JPH08269124A - High-rigidity propylene-ethylene block copolymer composition - Google Patents

Abstract

PURPOSE: To obtain a propylene-ethylene block copolymer, capable of satisfying specific conditions and useful for moldings having high impact resistance, etc., from a two-stage process by using a specified catalyst. CONSTITUTION: This composition is obtained by (A) homopolymerizing propylene in the first stage and providing the homopolymer in an amount of 60-95wt.% based on the total weight and then (B) copolymerizing propylene with ethylene in the second stage and affording a propylene-ethylene copolymer having 30-80wt.% ethylene content in an amount of 5-40wt.% based on the total weight. The maximal value [MFR (h)] and the minimal value [MFR (1)] of the polymer in the stage (A) have the relationship of formula I and the isotactic pentad fraction of the propylene polymer in the stage (A) is >=0.96. The Mw /Mn (Q value) of the polymer in the stage (A) is <=6. The homo- and copolymerizations are carried out so that the melt flow rate [MFR (i)] of the polymer in the stage (A) and the melt flow rate [MFR (ii)] of the polymer in the stage (B) may have the relationship of formula II.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a propylene / ethylene block copolymer composition for high rigidity molding. More specifically, the present invention relates to the polymer composition, which gives a molded article having high rigidity and high impact resistance without adding any special additive.

[0002]

2. Description of the Related Art Crystalline polypropylene (hereinafter sometimes referred to as polypropylene) as a general-purpose resin has high rigidity,
It has hardness, tensile strength and heat resistance. However, the impact resistance is insufficient, and there is a problem that it is difficult to use for a molded article that is subjected to mechanical impact or is used at a low temperature. In addition, when compared with other general-purpose resins such as ABS resin or high-impact polystyrene resin, not only impact resistance but also rigidity is poor. For specific applications of polypropylene and further for expanding demand, it is required to further improve not only the above-mentioned impact resistance but also rigidity. Crystalline polypropylene produced by using a stereoregular catalyst has excellent properties such as rigidity and heat resistance, but on the other hand, it has a problem that impact strength, especially impact strength at low temperature, is low. It was restricted. Therefore, as a method for solving this problem, propylene is used as another α-
A method of random or block copolymerization with an olefin such as ethylene is known. The obtained random copolymer has insufficient improvement in low-temperature impact resistance as compared with polypropylene, and its rigidity, strength, heat resistance and the like are rapidly lowered as the ethylene content is increased. Similarly, the block copolymer has significantly improved low-temperature impact resistance as compared with polypropylene, but has reduced rigidity, hardness, heat resistance and the like. Many methods have been proposed to improve the above-mentioned drawbacks of block copolymers.

For example, in JP-A Nos. 50-115296, 52-4588 and 53-35879,
A method for carrying out block copolymerization of propylene and ethylene in multiple stages is proposed. Also, for example, Japanese Patent Publication No. 47-8
No. 207, No. 49-13231, No. 49-13514
No. 1 proposes an improved method of adding a third component to the catalyst. Further, JP-A-55-764 and 54-15209
No. 5, No. 53-29390, and Japanese Patent Publication No. 55-8011 propose an improved method using a specific catalyst. However, the above proposals are based on polypropylene (homopolymer).
It is a technique for relaxation to reduce the degree of decrease in rigidity of the block copolymer obtained as compared with the above method, and it is still possible to achieve a rigidity value equal to or higher than that of the homopolymer. Not in. Further, Japanese Patent Application Laid-Open No. 58-201816 proposes a method for producing a high-rigidity propylene / ethylene block copolymer having a rigidity equal to or higher than that of polypropylene, but the impact resistance was not sufficiently improved.

In view of the above-mentioned state of the art, the inventors have earnestly studied to invent a propylene / ethylene block copolymer capable of obtaining a molded article having high rigidity and high impact resistance without adding a special additive. As a result, they have found that the copolymer can be obtained by the production under the limited conditions described below, and completed the present invention. As is apparent from the above description, an object of the present invention is to provide a propylene / ethylene block copolymer composition suitable for molded articles having high rigidity and high impact resistance.

[0005]

