JPH03162429A - Production of thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To efficiently obtain a high-strength thermoplastic elastomer having excellent elasticity in reduced rubber content by bringing grains of polymer consisting of a crystalline olefin polymer and amorphous olefin polymer into contact with a crosslinking agent at a specific temperature. CONSTITUTION:(A) 100 pts.wt. polymer grains consisting of (i) 20-80 pts.-wt. crystalline olefin polymer (e.g. crystalline propylene polymer) and (ii) amorphous olefin polymer (e.g. ethylene-alpha-olefin copolymer) and having 10-5000mum average grain, 1.0-3.0 geometric standard deviation and 0.2-0.7g/ml apparent density is brought into contact with (B) 0.01-2 pts.wt. crosslinking agent at a temperature less than either one higher temperature between melting point of the ingredient (i) and glass transition point of the ingredient (ii) and the polymer grains are subjected to crosslinking and graft modification in grains to provide the aimed elastomer having excellent impact resistance at low temperature, surface smoothness and coating properties.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a thermoplastic elastomer, and more particularly to a thermoplastic elastomer having excellent valve properties and high strength even with a small rubber content. The present invention relates to a method for producing a thermoplastic elastomer that can efficiently obtain a plastic elastomer. The present invention also relates to a method for producing a thermoplastic elastomer that has excellent heat resistance, tensile strength, weather resistance, flexibility, elasticity, and low-temperature impact resistance, as well as 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.

For example, in Japanese Patent Publication No. 53-34210, 60-8
0 parts by weight of monoolefin copolymer rubber and 40 to 20 parts by weight
A thermoplastic elastomer is disclosed that is dynamically partially cured with parts by weight of a polyolefin plastic. Furthermore, Japanese Patent Publication No. 53-21021 discloses (partially crosslinked copolymer rubber made of 12-ethylene-propylene-non-conjugated polyene copolymer rubber with a gel content of 30 to 90% by weight, and (b) polyolefin A thermoplastic elastomer comprising a resin is disclosed.
No. 448 discloses a thermoplastic elastomer in which an ethylene-propylene copolymer rubber and a polyolefin resin are dynamically partially or completely crosslinked.

By the way, JP-A-58-187412 discloses a propylene homopolymer block and a binary random copolymer block of propylene and ethylene or C4 to CI2 α-olefin with a propylene content of 100 to 100.
One or more of the 60% block [A] is 5
Olefin block copolymer containing 0 to 70 parts by weight and 30 to 50 parts by weight of one or more of two or more binary random copolymer blocks [B] of ethylene and propylene having an ethylene content of 30 to 85% by weight Crosslinked block copolymers derived from polymers and characterized by having a specific content of thermally xylene-insoluble components and specific flow properties are disclosed.

Also, JP-A-63-165414, JP-A-63-1
No. 65115, JP-A No. 63-161511i, and U.S. Pat. No. 4,454,306 disclose a propylene homopolymer block [A] produced using a specific Ziegler catalyst, and a propylene homopolymer block [A] produced using a specific Ziegler catalyst. An olefinic block copolymer consisting of a binary random copolymer block [B] and a propylene/ethylene binary random copolymer block [C] is heated at 230°C together with an organic peroxide, a divinyl compound, and an antioxidant. A method for producing a crosslinked olefin block copolymer is disclosed, which is characterized in that crosslinking is carried out at the following temperature.

Furthermore, JP-A No. 411-21731 discloses a copolymer portion consisting mainly of ethylene and 70 wt. % or less of other α-olefins, 3 to 30 wt. %, and a polymer portion consisting mainly of propylene of 97 to 70 wt. An organic peroxide is mixed with a block copolymer consisting of 180 to 270%.
A method for improving the processability of a block copolymer is disclosed, which is characterized by heat treatment at .degree.

The inventors have developed polymer particles as an economical process.
When we investigated the possibility of producing a thermoplastic elastomer through heat treatment while maintaining the particle shape, we found that if polymer particles with a specific morphology were used, they would be extremely uniform;
It has been discovered that even with a small rubber content, it has excellent elasticity and strength, and furthermore, when molded into a molded product, a molded product with excellent appearance, especially after painting, can be obtained. The present invention has now been completed.

Purpose of the Invention The present invention has excellent elasticity and strength even with a small rubber content, and is uniform in strength physical properties such as tensile strength, heat resistance, weather resistance, flexibility, elasticity, and surface properties. The object of the present invention is to provide a method for producing a thermoplastic elastomer that provides a molded article with excellent smoothness, paintability, and economical efficiency.

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 part and an amorphous olefin polymer part and a crosslinking agent into a 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 present invention, when producing a thermoplastic elastomer by bringing the above polymer particles into contact with a crosslinking agent,
A swelling solvent or a mineral oil softener may also be present.

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 radical initiator, and a graft modifier are combined into a crystalline elastomer. The method is characterized in that the thermoplastic elastomer is brought into contact at a temperature lower than the higher of either the melting point of the amorphous olefin polymer or the glass transition point of the amorphous olefin polymer to obtain an intraparticle crosslinked thermoplastic elastomer.

Furthermore, in the present invention, when producing a thermoplastic elastomer by bringing the above polymer particles, a radical initiator, and a graft modifier into contact with each other, a swelling solvent or a mineral oil-based softener may also be present. can.

A preferable group of polyolefin particles made of a thermoplastic elastomer produced as described above is composed of a crystalline olefin polymer part and an amorphous olefin polymer part, and has an α-olefin having 3 or more carbon atoms as a main component. It is made of intra-particle crosslinked thermoplastic elastomer, has an average particle diameter of 100 to 5000 μm, has a geometric standard deviation of 160 to 3.0, and has an apparent bulk specific gravity of 0.25 to 5000 μm.
0.70, and the particle aspect ratio is 1.0 to 3.0.
The amount of fine particles with a particle size of 100 μm or less is 20% by weight.
The following item (2) is characterized in that the cyclohexane-insoluble gel content is 10% by weight or more.

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 μm or more, preferably 10-5000 μm1, more preferably 100-4000 μm1, particularly preferably 300-4000 μm1
It is within the range of 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 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.5. , particularly preferably within the range of 1.0 to 1.3. 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 0.2 to 0.
．． 7g/ml, more preferably 0.3-0.7g/m
l, particularly preferably 0.35 to 0.60 g/ml
is within the range of

Further, in the polymer particles used in the present invention, the amount of particles passing through 150 mesh is preferably 30% by weight or less, more preferably 10% by weight or less, particularly preferably 2% by weight or less. In addition, such polymer particles have a fall time defined as below: 5 to 25 seconds, preferably 5 to 20 seconds.
The time is particularly preferably 5 to 15 seconds.

Note that the average particle diameter, apparent bulk density, and falling seconds of the polymer particles as described above are measured as follows.

Average particle size: 300 g of polymer particles were placed in a Nippon Rikagaku Kikai stainless steel sieve with a diameter of 200 cm and a depth of 45 cm (7 types of sieves with mesh openings of 7, 10, 14, 20, 42, 80, and 150 mesh in this order). The mixture was added to the top layer of a stack of saucers (stacked from above and saucers were further stacked on the bottom layer), and after the lid was placed on it, it was set in a +1DA SIEVE SHAKER (Iida Seisakusho) and shaken for 20 minutes.

After shaking for 20 minutes, place on each sieve. Measure the polymer heavy plate and compare the measured values. The numbers were plotted on established paper. the plot are connected by a curve, and the product is based on this curve. Particle diameter at calculated weight ffi 50% by weight (D5.) was determined, and this value was taken as the average particle diameter.

On the other hand, the same applies to the geometric standard deviation. In addition, 16 layers are accumulated from the small particle size. It was determined from the particle size (D, 6) in plate % and the above D50 value.

(Geometric standard deviation=D5o/Dl6) Apparent bulk density: Measured in accordance with Its K 6721-1977. (However, the inlet inner diameter of the funnel used was 92.9 mφ, and the outlet inner diameter was 9.5 mφ.) Dropping time: Using the bulk density measuring device as is, drop the sample into the favorite vessel, and then drop the sample from the receiver. After removing the raised sample with a glass rod, the sample in the 100 ml container is transferred again to the funnel with the damper inserted, and then the damper is pulled and the time required for the entire sample to fall from the bottom of the funnel (seconds) is the number of falling seconds.

