JP3162441B2 - High rigidity propylene copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene copolymer composition having high rigidity and high impact resistance and excellent moldability.

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2. Description of the Related Art In recent years, from the viewpoint of resource saving and energy saving, there has been a demand for thinner and lighter injection molded products or extruded molded products. Therefore, various improvement methods have already been proposed for improving the rigidity, impact resistance, and moldability of polypropylene to achieve a thinner and lighter injection-molded product. These suggested improvements include:
For example, Japanese Patent Application Laid-Open Nos. 54-11369 and 55-5-5
969, JP-A-55-115417, JP-A-61-1.
No. 69821, JP-A-61-69822, JP-A-61-69822
And the methods described in JP-A-69823.

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However, such various improvements have been made with respect to one or two of the above-mentioned properties of rigidity, impact resistance and moldability. However, these properties are not improved in all three properties, and in order to obtain the desired thin and lightweight injection molded products or extruded molded products, these rigidity, impact resistance and moldability are well-balanced. Without improvement, it was not possible to obtain a sufficiently satisfactory injection-molded product or extrusion-molded product having a reduced thickness and weight. Therefore, in order to obtain the desired injection-molded product or extrusion-molded product having a reduced thickness and weight, it has been strongly demanded that the rigidity, impact resistance, and moldability be further improved in a more balanced manner.

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[Means for Solving the Problems]

SUMMARY OF THE INVENTION In view of the above problems, the present inventors have conducted intensive studies to improve the balance of rigidity, impact resistance and moldability of a propylene copolymer composition. A propylene copolymer composition is produced by two-stage polymerization using a catalyst comprising a catalyst component and an organoaluminum compound component, wherein the first-stage polymer has a high MF
R and highly crystalline polypropylene are produced, and a propylene / ethylene copolymer having a low MFR is produced in the second step to obtain a propylene copolymer composition having high rigidity, high impact strength and excellent moldability. It has been found that the present invention has been completed.

That is, the high-rigidity propylene copolymer composition of the present invention is obtained by conducting at least two stages of a first stage and a second stage using a catalyst comprising a supported titanium-containing solid catalyst component and an organoaluminum compound component. The propylene copolymer composition produced in the step, wherein the first-stage polymer has an MFR of 30 to 300 g / 10 min, a boiling heptane-insoluble content of 97% by weight or more, and a density of 0.9070 g / cm. ^Three
As described above, the crystalline propylene polymer accounts for 70 to 97% by weight of the total polymer, and the second-stage polymer has an MFR
Is a propylene / ethylene copolymer having a reaction ratio (weight ratio) of propylene to ethylene of 80/20 to 20/80, and 3 to 30% by weight of the whole polymer, in the range of 0.001 to 1.0 g / 10 minutes. And the MFR of the entire copolymer composition is 5 to 5.
At 200 g / 10 min, the M of the first-stage polymer and the second-stage polymer
It is characterized in that the FR ratio is 100 to 100,000.

[I] Propylene Copolymer Composition (1) Constituents The highly rigid propylene copolymer composition of the present invention comprises a supported titanium-containing solid catalyst component and an organoaluminum compound component. At least two of the first and second stages using a catalyst comprising
It is composed of the following first-stage polymer and second-stage polymer produced by a step polymerization method. (a) First-stage polymer The first-stage polymerization, that is, the polymer produced by homopolymerization of propylene, has an MFR of usually 30 to 300 g / 1.
0 minutes, preferably 50 to 200 g / 10 minutes, and the boiling heptane-insoluble content is usually 97% by weight or more, preferably 98% by weight.
% Or more, and the density is usually 0.9070 g / c.
It is a crystalline propylene polymer having m ³ or more, preferably 0.9080 g / cm ³ or more. If the MFR is less than the above range, the moldability of the product will be poor, and if it exceeds the above range, the hydrogen concentration at the time of polymerization will be too high and the catalytic activity will be reduced, which is economically disadvantageous. If the boiling heptane insolubles and density are less than the above ranges, the rigidity of the product is reduced, and the features of the present invention are impaired.