The present invention includes the following 1) to 5).
It is composed of 1) A solid catalyst component (A) containing titanium, magnesium, halogen and a polycarboxylic acid ester as essential components, an organoaluminum compound (B) and a general formula R ⁴ _x R
⁵ _y Si (OR ⁶ ) _z (wherein R ⁴ and R ⁶ are hydrocarbon groups, R
⁵ represents a hydrocarbon group or a hydrocarbon group containing a hetero atom, and x + y + z = 4,0 ≦ x ≦ 2,1 ≦ y ≦ 3,1
≦ z ≦ 3. ) An organosilicon compound (C) represented by
As a first step, propylene homopolymerization is carried out in a polymerization step (I) using two or more polymerization vessels in series to produce 60 to 95% by weight of the total weight. Copolymerization of propylene and ethylene was carried out in a polymerization step (II) using one or more tanks as two stages, and the propylene / ethylene copolymerization part having an ethylene content of 30 to 80% by weight was added to 5% of the total weight. In the propylene / ethylene block copolymer produced by up to 40% by weight, the maximum value (hereinafter referred to as MFR (h)) and the minimum value (hereinafter referred to as MFR (h)) of the melt flow rate of the polymer obtained in each tank of the polymerization step (I). MFR
(Referred to as (l)) has a relationship of 0.1 ≦ Log (MFR (h) / MFR (l)) ≦ 1 (1), and the iso of the propylene polymer obtained in the polymerization step (I). The tactic pentad fraction (P) is 0.
96 or more, Mw / Mn (Q value) is 6 or less, and
The melt flow rate of the polymer obtained in the polymerization step (I) (hereinafter referred to as MFR (i)) and the melt flow rate of the polymer obtained in the polymerization step (II) (hereinafter referred to as MFR (ii)) are 3 ≦. A high-rigidity propylene / ethylene block copolymer composition having a relationship of Log (MFR (i) / MFR (ii)) ≦ 7 (2). 2) MFR of the polymer finally obtained is 0.1 or more and 10
The high-rigidity propylene / ethylene block copolymer composition according to the above item 1, which is 0 or less. 3) The high-rigidity propylene / ethylene block copolymer composition as described in 1) above, which is polymerized in a hydrocarbon solvent. 4) MFR (h) and MFR (1) described in 1) above are 0.2 ≦ Log (MFR (h) / MFR (1)) ≦ 0.
The high-rigidity propylene / ethylene block copolymer composition according to 1), which has a relationship of 5. 5) The high-rigidity propylene according to 1), wherein the MFR (i) and MFR (ii) described in 1) above have a relationship of 4 ≦ Log (MFR (i) / MFR (ii)) ≦ 6. Ethylene block copolymer composition.

In the present invention, a solid catalyst component (A) containing at least a magnesium atom, a titanium atom, a halogen atom, and a polyvalent carboxylic acid ester as a polymerization catalyst.
And a highly stereoregular catalyst system obtained by using the organoaluminum compound (B) and the electron donating compound (C) is used, but the catalyst is not particularly limited, and various known highly stereoregular polypropylenes can be used. It is possible to use a catalyst system that gives. A method for producing such a solid catalyst component (A) is, for example, JP-A-50-10838.
5, No. 50-126590, No. 51-20297.
No. 51, No. 51-28989, No. 51-64586, No. 51-92885, No. 51-136625, No. 52.
-87489, 52-100596, 52-1
47688, 52-104593, 53-25.
No. 80, No. 53-40093, No. 53-40094
No. 55-135102, No. 55-135103
No. 55, No. 55-152710, No. 56-811, No. 5
6-11908, 56-18606, 58-8
No. 3006, No. 58-138705, No. 58-138
706, 58-138707 and 58-1387.
08, 58-138709, 58-13871.
No. 0, No. 58-138715, No. 60-23404
No. 61, No. 61-21109, No. 61-37802, No. 61-37803, No. 62-104810, No. 62.
-104811, 62-104812, 62-
It can be manufactured according to the method disclosed in each publication such as 104813 and 63-54405.

Specific examples of the polyvalent carboxylic acid ester used in the solid component (A) are esters of phthalic acid, maleic acid, substituted malonic acid and the like with an alcohol having 2 or more carbon atoms. In the present invention, there are various magnesium compounds used in the above (A),
A magnesium compound with or without reducing ability is used. Examples of the former include dimethylmagnesium,
Examples thereof include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, ethyl magnesium chloride, propyl magnesium chloride and butyl magnesium chloride. Examples of the latter include magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide, magnesium methoxy chloride, alkoxy magnesium chloride such as ethoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium and butoxy magnesium. Mention may be made of alkoxy magnesium, magnesium laurate, magnesium carboxylates such as magnesium stearate and the like. Of these, particularly preferred compounds are magnesium halide, alkoxy magnesium chloride and alkoxy magnesium.

The titanium compound used as the solid catalyst component (A) in the present invention is usually Ti (OR) _A X.
_A compound represented by _4-A (R is a hydrocarbon group, X is a halogen, and 0≤A≤4) is most suitable. Specifically, TiCl
₄ , Titanium tetrahalide such as TiBr ₄ , Ti
Trihalogenated alkoxytitanium such as (OCH ₃ ) Cl ₃ and Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OCH ₃ ) ₂
Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ and other dihalogenated dialkoxy titanium, Ti (OCH ₃ ) ₃ Cl, Ti
Monohalogenated trialkoxy titanium such as (OC ₂ H ₅ ) ₃ Cl, Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ )
_{Tetraalkoxytitanium} such as ₄ , and particularly preferred is TiCl ₄ . In the preparation of the solid catalyst component (A), other electron donors such as alcohol, ether, phenol, silicon compound, aluminum compound and the like are made to coexist as necessary, in addition to the above titanium compound, magnesium compound and polyvalent carboxylic acid ester. be able to.