However, when measuring the number of seconds of falling, 1.5 to the average particle diameter of the sample By sieving particles that are 1.6 times larger The removed polymer particles were used.

In addition, when measuring the falling seconds, set the receiver on the vibration table of a powder tester (Hosokawa Micro T7pe PT-D, SER. No. 71190), and adjust the voltage of the rheostat so that the vibration width of the diaphragm is 1 + nm. The polymer particles were then dropped while being vibrated.

The polymer particles used in the present invention are composed of a crystalline olefin polymer part and an amorphous olefin polymer part, as described above, and have a so-called sea-island structure, but the amorphous olefin polymer part is , forming islands in the polymer particles. The average particle diameter of the island portion consisting of the amorphous olefin polymer portion (including some crystalline olefin polymer portion as the case may be) is 0.5 μm or less, preferably 0.1 μm.
m or less, more preferably o. oooooi~0.05μm
It is desirable that

Note that the average particle diameter of the island portion made of the amorphous olefin polymer portion in the polymer particles is measured as follows.

Using an ultramicrotome, the polymer particles were
Thinly slice at -140°C to a thickness of 0.000 pieces. then 0.5
Approximately 11 ml of an aqueous solution of R u O 4
Place the thinly sliced sample in the gas phase in a closed container for 30 minutes,
Dye the amorphous olefin polymer portion in the sample. Next, after reinforcing the dyed sample with carbon, it is observed with a transmission microscope, and the particle size of the island portion is determined for at least 50 particles, and the average value thereof is taken as the average particle size of the island portion.

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. The polymer particles obtained by this method usually have a transition metal content of 100 ppp in the ash.
m or less, preferably 10 ppm or less, particularly preferably 5
ppm or less, and the halogen content is usually a o o ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less. Contained in proportion.

In addition, when referring to a polymer in the present invention, the polymer is used with a concept including both a homopolymer 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-11pentene-1,2-methylbutene-L 3-methylbutene-11hexene-1,3-methylpentene-1,4-methylpentene-1,3.3 dimethylbutene-11 heptene-1, methylhexene-1,
Dimethylpentene-1, trimethylptene-11 ethylpentene-1, octene-11 methylpentene-1
, dimethylhexene-1, trimethylpentene-1, ethylhexene-11 methylethylpentene-1, diethylbutene-1, proylpentene-1, decene-11 methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-11 methylethyl heptene-1, diethylhexene-11 dodecene-1
and α-olefins such as 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, as the polyene compound, a polyene having two or more conjugated or non-conjugated olefinic double bonds is used, and as such a chain polyene compound, specifically, 1,4-hexadiene, 1.5-hexadiene, 1.7 octadiene, 1.9-decadiene, 2.4
．． 6-octatriene, 13.7-octatriene,!
．． 5.9-decatriene, divinylbenzene, etc. are used. Moreover, specifically as a cyclic polyene compound,
1.3-cyclopentadiene, 1.3-cyclohexadiene, 5-ethyl-13-cyclohexadiene,! ,3
-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-norbornene,
5 methylene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene,
Methylhydroindene, 2,3-diisopropylidene 5
-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2.5-norbornadiene, etc. are used.

Further, in the present invention, a polyene compound obtained by condensing a cyclopentadiene such as cyclopentadiene and an α-olefin such as ethylene, propylene, and putene-1 using a Diels-Alder reaction can also be used.

Furthermore, in the present invention, cyclic monoenes can also be used, and specific examples of such cyclic monoenes include cyclopropene, cycloptene, cyclopentene,
Monocycloalkenes such as cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, cycloeicosene, norbornene, 5
-Methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-
Dimethyl-2-norbornene, 5, 5. Bicycloalkenes such as 6-h-lymethyl-2-norbornene and 2-bornene, 2 3 31 7! -tetrahydride mouth-4.7
-methanol IH-indene, 3a, 5, 6. 1*
-Tetrahydride CI -4. Tricycloalkenes such as 7-methane-Ill-indene, 1,4.5.8-dimethano-12344a5.88g-octahydronaphthalene, and in addition to these compounds, 2-methyl 4,5
．． 8-dimethano-1. 2, 3, 4. 4! ，
5, 8. 81-octahydronaphthalene, 2-ethyl-1. 4, 5. 8-dimethano1. 2, 3.
4. 4l, 5. 8, 8! -octahydronaphthalene, 2-probyl-1. 4. 5. 8-dimethano-1. 2, 3. 4. 41. 5. 88a-
Octahydronaphthalene, 2-hexyl-1.458-
Dimethano-1. 2, 3. 4. 4, 5. 8
．． 8a-octahydronaphthalene, 2-stearyl 1. 4, 5. 8-dimethano-l. 2. 3.
4, 41, 5, 8. 81-octahyde naphthalene, 23-dimethyl-1. 4. 5. 8-dimethano-1. 2. 3, 4. 41. 5.88! -Octahide naphthalene, 2-methyl-3-ethyl-1.
4. 5. 8-dimethano-1. 2, 3. 4.
4m, 5, B, 8g-octahydronaphthalene, 2-chloro-1. 4, 5. 8-dimethano-1
2 3 4.41,5,8.8g-octahyde naphthalene, 2-bromo1. 4, 5. 8-dimethanol l. 2, 3, 4, 4! , 58.82-Octahide naphthalene, 2-fluoro-1458-dimethano-1. 2, 3, 4. '41, 5, 8. 81
-Octahide naphthalene, 2.3-dichloro1.
4. 5. 8-dimethano-l 2 3 4 4i,5
．． 8.8a-Tetracycloalkenes such as octahydronaphthalene, hexacycloalkenes [6.6,3,6 10,
13. o2,7. o9.14] A, futate, b, -
4,1l ,1 2,9 4.7 11.18 Pentasic mouth [8.8. l , l , 13, 8
12.17 80.0] Henikosen-5, Octashic 2,9 4
,7 11.18 13.16 3.8 units [8
,8,1,I. 1. 1. 0.0
+2. Examples include cyclic monoene compounds such as polycycloalkenes such as 170 codocosene-5.

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

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

An inert hydrocarbon can be used in this polymerization reaction or copolymerization reaction. Further, the raw material α-olefin 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, when producing polymer particles used as raw materials, 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 tank; or,
Examples include 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 at least two or more polymerization vessels. 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 to synthesize a crystalline olefin polymer part by gas phase polymerization and then synthesize an amorphous olefin polymer part by gas phase polymerization, or to synthesize a crystalline olefin polymer part by using a monomer as a solvent. After combining the
Examples include a method of synthesizing an amorphous olefin polymerization part by gas phase polymerization.

In the present invention, when carrying out the above polymerization reaction or copolymerization reaction, the catalyst component [A] containing a transition metal and the organometallic compound catalyst component [B ] is used.

The above catalyst component [A] is preferably a catalyst containing a transition metal atom of Group rVB or Group VB 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 transition metal atoms mentioned above, and catalyst components having conjugated π electrons in transition metal atoms of groups rVB and VB 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 etc. It is preferable to use a catalyst prepared in such a way that it can be used.

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

The average particle diameter of the solid catalyst component [A] as described above is:
Preferably 1-200 μm1, more preferably 5-10
Oμm1 is 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.
1 further g, preferably 1.0 to 26 1, particularly preferably 1.0 to 26 g
It is within the range of 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 decalin solvent has a concentration of 0. The dispersion prepared by adding the catalyst component [A] to a concentration of 1% by weight is placed in a measuring cell, a thin light is applied to this cell, and the change in intensity at the point where the particles pass through the thin light is continuously measured. Determine the particle size distribution by measuring the Based on this particle size distribution, the standard deviation (δ) is determined from the lognormal distribution function g. More specifically, the average particle diameter (θ5o)
, the particle size (θ
) is calculated as the ratio (θ50/θl6) of 16 standard deviations (δ). Note that the average g particle size of the catalyst is the weight average particle size.

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.