(B) Second-stage polymer The polymer produced by the second-stage polymerization, that is, the copolymerization of propylene and ethylene, usually has an MFR of 0.00
1 to 1.0 g / 10 min, preferably 0.002 to 0.2
g / 10 minutes, and the reaction ratio (weight ratio) of propylene to ethylene is usually 80/20 to 20/80, preferably 70/20.
/ 30 to 30/70 propylene / ethylene copolymer. If the MFR is less than the above range, the dispersion of the propylene / ethylene copolymer produced in the second stage in the product becomes poor, and the moldability and the product appearance deteriorate. When the MFR exceeds the above range, the rigidity and impact resistance of the product are reduced. Further, when the reaction ratio of propylene and ethylene is out of the above range and propylene becomes excessive and is polymerized, the impact resistance is reduced. Also, when the amount of ethylene is excessive, a resin having reduced impact resistance can be obtained.

(2) Amount ratio The propylene copolymer composition of the present invention comprises the above-mentioned first-stage polymer and second-stage polymer, and the ratio of the crystalline propylene polymer in the first-stage polymer is usually 70 to 97% by weight, preferably 80 to 95% by weight, and the proportion of the propylene / ethylene copolymer in the second stage polymer is usually 3 to 30% by weight, preferably 5 to 20% by weight. The MFR ratio of the first-stage polymer and the second-stage polymer is usually 100 to 100,000, preferably 500 to 50,000, and the MFR ratio of the entire copolymer composition
FR is usually 5 to 200 g / 10 min, preferably 10 to 1 g.
50 g / 10 min, more preferably 20 to 100 g / 10
Minutes. When the proportion of the first-stage polymer is less than the above range, the rigidity of the product is reduced, and when it exceeds the above range, the impact resistance is reduced. When the proportion of the second-stage polymer is less than the above range, the impact resistance is reduced, and when it exceeds the above range, the rigidity is reduced. When the MFR ratio of the first-stage polymer and the second-stage polymer is less than the above range, rigidity, impact resistance, and moldability are all decreased. The properties and appearance of the product deteriorate. If the MFR of the entire copolymer composition is less than the above range, the moldability will deteriorate, and if it exceeds the above range, the impact resistance will decrease.

(3) Physical Properties The high-rigidity propylene copolymer composition of the present invention is excellent in balance of mechanical strength, especially in balance of rigidity and impact resistance, and has good moldability. Suitable for injection molding or extrusion molding resin with reduced weight,
It is useful as a resource saving and energy saving material.

[II] Production of propylene copolymer composition (1) Catalyst The catalyst used in the at least two-stage polymerization method for producing the propylene copolymer composition of the present invention is a supported titanium-containing solid. Although it is composed of a catalyst component and an organoaluminum compound component, an electron donating compound can be used as the third component, if necessary. (a) Supported titanium-containing solid catalyst component The supported titanium-containing solid catalyst component contains magnesium, titanium, halogen, and an electron donor as essential components. In general, the magnesium component is introduced into the supported titanium-containing solid catalyst component by a magnesium halide, the titanium component is introduced by a titanium halide, and the halogen component is introduced by these compounds.

Magnesium halide The magnesium halide is preferably a magnesium dihalide, and specifically, magnesium chloride, magnesium bromide and magnesium iodide can be used. More preferably, it is magnesium chloride, particularly preferably substantially anhydrous. In addition, magnesium halide is magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, organomagnesium compound electron donor, halosilane, Magnesium halide obtained by treatment with alkoxysilane, silanol, aluminum compound, titanium halide compound, titanium tetraalkoxide, etc. may be used.

Titanium Halide Titanium halide is typically a halogen compound of trivalent or tetravalent titanium. Preferred halogenated titanium compounds are compounds represented by the general formula Ti (OR ¹ ) _n X _{4 -n} (R ¹ is a C _{1 to} C ₁₀ hydrocarbon residue, X is a halogen), and n = 0. It is a 1 or 2 tetravalent titanium halide compound. Specifically, TiCl ₄ , Ti
(OBu) Cl ₃ , Ti (OBu) ₂ Cl _{2 and the} like can be exemplified, but particularly preferred is. TiCl ₄ ,
A titanium tetrahalide such as Ti (OBu) Cl ₃ or a monoalkoxytrihalogenated titanium compound (O
Bu represents a butoxy group).

The electron donor, which is an essential component of the electron donor-supporting titanium-containing solid catalyst component, may be a polyvalent carboxylic acid ester or an organic silicon compound, and both of them may be used.

