JPH0425520A - Production of thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To obtain in good efficiency a thermoplastic elastomer which has excellent elasticity, even at a low rubber content, and high strengths by dynamically heat-treating polymer particles each comprising a crystalline olefin polymer part and an amorphous olefin polymer part, a flexible polymer and a crosslinking agent. CONSTITUTION:A thermoplastic elastomer is produced by dynamically heat- treating polymer particles each comprising a crystalline olefin polymer part and an amorphous olefin polymer part and having a means particle diameter of 10mum or above and an apparent bulk density of 0.2g/ml or above, a flexible polymer (e.g. ethylene/alpha-olefin copolymer rubber or a hydrogenated styrene/ conjugated diene block copolymer) and a crosslinking agent (e.g. organic peroxide). According to the above process, a thermoplastic elastomer which has excellent moldability and can give a molding which has excellent elasticity, even at a low rubber content, high strengths, uniformity and excellent impact strengths, tensile strength, toughness, heat resistance, low-temperature flexibility, surface smoothness, surface gloss, coatability, etc., can be obtained at a low cost.

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 method for producing a thermoplastic elastomer that has excellent elasticity and high strength even with a small rubber content. The present invention relates to a method for producing a thermoplastic elastomer that can be efficiently obtained. The present invention also relates to a method for producing a thermoplastic elastomer that has excellent moldability, heat resistance, tensile strength, weather resistance flexibility, elasticity, and impact resistance at low temperatures, as well as surface smoothness, surface gloss, 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 used for injection molding, For example, Japanese Patent Publication No. 53-34210 discloses that 60 to 80 parts by weight of a monoolefin copolymer can be formed by extrusion molding into a molded product with excellent heat resistance, tensile properties, weather resistance, flexibility, and elasticity. A thermoplastic elastomer is disclosed in which a composite rubber and 40 to 20 parts by weight of a polyolefin plastic are dynamically partially cured. In addition, in Japanese Patent Publication No. 53-2102, (
A thermoplastic elastomer comprising a) a partially crosslinked copolymer rubber comprising ethylene-propylene-nonconjugated polyene copolymer rubber and having a gel content of 30 to 90% by weight, and (b) a polyolefin resin is disclosed. . Furthermore, Japanese Patent Publication No. 55-18448 discloses a thermoplastic elastomer in which an ethylene-propylene copolymer rubber and a polyolefin resin are dynamically partially or completely crosslinked.

By the way, JP-A-58-187412 discloses a propylene homopolymer block and a binary random copolymer block of propylene and ethylene or an α-olefin of 04 to CI2 with a propylene content of 100%.
50 to 70 parts by weight of one or more of the blocks [A] of ~60% by weight, and an ethylene content of 30 to 85% by weight
It is derived from an olefinic block copolymer containing 30 to 50 parts by weight of one or more of two or more binary random copolymer blocks [B] of ethylene and propylene, and has a specific content of thermally xylene-insoluble components. A crosslinked block copolymer is disclosed that is characterized by having a certain fluidity.

Also, JP-A-63-165414, JP-A-6316
No. 5115, JP-A No. 63-161516, and U.S. Pat. No. 4,454.3H disclose that propylene homopolymer blocks [A and An olefinic block copolymer consisting of a binary random copolymer block [B] and a propylene/ethylene binary random copolymer block [C] was 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 by kneading and crosslinking at the following temperature.

Furthermore, JP-A No. 411-2173 discloses a copolymer portion consisting mainly of ethylene and 70 wt. % or less of other α-olefins, and a polymer portion consisting of 97 to 70 wt. % mainly composed of propylene. An organic peroxide is mixed with a block copolymer consisting of 180 to 270% by weight.
A method for improving the processability of a block copolymer is disclosed, which is characterized by heat treatment at .degree.

Furthermore, JP-A-52-37953 discloses (A) 40 to 90 parts by weight of monoolefin copolymer rubber and 60 to 10 parts by weight of (El crystalline polypropylene and/or crystalline ethylene/propylene block copolymer). After fully blending the above crystalline resin (B) in a kneader,
The above monoolefin copolymer rubber (A
) A method for producing a thermoplastic elastomer having excellent rubber elasticity is disclosed, which is characterized in that a crosslinking agent is added to the extent that the mixture is partially cured, and kneading is continued to allow the crosslinking agent to act.

The present inventors have studied how to economically produce a thermoplastic elastomer with excellent quality, and have found that if polymer particles with a specific morphology and a specific soft polymer are used, even with a small rubber content. It has excellent elasticity and strength, and when molded into a molded product, it has an excellent appearance, especially after painting, and has excellent surface gloss. The present invention was completed by discovering a method by which a plastic elastomer can be obtained.

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 with excellent moldability, which can give molded products with excellent smoothness, paintability, surface gloss, and economic efficiency.

Summary of the Invention A first method for producing a thermoplastic elastomer according to the present invention consists of a crystalline olefin polymer part and an amorphous olefin polymer part, has an average particle diameter of 10 μm or more, and is bulky in appearance. It is characterized by dynamically heat-treating polymer particles having a density of 0.2 g/ml or more, a soft polymer, and a crosslinking agent.

A second method for producing a thermoplastic elastomer according to the present invention comprises a crystalline olefin polymer portion and an amorphous olefin polymer portion, the average particle size is 10 μm or more, and the apparent bulk density is 0. It is characterized by dynamically heat-treating polymer particles having a concentration of .2 g/ml or more, a soft polymer, and a crosslinking agent in the presence of a crosslinking aid and/or a mineral oil softener.

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 10μ
m or more, preferably 10 to 8000 μm1, more preferably 100 to 400 μm1, particularly preferably 300 to 3
It is within the range of 000 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 3.01, preferably 1.0 to 2.0, more preferably 1.0 to 1.5, Particularly preferably 1.0 to 1. It is within the range of 3. Further, the apparent bulk density of the polymer particles used in the present invention due to natural fall is 0. 2g/ml or more, preferably 0,
2-0, 7 g/ml.

More preferably 0.3 to 0-7 g/ml, particularly preferably 0. 35-0. 60 g/ml (7) within range 1
．． − Do.

