JPH0425531A - Production of thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer composition improved in heat resistance, tensile properties, weathering resistance, flexibility, resiliency, flow and molding appearance by melt-kneading specified polymer particles with a crosslinking agent and a polyolefin. CONSTITUTION:A 2-20 C alpha-olefin is (co)polymerized in the presence of a catalyst to obtain noncrosslinked polymer particles having a mean particle diameter of 10mum or above, a geometrical standard deviation of 1.0-3.0 and an apparent bulk density of 0.2g/ml or above, not subjected to such a heat history as to impair its particle shape and comprising a crystalline olefin polymer part and an amorphous olefin polymer part. The particles and a crosslinking agent are melt-kneaded in the presence of a polyolefin to obtain the title composition containing the crosslinked polymer and the crosslinked polyolefin and/or the noncrosslinked polyolefin in a weight ratio of (90-50):(10:50).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a thermoplastic elastomer composition. The present invention relates to a method for producing a thermoplastic elastomer composition that can provide molded products with good quality and excellent appearance.

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 that (a) the rubber is made of ethylene-propylene-nonconjugated polyene copolymer rubber;
A thermoplastic elastomer comprising a partially crosslinked copolymer rubber having a gel content of 30 to 90% by weight and (b) a polyolefin resin is disclosed. In addition, special public service 55-1
No. 8448 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 C12, with a propylene content of 100 to 100.
60% by weight of one or more of the blocks [A]
Olefinic 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 coalescence 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. 63-161516, and U.S. Pat. No. 4,454,306 disclose a propylene homopolymer block [A] produced using a specific Ziegler catalyst, and propylene/ethylene 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-411-2+731 discloses that 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, 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 present inventors investigated how to economically produce thermoplastic elastomers with excellent quality, and found that if polymer particles with a specific morphology were used, they would have excellent elasticity even with a small rubber content. Moreover, it is possible to obtain a molded product which has excellent strength and also has an excellent appearance, especially after painting, when molded into a molded product, and the thermoplastic elastomer particles and crosslinked polyolefin and/or non-crosslinked polyolefin can be used together. A thermoplastic elastomer composition comprising:
The present inventors have discovered that it is possible to provide molded products that not only have excellent heat resistance, tensile properties, weather resistance, flexibility, and rebound properties, but also have good fluidity and excellent appearance, and have completed the present invention.

Purpose of the Invention The present invention provides a method for producing a thermoplastic elastomer composition that can provide molded products with excellent heat resistance, tensile properties, weather resistance, flexibility, and rebound properties, as well as good fluidity and excellent appearance. is intended to provide.

Summary of the Invention The method for producing a thermoplastic elastomer composition according to the present invention comprises producing polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion that have not undergone a thermal history that would impair the particle shape. It is characterized by crosslinking in the presence of a crosslinking agent and melt-kneading to obtain a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and/or a non-crosslinked polyolefin.

Examples of methods for manufacturing such thermoplastic elastomer compositions include the following three types of manufacturing methods.

(1) Non-crosslinked polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are melt-kneaded in the presence of a crosslinking agent and a polyolefin to form a crosslinked polymer and a crosslinked polyolefin. and/or a non-crosslinked polyolefin.

(2) By melt-kneading a crosslinked polymer obtained by crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part in the presence of at least a crosslinking agent and a polyolefin, A method for producing a thermoplastic elastomer composition, which comprises obtaining a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and/or a non-crosslinked polyolefin.

(3) Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are heated at the melting point of the crystalline olefin polymer or the glass transition of the amorphous olefin polymer in the presence of at least a crosslinking agent. A thermoplastic elastomer composition containing a crosslinked polymer and a polyolefin is obtained by melt-kneading the vapor-phase crosslinked polymer particles obtained by contacting the particles at a temperature lower than the higher of the two points in the presence of a polyolefin. A method for producing a thermoplastic elastomer composition, characterized in that it obtains a thermoplastic elastomer composition.

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

Polymer particles The polymer particles used in the present invention are polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion, which have not undergone a thermal history that would impair the particle shape, and are crosslinked. There are two types of polymer particles: non-crosslinked polymer particles and crosslinked polymer particles.

The above-mentioned crosslinked polymer particles are prepared by combining polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion, and a crosslinking agent at the melting point of the crystalline olefin polymer or the amorphous olefin. Particulate crosslinked thermoplastic elastomer particles obtained by contacting at a temperature below whichever is higher of the glass transition temperature of the polymer. In this specification,
Particulate crosslinking as described above is referred to as gas phase crosslinking, and such thermoplastic elastomer particles are sometimes referred to as gas phase crosslinked polymer particles.

The average particle diameter of the polymer particles (hereinafter sometimes simply referred to as "polymer particles") used in the present invention before melt crosslinking or gas phase crosslinking is usually 10 μm or more, preferably 10 μm or more.
~8000μm1 More preferably 100~4000μm
m1 is particularly preferably within the range of 300 to 3000 μm. Further, the geometric standard deviation indicating the particle size distribution of the polymer particles used in the present invention is usually 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.5. ,
Particularly preferably, it is within the range of 1.0 to 1.3. Also,
The apparent bulk density of the polymer particles used in the present invention due to natural fall is usually 0.2 g/m or more, preferably 0.
2-0, 7 g/ml, more preferably 0
．． 3-0.7 g/ml, particularly preferably 0.35-0.
It is within the range of 60g/ml.

Further, in the polymer particles used in the present invention, the particles passing through a 150 mesh sieve are preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 2% by weight or less.
% 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 double coalesced particles were placed in a stainless steel sieve made by Nippon Rikagaku Kikai 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). 11DA 5IEVE 5HAKER (Iida Seisakusho)
and shaken for 20 minutes.

