JP2769706B2 - Method for producing modified polyolefin particles - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for modifying polyolefin particles comprising a crystalline olefin polymer and an amorphous olefin polymer with glycidyl groups.

Technical Background of the Invention and Problems Thereof Conventionally, a method of imparting a polar group such as a carboxyl group or a glycidyl group to a polyolefin to modify the polyolefin has been used.

To modify such a polyolefin, a method in which a modifying agent is blended with the polyolefin, and the polyolefin is extruded in a molten state using an extruder or the like and modified under high temperature and high shearing force (melting method) or using the polyolefin as a solvent A method of dissolving and blending a denaturing agent with the solution to modify the polyolefin (solvent method) is employed.

Apart from such a method, Japanese Patent Publication No. 55-32722 discloses a method in which a granular olefin polymer is modified using a specific glycidyl compound at a temperature below the viscosity point of the olefin polymer. ing.

However, the modifier used in the method disclosed in such publication is a glycidyl compound having an ester bond.

An object of the present invention is to provide a method for producing a modified olefin particle by introducing a highly stable glycidyl group into a polymer constituting a polyolefin particle, and to provide a production method capable of reducing costs. The purpose is.

SUMMARY OF THE INVENTION The method for producing modified polyolefin particles according to the present invention comprises the steps of: preparing polyolefin particles and 0.01 to 50% by weight of allyl glycidyl ether and / or vinyl glycidyl ether based on 100 parts by weight of the polyolefin particles; The polyolefin particles have a swelling property with respect to the polyolefin particles and 10 to 50 parts by weight of a good solvent for the radical initiator, and 0.01 to 10 parts by weight of the radical initiator. It is characterized in that the polyolefin particles are kept in contact with each other at a temperature lower than the temperature at which they do not fuse with each other.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing a modified polyolefin according to the present invention will be specifically described.

In the present invention, when a polymer is referred to, the polymer is used as a concept including both a polymer and a copolymer.

The average particle size of the polyolefin particles as the raw material as used in the present invention is usually 10 to 5000 μm, preferably 100 to 4000 μm, more preferably 300 to 3000 μm
Within the range. The geometric standard deviation indicating the particle size distribution of the polyolefin particles used in the present invention is usually 1.
0 to 2.0, preferably 1.0 to 1.5, particularly preferably 1.0 to 1.3
Within the range. In addition, the apparent bulk density of the polyolefin particles used in the present invention by natural fall is usually 0.2 g / m
l or more, preferably 0.30 to 0.70 g / ml, particularly preferably 0.3 g
It is in the range of 5-0.60 g / ml.

As the polyolefin particles used in the present invention, it is preferable to use particles having the above properties, and there is no particular limitation on the method for producing the particles having such properties, but a method as described below. The polyolefin particles obtained by adopting this method have a transition metal content in the ash content of usually 100 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, and halogen content. Is usually contained in an amount of 300 ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less.

Polyolefin particles having the above-mentioned properties can be obtained, for example, by polymerizing or copolymerizing an α-olefin having 2 to 20 carbon atoms.

Examples of such α-olefins include ethylene,
Propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-
Methylpentene-1,4-methylpentene-1,3,3-
Dimethylbutene-1, heptene-1, methylhexene-
1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene
1, dimethylhexene-1, trimethylpentene-1,
Ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1,
Examples thereof include α-olefins such as methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, and hexadodecene-1.

Among them, α-olefins having 2 to 8 carbon atoms are preferably used alone or in combination.

In the present invention, the repeating unit derived from the above-mentioned α-olefin is usually 50 mol% or more, preferably 80 mol%, particularly preferably 90 mol% or more, more preferably 10 mol% or more.
Polymer particles containing 0 mol% are used.

In the present invention, examples of other compounds that can be used in addition to the above-mentioned α-olefin include a chain polyene compound and a cyclic polyene compound. In the present invention, the polyene compound is a polyene having two or more conjugated or non-conjugated olefinic double bonds. Examples of such a chain polyene compound include 1,4
-Hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7
-Octatriene, 1,5,9-decatriene, divinylbenzene and the like. Examples of the cyclic polyene compound include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene, 2 -Ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-
2,5-norbornadiene and the like.

In the present invention, a polyene compound obtained by condensing a cyclopentadiene such as cyclopentadiene with an α-olefin such as ethylene, propylene or butene-1 using a Diels-Under reaction can also be used. .

Further, in the present invention, a cyclic monoene compound can be used. Examples of such a cyclic monoene compound include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, and cyclododecene. , Tetracyclodecene, octacyclodecene,
Monocycloalkenes such as cycloeicosene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-
Norbornene, 5-isobutyl-2-norbornene, 5,
6-dimethyl-2-norbornene, 5,5,6-trimethyl-
Bicycloalkenes such as 2-norbornene and 2-bornene, 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H- In addition to tricycloalkenes such as indene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, and these compounds, 2-methyl-1 , 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene,
2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8- Dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-stearyl-1,4,
5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,
4a, 5,8,8a-octahydronaphthalene, 2-methyl-3
-Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene,
2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8
Tetra cycloalkenes such as a- octahydronaphthalene, hexacyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7,
0 ^9,14] heptadecene -4 pentacyclo [8,8,1 ^2,9, 1
^4,7, 1 _{11, 18,} 0, 0 ^3,8, 0 ^12,17] henicosenoic -5, octacyclo [8,8,1 ^2,9, 1 ^4,7, 1 _{11, 18,} 1 ^{13, 16} , 0,0 _3,8 , 0
^12,17 ] cyclic monoene compounds such as polycycloalkenes such as dococene-5.