Further, in the polymer particles used in the present invention, the amount of particles passing through a 150-mesh sieve is preferably 30% by weight or less, more preferably 10% by weight or less, particularly preferably 2% by weight or less. Further, such polymer particles have a fall time defined as below in seconds of 5 to 25 seconds, preferably 5 to 20 seconds, 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 Instruments stainless steel sieve with a diameter of 200 mm and a depth of 45 mm (7 types of sieves with openings of 7.10, 14.20, 42.80, and 150 mesh in this order). After processing the top tier of the plate (the tray is stacked on the bottom tier) and removing the lid, I
IIIA 5IEVESHAKER (Iida Seisakusho)
and shaken for 20 minutes. After shaking for 20 minutes, the polymer weight on each sieve was measured and the measured values were plotted on logarithm paper. Connect the plots with a curve,
Based on this curve, the particle diameter (D5o) at a cumulative weight of 50% was determined, and this value was taken as the average particle diameter.

On the other hand, the geometric standard deviation was similarly determined from the particle diameter (D, 6) of 16% by weight, which was integrated from the small particle diameter, and the value of D5o above.

(Geometric standard deviation - DsO/D+6) Apparent bulk density: Measured in accordance with Its K 6721-1977. (However, the inner diameter of the entrance of the funnel used was 92.9
mmφ, and the outlet inner diameter was 9.5 m+nφ. ) Using the device that measures falling seconds and bulk density as is, drop the sample into the receiver, scrape the raised sample from the receiver with a glass rod, and insert the damper again into the 100 ml container. After transferring the sample to the funnel, the damper was pulled, and the time (seconds) required for the entire sample to fall from the bottom of the funnel was defined as the falling number of seconds.

However, when measuring the number of seconds of falling, polymer particles were used in which particles 1.5 to 1.6 times the average particle diameter of the sample were removed using a sieve.

In addition, when measuring the falling seconds, use a powder tester (Hosokawa Micro Co., Ltd. Type PT-D, 5ERNo.
71190) on a vibration table, and the vibration width of the vibration plate is 1 m.
The voltage of the rheostat was adjusted so that the voltage was m, and the polymer particles were allowed to fall while being vibrated.

As mentioned above, the polymer particles used in the present invention are composed of a crystalline olefin polymer part and an amorphous olefin polymer part, and in many cases have a so-called sea-island structure. The part forms a high part in the polymer particle. The average particle diameter of the high portion consisting of the amorphous olefin polymer portion (including a part of the crystalline olefin polymer portion as the case may be) is 0.5 μm or less, preferably 0.1 μm or less, and more preferably 0.5 μm or less. 00001~0
．． It is desirable that the thickness is 0.05 μm. In addition, there are cases where a compatible structure is formed in which it is difficult to distinguish between high and sea areas.

Note that the average particle diameter of the high portion of the polymer particles consisting of the amorphous olefin polymer portion is measured as follows.

Using an ultramicrotome, the polymer particles were
Thinly slice at -140℃ to a thickness of 1,000 people. then 0.5
The thinly sliced sample is placed in the gas phase in a sealed container of about II containing 200 ml of an aqueous solution of 200% RuO4 for 30 minutes to stain the amorphous olefin polymer portion in the sample. Next, after reinforcing the dyed sample with carbon, it is observed using a transmission microscope, and the particle size at the top of at least 50 particles is determined, and the average value thereof is taken as the average particle size at the top.

As the polymer particles used in the present invention, it is preferable to use particles having the above-mentioned characteristics, and there are no particular limitations on the method for producing particles having such characteristics, but the method described below may be used. It is preferable to manufacture the polymer particles by adopting this method, and the transition metal content in the ash of the polymer particles is usually 100 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less.
pm or less, the halogen content is usually 300 ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm
It is contained in a proportion of less than m.

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-1,3-methylbutene-1, hexene-1,3-methylpentene-1,4-methylpentene-1, 1,33 dimethylbutene-j1 heptene-1, methylhexene-11
Dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene for ethylhexene, methylethylpentene-1, ethylbutene-1, propylpentene-1, decene- 1, methylnonene-1,
Mention may be made of α-olefins such as dimethyloctene-1, trimethylheptene, ethyloctene-1, methylethylhebutene-11 diethylhexene-1, dodecene-1 and hexadodecene-1.

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

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

In the present invention, other compounds that can be used in addition to the above α-olefins include, for example, chain polyene compounds and cyclic polyene compounds. In the present invention, as the polyene compound, a polyene having two or more conjugated or non-conjugated olefinic double bonds is used, and as such a quenched polyene compound, specifically, 1,4-hexadiene , 1.5-hexadiene, 1.7 octadiene, 1.9-decadiene, 2,4
．． 6-octatriene, I, 3,7-octatriene, 1,5,9-decatriene, divinylbenzene, etc. are used. Further, specific examples of the cyclic polyene compound include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-13-cyclohexadiene, 1
, 3-cyclohebutadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2
-Norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5
-Norbornagene and the like are used.

In addition, in the present invention, cyclopentadiene such as cyclopentadiene and ethylene, propylene, butene-
It is also possible to use a polyene compound obtained by condensing an a-olefin such as No. 1 using a Diels-Alder reaction.

Furthermore, in the present invention, cyclic monoenes can also be used, and specific examples of such cyclic monoenes include cyclopropene, cyclobutene, 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, 5.5.6-) Dimethyl-2-norbornene, bicycloalkenes such as 2-bornene, 233g, 7a-tetrahuman C7-4,7-methano-IH-indene, 3a, 5.6.7a -Tetrahydro-tricycloalkenes such as -4,7-methano-IH-indene, 1.4,5.8-dimethano 23.4.
4L5.88a-octahydronaphthalene, and in addition to these compounds, 2-methyl 1458-dimethano-1
, 2344a 5881-octahydronaphthalene, 2
-Ethyl-1,4,5,8-dimethano1,2.3.4.
4g, 5.8.8g-octahydronaphthalene, 2-
Propyl-1458-dimethano-12344a 588
Tooctahydronaphthalene, 2-hexyl-1,458
-Dimethano-1,234,4a 58.8g-Octahydronaphthalene, 2-stearyl-1458-Dimethano 1,2.3.4.4a, 5.8.81-Octahydronaphthalene, 2.3-dimethyl-14 ,58-dimethano-12344a 58.8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,435,8,8g-octahydronaphthalene, 2-chloro-145,8-dimethano-1,2
,3,4,4a, 5.8.81-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2
,3,4,4g 58.88-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,
3,4,4a, 5.8.8a-octahydronaphthalene, 2,3-dichloro-1458-dimethano-1,2,
3,4,4a, 5.8.8a-Tetracycloalkenes such as octahydronaphthalene, hexacyclo3.6
10.13.02.7, o9.14],, Putade [6
, 6, 1, ] , + 1.947 Sen-4, Pentacyclo [8, 8, 1, 11 ratio 18.
0.03°8,012°17] Henikosen-5, Oktatsuk. [8,8,,2,9,,4,7,,II, +
8. ．． 13. +6o, 03.8, 0+2°17]
Examples include cyclic monoene compounds such as polycycloalkenes such as tococene-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 (vapor 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 resulting 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 a raw material, a method of simultaneously producing a crystalline olefin polymer part and an amorphous olefin polymer part by supplying two or more types of monomers to a polymerization tank, or ,
One example is a method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion are carried out 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 preferred 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 synthesizing,
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 ] A catalyst consisting of 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.

