JPH02140247A - Production of thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer at a low cost by contacting a polymer particle composed of a crystalline olefin polymer part and an amorphous olefin polymer part with a crosslinking agent in the presence of a swelling solvent at a specific temperature, thereby performing the crosslinking in the particle. CONSTITUTION:The objective thermoplastic elastomer is produced by contacting (A) 100 pts.wt. of polymer particles composed of (A1) a crystalline olefin polymer part and (A2) an amorphous olefin polymer part and having an average particle diameter of 10-5,000mum, a geometrical standard deviation of 1-2 (representing the particle size distribution) and an apparent bulk density of >=0.2g/ml with (B) 0.01-5 pts.wt. of a crosslinking agent (preferably an organic peroxide or phenolic vulcanizing agent), (C) 1-100 pts.wt. of a swelling solvent (e.g., benzene) and preferably further (D) 0.1-2 pts.wt. of a processing assistant and 1-100 pts.wt. of a mineral oil softener and heating the composition at a temperature below the melting point of the component A1 or below the glass transition point of the component A2, thereby performing the crosslinking in the particle to obtain the objective elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a thermoplastic elastomer. , relates to a method for producing a thermoplastic elastomer that can provide molded articles with excellent surface smoothness and paintability.

Technical Background of the Invention Thermoplastic elastomers have been widely used as automobile parts such as bumper parts.

This thermoplastic elastomer has both thermoplastic and elastic properties, and can be molded into molded products with excellent heat resistance, tensile properties, weather resistance, flexibility, and elasticity by injection molding, extrusion molding, etc. be able to.

As such a thermoplastic elastomer, for example, Japanese Patent Publication No. 53-34210 discloses a method in which 60 to 80 parts by weight of monoolefin copolymer rubber and 40 to 20 parts by weight of polyolefin plastic are dynamically partially cured. A thermoplastic elastomer is disclosed. Also, special public service in 1973
Publication No. 21021 discloses that (a) it is made of ethylene-propylene-nonconjugated polyene copolymer rubber and has a gel content of 3
0 to 90% by weight of a partially crosslinked copolymer rubber; (b)
A thermoplastic elastomer comprising a polyolefin resin is disclosed. Further, Japanese Patent Publication No. 55-18448 discloses a thermoplastic elastomer in which an ethylene-propylene copolymer rubber and a polyolefin resin are dynamically partially or completely crosslinked.

Purpose of the Invention The present invention provides a molded product that has excellent uniformity between the resin component and the rubber component, and has excellent strength physical properties such as impact strength and tensile strength, toughness, heat resistance, flexibility at low temperatures, surface smoothness, and paintability. It is an object of the present invention to provide a method for manufacturing a thermoplastic elastomer that can provide high quality products and reduce manufacturing costs.

Summary of the Invention The first method for producing a thermoplastic elastomer according to the present invention is to combine polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion and a crosslinking agent in the presence of a swelling solvent. is brought into contact with the crystalline olefin polymer at a temperature lower than the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer, whichever is higher, to obtain an intraparticle crosslinked thermoplastic elastomer. .

Further, in the second method for producing a thermoplastic elastomer according to the present invention, polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a crosslinking agent and a crosslinking aid are mixed in a swelling solvent. the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer, whichever is higher, to obtain an intraparticle crosslinked thermoplastic elastomer. It is said that

DETAILED DESCRIPTION OF THE INVENTION The method for producing a thermoplastic elastomer according to the present invention will be specifically described below.

In the present invention, polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion are used.

The average particle diameter of the polymer particles used in the present invention is usually 1
0 to 5000 μm 1 preferably 100 to 4000 μm 1
More preferably, it is within the range of 300 to 3000 μm. Further, the geometric standard deviation indicating the particle size distribution of the polymer 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. is within the range of Further, the apparent bulk density of the polymer particles used in the present invention due to natural fall is usually 0.2 g/ml or more, preferably 0.30 to 0.70 g/ml, particularly preferably 0.35 to 0. -60 g/ml.

As the polymer particles used in the present invention, it is preferable to use particles having the above-mentioned characteristics, and there are no particular limitations on the method for producing particles having such characteristics, but the method described below may be used. It is preferable to manufacture the polymer particles by adopting this method, and the transition metal content in the ashes of the polymer particles obtained by adopting this method is usually 100 [)II
I or less, preferably 10 ppm or less, particularly preferably 5
ppm or less, the halogen content is usually 3001)I)m or less, preferably 100 ppm or less, particularly preferably 50
It is contained in a proportion of ppm or less.

In addition, when referring to a polymer in the present invention, the term "polymer" is used in a concept that includes both a polymer and a copolymer.

Polymer particles having the above characteristics can be obtained, for example, by polymerizing or copolymerizing α-olefins 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,L3-dimethylbutene-11butene-11methylhexene■,
Dimethylpentene-1, trimethylbutene-11 Ethylpentene-1, Octen Publishing, Methylpentene-1, Dimethylhexene-1, Trimethylpentene-1, Ethylhexene-1, Methylethylpentene-11 Diethylbutene-1, Propylpentene-1 1, Decene-1, Methylnonene-15 Dimethyloctene-1, Trimethylhebutene-1, Ethyloctene-■, Methylethylhebutene-1
, diethylhexene-1, dodecene-1 and hexadodecene-1.

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

In the present invention, polymer particles containing repeating units derived from the above α-olefin in an amount of usually 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 100 mol% are used. used.

In the present invention, other compounds that can be used in addition to the above α-olefins include, for example, chain polyene compounds and cyclic polyene compounds. In the present invention, the polyene compound is a polyene having two or more conjugated or non-conjugated olefinic double bonds,
Examples of such linear polyene compounds include 1,4-
Hexadiene, 1,5-hexadiene, ■, 7-octadiene, ■, 9-decadiene, 2,4.6-octatriene, 1,3.7-octatriene, 1,5.9-decatriene, divinylbenzene etc. can be mentioned.

