

Next, a method for producing ethylene homo- or copolymer as a raw material of the present invention will be described. The ethylene homopolymer and copolymer used in the present invention include (A) a carrier substance, (A) an organic aluminum compound, (C) a borate compound having active hydrogen, and (E) cyclopentadienyl or substituted cyclopentadiene. It is obtained by using a supported catalyst prepared from a titanium compound having an enyl group and an η bond, by copolymerizing ethylene alone or ethylene with an α-olefin having 3 to 20 carbon atoms in a slurry state.

The carrier substance (A) may be either an organic carrier or an inorganic carrier. As the organic carrier, preferably (1) an α-olefin polymer having 2 to 10 carbon atoms,
For example, polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylenebutene-1 copolymer, ethylene-hexene-1 copolymer, propylenebutene-1 copolymer, propylenedivinylbenzene copolymer (2) aromatic unsaturated hydrocarbon polymers such as polystyrene and styrene-divinylbenzene copolymers, and (3) polar group-containing polymers such as polyacrylates, polymethacrylates and polyacrylonitriles , Polyvinyl chloride, polyamide, polycarbonate and the like.

As the inorganic carrier, (4) an inorganic oxide such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , B ₂
O ₃ , CaO, ZnO, BaO, ThO, SiO ₂ -M
gO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —MgO, Si
O ₂ over V ₂ O _5, etc., (5) an inorganic halogen compounds, for _{example, MgCl 2, AlCl 3, MnCl} 2 , etc., (6) carbonate mineral, sulfates, nitrates, for example, Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Al
₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (N
(7) inorganic hydroxides such as Mg (O ₃ ) ₂
H) ₂ , Al (OH) ₃ , Ca (OH) _{2 and the} like. The most preferred support material is silica. The particle size of the carrier is arbitrary, but is generally 1 to 3000 µm, preferably 5 to 2000 µm, more preferably 10 to 100 µm.
The range is 0 μm.

The carrier material is treated with an organic aluminum compound (a). Examples of preferred organic aluminum compounds include trialkylaluminum, triethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like trialkylaluminum, diethylaluminummonochloride, diisobutylaluminummonochloride, ethylaluminum sesquichloride , Alkylaluminum hydrides such as ethylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, dimethylaluminum trimethylsiloxide,
Examples include aluminum alkoxides such as dimethylaluminum phenoxide, alumoxanes such as methylalumoxane, ethylaluminoxane, isobutylaluminoxane, and methylisobutylalumoxane. Of these, trialkylaluminum, aluminum alkoxide and the like are preferable. Most preferred are trimethylaluminum, triethylaluminum and triisobutylaluminum.

Further, as the supported catalyst used in the process for producing an ethylene homopolymer or copolymer used in the present invention, a borate compound having active hydrogen represented by the following general formula is used. This borate compound is an activator that reacts with a titanium compound (d) that is η-bonded to a cyclopentadienyl or substituted cyclopentadienyl group to convert (d) into a cation. The group (TH) having active hydrogen forms a chemical bond or a physical bond with the carrier when the borate compound is carried on the carrier material.

[B ^- Qn (Gq (TH) r) z] A ⁺ (where B represents boron) G represents a multi-bonded hydrocarbon radical. C1-20 alkylene, arylene, ethylene, and alkalilene radicals. Preferred examples of G include phenylene, bisphenylene, naphthalene, methylene, ethylene, and 1,3.
-Propylene, 1,4-butadiene and p-phenylenemethylene. The multi-bond radical G is a bond of r + 1, that is, one bond binds to a borate anion,
The other bond of G bonds to the (TH) group. T is O,
Represents an S, NR, or PR group, wherein R represents a hydrocarbanyl radical, a trihydroicarbanylsilyl radical, a trihydrocarbanylgermanium radical, or a hydride.

