JP2768475B2 - Method for producing modified polyolefin particles - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for modifying polyolefin particles with hydroxyl or amino groups.

TECHNICAL BACKGROUND OF THE INVENTION Conventionally, a method of modifying a polyolefin by imparting a polar group such as a carboxyl group to 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 Application Laid-Open No. 50-77493,
JP-A-5-32722 and JP-A-57-174309 disclose a method in which a granular olefin polymer is used and denatured at a temperature lower than the melting point of the granular olefin polymer.

However, the modifiers used in the method disclosed in such publications are maleic anhydride, epoxy compounds and the like, and no compounds having a hydroxyl group and compounds having an amino group are disclosed.

Object of the Invention It is an object of the present invention to provide a method for producing polyolefin particles in which the polyolefin is modified with a hydroxyl group and / or an amino group, and to provide a production method capable of reducing the production cost.

SUMMARY OF THE INVENTION A method for producing modified polyolefin particles according to the present invention comprises the steps of: converting polyolefin particles and a hydroxyl group-containing ethylenically unsaturated compound and / or an amino group-containing ethylenically unsaturated compound in the presence of a radical initiator. The polyolefin particles are modified by contacting the polyolefin particles with the ethylenically unsaturated compound at a temperature below which the particles do not fuse.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for producing modified polyolefin particles 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 used in the present invention is usually in the range of 10 to 5000 μm, preferably 100 to 4000 μm, and more preferably 300 to 3000 μm. Also,
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
-1.5, particularly preferably in the range of 1.0-1.3. Further, the apparent bulk density of the polyolefin particles used in the present invention by natural fall is usually 0.2 g / ml or more, preferably
It is in the range of 0.30 to 0.70 g / ml, particularly preferably 0.35 to 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 employing 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-
Methylpetene-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, methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1 And α-olefins such as 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-13-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, and 5-cyclohexadiene. 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.

Further, in the present invention, cyclopetadienes such as cyclopentadiene and ethylene, propylene, butene-
A polyene compound obtained by condensing an α-olefin such as 1 using a Diels-Alder 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, may be mentioned 0 ^12,17] docosenoic cyclic monoene compound poly cycloalkene such as -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] containing a transition metal of Group IVA, VA, Group VIA, Group VIIA and Group VIII, and a catalyst component [B] of an organometallic compound of Group I, II and III And a catalyst consisting of

The catalyst component [A] includes the periodic table IV A
Group, a catalyst containing a transition metal atom of group VA,
Among these, a catalyst component containing at least one 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-described transition metal atom, and a conjugated pi electron to a transition metal atom belonging to Group IVA or VA of Periodic Table IV. Examples of the catalyst component include a compound having a group having a coordinating group.

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. 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. The standard deviation (δ _g ) is determined from the lognormal distribution function based on the particle size distribution. 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 of a true sphere, an ellipsoid, a granule or the like, and the particle has an aspect ratio of preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less. It is as follows.

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 and 56-67311 and Japanese Patent Application Nos. 56-1811019 and 61-21109.

An example of a method for preparing the catalyst component [A] described in these publications or specifications will be described.

(1) A solid magnesium compound having an average particle diameter of 1 to 200 μm and a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less.
Pre-treating the electron donor complex with an electron donor and / or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound, or without pretreatment;
The reaction is carried out under a reaction condition with a liquid titanium halide compound, preferably titanium tetrachloride.

(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. Further, if necessary, the reaction is carried out with a liquid titanium compound, preferably 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 diameter 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, or a titanium compound. React with 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 / mmol of titanium. As described above, it is particularly preferable to have 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 magnesium compounds include magnesium oxide, magnesium hydroxide, inorganic magnesium compounds such as hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide and magnesium ujihalide. Organic magnesium compounds such as dialkyl magnesium and diaryl magnesium can be mentioned.

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, mail 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 cyclohexanecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, 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 include active hydrogen such as esters of organic or inorganic acids, alkoxy (aryloxy) lan compounds, ethers, ketones, tertiary amines, acid halides, and acid anhydrides. Organic acid esters and alkoxy (aryloxy) silane compounds are particularly preferable. Among them, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms, malonic acid, substituted malonic acid, substituted succinic acid, maleic acid And esters of dicarboxylic acids such as substituted maleic acid, 1,2-cyclohexanedicarboxylic acid, and phthalic acid with alcohols having 2 or more carbon atoms. Of course, these electron donors can be directly added when preparing the catalyst,
For example, a compound which can be converted to these electron donors is added to the reaction system without adding it to the reaction system as a raw material when preparing the catalyst component [A], and this compound is converted to the above electron donor in the catalyst preparation process. You can also.