Examples of cyclic polyene compounds include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 3-cyclohebutadiene, 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-
Examples include norbornene, 2-propenyl-2,5-norbornadiene, and the like.

In addition, in the present invention, cyclopentadiene such as cyclopentadiene and ethylene, propylene, butene-
It is also possible to use a polyene compound obtained by condensing an α-olefin such as (2) using a Diels-Alder reaction.

Furthermore, in the present invention, cyclic monoenes can also be used, and examples of such cyclic monoenes include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexeno, cycloheptene,
Monocycloalkenes such as cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, and cycloeicosene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene,
Bicycloalkenes such as 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5.6-)dimethyl-2-norbornene, 2-bornene, 2,
3.3a,7a-tetrahydro-4,7-methano-IH
-Indene, 3a, 5. B.

Tricycloalkenes such as 7a-tetrahydro-4,7-methano-111-indene, 1,4,5,8-dimethano-1,2°3.4.4a,5,8.8a-octahydronaphthalene, and In addition to 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-dimethano1.2,3,4,4a,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-dimethanol-1,2
,3,4,4a,5,8,8a-octahydronaphthalene,2-chloro-L4,5.8-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,
Tetracycloalkenes such as 3,4,4a, 5°8.8a-octahydronaphthalene, hexacyclo[8,8,
1,1"6.10,13.02,7.9"14]heptadecene-4, pentashif o [8,8,1""', l
``7.1'''', 0.0''''12.17.0 ]] Henkokosen-5 octacyclo[8,8
゜】0 1. 1, l 3・8 1
2・172,9 4,7 11.18,11.3.
1B, , , o ]] Cyclic monoene compounds such as polycycloalkenes such as tococene-5 can be mentioned.

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

The polymer particles used in the present invention are obtained by polymerizing or copolymerizing at least the above α-olefins in the presence of a catalyst, but the above polymerization reaction or copolymerization reaction is carried out in a gas phase. It can also be carried out in the liquid phase (liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is preferably carried out in a suspended state so that the resulting polymer particles can be obtained in a solid state. An inert hydrocarbon can be used as the solvent used in this polymerization reaction or copolymerization reaction. Furthermore, the α-olefin as a raw material may be used as a reaction solvent. Note that the above polymerization or copolymerization may be carried out by a combination of a liquid phase method and a gas phase method. In the production of the polymer particles used in the present invention, the above polymerization or copolymerization is preferably carried out using a gas phase method, or a method in which a reaction is carried out using an α-olefin as a solvent followed by a gas phase method. .

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 pot, or a method of simultaneously producing a crystalline olefin polymer portion and an amorphous olefin polymer portion; One example is a method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion can be carried out separately and in series using a polymerization vessel having a number of units or more. 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 preferred method is to synthesize a crystalline olefin polymer portion by gas phase polymerization and then synthesize an amorphous olefin polymer portion by gas phase polymerization, or to synthesize a crystalline olefin polymer portion using monomers as a solvent. After that, an amorphous first reflex polymerization part is synthesized by gas phase polymerization.

In the present invention, the catalyst used in the above polymerization reaction or copolymerization reaction is usually
A catalyst component [A] containing a transition metal of Group VA, Group VA, Group VIA, Group ■A, and Group ■; and an organometallic compound catalyst component [B] of Group I, Group ■, and Group ■ of the Periodic Table of the Elements. A catalyst is used.

The above catalyst component [A] is preferably a catalyst containing a transition metal atom of Group IVA or Group VA of the Periodic Table of the Elements, and among these, at least one selected from the group consisting of titanium, zirconium, hafnium, and vanadium. Catalyst components containing different types of atoms are more preferred.

Other preferred catalyst components [A] include catalyst components containing halogen atoms and magnesium atoms in addition to the above transition metal atoms, and catalyst components having conjugated π electrons in transition metal atoms of Groups IVA and VA of the periodic table. Catalyst components containing a group-coordinated compound may be mentioned.

In the present invention, the catalyst component [A] is present in the reaction system in a solid state during the polymerization reaction or copolymerization reaction as described above, or is present in a solid state by being supported on a carrier or the like. It is preferred to use a catalyst prepared in such a way that it can

The above catalyst component [A] will be explained in more detail by taking as an example a solid catalyst component [A] containing a transition metal atom, a halogen atom, and a magnesium atom.

The average particle diameter of the solid catalyst component [A] as described above is:
Preferably 1 to 200 μm, more preferably 5 to 10
0 μm2, particularly preferably within the range of 10 to 80 μm. Further, the geometric standard deviation (δ) as a measure of the particle size distribution of the solid catalyst [A] is preferably 1.0 to 3.0.
, more preferably 1.0 to 2.1, particularly preferably 1
．． It is within the range of 0 to 1.7.

Here, the average particle size and particle size distribution of the catalyst component [A] are:
It can be measured by a light transmission method.

Specifically, the concentration (content) of the decalinne-soluble solvent is 0.
．． A dispersion prepared by adding the catalyst component [A] to a concentration of about 1 to 0.5% by weight, preferably 0.1% by weight is placed in a measurement cell, and the cell is illuminated with a narrow light to detect particles. The particle size distribution is determined by continuously measuring the intensity of light passing through the liquid under certain settling conditions. Based on this particle size distribution, the standard deviation (δ) is determined from a lognormal distribution function. More specifically, considering the average particle size (θ50) and the small particle size, 16
The ratio (θ5o/θ1) to the particle diameter (θ16) in weight%
6) The standard deviation (δg) is determined. Note that the average particle diameter of the catalyst is the weight average particle diameter.

Further, the catalyst component [A] preferably has a shape such as a true sphere, an elliptical sphere, or a granule, and the aspect ratio of the particles is preferably 3 or less, more preferably 2 or less, particularly preferably 1. 5 or less.