The organoaluminum compound (B) used in the present invention has a general formula of AlR ² _m R ³ _n X.
_{3- (m + n)} (wherein R ² and R ³ represent a hydrocarbon group or an alkoxy group, X represents a halogen, and m and n are 0 ≦
An arbitrary number of m ≦ 3, 0 ≦ n ≦ 3, and 1.5 ≦ m + n ≦ 3 is shown. ) An organoaluminum compound represented by Specific examples include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, and tri-i-.
Examples thereof include butyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum monochloride, diethyl aluminum iodide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, and ethoxydiethyl aluminum. These organoaluminum compounds (B) can be used alone or in combination of two or more.

The electron donor component (C) used in the present invention is represented by the general formula R ⁴ _x R ⁵ _y Si (OR ⁶ ) _z (wherein R ⁴ and R ⁶ are hydrocarbon groups, and R ⁵ is carbonized). Indicating a hydrogen group or a hydrocarbon group containing a hetero atom, x + y + z =
4, 0 ≦ x ≦ 2, 1 ≦ y ≦ 3, 1 ≦ z ≦ 3. ) Organosilicon compounds represented by Specific examples thereof include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n.
-Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, i-butyltrimethoxysilane, i-butyltriethoxysilane, t- Butyltrimethoxysilane, t-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, neopentyltrimethoxysilane, neopentyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, di-n-butyldimethoxysilane , Di-i-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-pentyldimethoxysilane, dineopentyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Cyclohexyltrimethoxysilane,
Cyclohexyltriethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane,
3-isocyanatopropyltriethoxysilane, 2-
(3-Cyclohexenyl) ethyltrimethoxysilane etc. can be illustrated. These organosilicon compounds can be used alone or in admixture of two or more kinds at any ratio. Among these, particularly preferred organosilicon compounds are di-i-propyldimethoxysilane, t-butyltriethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane and cyclohexyltrimethoxysilane. The preferable addition amount of the organosilicon compound (C) is a molar ratio (B) / (C) of 1 to 15 with respect to the organoaluminum compound (B). If the addition amount is small, the improvement of rigidity is insufficient and too large. And the catalytic activity is reduced, which is not practical.

The solid catalyst component (A) is then used in combination with the organoaluminum compound (B) and the above-mentioned organosilicon compound (C) as a catalyst for the polymerization of propylene, or more preferably, it is reacted with an α-olefin. Used as a pre-activated catalyst. For pre-activation, 0.3 to 20 mol of organoaluminum (B) is used with respect to 1 mol of titanium in the solid catalyst component (A), 0 to 50 ° C. for 1 minute to 20 hours, and the α-olefin is adjusted to 0. It is desirable to react 1 to 10 mol, preferably 0.3 to 3 mol. The reaction of α-olefin for preactivation can be performed in an aliphatic or aromatic hydrocarbon solvent, or in a liquefied α-olefin such as liquefied propylene or liquefied butene-1 without using a solvent, and vaporized ethylene, propylene or the like. It is also possible to react in phases. Further, the α-olefin polymer or hydrogen obtained in advance can be made to coexist. Furthermore, the organic silane compound (C) can be added in advance in the preliminary activation. The α-olefin used for preactivating is ethylene, propylene, butene-1, hexene-
1, heptene-1, other linear monoolefins, 4
-Methyl-pentene-1, 2-methyl-pentene-1,
Branched chain monoolefins such as 3-methyl-butene-1, styrene and the like. These α-olefins may be used as a mixture of α-olefins to be polymerized. After the completion of the preliminary activation, the solvent, the organoaluminum compound and the unreacted α-olefin and the organoaluminum compound can be filtered off, removed by decantation, or dried to be used as a powder or granular material.

The pre-activated catalyst thus obtained contains propylene as n-hexane, n-heptane, n
-Slurry polymerization carried out in a hydrocarbon solvent such as octane, benzene or toluene, or bulk polymerization and gas phase polymerization carried out in liquefied propylene. In the case of slurry polymerization, the polymerization temperature is usually 20 to 90 ° C., preferably 5
It is 0 to 80 ° C., and the polymerization pressure is 0 to 5 MPa. In the case of gas phase polymerization, the polymerization temperature is usually 20 to 150.
And the polymerization pressure is 0.2 to 5 MPa.
Hydrogen is usually used for controlling the molecular weight, and MFR of the polymer finally obtained is carried out in the range of 0.1 to 1000.

The amount of polymerization in the polymerization step (I) is 60 to 95% by weight based on the total amount of the propylene / ethylene block copolymer composition finally obtained. If the amount of polymerization is less than the above range, the rigidity of the product will be deteriorated, and if it is too large, the improvement of low temperature impact strength will be insufficient. The polymerization in the polymerization step (I) is carried out using two or more polymerization vessels connected in series, and the maximum (MFR (h)) and minimum (MFR) of the melt flow index of the polymer obtained in each tank are obtained.
The relationship with (l)) is preferably 0.1 ≦ Log (MFR (h) / MFR (l)) ≦ 1 (1), and more preferably 0.2 ≦ Log (MFR (h) / MFR ( l)) ≦ 0.5 (3). When the MFR ratio is smaller than the range of the above formula (1), the rigidity of the product is deteriorated, and when it is large, the tensile elongation and impact resistance of the propylene / ethylene block copolymer composition finally obtained. It is not preferable because the property deteriorates. Further, the isotactic pentad fraction (P) of the polymer obtained in the polymerization step (I) is 0.96 or more, the weight average molecular weight (Mw) and the number average molecular weight measured by gel permeation chromatography (GPC). Ratio of (Mn) (Q
Value) is 6 or less. When the isotactic pentad fraction (P) is smaller than that of the present invention, the rigidity of the molded article is lowered, and when the Q value is larger than the present invention, the impact resistance of the molded article is unfavorably lowered.