After shaking for 20 minutes, place on each sieve. Measure the weight of the polymer and compare the measurements. The numbers were plotted on established paper. the plot are connected by a curve, and the product is based on this curve. Particle size at 50% calculated weight (D5o) 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 diameter (D16) in % and the above D5o value.

(Geometric standard deviation=D5o/D16) Apparent bulk density: Measured in accordance with Its K 6721-1977. (However, the inlet inner diameter of the funnel used was 92.9+nmφ, and the outlet inner diameter was 9.5 nmφ.
Met. ) Falling seconds: Using the bulk density measuring device as is, drop the sample into the receiver, scrape off 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, 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.

When measuring the falling seconds, set the receiver on the vibration table of a powder tester (Type PT-D, SER, No. 71190 manufactured by Hosokawa Micro), and adjust the voltage of the rheostat so that the vibration width of the diaphragm is 1 hour. The polymer particles were allowed to fall without being adjusted and 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 some crystalline olefin polymer portion as the case may be) is 0.5 μm or less, preferably 0.1 μm or less, and more preferably 0.1 μm or less. 0.00001
It is desirable that the thickness is 0.05 μm. In addition, there are cases where a compatible structure is formed in which the high part and the sea part cannot be distinguished.

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 section of a sealed container containing 200 ml of an aqueous solution of Ru 04 of 30 minutes for 30 minutes to stain the amorphous olefin polymer section 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, and the halogen content is usually 300 ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less.

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, pentene-1,2-methylbutene-1,3-methylbutene-1, hexene-1,3-methylpentene-1,4-methylpentene-1, L3.3 dimethylbutene-1, heptene-11 methylhexene-1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene-11 dimethylhexene-1, trimethylpentene-1, ethylhexene -1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene-11 published by dimethyloctene, trimethylhebutene-1
, ethyl octene-1, methylethylhebutene-1, diethylhexene-1, dodecene-1 and hexadodecene-1.

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

In the present invention, polymer particles containing repeating units derived from the above-mentioned α-olefin are usually 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 100 mol%. is 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, 1.3.7-octatriene,
1.5.9-Decatriene, divinylbenzene, etc. are used. Further, specific examples of the cyclic polyene compound include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5ethyl-13-cyclohexadiene, 1.3-cyclohexadiene,
-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-norbornadiene, etc. 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 α-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-
Bicycloalkenes such as dimethyl-2-norbornene, 5,5.6-drimethyl-2-norbornene, and 2-bornene, 2331.71-tetrahydro-4,7-methano-
Tricycloalkenes such as IH-indene, 3i, 5.6.71-tetrahydro-4,7-methano-IH-indene, 14.58-dimethano-12,3,4,4g
5.8.8 g-octahydronaphthalene, and in addition to these compounds, 2-methyl 14.58-dimethano-1
,2,3,4,4m, 5.8.8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-I
, 2.3.4.4! , 5.8.81-octahydronaphthalene, 2-propyl-1,4,58-dimethano-
12344! 588a-octahydronaphthalene, 2
-hexyl-145,8-dimethano-1,2,3,4,
4a, 5.8.8a-octahydronaphthalene, 2-
Stearyl-1,4,5,8-dimethano 12, 3.4.
4g, 5.8.8! -octahydronaphthalene, 23
-dimethyl-1,4,5,8-dimethano-1,2,3,
4,6,5883-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-], 2
．． 3.4.4a, 5.8.8a-Octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2
, 3,4,41,5,8,81-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,
3,4, 1588a-octahydronaphthalene, 2-
Fluoro-1458-dimethano-1234,4m, 5
．． 8.8a-octahydronaphthalene, 2.3-dichloro-1,4,5,8-dimethano-12,3,4,4t,
5.8.8m-Tetracycloalkenes such as octahydronaphthalene, hexacyclo[6,63,6]0. I
3. o2.7. o9.14 Ko, Butadaaaa 4.1.1
．． 1 2.9 4.7 11.18.0 Pentacyclo[8,8,l,1. 13.8
12.17 0. 0]]Henkokosen-5 octacyclo2.9 4.7 If, ill 13,16 3
．． 8 [Lll, I, 1. 1. 1
．． 0. [112,170 Cyclic monoene compounds such as polycycloalkenes such as tococene-5 can be mentioned.

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

The polymer particles used in the present invention 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 ] is used.

The above catalyst component [A] is preferably a catalyst containing a transition metal atom of Group IVB 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 IVB 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 a solid state in the reaction system during the polymerization reaction or copolymerization reaction as described above, or is present in a solid state by being supported on a carrier or the like. It is 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.
, 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 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 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 (δ 2 ) is determined as the ratio (θ5o/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
4 to 100, preferably 6 to 40, and the electron donor/titanium (molar ratio) is usually 0.1 to 10. Preferably it is within the range of 0.2 to 6. Further, the specific surface area of this catalyst component [A] is usually 3 rrf/g or more,
Preferably 40rd/g or more, more preferably 100rd/g or more
~800 go/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], or 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.