The aspect ratio is determined by observing the catalyst particle group with an optical microscope,
At that time, it is determined by measuring the long sleeve and short axis of 50 arbitrarily selected catalyst particles.

Further, 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 Within the range of 6 to 30, the halogen/titanium (atomic ratio) is usually
The electron donor/titanium (molar ratio) is usually in the range of 0.1 to 101, preferably 0.2 to 6. Further, the specific surface area of this catalyst component [A] is usually 3rrf/g or more, preferably 40rrf/g or more, and more preferably 100 to 8
It is within the range of 00rrf/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 above-mentioned catalyst [A] can be prepared by, for example, 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 ranges and a shape as described above, or by a method in which a catalyst is prepared in a liquid form. It can be produced by employing a method such as a method in which a magnesium compound and a liquid titanium compound are brought into contact 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], JP-A-55-N
No. 5102, No. 55-135103, No. 56-811
No. 56-67311 and patent application No. 56-18
No. 1019 and No. 6l-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 g-like 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 It is reacted with a liquid titanium halide compound, preferably titanium tetrachloride, under reaction conditions with or without pretreatment with reaction aids such as containing silicon compounds.

(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 (δ) of particle size distribution of 3.0 or less is precipitated.

g 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 bringing a liquid magnesium compound with reducing ability into preliminary contact with a reaction aid capable of eliminating the reducing ability of the magnesium compound, such as polysiloxane or a halogen-containing silicon compound, the average particle size can be reduced. 1-200μm1 Geometric standard deviation of particle size distribution (
After precipitating a solid component with δg) of 3.0 or less, this solid component is reacted with a liquid titanium compound, preferably titanium tetrachloride, or a titanium compound and 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.

(5) In methods (2) to (3), by coexisting an inorganic carrier such as silica or alumina or an organic carrier such as polyethylene, polypropylene, polystyrene, etc., the Mg compound is supported on these carriers.

Such a solid catalyst component [A] has the ability to produce a polymer having high stereoregularity with high catalytic efficiency. For example, this solid catalyst component [
When homopolymerizing propylene using A], polypropylene having an isotacticity index (insoluble content in boiling n-hebutane) of 92% or more, particularly 96% or more, is usually 3000 g or more per mmol of titanium. Preferably 5000g or more, particularly preferably 10000g
or more can be manufactured.

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

Specific examples of the magnesium compound include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide, and hydrotalcite, magnesium carboxylates, alkoxymagnesium, anthelminth magnesium,
In addition to alkoxymagnesium halide, allyloxymagnesium halide, and magnesium dihalide, organic magnesium compounds such as dialkylmagnesium, Grignard reagent, and diarylmagnesium are used.

As the titanium compound, specifically, titanium halides such as titanium tetrachloride and titanium trichloride, alkoxytitanium halide, allyloxytitanium halide, alkoxytitanium, allyloxytitanium, and the like are used. 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; Nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates are used.

Specifically, compounds that can be used as such electron donors include methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, and isopropanol. 1 to 1 carbon atoms, such as vinyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol
Alcohols of No. 8; Phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, probylphenol, 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, penzophenone, and benzoquinone; Aldehydes: Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, probyl 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, probyl 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 Diethyl, diisobutyl phthalate, di-n-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, di-n-hexyl phthalate, diisohexyl phthalate, di-n-heptyl phthalate, diisoheptyl phthalate, di-n-phthalate - Octyl, diisooctyl phthalate, di2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate with 2 to 3 carbon atoms
0 organic acid esters; C2-15 acid halides such as acetyl chloride, penzoyl chloride, toluyl chloride and anisyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and ethers having 2 to 20 carbon atoms, preferably diethers such as anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, triptylamine, piperidine, and Amines such as livenzylamine, aniline, pyridine, vicoline and tetramethylenediamine; Nitriles such as acetonitrile, penzonitrile and tolnitrile; po such as trimethyl phosphite, triethyl phosphite
Organic phosphorus compounds having a -c bond; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane are used.

These electron donors can be used alone or in combination.

Among such electron donors, preferable electron donors are:
Esters of organic or inorganic acids, alkoxy(aryloxy)silane compounds, ethers, ketones, tertiary amines,
Compounds without active hydrogen such as acid halides and acid anhydrides, and 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, translated malonic acid, substituted succinic acid, maleic acid,
Particularly preferred are esters and diethers of dicarboxylic acids such as substituted maleic acid, 1,2-cyclohexanedicarboxylic acid, and 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 during the preparation of the catalyst component [A]; for example, compounds that can be converted into these electron donors are added to the reaction system and this compound is added during the catalyst preparation process can also be converted into the above electron donor.

The catalyst component [A] obtained as described above can be purified by washing thoroughly with a liquid inert hydrocarbon compound after preparation. Specifically, hydrocarbons that can be used in this cleaning include n-pentane, isopentane, n-hexane, isohexane, n-
Hebutane, n-octane, isooctane, n-decane,
Aliphatic hydrocarbon compounds such as n-dodecane, kerosene, and liquid paraffin; cyclobentane, methylcyclopentane,
Alicyclic hydrocarbon compounds such as cyclohexane and methylcyclohexane; aromatic hydrocarbon compounds such as benzene, toluene, xylene and cymene; and halogenated hydrocarbon compounds such as chlorobenzene and dichloroethane.

Such compounds can be used alone or in combination.

In the present invention, the organometallic compound catalyst component [B] is
Preferably, organoaluminum compounds having at least one Al-carbon bond in the molecule are used.

Examples of such organoaluminum compounds include usually 1 to 15, preferably 1 to 4 hydrocarbon groups, which 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 a number such that 0≦q<3, and m+n+p
+q=3), and (i) a periodicity represented by the formula M' AI R' 4 (where M1 is Li, Na, K, and R1 has the same meaning as above) Examples include complex alkylated products of Group I metals and aluminum.

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

2 compound represented by the formula R', An (OR') (where R and R2 are 1 in the same meaning as above, and m is preferably a number of 1.5≦m≦3) .

A compound represented by the formula R', AIX (where R1 has the same meaning as above, X is halogen, and m preferably satisfies Q<m<3).

A compound represented by the formula RIIIAIH (this 3-
m Here R! has the same meaning as above, and m is preferably 2≦
m<3).

Compound (where R and R2 are the same as above, X1 is a halogen, Ohm≦3, 0≦n<3, 0≦q3,
m+n+q=3).

Examples of the organoaluminum compound represented by the above formula (1) include trialkylaluminiums such as triethylaluminum, tributylaluminum, and triisopropylaluminium, trialkenylaluminums such as triisoprenylaluminum, and diethylaluminum. Dialkyl aluminum alkoxides such as ethoxide, diptylaluminum butoxide, alkylaluminium sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, 12 represented by the formula R Al (OR'), etc. 2,50.5 Partially alkoxylated alkylaluminums having an average composition of Alkylaluminum sesquihalides F such as sesquibromide, partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, probylaluminum dichloride, butyl aluminum dibromide, diethylaluminum hydride, diptylaluminium Dialkyl aluminum hydrides such as hydride, partially hydrogenated alkyl aluminum dihydrides such as ethyl aluminum dihydride and probylaluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum poxy chloride, Partially alkoxylated and halogenated alkyl aluminums are used, such as ethyl aluminum ethoxy bromide.

Furthermore, the organoaluminum compound used in the present invention is
For example, it 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 (C2H5)2IOAI (C2H5)2, (C4
Examples include H9)2AIOAl(C4H9')2 and C6H5.

Further, as the organoaluminum compound represented by the above formula (i), specifically, Li At(C2H5)4
and LI At (C7 Hl5) 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, when carrying out the polymerization reaction, in addition to the catalyst component [A] and the organometallic compound catalyst component [B], an electron donor [C
] is preferably used in combination.

Specifically, such electron donors [C] include amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoamides, esters, thioethers, thioesters,
Acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes, organic acids, amides of metals belonging to Groups I, II, II, and II of the periodic table. and their acceptable salts. Note that the salts are organic acids and catalyst components [B
] By reaction with an organometallic compound used as
It can also be formed within the reaction system.