Further, other preferable catalyst components [A] include catalyst components containing halogen atoms and magnesium atoms in addition to the above-mentioned transition metal atoms, and catalyst components having conjugated π electrons in transition metal atoms of groups TVB 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

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 to 200 μm1, more preferably 5 to 10 μm
0 μm1, 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 more preferably 1.0 to 2.1, particularly preferably 1
．． It is within the range of 0 to 1.7.

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

Specifically, a dispersion prepared by adding the catalyst component [A] to a decalin solvent at a concentration of 0.1% by weight is placed in a measurement cell, and a narrow light is shined on this cell to detect the particles. Particle size distribution is determined by continuously measuring changes in the intensity of light passing through a narrow beam. Based on this particle size distribution, the standard deviation (δ) is determined from the lognormal distribution. More specifically, the standard deviation (δg) is determined as the ratio (θ50/θ16) between the average particle size (θ5o) and the particle size (θ16) which is 16% by weight considering the small particle size. Note that the average particle diameter of the catalyst is the weight average particle diameter.

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

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 axis 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 0.1-10, preferably 0.2-6. Further, the specific surface area of this catalyst component [A] is usually 3 m/g or more, preferably 40 nf/g or more, and more preferably 100 to 800 d.
/g.

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

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

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

Such a catalyst component [A] can be used as it is, or can be used after supporting a magnesium compound, a titanium compound, and, if necessary, an electron donor on a uniformly shaped carrier. It is also possible to prepare a finely powdered catalyst in advance and then granulate this finely powdered catalyst into the preferred shape described above.

Regarding such catalyst component [A], Japanese Patent Application Laid-Open No. 55-1
No. 35102, No. 55-135103, No. 56-81
No. 1, Publication No. 56-67311 and Patent Application No. 1982-1
No. 81019 and No. 6121109.

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

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

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

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

(3) By 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 having a value of δ ) 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 a tetrahydrogen-containing compound. The magnesium compound supported on the carrier is reacted with the titanium compound by contacting with titanium chloride or a titanium compound and an electron donor.

(5) In the method of (2) or 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 with an isotoughness index (insoluble content in boiling n-hebutane) of 92% or more, particularly 96% or more, is usually 3000 g or more per 1 mmol of titanium. , preferably 5000g or more, particularly preferably 10000g
or more can be manufactured.

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

Specifically, magnesium compounds include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide, and hydrotalcite, magnesium carboxylates, alkoxymagnesium, allyloxymagnesium,
In addition to alkoxymagnesium halide, allyloxymagnesium halide, and magnesium sybarite, 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, and allyloxytitanium 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, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, 1 to 1 carbon atoms, such as isopropyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol
8 Alcohols Phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol (these phenols may have a lower alkyl group); Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolylaldehyde and naphthaldehyde. Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl Methyl acid, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, phthalic acid Diethyl, di-isobutyl phthalate, di-n-butyl phthalate, di-n-phthalate
Pentyl, diisopentyl phthalate, c-n-hexyl phthalate, diisohexyl phthalate, di-n-heptyl phthalate, diisoheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate with 2 or more carbon atoms
30 organic acid esters; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride and anisyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and anisole; Ethers having 2 to 20 carbon atoms such as diphenyl ether; for example (where 2≦n≦10, and R1 to R25 are at least one selected from carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, boron, and silicon); A substituent having one type of element, R1-R21+ is bonded to the main chain through a carbon-carbon bond, and any R1-R26 may jointly form a ring other than a Hensen ring, Also, the main chain may contain elements other than carbon.) Polyethers represented by: More specifically, 2-(2-ethylhexyl)13-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-5-butyl-1,3-dimethoxy Propane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane,
2-cumyl 13-dimethoxypropane, 2-(2-phenylethyl)kawa, 3-dimethoxypropane, 2-(2-
cyclohexylethyl)-1,3-dimethoxypropane, 2-(pchlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3 -dimethoxypropane, 2(2-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1
, 3-dimethoxypropane, 2-(pt-butylphenyl)kawa, 3-dimethoxypropane, 2.2-dicyclohexyl-1,3-dimethoxypropane, 2.2-diethyl, 3-dimethoxypropane, 2.2-dipropyl-1,3-dimethoxypropane, 2.2-dibutyl-
1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-
Ethyl-1,3-dimethoxypropane, 2-methyl-2-
Isopropyl-13-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-13-dimethoxypropane, 2,2-bis(p-chlorophenyl) 1.3 -dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-
Isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 22-diisobutyl-13-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane,
22-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-jethoxypropane, 2,2-diisobutyl, 3-sibutquinpropane, 2-isobutyl-2-isopropyl- 1,
3 dimethoxypropane, 2,2-c-S-butyl-1,
3-dimethoxypropane, 2,2-di-1-butyl-1
, 3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-
isopentyl-13-dimethoxypropane, 2-phenyl-2-t\nji-13-dimethoxypropane, 2-
Cyclohexyl-2-cyclohexylmethyl-13-dimethoxypropane, 2,3-diphenyl-1,4-jethoxybutane, 2,3-dicyclohexyl-1,4-jethoxybutane, 2,2-dibenzyl-1,4-jethoxybutane, 23-diisopropyl-1,4-jethoxybutane, 2,2-bis(p-methylphenyltane, 2,3-bis(p-chlorophenyl)-1,4-
Dimethoxybutane, 2,3-bis(p-fluorophenyl)14-dimethoxybutane, 2,4-diphenyl-1
．． 5-methoxypentane, 2,5-diphenyl-1,
5-methoxyhexane, 2,4-diisopropyl-1
, 5-dimethoxypentane, 2,4-diisobutyl-1
, 5-dimethoxypentane, 2,4-diisoamyl-1
, 5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3
-diisoamyloxypropane, 1,2-diisobutoxypropane, 12-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3-diisoamyloxypropane, 113 diisoneopentyloxyethane, 1 .3-dineopentyloxypropane, 2.2-tetramethylene-
1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis(methoxymethyl)cyclohexane, 2,8- Dioxaspiro[5,5] undecane, 3,7-thioxabicyclo[3,3,II nonane, 37-thioxabicyclo[3
, 3,01 octane, 3,3-diisobutyl-5-oxononane, 6,6-dibutyldioxyhebutane, 1
．． 1-dimethoxymethylcyclopentane, 1,1-bis[dimethoxymethylcocyclohexane, 1,1-bismethoxymethyl]bicyclo[2,2,II hebutane, 1
．． 1-dimethoxymethylcyclopentane, 2-methyl-
2-methoxymethyl-1,3-dimethoxypropane, 2
-cyclohexyl-2-ethoxymethyl-1,3-jethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2 -isopropyl-2-isoamyl-1,3 dimethoxycyclohexane, 2-cyclohexyl-2methoxymethyl-1,3
-dimethoxycyclohexane, 2-isopropyl-2-
methoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-jethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxy Cyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-jethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3
-jetoxycyclohexane, 2-isobutyl-2-ethoxymethyl 13-dimethoxycyclohexane, and tris(p-methoxyphenyl)phosphine. Among these, 1,3-diethers are preferred;
In particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-
dimethoxypropane, 2,2-dicyclohexyl-1,
5 carbon atoms such as 3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, etc.
-40 diethers; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide.

Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylene diamine; Nitriles such as acetonitrile, benzonitrile and tolnitrile; trimethyl phosphite, phosphorous po with triethyl acid
An organic phosphorus compound 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 monocarphonic acids and alcohols having 1 to 8 carbon atoms,
malonic acid, substituted 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 [Al obtained as described above] can be purified by thoroughly washing it 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-heptane, n-octane, isooctane, n-decane, n-
- Aliphatic hydrocarbon compounds such as dodecane, kerosene, and liquid paraffin; Alicyclic hydrocarbon compounds such as dichloropentane, methylcyclopentane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon compounds such as benzene, toluene, xylene, and cymene; Mention may be made of 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
Preference is given to using organoaluminum compounds having at least one AI-carbon bond in the molecule.

Examples of such organoaluminum compounds include (where R1 and R2 are the number of carbon atoms or 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 of 0≦q<3, and m+n+p+q=3). Compounds, and complex alkylated products of a metal of Group 1 of the periodic table and aluminum represented by (where Ml is LiNa, and R1 has the same meaning as above).

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

compound (where R1 and R2 have the same meanings as above,
m is preferably a number such that 1.5≦m≦3).

A compound represented by the formula R' m AIX (this
m Trowel R1 has the same meaning as above, X is)\Rogen, m
is preferably Q < m < 3).

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

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

Specifically, the organoaluminum compound represented by the above formula (i) includes trialkylaluminums such as triethylaminium, tributylaluminum, and triisopropylaluminium, trialkenylaluminums such as triisoprenylaluminum, and dibutylaluminum butoxide. , dialkylaluminum alkoxides such as dibutylaluminum butoxide; alkylaluminum sesquialkoxy Fs such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide; dialkylaluminum nitrites such as diethylaluminum chloride, butylaluminum chloride, diethylaluminum bromide, alkylaluminum sesquipromide such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquipromide. halides, partially halogenated alkylaluminums such as alkylaluminum dino-1-lite such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, etc. , Alkylaluminums in which alkylaluminum haladride is partially hydrogenated, such as ethylaluminum dihydride, probylaluminum dihydride, etc., ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide, etc. Partially alkoxylated and halogenated alkyl aluminums are used.

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 (C2R5)2 AIoAI (C2H,5)2, (C
Examples include 4R9)2 A10AI (c4H9)2 and 6H5.

Further, as the organoaluminum compound represented by the above formula (ii), specifically, LiAl(C2H5)4 and LIAl(C
7H15)4, etc. Among these, in particular trialkylaluminum, mixtures of trialkylaluminum and alkyl aluminum halides,
Preference is given to using a mixture of trialkylaluminum and aluminum halide.

In addition, when carrying out the polymerization reaction, in addition to the catalyst component [Al and organometallic compound catalyst component [B], an electron donor [C
] is preferably used in combination.

Specifically, such an electron donor [C] is,
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 1, 2, 2 and 3 of the periodic table, and acceptable salts thereof. Note that salts are organic acids and catalyst components [
By reaction with the organometallic compound used as B],
It can also be formed within the reaction system.

Specific examples of these electron donors include the compounds exemplified above for the catalyst component [Al. 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.

In particular, when the electron donor in the catalyst component [Al 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 component [Al is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, the electron donor [C] is (However, in the above formula, R and R1 are It is preferable to use an alkoxy(aryloxy)silane compound represented by a hydrocarbon group (0≦n<4) or an amine with large steric hindrance.

Specifically, such alkoxy(aryloxy)silane compounds include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane,
Dimethylethoxysilane, diisopropyldimethoxysilane, 1-butylmethyldimethoxysilane, 1-butylmethyljethoxysilane, t-amylmethyljethoxysilane phenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis-o
- Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-)lylmethoxysilane, bis-p-tolyljethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, Toxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxysilane, decylmethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxy Silane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 0-butyltriethoxysilane,
Phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane Silane, 2-norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(allyloxY)silane, vinyltris(β)
-methoxyethoxysilane), dimethyltetraethoxysiloxane, etc.

Among these, especially ethyltriethoxysilane, n-propyltriethoxysilane, 1-butyltriethoxysilane,
Vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-
Preferred are tolylmethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, dichlorohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyljethoxysilane, ethyl silicate, and the like.

In addition, as the amine with large steric hindrance, 226.6
Particularly preferred are -titramethylpiperidine, 2.2.5.5-tetramethylpyrrolidine, or derivatives thereof, and tetramethylmethylenediamine. Among these compounds, alkoxy(aryloxy)silane compounds and the above-mentioned polyethers are particularly preferred as electron donors used as catalyst components.

Further, in the present invention, a catalyst component [i] containing a transition metal atom compound of Group IVB or Group 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 transition metals of Groups IVB and 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 cyclopentagenyl group, a methylcyclopentagenyl group, an ethylcyclopentagenyl group, a t-butylcyclopentagenyl group, and a dimethylcyclopentagenyl group. basis,
Examples include alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl groups, indenyl groups, and fluorenyl groups.