Furthermore, in the present invention, styrene and substituted styrene can also be used.

The polyolefin particles used in the present invention can be obtained by polymerizing or copolymerizing at least the α-olefin as described above in the presence of a catalyst. It can be carried out (gas phase method) or in the liquid phase (liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is preferably performed in a suspended state so that the polyolefin particles to be produced can be obtained in a solid state.

In the present invention, in producing polyolefin particles, a method of simultaneously producing a crystalline olefin polymer portion and an amorphous olefin polymer portion by supplying two or more types of monomers to a polymerization vessel, A method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion can be performed separately and in series using a polymerization vessel having at least two groups. In this case, the latter method is preferred from the viewpoint that the molecular weight, composition, and amount of the amorphous olefin polymer portion can be freely changed.

The most preferable method is a method of synthesizing a crystalline olefin polymer part by gas phase polymerization and then synthesizing an amorphous olefin polymer part by gas phase polymerization, or synthesizing a crystalline olefin polymer part using a monomer as a solvent. After that, a non-crystalline olefin polymer part is synthesized by gas phase polymerization.

As a solvent used in the polymerization reaction or the copolymerization reaction, an inert hydrocarbon can be used.
Further, an α-olefin as a raw material may be used as a reaction solvent. The above polymerization or copolymerization may be performed by combining a liquid phase method and a gas phase method. In the production of the polymer particles used in the present invention, the polymerization or copolymerization is preferably carried out by a gas phase method, or a method of performing a reaction using an α-olefin as a solvent and then combining the gas phase method. .

In the present invention, the catalyst used in the above polymerization reaction or copolymerization reaction is usually a periodic table of elements.
A catalyst component [A] having a transition metal of Group IVA, Group VA, Group VIA, Group VIIA and Group VIII;
A catalyst comprising a Group III organometallic compound catalyst component [B] is used.

As the catalyst component [A], the periodic table IVA
A catalyst containing a transition metal atom of Group III or VA is preferable, and among them, a catalyst component containing at least one kind of atom selected from the group consisting of titanium, zirconium, hafnium and vanadium is more preferable.

Further, as another preferred catalyst component [A], a catalyst component containing a halogen atom and a magnesium atom in addition to the above transition metal atom, and a transition metal atom belonging to Group IVA or VA of the periodic table having a conjugated π electron. A catalyst component containing a compound having a group coordinated is exemplified.

In the present invention, the catalyst component [A] is present in the reaction system in a solid state in the above-mentioned polymerization reaction or copolymerization reaction, or is present in a solid state by being supported on a carrier or the like. It is preferred to use a catalyst prepared so that

The above-mentioned catalyst component [A] will be described in further detail by taking the above-mentioned solid catalyst component [A] containing a transition metal atom, a halogen atom and a magnesium atom as an example.

The average particle diameter of the solid catalyst component [A] as described above is preferably 1 to 200 μm, more preferably 5 to 100 μm.
μm, particularly preferably in the range from 10 to 80 μm. Further, the geometric standard deviation (δ _g ) as a scale for observing the particle size distribution of the solid catalyst [A] is preferably in the range of 1.0 to 3.0, more preferably 1.0 to 2.1, and particularly preferably 1.0 to 1.7.

Here, the average particle size and the particle size distribution of the catalyst component [A] can be measured by a light transmission method. Specifically, a dispersion prepared by adding the catalyst component [A] to the decalin-insoluble solvent so that the concentration (content) becomes about 0.1 to 0.5% by weight, preferably 0.1% by weight is taken into a measurement cell. ,
The cell is irradiated with fine light and the particle size distribution is measured by continuously measuring the intensity of light passing through the liquid in a sedimented state with particles. Based on the particle size distribution, a standard deviation (δ _g ) is obtained from a lognormal distribution function. More specifically, the standard deviation (δ _g ) is determined as the ratio (θ ₅₀ / θ ₁₆ ) between the average particle diameter (θ ₅₀ ) and the particle diameter (θ ₁₆ ) which becomes 16% by weight in view of the small particle diameter. Can be The average particle size of the catalyst is a weight average particle size.

The catalyst component [A] preferably has a shape such as a true sphere, an oval sphere, or a granule, and the particle has an aspect ratio of preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. It is.

When the catalyst component [A] has a magnesium atom, a titanium atom, a halogen atom, and an electron donor, the ratio of magnesium / titanium (atomic ratio) is preferably larger than 1, and this value is usually 2 to 50, and preferably 2 to 50. In the range of 6 to 30 and the halogen / titanium (atomic ratio) is usually 4
-100, preferably 6-40, and the electron donor / titanium (molar ratio) is usually 0.1-10, preferably 0.2-10.
-6. The specific surface area of the catalyst component [A] is usually 3m ² / g or more, preferably 40 m ² / g or more, more preferably in the range of 100~800m ² / g.

