JP2002356525A - Propylene block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene block copolymer excellent in rigidity and impact resistance. SOLUTION: The copolymer comprises a polypropylene of 20-80 wt.% and an ethylene-propylene copolymer of 20-80 wt.% in which an indeterminated ethylene-propylene copolymer part is micro-dispersed in the polypropylene. An average diameter of the parts as a circle having the same area and an average size of particles of 90% in the accumulative size distribution satisfy with specified equations.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a block copolymer comprising a propylene polymer and an ethylene-propylene copolymer, and more particularly, to a propylene polymer even when the ratio of the rubber component ethylene-propylene copolymer is high. The present invention relates to a propylene block copolymer which is highly dispersed in a coalesced substance, has no problem of polymer particles due to a small amount of a rubber component on a surface, and has good impact resistance.

[0002]

2. Description of the Related Art Isotactic polypropylene is
While having excellent properties of rigidity and heat resistance, there is a problem that the impact resistance is poor. In order to improve the impact resistance while maintaining the rigidity of the polypropylene, various techniques for forming a resin composition by blending an ethylene-propylene rubber with a crystalline polypropylene by a polymer blend have been developed. However, it is difficult to highly disperse heterogeneous polymers at a micro level using this polymer blending technique, and as a result, it is difficult to prepare a resin composition having well-balanced properties while maintaining high rigidity and impact resistance. Met. Further, in the case of a polymer blend, a step of blending and kneading different kinds of polymers is required, so that the cost is extremely high, and the production cost is sometimes more than twice that of a normal propylene polymer.

On the other hand, as a method for improving the problems of such a polymer blend, a method using a chemical blend in which propylene and ethylene or other olefins are polymerized stepwise to form a block copolymer has been studied for a long time. ing. In general, block copolymers based on chemical blends are produced by two-stage or multi-stage polymerization, usually by first polymerizing propylene and then copolymerizing ethylene with propylene or another olefin. At this time, in order to improve the impact resistance, the proportion of the rubbery polymer produced by copolymerization of ethylene and propylene is increased, but the produced rubber component precipitates on the surface of the polymer particles. ,
Accordingly, adhesion between polymer particles and adhesion of the polymer to the inner wall of the device occur. For this reason, it is difficult to produce a long-term stable block copolymer.

A propylene block copolymer is a propylene polymer section (or matrix) in which an ethylene-propylene copolymer is dispersed, whereas a conventional propylene block copolymer has ethylene-propylene copolymer particles (or section). ) Is very large, and as a result, the ethylene-propylene copolymer block particles grow on the surface of the polymer particles as described above, and especially after crystallization of the copolymer, grow larger and become microscopically highly dispersed. There is a problem that it is difficult to make the block copolymer, and as a result, the impact resistance is not improved despite the increase in the content ratio of the rubber component. As described above, the conventional propylene block copolymer has not yet improved the impact resistance significantly.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel structure in which an ethylene-propylene copolymer as a rubber component in a propylene polymer is highly dispersed even at a very high rubber component ratio. The present invention further provides a propylene block copolymer having very low adhesion of polymer particles and extremely good impact resistance.

[0006]

Under these circumstances, the present inventors have conducted intensive studies and as a result, have found that if a specific solid catalyst component is used, propylene is polymerized, and then ethylene and propylene are copolymerized. Ethylene-propylene copolymer which is a rubber component in a propylene polymer at a high ratio,
In addition, a propylene block copolymer having a novel structure excellent in impact resistance that can be blended in a high dispersion can be obtained. Further, this propylene block copolymer has a small rubber ratio on the particle surface, The present inventors have found that it is possible to stably produce a high-quality block copolymer without causing adhesion between the blocks and the inner wall of the apparatus, and have completed the present invention.

That is, the present invention relates to a propylene polymer 2
0-80% by weight and ethylene-propylene copolymer 20
A propylene block copolymer comprising at least about 80% by weight of ethylene oxide having an irregular shape in the propylene polymer.
When the propylene copolymer section is finely dispersed and the irregular-shaped ethylene-propylene copolymer section is converted into a circle having the same area, the average diameter (Dr) of the ethylene-propylene copolymer section becomes The following formula (1): Dr (μm) ≦ 0.005 × A (1) (where A represents the content (% by weight) of the ethylene-propylene copolymer in the propylene block polymer, and 20 ≦ A (weight%) ≦ 80) is provided.

Also, a propylene polymer of 20 to 80% by weight
And a propylene block copolymer comprising 20 to 80% by weight of an ethylene-propylene copolymer, wherein the propylene polymer and the ethylene-propylene copolymer are mixed and mixed with each other, and the propylene having an irregular shape. A polymer section and an ethylene-propylene copolymer section are formed, and when the ethylene-propylene copolymer section is converted into a circle having the same area, the average diameter of the ethylene-propylene copolymer section is ( (Dr) satisfies the following formula (1); Dr (μm) ≦ 0.005 × A (1) (where A is as defined above), which provides a propylene block copolymer. It is.

Further, the present invention relates to a propylene polymer 20 to
80% by weight, ethylene-propylene copolymer 20 to 8
A propylene block copolymer having a mean particle size of 100 to 5000 μm and containing 0% by weight, wherein the proportion of the ethylene-propylene copolymer on the particle surface is equal to the total ethylene-propylene block copolymer. 0.3 area% or less of the propylene block copolymer.

The present invention is also obtained by polymerizing propylene and then copolymerizing ethylene and propylene, or containing magnesium, titanium and halogen atoms, having an average particle size of 1 to 100 μm, and a specific surface area. Is 1
The cumulative pore volume of pores having a pore diameter of 100 to 500 m ² / g, a pore volume of less than 0.2 ml / g, and a pore diameter of 100 ° or less is 5
An object of the present invention is to provide the propylene block copolymer obtained by polymerizing propylene with a polymerization catalyst containing a solid catalyst component having a pore distribution of 0% or more and then copolymerizing ethylene and propylene.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The propylene block copolymer of the present invention comprises 20 to 80% by weight, preferably 30 to 70% by weight of a propylene polymer (hereinafter also referred to as "PP part").
And an ethylene-propylene copolymer (hereinafter referred to as “rubber part”).
Also called. ) 20-80% by weight, preferably 30-70%
% By weight of the block copolymer, wherein the ethylene-propylene copolymer section of irregular shape (hereinafter, also referred to as “rubber section”) is finely dispersed in the propylene polymer; In other words, the propylene polymer and the ethylene-propylene copolymer are mixed and mixed with each other, and both the propylene polymer section and the ethylene-propylene copolymer section having irregular shapes (hereinafter, also referred to as “PP section”). ), And when the rubber section is converted into a circle having the same area, the average diameter (Dr) of the rubber section satisfies the above equation (1), preferably the following equation (4); 0.02 ≦ Dr (μm) ≦ 0.0045 × A (4) (where A is as defined above), more preferably the following formula (5): 0.02 ≦ Dr (μm) ≦ 0.004 × A (5) (where A is as defined above).