In addition, when this catalyst component [A] has a magnesium atom, a titanium atom, a halogen atom, and an electron donor, the magnesium/titanium (atomic ratio) is preferably larger than 1, and this value is usually 2 to 50, preferably The halokene/titanium (atomic ratio) is usually in the range of 4 to 100, preferably 6 to 40, and the electron donor/titanium (molar ratio) is usually in the range of 0.6 to 30. 1-10. Preferably it is within the range of 0.2 to 6. Further, the specific surface area of this catalyst component [A] is usually 3 #/g or more, preferably 40 #/g or more, and more preferably within the range of 100 to 800 #/g.

In such a catalyst component [A], the titanium compound in the catalyst component is generally not desorbed by simple operations such as washing with hexane at room temperature.

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

The catalyst component [A] as described above can be prepared, for example, by a method in which a catalyst is prepared after forming a magnesium compound having an average particle diameter and particle size distribution within the above-mentioned range and a shape as described above, or by a method in which a catalyst is prepared after forming a magnesium compound having an average particle size and particle size distribution within the above-mentioned range, or by a method in which a catalyst is prepared after forming a magnesium compound having an average particle size and a particle size distribution within the above-mentioned range, and a magnesium compound having a shape as described above. It can be produced by employing a method such as a method of bringing a compound into contact with a liquid titanium compound to form a solid catalyst having the particle properties as described above.

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 uniformly shaped carrier. It is also possible to prepare a finely powdered catalyst in advance and then granulate this finely powdered catalyst into the preferred shape described above.

Regarding such catalyst component [A], Japanese Patent Application Laid-Open No. 55-1
No. 35102, No. 55-135103, No. 56-81
No. 1, Publication No. 56-67311 and Patent Application No. 1982-1
No. 81019 and No. 61-21109.

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

(1) A solid magnesium compound/electron donor complex with an average particle diameter of 1 to 200 μm and a geometric standard deviation (δ) of particle size distribution of 3.0 or less is combined with an electron donor and/or an organoaluminum compound or a halogen-containing silicon. With or without pretreatment with reaction aids such as compounds, it is reacted with a liquid titanium halide compound, preferably titanium tetrachloride, under reaction conditions.

(2) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted, preferably in the presence of an electron donor, so that the average particle size is 1 to 200 μm.
A solid component having a geometric standard deviation (δg) of particle size distribution of 3.0 or less is precipitated.

Further, if necessary, it is reacted with a liquid titanium compound, preferably titanium tetrachloride, or with a liquid titanium compound and an electron donor.

(3) By preliminary contacting a liquid magnesium compound with reducing ability with a reaction aid capable of eliminating the reducing ability of the magnesium compound, such as polysiloxane or a halogen-containing silicon compound,
After precipitating a solid component with an average particle size of 1 to 200 μm and a geometric standard deviation (δ) of particle size distribution of 3.0 or less, this solid component is mixed with a liquid titanium compound, preferably titanium tetrachloride, or a titanium compound and React with an electron donor.

(4) After bringing a magnesium compound having reducing ability into contact with an inorganic or organic carrier such as silica, the carrier is then brought into contact with a halogen-containing compound or without contacting with a liquid titanium compound, preferably tetrachloride. The magnesium compound supported on the carrier is reacted with the titanium compound by contacting with titanium or the titanium compound and an electron donor.

Such a solid catalyst component [A] has the ability to produce a polymer having high stereoregularity with high catalytic efficiency. For example, when propylene is homopolymerized under the same conditions, the isotuffity
Usually 3000 g or more, preferably 5000 g or more of polypropylene with an index (boiling n-hebutane insoluble content) of 92% or more, especially 96% or more, per 1 mmol of titanium.
Particularly preferably, it has the ability to produce 10,000 g or more.

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

Examples of magnesium compounds include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide, and hydrotalcite, magnesium carboxylates, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halides, allyloxymagnesium halides, and magnesium cybaride. In addition, organic magnesium compounds such as dialkylmagnesium and diarylmagnesium can be mentioned.

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

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

Specific examples of compounds that can be used as such electron donors include methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, 1 to 1 carbon atoms, such as isopropyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol
Alcohols of 8; C6-20 phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol (these phenols may have a lower alkyl group) Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; Aldehydes 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, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl Methyl acid, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, phthalic acid Organic acid esters having 2 to 30 carbon atoms such as diethyl, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride , benzoyl chloride, toluyl chloride and anisyl chloride; acid halides having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and anisole and diphenyl ether; Ethers: Acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylene diamine; acetonitrile, benzonitrile and tolnitrile,
Nitriles such as; po such as trimethyl phosphite and triethyl phosphite
Organic phosphorus compounds having a -c bond; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane; and the like. These electron donors can be used alone or in combination.

Among such electron donors, preferred electron donors include those containing active hydrogen such as esters of organic or inorganic acids, alkoxy(aryloxy)silane compounds, ethers, ketones, tertiary amines, acid halides, and acid anhydrides. Organic acid esters and alkoxy(aryloxy)silane compounds are particularly preferred, and among them, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms, malonic acid, substituted malonic acid, substituted succinic acid, and maleic acid. , substituted maleic acid, ■, 2-cyclohexanedicarboxylic acid,
Particularly preferred are esters of dicarboxylic acids such as phthalic acid and alcohols having 2 or more carbon atoms.

Of course, these electron donors do not need to be added to the reaction system as raw materials when preparing the catalyst component [A]. For example, compounds that can be converted into these electron donors may be added to the reaction system and added during the catalyst preparation process. This compound can also be converted into the electron donor described above.