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, (i) formula _{^{R 1 m Al (OR 2)}} n H p X q ( wherein R ¹ and R ² are carbon atoms, 1-15 usually 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 The same meaning), and a complex alkylated product of aluminum and a metal of Group I of the periodic table.

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

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

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 is preferably 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 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 triethylaluminum, tributylaluminum and triisopropylaluminum; trialkenylaluminums such as triisoprenylaluminum; diethylaluminum ethoxide And dialkylaluminum alkoxides such as dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially having an average composition represented by the formula R ¹ _2.5 Al (OR ² ) _0.5 Alkoxyalkyl aluminums, diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum chloride Dialkylaluminum halides such as amide, alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide, 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 ethoxy Partially alkoxylated and halogenated alkyl aluminums such as chloride, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide can be mentioned.

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 include: 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, it is particularly preferable to use a trialkylaluminum, a mixture of a trialkylaluminum and an alkylaluminum halide, and 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 are organic acid esters, alkoxy (aryloxy) silane compounds, ethers, ketones, acid anhydrides, amides and the like, and particularly electron donors in the catalyst component [A]. When the compound 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] has 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 Groups IVA and 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 ] Can be preferably used.

Here, examples of transition metals of Group IVA and Group VA of 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 cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, t-butylcyclopentadienyl group, and dimethylcyclopentadienyl. Groups, alkyl-substituted cyclopentadienyl groups such as pentamethylclopentadienyl 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 an ethylene bisindenyl group, isopropyl (cyclopentadienyl-1-
Fluorenyl) group and the like.

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) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium 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) phenyl zirconium mono Chloride, 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 ethoxycyclolide, bis (methylcyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium phenoxycyclolide 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-i (Denyl) 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 preliminarily polymerizing as described above, or without preliminarily polymerizing, and then introducing the above-mentioned monomer into a reaction system and performing a polymerization reaction (main polymerization). 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-mentioned polyolefin particles is modified with a hydroxyl group-containing ethylenically unsaturated compound and / or an amino group-containing ethylenically unsaturated compound (modifier 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 a hydroxyl group-containing ethylenically unsaturated compound and / or an amino group-containing ethylenically unsaturated compound in the presence of a radical initiator.

Examples of the hydroxyl group-containing ethylenically unsaturated compound used in the present invention include, for example, hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol Mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6
(Meth) acrylic esters such as -hydroxyhexanoyloxy) ethyl acrylate.

Further, as the hydroxyl group-containing ethylenically unsaturated compound, in addition to the above (meth) acrylic acid ester, 10-undecene-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, Use of hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol, etc. Can be.

These hydroxyl group-containing ethylenically unsaturated compounds can be used alone or in combination.

Among such compounds, particularly in the present invention, 2
It is preferable to use -hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

The amino group-containing ethylenically unsaturated compound that can be used in the present invention is a compound having an ethylenic double bond and an amino group, and such a compound includes an amino group represented by the following formula or a substituted compound. A vinyl monomer having at least one kind of amino group can be used.

However, in the above formula, R ¹ is a hydrogen atom, a methyl group,
Represents any atom or group among ethyl groups,
² is a hydrogen atom, having 1 to 12 carbon atoms, preferably having 1 to 1 carbon atoms.
8 alkyl groups, 6 to 12 carbon atoms, preferably 6 to 6 carbon atoms
And represents any atom or group among the 8 cycloalkyl groups. In addition, the above-mentioned alkyl group and cycloalkyl group may further have a substituent.

Specific examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, phenylaminoethyl methacrylate, and cyclohexyl methacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminoethyl and methacryloyloxyethyl acid phosphate monomethanol amino half sol, N
Vinylamine derivatives such as -vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methallylamine, N-methylacrylamine, N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide, acrylamide and Acrylamide derivatives such as N-methylacrylamide, aminostyrenes such as p-aminostyrene, 6-aminohexylsuccinimide, 2-aminoethylsuccinimide and the like are used. These compounds can be used alone or in combination. Among them, acrylamine, aminoethyl methacrylate, aminopropyl methacrylate N, N-dimethylaminopropylacrylamide, aminostyrene and the like are preferable.