Also, the propylene block copolymer of the present invention has a particle diameter (Dr90) at 90% of the cumulative particle size distribution of the ethylene-propylene copolymer section diameter.
Satisfies the following formula (3); Dr90 (μm) ≦ 0.01 × A (3) (where A is as defined above), preferably the following formula (6): 0.05 ≦ Dr90 (μm) ) ≦ 0.01 × A (6) (wherein, A is as defined above).

1 and 2 are cross-sectional TEM (transmission electron microscope) photographs of the propylene block copolymer of the present invention. FIG.
9% by weight, FIG. 2 shows 36.5% by weight of the PP portion and the rubber portion 6
It is 3.5% by weight. As described above, the propylene block copolymer of the present invention has a very small and irregularly shaped rubber section (black section) finely or highly dispersed in the PP section (white section), or When the PP part and the rubber part are mixed and mixed, and the PP part is large, the rubber part enters the finely cracked or island-like part of the PP part which becomes the matrix phase, When the rubber section is observed to be in a dispersed state and the rubber part is mixed in a large amount, the rubber part becomes a matrix phase, and the PP part enters the cracked or island-shaped part of the part, and the PP part section is formed. Observed in a dispersed state. When the blending ratio of the PP portion and the rubber portion is close to each other, such as 30 to 70% by weight: 70 to 30% by weight, neither of them can be distinguished from the matrix phase or the dispersed phase, and the fine particles having irregular shapes from each other. Are mixed (see FIGS. 1 and 2).

In the present invention, the rubber section is
One unit of an irregularly shaped rubber part, such as particles or threads, finely dispersed in the PP part.
Unit, and when multiple sections are continuous,
The part whose minimum width is less than 0.01 μm is regarded as a PP part and is regarded as one unit. The average diameter was calculated by image analysis of a TEM photograph of the cross section of the copolymer, obtaining the area of each rubber section, and converting it to the diameter of a circle having the same area.

The rubber portion may contain a crystalline ethylene polymer. When the rubber portion is composed of a crystalline ethylene polymer and an ethylene-propylene copolymer rubber, the rubber portion contains 1 to 80% by weight, preferably 10 to 50% by weight, of the ethylene-propylene copolymer. The coalesced rubber is the rest.

Further, in the propylene block copolymer of the present invention, the average diameter (Dpp) of the propylene polymer section (hereinafter also referred to as PP section) is as follows:
Formula; 5.0 ≧ Dpp ≧ e− ^0.02 × ^A (2) (wherein, A is as defined above). In the present invention, the PP section is one unit of particles in which an irregular rubber part such as a particle or a thread is present around the PP part. An independent part is defined as one unit. If continuous, the minimum width is 0.2 μm
The portion less than is regarded as a rubber part and is regarded as one unit. The average diameter was calculated by image analysis of a TEM photograph of the cross section of the polymer, obtaining the area of each PP section, and converting the area to the diameter of a circle having the same area.

As described above, according to the present invention, the average diameter of the PP section, which is the PP section particles, decreases as the proportion (block ratio) of the rubber section increases, and the structure is basically different. . That is, the PP portion of the conventional propylene block copolymer is not regarded as a PP portion section, and is basically in a continuous matrix state, and has a structure in which a rubber portion exists in pores inside the PP portion. there were. However, the propylene block copolymer of the present invention forms a PP section having a very small average diameter (or volume) of one unit, particularly when the rubber part ratio exceeds 50% by weight, and the diameter or the diameter of the PP section is increased around or inside the section. It has a structure in which there is an irregularly shaped rubber portion such as a very small particle or thread.

In the propylene block copolymer of the present invention, the average diameter of the PP section is 0.5 to 20 times, preferably 1.0 to 1 times the average diameter of the rubber section.
It is 5 times, particularly preferably 3.0 to 12 times. The above PP
The average diameter of the section varies depending on the proportion of the rubber section in the propylene block copolymer. The higher the proportion of the rubber section, the smaller the average diameter of the PP section and the larger the average diameter of the rubber section. . That is, as the ratio of the rubber portion increases, the PP portion particles are subdivided. As described above, since the rubber portion can be finely dispersed in the PP portion, the ratio of the rubber portion in the copolymer can be increased to 50% or more, and even in such a case, the weight is reduced as described later. The rubber part on the surface of the coalesced particles does not precipitate, there is no adhesion of the polymer particles, and the fluidity is maintained.

Table 2 shows preferred characteristics of the propylene block copolymer of the present invention. In Table 1, "MFR"
Indicates a melt flow rate value, and “(η)” indicates an intrinsic viscosity.

[0020]

[Table 1] ─────────────────────────────────── PP section Rubber section ─────── Ｍ MFR (g / 10 minutes) 0.1 to 500 − (η) − 1.0 to 20 Xylene solubles (% by weight)-15 to 70 Ethylene content (% by weight)-10 to 90 Xylene insolubles (% by weight) 30 to 85 20 to 80 mm ─────────────────────

The propylene block copolymer of the present invention is in the form of particles having an average particle size of 100 to 5000 μm, and the ethylene-propylene copolymer deposited on the particle surface is composed of the entire ethylene-propylene copolymer. It is 0.3% by volume or less, preferably 0.2% by volume or less, particularly preferably 0.1% by volume or less of the propylene copolymer, and the rubber portion existing on the surface of the copolymer particles is extremely small. Has features. In the conventional propylene block copolymer or its production method, when the proportion of the rubber part is low, the rubber part is generated inside the polymer particles or inside the matrix of the PP part, and is precipitated on the surface of the polymer particles. However, when the proportion of the rubber portion is high, the PP portion is cracked and the rubber portion is deposited on the polymer surface. For this reason, the polymer particles show adhesion, and as a result, the polymer particles adhere to each other and aggregate,
It adhered to the inner wall of the reaction tank or the inner wall of the transfer pipe, causing a trouble. In the propylene block copolymer of the present invention, even when the proportion of the rubber part is as high as 50% by weight or more, the rubber part is scarcely present on the polymer particle surface,
Almost no adhesion is seen. The ratio of the rubber part precipitated on the particle surface is determined by image analysis of a cross-sectional photograph of the polymer by TEM (transmission electron microscope), and the area of the rubber part precipitated on the particle surface and the total rubber part It is calculated by converting the area to the capacity.