The catalyst component [A] obtained as described above can be purified by washing thoroughly with a liquid inert hydrocarbon compound after preparation. Examples of hydrocarbons that can be used during this cleaning include n-pentane, isopentane, n-hexane, isohexane, n-hebutane, low octane, isooctane, n-decane, n-dodecane, kerosene, liquid paraffin. Aliphatic hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane; Aromatic hydrocarbon compounds such as benzene, toluene, xylene, cymene; Chlorbenzene, Mention may be made of halogenated hydrocarbon compounds such as dichloroethane.

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 Ag-carbon bond in the molecule.

Examples of such organoaluminum compounds include (where R and R2 are the number of carbon atoms, usually 1 to 15,
The hydrocarbon groups preferably contain 1 to 4 and may be the same or different from each other. X is a halogen atom, m is 0
≦m≦3, n is 0≦n×3, p is 0≦p<3, q is 0≦
An organoaluminum compound represented by the number q<3 and m+n+p+q=3, and (ii) formula M' A, Q R' (where Ml is Lj, Na, and R1 is Examples include complex alkylated products of aluminum and metals of Group 1 of the periodic table represented by the same meanings as above).

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

m expressed by the formula RAil(OR)
3-m compound (where R1 and R2 have the same meanings as above, m
is preferably a number of 1.5≦m≦3).

Compounds of the formula Rlm A, II) X (where R1 has the same meaning as above, X is halogen, and m preferably Q<m<3).

A compound represented by the formula R' r, lA, ill H (
Here, R1 has the same meaning as above, and m is preferably 2≦
m<3).

Compound (where R1 and R2 are the same as above. X is halogen, 0<m≦3.0≦n<3.0≦q3, m+n
+q=3).

Specific examples of the organoaluminum compound represented by the above formula (i) include trialkylaluminiums such as triethylaminium, tributylaluminum and triisopropylaluminium, trialkenylaluminums such as triisoprenylaluminum, diethylaluminum ethoxy dialkylaluminum alkoxides such as dibutylaluminum dibutoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; Partially alkoxylated alkylaluminums having , dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide, alkyls such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquipromide aluminum sesquihalides, partially halogenated alkylaluminums such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Alkylaluminums in which alkylaluminum dihydrides are partially hydrogenated, such as ethylaluminum dihydride and probylaluminum dihydride; ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide; Partially alkoxylated and halogenated alkyl aluminums may be mentioned.

Further, the organoaluminum compound may be a compound similar to the compound represented by 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 (CH) A, 11! OAΩ (C2H5)2, (
CH) A, Ill 01 (C4H9) 2,
and 6H5.

Furthermore, examples of the organic aluminum compound represented by the above formula (ii) include LiAΩ (C2H5)4 and LIAg (C7H15)4. Among these, it is particularly preferable to use trialkylaluminum, a mixture of trialkylaluminum and alkyl aluminum halide, and a mixture of trialkylaluminum and aluminum halide.

In addition, the catalyst component [A] and the organometallic compound catalyst component [B]
] In addition to this, it is preferable to use an electron donor [C] together.

Examples of the electron donor [C] that can be used here include amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoamides, esters, and thioethers. , thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes,
Mention may be made of organic acids and amides of metals belonging to Groups 1, 2, 3 and 3 of the periodic table, and their acceptable salts. Note that salts can also be formed in the 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 for catalyst component [A]. Among such electron donors, particularly preferred electron donors are:
Organic acid esters, alkoxy(aryloxy)silane compounds, ethers, ketones, acid anhydrides, amides, etc.
Particularly 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.

Further, 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] can be represented by the formula RSj (OR
') n 4-n (However, in the above formula, R and R1 represent a hydrocarbon group, and 0≦n<4) and an alkoxy(aryloxy)silane compound and a highly sterically hindered amine are used. It is preferable.

Specific examples of such alkoxy(aryloxy)silane compounds include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane,
Dimethylethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis-o-tolyl Dimethoxysilane, bis-m-)lyldimethoxysilane, bis-p-tolylmethoxysilane, bis-p-tolyljethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethylmethoxysilane, cyclohexylmethyljethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxysilane, decylmethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane,
Methyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, l5o-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyl Triisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane,
2-norbornanetriethoxysilane, 2-norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(at Iyloxy)silane, vinyltris(β
-methoxyethoxysilane), dimethyltetraethoxydisiloxane, etc., especially ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, Diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolylmethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, dichlorohexylmethyldimethoxysilane, 2-
norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyljethoxysilane,
Ethyl silicate and the like are preferred.

Further, as the amine with large steric hindrance, 2.2,8
．． Particularly preferred are B-tetramethylpiperidine, 2,2,5.5-tetramethylpyrrolidine, or derivatives thereof, and tetramethylmethylenediamine. Among these compounds, alkoxy(aryloxy)silane compounds are particularly preferred as electron donors used as catalyst components.

In addition, in the present invention, a catalyst component [A] containing a transition metal atom compound of Groups IVA and VA of the Periodic Table of Elements having a group having conjugated π electrons as a ligand, and an organometallic compound catalyst component [B] A catalyst consisting of can be preferably used.

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

In addition, examples of the group having a conjugated π electron as a ligand include a cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a t-butylcyclopentagenyl group, and a dimethylcyclopentagenyl group. basis,
Examples include alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl groups, indenyl groups, and fluorenyl groups.

Preferred examples include a group in which at least two of these cycloalkagenyl skeleton-containing ligands are bonded via a lower alkyl group or a group containing silicon, phosphorus, oxygen, or nitrogen.

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

One or more, preferably two, such ligands having a cycloalkagenyl skeleton are coordinated to the transition metal.

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

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, and propyl groups. , isopropyl group, butyl group, etc.; cycloalkyl group includes cyclopentyl group, cyclohexyl group, etc.; aryl group includes phenyl group, tolyl group, etc.; aralkyl group includes benzyl group, Examples include a neophyll group.