Specific examples of these electron donors include the compounds exemplified above for catalyst component [A]. Among such electron donors, particularly preferred electron donors are:
These include organic acid esters, alkoxy(aryloxy)silane compounds, ethers, ketones, acid anhydrides, amides, and the like.

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.

In addition, when the electron donor in the catalyst ingredient [A] is an ester of dicarboxylic acid and an alcohol having 2 or more carbon atoms, the electron donor [C] has the formula R Si
(OR') n 4-n (However, in the above formula, R and R1 represent a hydrocarbon group, and 0≦
alkoxy (aryloxy) represented by n<4)
It is preferable to use a silane compound or a highly sterically hindered amine.

Specifically, such alkoxy(aryloxy)silane compounds include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane,
Dimethylethoxysilane, diisopropyldimethoxysilane, (-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, 1-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-butylmethyldimethoxysilane) 〇-Tolyldimethoxysilane, bis-tolyldimethoxysilane, bis-p-tolylmethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,
Cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxysilane, decylmethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chlorotrimethoxysilane Methoxysilane, methyltriethoxysilane, vinyltriethoxysilane, 1-butyltriethoxysilane, n-butyltriethoxysilane, 0-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, Chlortriethoxysilane, ethyltriisobropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-
Norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy (allyloB) silane, vinyl tris (β-methoxyethoxysilane), dimethyltetraethoxydisiloxane, and the like are used.

Among these, especially ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane,
Vinyltriethoxysilane, phenyltriethoxysilane, vinyltriptoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-
Tolylmethoxysilane, p-1lylmethyldimethoxysilane, dicyclohexyldimethoxysilane, dichlorohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, ethyl silicate, and the like are preferred.

The amines with large steric hindrance include 2, 2.
6. 6-tetramethylpiperidine, 2. 2, 5
．． Particularly preferred are 5-tetramethylpyrrolidine, derivatives thereof, and tetramethylmethylenediamine. Among these compounds, alkoxy(aryloxy)silane compounds and diethers are particularly preferred as electron donors used as catalyst components.

In addition, in the present invention, a catalyst component [i1] containing a transition metal atom compound of groups rVB and VB of the periodic table of elements having a group having conjugated π electrons as a ligand, and an organometallic compound catalyst component [i] A catalyst consisting of can be preferably used.

Here, examples of the transition metals of Group IVB and Group VB 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 cyclopentadienyl group, a methylcyclobentadienyl group, an ethylcyclopentadienyl group, a t-butylcyclopentadienyl group, and a dimethylcyclobentadienyl group. basis,
Examples include alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl groups, indenyl groups, and fluorenyl groups.

Preferred examples include groups in which at least two of these ligands having a cycloalkylene skeleton are bonded via a lower alkylene group or a group containing silicon, phosphorus, oxygen, or nitrogen.

Examples of such groups include groups such as ethylenebisindenyl group and isoprobyl (cyclobentadienyl-1-fluorenyl) group.

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

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 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 probyl groups. , isopropyl group, butyl group, etc.; cycloalkyl groups include cyclopentyl group, cyclohexyl group, etc.; aryl groups include phenyl group, tolyl group, etc.; aralkyl groups include benzyl group, etc. , neophyll group, etc.

Examples of the alkoxy group include a methoxy group, ethoxy group, and a putoxy group, and 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 cycloalkadidienyl skeleton used in the present invention, for example, when the valence of the transition metal is 4, more specifically, the transition metal compound has the following formula: R2 R3 R' R5 Mkl
mn (wherein M is zirconium, titanium, hafnium, or panadium, R2 is a group having a cycloal34cadienyl skeleton, RR and R5
is a group having a cycloalkadienyl skeleton, an alkyl group,
It is 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).

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

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

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis ( Cyclopentadienyl)phenylzirconium hydride, Bis(cyclopentadienyl)penzylzirconium hydride, Bis(cyclopentadienyl)neopentylzirconium hydride, Bis(methylcyclopentadienyl)zirconium monochloride hydride, Bis(indenyl) ) Zirconium monochloride monohydride, Bis(cyclopentadienyl)zirconium dichloride, Bis(cyclopentadienyl)zirconium dipromy
Bis(cyclopentadienyl)methylzirconium monochloride, Bis(cyclopentadienyl)ethylzirconium monochloride, Bis(cyclopentadienyl)cyclohexylzirconium monochloride, Bis(cyclopentadienyl)phenylzirconium monochloride , Bis(cyclopentagenyl)benzylzirconium monochloride, Bis(methylcyclobentagenyl)zirconium dichloride, Bis([-butylcyclopentagenyl)zirconium dichloride, Bis(indenyl)zirconium dichloride, Bis(indenyl)zirconium dibromide , bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)zirconium methoxychloride, bis(cyclopentadienyl) ) Zirconium ethoxy chloride, Bis(methylcyclopentadienyl)zirconium ethoxychloride, Bis(cyclopentadienyl)zirconium phenoxychloride, Bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl) Diphenylzirconium, Ethylenebis(indenyl)methylzirconium, Ethylenebis(indenyl)ethylzirconium monochloride, Ethylenebis(indenyl)zirconium dichloride, Isoprobilbisindenylzirconium dichloride, Isoprobyl(cyclopentadienyl)-1-fluore ethylene bis(indenyl) zirconium methoxy monochloride, ethylene bis(indenyl) zirconium ethoxy monochloride, ethylene bis(indenyl) zirconium phenoxy monochloride, ethylene bis(indenyl) zirconium phenoxy monochloride, ethylene bis(indenyl) zirconium dipromide, ethylene bis(indenyl) zirconium methoxy monochloride enyl) zirconium dichloride, propylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(toptylcyclopentadienyl)zirconium dichloride, ethylenebis(4.5,6.7-tetrahydro-l-indenyl)dimethylzirconium, ethylene bis(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 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-methoxyl-indenyl)zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylnonbis(4.7- dimethoxy l-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.

In this case, as the organometallic compound catalyst component [i1, a conventionally known aluminoxane or organoaluminumoxy compound is used. This organoaluminumoxy compound is obtained, for example, by reaction of an organoaluminum compound with water, or by reaction of an aluminoxane dissolved in a hydrocarbon solution with water or an active hydrogen-containing compound.

Such organoaluminumoxy 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] or catalyst components (i) and (i
), catalyst component [A] or catalyst component (i) is usually 0.001 to 0.5 mmol, preferably 0.001 to 0.5 mmol in terms of transition metal, for example, per 11 polymerization volumes.
The organometallic compound catalyst [B] is used in an amount of 0.005 to 0.5 mmol, and the amount of the organometallic compound catalyst [B] is determined based on 1 mole of transition metal atoms of the catalyst component [A] in the polymerization system. The metal atoms of B] are generally used in an amount of 1 to 10,000 mol, preferably 5 to 500 mol. Furthermore, when using the electron donor [C], the electron donor [C] is 100 mol or less, preferably 1 to 50 mol, per 1 mol of the transition metal atom of the catalyst component [A] in the polymerization system. , particularly preferably in amounts of 3 to 20 mol.

The polymerization temperature when performing polymerization using the above catalyst is usually 20 to 200°C, preferably 50 to 100°C, and the pressure is normal pressure to 100 kg/caf, preferably 2 to 100°C.
It is 50 kg/alf.

Further, in the present invention, it is preferable to carry out preliminary polymerization prior to main polymerization. When performing prepolymerization, at least the catalyst component [A] and the organometallic compound catalyst component [B] are used in combination, or the catalyst component (i) and the catalyst component (i) are used in combination. .

(Left below) Polymerization m in prepolymerization is usually l/g of titanium catalyst component when titanium is used as the transition metal.
-2000g, preferably 3-1000g, particularly preferably 10-500g.

Prepolymerization is preferably carried out using an inert hydrocarbon solvent, and such inert hydrocarbon solvents include:
Specifically, propane, butane, l-bentane, i-pentane, n-hexane, i-hexane, n-hebutane,
Aliphatic hydrocarbons such as n-octane, -octane, n-decane, rhododecane, kerosene, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, etc. aromatic hydrocarbons, halogenated hydrocarbon compounds such as methylene chloride, ethyl chloride, ethylene chloride, and chlorobenzene. Among these, aliphatic hydrocarbons are preferred, and aliphatic hydrocarbons having 4 to 10 carbon atoms are particularly preferred. Furthermore, the single compound used in the reaction can also be used as a solvent.