Such a catalyst component [A] generally does not desorb the titanium compound in the catalyst component by a simple operation such as hexane washing at room temperature.

In addition, the catalyst component [A] used in the present invention may contain other atoms and metals in addition to the above components, and further, a functional group or the like is introduced into the catalyst component [A]. May be further diluted with an organic or inorganic diluent.

The catalyst component [A] as described above includes, for example, an average particle diameter,
The particle size distribution is in the above-mentioned range, and furthermore, after forming the magnesium compound as described above, a method of preparing a catalyst, or contacting a liquid magnesium compound and a liquid titanium compound to obtain the above-mentioned particle properties Can be produced by employing a method such as a method of forming a solid catalyst so as to have

Such a catalyst component [A] can be used as it is, or can be used after supporting a magnesium compound, a titanium compound and, if necessary, an electron donor on a carrier having a uniform shape. A finely divided catalyst may be prepared and then the finely divided catalyst may be granulated into the preferred shapes described above.

Such a catalyst component [A] is disclosed in JP-A-55-13.
Nos. 5102, 55-135103, 56-811, 56-67311 and Japanese Patent Application Nos. 56-18119 and 61-210109.

Examples of components for preparing the catalyst component [A] described in these publications or specifications are shown below.

(1) A solid magnesium compound / electron donor complex having an average particle size of 1 to 200 μm and a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less, an electron donor and / or an organoaluminum compound or a halogen-containing silicon compound And a reaction with a liquid titanium halide compound, preferably titanium tetrachloride, under the reaction conditions, with or without pretreatment.

(2) reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor, to have an average particle diameter of 1 to 200 μm;
A solid component having a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less is precipitated. If necessary, a liquid titanium compound,
Preferably, it is reacted with titanium tetrachloride or with a liquid titanium compound and an electron donor.

(3) By pre-contacting a liquid magnesium compound having a reducing ability with a reaction aid capable of eliminating the reducing ability of a magnesium compound such as a polysiloxane or a halogen-containing silicon compound,
After depositing a solid component having an average particle size of 1 to 200 μm and a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less, the solid component is converted into a liquid titanium compound, preferably titanium tetrachloride,
Alternatively, it is reacted with a titanium compound and an electron donor.

(4) After contacting a magnesium compound having a reducing ability with an inorganic carrier such as silica or an organic carrier, and then contacting the carrier with a halogen-containing compound or without contacting the same, a liquid titanium compound, preferably tetrachloride Contacting titanium or a titanium compound and an electron donor to react a magnesium compound supported on a carrier with a titanium compound or the like.

Such a solid catalyst component [A] has a property that a polymer having high stereoregularity can be produced with high catalytic efficiency. For example, when propylene homopolymerization is carried out under the same conditions, polypropylene having an isotacticity index (boiling n-heptane insoluble matter) of 92% or more, particularly 96% or more is usually 3000 g or more, preferably 5000 g or more per 1 mmol of titanium. , Particularly preferably having an ability to produce 10,000 g or more.

Examples of a magnesium compound, a halogen-containing silicon compound, a titanium compound, and an electron donor that can be used in the preparation of the catalyst component [A] as described above are shown below. The aluminum component used in the preparation of the catalyst component [A] is a compound exemplified in the later-described organometallic compound catalyst component [B].

Examples of the magnesium compound include magnesium oxide, magnesium hydroxide, inorganic magnesium compounds such as hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, and magnesium ujihalide. And organic magnesium compounds such as dialkylmagnesium and diarylmagnesium.

Examples of titanium compounds include titanium halides such as titanium tetrachloride, alkoxytitanium halides, allyloxytitanium halides, alkoxytitanium, allyloxytitanium and the like. Among these, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred.

Examples of electron donors include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes; ammonia, amines , Nitriles and nitrogen-containing electron donors such as isocyanates.

Specific examples of the compound that can be used as such an electron donor include methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, and isopropyl alcohol. , Cumyl alcohol and isopropyl benzyl alcohol
18 alcohols; phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol (these phenols may have a lower alkyl group) A ketone having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; an aldehyde having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolylaldehyde and naphthaldehyde Methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, benzoate Methyl acrylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, anisic acid Methyl, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, Organic acid esters having 2 to 30 carbon atoms such as di-n-butyl luate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid C2 to C15 acid halides such as chloride and anisic acid chloride; C2 to C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and anisole and diphenyl ether; Acid amides such as benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine Amines such as acetonitrile, benzonitrile and tolunitrile; PO such as trimethyl phosphite and triethyl phosphite
Organic phosphorus compounds having a -P bond Examples thereof include ethyl silicate and alkoxysilanes such as diphenyldimethoxysilane. These electron donors can be used alone or in combination.