In the polymerization step (II), the polymerization temperature is usually 20 to
It is carried out by copolymerizing ethylene and propylene at 80 ° C., preferably 40 to 70 ° C. and a pressure of 0 to 5 MPa. The method of supplying ethylene and propylene to the polymerization vessel and the polymerization mode are not limited. Hydrogen is usually used to control the molecular weight, and the concentration in the gas phase is 0.1 to 10
Carried out in mol%. The polymerization in the polymerization step (II) is carried out using one polymerization vessel or two polymerization vessels connected to each other.
The ethylene content in the portion polymerized in the polymerization step (II) is 3
It is 0 to 80% by weight, more preferably 40 to 70% by weight. When the ethylene content is out of the above range, the resulting polymer has poor rigidity and impact resistance, which is not preferable. The polymerization amount in the polymerization step (II) is 5 to 40% by weight based on the total amount of the polymer finally obtained. In addition to ethylene and propylene, other α-olefin, non-conjugated diene and the like may be used together. The relationship between the MFR (i) of the polymer obtained in the polymerization step (I) and the MFR (ii) of the polymer obtained in the polymerization step (II) is 3 ≦ Log (MFR (i) / MFR (ii)) ≦ 7. (2) is preferable, and more preferably 4 ≦ Log (MFR (i) / MFR (ii)) ≦ 6 (4). MFR (i) is the measured value only for the polymer in the polymerization step (I), and MFR (ii) is the MFR after completion of the second stage.
Measured value {MFR (i + ii)}, polymer fraction (W1) in polymerization step (I) and polymer fraction (W in polymerization step (II)
It is a value calculated by the following equations (5) and (6) from 2). LogMFR (T) = W1 × LogMFR (i) + W2 × LogMFR (ii) (5) W1 + W2 = 1 (6) Log (MFR (i) / MFR (ii)) is the above formula (2).
If it is out of the range, the resulting polymer is inferior in impact resistance and tensile elongation, which is not preferable. MF of polymer finally obtained
R is preferably in the range of 0.1 to 100, more preferably 1 to 80. When the MFR is smaller than that of the present invention, moldability is lowered, and when the MFR is larger than the present invention, impact resistance is lowered, which is not preferable.

Rigidity, heat resistance (heat resistant rigidity, heat deformation temperature, etc.), dimensional stability (molding shrinkage ratio, warp deformability, etc.) of a molded product obtained by using the copolymer composition of the present invention, For the purpose of improving paintability and abrasion resistance, etc., an inorganic filler can be added to the high-rigidity propylene / ethylene block copolymer composition of the present invention within a range that does not impair the object of the present invention. Is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 25 parts by weight with respect to 100 parts by weight of the high-rigidity propylene / ethylene block copolymer composition. Examples of the inorganic filler include talc, calcium carbonate, potassium titanate whiskers, mica, glass fiber, barium sulfate and magnesium sulfate, and these may be used alone or in combination. Among the inorganic fillers, talc is preferable, Talc having an average particle size of 5 μm or less, preferably 2 μm or less in terms of impact resistance, and 5% by weight or less of a particle size component exceeding 10 μm, preferably 1% by weight or less in terms of impact resistance is more preferable. Impact resistance of the obtained molded product,
In order to improve dimensional stability (coefficient of linear expansion, warpage deformation of molded products, etc.) and paintability, the high-rigidity propylene / ethylene block copolymer composition of the present invention contains amorphous or low crystalline ethylene / α. -Olefin copolymer, polyethylene (high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, etc.) or styrene-based elastomer can be compounded within a range that does not impair the object of the present invention. The range is preferably 1 to 20 parts by weight, and more preferably 1 to 20 parts by weight of the amorphous or low crystalline ethylene / α-olefin copolymer with respect to 100 parts by weight of the high-rigidity propylene / ethylene block copolymer composition. It can be illustrated that 10 parts by weight are blended. Examples of the amorphous or low crystalline ethylene / α-olefin copolymer include amorphous ethylene / propylene copolymer and amorphous ethylene / 1-butene copolymer, and among them, amorphous ethylene -Α-olefin copolymers are preferred.
As the amorphous ethylene / α-olefin copolymer,
Propylene content is 20 to 50% by weight, preferably 20
~ 35 wt%, Mooney viscosity [ML1 + 4 (100 ° C)]
Is 5 to 60, preferably 10 to 50 and MFR (23
0 ° C .; 21.18 N) is 0.1 to 20 g / 10 min,
An amorphous ethylene / propylene copolymer of preferably 0.5 to 10 g / 10 min can be exemplified. Further, if necessary, the high-rigidity propylene / ethylene block copolymer composition of the present invention contains an antioxidant, an antistatic agent, a colorant (pigment), a nucleating agent, within a range that does not impair the object of the present invention. One or more kinds of various additives such as a slip agent, a release agent, a flame retardant, an ultraviolet absorber, a weather resistance agent, a plasticizer and a radical generator can be blended.