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

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

For example, when the valence of the transition metal is 4, the transition metal compound containing a ligand having a cycloalkagenyl skeleton used in the present invention has the following formula: R2R3R4R5M k l m n ( In the formula, M is zirconium, titanium, hafnium, vanadium, etc., R2 is a group having a cycloalkashenyl skeleton, RR and R5 are a group having a cycloalkagenyl 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 is represented by k+, Q+m+n-4.

Particularly preferably, R and R3 in the above formula are groups having a cycloalkagenyl group skeleton, and these two groups having a cycloalkagenyl skeleton include a lower alkyl group or silicon, phosphorus, oxygen, or nitrogen. It is a compound that is bonded through a group.

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton in which M is zirconium will be exemplified.

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl) phenylzirconium hydride, bis(cyclopentagenyl)benzylzirconium hydride, bis(cyclopentagenyl)neopentylzirconium hydride, bis(methylcyclopentagenyl)silconylam monochloride hydride, bis(indenyl) ) Zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium dichloride, Bis(cyclopentagenyl)zirconium dibromi
bis(cyclopentagenyl)methylzirconium monochloride, bis(cyclopentagenyl)ethylzirconium monochloride, bis(cyclopentagenyl)cyclohexylzirconium monochloride, bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, bis(methylcyclopentagenyl)zirconium dichloride, bis(L-butylcyclopentagenyl)zirconium dichloride bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dichloride (cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium diphenyl, bis(cyclopentagenyl)zirconium dibenzyl, bis(cyclopentagenyl)zirconium methoxychloride, bis(cyclopentagenyl)zirconium ethoxy Chloride, Bis(methylcyclopentagenyl)zirconium ethoxychloride, Bis(cyclopentagenyl)zirconium phenoxychloride, Bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis (indenyl)methylzirconium ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, isopropylbisindenylzirconium dichloride, isopropyl(cyclopentagenyl)-1-fluorenylzirconium chloride, ethylenebis(indenyl) ) Zirconium dibromide, Ethylene bis(indenyl) zirconium methoxy monochloride, Ethylene bis(indenyl) zirconium ethoxy monochloride, Ethylene bis(indenyl) zirconium phenoxy monochloride, Ethylene bis(cyclopentajenyl) zirconium dichloride, Propylene bis( cyclopentagenyl) zirconium dichloride, ethylenebis(t-butylcyclopentagenyl)silconium dichloride, ethylenebis(4,5,6,7-tetrahydro-indenyl)dimethylzirconium, ethylenebis(4,5,6) ,7-tetrahydro-1-indenyl)methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl) ) zirconium dichloride, ethylenebis(4-methyl-1-indenyl)zirconium dichloride, ethylenebis(5-methyl-1-indenyl)zirconium dichloride, ethylenebis(6-methyl-■-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-simethoxy1-indenyl)
Zirconium dichloride.

In the above zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, vanadium metal, etc. can also be used.

Also, in this case, the organometallic compound catalyst component [B]
It is preferable to use an organoaluminum compound obtained by the reaction of an organoaluminum compound and water, or the reaction of an aluminoxane solution, such as a hydrocarbon solution, with water or an active hydrogen-containing compound.

Such organoaluminum compounds are insoluble or poorly soluble in benzene at 60°C.

In the present invention, the amount of catalyst used varies depending on the type of catalyst used, but for example, the amount of the catalyst component [A
], organometallic oxide catalyst component [B] and electron donor [
C], the amount of catalyst component [A] used is, for example, usually 0.0 in terms of transition metal per 1 g of polymerization volume.
01-0.5 mmol, preferably 0.005-065
The amount of the organometallic compound and catalyst [B] to be used is set to be within the range of millimole, and the amount of the organometallic compound and catalyst [B] is set to be within the range of millimole. The amount of metal atoms in the catalyst [B] is usually set in the range of 1 to 10,000 mol, preferably 5 to 500 mol. Furthermore, when using the electron donor [C],
The amount used is 100 mol or less, preferably 1 mol or less, per 1 mol of transition metal atoms of the catalyst component [A] in the polymerization system.
It is set within the range of 50 moles, particularly preferably 3 to 20 moles.

The polymerization temperature during polymerization using the above catalyst is usually 20 to 200°C, preferably 50 to 1,00°C, and the pressure is normal pressure to 100 kg/cr, preferably 2 to 50 kg/cr.
Polymerization is carried out within the range of c♂.

Further, in the present invention, it is preferable to carry out preliminary polymerization prior to main polymerization. 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 amount of polymerization in prepolymerization is usually 1 g per 1 g of titanium catalyst component.
-2000g, preferably 3-1000g, particularly preferably 10-500g.

Prepolymerization is preferably carried out using an inert hydrocarbon solvent; examples of inert hydrocarbon solvents that can be used in this case include propane, butane, n-pentane, -pentane, n- hexane, i-hexane,
Aliphatic hydrocarbons such as n-hebutane, n-octane, 1-octane, n-decane, n-dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclopentane, benzene,
Mention may be made of aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbon compounds such as methylene chloride, ethyl chloride, ethylene chloride and chlorobenzene. Among these inert hydrocarbon solvents,
Aliphatic hydrocarbons are preferred, and aliphatic hydrocarbons having 4 to 10 carbon atoms are particularly preferred. Furthermore, the monomer used in the reaction can also be used as a solvent.

Examples of α-olefins used in this prepolymerization include ethylene, propylene, ■-butene, ■pentene,
-methyl-1-pentene, 3-methyl-1-pentene,
1-carbon number such as 1-heptene, ■-octene, 1-decene, etc.
α-olefins having a carbon number of 0 or less are preferable, and further have a carbon number of 3
-6 α-olefins are preferred, with propylene being particularly preferred. These α-olefins can be used alone, or two types can be used in combination as long as a crystalline polymer is produced.