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

In particular, polymer particles containing a large amount of amorphous olefin polymer moiety and having good particle properties, such as polymer particles containing 30% by weight or more of amorphous olefin polymer moiety and having good particle properties. To obtain a prepolymerization of e.g.
A method is proposed in which brobylene and ethylene are copolymerized using a mixed gas consisting of ~98 mol% propylene and 30~2 mol% ethylene.

The polymerization temperature in prepolymerization varies depending on the α-olefin and inert solvent used and cannot be unconditionally defined, but it is generally -40 to 80°C, preferably -2
The temperature is 0 to 40°C, particularly preferably -10 to 30°C. For example, when propylene is used as α-olefin, -40 to 70°C; when 1-butene is used,
-40 to 40°C, -4 when using 4-methyl-1-pentene and/or 3-methyl-1-pentene
It is within the range of 0 to 70°C. Note that hydrogen gas can also be allowed to coexist in the reaction system for this prepolymerization.

After carrying out preliminary polymerization as described above, or without carrying out preliminary polymerization, the above-mentioned single body is then introduced into the reaction system and a polymerization reaction (main polymerization) is carried out 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 -
The temperature is 50 to 200°C, preferably 0 to 150°C. The polymerization pressure is usually normal pressure to 100 kg/d1, preferably normal pressure to 50 kg/cnf, and the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods.

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

The polymer particles thus obtained contain 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 20 to 80% by weight.
, preferably 25 to 70% by weight, more preferably 30% by weight
It is desirable that the content be within the range of 60% by weight, particularly preferably 33% to 55% by weight. In the present invention, the content of such amorphous olefin polymer is determined at 23°C.
It can be determined by measuring the amount of components soluble in n-decane.

Furthermore, the polymer particles used in the present invention have a temperature that is higher than the melting point of the crystalline olefin polymer portion or the glass transition point of the amorphous olefin polymer portion of the polymers constituting the polymer particles. Preferably, the particles are polymer particles that have not been substantially heated above.

In this way, polymer particles that have never been substantially heated to a temperature higher than the melting point of the crystalline olefin polymer portion or the glass transition point of the amorphous olefin polymer portion, whichever is higher, are amorphous. The average particle diameter of the island portion consisting of the polyolefin polymer portion is 0.5 μm or less, preferably 0.1 μm or less, and more preferably 0.00001 to 0.05 μm.

The "amorphous olefin polymer portion" herein refers to a polymer that dissolves in n-decane at 23°C, and specifically refers to a polymer portion that has been solvent-fractionated 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.
The polymer obtained by separating by filtration using a G-4 glass filter after a period of time and removing n-decane from the obtained filtrate is referred to as "amorphous olefin polymer portion".

In the present invention, the above polymer particles and a crosslinking agent are combined into
Intragranular crosslinked thermoplastic elastomers are produced by contacting at a temperature below the higher of the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer.

Such crosslinking agents include organic peroxides, sulfur,
Phenolic vulcanizing agents, oximes, polyamines, etc. are used, and among these, organic peroxides and phenolic vulcanizing agents are preferred from the viewpoint of the physical properties of the thermoplastic elastomer obtained. Particularly preferred are organic peroxides.

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

In addition, specific examples of organic peroxides include dicumyl peroxide, di-1ct+-butyl peroxide,
2.5-dimethyl-2.5-bis(ic rt-butylperoxy)hexane, 2.5-dimethyl-25-bis(l e r I-butylperoxy)hexane-3
, 1.3-bis(je t +-butylperoxyisopropyl)benzene, 1.1-bis(l cr t
-butylperoxy) -3.3.5- trimethylcyclohexane, n-butyl-4,4-bis(tel-butylperoxy)valerate, dibenzoyl peroxide, 'jetj-butylperoxybenzoate, and the like are used. Among these, dibenzoyl peroxide is selected from the viewpoints of crosslinking reaction time, odor, and scorch stability. 3-
Bis(+erj-butylperoxyisobrobyl)benzene is preferred.

Further, in order to achieve a uniform and moderate crosslinking reaction, it is preferable to include a crosslinking aid. Specific examples of crosslinking aids include sulfur, p-quinonedioxime, p,1-dibenzoylquinonedioxime, N-methyl-N,4-dinitrosoaniline, nitrobenzene, diphenylguanidine, and trimethylolpropane. -N,N'-ta-phenylene dimaleimide and other peroxy crosslinking coagents, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,
Polyfunctional methacrylate monomers such as allyl methacrylate, polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate, and the like are used. By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is easy to handle, has good compatibility with polymer particles, has an organic peroxide solubilizing effect, and also works as a dispersion aid for peroxide, so that the crosslinking reaction is carried out homogeneously. ,
This is most preferable because a thermoplastic elastomer with well-balanced fluidity and physical properties can be obtained.

In the present invention, such a crosslinking aid is used in an amount of 0.1 to 2 parts by weight, particularly 0.3 parts by weight, based on 100 parts by weight of the polymer particles.
It is used in an amount of ~1 part by weight, and by blending within this range, a thermoplastic elastomer that has excellent fluidity and whose physical properties do not change due to the thermal history during processing and molding of the thermoplastic elastomer can be obtained.

In the present invention, when producing a thermoplastic elastomer, the crosslinking reaction of the polymer particles can also be carried out in the presence of a mineral oil softener in addition to the polymer particles, crosslinking agent and crosslinking aid.

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 plaque, 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.

Such a mineral oil-based softener is used in an amount of 1 to 100 parts by weight, preferably 3 to 90 parts by weight, and more preferably 3 to 90 parts by weight, based on 100 parts by weight of the polymer particles, in order to further improve the flow characteristics, that is, the moldability of the thermoplastic elastomer. It is preferably blended in an amount of 5 to 80 parts by weight.

Further, in the present invention, it is also possible to use a crosslinking agent, and if necessary, a crosslinking aid and a mineral oil softener diluted in a swelling solvent. The swelling solvent dilutes the cross-linking agent and, if necessary, the cross-linking co-agent, to aid in their dispersion on the surface of the polymer particles, and also swells the polymer particles, at which time the cross-linking agent and cross-linking co-agent are incorporated into the polymer particles. Since it has the function of transporting the agent, the use of a swelling solvent allows the crosslinking reaction to occur uniformly even inside 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 the crosslinking reaction near the surface of the polymer particles. In any case, the type of swelling solvent selected for the reaction depends on the type of polymer particles used. Of course, the crosslinking reaction is possible without using any swelling solvent.

Specifically, such swelling solvents include benzene,
Aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene; Chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, dichloroethylene, trichlorethylene and other chlorinated hydrocarbon solvents, methanol, ethanol, n-propanol, iso-propanol, n
Alcohol solvents such as -butanol, lee-butanol, and terl-butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; dimethyl ether, diethyl ether, and di-n-amyl ether. , ether solvents such as tetrahydrofuran, dioxane, anisole, etc. are used.

Such a swelling solvent is desirably used in an amount of 1 to 100 parts by weight, preferably 5 to 60 parts by weight, and more preferably 10 to 40 parts by weight, based on 100 parts by weight of the polymer particles.

When the swelling solvent mentioned above 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 the crosslinking agent and crosslinking coagent are dissolved. It plays a role in making it easier to penetrate into the particles.

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

Furthermore, in the present invention, a crosslinking reaction of the polymer particles can be carried out by bringing the polymer particles, a radical initiator, and a graft modifier into contact with each other. At this time, a crosslinking agent other than the radical initiator may also be present.

Such graft modifiers include glycidyl group-containing ethylenically unsaturated compounds, carboxyl group-containing ethylenically unsaturated compounds, acid anhydrides of these compounds and their derivatives, hydroxyl group-containing ethylenically unsaturated compounds, and amino group-containing ethylenically unsaturated compounds. Mention may be made of unsaturated compounds.