Next, the method for producing the propylene block copolymer of the present invention will be described. Propylene block copolymer of the present invention is carried out by two or more stages of multi-stage polymerization,
Usually, it is obtained by polymerizing propylene in the presence of a polymerization catalyst in the first stage and copolymerizing ethylene and propylene in the second stage. It is also possible to polymerize α-olefins other than propylene in the second or subsequent stage, either coexisting or alone. Examples of the α-olefin include ethylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, 1-hexene, 1-octene and the like. Specifically, in the first stage, the polymerization is performed by adjusting the polymerization temperature and time so that the PP part ratio becomes 20 to 80% by weight, and then, in the second stage, ethylene and propylene or other α-olefin are added. And polymerized so that the rubber part ratio becomes 20 to 80% by weight. The polymerization temperatures in the first and second stages are both 2
The temperature is not higher than 00 ° C, preferably not higher than 100 ° C, and the polymerization pressure is not higher than 10 MPa, preferably not higher than 5 MPa. Further, in the case of polymerization time or continuous polymerization in each polymerization step,
The residence time is usually between 1 minute and 5 hours. Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon such as cyclohexane and heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method using substantially no solvent. . Preferred polymerization methods include a bulk polymerization method and a gas phase polymerization method.

The polymerization catalyst used for producing the propylene block copolymer of the present invention includes a solid catalyst component containing magnesium, titanium, a halogen and an electron donating compound, an organic aluminum compound, and if necessary, an external catalyst. A catalyst combining an electron donating compound is used.

The novel and unique structure of the propylene block copolymer of the present invention as described above is mainly due to the structure of the solid catalyst component used in the polymerization, and has the particle characteristics shown in Table 2. A solid catalyst component containing magnesium, titanium, halogen and an electron donating compound is used. Specific surface area and pore volume were determined by the BET method, and pore distribution was determined by t-
Using the plot method, the relative pressure obtained during the analysis and the adsorption volume data set were used to calculate BJH (Barrett, Joyner, Halal).
enda) method. These series of data are asap 2
405 (Shimadzu Corporation).

[0025]

[Table 2] ─────────────────────────────────── Preferably, particularly preferably ────── ───────────────────────────── Average particle size (μm) 1-100 20-50 Specific surface area (m2 / g) 100- 500 200-500 Pore volume (ml / g) 0.3 or less 0.1-0.2 Pore distribution 1 Cumulative pore size with a pore diameter of 100 mm or less Cumulative pore volume with a pore diameter of 100 mm or less is greater than 50% Pore volume is greater than 80% Pore distribution 2 Cumulative with a pore diameter of 50 mm or less Cumulative with a pore diameter of 50 mm or less Pore volume is 30% or more Pore volume is 50% or more ─────────────────────────

As described above, the solid catalyst used in the production of the propylene block copolymer of the present invention is characterized by a small pore volume, few relatively large pores having a diameter of 100 mm or more, and conversely, a diameter of 100 mm. The following fine pores are finely dispersed. The particles are formed by agglomeration of fine primary particles to form secondary particles, and the average diameter of the primary particles is 0.01 to 0.1 μm.

The solid catalyst component as described above is prepared by contacting a magnesium compound, a titanium halide compound and an electron donating compound. As the magnesium compound, magnesium halide such as magnesium dichloride or alkoxymagnesium is preferably used.
Examples of dialkoxymagnesium include diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. Of these, magnesium dichloride and diethoxymagnesium are preferred. Further, in order to prepare a solid catalyst component having the above-described particle characteristics, it is desirable that these magnesium compounds serving as a carrier also have particle characteristics substantially equivalent to the particle characteristics of the above-described solid catalyst component. Such a magnesium compound carrier is prepared by various methods. In the case of magnesium dichloride or diethoxymagnesium, first, it is finely divided by mechanical pulverization or pulverization such as a vibration mill or a homogenizer, and this is subjected to spray drying or the like. The particles are aggregated by the method to form carrier particles.

Of the above magnesium compounds, diethoxymagnesium is particularly preferred. The bulk specific gravity of diethoxymagnesium is 0.20 to 0.40 g / ml, more preferably 0.23 to 0.37 g / ml, and particularly preferably 0.1 to 0.3 g / ml.
It is desirable to use one in the range of 25 to 0.35 g / ml. When the bulk specific gravity is less than 0.20 g / ml, it becomes impossible to obtain a polyolefin having a high bulk specific gravity and a high stereoregularity in a high yield. On the other hand, bulk specific gravity is 0.40 g / ml
Exceeding the particle size adversely affects the particle properties of the produced polyolefin. Here, the bulk specific gravity is JIS K6721.
(1977).

The pore volume of diethoxymagnesium is preferably from 0.01 to 0.1 ml / g, more preferably from 0.01 to 0.06 ml / g, even more preferably from 0.015 to 0.1 ml / g. It is desirably in the range of 05 ml / g. When such a solid catalyst component prepared using porous diethoxymagnesium having a relatively small specific range of pore volume is subjected to the polymerization of olefins, it has high stereoregularity and excellent particle properties. In the case of block copolymerization, it is possible to obtain a copolymer with excellent particle properties in a high yield even when the production ratio of the rubbery polymer is high. Becomes

Further, the pore volume distribution of diethoxymagnesium is expressed as ln (R90 / R10) (where R90 is the pore radius at 90% in the cumulative pore volume, and R10 is the pore radius at 10% in the cumulative pore volume. Is 1.5 or more, preferably in the range of 1.5 to 3.5, and more preferably in the range of 2.0 to 3.0. Those having a certain wide pore volume distribution are preferred. Here, the pore volume distribution is measured by a method using an adsorption isotherm of nitrogen gas.

[0031] Further, the nitrogen adsorption specific surface area of diethoxy magnesium (N ₂ SA) is, 5 to 50 m ² / g, preferably 10 to 40 m ² / g, more preferably 15 to 30 m ²
/ G is preferable, and it is more preferable to use those having a spherical or elliptical spherical shape and a narrower particle size distribution. Here, the term “spherical or elliptical sphere” does not necessarily mean a true sphere or an elliptical sphere having a smooth surface when observed under a microscope. 3 or less, preferably 1-2, more preferably 1-1.5. Therefore, for example, a potato-like shape, that is, a particle shape having irregularities on the surface can be used. The solid catalyst component obtained using the spherical or elliptical spherical diethoxymagnesium is also spherical or elliptical spherical, and the polyolefin produced using the solid catalyst component also has the same spherical or elliptical spherical shape, As a result, a polymer having excellent fluidity is obtained, which is an advantage in the polyolefin production process.