Among such electron donors, preferred electron donors are esters of organic acids or inorganic acids, alkoxy (aryloxy) silane compounds, ethers, ketones, tertiary amines,
Compounds having no active hydrogen such as acid halides and acid anhydrides, and particularly preferred are organic acid esters and alkoxy (aryloxy) silane compounds, among which esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms,
Malonic acid, substituted malonic acid, substituted succinic acid, maleic acid,
Substituted maleic acid, 1,2-cyclohexanedicarboxylic acid,
Esters of dicarboxylic acids such as phthalic acid and alcohols having 2 or more carbon atoms are particularly preferred. Of course, these electron donors can be added directly when preparing the catalyst, or can be added to the reaction system without adding them to the reaction system as a raw material when preparing the catalyst component [A]. A compound that can be converted can be blended, and this compound can be converted to the electron donor during the catalyst preparation process.

The catalyst component [A] obtained as described above can be purified by sufficiently washing it with a liquid inert hydrocarbon compound after preparation. Examples of hydrocarbons that can be used in this washing include n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene, fluid Aliphatic hydrocarbon compounds such as paraffin; cycloaliphatic hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbon compounds such as benzene, toluene, xylene and cymene; chlorobenzene; Halogenated hydrocarbon compounds such as dichloroethane can be mentioned.

Such compounds can be used alone or in combination.

As the organometallic compound catalyst component [B] used in the present invention, it is preferable to use an organoaluminum compound having at least one Al-carbon bond in the molecule.

Examples of such organoaluminum compounds include: (i) Formula R ¹ _m Al (OR ² ) _{n Hp} X _q (where R ¹ and R ² are each a number of carbon atoms, usually 1 to 15, preferably 1 X is a halogen atom, and m is 0 ≦ m.
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <
A number of 3, yet m + n + p + q = organic aluminum compound represented by 3 a is), and (ii) formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, K, and the R ¹ is the A complex alkyl compound of a metal of Group I of the periodic table and aluminum represented by the same meaning).

Specific examples of the organoaluminum compound represented by the above formula (i) include the compounds described below.

A compound represented by the formula R ¹ _m Al (OR ² ) _3-m (where R ¹ and R
² has the same meaning as described above, and m is preferably 1.5 ≦ m ≦ 3
Number).

A compound represented by the formula R ¹ _m AlX _3-m (where R ¹ has the same meaning as described above, X is a halogen, and m is preferably 0 <m
<3).

A compound represented by the formula R ¹ _m AlH _3-m (where R ¹ has the same meaning as described above, and m preferably satisfies 2 ≦ m <3).

A compound represented by the formula R ¹ _m Al (OR ² ) _n X _q (where R ¹ and R ² are the same as above; X is a halogen, 0 <m ≦ 3, 0 ≦ n
<3, 0 ≦ q <3, and m + n + q = 3).

Specific examples of the organoaluminum compound represented by the above formula (i) include trialkylaluminums such as triethylaminium, tributylaluminum and triisopropylaluminum, trialkenylaluminums such as triisoprenylaluminum, and diethylaluminum. Dialkyl aluminum alkoxides such as ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquibutoxide and butyl aluminum sesquibutoxide; having an average composition represented by formula R ¹ _2.5 Al (OR ² ) _0.5 Alkyl aluminums partially alkoxylated, diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide Such as dialkylaluminum halides, such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide, and alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Partially halogenated alkylaluminums, dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, and alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride are partially hydrogenated Alkyl aluminums, ethyl aluminum ethoxychlor , It may be mentioned partially alkoxylated and halogenated alkylaluminum such as such as butyl aluminum butoxide cycloalkyl chloride and ethylaluminum ethoxy bromide.

The organoaluminum compound may be a compound similar to the compound represented by the formula (i), such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Specific examples of such _{compounds, (C 2 H 5) 2} AlOAl (C 2 H 5) 2, (C 4 H 9) 2 AlOAl (C 4 H 9) 2, and And the like.

Examples of the organoaluminum compound represented by the formula (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among these, especially trialkylaluminums, mixtures of trialkylaluminums and alkylaluminum halides,
It is preferable to use a mixture of a trialkylaluminum and an aluminum halide.

It is preferable to use an electron donor [C] in addition to the catalyst component [A] and the organometallic compound catalyst component [B].

Examples of the electron donor [C] that can be used here include amines, amides, ethers, ketones,
Nitriles, phosphines, stibines, arsines,
Phosphoamides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes,
Alcoholates, alkoxy (aryloxy) silanes, organic acids and groups I, II, III of the periodic table
Mention may be made of amides of metals belonging to groups IV and IV and their acceptable salts. The salts are
It can also be formed in a reaction system by a reaction between an organic acid and an organometallic compound used as the catalyst component [B].

Specific examples of these electron donors include the compounds exemplified above as the catalyst component [A]. Among these electron donors, particularly preferred electron donors include organic acid esters, alkoxy (aryloxy) silane compounds, ethers, ketones, acid anhydrides and amides. In particular, when the electron donor in the catalyst component [A] is a monocarboxylic acid ester, the electron donor is preferably an alkyl ester of an aromatic carboxylic acid.

When the electron donor in the catalyst component [A] is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, the electron donor [C] may have the formula R _n Si (OR ¹ ) _4- It is preferable to use an alkoxy (aryloxy) silane compound represented by _n (where R and R ¹ represent a hydrocarbon group and 0 ≦ n <4) and an amine having a large steric hindrance.