Examples of glycidyl group-containing ethylenically unsaturated compounds include (meth)acrylic acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glucidyl ether, vinyl glucidyl ether, maleic acid diglycidyl ester, and methyl maleate. Glycidyl ester, isopropyl maleate glycidyl ester, 1-butyl glycidyl maleate, diglycidyl fumarate, methyl diglycidyl fumarate, isopropyl fricidyl fumarate, diglycidyl itaconate, methyl di-itaconate Glycidyl esters of conjugated unsaturated dicarboxylic acids such as glycidyl ester, isopropyl itaconate glycidyl ester, 2-methyleneglutarate diglycidyl ester, 2-methylenegluconic acid methylglycidyl ester, butenedicarboxylic acid monoglycidyl ester, 3.4-epoxy Butene, 3,4-epoxy-3-methyl=1-butene, vinylcyclohexene monoxide,
Glycidyl compounds such as p-glycidylstyrene are used.

Specifically, carboxyl group-containing ethylenically unsaturated compounds, acid anhydrides of these compounds, and derivatives thereof include:
Acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, nadic acid Acid anhydrides and derivatives thereof, such as acid halides, amides, imides, esters, etc., are used. Specifically, maleyl chloride, malenylimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, etc. are used. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.

Specifically, the hydroxyl group-containing ethylenically unsaturated compounds include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-3-
7-enoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, tetramethylol ethane (Meth)acrylic esters such as mono(meth)acrylate, butanediol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and 2-(6-hydroxyhexanoyloxy)ethyl acrylate are used.

In addition to the above (meth)acrylic acid ester, 10
-undecen-1-ol, l-octen-3-ol, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2-(
meta) acroyloxyethyl acid phosphate,
Glycerin monoallyl, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol,
Glycerin monoalcohol and the like can also be used.

Further, 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 examples of such a compound include an amino group or a substituted compound represented by the following formula. Bi having at least one type of amino group. However, in the above formula, Rl represents any atom or group among a hydrogen atom, a methyl group, and an ethyl group, and R2 represents a hydrogen atom, a carbon number of 1 to 12,
Preferably an alkyl group having 1 to 8 carbon atoms, 6 to 12 carbon atoms
, preferably any atom or group of a cycloalkyl group having 6 to 8 carbon atoms.

Note that the above alkyl group and cycloalkyl group may further have a substituent.

Specifically, such amino group-containing ethylenically unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, phenylaminoethyl methacrylate, and cyclomethacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as hexylaminoethyl and methacryloyloxyethyl acid phosphate monomethanol amino halfsol, N-
Vinylamine derivatives such as vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methallylamine, N-methylacrylamine, N,ll-dimethylacrylamide and N,N-dimethylaminopropylacrylamide, acrylamide and N - Acrylamide derivatives such as methylacrylamide and aminostyrenes such as p-aminostyrene are used. These compounds are
Can be used alone or in combination.

Among these, acrylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, etc. are preferred.

The above polar group-containing ethylenically unsaturated compounds can be used alone or in combination of two or more.

The polar group-containing ethylenically unsaturated compound as described above is usually used in an amount of 0.01 to 50 parts by weight per 100 parts by weight of the polymer particles.
It is used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 40 parts by weight.

In addition, when using polar group-containing ethylenically unsaturated compounds (modifiers) in combination, a plurality of polar group-containing ethylenically unsaturated compounds can be used in any ratio.

When using such a graft modifier, it is necessary to carry out the crosslinking reaction in the presence of a radical initiator,
The amount of the radical initiator is 0.0% per 100 parts by weight of the polymer particles.
It is desirable to use it in an amount of 0.02 parts by weight or more, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.

As the radical initiator, for example, organic peroxides such as those mentioned above are used. Moreover, such radical initiators can be used alone or in combination.

Furthermore, in addition to the graft modifier and the radical initiator, crosslinking agents other than the radical initiator, such as sulfur and phenolic vulcanizing agents, can also be 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. Generally, the above reaction is carried out at a temperature within a range 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 polymer having a high melting point is polypropylene, high density polyethylene, or low density polyethylene, the upper limit of the reaction temperature is about 150°C, about 120°C, and about 90°C, respectively.

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

In the present invention, it is most preferable to carry out a crosslinking reaction by simultaneously bringing the polymer particles into contact with the crosslinking agent and, if necessary, a crosslinking aid and a mineral oil softener. The crosslinking reaction can also be carried out by bringing the agent, crosslinking aid, and mineral oil softener into contact with each other separately.

Furthermore, the polymer particles are brought into contact with the graft modifier, the radical initiator, and, if necessary, a crosslinking agent, a crosslinking aid, and a mineral oil softener at the same time to crosslink and graft modify the polymer particles. However, the crosslinking reaction and the graft modification reaction can also be carried out by separately contacting the polymer particles and the graft modifier with a radical initiator, a crosslinking agent, a crosslinking aid, and a mineral oil softener. ．． 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 portion) is fixed within the particles at the molecular segment level.

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

In addition, in polyolefin particles made of intraparticle crosslinked thermoplastic elastomer, the insoluble gel content that is not extracted by cyclohexane, measured as follows, is 10% by weight or more, preferably 40 to 100% by weight, more preferably is preferably 60 to 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+nIllX1mmX0.
5) Weigh out approximately 100 cm and place it in an airtight container.
After 48 hours of immersion in cc of cyclohexane at 23°C, the sample is taken out and dried. If the thermoplastic elastomer contains cyclohexane-insoluble fillers, pigments, etc., the weight of the cyclohexane-insoluble fillers, pigments, etc. other than the polymer components is subtracted from the weight of this dry residue after drying. The corrected final weight (Y) of On the other hand, the weight of the sample pellet indicates that there are cyclohexane-soluble or cyclohexane-soluble components other than the ethylene/α-olefin copolymer, 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 initial weight (X) A preferable group of polyolefin particles made of a thermoplastic elastomer produced as described above has an average particle diameter of 1
00-5000μm1 preferably 200-4000μm
1, more preferably in the range of 300 to 3000 μm. Moreover, the polyolefin particle group according to the present invention has a geometric standard deviation indicating the particle size distribution of the particles of 1.0 to 3.0, preferably 1.0 to 3.0, more preferably 1.0 to 1.0 to 2.0.
5 more preferably 1.0 to l. It is within the range of 3.

Further, the polyolefin particle group according to the present invention has an apparent bulk specific gravity of 0.25 to 0.70, preferably 0.30 to 0.6.
0, more preferably within the range of 0.35 to 0.50. Further, the polyolefin particle group according to the present invention has a particle aspect ratio of 1.0 to 3.0, preferably 1.0 to 2.0.
0, more preferably within the range of 1.0 to 1.5. Moreover, the polyolefin particle group according to the present invention has a particle size of 10
Fine particles m of 0 μm or less are 20% by weight or less, preferably 0
It is within the range of ~10% by weight, more preferably ~2% by weight.

Further, a stabilizer may be added to the polymer particles used in the present invention or the thermoplastic elastomer produced in the present invention. As such stabilizers, specifically, phenol stabilizers, phosphorus stabilizers, sulfur stabilizers, hindered amine stabilizers, higher fatty acid stabilizers, etc. are used.

The stabilizer as described above is desirably used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the polymer particles.

The thermoplastic elastomer produced by the present invention also contains fillers such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder,
Asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass bulbs, shirasu balloons, carbon fibers, or colorants such as carbon plaque, titanium oxide, zinc white, red iron oxide, Ultramarine blue, navy blue, azo dyeing, nitroso dye, lake pigment, lid cyanine pigment, etc. can also be blended.

Effects of the Invention According to the present invention, since the crosslinking reaction of the polymer particles is carried out at a low temperature, thermal decomposition of the polymer particles can be suppressed.
A thermoplastic elastomer that can provide molded products with excellent physical strength properties such as impact strength and tensile strength, toughness, heat resistance, flexibility at low temperatures, surface smoothness, and paintability can be obtained at a low manufacturing cost.

In particular, amorphous olefin polymerization a at the molecular segment level
A thermoplastic elastomer in which S (rubber component) is fixed within the particles can provide a shaped article with better flexibility at low temperatures, surface smoothness, and paintability.

The thermoplastic elastomer obtained according to the present invention can be shaped using molding equipment commonly used for thermoplastic polymers, and is suitable for extrusion molding, calendar molding, and especially injection molding.