Catalyst component [A] as shown in 2 can be used as it is, or it 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 (δ) 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 with 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 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 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 having an isotoughness index (insoluble content in boiling n-heptane) 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 hyde 0 talcite, magnesium carboxylates, alkoxymagnesium, allyloxymagnesium,
In addition to alkoxymagnesium halide, allyloxymagnesium halide, and magnesium cybaride, 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, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, 1 to 1 carbon atoms, such as isopropyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol
Alcohols of 8; C6-20 phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol (these phenols may have a lower alkyl group) Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolylaldehyde and naphthaldehyde. Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluyl Methyl acid, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, phthalic acid 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; 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); It is a substituent having one type of element, R-R2I' is bonded to the main chain through a carbon-carbon bond, and any R1-R26 may jointly form a ring other than a benzene ring. , and the main chain may contain elements other than carbon. More specifically, 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl, 3-dimethoxypropane, 2-5-butyl-1,3- Dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-13-dimethoxypropane, 2
-cumyl-13-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2
-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-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-(p-1-butylphenyl)-1,3-dimethoxypropane, 2.2-
dicyclohexyl-1,3-dimethoxypropane, 2.
2-diethyl-1,3-dimethoxypropane, 2,2-
Dipropyl-1,3-dimethoxypropane, 22-dibutyl-1,3-dimethoxypropane, 2-methyl-2-
Propyl-1,3-dimethoxypropane, 2-methyl-
2-benzyl-13-dimethoxypropane, 2-methyl-2-ethyl-13-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2
-Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-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) to 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl -1,3-dimethoxypropane, 22-bis(cyclohexylmethyl)-
1,3-dimethoxypropane, 22-diisobutyl-1
, 3-jethoxypropane, 2,2-diisobutyl-1
, 3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-
S-butyl-1,3-dimethoxypropane, 2,2-sheetbutyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxy Propane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-13-dimethoxypropane, 2,3-diphenyl-14-jethoxybutane, 2,3-dicyclohexyl -1,4-jethoxybutane, 2,2-dibenzyl-
1,4-jethoxybutane, 2,3-diisopropyl-
1,4-jethoxybutane, 2.2-bis(p-methylphenyl)-1,4-dimethoxybutane, 2.3-bis(p-chlorophenyl)-1,4-dimethoxybutane,
2.3-bis(p-fluorophenyl) 1,4-dimethoxybutane, 2.4-diphenyl-15-dimethoxypentane, 2.5-diphenyl-15-dimethoxyhexane, 2.4-diisopropyl-1,5- Dimethoxypentane, 2.4-diisobutyl-1,5-dimethoxypentane, 2.4-diisoamyl-15-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1.3-diisoamyloxypropane, 1 .2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane,
1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene, 3-dimethoxypropane, 2,2-pentamethylene -13-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis(methoxymethyl)cyclohexane, 2.8-dioxaspiroT5.5) undecane, 3.7-thioxabicyclo[ 3,3,1] Nonane,
3.7-thioxabicyclo[3,3,01 octane, 3
, 3-diisobutyl-1,5-oxononane, 6.6-
Dibutyldioxyhebutane, 1,1-dimethoxymethylcyclopentane, 1,1-bis[dimethoxymethylcocyclohexane, 1,1-bismethoxymethyl]bicyclo[2,2,l]hebutane, 1,1 -dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-13-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 3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxy Methyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-13-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1, 3-jethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2isopropyl-2-ethoxymethyl-1,3-jethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1
, 3-dimethoxycyclohexane, 2-isobutyl-2
-Ethoxymethyl-1,3-jethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-13-dimethoxycyclohexane, tris(p-methoxyphenyl)
An example is phosphine. Of these, 1.3
-Diethers are preferred, especially 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-
2-isopentyl-1,3-dimethoxypropane, 2.
2-dicyclohexyl-1,3-dimethoxypropane,
2. C5-40 diethers such as 2-bis(cyclohexylmethyl)-1,3-dimethoxypropane; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, Amines such as tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile 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, 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 [AJ. It can also be converted into the above electron donor.

The catalyst component [AJ] 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-hebutane, n-octane, isooctane, n-decane, n-
-Aliphatic hydrocarbon compounds such as dodecane, kerosene, and liquid paraffin; Ring hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon compounds such as benzene, toluene, xylene, and cymene; chlorobenzene; , dichloroethane, and other halogenated hydrocarbon compounds.

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 AJ-carbon bond in the molecule are used.

Examples of such organoaluminum compounds include (where R1 and R2 usually have 1 to 15 carbon atoms).
, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is a halogen atom, m
is a number of 0≦m≦3, n is 0≦n<3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3), and ( have the same meanings as above) complex alkylated products of metals of Group 1 of the periodic table and aluminum, and the like.

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

and m is preferably a number of 1.5≦m≦3).

A compound represented by the formula R1mAlx (where R1 has the same meaning as above, and X is)\logen, m
is preferably 0 < m < 3).

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

is halogen, 0<m≦3, O≦n<3, O≦q<3,
m+n+q=3).

Specifically, the organoaluminum compound represented by the above formula (i) includes trialkylaluminums such as triethylaluminum, tributylaluminum, and triisopropylaluminium, trialkenylaluminums such as triisoprenylaluminum, and diethylaluminum ethoxy. 2,5
Partially alkoxylated alkylaluminums having an average composition of Alkylaluminum sesquihalides such as sesquipromide, partially halogenated alkylaluminiums such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, diethylaluminum hydride, dibutylaluminum hydride, etc. dialkylaluminum hydrides, partially hydrogenated alkyl aluminum dihydrides such as ethyl aluminum dihydride, probyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum Partially alkoxylated and halogenated alkyl aluminums such as ethoxypromide 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 Al0A1 (C2R5)2, (C4
H9) 2 people l0AI (C4H9)2, and so on.

Further, as the organoaluminum compound represented by the above formula (i), specifically, LiAI(C2R5), i
and Li AA (C7H,) 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 1, 2, 2, and 2 of the periodic table. and their acceptable salts. Note that the salts are organic acids and catalyst components [B
] It can also be formed in the reaction system by reaction with an organometallic compound used as a compound.

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.

Further, when the electron donor in the catalyst component [A] is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, the electron donor [C] has the formula RSi (OR
') n 4-n (However, in the above formula, R and R1 represent a hydrocarbon group, and 0≦n<4) or an amine with large steric hindrance is used. is preferred.