Specific examples of such an alkoxy (aryloxy) silane compound include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldimethoxysilane. Ethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane,
Bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolylmethoxysilane,
Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethylmethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxy Silane, decylmethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso- Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltrimethylsilane Allyloxy silane, vinyl tris (β-methoxyethoxy silane), dimethyltetraethoxydisiloxane, etc., especially ethyl triethoxy silane,
n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolylmethoxysilane, p-tolylmethyl Preferred are dimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, ethyl silicate and the like.

As the amine having a large steric hindrance, 2,2,6,6
-Tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, or derivatives thereof, tetramethylmethylenediamine and the like are particularly preferred. Among these compounds, an alkoxy (aryloxy) silane compound is particularly preferred as the electron donor used as a catalyst component.

Further, in the present invention, a catalyst component [A] containing a transition metal atom compound of Group IVA or VA of the Periodic Table of the Elements having a group having a conjugated π electron as a ligand, and a catalyst component [B] of an organometallic compound The following catalyst can be preferably used.

Here, examples of the transition metals of Groups IVA and VA in the periodic table of the elements include metals such as zirconium, titanium, hafnium, chromium, and vanadium.

Examples of the ligand having a group having a conjugated π electron include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a t-butylcyclopentadienyl group, and a dimethylcyclopentadienyl group. Groups, alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl group, indenyl group, fluorenyl group and the like.

A preferred example is a group in which at least two ligands having a cycloalkadienyl skeleton are bonded via a lower alkyl group or a group containing silicon, phosphorus, oxygen, and nitrogen.

Examples of such a group include groups such as an ethylenebisindenyl group and an isopropyl (cyclopentadiethyl-1-fluorenyl) group.

One or more ligands having such a cycloalkadienyl skeleton coordinate with the transition metal, and
One is coordinated.

The ligand other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like.Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.Examples of the aryl group include a phenyl group and a tolyl group.Examples of the aralkyl group include a benzyl group, A neofil group is exemplified.

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

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

Such a transition metal compound containing a ligand having a cycloalkadienyl skeleton used in the present invention, for example, when the valence of the transition metal is 4, more specifically, a compound represented by the formula R ² _k R ³ _l R ⁴ _m R ⁵ _n M (wherein, M is zirconium, titanium, hafnium, vanadium or the like, R ² is a group having a cycloalkadienyl skeleton, and R ³ , R ⁴ and R ⁵ are cycloalkaline A group having a dienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom or hydrogen, k is an integer of 1 or more, and k + l + m + n = 4) It is.

Particularly preferably, in the above formula, R ² and R ³ are groups having a cycloalkadienyl skeleton, and the two groups having a cycloalkadienyl skeleton are preferably a lower alkyl group or silicon, phosphorus, oxygen, nitrogen Is a compound bonded via a group containing

Hereinafter, specific examples of the transition metal compound containing a ligand having a cycloalkadienyl skeleton in which M is zirconium will be described.

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis ( Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium Monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyldi Cuconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride bis (indenyl) zirconium dichloride, bis (indenyl) ) Zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopen Dienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (methylcyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium phenoxy Chloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) diethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium, ethylenebis (indenyl) ethylzirconium monochloride, ethylenebis (indenyl) zirconium dichloride , Isopropyl bisindenyl zirconium dichloride, isopropyl (cyclopentadienyl) 1-fluorenyl zirconium chloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) zirconium methoxymonochloride, ethylenebis (indenyl) zirconium ethoxymonochloride, ethylenebis (indenyl) zirconium phenoxymonochloride, ethylenebis ( Cyclopentadienyl) zirconium dichloride, propylene bis (cyclopentadienyl) zirconium dichloride, ethylenebis (t-butylcyclopentadienyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ) Dimethyl zirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-yne) Nil) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) ) Zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy-1-indenyl) zirconium dichloride, ethylenebis (2 , 3-Dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl)
Zirconium dichloride.

In the above zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, vanadium metal, or the like can also be used.

In this case, the organometallic compound catalyst component [B]
Preferably, an organic aluminum compound obtained by a reaction between an organic aluminum compound and water or a solution of an aluminoxane, for example, a hydrocarbon solution and water or an active hydrogen-containing compound is used.

Such an organoaluminum compound is insoluble or hardly soluble in benzene at 60 ° C.

In the present invention, the amount of the catalyst used depends on the type of the catalyst to be used and the like. For example, when the catalyst component [A], the organometallic compound catalyst component [B] and the electron donor [C] are used as described above. The amount of the catalyst component [A] used is
For example, it is usually 0.1 in terms of transition metal per polymerization volume.
The amount is set so as to be in the range of 001 to 0.5 mmol, preferably 0.005 to 0.5 mmol, and the amount of the organometallic compound catalyst [B] used is determined by the amount of the transition metal atom of the catalyst component [A] in the polymerization system. The metal atom of the organometallic compound catalyst [B] is usually from 1 to 10,000 mol, preferably from 5 to 1 mol, per mol.
The amount is set to be in the range of ~ 500 mol. When the electron donor [C] is used, the amount is preferably 100 mol or less, more preferably 1 to 50 mol, and particularly preferably 1 mol of the transition metal atom of the catalyst component [A] in the polymerization system. Is set in the range of 3 to 20 mol.