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

Examples of such groups include groups such as ethylene hisindenyl group and isopropyl (fluorenyl for cyclopentagenyl) group.

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

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

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

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

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

For example, when the valence of the transition metal is 4, the transition metal compound containing a ligand having a cycloalkagenyl skeleton used in the present invention has the following formula: R2R3R4R5M k l m n ( In the formula, M is zirconium, titanium, hafnium, vanadium, etc., R2 is a group having a cycloalkashenyl skeleton, RR and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cycloalkyl group, It is 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+7 +m+n=4).

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

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

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, His(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, His (cyclopentagenyl) phenylsilconium hydride, bis(cyclopentagenyl)pencylzirconium hydride, bis(cyclopentagenyl)neopentylzirconium hydride, bis(methylcyclopentagenyl)zirconium monochloride hydride, bis( indenyl) zirconium monochloride monohytride, his(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium dibromite, bis(cyclopentagenyl) methylzirconium monochloride, bis(cyclopentagenyl) zirconium dibromite ) ethylzirconium monochloride, bis(cyclopentadienyl)cyclohexylzirconium monochloride, bis(cyclopentagenyl)phenylsilconium monochloride, bis(cyclopentagenyl)hensylzirconium monochloride, bis(methylcyclopentagenyl) his(1-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium dichloride, pentagenyl) zirconium phenyl, his(cyclopentajenyl) zirconium dimethyl, bis(cyclopentajenyl) zirconium methoxychloride, bis(cyclopentadienyl) zirconium ethoxychloride, bis(methylcyclopentajenyl) zirconium Ethoxychloride, Bis(cyclopentagenyl)zirconium phenoxychloride, Bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis(indenyl)methylzirconium, Ethylenebis(indenyl) Ethylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, isopropylbisindenylzirconium dichloride, isopropyl(cyclopentagenyl)-1-fluorenylzirconium chloride, ethylenebis(indenyl)zirconium compound mid, ethylenebis(indenyl) ) Zirconium methoxy monochloride, Ethylene bis(indenyl) zirconium ethoxy monochloride, Ethylene bis(indenyl) zirconium phenoxy monochloride, Ethylene bis(cyclopentajenyl) zirconium dichloride, Propylene bis(cyclopentajenyl) zirconium dichloride, Ethylene bis (l-butylcyclopentadienyl)silconium dichloride, ethylenebis(4,5,6,7-tetrahydro-indenyl)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methyl Zirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, ethylenebis(456,7-tetrahydro-1-indenyl)silconium dichloride, ethylenehis(4-methyl-1-indenyl) ) Zirconium dichloride, Ethylenebis(5-methyl-1-indenyl)zirconium dichloride, Ethylenebis(6-methyl-1-indenyl)zirconium dichloride, Ethylenebis(7-methyl-1-indenyl)zirconium dichloride, Ethylenebis(5) -methoxy-1-indenyl) zirconium dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(i,7-simethoxy 1) -indenyl)
Zirconium dichloride.

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

Also, in this case, the organometallic compound catalyst component [ii]
As such, a conventionally known aluminoxane or organoaluminumoxy compound may be 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.

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 (1) 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, per polymerization volume II, for example.
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 -100 kg/at! , preferably 2~
It is 50 kg/cJ.

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

(Left below) When using titanium as the transition metal, the amount of polymerization in prepolymerization is usually 1 g per 1 g of titanium catalyst component.
-2000 g, preferably 3-1000 g, particularly preferably 10-500 g.

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

Specifically, the α-olefin used in this prepolymerization includes ethylene, propylone, 1-butene, 1-
Pentene, 4-methyl-1-pentene, 3-methyl publication-
α-olefins having 10 or less carbon atoms such as pentene, 1-heptene, 1-octene, and 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 part and having good particle properties, for example, polymer particles containing more than 30% by weight of amorphous olefin polymer part and having good particle properties. To obtain particles, the prepolymerization is carried out at e.g.
A method has been proposed in which propylene and ethylene are copolymerized using a mixed gas consisting of ~98 mol% propylene and 30~2 mol% ethylene.

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

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

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/d, preferably normal pressure to 50 kg/ad, 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 23
It can be determined by measuring the amount of components soluble in n-decane at °C.

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.

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 the "amorphous olefin polymer portion".

The soft polymers used in the present invention include peroxide crosslinked olefin copolymer rubber, propylene/α-olefin copolymer rubber having 4 or more carbon atoms, styrene-
Examples include hydrogenated products of conjugated diene block copolymers.

The peroxide crosslinked olefin copolymer rubber used in the present invention includes olefins such as ethylene propylene copolymer rubber (EPR), ethylene-propylene non-conjugated diene rubber (EPDM), and ethylene-butadiene copolymer rubber. It is an amorphous elastic copolymer that is a product component, and refers to a rubber that becomes crosslinked when mixed with an organic peroxide and kneaded under heating, resulting in decreased fluidity or no fluidity. Incidentally, the non-conjugated diene refers to dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, ethylidenenorbornene, and the like.

In the present invention, among these copolymer rubbers, ethylene-propylene copolymer rubber (EPR) and ethylene-propylene non-conjugated diene rubber (EPDM) are preferably used, and the molar ratio of ethylene units to propylene units (
Ethylene-propylene copolymer rubber with a molar ratio of 50150 to 90/10 (ethylene/propylene) and ethylene-propylene non-conjugated diene rubber are used, particularly ethylene-propylene copolymers with a molar ratio of 55/45 to 85/15. Rubber, ethylene-propylene non-conjugated diene rubber is preferably used. Among them, ethylene propylene non-conjugated diene copolymer rubber, especially ethylene-propylene-5
-Ethylidene-2-norbornene copolymer rubber and ethylene-propylene-5ethylidene-2-norbornene-dicyclopentadiene quaternary copolymer yield thermoplastic elastomers with excellent heat resistance, tensile properties, and rebound resilience. It's very good.

In addition, the iodine value (degree of unsaturation) of the above copolymer rubber is 16
It is preferable that it is below. By using the copolymer rubber having an iodine value within this range, a thermoplastic elastomer with an excellent balance between fluidity and rubber properties can be obtained.