Further, in the present invention, the hydroxyl group-containing ethylenically unsaturated compound and the amino group-containing ethylenically unsaturated compound can be used alone or in combination.

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

As a radical initiator that can be used in the present invention, an organic peroxide, an 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-butyl peroxide benzoate 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. 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 method for producing modified polyolefin particles according to the present invention,
The hydroxyl group-containing ethylenically unsaturated compound and / or the amino group-containing ethylenically unsaturated compound are used in an amount of usually 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. .

When a hydroxyl group-containing ethylenically unsaturated compound and an amino group-containing ethylenically unsaturated compound are used in combination, the hydroxyl group-containing ethylenically unsaturated compound and the amino group-containing ethylenically unsaturated compound are used at an arbitrary ratio. be able to.

Further, the radical initiator is usually 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight of the polyolefin particles.
Used in an amount of ８8 parts by weight.

In the present invention, as described above, the polyolefin particles and the hydroxyl group-containing ethylenically unsaturated compound and / or the amino group-containing ethylenically unsaturated compound are brought into contact with each other in the presence of a radical initiator, and the polyolefin particles and the compound are mixed with each other. Is reacted. This reaction can also be performed in the presence of a solvent.

In the present invention, a solvent having a swelling property with respect to the polyolefin particles is preferably used as the solvent.

That is, by using the swelling solvent as described above, the hydroxyl group-containing ethylenically unsaturated compound and / or the amino group-containing unsaturated compound and the radical initiator are favorably conveyed to the inside of the polyolefin particles. It becomes uniformly denatured even inside.

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 solvent. 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.

As described above, the solvent as described above, when contacted with the polyolefin particles used in the present invention, swells the polyolefin particles, particularly the amorphous olefin polymer portion of the polymer particles, and causes a modifier and radical initiation. The agent plays a role of facilitating penetration into the particles.

When using the swelling solvent as described above, the swelling solvent is usually 1 to 50 parts by weight based on 100 parts by weight of the polyolefin particles.
It is used in an amount of 5 parts by weight, preferably 5 to 40 parts by weight.

In the method for producing modified polyolefin particles according to the present invention, the method and the method for contacting a polyolefin particle as described above, a hydroxyl group-containing ethylenically unsaturated compound and / or an amino group-containing ethylenically unsaturated compound with a radical initiator The order is not particularly limited, and various methods can be adopted.

Examples of the contact sequence or contact method of the above components in the present invention include a method of mixing and reacting polyolefin particles with an amino group-containing ethylenically unsaturated compound and a radical initiator, and a method of mixing polyolefin particles with a radical initiator. And then heating the polyolefin particles so that the reaction can proceed substantially, for example, by blending a hydroxyl group-containing ethylenically unsaturated compound and / or an amino group-containing ethylenically unsaturated compound. After heating the particles so that the reaction can proceed substantially, the polyolefin particles and the hydroxyl group-containing ethylenically unsaturated compound and / or the amino group-containing ethylenically unsaturated compound and the radical initiator are simultaneously reacted. Or the method of dividing and mixing, polyolefin particles and radio The initiator are mixed, and a method of contacting a hydroxyl group-containing ethylenically unsaturated compound in a gaseous state and / or amino group-containing ethylenically unsaturated compounds with heating.

The contact between the polyolefin particles and the hydroxyl group-containing ethylenically unsaturated compound and / or the amino group-containing ethylenically unsaturated compound is performed at a temperature capable of maintaining the original shape of the polyolefin particles. That is, in the present invention, the modification reaction is performed at a temperature not higher than the temperature at which the polyolefin particles do not fuse with each other. Generally, the temperature at which the polyolefin particles can be modified while maintaining their original shape is a temperature lower than the melting point or glass transition point of the polymer. 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 impart polarity to the particles, they can be effectively used, for example, as a raw material 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 melting temperature of the polyolefin particles or less, the deterioration that occurs when the polyolefin is modified is small, and the powder characteristics of the used polyolefin particles are reduced. The denaturation can be performed without changing the conditions.