The analysis of various physical properties and the measuring method according to the examples described below are shown below. MFR; ASTM D-1238 (unit: g / 10m
in) 230 ° C., 2.16 kg load Isotactic pentad fraction (P); macrom
olecules 8687 (1975). It is the isotactic fraction in pentad units in the polypropylene molecular chain using ¹³ C-NMR. Average molecular weight (Mn, Mw); Dissolve a sample in ortho-dichlorobenzene at 135 ° C., and make 150C type GPC (Gel Permeation Chrom manufactured by Waters).
Atograph). Column used TSK
GEL GMH6-HT ethylene content; by infrared absorption spectroscopy. (Unit: wt%) Polymerization ratio (W1, W) between the polymerization step (I) and the polymerization step (II)
2); Make a copolymer in which the reaction amount ratio of ethylene / propylene is changed in advance, use this as a standard sample, and make a calibration curve by infrared absorption spectrum to obtain the reaction amount ratio of ethylene / propylene in the polymerization step (II). Furthermore, it was calculated from the ethylene content in the total polymer. (Weight / weight) Flexural modulus; based on JIS K7203 (unit: MPa). Tensile strength; conforms to JIS K7113 (unit: MPa). Tensile elongation according to JIS K7113 (unit:%). HDT; conforms to JIS K7207 (unit: ° C). Izod impact strength (II); conforms to JIS K7110 (unit: J / m). As described above, the present invention makes it possible to achieve an effect far exceeding the known art by using specific polymerization conditions, and the present invention will be described in more detail with reference to Examples. It is not limited to this.

[0017]

【Example】

Example 1 (Catalyst Preparation-Solid Titanium Catalyst Component Preparation) 150 g of magnesium ethoxide, 275 ml of 2-ethylhexyl alcohol and 300 ml of a mixture of toluene were stirred at 93 ° C. for 3 hours under a carbon dioxide atmosphere of 0.3 MPa. After stirring, add 400 ml of toluene and 400
ml n-decane was added. Hereinafter this solution is referred to as a magnesium carbonate solution. 100 ml of toluene, 30 ml
Chlorobenzene, 9 ml tetraethoxysilane,
8.5 ml of titanium tetrachloride and 100 ml of Isopar G (isoparaffin hydrocarbon having an average carbon number of 10, boiling point 156 to 176 ° C.) were stirred at 30 ° C. for 5 minutes, and 50 ml of the magnesium carbonate was added. After stirring this for 5 minutes, 22 ml of tetrahydrofuran was added,
The mixture was stirred at 0 ° C for 1 hour. After the stirring was stopped and the supernatant was removed, the produced solid was washed with 50 ml of toluene.
100 ml of chlorobenzene and 100 m were added to the obtained solid.
l of titanium tetrachloride was added, and the mixture was stirred at 135 ° C. for 1 hour. After stopping the stirring and removing the supernatant, 250 ml of chlorobenzene, 100 ml of titanium tetrachloride and 2.1 ml of
1. Add ml of di-n-butyl phthalate and add 1.
Stir for 5 hours. After removing the supernatant, the solid was washed successively with 600 ml of toluene, 800 ml of Isopar G, and 400 ml of hexane to collect a solid catalyst component. The composition of this solid catalyst component is 2.3% by weight titanium and 55% chlorine.
% By weight, 17% by weight of magnesium and di-n-phthalate
Butyl was 7.5% by weight.

Preparation of Pre-Activated Catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 50 L with nitrogen gas, 40 L of n-hexane was charged, and 75 g of the above solid product and 13 g of triethylaluminum were added at room temperature. After that, 100 g of propylene was supplied over 120 minutes to remove unreacted propylene and n-hexane under reduced pressure to obtain 150 g of preactivated catalyst.