Q is 1 or more, and preferably 1. TH
The group is —OH, —SH, —NRH, or —PRH, wherein R is a hydrocarbyl radical having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, or hydrogen. Preferred R groups are alkyl, cycloalkyl, allyl, allylalkyl or alkylallyl having 1 to 18 carbon atoms. -OH, -SH, -N
The RH or -PRH group is, for example, -C (O) -OH,
—C (S) —SH, —C (O) —NRH, and —C
It may be an (O) -PRH group. The most preferred group having active hydrogen is an -OH group. Q is hydride, dihydrocarbylamide, preferably dialkylamide,
Halide, hydrocarbyl oxide, alkoxide,
Allyl oxide, hydrocarbyl, substituted hydrocarbyl radical and the like. Here, n + z is 4.

[B ^- Qn (Gq (TH)]
r) z], for example, triphenyl (hydroxyphenyl) borate, diphenyldi (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluoro) Phenyl) (hydroxyphenyl) borate, tris (2,
4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-ditrifluoromethylphenyl) (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 and tris (pentafluorophenyl) (6-hydroxy-2naphthyl) borate, most preferably tris (pentafluorophenyl) (4-hydroxyphenyl) borate. It is. Further, the —OH group of the borate compound is replaced with —NHR (where R is methyl, ethyl,
(t-butyl) is also preferable.

Examples of the counter cation of the borate compound include a carbonium cation, a tropylluium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. In addition, metal cations and organic metal cations whose self-confidence is easily reduced are also exemplified. Specific examples of these cations include triphenylcarbonium ion, diphenylcarbonium ion, cycloheptatrinium, indenium, triethylammonium, tripropylammonium, tributylammonium,
Dimethyl ammonium, dipropyl ammonium,
Dicyclohexylammonium, trioctylammonium, N, N-dimethylammonium, diethylammonium, 2,4,6-pentamethylammonium, N, N-dimethylbenzylammonium, di-ammonium
(I-propyl) ammonium, dicyclohexylammonium, triphenylphosphonium, triphosphonium, tridimethylphenylphosphonium, tri (methylphenyl) phosphonium, triphenylphosphonium ion, triphenyloxonium ion, triethyloxonium ion, Pyrinium,
Silver ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, and ferrocenium ion are exemplified. Of these, ammonium ions are particularly preferred.

In the present invention, a titanium compound (d) which is η-bonded to a cyclopentadienyl or substituted cyclopentadienyl group represented by the following general formula is used.

Embedded image

Here, Ti is a titanium atom in an oxidation state of +2, +3, +4, Cp is a cyclopentadienyl or substituted cyclopentadienyl group which is η-bonded to titanium, X1 is an anionic ligand, X2 is a neutral conjugated diene compound. n + m is 1 or 2, Y is —O—, —S—, —NR— or —PR—, and Z is SiR ₂ , CR ₂ , SiR ₂ —SiR ₂ , CR ₂ C
R ₂ , CR = CR, CR ₂ SiR ₂ , GeR ₂ , BR ₂
R is hydrogen, hydrocarbyl in each case,
It is selected from silyl, germum, cyano, halo or combinations thereof and combinations thereof having up to 20 non-hydrogen atoms.

The substituted cyclopentadienyl group includes 1
Species or more of C1-C20 hydrocarbyl, C1-C20 halohydrocarbyl, halogen or C1-C20 hydrocarbyl-substituted Group 14 metalloid-substituted cyclopentadiene Enyl, indenyl, tetrahydroindenyl, fluorenyl or octafluorenyl, preferably having 1 carbon atom;
A cyclopentadienyl group substituted with an alkyl group of 1 to 6;

As X1 and X2, for example, in the above formula, when n is 2, m is 0, and the oxidation number of titanium is +4, X1 is selected from methyl and benzyl, and n is 1, m
Is 0 and the oxidation number of titanium is +3, X1 is 2- (N,
If N-dimethyl) aminobenzyl and the oxidation number of titanium are +4, X1 is 2-butene-1,4-diyl, and if n is 0, m is 1 and the oxidation number of titanium is +2, X2 is 1,4. Diphenyl-1,3-butadiene or 1,3-pentadiene.