The average particle size of diethoxymagnesium is 1 to 100 μm, preferably 10 to 80 μm, and more preferably 15 to 60 μm, and the particle size distribution is small in fine and coarse powder and narrow in particle size distribution width. It is desirable to use Specifically, particles of 5 μm or less are 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, and particles of 100 μm or more are 10% by weight or less, preferably 5% by weight or less. Things. Further, the particle size distribution was calculated as (D90-D10) / D50.
(Where D90 is the particle size at an integrated particle size of 90% by weight, D10 is the particle size at an integrated particle size of 10% by weight, D10
50 represents the particle size at 50% by weight in the integrated particle size)
Is 3 or less, preferably 2.5, more preferably 2 or less. By using the dialkoxymagnesium having a small amount of fine powder as described above, it is possible to reduce the resulting fine powder of the polyolefin.

As described above, diethoxymagnesium having a high bulk specific gravity, a spherical or elliptical spherical shape having a specific pore volume, and a narrow particle size distribution with few fine powders and coarse powders is preferably used, for example, by the following method. . That is, magnesium metal and ethanol are directly reacted in the absence of a solvent or in the presence of a catalyst to produce diethoxymagnesium. In this method, the final addition ratio of the metal magnesium and the ethanol to the reaction system is set to be metal magnesium / ethanol (weight ratio) = 1/9 to 15/1,
The final addition ratio of metal magnesium and ethanol,
Add continuously or intermittently to the ethanol reaction system,
The reaction is allowed to proceed for 80 minutes, and then kept under reflux of ethanol for 1 to 30 hours to perform an aging reaction. The metal magnesium used in the above method is preferably, for example, a powdery material having good reactivity of several tens to several hundreds mesh, more specifically, about 100 mesh.

Examples of the catalyst include alkyl halides such as methyl bromide, methyl chloride, ethyl bromide and ethyl chloride; metal halides such as magnesium chloride and aluminum chloride; dialkoxy magnesium such as diethoxymagnesium; Iodine, acetate and the like are used, and among them, iodine is preferably used.

Further, in order to prepare a solid catalyst component having an average particle diameter, a specific surface area, a pore volume, and a pore distribution in the above specific ranges, in addition to the above-mentioned characteristics of diethoxymagnesium, It is important that the primary particles are agglomerated with a certain strength to form secondary particles. The size of the primary particles is 0.01 to 0.1 μm. Such diethoxymagnesium can be obtained by adjusting the preparation conditions, and primary particles become smaller by increasing the initial reaction rate. As a specific means, the amount of the catalyst present during the reaction between the metal magnesium and ethanol is increased, and more specifically, the amount of the catalyst such as iodine is adjusted to 0.1 g or more, preferably 0.13 g or more per 1 g of the metal magnesium subjected to the reaction. Particularly preferred is a method in which 0.15 g or more is added, or a method in which the addition rate is increased when metal magnesium and ethanol are continuously or intermittently added to an ethanol reaction system.

As the titanium halide compound, specifically, TiCl ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₃ H ₇ ) C
l ₃ , Ti (OnC ₄ H ₉ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ ,
Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OnC ₄ H ₉ ) ₂ Cl ₂ , Ti (OCH ₃ ) ₃ Cl, Ti
(OC ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₃ Cl, Ti (OnC ₄ H ₉ ) ₃ Cl and the like are exemplified, and among them, TiCl ₄ is preferably used. These tetravalent titanium halide compounds can be used alone or in combination of two or more.

The electron donating compound is an organic compound containing an oxygen atom or a nitrogen atom, for example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides. , Nitriles, isocyanates, and organosilicon compounds containing a Si-OC bond. In particular,
Alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9-bis (methoxymethyl) Ethers such as fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, ethyl anisate, ethyl anisate, etc. Carboxylic acid esters, diethyl maleate, dibutyl maleate, dimethyl adipate,
Dicarboxylic acid esters such as diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, diester phthalate, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone, phthalic dichloride, Acid halides such as terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde and benzaldehyde; amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine; oleic acid amides and stearic acid amides Amides, acetonitrile, benzonitrile, nitriles such as tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, E alkenyl alkoxysilanes, alkylalkoxysilanes, and organic silicon compound containing a phenylalkyl alkoxysilane, cycloalkyl alkoxysilane, Si-O-C bonds, such as cycloalkylalkyl alkoxysilane.

Of the above electron-donating compounds, esters, especially aromatic dicarboxylic diesters are preferably used, and phthalic diester is particularly preferred. Specific examples of these phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, and di-n-phthalate.
Butyl, di-iso-butyl phthalate, ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl) Di-n-pentyl phthalate, di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis-phthalic acid (2 , 2-dimethylhexyl), bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate,
Di-iso-decyl phthalate, bis (2,2-
Dimethylheptyl), n-butyl phthalate (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso-hexyl), iso-pentyl phthalate ( Heptyl), n-pentyl phthalate (2-ethylhexyl), n-pentyl phthalate (iso-nonyl),
Iso-pentyl phthalate (n-decyl), n-phthalic acid
-Pentylundecyl, iso-pentyl phthalate (i
(so-hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl) ), N-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (iso-nonyl), n-heptyl phthalate (n
eo-decyl), 2-ethylhexyl phthalate (iso
-Nonyl) is exemplified. One or more of these are used. The above esters are preferably used in combination of two or more. In this case, the total number of carbon atoms in the alkyl group of the ester used is 4 or more as compared with that of the other esters. It is desirable to combine

Further, those obtained by substituting one or two alkyl groups having 1 to 5 carbon atoms or halogen atoms such as chlorine, bromine and fluorine on the aromatic ring of these phthalic acid diesters are also preferably used. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, dineopentyl 4,5-dimethylphthalate, 4,5
-Dineopentyl diethyl phthalate, diethyl 4-chlorophthalate, di-n-butyl 4-chlorophthalate, 4-
Diisobutyl chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, 4-
Diethyl bromophthalate, 4-bromophthalic acid di-n-
Butyl, diisobutyl 4-bromophthalate, diisohexyl 4-bromophthalate, diisooctyl 4-bromophthalate, diisonopentyl 4-bromophthalate, 4,
Examples thereof include diethyl 5-dichlorophthalate, di-n-butyl 4,5-dichlorophthalate, diisohexyl 4,5-dichlorophthalate, and diisooctyl 4,5-dichlorophthalate.