Such thermoplastic elastomers are used in body panels, bumper parts, side shields, automotive 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. Leisure goods such as bat grips, swimming fins, underwater glasses, waterproof sheets, water-stopping materials, joint materials, construction window frames, construction gaskets, decorative rigid wood covering materials, and other civil engineering and construction materials parts, gaskets, Used for waterproof cloth, garden hoses, belts, etc.

[Examples] The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

[Adjustment of catalyst component [A]] A high-speed stirring device (manufactured by Tokushu Kika Kogyo) with an internal volume of 2 liters was heated to sufficient N.
After 2 substitutions, 700 ml of refined kerosene, commercially available Mg CI
2 Log, 24.2 g of ethanol and 3 g of the trade name Mazol 320 (manufactured by Kao Atlas ■, sorbitan distearate) were added, and the system was heated to 120° C. with stirring.
Stirred for 30 minutes at 0 0 +pm. Under high-speed stirring, using a Teflon tube with an inner diameter of -10
The liquid was transferred to a 2-liter glass flask (equipped with a stirrer) filled with 1 liter of refined kerosene cooled to .degree. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

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 system was heated to 120°C. After stirring and mixing at 120° C. for 2 hours, the solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and 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 proportions 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 in terms of atoms. The average particle size is 64 μm, and the geometric standard deviation (δ) of the particle size distribution is 1.
．． A true spherical catalyst of No. 5 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 a certain amount of the above T1 catalyst [A] were added to 200 ml of purified hexane in terms of titanium atoms. After charging the Ti catalyst component [. A]
2.8 g of propylene was polymerized per Ig. After the prepolymerization, the liquid part was removed by filtration, and the separated solid part was resuspended in decane.

[Polymerization] Production of copolymer (I) 2.0 kg of propylene and 11N liter of hydrogen were added to the polymerization vessel of 17I at room temperature, and the temperature was raised to 50°C. 15 mmol of triethylaluminum and 1.5 mmol of cyclohexylmethyldimethoxysilane were added. 0.05 mmol of the prepolymerized product of the catalyst component [A] was added in terms of titanium atoms, and the temperature inside the polymerization vessel was maintained at 70°C. After reaching 70℃ 3
After 0 minutes, 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. That is, ethylene was supplied to the polymerization reactor at a rate of 480 Nl/hr, propylene at 720 Nl/hr, and hydrogen at a rate of 12 Nl/hr. The pressure inside the polymerization vessel is 10kg/cut
・Adjusted the vent opening of the polymerization vessel so that the temperature was G. The temperature during copolymerization was kept at 70°C. After 120 minutes of copolymerization time, the resulting polymer was depressurized and weighed 2.6 kg.
The MI was 2.5 g/10 min at 30° C. under a 2-glare load, the ethylene content was 29 mol%, and the apparent bulk specific gravity was 0.45.

Further, the amount of components soluble in n-decane at 23° C. was 36% by weight, and the content of ethylene in the soluble components was 44% by mole.

The above copolymer (I) powder has an average particle diameter of 2100
μm, the particles passing through 150 mesh were 0.2% by weight, and the falling time was 13.2 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.4.

Preparation of copolymer (n) 2.0 kg of propylene and 19 N liters of hydrogen were added to a polymerization vessel 17A' at room temperature, and the temperature was raised to 50°C. 15 mmol of triethylaluminum, 1.5 mmol of cyclohexylmethyldimethoxysilane, 0.05 mmol of the prepolymerized product of the catalyst component [A] was added in terms of titanium atoms, and the temperature inside the polymerization vessel was maintained at 70°C. Thirty minutes after the temperature reached 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. That is, 480 NI of ethylene! /h, propylene was fed to the polymerization reactor at a rate of 720 NA'/h, and hydrogen at a rate of 12 Nl/h. The pressure inside the polymerization vessel is 10kg/a
The vent opening of the polymerization reactor was adjusted so that the temperature was l●G. The temperature during copolymerization was kept at 70°C. After copolymerization time of 150 minutes, the resulting polymer weighed 2.5 kg,
MI = 3, 9 g/1 under 230℃ and 2 hearing loads
0 minutes, ethylene content 28 mol%, apparent bulk specific gravity 0.47
Met.

In addition, the amount of n-decane soluble components at 23°C was 28% by weight,
The ethylene content in the soluble fraction was 47 mol%.

The powder of the above copolymer (If) has an average particle diameter of 220
0 μm, and particles passing through 150 mesh are 0.1
% by weight, and the falling time was 8.5 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.5.

Examples 1 to 3 1 equipped with a stirring blade having a helical double ribbon
A 5J stainless steel autoclave was charged with 3 kg of the polymer particles obtained as described above, and the inside of the system was completely replaced with nitrogen. Thereafter, a crosslinking mixture having a compounding ratio as shown in Table 1 was added dropwise to the polymer particles at room temperature for 10 minutes while stirring the polymer particles, and the mixture was further stirred for 30 minutes. was impregnated with the reagent. Then, the temperature in the system was set to 100°C, and the reaction was carried out for 4 hours. After the reaction, the temperature inside the system was lowered to 80° C. and dried under reduced pressure.

MFR of the obtained thermoplastic elastomer. The gel fraction was measured, and the obtained thermoplastic elastomer particles were injection molded as described below, and the injection molded appearance and sheet properties were evaluated.

First, thermoplastic elastomer particles were injection-molded using the equipment and conditions described below to produce a 3 mm thick square plate, and test pieces were cut from the obtained square plate to determine bow tensile properties, initial bending modulus, and Izod. Impact strength was measured.

Molding conditions Molding machine: Dynamelter (manufactured by Meiki Seisakusho) Molding temperature: 2
00℃ Injection pressure: Primary pressure 1300 kg/car Secondary pressure 700 kg/cnr Injection pressure: Maximum molding speed = 90 seconds/l Cycle gate: Direct gate (land length 10to, width 101l!II11 depth 3m
) Physical property evaluation tensile properties: Tensile strength at break (Tb, kg/ad) JIS
Measured according to K-6301.

Initial bending modulus (FM, kg/rrf) ASTM
Measured according to D790.

Izod impact strength (IZOD kg-cm/cm)
Measured according to ASTM D 256.

(With notch) Heat resistance was evaluated as heat sag at 100°C. Note that heat sag was measured as follows.

That is, a test piece with a length of 120cm, a width of 20cm, and a thickness of 3+cm was fixed at 20m from the end with a clip.
After aging at 100° C. for 1 hour, heat resistance (heat sag) was evaluated by measuring how much the other end sagged from the fixed side.

The results are shown in Table 1.

Comparative Example 1 Mooney viscosity ML (IOG'c) is 10,
1+4 EPDM with an ethylene content of 75 mol% and an ethylidene norbornene content with an iodine number of 10 39
Weight part and MFR (230℃, 2.16kg) are 7
After kneading 55 parts by weight of homopolypropylene having a g/:LO content and 6 parts by weight of paraffin-based process oil using a Banbury mixer, the mixture was formed into a sheet using a mouth hole, and pellets were made using a square pelletizer.

To 100 parts by weight of this pellet, 0.00% of di-1-butylperoxydiisopropylbenzene {4 parts by weight and 0.21 parts by weight of divinylbenzene were blended using a Henschel mixer, and then dynamically crosslinked using an extruder at an extrusion temperature of 250°C to create a thermoplastic elastomer.

This thermoplastic elastomer was evaluated in the same manner as in the examples.

The results are shown in Table 1.

Table 1 BPD: Benzoyl peroxide DVB: Divinylbenzene Example 4 [Polymerization Production of copolymer particles (m) 2.5 kg of propylene and 9N liter of hydrogen were added to a 17-liter polymerization vessel at room temperature, and then the temperature was raised. At 50°C, 15 mmol of triethylaluminum, 1.5 mmol of diphenyldimethoxysilane, the catalyst component [A
] was added in an amount of 0.05 mmol in terms of titanium atoms, and the temperature inside the polymerization vessel was maintained at 70°C. Ten minutes after the temperature reached 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. That is, 480 Nll of ethylene
At the same time, propylene was supplied to the polymerization reactor at a rate of 120 N/hr and hydrogen at a rate of 12 N/hr.