In the present invention, it is preferable to carry out preliminary polymerization prior to the main polymerization using the above-mentioned catalyst. In the prepolymerization, at least the catalyst component [A] and the organometallic compound catalyst component [B] are used in combination as a catalyst.

When titanium is used as the transition metal, the polymerization amount in the prepolymerization is usually 1 per 1 g of the titanium catalyst component.
~ 2000g, preferably 3 ~ 1000g, particularly preferably 10 ~ 50g
It is 0g.

The prepolymerization is preferably carried out using an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent that can be used in this case include propane, butane, n-pentane, i-pentane, and n-pentane. Hexane, i-hexane,
n-heptane, n-octane, i-octane, n-decane, n-dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbon compounds such as methylene chloride, ethyl chloride, ethylene chloride and chlorobenzene. Among such inert hydrocarbon solvents,
Aliphatic hydrocarbons are preferred, and aliphatic hydrocarbons having 4 to 10 carbon atoms are particularly preferred. Further, a monomer used in the reaction can be used as a solvent.

Examples of the α-olefin used in the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene. Α-olefins having 10 or less carbon atoms, such as, 1-decene, are preferred, α-olefins having 3 to 6 carbon atoms are more preferred, and propylene is particularly preferred. These α-olefins can be used alone or in combination of two or more as long as a crystalline polymer is produced.

The polymerization temperature in the prepolymerization differs depending on the α-olefin used and the use of the inert solvent and cannot be unconditionally specified, but is generally -40 to 80 ° C, preferably -20 to
It is in the range of 40 ° C, particularly preferably -10 to 30 ° C. For example, when using propylene as the α-olefin, -40 to 70 ° C., and when using 1-butene, -40 to 70 ° C.
~ 40 ° C, 4-methyl-1-pentene and / or 3-
When using methyl-1-pentene, the temperature is set in the range of -40 to 70C. It should be noted that a hydrogen gas can also be allowed to coexist in the reaction system for this preliminary polymerization.

It is possible to produce polyolefin particles by conducting the polymerization reaction (main polymerization) after or without conducting the prepolymerization as described above, and then introducing the above-mentioned monomer into the reaction system. it can.

The monomer used in the main polymerization may be the same as or different from the monomer used in the prepolymerization.

The polymerization temperature of the main polymerization of such an olefin is usually
It is in the range of -50 to 200C, preferably 0 to 150C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 5
Under a condition of 0 kg / cm ² , the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system.

The molecular weight of the obtained olefin polymer is hydrogen and / or
Or it can be adjusted by the polymerization temperature.

Further, in the present invention, usually, the polyolefin particles obtained as described above are used as they are in the modification reaction without going through a pulverizing or granulating step.

In the present invention, the polyolefin constituting the above polyolefin particles is modified with an ethylenically unsaturated group-containing epoxy compound (modified monomer).

In the method for producing modified polyolefin particles according to the present invention,
The polyolefin particles are modified by bringing the above-mentioned polyolefin particles into contact with allyl glycidyl ether and / or vinyl glycidyl ether at a temperature that maintains the shape of the polyolefin particles in the presence of a radical initiator and a solvent.

The glycidyl ether used in the present invention includes, for example, an unsaturated group such as allyl glycidyl ether, 2-methylallyl glycidyl ether and vinyl glycidyl ether, and a glycidyl group bonded to the group having the unsaturated group by an ether bond. Compounds can be mentioned.

Among such compounds, it is particularly preferable to use allyl glycidyl ether in the present invention.

These glycidyl compounds can be used alone or in combination.

Since such a compound does not have a carbonyl group in the molecule, the glycidyl group is not eliminated by hydrolysis and has very high hydrolysis resistance.

However, in the present invention, maleic acid diglycidyl ester, maleic acid methyl glycidyl ester, maleic acid isopropyl glycidyl ester, maleic acid-
t-butyl glycidyl ester, diglycidyl fumarate, methyl diglycidyl fumarate, isopropyl brisidyl fumarate, diglycidyl itaconate, methyl diglycidyl itaconate, isopropyl glycidyl itaconate, 2
It is also possible to use a small amount of a glycidyl ester of a conjugated unsaturated dicarboxylic acid such as methylene glutaric acid diglycidyl ester, 2-methylene glutaric acid methyl glycidyl ester, butene dicarboxylic acid monoglycidyl ester and the like. Also. In addition to the above esters, for example, 3,4-
Other glycidyl compounds such as epoxybutene, 3,4-epoxy-3-methyl-1-butene, vinylcyclohexene monoxide and p-glycidylstyrene can also be used in small amounts.

In the method for producing modified polyolefin particles according to the present invention, a radical initiator is used.

As the radical initiator that can be used in the present invention, usually, an organic peroxide azo compound or the like is used.