Specific examples of the preferable polyvalent carboxylic acid ester include (a) diethyl succinate,
Dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl methylmalonate,
Diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl allyl malonate, diethyl diisobutyl malonate, diethyl dinormal butyl malonate, dimethyl maleate, maleate Monooctyl acid, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate,
Diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-fumarate
Aliphatic polycarboxylic acid esters such as 2-ethylhexyl, diethyl itaconate, dibutyl itaconate, dioctyl citraconic acid, and dimethyl citraconic acid;
Diethyl 1,2-cyclohexanecarboxylate, 1,2-
Aliphatic polycarboxylic acid esters such as diisobutyl cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate,

(C) monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, mono-normal butyl phthalate, diethyl phthalate,
Ethyl isobutyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-ethyl phthalate aromatic polycarboxylic acid esters such as n-octyl, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, ( D) Different carbon polycarboxylic acid esters such as 3,4-furandicarboxylic acid and the like.

Preferred among these polycarboxylic acid esters are esters of phthalic acid, maleic acid, substituted malonic acid and the like and alcohols having 2 or more carbon atoms, and particularly preferred are phthalic acid and 2 or more carbon atoms. Diester with alcohol. Specific examples of preferred organic silicon compounds include those represented by the following chemical structural formulas.

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When these electron-donating compounds are contained in the supported titanium-containing solid catalyst component, it is not always necessary to use them as starting materials, and they are converted into these compounds during the preparation of the supported titanium-containing solid catalyst component. The compounds which can be used may be converted into these compounds at the stage of the preparation.

Preparation of Supported Titanium-Containing Solid Catalyst Component In preparing the supported titanium-containing solid catalyst component, the magnesium halide is desirably preliminarily treated. The preliminary treatment can be performed by various conventionally known methods, and specific examples thereof include the following methods (A) to (H). (A) magnesium dihalide, or magnesium dihalide and a halogen compound of titanium, silicon or aluminum or a halogenated hydrocarbon compound,
Smash. The pulverization can be performed using a ball mill or a vibration mill. (B) A magnesium dihalide is dissolved using a hydrocarbon or a halogenated hydrocarbon as a solvent and an alcohol, a phosphoric acid ester or a titanium alkoxide as a dissolution promoter. Next, a poor solvent, an electron donor such as an inorganic halide or an ester, or a polymer silicon compound such as methylhydrogenpolysiloxane is added to the solution to precipitate dissolved magnesium dihalide from the solution.

(C) Contacting mono- or dialcoholate or magnesium carboxylate of magnesium with a halogenating agent. (D) Contact reaction between magnesium oxide and chlorine or AlCl ₃ . (E) MgX ₂ .nH ₂ O (X is a halogen) is contacted with a halogenating agent or TiCl ₄ . (F) A contact reaction of MgX ₂ .nROH (X is a halogen, R is an alkyl group) with a halogenating agent or TiCl ₄ . (G) Grignard reagent, MgR ₂ compound (R is an alkyl group), or a complex of a MgR ₂ compound and trialkylaluminum compound, a halogenating agent, for example _{AlX 3, AlR m X 3-} m (X is Halogen, R is an alkyl group), SiCl ₄ or SiCl ₃ . (H) contacting a Grignard reagent with silanol or with polysiloxane, H ₂ O or silanol,
Thereafter, a contact reaction is performed with a halogenating agent or TiCl ₄ .

The details of the pretreatment of the magnesium halide are described in JP-B-46-611 and JP-B-46-611.
No.34092, No.51-3514, No.56-
No.67311, No.53-40632, No.56
-50888, JP-B-57-48565, JP-B-5
No. 2-36786, JP-B-58-449, JP-A-Sho 53
JP-A-45686, JP-A-50-126590, JP-A-54-31092, JP-A-55-135102, JP-A-55-135103, JP-A-56-811, and JP-A-56-11908 No., JP-A-57-180612
JP-A-58-5309, JP-A-58-5310
And JP-A-58-5311. The contact between the pretreated magnesium chloride, the titanium halide and the electron donating compound may be carried out by forming a complex of the titanium halide and the electron donating compound and then contacting the complex with the magnesium chloride. And titanium halide, and then contact with an electron donor compound, or magnesium chloride and an electron donor compound and then contact with titanium halide.