The catalyst used in the present invention can be obtained by carrying the component (a), the component (c) and the component (d) on the component (a), and the component (a) is supported on the component (a). The method is optional, but generally, component (a), component (c) and component (d) are dissolved in an inert solvent in which each can be dissolved, and after mixing with component (a), the solvent is distilled off. After the components (a), (c) and (d) are dissolved in an inert solvent, the solids are concentrated to the extent that no solid precipitates out, and the whole amount of the next concentrated liquid is reduced to particles. A method of adding an amount of the component (a) that can be held in the container, a method of first supporting the component (a) and the component (c) on the component (a), and then supporting the component (d). A) a method of sequentially supporting the component (d) and the component (c),
Component (A), Component (A), Component (C), and Component (D)
Is carried out by co-grinding.

The component (c) and the component (d) of the present invention are generally solids, and the component (a) has a pyrophoric property. May be diluted before use. As the inert solvent used for this purpose, for example, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; and ethyl chloride; Examples thereof include halogenated hydrocarbons such as chlorobenzene and dichloromethane, and mixtures thereof. 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) is 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol, preferably 1 × 10 ⁻⁴ to 5 × 10 ⁻² mol, in terms of Al atom, per gram of component (a). Component (c) is 1 × ¹⁰⁻⁷ mol to 1 × ¹⁰⁻³ mol, preferably 5 × 1 mol.
^0-7 mol to 5 x ^10-4 mol, component (d) is 1 x ^10-7
1 × 10 ^-3 mol mol, preferably from 5 × 10 ^-4 mol 5 × 10 ^-7 mol. Each amount to be used and the loading method are determined by activity, economy, powder characteristics, scale in the reactor, and the like. The obtained supported catalyst may be washed by a method such as decantation or filtration using an inert hydrocarbon solvent for the purpose of removing the organic aluminum compound, borate compound, and titanium compound that are not supported on the support. it can.

The above series of operations such as dissolving, contacting, washing, etc.
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.

In the polymerization of ethylene homopolymer or copolymer, the polymerization pressure is generally 1 to 100 atm, preferably 3 to 30 atm, and the polymerization temperature is 20 to 1 atm.
15 ° C, preferably 50 ° C to 90 ° C, is suitable. However, the upper limit of the temperature is the temperature at which the produced ethylene homopolymer or copolymer can substantially maintain a slurry state, and if it exceeds this value, the molecular terminal double bond of ethylene homopolymer or copolymer Is increased. As the solvent used in the slurry method, the inert hydrocarbon solvent described above in the present invention is preferable, and particularly, isobutane, isopentane, heptane, hexane, octane and the like are preferable.

The comonomer which 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, and the alkyl group is linear;
It is branched or cyclic. )

Such comonomers include, for example, propylene, 1-butene, 1-pentene, 1-hexene,
Methyl-1-pentene, 1-octene, 1-decene, 1
-Dodecene, 1-tetradecene, 1-hexadecene, 1
Selected from the group consisting of -octadecene, 1-eicosene, vinylcyclohexane, and styrene, having 3 to 2 carbon atoms
0 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
The linear, branched or cyclic diene having 4 to 20 carbon atoms selected from the group consisting of 8,8a-octahydronaphthalene is, for example, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene. , 1,4-hexadiene, and cyclohexadiene. In the present invention, in particular, 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 alone can polymerize ethylene or ethylene and α-olefin. However, in order to prevent poisoning of the solvent and the reaction system, an organic aluminum compound is added as an additional component. It is also possible to use. Examples of preferred organic aluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, Alkyl aluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, etc., aluminum alkoxides such as diethylaluminum ethoxide, dimethylaluminum trimethylsiloxide, dimethylaluminum phenoxide, etc., methylalumoxane, ethylaluminoxane, isobutyl Rumikisan,
Alumoxanes such as methylisobutylalumoxane and the like can be mentioned. Of these, trialkylaluminum, aluminum alkoxide and the like are preferable. Most preferred are trimethylaluminum, triethylaluminum and triisobutylaluminum.