Examples of the organic peroxide used as a radical initiator in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2,5 -Dimethyl-2,5-bis (tert-butylperoxy) hexyne-
3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)
-3,3,5-trimethylcyclohexane, n-butyl-4,4
-Bis (tert-butylperoxy) valerate, dibenzoyl peroxide, tert-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide , 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide and the like. In addition, examples of the azo compound include azobisisobutyronitrile and the like. Such radical initiators can be used alone or in combination. Among such radical initiators, dibenzoyl peroxide is particularly preferred.

In the present invention, the above-mentioned modification reaction is carried out using polyolefin particles, an ethylenically unsaturated group-containing epoxy compound, a radical initiator and a solvent as described above.

In the present invention, a solvent having a swelling property for the polyolefin particles and a good solvent for the radical initiator is used.

That is, in the present invention, when the solvent comes into contact with the polyolefin particles, the solvent has a role of swelling the polyolefin particles and facilitating penetration of the modifier and the radical initiator into the particles.

Examples of the swelling solvent that can be used in the present invention include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; pentane, hexane, heptane, octane, nonane, and aliphatic hydrocarbon solvents such as decane; cyclohexane; and methyl. Alicyclic hydrocarbon solvents such as cyclohexane and decahydronaphthalene, and chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene can be exemplified. .

It is also possible to mix an appropriate amount of a poor solvent with the above-mentioned solvents. Examples of the poor solvent include alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate; Examples include ester solvents such as dimethyl phthalate, and ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, and dioxyanisole.

In the method for producing modified polyolefin particles according to the present invention,
The allyl glycidyl ether and / or vinyl glycidyl ether is used in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the polyolefin particles.

The radical initiator is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the polyolefin particles.

When allyl glycidyl ether and vinyl glycidyl ether are used in combination, the proportion of allyl glycidyl ether and vinyl glycidyl ether used can be appropriately set in consideration of the properties of the resulting modified polyolefin particles.

The swelling solvent as described above is usually 10 to 50 parts by weight, preferably 12 to 50 parts by weight, based on 100 parts by weight of the polyolefin particles.
Used in an amount of 40 parts by weight.

In the method for producing the modified polyolefin particles according to the present invention, there is no particular limitation on the contact method and the contact order of the above-mentioned polyolefin particles, allyl glycidyl ether and / or vinyl glycidyl ether, a radical initiator and a solvent, and various methods are applicable. A method can be adopted.

In the present invention, as an example of the contact sequence or the contacting method of the above components, the polyolefin particles are mixed with a solution in which allyl glycidyl ether and / or vinyl glycidyl ether and a radical initiator are dissolved in a solvent, and then reacted. After mixing the polyolefin particles with a radical initiator dissolved in a solvent, and then heating the polyolefin particles to a state in which the reaction can substantially proceed, allyl glycidic ether and / or vinyl glycidyl ether After heating the polyolefin particles to a state in which the reaction can proceed substantially by heating or the like, allyl glycidyl ether and / or vinyl glycidyl ether and a radical initiator were dissolved in a solvent in the polyolefin particles. Put the solution all at once A method of blending divided and, a radical initiator dissolved in the polyolefin particles and a solvent are mixed, and a method of contacting with allyl glycidyl ether and / or vinyl glycidyl ether in a gaseous state or the like while heating.

The reaction between such polyolefin particles and allyl glycidyl ether and / or vinyl glycidyl ether is performed at a temperature that can substantially maintain the shape of the polyolefin particles. That is, in the present invention, the denaturation reaction is performed at a temperature lower than the temperature at which the polyolefin particles are melted and the particles are not fused to each other. Generally, the temperature at which the modification can be performed in such a state varies depending on the type of the polyolefin, and can be substantially known in advance. The lower limit of the reaction temperature in such a reaction is not particularly limited because the radical initiator is decomposed even at a very low temperature, but is usually 0 ° C. in consideration of the reaction efficiency.

If the upper limit of the modification temperature by the polyolefin constituting the polyolefin particles is shown, the upper limit of the modification temperature of the polyolefin particles containing polypropylene as a main component is about 150 ° C., and the upper limit of the polyolefin particles containing high density polyethylene as a main component is The upper limit of the modification temperature of polyolefin particles containing low-density polyethylene as a main component is around 90 ° C.

In the present invention, the reaction time for denaturation can be appropriately set in consideration of conditions such as the reaction temperature.
It is 1/60 to 20 hours, preferably 0.5 to 15 hours.

The reaction as described above can be used without any particular limitation as long as it is a device capable of mixing and heating the polyolefin particles. For example, any of a vertical reactor and a horizontal reactor can be used. Specific examples include a fluidized bed, a moving bed, a loop reactor, a horizontal reactor with stirring blades, a rotating drum, and a vertical reactor with stirring blades.

By contacting the polyolefin particles and the modifying monomer in this way, the resulting modified polyolefin particles have an average particle diameter of usually 100 to 5000 μm, preferably 200 to 4000 μm, particularly preferably in the range of 300 to 3000 μm. The geometric standard deviation is usually in the range of 1.0 to 2.0, preferably 1.0 to 1.5, particularly preferably 1.0 to 1.3,
The apparent specific gravity is usually 0.25 to 0.7, preferably 0.30 to 0.6
0, particularly preferably in the range of 0.35 to 0.50, 100 μm
The content of the following fine particles is usually 20% by weight or less, preferably 0 to 10% by weight, particularly preferably 0 to 2% by weight. The average of the major axis / minor axis values of the particles is usually
1.0-3.0, preferably 1.0-2.0, particularly preferably 1.0-
It is in the range of 1.5.