The solid catalyst component is the above magnesium compound,
It can be prepared by contacting a titanium halide compound and an electron donating compound, and this contact can be carried out in the absence of an inert organic solvent, but in consideration of easiness of operation, The treatment is preferably performed in the presence of the solvent. Examples of the inert organic solvent used include saturated hydrocarbon compounds such as hexane, heptane, and cyclohexane; aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene; ortho-dichlorobenzene, methylene chloride, carbon tetrachloride, and dichloroethane. Among them, the aromatic hydrocarbon compounds having a boiling point of about 90 to 150 ° C. and in a liquid state at room temperature, specifically, toluene, xylene,
Ethylbenzene is preferably used. Contact of each component, under an atmosphere of inert gas, under the condition of removing water, etc.,
This is performed while stirring in a vessel equipped with a stirrer. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact and stirred or mixed or dispersed or suspended for denaturation treatment. When it is obtained, a temperature range of 40 to 130 ° C. is preferable. When the temperature during the reaction is lower than 40 ° C., the reaction does not proceed sufficiently. As a result, the performance of the prepared solid catalyst component becomes insufficient, and when the temperature exceeds 130 ° C., evaporation of the used solvent becomes remarkable. Control of the reaction becomes difficult.
The reaction time is at least 1 minute, preferably at least 10 minutes, more preferably at least 30 minutes. When the above-mentioned specific magnesium compound is used as a carrier, it is necessary to prepare a solid catalyst component by contacting with a titanium halide compound and an electron-donating compound while maintaining the particle characteristics as they are, especially using diethoxymagnesium. In such a case, the contact with the titanium halide compound causes a rapid halogenation reaction to proceed and the particles may be destroyed. Therefore, it is necessary to pay particular attention to the conditions of the contact reaction in the initial stage.

Preferred methods for preparing the solid catalyst component include the following methods. For example, a suspension is formed by suspending a dialkoxymagnesium in a liquid aromatic hydrocarbon compound at room temperature, such as toluene, and then suspending the suspension in titanium tetrachloride to lower the temperature of the reaction system. Add while maintaining. The preferred temperature range at this time is -15 to 5 ° C, more preferably -10 to 0 ° C.
° C. After completion of the addition, the mixture is kept at a low temperature to carry out an aging reaction. The preferred temperature range at this time is -15 to 5C, more preferably -10 to 0C. Then raise the temperature to 70-1
React at 20 ° C. At this time, before or after contacting the above-mentioned suspension with titanium tetrachloride, an electron-donating compound such as phthalic acid diester is contacted at -20 to 130 ° C to obtain a solid reaction product. After washing the solid reaction product with a liquid aromatic hydrocarbon compound at room temperature, titanium tetrachloride is added again in the presence of the aromatic hydrocarbon compound, and the contact reaction is carried out at 70 to 120 ° C., and further at room temperature. The solid catalyst component is obtained by washing with a liquid hydrocarbon compound. Further, repeated contact with titanium tetrachloride is also a preferred embodiment for improving the activity of the catalyst.

The ratio of the amounts of the respective compounds varies depending on the preparation method and cannot be specified unconditionally. For example, 0.5 mol of the titanium halide compound per 1 mol of the magnesium compound is used.
To 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol.
It is 1 to 10 mol, preferably 0.01 to 1 mol, and more preferably 0.02 to 0.6 mol.

As the organoaluminum compound used for forming the polymerization catalyst, triethylaluminum, diethylaluminum chloride, tri-iso-
Butyl aluminum, diethyl aluminum bromide and diethyl aluminum hydride;
Species or two or more species can be used. Preferably, they are triethyl aluminum and tri-iso-butyl aluminum.

As the external electron donating compound used in forming the polymerization catalyst, the same electron donating compound as the above-mentioned solid catalyst component can be used. Among them, 9,9-bis ( Methoxymethyl) fluorene,
Ethers such as 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, esters such as methyl benzoate and ethyl benzoate, and organosilicon compounds are preferred. As the organosilicon compound, a compound represented by the general formula R ¹ _q S
i (OR ² ) _4-q (wherein, R ¹ is an alkyl group having 1 to 12 carbon atoms,
Cycloalkyl group, phenyl group, vinyl group, allyl group,
Represents an aralkyl group, which may be the same or different. R ²
Represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different. q is an integer of 0 ≦ q ≦ 3. ) Is used. Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

Specific examples of the above organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n
-Propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxysilane, tri-
t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n
-Propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane,
Di-iso-propyldiethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane 4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxy Silane, cyclohexyl cyclopentyl distearate propoxysilane, 3-methyl-cyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxysilane, 3,5-dimethyl-cyclohexyl cyclopentyl dimethoxy silane, 3
-Methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane Cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, Cyclohexyl (n-propyl ) Diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Silane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane , Iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, Examples include cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane Ethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane,
Dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentyl Ethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used. Objects may be used in combination singly or in combination.

A solid catalyst component, an organoaluminum compound,
The use ratio of the external electron donating compound and the amount of the external electron donating compound are not particularly limited as long as they do not affect the effects of the present invention, and are not particularly limited. 1 to 20 per mole
It is used in the range of 00 mol, preferably 50 to 1000 mol. The external electron donating compound is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the organic aluminum compound.

The order of contact of the components is arbitrary, but it is preferable to first charge the organoaluminum compound in the polymerization system, then contact the external electron donating compound, and further contact the solid catalyst component.

Further, in producing the propylene block copolymer of the present invention using the above-mentioned catalyst, a preliminary reaction is required prior to the main polymerization in order to further improve the catalytic activity, stereoregularity, and particle properties of the produced polymer. It is desirable to carry out the polymerization. In the prepolymerization, the same monomers as olefins or styrene used in the main polymerization can be used.
In performing the prepolymerization, the order of contact of each component and the monomer is arbitrary, but preferably, the organoaluminum compound is first charged into a prepolymerization system set in an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene. And
Next, after contacting the solid catalyst component, an olefin such as propylene and / or one or more other olefins are contacted. When prepolymerization is performed by combining an external electron donating compound, the organoaluminum compound is first charged into a prepolymerization system set in an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene, and then the external electron donating compound is used. It is desirable to use a method in which a compound is brought into contact with a solid catalyst component, and then an olefin such as propylene and / or one or more other olefins are brought into contact.

[0049]

EXAMPLES Next, examples of the present invention will be specifically described in comparison with comparative examples. In addition, each characteristic of the polymer was evaluated by the following methods.