Polymerization step (I) A stainless steel polymerization vessel with an internal volume of 500 L equipped with a turbine type stirring blade, which had been purged with nitrogen, had 250 L of n-hexane, 89 g of triethylaluminum and di-organosilicon compound.
69 g of i-propyldimethoxysilane was charged, then 15 g of the preliminary activation catalyst was added, and the temperature inside the vessel was 70 ° C.
After the temperature was raised to 1, the total pressure was 0.8 MPa, and while maintaining the hydrogen / propylene concentration ratio in the gas phase part at 0.24, propylene and hydrogen were supplied to carry out the first stage polymerization for 1 hour, and then propylene was added. Was stopped, the temperature inside the vessel was cooled to 30 ° C., and hydrogen and unreacted propylene were discharged. Then, a part of the polymerized slurry was extracted, and the MFR was measured and the Mg in the polymer was
Inductively coupled plasma optical emission spectroscopy (ICP method) was used to determine the polymer yield per unit weight of catalyst.
After heating the inside of the vessel to 70 ° C, supply propylene and hydrogen,
After carrying out the second stage polymerization for 1 hour while maintaining the total pressure at 1.0 MPa and the hydrogen / propylene concentration ratio in the gas phase at 0.24, the supply of propylene was stopped and the temperature inside the vessel was set to 30 ° C. After cooling to room temperature, hydrogen and unreacted propylene were released. Then, a part of the polymerized slurry was extracted, the MFR was measured, and the Mg content in the polymer was determined by the ICP method to determine the second-stage polymer yield. Then, using the yield value of the first stage, the ratio of the polymerization amounts of the first stage and the second stage was determined. Furthermore, LogMFR = a × LogMFR ₁ + (1-a) × Lo
gMFR ₂ a: 1st stage polymerization ratio MFR: 2nd stage end MFR MFR ₁ and MFR ₂ : _1st and 2nd stage MFR substituting the values of MFR ₁ and MFR for 2nd stage Eye MFR
I asked for ₂ . Then, after the temperature inside the vessel was raised to 70 ° C., propylene and hydrogen were supplied to maintain the total pressure at 1.2 MPa and the hydrogen / propylene concentration ratio in the gas phase portion at 24% for 1 hour in the third stage. After carrying out the polymerization, the supply of propylene was stopped,
The temperature inside the vessel was cooled to 30 ° C., and hydrogen and unreacted propylene were discharged. Then, pull out a part of the polymerization slurry,
MFR is measured and the Mg content in the polymer is measured by IC
It was determined by the P method, and the ratio of the third stage polymerization was determined. Furthermore, LogMFR = a × LogMFR ₁ + b × LogMFR
₂ + c × LogMFR ₃ a + b + c = 1 a: 1st stage polymerization ratio, b: 2nd stage polymerization ratio, c: 3rd stage polymerization ratio MFR: 3rd stage final extraction product MFR MFR ₁ , MFR ₂ , MFR ₃ : 1st stage, 2nd stage,
The values of MFR ₁ , MFR ₂ and MFR were substituted into the MFR at the third stage to obtain MFR ₃ at the third stage.

Polymerization step (II) After the temperature inside the vessel was raised to 60 ° C., the ethylene feed ratio was changed to 35
Ethylene and propylene were continuously supplied for 2 hours so that the weight% was adjusted. The total supply of ethylene was 4.5 kg. During the polymerization, hydrogen was supplied so that the gas phase hydrogen concentration was 1 mol%. After the polymerization for 2 hours, the supply of ethylene and propylene was stopped, the temperature inside the vessel was cooled to 30 ° C., and then unreacted ethylene and propylene were discharged. Then, 50 L of methanol was supplied into the polymerization vessel, and the temperature inside the vessel was raised to 60 ° C. After 30 minutes, 0.5 L of caustic soda water of 20% by weight was further added and stirred for 20 minutes, and 100 L of pure water was added.
The internal temperature was cooled to 30 ° C. After extracting the water tank, 300 L of pure water was further added, and the mixture was washed with stirring water for 10 minutes, and then the water tank was extracted. Then, the hexane slurry was extracted, filtered, and dried. The resulting propylene / ethylene block copolymer composition was analyzed, and the values are shown in Table 1.

Production of Injection-Molded Product To 3.0 kg of the product powder obtained above, 0.003 kg of a phenolic heat stabilizer, calcium stearate of 0.
003 kg was added, and the mixture was mixed for 10 minutes at room temperature with a high-speed stirring mixer (Note. Henschel mixer, trade name), and the mixture was granulated using an extruder with a screw diameter of 40 mm. Then, the granulated product is melted at a temperature of 230
A JIS type test piece was prepared at a temperature of 50 ° C. and a mold temperature of 50 ° C., and the test piece was conditioned for 72 hours in a room with a humidity of 50% and a room temperature of 23 ° C. Then, the physical property values were measured as shown in Table 1 below.

Examples 2, 3 and Comparative Example 1 Same as Example 1 except that the addition amount of di-i-propyldimethoxysilane was changed to 27.4 g, 13.7 g and 6.9 g in the polymerization step (I). The results obtained in Table 1 are shown in Table 1. When the isotactic pentad fraction (P) of the polymer obtained in the polymerization step (I) is smaller than that of the present invention, the rigidity of the molded product is poor.

[0023]

[Table 1]

Example 4 In the polymerization step (I), the hydrogen / propylene concentration ratios of the gas phase portions of the first, second and third stages were 0.3, 0.23,
Table 2 shows the results obtained in the same manner as in Example 2 except that the content was changed to 0.16.

Example 5 In the polymerization step (I), the hydrogen / propylene concentration ratio in the gas phase of the first and second stages was changed to 0.22, respectively, and the polymerization in the third stage was omitted. The results obtained in the same manner as in Example 4 are shown in Table 2.

Comparative Example 2 In the polymerization step (I), the hydrogen / propylene concentration ratios of the gas phase portions of the first and second stages were 0.21 and 0.23, respectively, and the polymerization time of each stage was 1.5 hours. Table 2 shows the results obtained in the same manner as in Example 5 except that the above was changed to. Log (MFR (h) / M
Since the value of FR (l)) is smaller than that of the present invention, the rigidity of the molded product is inferior to that of Example 5.