The modified ethylene polymer is obtained by reacting the ethylene homopolymer or copolymer obtained by the above-mentioned method with oxygen and / or a radical generator at a temperature of 185 ° C. or more. When using oxygen, the concentration of oxygen is 1 to 30.
Ethylene homopolymer or copolymer is reacted with oxygen under a mixed gas of oxygen and nitrogen which is volume%. The reaction temperature is 1
It is 85 ° C. or higher, preferably in the range of 200 to 280 ° C., and when the reaction temperature is low, the modifying effect is small.
The reaction time is preferably 1 minute or more, preferably 1 to 5 minutes from the viewpoint of productivity of an extruder or the like.

The radical generator used satisfies the following conditions. That is, it is a radical generator having a decomposition temperature of 150 to 220 ° C. for setting the half-life to 1 minute.
This radical generator is used at a temperature of 185 ° C. or higher. The radical generator is preferably added in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the ethylene homopolymer or copolymer to react with the ethylene homopolymer or copolymer. When the decomposition temperature is low, the radical generator is decomposed into radicals before the radical generator is sufficiently dispersed in ethylene homo- or copolymer, and as a result, a gel in which partially highly crosslinked has progressed is formed. Occurs in large quantities. When the decomposition temperature exceeds this range, the radical generator is not sufficiently decomposed under ordinary conditions. Preferably, a radical generator having a decomposition temperature of 160 to 220 ° C. for setting the half life to 1 minute is preferable. If the amount of the radical generator is less than the above range, a sufficient modifying effect cannot be obtained. If the amount exceeds this range, a large amount of gel is generated. The reaction temperature is 185 ° C or higher,
Preferably, the temperature is in the range of 200 to 260 ° C and the residence time is in the range of 1 to 5 minutes.

As the reactor, a known single-screw or twin-screw extruder, Banbury mixer, roll mill, or the like is used. Preferably, a single-screw and twin-screw extruder is preferred in view of productivity. When the reforming reaction of the present invention is carried out, first, ethylene alone or a copolymer is reacted with oxygen and / or a radical generator under the absence of a compound having an antioxidant function, and after the reaction, a known antioxidant is used. Most preferably, a stabilizer such as is added. As this method, for example, a method in which oxygen and / or a radical generator is reacted with ethylene alone or a copolymer in the first half of a single extruder and the reaction is stopped by adding a stabilizer in the second half, or 2
A series of extruders are connected in series, a reforming reaction is performed in the former machine, a stabilizer is added in the latter machine, or a reforming reaction is performed in one extruder to form a pellet once, and then a stabilizer is added to the pellet, Further, there is a method of extruding.

The mixing method of the radical generator and the ethylene homopolymer or copolymer is not particularly limited, but it is necessary to disperse the radical generator in the powder, pellet or melt of the ethylene homopolymer or copolymer as uniformly as possible. is there. In particular, a method of uniformly mixing a radical generator using a powder of ethylene alone or a copolymer is most preferable. For example, a method in which a radical generator is dissolved in a solvent and added to a powder of ethylene alone or a copolymer. Alternatively, a method using a high-concentration masterbatch prepared by extruding a radical generator with ethylene homopolymer or copolymer at a low temperature and the like may be used.

The radical generator includes an inorganic radical generator and an organic radical generator, and an organic radical generator is particularly preferable. As an organic radical generator, for example,

Embedded image (Where R _3, R _{4 and} R ₅ are an alkyl group, a substituted alkyl group,
Represents an alkylene group or a substituted alkylene group. ).

As the organic radical generator, for example,
1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t- Hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5
-Trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxyban Zoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-
Butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl Cumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3, preferably, dicumyl peroxide, 2,5
-Dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like.