(Melt Index (Melt Flow Rate) Value (MFR)) Measured according to the method of ASTM D1238.

(Flexural Modulus) After blending a heat-resistant stabilizer with a polymer, the polymer was pelletized by an extruder, molded by an injection molding machine to prepare a measurement sample, and measured at 23 ° C. in accordance with ASTM D790.

(Izod impact strength) After blending a heat-resistant stabilizer with a polymer, the extruder pelletizes the resulting product, and forms a measurement sample by molding using an injection molding machine.
For notched injection molded specimens according to 56, 23
Measured in ° C.

(Composition of propylene block copolymer) Rubber part ratio (block ratio), rubber part ratio on the surface, average diameter of PP section, average diameter of rubber section,
Rubber section diameter cumulative distribution 90% and Dpp / Dr
Was analyzed using a transmission electron microscope (model H-7100FA; manufactured by Hitachi, Ltd.) and an image processing apparatus (model LUZEX F; manufactured by Nireco). MFR is ASTM
It measured according to the method of D1238. The xylene insoluble content in the PP part was determined by the following method. 4.0 g of the polymer are charged to 200 ml of para-xylene and have a boiling point of (138).
C) for 2 hours to dissolve the polymer. Then 23 ° C
The mixture was cooled to room temperature, and the dissolved component and the insoluble component were separated by filtration.
The dissolved component was dried by heating, and the obtained polymer was used as a xylene dissolved component (XS) (% by weight).

(Ethylene Content, EPR Content) The ethylene content in the propylene block copolymer is ¹³ C—N
Quantification by MR. The content of the ethylene propylene rubber component (EPR) in the propylene block copolymer was measured by the following method. In a 1 liter flask equipped with a stirrer and cooling tube, about 2.5
g, 2,6-di-t-butyl-p-cresol 8 mg, p
-250 ml of xylene was charged and stirred at the boiling point until the copolymer was completely dissolved. Next, the flask was cooled to room temperature and left for 15 hours to precipitate a solid. This was separated into a solid and a liquid phase by a centrifuge. Thereafter, the separated solid matter is placed in a beaker, and 500 ml of acetone is placed.
After stirring at room temperature for 15 hours, the solid was filtered and dried, and the weight was measured (this weight is referred to as B). The same operation was carried out also on the separated liquid phase portion to precipitate a solid substance, and the weight was measured (this weight is referred to as C 2). The content (% by weight) of the ethylene propylene rubber component (EPR) in the copolymer was calculated by the formula [C (g) / [B (g) + C (g)] × 100].

(Fluidity of propylene block copolymer)
As shown in FIG. 3, a funnel 1 (upper diameter: 91 mm, damper position diameter: 8 mm, inclination angle: 20 °, height to the damper position; 114 mm) with a damper 2 interposed at the outlet position is set on the upper part, First, 50 g of the polymer was charged into the upper funnel 1 using a device in which a container-shaped receiver 3 (inner diameter: 40 mm, height: 81 mm) was installed at a lower part of the damper 2 with a spacing of 38 mm. 2 was opened to drop the polymer into the receiver 3, and the time during which all the polymer dropped was measured. This operation was carried out using a propylene block copolymer and the same solid catalyst component as used for the polymerization of this propylene block copolymer.
Of the propylene polymerization reaction in the production of the heavy propylene block copolymer of Example 1), and the drop times are T1 and T2, respectively.
The value determined by / T2 was shown as fluidity.

Example 1 (Preparation of diethoxymagnesium) Ethanol 1000
Dissolve 100 g of iodine in ml and heat to reflux.
Was. This contains a slurry of metallic magnesium and ethanol
Is added continuously over 2 hours to add metallic magnesium
A total of 500 g was added and reacted under reflux. At this time,
The amount of knol was 7.6 l. After that, aged for 3 hours
The solid obtained is washed with ethanol, dried and dried.
Thus, a diethoxymagnesium powder was obtained. This diethoxy
When magnesium was analyzed, the bulk specific gravity was 0.31 g / m.
l, specific surface area (N_Two SA) 19.8 m^Two/ G, sphericity (l /
w) 1.10, average particle size 25 μm, pore volume 0.02 ml
/ G, pore distribution [ln (R90 / R10)] 2.30,
5% or less fine powder content 5%, particle size distribution [(D90-D
10) / D50] was 1.05.

(Preparation of Solid Catalyst Component) In a 2000 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas, 150 g of the above-mentioned magnesium diethoxy, 750 ml of toluene and 54 ml of di-n-butyl phthalate were placed. Into a suspended state. The suspension was then continuously added over 1 hour to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride previously charged in a 3000 ml round bottom flask equipped with a stirrer and thoroughly purged with nitrogen gas. Was added. At that time, the temperature of the reaction system was maintained at -5 ° C. The mixed solution was stirred at -5 ° C for 1 hour, then heated to 100 ° C over 4 hours, and stirred for 2 hours.
Allowed to react for hours. Then, after the completion of the reaction, the product was heated to 80 ° C.
The reaction was carried out for 2 hours with stirring while maintaining the temperature.
Next, the product was washed with heptane at 40 ° C. seven times, filtered and dried to obtain a powdery solid catalyst component. The titanium content of the solid catalyst component was measured and found to be 3.15% by weight. Average particle size of the solid catalyst component, specific surface area,
The pore volume and pore distribution were measured. Table 3 shows the results.

(Production of Propylene Block Copolymer) Triethylaluminum (TE) was placed in a 2.0-liter autoclave equipped with a stirrer completely purged with nitrogen gas.
AL), cyclohexylmethyldimethoxysilane (CM
DMS) and 0.0026 mmol of the solid catalyst component as titanium atoms were charged to form a polymerization catalyst.
At this time, Ti, TEAL and CMD in the solid catalyst component
The molar ratio of MS (Ti / TEAL / CMDMS) is 1 /
400/67. Thereafter, 2.0 liters of hydrogen gas and 1.2 liters of liquefied propylene were charged, and a propylene polymerization reaction was performed at 70 ° C. for 1 hour.
The polymerization reaction was carried out so as to be in% by weight. Then, while supplying ethylene gas and propylene gas at an ethylene / propylene molar ratio of 0.7, polymerization is performed at 70 ° C. for 2 hours in a gas phase at a pressure of 1.7 MPa so that a rubber portion ratio becomes about 30% by weight. Then, a propylene block copolymer was produced. FIG. 1 shows a TEM (transmission electron microscope) photograph of the obtained propylene block copolymer. FIG. 1 shows a rubber portion ratio (block ratio), a rubber portion ratio on the surface, ethylene content, EPR content, PP portion MFR, PP Xylene insolubles, PP section average diameter, rubber section average diameter, rubber section diameter cumulative distribution 90%, Dpp / Dr, M
Table 3 shows I, flexural modulus and Izod impact strength. The MFR of the PP part and the xylene-insoluble content of the PP part are obtained by measuring a reaction product after the propylene polymerization reaction.