Specifically, such alkoxy(aryloxy)silane compounds include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane,
Dimethylethoxysilane, diisopropyldimethoxysilane, (-butylmethyldimethoxysilane, 1-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis-〇-tolyl) Dimethoxysilane, bis-m-1-lyldimethoxysilane, bis-p-tolylmethoxysilane, bis-p-tolyljethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxy Silane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxysilane, decylmethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane , vinyltriethoxysilane, [-butyltriethoxysilane, n-butyltriethoxysilane, 0-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane , vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2
-Norbornanetriethoxysilane, 2-norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(al171oxma)silane, vinyltris(β-methoxyethoxysilane), dimethyltetraethoxydisiloxane, etc. is used.

Among these, especially ethyltriethoxysilane, n-propyltriethoxysilane, t-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.

Particularly suitable examples of the highly sterically hindered amine include 226-rotetramethylpiperidine, 2,2,55-tetramethylpyrrolidine, 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.

(Left below) In addition, in the present invention, a catalyst component [i] containing a compound of a transition metal atom 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 A catalyst consisting of component [i] can be preferably used.

Here, examples of transition metals of groups rVB 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 (-butylcyclopentagenyl group, a dimethylcyclopentagenyl group) basis,
Examples include alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl groups, indenyl groups, and fluorenyl groups.

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

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

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

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

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

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

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

For example, when the valence of the transition metal is 4, the transition metal compound containing a ligand having a cycloalkagenyl skeleton used in the present invention has the following formula: R2R3R4R5M k 1 m n ( In the formula, M is zirconium, titanium, hafnium, vanadium, etc., R2 is a group having a cycloalkashenyl skeleton, RSR 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+A'+m+n=4).

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

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

Bis(cyclopentagenyl)zirconium monochloride monohydride, Bis(cyclopentagenyl)zirconium monopromide monohydride, Bis(cyclopentagenyl)methylzirconium hydride, Bis(cyclopentagenyl)ethylzirconium hydride, Bis (cyclopentagenyl) phenylzirconium hydride, bis(cyclopentagenyl)benzylzirconium hydride, bis(cyclopentagenyl) neopentylzirconium hydride, bis(methylcyclopentagenyl)zirconium monochloride hydride, bis(indenyl) Zirconium monochloride monohydride, bis(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium dimethyl
bis(cyclopentagenyl)methylzirconium monochloride, bis(cyclopentagenyl)ethylzirconium monochloride, bis(cyclopentagenyl)cyclohexylzirconium monochloride, bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, bis(methylcyclopentagenyl)zirconium dichloride, bis(i-butylcyclopentagenyl)zirconium dichloride bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis (cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium diphenyl, bis(cyclopentagenyl)zirconium dibenzyl, bis(cyclopentagenyl)zirconium methoxychloride, bis(cyclopentagenyl)zirconium ethoxy Chloride, Bis(methylcyclopentagenyl)zirconium ethoxychloride, Bis(cyclopentagenyl)zirconium phenoxychloride, Bis(fluorenyl)zirconium dichloride, Ethylenebis(indenyl)diethylzirconium, Ethylenebis(indenyl)diphenylzirconium, Ethylenebis (indenyl)methylzirconium, ethylenebis(indenyl)ethylzirconium monochloride, ethylenebis(indenyl)zirconium dichloride, isopropylbisindenylzirconium dichloride, isopropyl(cyclopentadienyl)fluorenylzirconium chloride, ethylenebis(indenyl) ) Zirconium dibromide, Ethylene bis(indenyl) zirconium methoxy monochloride, Ethylene bis(indenyl) zirconium ethoxy monochloride, Ethylene bis(indenyl) zirconium phenoxy monochloride, Ethylene bis(cyclopentajenyl) zirconium dichloride, Propylene bis( cyclopentagenyl) zirconium dichloride, ethylenebis(t-butylcyclopentagenyl)silconium dichloride, ethylenebis(45,6,7-tetrahydro-1-indenyl)dimethylzirconium, ethylenebis(45,6,7- Tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)
Zirconium dichloride, Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, Ethylenebis(4-methyl-1-indenyl)zirconium dichloride, Ethylenebis(5-methyl-indenyl)zirconium dichloride, Ethylenebis(6-methyl-1-indenyl)zirconium dichloride, Ethylenebis(7-methyl-1-indenyl)zirconium dichloride, Ethylenebis(5-methoxy-1-indenyl)zirconium dichloride, Ethylenebis(2,3-dimethyl) -1-indenyl) zirconium dichloride, ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride, ethylenebis(4,7-dimethoxy-indenyl)zirconium dichloride.

In the above-mentioned 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 [i]
As such, 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.

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 when catalyst component (i) and (
When using catalyst component [A] or catalyst component (j), for example, the amount of catalyst component [A] or catalyst component (j) is usually 0.001 to 0.5 mmol in terms of transition metal, preferably 0.
．． 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. Bl] metal atoms usually 1 to 10,000 mol,
Preferably it is used in an amount of 5 to 500 mol. moreover,
When using an electron donor [C], the electron donor [C] is
It is used in an amount of 100 mol or less, preferably 1 to 50 mol, particularly preferably 3 to 20 mol, per 1 mol of transition metal atoms of catalyst component [A] in the polymerization system.

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/cf11, preferably 2 to 200°C.
It is 50 kg/ci.

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.

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

Prepolymerization can be carried out using inert hydrocarbon solvents. 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, 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, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-
α-olefins having 10 or less carbon atoms, such as pentene, 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 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 cannot be generally specified, but 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 propylene is used as the α-olefin, -40 to 70°C; when 1-butene is used,
-40 to 40°C, -40°C 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 performing prepolymerization as described above, or without performing prepolymerization, 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/d1, preferably normal pressure to 50 kg/co? 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.

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".

Among the polymer particles used in the present invention, non-crosslinked polymer particles are the above-mentioned polymer particles, and gas-phase crosslinked polymer particles are the above-mentioned polymer particles and a crosslinking agent. Crosslinked polymer particles (particulate crosslinked thermoplastic elastomer).