The polymerization temperature in the prepolymerization varies depending on the α-olefin used and the inert solvent used, and cannot be generally specified, but is generally between -40 and 80°C, preferably between -22°C.
It is in the range of 0 to 40°C, particularly preferably -10 to 30°C. For example, when propylene is used as the α-olefin, 40~. Set within the range of 70°C, 40 to 40°C when using -butene, and 40 to 70°C when using 4-methyl-1-pentene and/or 3-methyl-1-pentene. be done. Note that hydrogen gas can also be allowed to coexist in the reaction system for this prepolymerization.

After prepolymerizing as described above, or without prepolymerizing, the above-mentioned monomer is then introduced into the reaction system and a polymerization reaction (main polymerization) is performed to produce polymer particles. Can be done.

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

The polymerization temperature for the main polymerization of such olefins is usually -
It is within the range of 50 to 200°C, preferably 0 to 150°C. The polymerization pressure is usually normal pressure to 100 kg/c4, preferably normal pressure to 50 kg/cJ, and the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods. can.

The molecular weight of the resulting olefin polymer can be controlled by hydrogen and/or polymerization temperature.

Moreover, the polymer particles obtained in this way are composed of a crystalline olefin polymer portion and an amorphous olefin polymer portion. In the present invention, the amorphous olefin polymer portion in the polymer particles is usually within the range of 20 to 80% by weight, preferably 25 to 70% by weight, and more preferably 30 to 60% by weight. It is desirable that it be included. The content of such amorphous olefin polymer is
In the present invention, it can be determined by measuring the amount of components soluble in n-decane at 23°C.

Furthermore, in the present invention, among the polymers constituting the polymer particles, the polymer particles have been heated at least once to a temperature higher than the melting point of a crystalline olefin polymer or the glass transition point of an amorphous olefin polymer. Preference is given to using polymer particles that are free of oxidation.

To prepare the thermoplastic elastomer in the present invention,
Approximately 0.0 parts per 100 parts by weight of the above polymer particles
A crosslinking agent of 1 to 5 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.05 to 1 part by weight is blended to improve the melting point or amorphousness of the crystalline olefin polymer constituting the polymer particles. Intraparticle crosslinking may be carried out by bringing the polymer particles into contact with the crosslinking agent at a temperature lower than the higher of the glass transition points of the olefin polymer.

The polymer particles used in this case have a ratio of amorphous olefin polymer portion in the polymer particles of 20 to 80.
% by weight of polymer particles is used, preferably 25-70% by weight, more preferably 30-60% by weight.

The "amorphous olefin polymer" referred to here refers to the n
-It refers to a polymer that dissolves in decane, and specifically refers to a polymer that has been subjected to solvent fractionation by the following method.

That is, in this specification, while stirring a solution of n-decane (500 ml) to which polymer particles (3 g) were added,
After performing the dissolution reaction at 145°C, stirring was stopped, and the temperature was cooled to 80°C for 3 hours, to 23°C for 5 hours, and then further cooled to 23°C for 5 hours.
A polymer obtained by filtering and separating using a G-4 glass filter after a period of time and removing n-decane from the obtained filtrate is referred to as an "amorphous olefin polymer."

Examples of crosslinking agents used in the present invention include organic peroxides, sulfur, phenolic vulcanizing agents, oximes, and polyamines. Phenolic vulcanizing agents are preferred.

As the phenolic vulcanizing agent, an alkylphenol formaldehyde resin, a triazine-formaldehyde resin, and a melamine-formaldehyde resin can be used.

Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2.5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 2.5-dimethyl-2,5-bis(tert-butylperoxide). peroxy)hexyne-3,■,3-bis(ter)
t-butylperoxyisopropyl)benzene, ■, 1
-bis(tert-butylperoxy) -3,3,5
-)limethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, dibenzoyl peroxide, tert-butylperoxybenzoate, etc. can be used. Among these, dibenzoyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene are preferred from the viewpoint of crosslinking reaction time, odor, and scorch stability.

Further, in order to achieve a uniform and moderate crosslinking reaction, it is preferable to include a crosslinking aid. Examples of crosslinking aids include sulfur, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N,N- Peroxy crosslinking coagents such as m-phenylene dimaleimide or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. Polyfunctional vinyl monomers such as vinyl butyrad or vinyl stearate may be exemplified. With such a compound, a uniform and mild crosslinking reaction can be expected. In particular, in the present invention, when divinylbenzene is used, it is easy to handle, has good compatibility with polymer particles, has an organic peroxide solubilizing effect, and acts as a peroxide dispersion aid, so that the crosslinking effect due to heat treatment is reduced. This is most preferable because it yields a thermoplastic elastomer that is homogeneous and has well-balanced fluidity and physical properties. In the present invention, the blending amount of such a crosslinking aid or polyfunctional vinyl monomer is 0.1 to 2 parts by weight per 100 parts by weight of the polymer particles.
In particular, the range of 0.3 to 1 weight is preferable, and by blending within this range, a thermoplastic elastomer can be obtained that has excellent fluidity and does not cause changes in physical properties due to thermal history during processing and molding of the thermoplastic elastomer. It will be done.

In the present invention, in addition to the polymer particles and the crosslinking agent, or in addition to these components and the crosslinking aid, a mineral oil softener may be added to carry out the crosslinking reaction.

Mineral oil-based softeners usually weaken the intermolecular forces of rubber during roll processing, making processing easier.
A high boiling point petroleum distillate that is used to help disperse carbon black, white carbon, etc., or to reduce the hardness of vulcanized rubber and increase its flexibility or elasticity. , paraffinic, naphthenic,
Alternatively, aromatic mineral oil or the like may be used.