In the present invention, the peroxide crosslinked olefin copolymer rubber such as the ethylene-propylene copolymer rubber and ethylene-propylene non-conjugated diene rubber constitutes the amorphous olefin polymer portion of the polymer particles. The intrinsic viscosity ratio ([η]b/[η],) between the intrinsic viscosity [η] of the rubber component to be used and the intrinsic viscosity [η]ゎ of the peroxide crosslinked olefin copolymer rubber is 1.3 or more, or 0
．． It is preferable that it is 8 or less from the viewpoint of improving moldability (fluidity).

Note that the value of the above-mentioned intrinsic viscosity is a value measured in a decalin solvent at 135°C.

In the present invention, the peroxide crosslinked olefin copolymer rubber as described above is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 25 parts by weight, based on 100 parts by weight of the polymer particles. Used in parts by weight.

In the present invention, peroxide crosslinked olefin copolymer rubber, particularly EPR, EPDM, is used as the soft polymer.
When used in the above ratio, a thermoplastic elastomer with excellent moldability that can provide molded products with low rigidity and low hardness can be obtained.

The propylene/α-olefin copolymer rubber having 4 or more carbon atoms used in the present invention refers to propylene and, for example, 1-
Butene, 4-methyl-1-pentene, 1-octene, 1-
It is obtained by copolymerization with one or more α-olefins such as decene, and the propylene unit content is usually in the range of 40 to 90 mol%, preferably 55 to 85 mol%, and The degree of crystallinity measured by line diffraction is usually 40% or less, preferably within the range of 10 to 30%.

Regarding such copolymers, for example, Japanese Patent Publication No. 57-
It is described in Japanese Patent Publication No. 11322 and Japanese Patent Publication No. 57-36859.

In the present invention, propylene with 4 carbon atoms as described above is used.
The above a-olefin copolymer rubber has polymer particles 1
00 parts by weight, usually 5 to 70 parts by weight, preferably 2 parts by weight.
It is used in an amount of 0 to 60 parts by weight, more preferably 30 to 50 parts by weight.

In the present invention, when propylene/α-olefin copolymer rubber having 4 or more carbon atoms is used as the soft polymer in the above ratio, a molded product with excellent appearance, especially surface gloss, can be provided. A thermoplastic elastomer with excellent properties can be obtained.

The hydrogenated product of the styrene-conjugated diene block copolymer used in the present invention has the following formula [I]S (D-8)
n...[1] (wherein, S is a styrene polymer block, D is a conjugated diene polymer block,
n is an integer of 1 to 5), and examples of the conjugated diene represented by D include butadiene, isoprene, and the like.

Such a styrene/conjugated diene block copolymer is
For example, it is disclosed in Japanese Patent Publication No. 51-102743. In addition, as commercially available products, styrene-butadiene-styrene block copolymers are Kraton 1101 and Kraton 1102, and styrene-isoprene-styrene block copolymers are Kraton 1107 and 1111.
Since it is commercially available under the trade name of [Shell Kagaku ■], hydrogenated products of styrene-conjugated diene block copolymers can be obtained by hydrogenating these styrene-conjugated diene block copolymers. A hydrogenated product of styrene-isobutylene-styrene block copolymer is also commercially available under the trade name Kraton G-1652.

The hydrogenated styrene-conjugated diene block copolymer preferably used in the present invention has an intermediate soft segment composed of ethylene-butylene (EB) and a terminal heart segment composed of polystyrene (S). It is a hydrogenated product of block copolymer (5EBS).

The method for producing the styrene block copolymer represented by the above formula [I] is widely known, and a typical method is as follows:
For example, it is disclosed in US Pat. No. 3,265,765. The method generally involves preparing a mixture containing styrene and a conjugated diene with the following formula [11] % formula % [] (wherein R is an aliphatic, cycloaliphatic or aromatic hydrocarbon residue, and X is 1 This is a method for producing a block copolymer of formula [I] by carrying out solution polymerization in the presence of a catalyst represented by:

The method for producing the hydrogenated product of the styrene block copolymer of the above formula [I] is described, for example, in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 6636-1983, Japanese Patent Publication No. 20504-1974, Japanese Patent Publication No. 3555-1987, etc. It is stated in the official gazette.

The styrene-conjugated diene block copolymer used in the present invention has a melt flow rate [MFRASTMD I2
38. (L)] is usually 30 g/10 minutes or less, preferably 5 g/10 minutes or less, and has a hardness (IIs A
type) is usually 40-80, preferably 50-70.

In the present invention, the hydrogenated substance of the styrene-conjugated diene block copolymer as described above is usually 5 to 50 parts by weight, preferably 7 to 40 parts by weight, based on 100 parts by weight of the polymer particles.
It is used in an amount of 10 to 30 parts by weight, more preferably 10 to 30 parts by weight.

In the present invention, when a hydrogenated product of styrene-conjugated diene block copolymer is used as the soft polymer in the above ratio, a thermoplastic elastomer that has excellent moldability and can provide a molded product with an excellent appearance can be obtained. is obtained.

To prepare the thermoplastic elastomer in the present invention,
The polymer particles as described above, the soft polymer, and the crosslinking agent may be dynamically heat-treated to partially or completely crosslink.

Dynamic heat treatment here means kneading in a molten state. In this case, the crosstalk device is an open type device such as a mixing roll, or a Banbury mixer 1.
Closed equipment such as extruders, kneaders or continuous mixers may be used. Among these kneading devices,
In particular, an extruder is preferably used.

The kneading is preferably carried out in a non-release type device, and preferably in an atmosphere of an inert gas such as nitrogen or carbon dioxide gas. The temperature is usually 150 to 280°C, preferably 170 to 240°C, and the kneading time is usually 1 to 20°C.
minutes, preferably 1 to 10 minutes.

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, alkylphenol formaldehyde resin, triazine-formaldehyde resin, melamine-formaldehyde resin, and aldehyde resin are used.

In addition, specific examples of organic peroxides include dicumyl peroxide, C1e+l-butyl peroxide,
25-dimethyl-2,5-bis(+eT 1-butylperoxy)hexane, 2,5-dimethyl-25-his(left-butylperoxy)hexane-3,13
-His(left-butylperoxyisopropyl)benzene, 1,1-bis(leaf-butylperoxy)
-3,3,5-trimethylcyclohexane, n-butyl-44-bis(left-butylperoxy)valerate, dihenzoyl peroxide, +e+l-butylperoxyhensiatate, etc. are used. Among these, dihenzoyl peroxide and 1,3-bis(leaf-butylperoxyisopropyl)benzene are preferred from the viewpoint of crosslinking reaction time, odor, and scorch stability.