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

[Example] [Adjustment of the catalyst component [A]] A high-speed stirrer (manufactured by Tokushu Kika Kogyo Co., Ltd.) with an internal volume of 2 was sufficient
After replacing with N ₂ , 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. The mixture was stirred at 800 rpm for 30 minutes. Under high-speed stirring, using a Teflon tube having an inner diameter of 5 mm, the solution was transferred to a glass flask (with a stirrer) 2 into which purified kerosene 1 previously cooled to −10 ° C. was stuck.
The resulting solid 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, a 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). This component is composed of titanium 2.2% by weight, chlorine 63% by weight, magnesium 20% by weight, diisobutyl phthalate 5.5% in atomic conversion.
% By weight. A spherical catalyst having an average particle size of 64 μm and a geometric standard deviation (δ _g ) of the particle size distribution of 1.5 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 Nl / hour over 1 hour to polymerize 2.8 g of propylene per 1 g of the Ti catalyst component [A]. . After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

[Polymerization] [I] 5 kg of propylene was added to a homopolymerizer 17 at room temperature, and hydrogen 1.5
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 added in an amount of 0.1% in terms of titanium atom.
After adding 08 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.

[II] 2.5 kg of propylene and hydrogen 2 at room temperature in a polymerization vessel of copolymer 17
After the addition of 0N-liter, the temperature was raised, and at 50 ° C., 15 mmol of triethylaluminum and 1.5 mmol of diphenyldimethoxysilane were added.
The prepolymerized product of the catalyst component [A] was added in an amount of 0.05 mmol in terms of titanium atom, and the temperature in the polymerization vessel was maintained at 70 ° C. Fourteen minutes after the temperature reached 70 ° C., the vent valve was opened, and propylene was purged until the pressure in the polymerization reactor became normal. After purging, copolymerization was performed, that is, ethylene was supplied to the polymerization reactor at a rate of 480 Nl / hr, propylene was supplied at a rate of 720 Nl / hr, and hydrogen was supplied at a rate of 12 Nl / hr. The vent opening of the polymerization vessel was adjusted so that the pressure in the polymerization vessel was 10 kg / cm ² · G. The temperature during the copolymerization was kept at 70 ° C. After 60 minutes of copolymerization time, the obtained polymer was depressurized and weighed 3.2 kg, MI at 230 ° C. under a load of 2 kg = 10 g / 10 minutes,
The ethylene content was 25 mol%, and the apparent bulk specific gravity was 0.42. Further, the amount of n-decane soluble component at 23 ° C. was 25% by weight, and the ethylene content in the soluble component was 50 mol%.

Examples 1 to 3 A monomer (modifying agent), benzoyl peroxide (BPO), and toluene were added to 100 parts by weight of the copolymer at the ratio shown in Table 1, and mixed at room temperature. 10g of this mixture is 25m in diameter
weighed in a test tube of m, cooled with liquid nitrogen and frozen, then evacuated the system, replaced with nitrogen, returned to room temperature, and then placed in a 100 ° C oil bath and reacted for 4 hours. Was.

The polyolefin particles after the reaction are put in P-xylene at 130 ° C.
And allowed to cool, then precipitated with methanol, and purified.

The amount of grafting was determined by IR using a previously prepared calibration curve.

Example 4 A glass reactor equipped with a spiral type double ribbon stirring blade and a dropping funnel was charged with 300 g of a homopolymer, and the system was completely replaced with nitrogen. Then toluene 52
g, N, N-dimethylamino methacrylate 9.1 g, BPO 0.5
A solution consisting of 1 g was placed in a dropping funnel, and the PP was added dropwise with stirring at room temperature for 10 minutes.
Stir for minutes. Next, the temperature in the system is set to 100 ° C., and the reaction is performed for 4 hours.

After the reaction, the polyolefin particles are dissolved in xylene at 130 ° C., allowed to cool, and precipitated with acetone for purification. When the amount of grafting was measured, 0.25% by weight of N, N-dimethylaminomethacrylate was grafted. The MFR of the graft polymer is 1.1 g / 10 minutes.

──────────────────────────────────────────────────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-60-55014 (JP, A) JP-A-61-223015 (JP, A) JP-A-62-30110 (JP, A) JP-A-1-299810 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 251/00-292/00 C08F 8/00

Claims (2)

(57) [Claims] A polyolefin particle and a hydroxyl group-containing ethylenically unsaturated compound and / or an amino group-containing ethylenically unsaturated compound in the presence of a radical initiator at a temperature below the temperature at which the polyolefin particles do not fuse together. And modifying the polyolefin particles by contacting the polyolefin particles with the ethylenically unsaturated compound. 2. The method for producing modified polyolefin particles according to claim 1, wherein the modification is performed in the presence of a solvent capable of swelling the polyolefin particles.