As the crosslinking agent used in the present invention (including when used in the production of gas phase crosslinked polymer particles), organic peroxides, sulfur, phenolic vulcanizing agents, oximes, polyamines, etc. are used. Among these, organic peroxides and phenolic vulcanizing agents are preferred from the viewpoint of 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.

Further, specific examples of the organic peroxide include dicumyl peroxide, di-1erl-butyl peroxide,
2,5-dimethyl-2,5-bis(l-butylperoxy)hexane, 2,5-dimethyl-2,5
-bis(le-butylperoxy)hexyne-3,1
, 3-bis(fer l-butylperoxyisopropyl)benzene, 1j-bis(lerl-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(le- butyl peroxy) valerate, dibenzoyl peroxide, terf
-butyl peroxybenzoate, etc. are used. Among these, dibenzoyl peroxide, 1,3-bis(lerj
-butylperoxyisopropyl)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, 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, sibinylhenzen is easy to handle, has good compatibility with polymer particles, and has an organic peroxide solubilizing effect and also acts as a peroxide dispersion aid, so that the crosslinking reaction occurs homogeneously and the fluidity increases. 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 auxiliary agent 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 composition or gas-phase crosslinked polymer particles, in addition to the polymer particles, crosslinking agent, and crosslinking aid, peroxide non-crosslinked type typified by polyisobutylene, butyl rubber, etc. It is also possible to carry out the crosslinking reaction of the polymer particles in the presence of hydrocarbon rubbery substances and/or mineral oil softeners.

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, during the production of gas-phase crosslinked polymer particles, 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; and alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene. ．． Chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, dichloroethylene, trichlorethylene, methanol, ethanol, n-propanol, l5O-propanol tool,
Alcohol solvents such as n-butanol, 5ec-butanol, tell-butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethyl phthalate, dimethyl ether, diethyl ether, di-n-amyl Ether solvents such as ether, tetrahydrofuran, dioxane, and anisole 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 as described 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 relative to 100 parts by weight of the polymer particles, and the gas phase crosslinking reaction in the present invention is different from a solvent suspension reaction in which a large excess of solvent is used.

The gas phase crosslinking reaction in the present invention is carried out at a temperature that melts the polymer particles and does not cause them to fuse together. - For boat fishing, the above reaction is carried out at a temperature in the range from 0° C. to below the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer, whichever is higher. For example, when the above-mentioned polymers having high melting points are polypropylene, high density polyethylene, and low density polyethylene, the temperature is about 150°C, 1
The upper limit of the reaction temperature is around 20°C and around 90°C.

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 gas phase crosslinking reaction is carried out, and the pressure is 0.
~50 kg/ad, preferably 1-20 kg/c! 11
More preferably, it is 1 to 5 kg/ad. The gas phase crosslinking reaction can be carried out either batchwise or continuously.

When producing gas-phase crosslinked polymer particles, it is best to bring the polymer particles, a crosslinking agent, and, if necessary, a crosslinking aid and a mineral oil softener into contact at the same time to carry out a gas-phase crosslinking reaction. Most preferably, the gas phase crosslinking reaction can also be carried out by separately contacting the polymer particles with 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 component) is fixed within the particles at the molecular segment level.

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

In addition, in crosslinked polymer 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 40 to 100% by weight. 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. Approximately 100 μ sample pellets of thermoplastic elastomer (size of each pellet: 1 × 1 mm × 0.5 =) were weighed and immersed in 30 cc of cyclohexane at 23°C for 48 hours in a closed container. Remove and dry. 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) is obtained by subtracting the weight of these cyclohexane-insoluble fillers, pigments, and other components other than the polyolefin resin.

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

Corrected final weight (Y) Gel content (%) =
It is in the range of 5000 μm, preferably 200 to 4000 μm, and more preferably 300 to 3000 μm. Further, the crosslinked polymer particles used in the present invention have a geometric standard deviation representing the particle size distribution of 1.0 to 3.0, preferably 1.0 to 2.0, more preferably 1.0 to 1.0. 5, more preferably within the range of 1.0 to 1.3.

Further, the crosslinked polymer particles used in the present invention have 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 crosslinked polymer particles used in the present invention have an 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. Further, the crosslinked polymer particles used in the present invention have a particle size of 10
The amount of fine particles of 0 μm or less is 20% by weight or less, preferably 0
-10% by weight, more preferably 0-2% by weight.

In addition, the crosslinked polymer particles (thermoplastic elastomer particles) produced as described above contain fillers such as calcium carbonate, calcium silicate, clay kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, and sulfuric acid. barium, aluminum sulfate, calcium sulfate,
Basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass bulb, shirasu balloon, carbon fiber or coloring agents such as carbon black, titanium oxide, zinc white, red iron, ultramarine blue, deep blue, azo dyeing, nitroso dye, lake pigment, Phthalocyanine pigments and the like can also be blended.

The crosslinked polymer particles used in the present invention are polymer particles obtained by performing a crosslinking reaction (gas phase crosslinking reaction) of polymer particles at low temperatures, so thermal decomposition of the polymer particles can be suppressed. It is possible to 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.

In particular, crosslinked polymer particles (thermoplastic elastomers) in which amorphous olefin polymer parts (rubber components) are fixed at the molecular segment level have improved flexibility, surface smoothness, and paintability at low temperatures. Can give excellent molded products.

Polyolefins The polyolefins used in the present invention include ethylene, propylene, I-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4- Homopolymers or copolymers of α-olefins such as methyl-1-pentene and 1-octene, or copolymers of α-olefins with small amounts of other polymerizable monomers, e.g. Ethylene-
Examples include polyolefins such as vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methacrylic acid copolymer.

In the present invention, the polyolefin has a weight ratio of the crosslinked polymer to the crosslinked polyolefin and/or non-crosslinked polyolefin (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) constituting the thermoplastic elastomer composition of 90/10. It is used at a ratio of ~5/95.