Comparative Example 3 In the polymerization step (I), the hydrogen / propylene concentration ratio in the first step was changed to 0.18, the polymerization time was changed to 3 hours, and the second and third steps were omitted. The results obtained in the same manner as in Example 4 are shown in Table 2. The rigidity of the molded product is inferior to that of Example 4.

Comparative Example 4 In the polymerization step (I), the hydrogen / propylene concentration ratios of the gas phase portions of the first, second and third stages were 0.45 and 0.23, respectively.
Table 2 shows the results obtained in the same manner as in Example 4 except that the value was changed to 0.10. Log (MFR (h) / MFR (l))
Is larger than that of the present invention, the tensile elongation and impact resistance of the molded product are inferior to those of Example 4.

[0029]

[Table 2]

Example 6 In the polymerization step (I), the hydrogen / propylene concentration ratio in the gas phase portions of the first, second and third steps was set to 0.35, and the gas phase hydrogen concentration in the polymerization step (II) was changed to Example 2 except that the content was changed to 0.2 mol%.
Results obtained in the same manner as in Table 3 are shown in Table 3.

Example 7 In the polymerization step (I), the hydrogen / propylene concentration ratio in the first, second and third gas phase portions was set to 0.20, and the gas phase hydrogen concentration in the polymerization step (II) was changed to Table 3 shows the results obtained in the same manner as in Example 2 except that the content was changed to 3 mol%.

Comparative Example 5 In the polymerization step (I), the hydrogen / propylene concentration ratio in the first, second and third gas phase portions was set to 0.60, and the gas phase hydrogen concentration in the polymerization step (II) was changed to Table 3 shows the results obtained in the same manner as in Example 2 except that the content was changed to 0.05 mol%. MFR ratio of polymerization step (I) and polymerization step (II) Log (MFR (i) / MF
Since R (ii)) is larger than that of the present invention, impact resistance is Example 2
Inferior.

Comparative Example 6 In the polymerization step (I), the hydrogen / propylene concentration ratios of the first, second and third vapor phase parts were respectively set to 0.18, and the vapor phase hydrogen concentration in the polymerization step (II) was changed. Table 3 shows the results obtained in the same manner as in Example 2 except that the content was changed to 10 mol%. MFR ratio of polymerization step (I) and polymerization step (II) Log (MFR
Since (i) / MFR (ii)) is smaller than that of the present invention, rigidity,
The impact resistance and tensile elongation are inferior to those of Example 2.

[0034]

[Table 3]

Example 8 In the polymerization step (I), the hydrogen / propylene concentration ratio in the gas phase portions of the first, second and third steps was set to 0.08, and the gas phase hydrogen concentration in the polymerization step (II) was changed to Table 4 shows the results obtained in the same manner as in Example 3 except that the total amount of ethylene fed was changed to 0.5 mol% and 2 kg.

Example 9 In the polymerization step (I), the hydrogen / propylene concentration ratio of the first, second and third vapor phase parts was set to 0.17, and the gas phase hydrogen concentration in the polymerization step (II) was changed to Table 4 shows the results obtained in the same manner as in Example 3 except that the amount of ethylene fed was changed to 0.5% by weight, the amount of ethylene fed was changed to 65% by weight, and the total amount of ethylene fed was changed to 7 kg.

Comparative Example 7 Table 4 shows the results obtained in the same manner as in Example 9 except that ethylbenzoate was used as an electron donor in the preparation of the solid catalyst component (A). The rigidity and impact resistance are significantly inferior to those of Example 9.

Comparative Example 8 As the solid catalyst component (A), the reduction catalyst described in the Examples of JP-A-58-201816, diethyl aluminum chloride as the organoaluminum compound (B), and organosilicon compound (C). Table 4 shows the results obtained in the same manner as in Example 9 except that methyl p-toluate was used instead of. Rigidity, tensile elongation, and impact resistance are inferior to those of Example 9.

[0039]

[Table 4]

Examples 10 to 14 Except that t-butyltrimethoxysilane, t-butyltriethoxysilane, i-butyltrimethoxysilane, cyclohexyltrimethoxysilane and di-i-butyldimethoxysilane were used as the organosilicon compound. The results obtained in the same manner as in Example 2 are shown in Table 5.

[0041]

[Table 5]

Comparative Examples 9 to 12 Table 6 shows results obtained in the same manner as in Example 2 except that methyl p-toluate, triethylamine, acetophenone and diethylene glycol dimethyl ether were used as electron donors instead of the organosilicon compound. The rigidity is inferior to that of the second embodiment.

[0043]

[Table 6]

Example 15, Comparative Examples 13 and 14 The ethylene supply ratios in the polymerization step (II) were 25% by weight, 15% by weight and 90% by weight, respectively, and the total amount of ethylene supplied was 3.5 kg, 2.5 kg, Table 7 shows the results obtained in the same manner as in Example 1 except that the weight was changed to 7.0 kg. Example 15
In comparison, Comparative Example 13 has a smaller content of ethylene in the polymerized portion in the polymerization step (II) than that of the present invention, resulting in poor rigidity and impact resistance of the molded product, and Comparative Example 14 has a large content of ethylene. Poor tensile elongation and impact resistance.