Example 2 (Production of Propylene Block Copolymer)
The same as Example 1 except that propylene polymerization was performed at 70 ° C. for 0.5 hour and ethylene propylene copolymerization was performed at 70 ° C. for 2 hours to produce a propylene block copolymer in order to obtain 3.5% by weight. In the way. FIG. 2 shows a TEM (transmission electron microscope) photograph of the obtained propylene block copolymer, and Table 3 shows the same characteristic values as in Example 1.

Example 3 (Preparation of Diethoxymagnesium) Ethanol 1000
Dissolve 100 g of iodine in ml and heat to reflux.
Was. This contains a slurry of metallic magnesium and ethanol
Is added continuously over 1 hour to add metallic magnesium
A total of 500 g was added and reacted under reflux. At this time,
The amount of knol was 7.6 l. After that, aged for 3 hours
The solid obtained is washed with ethanol, dried and dried.
Thus, a diethoxymagnesium powder was obtained. This diethoxy
Analysis of magnesium revealed a bulk specific gravity of 0.30 g / m.
l, specific surface area (N_Two SA) 20.5m^Two/ G, sphericity (l /
w) 1.05, average particle size 24 μm, pore volume 0.018
ml / g, pore distribution [ln (R90 / R10)] 2.1
0, 5 μm or less fine powder content 5%, particle size distribution [(D90
-D10) / D50] was 1.05.

(Preparation of solid catalyst component and production of propylene block copolymer) Preparation of solid catalyst component and production of propylene block copolymer in the same manner as in Example 1 except that diethoxymagnesium obtained above was used. Was done.
Table 3 shows the obtained results.

Example 4 (Preparation of solid catalyst component) 150 g of the diethoxymagnesium prepared in Example 1, 750 ml of toluene and phthalic acid were placed in a 2000 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas. 54 ml of di-n-butyl were charged and suspended. The suspension was then continuously added over 1 hour to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride previously charged in a 3000 ml round bottom flask equipped with a stirrer and thoroughly purged with nitrogen gas. Was added. At that time, the temperature of the reaction system was kept at -8C.
The mixed solution was stirred for 1 hour while being kept at -8 ° C, and then heated to 100 ° C over 4 hours, and reacted for 2 hours while stirring. Then, after the completion of the reaction,
The contact reaction was carried out for 2 hours while stirring at a temperature of ° C. The product is then washed seven times with heptane at 40 ° C.,
After filtration and drying, a powdery solid catalyst component was obtained. The titanium content in the solid catalyst component was measured and found to be 3.15
% By weight. The average particle size, specific surface area, pore volume, and pore distribution of the solid catalyst component were measured. Table 3 shows the results.

(Production of propylene block copolymer) A propylene block copolymer was produced in the same manner as in Example 1 except that the solid catalyst component obtained above was used. Table 3 shows the obtained results.

Comparative Example 1 (Preparation of Diethoxymagnesium) A ball mill having an internal volume of about 10 liters was obtained by replacing 1 kg of a commercially available granular diethoxymagnesium (product name: magnesium ethylate, particle size: 500-1500 μm) manufactured by Huls with nitrogen gas. And crushed for 5 minutes. As a result of measuring the physical properties of the obtained diethoxymagnesium, the bulk specific gravity measured according to JIS K6721 was 0.41 g / ml, and the specific surface area (N ₂ S
A): 9.8 m ² / g, sphericity (l / w): 2.0, average particle size: 101.9 μm, pore volume: 0.010 ml / g
g, pore distribution [In (D90 / D10)] is 2.63;
The content of fine powder of 5 μm or less is 4.1%, and the particle size distribution [(D9
0-D10) / D50] was 2.44.

(Preparation of solid catalyst component) 150 g of the above granular diethoxymagnesium was placed in a 2000 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas.
750 ml of toluene and 54 m of di-n-butyl phthalate
l was charged and suspended. Then, the suspension solution is
Equipped with a stirrer and having a capacity of sufficiently replaced with nitrogen gas 300
Toluene 450 previously charged in a 0 ml round bottom flask
ml and a solution of 300 ml of titanium tetrachloride were added continuously over 1 hour. At that time, the temperature of the reaction system was kept at 5 ° C. Thereafter, the temperature was raised to 100 ° C. over 4 hours, and the reaction was carried out for 2 hours while stirring. Next, after completion of the reaction, the product was contact-reacted for 2 hours while stirring at a temperature of 80 ° C. Next, the product was washed with heptane at 40 ° C. seven times, filtered and dried to obtain a powdery solid catalyst component. The titanium content in the solid catalyst component was measured.
It was 15% by weight. The average particle size, specific surface area, pore volume, and pore distribution of the solid catalyst component were measured. Table 3 shows the results.

(Production of propylene block copolymer) An experiment was carried out in the same manner as in Example 1 to obtain a propylene block copolymer. Table 3 shows the characteristic values of the obtained propylene block copolymer.

Comparative Example 2 (Preparation of solid catalyst component) 95.2 magnesium dichloride
g, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a homogeneous solution. 21.3 g of phthalic anhydride was added to this solution, and further stirred at 130 ° C. for 1 hour. Mixing was performed, and phthalic anhydride was dissolved to obtain a homogeneous solution. After cooling to room temperature,
75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride, and then the temperature was raised to 110 ° C., and when it reached 110 ° C., 5.22 g of diisobutyl phthalate was added, and the mixture was reacted with stirring for 2 hours. At the end of the reaction, the product
After resuspension in 5 ml of titanium tetrachloride, it was treated at 110 ° C. for 2 hours. Next, the product was washed with heptane at 40 ° C. seven times, filtered and dried to obtain a powdery solid catalyst component.
When the titanium content in this solid catalyst component was measured,
It was 2.80% by weight. Average particle size of the solid catalyst component,
The specific surface area, pore volume and pore distribution were measured. Table 3 shows the results.

(Production of Propylene Block Copolymer)
Propylene polymerization was performed at 0 ° C. for 1 hour, and ethylene propylene copolymerization was performed at 70 ° C. for 1 hour to produce a propylene block copolymer. Was. Table 3 shows the characteristic values of the obtained propylene block copolymer.