The modified ethylene polymer of the present invention may contain a phenol stabilizer and / or an organic phosphite stabilizer and / or an organic thioether stabilizer and / or a stabilizer such as a metal salt of a higher fatty acid according to the present invention. It can be added in a range that does not impair the purpose. Phenolic stabilizers include 2,6-di-tert-butyl-4-methylphenol,
2,6-dicyclohexyl-4-methylphenol,
2,6-diisopropyl-4-ethylphenol, 2,
6-t-amyl 4-methylphenol, 2,6-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-tert-butyl-4-hydroxy) hydrocinnamate) methane, 2,2 ^, -methylenebis (4-methyl-6-tert-butylphenol), 4,4 ^, butylidenebis (3-methyl-6-tert-butylphenol), 4,4 ^, -thiobis (3-methyl-6-t-butylphenol), 2,2 ^, -thiobis (4-methyl-6
-Tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, 1,3,5-tris (2-methyl-4-hydroxy-5-tert-butylphenol) Methane, tetrakis (methylene (3,5-dibutyl-4-hydroxyphenyl) propionate) methane, β- (3,5-di-tert-butyl-4-hydroxyphenol) propionic acid alkyl ester,
2,2 ^, -oxamidobis (ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis (methylene (2,4-di-tert-butyl-4-hydroxyl) propionate), n-octadecyl-3- (4 ^, -hydroxy-3,5 -di-t-butylphenyl) propionate, 2,6-di-t-butyl-p over-cresol, 2,4,6 Torisu ^{(3, 5,} di ^t-butyl-4, over-hydroxybenzyl-thio no 1,
3,5-triazine, 2,2 ^, -methylenebis (4-methyl-6-tert-butylphenol), 4,4 ^, -methylenebis (2,6-di-tert-butylphenol), 2,2
^, -Methylenebis (6- (1-methylcyclohexyl)
-P-cresol), bis (3,5-bis (4-hydroxy-3-tert-butylphenyl) butylic 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-tert-butylbenzyl) isocyanurate, 1,3,5 tris (3,5-di-tert-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) propionyloxyethyl) isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine, 4, 4 ^, thiobis (6-t-butyl-m
-Cresol).

Examples of the organic phosphite-based stabilizer include trioctyl phosphite, trilauryl phosphite,
Tridecyl phosphite, octyl diphosphite,
Tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,1 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite, 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 Dendiphenol 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-tert-butylphenyl) pentaerythritol diphosphide, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphide, tris ((4,4 ^, -isopropylidene) Bis (2-tert-butylphenol)) phosphide, di (nonylphenyl) pentaerythritol diphosphide, tris (1,3-distearoyloxyisopropyl) phosphite,
4,4 ^, -isopropylidenebis (2-tert-butylphenol) di (nonylphenyl) phosphide, 9,10
Dihydro-9-oxa10-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.
Polyhydric alcohols of alkylthiopropionic acid such as laurilu, stearyl, etc. (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate)
Esters, for example, pentaerythitol tetralauryl thiopropionate. More specifically, dilauryl thiopropionate, dimyristyl thiopropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutyrate and the like can be mentioned.

Examples of the metal salts of higher fatty acids include alkaline earth metal salts such as magnesium, calcium and barium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, caprylic acid, arachidic acid, palmitic acid and behenic acid. 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.

The modified ethylene polymer of the present invention is used alone,
Or may be used by mixing, pigment, dye, nucleating agent,
Lubricants, carbon black, talc, inorganic fillers such as glass fiber or reinforcing agents, flame retardants, neutron blocking agents and other additives commonly added to polyolefins can be added within a range that does not impair the purpose of the present invention. . The modified ethylene polymer of the present invention is molded by a known molding method such as injection molding, blow molding, pipe, film, compression molding, etc., and is particularly preferably used for injection blow molding.

[0047]

The present invention will be described below in more detail with reference to examples and the like, but these do not limit the scope of the present invention. The melt index is a value measured at 190 ° C. under a load of 2.16 kg according to ASTM-D-1238. Moldability (MIR) MIR is measured at a temperature of 190
It is a value obtained by dividing the value of the melt index measured at a temperature of 190 ° C. and a load of 2.16 Kg by the melt index at a temperature of 190 ° C. and a load of 21.6 kg. The larger the value, the better the moldability.