Since such modified polyolefin particles only impart polarity to the particles, they can be effectively used as, for example, raw materials for powder coatings.

Effect of the Invention According to the method for producing modified polyolefin particles according to the present invention, since the modification is performed at a temperature lower than the melting temperature of the polyolefin particles, the deterioration of the polyolefin particles is small, and the powder characteristics and the like of the used polyolefin particles are changed. Without denaturation.

Moreover, when the modification is performed using a solvent capable of swelling the polyolefin particles, the epoxy compound having an ethylenically unsaturated group and the radical initiator are transported into the polyolefin particles, thereby uniformly modifying the polyolefin particles. it can.

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

EXAMPLES high-speed stirrer [adjusting the catalyst component [A]] internal volume 2l of the (manufactured by Tokushu Kika Kogyo Co., Ltd.) sufficient N ₂
After the replacement, 700 ml of purified kerosene, 10 g of commercially available MgCl ₂ , 24.2 g of ethanol and ₃ g of Emazol 320 (trade name, sorbitan distearate, manufactured by Kao Atlas Co., Ltd.) were added, and the system was heated to 120 ° C. with stirring. And stirred at 800 rpm for 30 minutes. Under high-speed stirring, the solution was transferred to a 2 liter glass flask (with a stirrer) into which purified kerosene 1 previously cooled to −10 ° C. was charged using a Teflon tube having an inner diameter of 5 mm. The resulting fixation was collected by filtration and washed sufficiently with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was treated with 120 ml of titanium tetrachloride.
The temperature was raised to ° C. After stirring and mixing at 120 ° C. for 2 hours, the solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and again stirred and mixed at 130 ° C. for 2 hours. Further, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component (A). The components consist of titanium 2.2% by weight, chlorine 63% by weight, magnesium 20% by weight, and diisobutyl phthalate 5.
It was 5% by weight. A spherical catalyst having an average particle size of 64 μm and a standard deviation (δ _g ) of 1.5 in the particle size distribution was obtained.

[Preliminary polymerization] The following preliminary polymerization was performed on the catalyst component [A].

After charging 200 ml of purified hexane into a 400 ml glass-made reactor purged with nitrogen, 20 mmol of triethylaluminum, 4 mmol of diphenyldimethoxysilane and
After charging 2 mmol of the Ti catalyst component [A] in terms of titanium atoms, propylene was supplied at a rate of 5.9 N · l / hour over 1 hour, and 2.8 g of propylene was added per 1 g of the Ti catalyst component [A]. Polymerized. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

[Polymerization] [I] Homopolymer To a 17 L polymerization vessel was added 5 kg of propylene at room temperature, and 1.5 L of hydrogen was added.
Was added, and the temperature was raised. At 50 ° C., 8 mmol of triethylaluminum, 8 mmol of diphenyldimethoxysilane and the prepolymerized product of the catalyst component [A] were converted to 0.08 in terms of titanium atom.
After the addition of mmol, the inside of the polymerization vessel was kept at 70 ° C. for 1 hour and 20 minutes. Thereafter, the remaining propylene was purged to recover the polymer. The obtained polymer had [η] = 3.5 dl / g, apparent bulk specific gravity of 0.46 g / ml, and the yield was 3.3 kg.

Examples 1 to 3 100 parts by weight of polypropylene (PP) shown in Table 1 were charged into a stainless steel autoclave equipped with a stirring blade having a helical double ribbon, and the system was completely purged with nitrogen. Then, while stirring the polypropylene at room temperature,
Allyl glycidyl ether (AG
E), a solution composed of benzoyl peroxide (BPO), and toluene was added dropwise over 10 minutes.
Stir for a minute.

Thereafter, the temperature in the system is set to 100 ° C., and the reaction is performed for 4 hours.

The polymer after the reaction is dissolved in P-xylene at 130 ° C., allowed to cool, precipitated with acetone, and purified by removing unreacted substances.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akinori Toyoda 6-1, 1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industries, Ltd. (72) Norio Kashiwa, Waki-Waki, Kuga-gun, Yamaguchi Prefecture 6-1-2, Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-2-140206 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 8/00- 8/50

Claims (1)

(57) [Claims] 1. Polyolefin particles and 0.01 to 50 parts by weight of allyl glycidyl ether and / or vinyl glycidyl ether with respect to 100 parts by weight of the polyolefin particles; 100 parts by weight of the polyolefin particles with respect to the polyolefin particles In the presence of 10 to 50 parts by weight of a good solvent for the radical initiator and 0.01 to 10 parts by weight of the radical initiator, the polyolefin particles have a swelling property with respect to the radical initiator at a temperature below the temperature at which the polyolefin particles do not fuse with each other. A method for producing modified polyolefin particles, wherein the shape of the polyolefin particles is maintained and contacted.