In the present invention, such a crosslinking agent is used in polymer particles 1
00 parts by weight, about 0.01 to 2 parts by weight, preferably 0.03 to 1.0 parts by weight, more preferably 0.05 to 1.0 parts by weight.
It is used in an amount of 0.5 parts by weight.

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, p'-dibenzoylquinonedioxime, N-methyl N4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane NN'- Peroxy crosslinking aids such as m-phenylene dimaleimide or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. , polyfunctional vinyl monomers such as vinyl butyrald or vinyl stearate. 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 peroxide dispersion aid, so that the crosslinking reaction is homogeneous and the fluidity is improved. This is most preferable because a thermoplastic elastomer with well-balanced properties 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 to 2 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 with 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 polymer particles is carried out as necessary using a peroxide non-crosslinkable hydrocarbon rubber-like material such as polyisobutylene, butyl rubber, etc. and/or a mineral oil-based softener. It can also be carried out in the presence of an agent.

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

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, 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 fibers, glass bulbs, shirasu balloons, carbon fibers or coloring agents such as carbon black, titanium oxide, zinc white, henkara , ultramarine blue, navy blue, azo dyeing, nitroso dyes, lacquer pigments, phthalocyanine pigments, etc. can also be blended.

The thermoplastic elastomer thus obtained has an insoluble gel content that is not extracted by cyclohexane, measured as follows, of 10% by weight or more, preferably 40 to 1% by weight.
00% by weight, more 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. Weigh out approximately 100 mg of sample pellets of thermoplastic elastomer (size of each pellet: 1 mm x 1 stroke x 0.5 anus), and place this in a sealed container to 30 cc.
After soaking in cyclohexane for 48 hours at 23°C, the sample was 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, if the weight of the sample pellet contains 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. The corrected initial weight (
X).

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

Corrected final weight (Y) Gel content (%) = It has excellent moldability and can provide molded products with excellent physical properties such as impact strength and tensile strength, toughness, heat resistance, flexibility at low temperatures, surface smoothness, surface gloss, and paintability. thermoplastic elastomers can be obtained at low production costs.

In particular, thermoplastic elastomers in which amorphous olefin polymer parts (rubber components) are fixed within the particles at the molecular segment level have at least high strength in the rubber content, are uniform, and have low flexibility at low temperatures. , molded products with even better surface smoothness and paintability can be obtained. It has an especially excellent appearance after painting.

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

Such thermoplastic elastomers are used in body panels, bumper parts, sight shields, automotive parts such as steering wheels, footwear such as shoe soles and sandals, electrical parts such as wire sheaths, connectors, cap plugs, and packing, and golf club grips. , leisure goods such as baseball bat grips, swimming fins, underwater glasses, waterproof sheets, waterproof materials,
It is used for civil engineering and construction parts such as joint materials, architectural window frames, architectural gaskets, and covering materials for decorative rigid boards, gaskets, waterproof cloth, garden hoses, and belts.

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

[Example] [Adjustment of catalyst component [A]] Internal volume 27! After thoroughly purging the high-speed stirring device (manufactured by Tokushu Kika Kogyo) with N2, 700 ml of refined kerosene was added. Commercially available Mgcz
210 g of ethanol, 24.2 g of ethanol, and 3 g of Emazol 320 (trade name, manufactured by Kao Atlas ■, sorbitan distearate) were added, and the system was heated to temperature with stirring, and stirred at 120° C. 800 + pm for 30 minutes. Rinse thoroughly using a Teflon tube with an inner diameter of 5 mm under high-speed stirring.
Refined kerosene II cooled to 10'C is loaded 2
The solution was transferred to No. 1 glass flask (equipped with a stirrer). 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 chain thread was heated to 120°C. ] After stirring and mixing at -20°C for 2 hours, the solid part was collected by filtration, and again 1
The mixture was suspended in 50 ml of titanium tetrachloride and stirred and mixed again at 130° C. for 2 hours.

Furthermore, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to remove the solid catalyst component (
A) was obtained. The components are 2.2% by weight of titanium in terms of atoms;
The contents were 63% by weight of chlorine, 20% by weight of magnesium, and 5.5% by weight of diisobutyl phthalate. Average particle size is 64μm
A truly spherical catalyst with a geometric standard deviation (δ) of particle size distribution of 1.5 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 the above T1 catalyst component [A] were added in an amount of 2 in terms of titanium atoms.
After charging mmol, propylene was fed at a rate of 5.9 Nll/hour over 1 hour, and Ti catalyst component [A11g
2.8 g of propylene was polymerized per batch. Humidity was maintained at 20±28C during polymerization. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

[Production of Polymerization Copolymer (1) 2.0 kg of propylene and 19N liters of hydrogen were added to the polymerization vessel of 201 at room temperature, and then the temperature was raised, and at 50°C, 15 mmol of triethylaluminum and 1.5 mmol of dicyclohexyldimethoxysilane were added. mmol, 0.05 mmol of the prepolymerized product of catalyst component [A] was added in terms of titanium atoms,
The temperature inside the polymerization vessel was maintained at 70°C. 30 after reaching 70℃
Then, the vent valve was opened and propylene was purged until the inside of the polymerization vessel reached normal pressure, and homopolymerization of propylene was carried out. After purging, copolymerization was carried out subsequently.

That is, when ethylene is 48ONiy, propylene is 72ONiy.
ONA/h, hydrogen was fed to the polymerization reactor at a rate of 12 Nl/h. The opening degree of the vent of the polymerization vessel was adjusted so that the pressure inside the polymerization vessel was 10 kg/crl·G.

The temperature during copolymerization was kept at 70°C. Copolymerization time is 150
Copolymerization was carried out for minutes.

Table 1 shows the physical properties of the obtained copolymer (1).

Production of copolymers (2) and (3) In the production of copolymer (1), the prepolymerization conditions were changed as shown below, and the copolymerization conditions were as shown in Table 1. In the same manner as producing polymer (1),
Copolymers (2) to (3) were produced.

Table 1 shows the physical properties of the obtained copolymers (2) and (3).

[Prepolymerization] Catalyst component [A] was subjected to the following prepolymerization. After charging 400 ml of purified hexane into a nitrogen-purged 11 glass reactor, 1.32 mmol of triethylaluminum, 0.27 mmol of cyclohexylmethyldimethoxysilane, and 0.2 mmol of the Ti catalyst component [A] were added in terms of titanium atoms.
After charging 132 mmol, propylene gas and ethylene gas were charged at 8.4 NA/hr and 1.0 NA/hr, respectively. The mixture was fed into the liquid phase of the polymerization vessel for 100 minutes with mixing at a rate of ONI/hour. Moreover, the humidity was maintained at 20±2° C. during the prepolymerization. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

As a result of the analysis, approximately 92 g of polymer was present on 11 g of the used T1 catalyst component [A] in the prepolymerized solid catalyst, while the used Ti catalyst component [A] was present in the separated filtrate.
There was an equivalent of 6.2 g of solvent soluble polymer per Ig.