In addition, in order to further improve the flow characteristics, that is, the moldability of the thermoplastic elastomer, the mineral oil softener is used in an amount of 1 to 1-00 parts by weight, preferably 3 to 90 parts by weight, per 1.00 parts by weight of the polymer particles. , more preferably in an amount of 5 to 80 parts by weight.

In addition, in the present invention, a crosslinking agent, further a crosslinking aid,
Use a mineral oil softener diluted in a swelling solvent. The swelling solvent has the function of diluting the crosslinking agent and crosslinking auxiliary agent to help them disperse on the surface of the polymer particles, and also swelling the polymer particles and transporting the crosslinking agent and crosslinking auxiliary agent into the polymer particles. Therefore, the crosslinking reaction can be uniformly carried out to the inside of the polymer particles. Furthermore, if a poor solvent for the olefin polymer is used as the swelling solvent, it is also possible to selectively carry out a crosslinking reaction near the surface of the polymer particles. In any case, the type of swelling solvent selected for the reaction varies depending on the type of polymer particles used. Specifically, the swelling solvent used in the present invention includes aromatic hydrocarbon solvents such as benzene, toluene, and xylene;
Aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloride Chlorinated hydrocarbon solvents such as methylene, chloroform, carbon tetrachloride, tetrachloroethane, dichloroethylene, and trichlorethylene, methanol, ethanol, n-propertool, 15O-propertool, n-butanol, 5ee-butanol, tert −
Alcohol solvents such as butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethyl phthalate, dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, dioxane, anisole, etc. Examples include ether solvents.

The swelling solvent is used in an amount of 1 to 10 parts by weight per 100 parts by weight of the polymer particles.
It is used in an amount of 0 parts by weight, preferably 5 to 60 parts by weight, more preferably 10 to 40 parts by weight.

When the solvent as described in item 1 comes into contact with the polymer particles used in the present invention, it swells the polymer particles, especially the amorphous olefin polymer portion of the polymer particles, and removes the crosslinking agent and crosslinking coagent. plays a role in making it easier to penetrate into the particles.

However, the amount of the solvent used in the present invention is 200 parts by weight or less with respect to 100 parts by weight of the polymer particles,
The crosslinking reaction in the present invention is different from a solvent suspension reaction in which a large excess of solvent is used.

The reaction in the present invention is carried out at a temperature that melts the polymer particles and does not cause them to fuse together. −・
For boat fishing, the reaction described in item 1 is carried out at a temperature ranging from 0° C. to less than the higher of the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer.

For example, when the above polymer having a high melting point is polypropylene, high density polyethylene, or low density polyethylene, the upper limit of the reaction temperature is around 150°C, around 120°C, and around 90°C, respectively.

In addition, the reaction time is 1 to 30 times, preferably 2 to 10 times, the half-life time of the crosslinking agent at the temperature at which the crosslinking reaction is carried out.
More preferably, the time is 3 to 7 times longer, and the pressure is 0 to 7 times longer.
50 kg/cJ, preferably 1 to 20 kg/c, more preferably 1 to 5 kg/c. The crosslinking reaction can be carried out either batchwise or continuously.

In the present invention, it is most preferable to carry out the crosslinking reaction after bringing the crosslinking agent and the polymer particles into contact, or after bringing the crosslinking agent and the crosslinking aid into contact with the polymer particles. Alternatively, the crosslinking reaction can be carried out while supplying the crosslinking agent, crosslinking aid, and polymer particles to the reactor together or separately.

When a polymer particle consisting of a crystalline olefin polymer part and an amorphous olefin polymer part is crosslinked in this way, a crosslinking reaction occurs inside the polymer particle, and in particular, the amorphous olefin polymer part of the polymer particle A crosslinking reaction occurs at the coalescing portion, and the amorphous olefin polymer portion (rubber component) is fixed within the particles at the molecular segment level.

The reaction device used in the present invention is a device capable of mixing at least polymer particles, and may be either a vertical or horizontal reactor. When heat treatment is performed, a reactor capable of mixing and heat treatment of polymer particles is used. Specific examples of the reaction apparatus used in the present invention include a fluidized bed, a moving bed, a loop reactor, a horizontal reactor with stirring blades, a rotating drum, and a stationary reactor with stirring blades.

The intraparticle crosslinked thermoplastic elastomer thus obtained has an insoluble gel content that is not extracted by cyclohexane, measured as follows, of 10% by weight or more, preferably 40 to 100% by weight, more preferably 40 to 100% by weight. 60～
It is desirable that the amount is 99% by weight, particularly preferably 80 to 98% by weight.

Note that the above gel content of 100% by weight indicates that the obtained thermoplastic elastomer is completely crosslinked.

Here, the measurement of the cyclohexane-insoluble gel content is performed as follows. Sample pellets of thermoplastic elastomer (size of each pellet + 1 mm x 1, mm x 0
, 5 mm) was weighed out and added to 30 cc of cyclohexane in a sealed container at 23°C for 4 hours.
After 8 hours of immersion, the sample is removed and dried. If the thermoplastic elastomer contains a cyclohexane-insoluble filler, Face 1, etc., the weight of this dry residue is determined by calculating the amount of cyclohexane-insoluble filler other than the polymer component,
The corrected final weight after drying (Y) is obtained by subtracting the weight of pigment and other items. On the other hand, the weight of the sample pellets indicates that cyclohexane-soluble components other than the ethylene/α-olefin copolymer are contained, such as plasticizers, cyclohexane-soluble rubber components, and cyclohexane-insoluble fillers and pigments in the thermoplastic elastomer. In this case, the corrected initial weight (X) is obtained by subtracting the weight of these cyclohexane-insoluble fillers, pigments, and other components other than the polyolefin resin.

From these values, the cyclohexane-insoluble gel content is determined by the following formula.

Corrected final weight (Y) Gel content (%) − Thermoplastic elastomers can be obtained at low manufacturing costs and can provide molded products with excellent physical properties such as impact strength and tensile strength, toughness, heat resistance, flexibility at low temperatures, surface smoothness, and paintability. It will be done.