Molecular weight distribution: The measuring apparatus used for the measurement was Waters 150-C ALC / GPC, the columns were Shodex AT-807S and Tosoh TSK-gelGMH-H6 in series, and the solvent was 10 ppm. The measurement was performed at 140 ° C. using trichlorobenzene containing Irganox 1010. A calibration curve was prepared using commercially available monodisperse polystyrene as a standard substance. Terminal double bond: Ethylene homo- or copolymer powder was pressed at 180 ° C. to form a film. The infrared absorption spectrum (IR) of this film was measured using FT manufactured by JASCO Corporation.
-IR-5300A was used for the measurement. Vinyl group 910cm ^-1, vinylidene groups is calculated from the following equation from the absorbance of the peak of ^878cm-1. Vinyl group (q / 1000C) = 0.98 × ΔA ₉₁₀ / t Vinylidene group (q / 1000C) = 0.91 × ΔA ₈₈₇
/ T where ΔA is the absorbance and t is the film thickness (mm).

D value: ¹³ C-NMR is from JEOL JNM
Using a Model 400, 13% by weight of an ethylene polymer was dissolved in orthodichlorobenzene / deuterated benzene (10/3), and the temperature was 120 ° C., the pulse was 45 ° C. (Interval 1.689).
Second), and measured 20,000 times in total. Cαα 40.1
5 ppm, Cαγ 34.48 ppm, Cαδ 3
4.32 ppm, Cβδ 37.24 ppm, Cδδ
The integrated value of the peak attributed to 39.61 ppm and Cγδ30.47 ppm was obtained, and (XX) = (Cαα) (XE) = (Cαγ) + (Cαδ) (EE) = 1/2 [(Cβδ) + (Cδδ )] + ／
Each diat is obtained by (Cγδ), and D = 4 (XX) × (EE)
/ (EX) ² . The larger this value is, the higher the ratio of the comonomer being continuously inserted is.

Mechanical properties: 500 ppm of Irganox 1010 (trade name) was added to the modified ethylene polymer and extruded, and the obtained pellet was heated at 200 ° C. and 1 ° C. with a press molding machine.
Melted at 00 kg / cm ² for 3 minutes, and then cooled at 10 ° C./min. From the obtained molded plate, cut out a No. 1 EA type test specimen according to JIS-K711 and determine the Charpy impact strength at −20 ° C. Was. Gel evaluation: Irganox 10 for modified ethylene polymer
10 (trade name), 500 ppm, and screw diameter 2
Using a 5 mm inflation film forming machine, a film of about 100 microns was prepared, and the gel was visually evaluated according to the following evaluation criteria. No gel; 1 Some gel; 2 Gel present; 3 Abundant gel; 4

Example 1 Preparation of Ethylene Polymer 6.2 g (8.8 mmol) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was added to 4 liters of toluene.
It stirred at 30 degreeC for 30 minutes. Next, 40 ml of a 1 mol / l toluene solution of trihexylaluminum was added to this 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 placed in 1.7 l of toluene and stirred. To the silica slurry solution, the above-mentioned triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate and trihexylaluminum toluene solution were added, and the mixture was added for 9 hours.
Stirred at 0 ° 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 titanum (N-1,1-dimethylethyl) dimethyl (1- (1,2,3,4,5-eta) -2,3
4,5 over tetramethyl-2,4-over cyclopentadiene-1 Iru) Shiranaminato) ((2-) N) over (eta ⁴ over 1,3 Pentajien) of ISOPAR ^TM E (US, E
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 a total pressure of 8 kg / cm ² was obtained with a mixed gas of ethylene, 1-butene and hydrogen (gas composition: ethylene 700 g, 1-butene 8 g, hydrogen 0.3 l).
By replenishing the mixed gas of the above composition, the total pressure is 8 kg / c
The polymerization was carried out for 2 hours while maintaining m ² to obtain an ethylene copolymer. Melt index of the obtained ethylene copolymer,
The MIR, molecular weight distribution, terminal double bond amount, density and D value are shown in Table 1.

Preparation of Modified Ethylene Polymer (1) 0.3 g of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (half-life 1 minute, decomposition temperature 179.8 ° C.) in 500 ml of hexane And 3 kg of the ethylene copolymer powder obtained by the above adjustment
And mixed by stirring with a Hensiel mixer. This powder was extruded at 200 ° C. with an extruder having a screw diameter of 25 mm. At that time, the inside of the extruder and the hopper were extruded while purging with nitrogen. 500 ppm of Irganox 1010 was added to the obtained pellet, and extruded again with a 25 mm extruder. Using this pellet, mechanical properties, moldability, and gel were evaluated. The results are shown in Table 1.