In the present invention, when a polyolefin is used in the above blending ratio, a thermoplastic elastomer composition that has better fluidity and can provide molded articles with excellent appearance can be obtained.

In the present invention, the weight ratio of the crosslinked polymer and the crosslinked polyolefin and/or non-crosslinked polyolefin constituting the thermoplastic elastomer composition (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) is 5/
95-49151, preferably 10/90-40/60
When polyolefin is used in a proportion that
Properties such as cold resistance can be improved. Moreover, unlike conventional polyolefin-rubber compositions, the composition does not extremely deteriorate fluidity and cause poor appearance. In particular, for soft polyolefins such as low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer, it is necessary to not only prevent sink marks but also to prevent sink marks.
Rubber properties such as heat resistance and permanent elongation can be improved.

On the other hand, in the present invention, the weight ratio of the crosslinked polymer to the crosslinked polyolefin and/or non-crosslinked polyolefin (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) is 90/10 to 50150, preferably 77/23 to 67. The thermoplastic elastomer composition of No./33 can be molded using equipment used in the molding of ordinary thermoplastics, and is suitable for extrusion molding, calendar molding, and especially injection molding. In addition, this thermoplastic elastomer composition is polyolefin-rich in which the weight ratio of crosslinked polymer to crosslinked polyolefin and/or non-crosslinked polyolefin (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) is 5/95 to 49151. Compared to thermoplastic elastomer compositions, it has even better rubber properties such as heat resistance, tensile properties, flexibility, and rebound resilience, and has even better fluidity.
It is possible to provide large, thick-walled products with excellent appearance without flow marks or sink marks.

In the present invention, in addition to the above polymer particles (including gas-phase crosslinked polymer particles) and polyolefin, conventionally known heat stabilizers, weather stabilizers, antiaging agents, antistatic agents, pigments, dyes, and fillers are used. , flame retardant, nucleating agent, lubricant, slip agent,
Additives such as antiblocking agents can be added within the range that does not impair the purpose of the present invention.

Manufacturing method In order to manufacture the thermoplastic elastomer composition in the present invention, for example, a mixture containing non-crosslinked polymer particles as described above, a crosslinking agent, and a polyolefin is melt-kneaded, and partially or Complete crosslinking is sufficient.

The above-mentioned crosslinking agent is about 0% per 100 parts by weight of the polymer particles.
．． It is used in an amount of 0.01 to 2 parts by weight, preferably 0.03 to 1.0 parts by weight, more preferably 0.05 to 0.5 parts by weight.

As the mixing device used in the above-mentioned melt-kneading, an open-type device such as a mixing roll, or a non-open-type device such as a Banbury mixer 1 extruder, a Niegoo, or a continuous mixer can be used. Among such kneading devices, an extruder is particularly preferably used.

The kneading is preferably carried out in a non-release type device, and preferably carried out under 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.

According to this production method, a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and/or a non-crosslinked polyolefin is obtained.

In addition, in the present invention, a crosslinked polymer obtained by crosslinking the above-mentioned uncrosslinked polymer particles in at least the presence of a crosslinking agent and a polyolefin are kneaded to partially or completely crosslink. By carrying out this process, it is also possible to produce a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and/or a non-crosslinked polyolefin.

The apparatus and melt-crossing conditions used for the above-mentioned melting and kneading are the same as the above-mentioned kneading apparatus and melt-crossing conditions.

Furthermore, in the present invention, a thermoplastic elastomer composition containing a crosslinked polymer and a polyolefin can also be produced by melt-kneading a mixture containing the above gas-phase crosslinked polymer particles and a polyolefin.

The apparatus used for the above melting and mixing is the same as the above-mentioned kneading apparatus.

The kneading is preferably carried out in a non-release type device, and preferably carried out under 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.

Effects of the Invention According to the present invention, there is provided a thermoplastic elastomer composition that has excellent heat resistance, tensile properties, weather resistance, flexibility, and rebound resilience, and can provide molded products with good fluidity and excellent appearance. be able to.

In the thermoplastic elastomer composition obtained by the production method according to the present invention, the weight ratio of crosslinked polymer to crosslinked polyolefin and non-crosslinked polyolefin (crosslinked polymer/
crosslinked polyolefin and non-crosslinked polyolefin) is 5
The thermoplastic elastomer composition of /95-49151 is
It has the effect of preventing sink marks, which are a disadvantage of polyolefins, and improving properties such as impact resistance and cold resistance. Moreover,
Unlike conventional polyolefin-rubber compositions, there is no possibility of extremely poor fluidity and poor appearance. In particular, thermoplastic elastomer compositions using soft polyolefins such as low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer are suitable for use in rubbers with anti-sink effect, heat resistance, and permanent elongation. It has the effect of improving physical properties.

Furthermore, in the thermoplastic elastomer composition obtained by the production method according to the present invention, the weight ratio of the crosslinked polymer to the crosslinked polyolefin and/or non-crosslinked polyolefin (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) is Thermoplastic elastomer compositions rich in thermoplastic elastomer (cross-linked polymer) of 90/10 to 50150 can be molded using equipment used in the molding of conventional thermoplastics, such as extrusion molding, calender molding and especially injection molding. Suitable for molding. Also,
This thermoplastic elastomer composition is a polyolefin-rich thermoplastic having a weight ratio of crosslinked polymer to crosslinked polyolefin and/or non-crosslinked polyolefin (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) of 5/95 to 49151. Compared to elastomer compositions, it has better rubber properties such as heat resistance, tensile properties, flexibility, and rebound resilience, and has even better fluidity and an excellent appearance with no flow marks or sink marks. This has the effect of being able to provide large, thick-walled products.