In particular, thermoplastic elastomers in which rubber components are fixed at the molecular segment level can provide molded products with even better flexibility, surface smoothness, and paintability at low temperatures.

The thermoplastic elastomer obtained by the production method according to the present invention can be molded using molding equipment used for ordinary thermoplastic polymers, such as extrusion molding, calendar molding,
Particularly suitable for injection molding.

Such thermoplastic elastomers are used in body panels, bumper parts, sight shields, automobile parts such as steering wheels, footwear such as shoe soles and sandals, electrical parts such as wire sheaths, connectors, and cap plugs, golf club grips, and baseball parts. It is used for leisure goods such as bat grips, swimming fins, underwater glasses, gas getters, waterproof cloth, garden hoses, and belts.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

[Example] [Adjustment of catalyst component [A]] A high-speed stirring device (manufactured by Tokushu Kika Kogyo) with an internal volume of 2 g was heated with sufficient N.
After 2 substitutions, 700 ml of refined kerosene, commercially available MgC,
172] 24.2 f of Og1 ethanol and 3 g of Emazol 320 (trade name, manufactured by Kao Atlas ■, sorbitan distearate) were added, and the system was heated to temperature with stirring, and stirred at 120° C. and 800 rpm for 30 minutes. Under high-speed stirring, using a Teflon tube with an inner diameter of 5 mm,
2g filled with 1g of refined kerosene cooled to 10℃
The liquid was transferred to a glass flask (equipped with a stirrer). The produced solid was collected by filtration and thoroughly washed with hexane [7, after which a carrier was obtained.

After 7.5 g of the carrier was suspended in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added, and the temperature of the chain thread was raised to 120°C. After stirring and mixing for 2 hours at 120°C, the solid part was collected by filtration and poured into 150 ml of water again.
The mixture was suspended in titanium tetrachloride and stirred and mixed again 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 were 2.2% by weight of titanium, 63% by weight of chlorine, 20% by weight of magnesium, and 5.5% by weight of diisobutyl phthalate. A truly spherical catalyst with an average particle size of 64 μm and a geometric standard deviation (δ) of particle size distribution of 1-35 was obtained.

[Preliminary polymerization] The catalyst component [A] was subjected to the following preliminary polymerization.

After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 20 mmol of triethylaluminum, 4 mmol of diphenyldimethoxysilane, and the above Tj catalyst component [A] were added in an amount of 2 in terms of titanium atoms.
After charging mmol, propylene was fed at a rate of 5.9 In/hour over 1 hour, and the TI catalyst component [Al1. g
2.8 g of propylene was polymerized per batch. After the T-prepolymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

[Polymerization co[I] copolymerization (1) 1, 7. 2.5 kg of propylene and 9N liters of hydrogen were added to a polymerization reactor at room temperature, and the temperature was raised to 50'C to form a prepolymerized product of 15 mmol of triethylaluminum, 1.5 mmol of diphenyldimethoxysilane, and catalyst component [A]. Add 0.05 mmol in terms of titanium atoms,
The temperature inside the polymerization vessel was maintained at 70°C. Ten minutes after reaching 70°C, the vent valve was opened and propylene was purged until the inside of the polymerization vessel reached normal pressure. After purging, copolymerization was carried out subsequently. Ethylene at 48ONΩ/hour, propylene at 72011/hour, hydrogen at 12NΩ/hour. It was fed to the polymerization reactor at a rate of Q/hour. The pressure inside the polymerization vessel is 1. O kg/
The opening degree of the vent of the polymerization vessel was adjusted so that cd.G. The temperature during copolymerization was kept at 70°C. After a copolymerization time of 85 minutes, the resulting polymer weighed 3.1 kg after depressurization, and the Ml-3.9 g/l.
0 minutes, ethylene content 28 mol%, apparent bulk specific gravity 0.39
Met. Further, the amount of components soluble in n-decane at 23° C. was 37% by weight, and the content of ethylene in the soluble components was 49% by mole.

Example 1 1 equipped with a stirring blade having a helical double ribbon
-51 A stainless steel autoclave is charged with 3 kg of polymer particles obtained by copolymerization (1), and the inside of the system is completely replaced with nitrogen. Thereafter, a mixed solution having the compounding ratio shown in Table 1 is added dropwise to the polymer particles over a period of 10 minutes at room temperature while stirring, and the mixture is further stirred for 30 minutes to impregnate the polymer particles with these reagents.

Next, the temperature in the system was set to 100°C, and the reaction was carried out for 4 hours. After the reaction, the temperature in the system was lowered to 80°C, and acetone 7,
5 kg was added and stirred at 80° C. for 1 hour, then the polymer was extracted and filtered, washed three times with 9 kg of acetone, and then dried under reduced pressure.

The MFR and gel fraction of the obtained thermoplastic elastomer are measured. In addition, the obtained thermoplastic elastomer is injection molded, and the injection molded appearance and sheet properties are evaluated.

Table 1 shows the physical properties.

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Claims (1)

[Scope of Claims] 1) Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part and a crosslinking agent are mixed in the presence of a swelling solvent at the melting point of the crystalline olefin polymer or A method for producing a thermoplastic elastomer, which comprises contacting an amorphous olefin polymer at a temperature lower than the higher of the glass transition points of the amorphous olefin polymer to obtain an intraparticle crosslinked thermoplastic elastomer. 2) Polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion, a crosslinking agent, and a crosslinking aid are combined in the presence of a swelling solvent at the melting point of the crystalline olefin polymer or the amorphous 1. A method for producing a thermoplastic elastomer, which comprises contacting a thermoplastic olefin polymer at a temperature lower than the higher of the glass transition points of the olefin polymer to obtain an intraparticle crosslinked thermoplastic elastomer.