Example 2 Preparation of Modified Ethylene Polymer (2) Using the ethylene copolymer prepared in Example 1, 270 ° C.
The hopper of the 25 mm extruder and the inside of the extruder are replaced with a mixed gas of oxygen and nitrogen of 20% by volume of oxygen and sufficiently replaced, and the ethylene copolymer is discharged while flowing the mixed gas into the hopper and the extruder. Extruded. 500 ppm of Irganox 1010 was added to the obtained pellet,
It was extruded again with a 25 mm extruder. Using this pellet, mechanical properties, moldability, and gel were evaluated. The results are shown in Table 1.

Examples 3 to 9 Ethylene gas, butene,
Except for changing the amount of hydrogen, the ethylene homopolymers (Examples 8 and 9) and the copolymers (Examples 3 to 7) described in Table 1 were prepared according to the production method of Example 1. The type of radical generator,
Except for the amount, oxygen concentration and extrusion temperature, the reforming method of Example 1 or Example 2 was followed. 500 ppm of Irganox 1010 was added to the resulting modified ethylene polymer, and 25
Extruded with a mm extruder. Using this pellet, mechanical properties, moldability, and gel were evaluated. The results are shown in Table 1.

(Comparative Examples 1-2) Ethylene gas, butene,
Except for changing the amount of hydrogen, the ethylene copolymer described in Table 1 was prepared according to the production method of Example 1. Furthermore, the reforming method of Examples 1 and 2 was followed except for the type, amount, oxygen concentration, and extrusion temperature of the radical generator. 500 ppm of Irganox 1010 was added to the obtained modified ethylene polymer, and the mixture was extruded again with a 25 mm extruder. Using this pellet, the mechanical properties, moldability and gel shown in Table 1 were evaluated. The results are shown in Table 1. In Comparative Example 1, the raw material ethylene copolymer had a high melt index and the mechanical properties were poor, and in Comparative Example 2, the raw material ethylene copolymer had a too low melt index and an ultrahigh molecular weight gel was present.

Comparative Examples 3 and 4 Ethylene Polymer with Ziegler Catalyst The ethylene polymers of Comparative Examples 3 and 4 were prepared using a Ziegler catalyst prepared from magnesium chloride hexahydrate, 2-ethylhexanol and magnesium chloride, which are already well known. The copolymer was polymerized. The obtained ethylene copolymer was modified using the modification methods of Examples 1 and 2. 500 ppm of Irganox 1010 was added to the obtained modified ethylene polymer, and the mixture was extruded again with a 25 mm extruder. Using this pellet, mechanical properties, moldability, and gel were evaluated. The results are shown in Table 1. The resulting modified ethylene polymer produced a large amount of gel. This is because the molecular weight distribution of the ethylene copolymer as the raw material is wide, so that it is presumed that the high molecular weight component was crosslinked and gel was generated, and the mechanical properties were also poor.

(Comparative Example 5) Zirconocene-catalyzed ethylene polymer Silica (Grand 952, trade name, manufactured by Fuji Devison) was placed in a sufficiently nitrogen-dried 200 ml flask.
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.
mol, and triisobutylaluminum (1.0 m
(ol / l) 0.12 mmol was added to synthesize a catalyst. The resulting suspension was deaerated in vacuo with 0.8 l of dehydrated and deoxygenated hexane and placed in a 1.5 l reactor purged with nitrogen.

The temperature in the vessel was set at 75 ° C., and the amount of a mixed gas of ethylene, 1-butene and hydrogen was adjusted (gas composition: ethylene 700 g, 1-butene 14 g, hydrogen 0.3 l), and the total pressure was 8 kg / cm ² . did. By supplying the mixed gas, polymerization was carried out for 2 hours while maintaining the total pressure at 10 kg / cm ² to obtain an ethylene copolymer. The obtained ethylene polymer was reformed using the reforming method of Example 1, 500 ppm of Irganox 1010 was added, and the mixture was extruded again with a 25 mm extruder. Although the physical properties of the resulting modified ethylene polymer were good, sufficient moldability could not be obtained due to the narrow original molecular weight distribution, and the gel had many gels due to many terminal double bonds.