The thermoplastic elastomer composition according to the present invention having the above-mentioned effects can be used for body panels, bumper parts, site shields, automobile parts such as steering wheels, footwear such as shoe soles and sandals, electric wire coverings, connectors, and cap plugs. electrical parts such as golf club grips, baseball bat grips, swimming fins, swimming goggles and other leisure goods, waterproof sheets, water-stopping materials, joint materials, architectural window frames, architectural gaskets, covering materials for decorative rigid boards, etc. Used for civil engineering and construction parts, gaskets, waterproof fabrics, 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 21 was heated to sufficient N.
After 2 substitutions, 700ml of refined kerosene, commercially available Mg C1
210 g - 24.2 g of ethanol and 3 g of Emazol 320 (manufactured by Kao Atlas ■, sorbitan distearate) were added, and the system was heated to 120° C. with stirring.
Stirred at 0.00 + pm for 30 minutes. Under high speed stirring, inner diameter 5m
Using a Teflon tube, the liquid was transferred to a No. 21 glass flask (equipped with a stirrer) filled with refined kerosene II that had been cooled in advance to -10°C. 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 120°C for 2 hours, the solid part was collected by filtration and heated again at 150°C.
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 (
I got ^). 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 2 mmol of the T1 catalyst component [A] were charged in terms of titanium atoms. Thereafter, propylene was fed at a rate of 5.9 Nl/hour over 1 hour, and 2.8 g of propylene was polymerized per 31 g of the T1 catalyst component [A]. Humidity during polymerization was 20
It was kept at ±2°C. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

[Polymerization] Production of copolymer (+) After adding 2.0 kg of propylene and 19N liter of hydrogen to the polymerization vessel of 201 at room temperature, 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, the copolymerization was carried out sequentially: ethylene at 48 ONI/h, propylene at 72 ONI/h,
Hydrogen was supplied to the polymerization reactor at a rate of 12 NA'/hour. The temperature during the copolymerization was maintained at 70° C. while the vent opening of the polymerization vessel was adjusted so that the pressure inside the polymerization vessel was 10 kg/al·G. Copolymerization was carried out for a copolymerization time of 150 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 (1) to (3).

"Pre-polymerization" The catalyst component [A] was subjected to the following pre-polymerization. After charging 400 ml of purified hexane into 11 glass reactors purged with nitrogen, 1.32 mmol of triethylaluminum and 0 cyclohexylmethyldimethoxysilane were added. .27 mmol and the Ti catalyst component [A] is 0.27 mmol in terms of titanium atoms.
After charging 132 mmol, propylene gas and ethylene gas were added at 8.4 N1/hr and 1. The mixture was supplied to the liquid phase of the polymerization vessel for 100 minutes at a rate of ON1/hour while being mixed. 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 analysis, approximately 92 g of polymer was present on the used Ti catalyst component [A] Ig in the prepolymerized solid catalyst, while in the separated filtrate, the used Ti catalyst component [A]
There was an equivalent of 6.2 g of solvent soluble polymer per Ig.

Table Example 1 100 parts by weight of the powder of copolymer (3) obtained as described above and 20.2 parts by weight of 1,3-bis(tell-butylperoxyisopropyl)hen were mixed with 0.3 parts by weight of divinylbenzene. parts by weight and a solution dissolved and dispersed in 5 parts by weight of paraffinic process oil were mixed using a tumbler blender, and the solution was uniformly adhered to the powder surface of copolymer (3).

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.

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

100 parts by weight of the obtained pellets and MFR (ASTMD
1238 230℃)13. Polypropylene 40 with density 0.91g/cd and initial bending modulus 9.000kg/-
The physical properties and moldability of a thermoplastic elastomer composition obtained by extruding parts by weight using an extruder at 210°C were evaluated as follows.

First, the pellets were injection molded using the following equipment and conditions to produce square plates of 3" and 8" thickness, and the moldability was evaluated. Also, the thickness 3r obtained in this way
A test piece was cut from a square plate of Im, and its tensile properties, initial bending modulus, and Izot impact strength were measured.

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

Depth 3) Formability Judgment Criteria j) Flow marks 1: Flow marks are extremely numerous 2: Flow marks are considerably seen on the entire surface of the molded product 3: Flow marks are slightly seen on the entire surface of the molded product 4: Slight flow marks only seen on the opposite side of the gate 5: No flow marks seen at all 2) Sink mark 1: Sink mark seen over the entire surface 2: Sink mark seen on the opposite side of the gate 3: No flow mark seen at all Physical property evaluation Tensile properties: 100% tensile stress (Mloo, kg/ad) Tensile strength at break (Tb, kg/al) Elongation at break
(Eb, %) Measured in accordance with JIS K-6301.

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

Izod impact strength (IzOD kg-a [l/Cm)
Measured according to ASTM D 256.

(With a notch) Example 2 After mixing the powder of copolymer (3) obtained by mixing in a tumble blender in Example 1 with polypropylene, the powder was heated by extruding it at 210°C in a nitrogen atmosphere with an extruder. The same procedure as in Example 1 was carried out except that a plastic elastomer composition was obtained.

The results are shown in Table 2. Example 3 The procedure of Example 1 was repeated except that copolymer (2) was used instead of copolymer (3), and the results shown in Table 2 were obtained.

The powder of the above copolymer (2) has an average particle size of 2100
μm, the apparent density is 0.43 g/ml, and 1
The amount of particles passing through the 50 mesh was 0.1% by weight, and the falling time was 9.3 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.5.

Example 4 In Example 1, low density polyethylene (melt index (190°C): 23) was used instead of polypropylene.
．． Example 1 except that a density of 0.916 g/cd) was used.
The results shown in Table 2 were obtained in the same manner as above.

Example 5 In Example 1, ethylene-vinyl acetate copolymer (melt index (190
℃)15. The same procedure as in Example 1 was carried out, except that copolymer (1) was used instead of copolymer (3), and the results shown in Table 2 were obtained.