Table Example 1 Powder 100 of copolymer (1) obtained as above
parts by weight and ethylene-propylene-5-ethylidene-2
-Norbornene copolymer rubber [ethylene/propylene (
Molar ratio: 64/36, iodine value: 18, intrinsic viscosity [η]
:0.9dn/g] and 0.2 parts by weight of 13-bis(Ie+1-butylperoxyisopropyl)benzene are dissolved and dispersed in 0.3 parts by weight of divinylbenzene and 5 parts by weight of paraffinic process oil. were mixed using a tumbler blender, and the above solution was uniformly applied to the powder surface of copolymer (1).

The powder of the above copolymer (1) has an average particle diameter of 2200
μm, the apparent density is 0.45 g/ml, and 1
The amount of particles passing through 50 meshes was 0.1% by weight, and the falling time was 8.3 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.5.

This powder was then extruded using an extruder at 210° C. under a nitrogen atmosphere to obtain thermoplastic elastomer pellets.

The physical properties and moldability of the obtained pellets were evaluated as follows.

First, the pellets were injection molded using the following equipment and conditions to produce a 3-thick square plate, and the moldability was evaluated. In addition, test pieces were cut from the square plates obtained in this way, and the tensile properties, initial bending modulus, Izot impact strength,
Hardness and surface gloss were measured.

Molding conditions Molding machine: Dynamelter (manufactured by 8-ki Seisakusho) Molding temperature: 2
00℃ Injection pressure Crab sinking pressure 1300kg/aIr secondary pressure
700kg/al Injection speed/Maximum molding speed/90 seconds/1 cycle Gate: Direct gate (Land length 10mm in 10-1.

Depth 3-) Formability Judgment Criteria Items with extremely large numbers of flow marks 2 Items with significant flow marks visible on the entire surface of the molded item 3 Items with slight flow marks visible on the entire surface of the molded item 4 Items with 4: On the opposite side of the gate 5: Flow marks or no flow marks at all Physical property evaluation Tensile properties 100% tensile stress (Mloo, kg/cJ) Tensile strength at break (T, , kg/alj) Elongation at break
(EIl, %) Measured according to JIS K-6301.

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

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

(With notch) Hardness: Measured in accordance with STM D256 or Kawa SK-6301.

Surface gloss (gloss) Measured at an incident angle of 600 in accordance with IIS z-87411m.

The results are shown in Table 2.

Example 2 The same procedure as Example 1 was carried out except that the amount of paraffinic process oil was changed to 10 parts by weight.

The results are shown in Table 2. Example 3 100 parts by weight of powder of copolymer (2), 20 parts by weight of the ethylene-propylene copolymer rubber of Example 1, and 1.3-
A solution in which 0.2 parts by weight of bis(tell-butyloxyisopropyl)benzene is dissolved and dispersed in 0.3 parts by weight of divinylbenzene is mixed with a tumble blender, and the above solution is applied to the powder surface of copolymer (2). It adhered evenly.

The powder of the above copolymer (2) has an average particle size of 2100
μm, and the apparent density is 0. ．． It is 43g/ml,
The particles passing through 150 meshes are 0.1% by weight,
The falling time was 9.3 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.5.

Next, this powder was extruded with an extruder at 210° C. under a nitrogen atmosphere to obtain thermoplastic elastomer pellets.

The physical properties and moldability of the obtained pellets were evaluated in the same manner as in Example 1.

The results are shown in Table 2.

Example 4 The same procedure as Example 3 was carried out except that copolymer (3) was used instead of copolymer (2).

The powder of the above copolymer (3) has an average particle size of 2000
μm, the apparent density is 0.40 g/ml, and 1
The amount of particles passing through the 50 mesh was 0.2% by weight, and the falling time was 10.3 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.6.

The results are shown in Table 2.

Example 5 The same procedure as Example 3 was carried out except that copolymer (1) was used instead of copolymer (2).

The results are shown in Table 2.

Table *B Examples 6 to 7 without destruction In Examples 3 to 4, instead of the ethylene-propylene 5-ethylidene-2-norbornene copolymer rubber, propylene unit content 70 mol%, MFR (23t1°C)
7g/10min propylene/1-butene copolymer rubber (P
The procedure was the same as in Examples 3 and 4, except that 43 parts by weight of BII) was used.

The results are shown in Table 3.

Table Examples 8 to 10 In Examples 2 to 4, styrene with a melt flow rate of 0.01 g/10 minutes and a JIS A type spring hardness of 50 was used instead of the ethylene-propylene 5-ethylidene-2-norbornene copolymer rubber. The same procedure as Examples 2 to 4 was carried out except that 20 parts by weight of the hydrogenated product of the butadiene block copolymer (5-EB-3) was used.

The results are shown in Table 4.

table teenager Reason Man

Claims (1)

[Scope of Claims] 1) Consists of a crystalline olefin polymer part and an amorphous olefin polymer part, and has an average particle diameter of 10 μm or more,
A method for producing a thermoplastic elastomer, comprising: dynamically heat-treating polymer particles having an apparent bulk density of 0.2 g/ml or more, a soft polymer, and a crosslinking agent. 2) consists of a crystalline olefin polymer part and an amorphous olefin polymer part, and has an average particle diameter of 10 μm or more,
Polymer particles having an apparent bulk density of 0.2 g/ml or more, a soft polymer, and a crosslinking agent are dynamically heat-treated in the presence of a crosslinking aid and/or a mineral oil softener. A method for producing a thermoplastic elastomer. 3) The polymer particles have a crystalline olefin polymer portion 80
~20 parts by weight and 20 to 80 parts of amorphous olefin polymer
3. The method for producing a thermoplastic elastomer according to claim 1 or 2, characterized in that it consists of parts by weight. 4) The soft polymer is an ethylene-α-olefin copolymer rubber, a propylene/α-olefin copolymer rubber having 4 or more carbon atoms, or a hydrogenated product of a styrene-conjugated diene block copolymer. A method for producing a thermoplastic elastomer according to any one of claims 1 to 3.