[0045]

[Table 7]

Example 16 3.0 kg of the product powder of the propylene / ethylene block copolymer composition obtained in Example 2 was added to 0.003 kg of a phenolic heat stabilizer and 0.0 of calcium stearate.
03 kg, 0.03 kg of talc having a bulk specific gravity of 0.39 and an average particle size of 10 μm were added, and mixed for 10 minutes at room temperature with a high-speed stirring mixer (Note. Henschel mixer, trade name), and the mixture with a screw diameter of 40 mm Granulation was performed using an extrusion granulator. Then, the granulated product is melted at a molten resin temperature of 2 with an injection molding machine.
A JIS type test piece was prepared at 30 ° C. and a mold temperature of 50 ° C., and the condition of the test piece was adjusted for 72 hours in a room with a humidity of 50% and a room temperature of 23 ° C. Then, when the physical properties were measured, the bending elastic modulus was 1750 MPa, the tensile strength was 38 MP.
a, tensile elongation 380%, HDT 127 ° C., Izod impact 119 J / m.

Example 17 3.0 kg of the product powder of the propylene / ethylene block copolymer composition obtained in Example 2 was added to 0.003 kg of a phenolic heat stabilizer and 0.0 of calcium stearate.
The same procedure was performed as in Example 16 except that 0.15 kg of talc having a bulk specific gravity of 0.12 cm ² / g and a bulk specific gravity of 0.12 cm ² / g was added, and the physical properties were measured. The flexural modulus was 1870 MPa and the tensile strength was measured. 38 MPa, tensile elongation 380%, HDT 131 ° C., and Izod impact 98 J / m.

3.0 kg of the product powder of the propylene / ethylene block copolymer composition obtained in Example 2 was added to 0.003 kg of a phenolic heat stabilizer, 0.003 kg of calcium stearate, and an amorphous ethylene / α-olefin copolymer. The polymer has a propylene content of 26% by weight,
Mooney viscosity [ML1 + 4 (100 ° C.)] was the same as in Example 16 except that 0.06 kg of an amorphous ethylene / propylene copolymer having a viscosity of 24 was added, and the physical properties were measured. Strength 36MP
a, tensile elongation 490%, HDT 115 ° C., Izod impact 121 J / m.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram (flow sheet) showing a method for manufacturing a composition of the present invention.

Claims (5)

[Claims] 1. A solid catalyst component (A) containing titanium, magnesium, halogen and a polycarboxylic acid ester as essential components, an organoaluminum compound (B) and a general formula R ⁴ _x R ⁵ _y Si (OR ⁶ ) _z. (In the formula, R ⁴ and R ⁶ represent a hydrocarbon group, R ⁵ represents a hydrocarbon group or a hydrocarbon group containing a hetero atom, and x + y + z = 4,0 ≦ x ≦ 2,1 ≦ y ≦
3, 1 ≦ z ≦ 3. 2) is used as the first step by using a catalyst system in which an organosilicon compound (C) represented by
Propylene homopolymerization was carried out in a polymerization step (I) using a tank or more polymerization vessels in series to produce 60 to 95% by weight of the total weight, and as a second step, polymerization using one or more vessel polymerization machines. A propylene / ethylene block copolymer produced by copolymerizing propylene and ethylene in step (II) to produce a propylene / ethylene copolymer part having an ethylene content of 30 to 80% by weight based on the total weight of 5 to 40% by weight. In the polymer, the maximum value (hereinafter referred to as MFR (h)) and the minimum value (MF) of the melt flow rate of the polymer obtained in each tank of the polymerization step (I)
R (l)) has a relationship of 0.1 ≦ Log (MFR (h) / MFR (l)) ≦ 1 (1), and the propylene polymer obtained in the polymerization step (I) is Isotactic pentad fraction (P) is 0.
96 or more, Mw / Mn (Q value) is 6 or less, and
The melt flow rate of the polymer obtained in the polymerization step (I) (hereinafter referred to as MFR (i)) and the melt flow rate of the polymer obtained in the polymerization step (II) (hereinafter referred to as MFR (ii)) are 3 ≦. A high-rigidity propylene / ethylene block copolymer composition having a relationship of Log (MFR (i) / MFR (ii)) ≦ 7 (2). 2. The MFR of the polymer finally obtained is 0.
The high-rigidity propylene / ethylene block copolymer composition according to claim 1, which is 1 or more and 100 or less. 3. The high-rigidity propylene / ethylene block copolymer composition according to claim 1, which is polymerized in a hydrocarbon solvent. 4. The MFR (h) and MFR according to claim 1.
(1) is 0.2 ≦ Log (MFR (h) / MFR (1)) ≦ 0.
The high-rigidity propylene / ethylene block copolymer composition according to claim 1, having a relationship of 5. 5. The MFR (i) and MFR according to claim 1.
The high-rigidity propylene / ethylene block copolymer composition according to claim 1, wherein (ii) has a relationship of 4 ≦ Log (MFR (i) / MFR (ii)) ≦ 6.