Comparative Example 6 An ethylene copolymer was prepared by a solution method in the same manner as in Example 1 except that the amounts of ethylene gas, butene and hydrogen were changed and the polymerization temperature was 160 ° C. Irganox 1010 was added to the obtained modified ethylene polymer at 500 pp.
m was extruded again with a 25 mm extruder. Using the pellets of the obtained modified ethylene polymer, the mechanical properties, moldability and gel shown in Table 1 were evaluated. The results are shown in Table 1. A large amount of gel was generated with many terminal double bonds.

(Comparative Examples 7 to 10) The ethylene copolymer of Example 1 was modified according to the method shown in Table 1. Irganox 101 was added to the resulting modified ethylene polymer.
0 and 500 ppm were added and extruded again with a 25 mm extruder. Using this pellet, mechanical properties, moldability, and gel were evaluated. The results are shown in Table 1. Comparative Example 7 was not sufficiently improved in moldability due to low oxygen concentration. In Comparative Example 8, a gel was generated due to a high oxygen concentration. In Comparative Example 9, since the decomposition temperature of the radical generator was low, the radical generator was not dispersed in the ethylene polymer, and a large amount of gel was generated. In Comparative Example 10, the radical generator had a high decomposition temperature, and the radical generating agent was not sufficiently decomposed under normal extrusion conditions, so that the reforming effect was small.

[0063]

[Table 1]

[0064]

The modified ethylene polymer of the present invention has excellent mechanical properties and moldability, and has no gel in the molded article. Since these modified ethylene polymers have a low viscosity at a high shear rate and a large melt tension, they are preferably used particularly for injection blow molding.

Claims (5)

[Claims] (A) a melt index at a load of 2.16 kg at 190 ° C. of 0.1 to 100 g / 10 minutes; and (B) a molecular weight distribution of 3 to 7 measured by gel permeation chromatography. , (C) the vinyl group present at the molecular end of the polymer is 0.02 (months / 1000 carbons) or less, and (D) the vinylidene group present at the molecular end of the polymer is 0.02 (months). / 1000 carbons)
The following ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is mixed with a mixed gas of oxygen and nitrogen having an oxygen concentration of 1 to 30% by volume and / or
Alternatively, the modified ethylene polymer is reacted with a radical generator having a decomposition temperature of 150 ° C. to 220 ° C. for a half-life of 1 minute at a temperature of 185 ° C. or more. 2. The amount of a dyad in which an α-olefin is continuously inserted in an ethylene copolymer (hereinafter referred to as (XX)), the amount of a dyad in which ethylene is continuously inserted (hereinafter referred to as (EE)), and ethylene and The amount of dyad into which the α-olefin was continuously inserted (hereinafter referred to as (EX)) was calculated by D = 4 (XX) × (EE) / (EX) ² , and the ethylene value was 1.3% or less. The modified ethylene polymer according to claim 1, wherein a polymer is used. 3. A carrier material, (a) an organic aluminum compound, (c) a borate compound having active hydrogen,
And (d) using an ethylene homopolymer or copolymer obtained in a slurry state using a supported catalyst prepared from a titanium compound bonded to a cyclopentadienyl or substituted cyclopentadienyl group and η-bonded. The modified ethylene polymer according to claim 1 or 2, wherein 4. A decomposition temperature of 1 minute for setting a half-life to 1 minute.
A radical generator at 50 to 220 ° C is used in an amount of 0.001 to 0.
4. The method according to claim 1, wherein 1 part by weight is added.
A method for producing the modified ethylene polymer according to the above. 5. The process for producing a modified ethylene polymer according to claim 1, wherein a mixed gas of oxygen and nitrogen having an oxygen concentration of 2 to 19% by volume is used.