Comparative Example 3 (Preparation of Diethoxymagnesium) Ethanol 1000
10 g of iodine was dissolved in ml and heated to reflux.
A slurry of magnesium metal and ethanol was continuously added thereto over 2 hours, and a total of 500 g of magnesium metal was added and reacted under reflux. At this time, the amount of ethanol was 7.6 l. Thereafter, an aging reaction was performed for 3 hours, and the obtained solid was washed with ethanol and dried to obtain a diethoxymagnesium powder. When this diethoxymagnesium was analyzed, the bulk specific gravity was 0.26 g / ml, the specific surface area (N ₂ SA) was 19.8 m ² / g, and the sphericity (l / w)
1.10, average particle size 31 μm, pore volume 0.03 ml /
g, pore distribution [ln (R90 / R10)] 2.30, 5
5% or less fine powder content, particle size distribution [(D90-D1
0) / D50] was 1.05.

(Preparation of solid catalyst component) In a 2000 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas, 150 g of the above-mentioned magnesium diethoxy, 750 ml of toluene and 54 ml of di-n-butyl phthalate were placed. Into a suspended state. The suspension was then continuously added over 1 hour to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride previously charged in a 3000 ml round bottom flask equipped with a stirrer and thoroughly purged with nitrogen gas. Was added. At that time, the temperature of the reaction system was kept at 10 ° C. The mixed solution was stirred for 1 hour while maintaining the temperature at 10 ° C., and then heated to 100 ° C. over 4 hours.
Allowed to react for hours. Then, after the completion of the reaction, the product was heated to 80 ° C.
The reaction was carried out for 2 hours with stirring while maintaining the temperature.
Next, the product was washed with heptane at 40 ° C. seven times, filtered and dried to obtain a powdery solid catalyst component. The titanium content of the solid catalyst component was measured and found to be 2.70% by weight. Average particle size of the solid catalyst component, specific surface area,
The pore volume and pore distribution were measured. Table 3 shows the results.

(Production of propylene block copolymer) A copolymer was produced in the same manner as in Example 1 except that the solid catalyst component obtained as described above was used. Table 3 shows the obtained results.

[0072]

[Table 3]

[0073]

The propylene block copolymer of the present invention has a novel structure in which an ethylene-propylene copolymer as a rubber component can be blended in a high proportion and a high dispersion in a propylene polymer. Furthermore, since the rubber ratio on the particle surface is small and there is no occurrence of adhesion between polymer particles or adhesion to the inner wall of the device, it is possible to produce a stable and high-quality block copolymer. Further, because of having such a unique structure, both performances of rigidity and impact resistance are well-balanced, and they are particularly useful for applications such as automobile parts such as bumpers and home electric parts.

[Brief description of the drawings]

FIG. 1 is a TEM (transmission electron microscope) photograph of a cross section of a propylene block copolymer of Example 1.

FIG. 2 is a TEM (transmission electron microscope) photograph of a cross section of the propylene block copolymer of Example 2.

FIG. 3 is a drawing of an apparatus for measuring the fluidity of a propylene block copolymer.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hidetoshi Umebayashi 3-3-5 Chigasaki, Chigasaki City, Kanagawa Prefecture Toho Catalyst Co., Ltd. (72) Inventor Makoto Nakano 3-3-5 Chigasaki Chigasaki City, Kanagawa Prefecture Toho Cata F-term in List Inc. (reference) 4J026 HA04 HA34 HA35 HB03 HB04 HB27 HB34 HB35 HB45 HB48 HE01

Claims (8)

[Claims] 1. 20 to 80% by weight of a propylene polymer,
A propylene block copolymer comprising 20 to 80% by weight of an ethylene-propylene copolymer, wherein an irregular-shaped ethylene-propylene copolymer section is finely dispersed in the propylene polymer. When the shape of the ethylene-propylene copolymer section is converted into a circle having the same area, the average diameter (Dr) of the ethylene-propylene copolymer section is expressed by the following formula (1); Dr (μm) ≦ 0.005 × A (1) (where A represents the content (% by weight) of the ethylene-propylene copolymer in the propylene block polymer, and satisfies 20 ≦ A (% by weight) ≦ 80). Propylene block copolymer. 2. 20 to 80% by weight of a propylene polymer,
A propylene block copolymer comprising 20 to 80% by weight of an ethylene-propylene copolymer, wherein the propylene polymer and the ethylene-propylene copolymer are mixed and mixed with each other, and the propylene polymer has an irregular shape. Section and an ethylene-propylene copolymer section, and when the ethylene-propylene copolymer section is converted into a circle having the same area, the average diameter of the ethylene-propylene copolymer section is (D
r) is the following formula (1); Dr (μm) ≦ 0.005 × A (1) (In the formula, A represents the content (% by weight) of the ethylene-propylene copolymer in the propylene block polymer. , And 20 ≦ A (% by weight) ≦ 80. 3. The average diameter (Dpp) (μm) when the propylene polymer section is converted into a circle having the same area.
Is the following formula (2); 5.0 ≧ Dpp (μm) ≧ e- ^0.02 * ^A (2) (where A is as defined above), wherein the propylene block copolymer according to claim 2 is satisfied. 4. A propylene polymer comprising 30 to 70% by weight,
The propylene block copolymer according to claim 1 or 2, wherein the content of the ethylene-propylene copolymer is 30 to 70% by weight. 5. The particle diameter (Dr90) at 90% of the cumulative particle size distribution of the diameter of the ethylene-propylene copolymer section is represented by the following formula (3): Dr90 (μm) ≦ 0.01 × A (3) (3) The propylene block copolymer according to claim 1 or 2, wherein A has the same meaning as defined above. 6. 20 to 80% by weight of a propylene polymer,
The propylene block copolymer is a particulate propylene block copolymer having an average particle diameter of 100 to 5000 μm and containing 20 to 80% by weight of an ethylene-propylene copolymer. Ethylene
A propylene block copolymer, which is 0.3% by volume or less of the propylene block copolymer. 7. The propylene block copolymer according to claim 1, which is obtained by polymerizing propylene and then copolymerizing ethylene and propylene. 8. It contains magnesium, titanium and halogen atoms, has an average particle size of 1 to 100 μm and a specific surface area of 10 μm.
0 to 500 m ² / g, the pore volume is less than 0.2 ml / g, and the cumulative pore volume of pores having a pore diameter of 100 ° or less is 50.
The propylene block according to any one of claims 1 to 6, wherein the propylene block is obtained by polymerizing propylene with a polymerization catalyst containing a solid catalyst component having a pore distribution of not less than 0% and then copolymerizing ethylene and propylene. Copolymer.