The opening degree of the vent of the polymerization vessel was adjusted so that the pressure inside the polymerization vessel was 10 kg/cnf-G. Temperature during copolymerization is 70℃
I kept it. After copolymerization time of 85 minutes, the resulting polymer was depressurized and weighed 3.1 kg, MI at 230°C under 2 kg load = 3.9 g/10 min, and ethylene content was 28 mol%.
, and the apparent bulk specific gravity was 0.39. The content of the 23 DEG Cn-decane soluble component was 37% by weight, and the ethylene content in the soluble component was 49% by mole.

The average particle diameter of the obtained polymer was 1.9 mm, the geometric standard deviation was 1.3, and the content of fine particles of 100 μm or less contained in this polymer was 0.0% by weight. The number of seconds was 13.1 seconds.

Next, 3 kg of the copolymer particles (III) obtained as described above are charged into a 15 g stainless steel autoclave equipped with a stirring blade having a helical double ribbon, and the inside of the system is completely replaced with nitrogen. Thereafter, a mixture solution having the compounding ratio shown in Table 2 was added to the polymer particles at room temperature for 1 hour while stirring the polymer particles.
The reagents were added dropwise for 0 minutes and stirred for an additional 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. ．． Add 5 kg, 8
After stirring at 0° C. for 1 hour, 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. Further, the obtained thermoplastic elastomer was injection molded in the same manner as in Example 1, and the injection molded appearance and sheet properties were evaluated.

Table 2 shows the physical properties.

Table 2 * Elongation % Example 5 1 equipped with a stirring blade having a helical double ribbon
3 kg of polymer particles (III) obtained in the same manner as in Example 4 was charged into a 5 liter stainless steel autoclave.
Completely replace the system with nitrogen. Thereafter, while stirring the polymer particles, a mixed solution having the compounding ratio shown in Table 3 was added at room temperature for 10 minutes.
The reagents are added dropwise for 30 minutes and stirred for an additional 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, lower the temperature in the system to 80°C, add 7.5 kg of acetone, and lower the temperature to 80°C.
After stirring for 1 hour, 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 3 shows the physical properties.

Table 3 Example 6 1 equipped with a stirring blade having a helical double ribbon
A 5L stainless steel autoclave was charged with 3 kg of polymer particles (I [[) obtained in the same manner as in Example 4,
Completely replace the system with nitrogen.

Thereafter, a mixed solution having the compounding ratio shown in Table 4 is added dropwise to the polymer particles over 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 4 shows the physical properties.

Table 4 Example 7 L equipped with a stirring blade having a helical double ribbon
3 kg of polymer particles (II[) obtained in the same manner as in Example 4 were charged into a 5 L stainless steel autoclave,
Completely replace the system with nitrogen. Thereafter, while stirring the polymer particles, a mixed solution having the compounding ratio shown in Table 5 was added at room temperature for 10 min.
The reagents are added dropwise for 30 minutes and stirred for an additional 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, lower the temperature in the system to 80°C, add 7.5 kg of acetone, and lower the temperature to 80°C.
After stirring for 1 hour, 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.

Table 5 shows the physical properties.

Table 5 Example 8 1 equipped with a stirring blade having a helical double ribbon
A 5-liter stainless steel autoclave is charged with 3 kg of polymer particles (III) obtained in the same manner as in Example 4, and the inside of the system is completely replaced with nitrogen. Thereafter, a mixture of 8 g of dibenzoyl peroxide, 1 lg of divinylbenzene, and 400 g of toluene as shown in Table 6 was added dropwise to the polymer particles over 10 minutes at room temperature while stirring, and then
Stir for a minute 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, 7.5 kg of acetone was added, and the mixture was stirred at 80°C for 1 hour.
The polymer is extracted and filtered, washed three times with 9 kg of acetone, and then dried under reduced pressure.

The MFR1 gel fraction of the obtained thermoplastic elastomer is measured. In addition, the obtained thermoplastic elastomer is injection molded, and the injection molded appearance and sheet properties are evaluated.

Table 6 shows the physical properties.

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, at the melting point of the crystalline olefin polymer or the amorphous olefin polymer. A method for producing a thermoplastic elastomer, which comprises contacting at a temperature lower than the higher of the glass transition points of the elastomer to obtain an intragranular crosslinked thermoplastic elastomer. 2. Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a crosslinking agent, and a crosslinking aid are added to the melting point of the crystalline olefin polymer or the glass of the amorphous olefin polymer. 1. A method for producing a thermoplastic elastomer, which comprises contacting at a temperature lower than the higher of the transition points to obtain an intraparticle crosslinked thermoplastic elastomer. 3. Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a crosslinking agent, and a mineral oil softener are added to the melting point of the crystalline olefin polymer or the amorphous olefin polymer. 1. A method for producing a thermoplastic elastomer, which comprises contacting at a temperature lower than the higher of the glass transition points of to obtain an intragranular crosslinked thermoplastic elastomer. 4. Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a crosslinking agent, and a swelling solvent are mixed at the melting point of the crystalline olefin polymer or the glass transition temperature of the amorphous olefin polymer. A method for producing a thermoplastic elastomer, which comprises contacting the points at a temperature lower than the higher of the points to obtain an intraparticle crosslinked thermoplastic elastomer. 5. Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a radical initiator, and a graft modifier are added to the melting point of the crystalline olefin polymer or the temperature of the amorphous olefin polymer. 1. A method for producing a thermoplastic elastomer, which comprises contacting the thermoplastic elastomer at a temperature lower than the higher of the glass transition points to obtain a thermoplastic elastomer crosslinked and graft-modified within the particles. 6. Polymer particles are crystalline olefin polymer portion 80-2
6. The method according to claim 1, comprising: 0 part by weight and 20 to 80 parts by weight of the amorphous olefin polymer. 7. The method according to any one of claims 1 to 5, wherein the crystalline olefin polymer portion consists of a crystalline propylene polymer. 8. The method according to any one of claims 1 to 5, wherein the amorphous olefin polymer portion comprises an ethylene/α-olefin copolymer. 9. The method according to any one of claims 1 to 5, wherein the average particle diameter of the polymer particles is 10 to 5000 μm. 10. The method according to any one of claims 1 to 5, wherein the polymer particles have a geometric standard deviation of 1.0 to 3.0. 11. Apparent density of polymer particles is 0.2 to 0.7 g/m
6. The method according to any one of claims 1 to 5, wherein 12. Apparent density of polymer particles is 0.3 to 0.7 g/m
6. The method according to any one of claims 1 to 5, wherein 13. The crosslinking agent is added in an amount of 0.0% per 100 parts by weight of the polymer particles.
6. A method according to any one of claims 1 to 5, used in an amount of 0.01 to 2 parts by weight. 14. The crosslinking aid is 0 parts by weight per 100 parts by weight of the polymer particles.
．． 3. A method according to claim 2, which is used in an amount of 1 to 2 parts by weight. 15. The method according to claim 3, wherein the mineral oil softener is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the polymer particles. 16. The swelling solvent is 1 part by weight per 100 parts by weight of the polymer particles.
5. A method according to claim 4, used in an amount of ~100 parts by weight. 17. Claim 5, wherein the graft modifier is used in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the polymer particles.
The method described in section. 18. A plurality of granular polyolefins consisting of an intraparticle crosslinked thermoplastic elastomer consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, and whose main component is an α-olefin having 3 or more carbon atoms. Particles having an average particle diameter of 100 to 5000 μm, a geometric standard deviation of 1.0 to 2.0, and an apparent bulk specific gravity of 0.25.
~ 0.70, and the particle aspect ratio is 1.0 to 3.0
The amount of fine particles with a particle size of 100 μm or less is 20% by weight.
A group of polyolefin particles made of a thermoplastic elastomer having the following amount and having a cyclohexane-insoluble gel content of 10% by weight or more. 19. Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part, a radical initiator, and a graft modifier are combined with a crosslinking agent, a crosslinking aid, a swelling solvent, and a mineral oil softener. In the presence of at least one member selected from the group consisting of A method for producing a thermoplastic elastomer cross-linked and graft-modified with.