The powder of the above copolymer (1) has an average particle diameter of 2200μ
m, the apparent density is 0.45 g/ml, and 15
The particles passing through the 0 mesh were 0.1% by weight, the falling time was 8.3 seconds, and the geometric standard deviation was 1.6.

Example 6 In Example 1, linear low density polyethylene (melt index (190°C) =
2. The same procedure as in Example 1 was carried out except that the density was 0.720 g/cj), and the results shown in Table 2 were obtained.

Example 7 In Example 1, ethylene-propylene copolymer (melt index (190°C)
)=4. The same procedure as in Example 1 was conducted except that 150 parts by weight (density: 0.925 g/aj) was used.

The results are shown in Table 3.

Example 8 In Example 7, low density polyethylene (melt index (19) was used instead of the ethylene-propylene copolymer.
0°C): 23. The same procedure as in Example 7 was carried out except that the density was 0.916 g/all).

The results are shown in Table 3.

Example 9 In Example 7, ethylene-vinyl acetate copolymer (melt index (190°C): 15. Vinyl acetate content 15% by weight) was used instead of ethylene-propylene copolymer.
, average particle diameter of 1200 μm) was used.
I did the same thing.

The results are shown in Table 3.

\ Table Example 10 1 equipped with stirring blades having spiral double ribbons
Particles of the copolymer (3) obtained as described above were charged into a stainless steel autoclave, and the system was completely purged with nitrogen. After that, a crosslinking mixture (benzoyl peroxide (BPO) 0.15% by weight, divinylbenzene (DV&) 0.15% by weight, toluene 500ml
and oil (6% by weight) were added dropwise to the polymer particles at room temperature for 10 minutes while stirring the polymer particles, and
Stirring was performed for a minute to impregnate the polymer particles with these reagents. 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 yarn was lowered to 80° C., and the yarn was dried under reduced pressure.

100 parts by weight of the obtained thermoplastic elastomer and MFR1
3. Density 0. 91 g/cj, initial bending modulus 900
A thermoplastic elastomer composition obtained by extruding 40 parts by weight of 0 kg/cIl polypropylene at 210°C using an extruder was evaluated in the same manner as in Example 1.

The results are shown in Table 4.

Example 11 In Example 10, low density polyethylene (melt index (190°C): 2) was used instead of polypropylene.
3. The same procedure as in Example 10 was carried out except that a density of 1], 916 g/cj) was used, and the results shown in Table 4 were obtained.

Example 12 In Example 10, ethylene-vinyl acetate copolymer (melt index: 19
0°C): I5. The same procedure as in Example 10 was carried out except that vinyl acetate (with a vinyl acetate content of 14% by weight) was used, and the results shown in Table 4 were obtained.

Example 13 In Example 10, linear low density polyethylene (melt index: 190°C) was used instead of polypropylene.
, 2. The same procedure as in Example 10 was carried out except that a density of 0.920 g/cd) was used, and the results shown in Table 4 were obtained.

Example 14 In Example 10, ethylene-propylene copolymer (melt index (190
℃) 4. Density 0.925 g/(ml)150
The same procedure as Example 1o was carried out except that parts by weight were used.

The results are shown in Table 5.

Example 15 In Example 14, low density polyethylene (melt index (1
90℃)23. The same procedure as in Example 14 was carried out except that the density was 0.916 g/ad).

The results are shown in Table 5.

Example 16 In Example 14, ethylene-vinyl acetate copolymer (melt index (190°C) 15. Vinyl acetate content 15% by weight) was used instead of ethylene-propylene copolymer.
) was used in the same manner as in Example 14.

The results are shown in Table 5.

table table teenager Reason Man

Claims (1)

[Scope of Claims] 1) Polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion that have not undergone a thermal history that would impair the particle shape are crosslinked in the presence of a crosslinking agent, and A method for producing a thermoplastic elastomer composition, which comprises melt-kneading to obtain a thermoplastic elastomer composition containing a crosslinked polymer and a crosslinked polyolefin and/or a non-crosslinked polyolefin. 2) Non-crosslinked polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are melt-kneaded in the presence of a crosslinking agent and a polyolefin to form a crosslinked polymer, a crosslinked polyolefin and The method for producing a thermoplastic elastomer composition according to claim 1, characterized in that a thermoplastic elastomer composition containing a non-crosslinked polyolefin and/or a non-crosslinked polyolefin is obtained. 3) Crosslinking by melt-kneading a crosslinked polymer obtained by crosslinking polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part in the presence of at least a crosslinking agent and a polyolefin. The method for producing a thermoplastic elastomer composition according to claim 1, characterized in that a thermoplastic elastomer composition containing a polymer and a crosslinked polyolefin and/or a non-crosslinked polyolefin is obtained. 4) Polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are heated to the melting point of the crystalline olefin polymer or the glass transition point of the amorphous olefin polymer in the presence of at least a crosslinking agent. The vapor-phase crosslinked polymer particles obtained by contacting at a temperature lower than the higher of the above temperatures are melt-kneaded in the presence of a polyolefin to form a thermoplastic elastomer composition containing the crosslinked polymer and the polyolefin. A method for producing a thermoplastic elastomer composition according to claim 1, characterized in that the thermoplastic elastomer composition is obtained. 5) The weight ratio of the crosslinked polymer and the crosslinked polyolefin and/or non-crosslinked polyolefin constituting the thermoplastic elastomer composition (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) is from 90/10 to
Claims 1 to 4 characterized in that the ratio is 50/50.
A method for producing a thermoplastic elastomer composition according to any one of Items 1 to 3. 6) The weight ratio of the crosslinked polymer and the crosslinked polyolefin and/or non-crosslinked polyolefin constituting the thermoplastic elastomer composition (crosslinked polymer/crosslinked polyolefin and/or non-crosslinked polyolefin) is 5/95 to 4.
5. The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the ratio is 9/50.