As a contacting method, a pulverizing contact such as a ball mill or a vibrating mill may be used, or magnesium chloride or an electron donor treated product of magnesium chloride may be added to a liquid phase of titanium halide. Washing with an inert solvent may be performed after the three- or four-component contact or at an intermediate stage between the respective component contacts. The supported titanium-containing solid catalyst component thus produced has a titanium halide content of 1 to 20% by weight, preferably 1.5 to 15% by weight, and a magnesium halide content of 50 to 98% by weight, preferably Is 60 to 90% by weight, and the molar ratio of the electron donor compound to the titanium halide is about 0.05 to 2.0, preferably about 0.2 to 1.5.

(B) Organoaluminum Compound Component The organoaluminum compound component used in the present invention may be a compound represented by the general formula: AlR _n X _3-n (where R is 1 carbon atom)
~ 12 hydrocarbon residues, X represents a halogen or alkoxy group, and n represents 0 <n≤3. Such an organoaluminum compound component is specifically, for example, triethylaluminum, tri-n-
Propyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, triisohexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum monochloride, diethyl aluminum sesquichloride, diethyl aluminum Monoethoxyside and the like. Of course, two or more of these organoaluminum compounds can be used in combination. The use ratio of the organoaluminum compound component and the supported titanium-containing solid catalyst component used in the polymerization of the α-olefin can vary widely, but is generally 1 to 1,000 per titanium atom contained in the solid catalyst component. Preferably 1
An organoaluminum compound can be used at a ratio of 0 to 500 (molar ratio).

(C) Electron Donating Compound In producing the propylene copolymer composition of the present invention by at least two-stage polymerization, an electron donating compound may be added as necessary. As the electron donating compound,
Organosilicon compounds are preferably used. Specific examples of the organosilicon compound are the same as those contained in the supported titanium-containing solid catalyst component. The amount of addition of the electron donating compound is usually 0.01 to 1.0, preferably 0.02 to 0.
5

(2) Polymerization Method (a) Raw Materials Used The raw materials used in producing the high-rigidity propylene copolymer composition of the present invention are propylene and ethylene, and the object of the present invention is impaired if necessary. Other amounts of other olefins, such as butene-1, 4-methylpentene-1 and the like, can also be used.

(B) Multi-stage polymerization In order to produce the high-rigidity propylene copolymer composition of the present invention, the raw material is prepared by using a catalyst comprising the supported titanium-containing solid catalyst component and the organoaluminum compound component. It is produced by at least two-stage polymerization using propylene and ethylene. The first stage polymerization is highly crystalline,
This is a step of producing a high MFR propylene homopolymer, and the second stage polymerization is a step of producing a low MFR propylene / ethylene copolymer. The polymerization may be a continuous type or a batch type, and a slurry polymerization method using an inert hydrocarbon solvent, a bulk polymerization method using propylene itself as a medium, or a gas phase polymerization method can be employed.
° C, preferably at a temperature of 50 to 80 ° C, normal pressure to 50 kg /
The polymerization reaction is carried out under a pressure of cm ² G, preferably 3 to 40 kg / cm ² G. In the first-stage polymerization, it is necessary to increase the concentration of hydrogen, which is a molecular weight regulator, in order to obtain a polymer having a high MFR. Conversely, in the second-stage polymerization, it is necessary to obtain a copolymer having a low MFR. It is necessary to keep the hydrogen concentration extremely low or in a substantially hydrogen-free state.

First-stage polymerization The first-stage polymerization is carried out by homopolymerization of propylene to obtain MF.
R is usually 30 to 300 g / 10 min, preferably 50 to 2
00g / 10 minutes, and the boiling heptane-insoluble content is usually 97%.
% By weight, preferably 98% by weight or more, and the density is usually 0.9070 g / cm ³ or more, preferably 0.1% by weight.
The operation is performed so that a crystalline propylene polymer of 9080 g / cm ³ or more is produced. In order to increase the above-mentioned density and boiling heptane-insoluble matter, it is important to use a supported titanium-containing solid catalyst component. In order to increase the MFR, it is important to increase the concentration of hydrogen, which is a molecular weight regulator. If the MFR is less than the above range, the moldability of the product will be poor, and if it exceeds the above range, the hydrogen concentration at the time of polymerization will be too high and the catalytic activity will be reduced, which is economically disadvantageous. If the boiling heptane insolubles and density are less than the above ranges, the rigidity of the product is reduced, and the features of the present invention are impaired.

Second Stage Polymerization In the second stage polymerization, MFR is usually 0.001 to 1.0 g / 10 min, preferably 0.002 to 0.2 g / 10 min by copolymerization of propylene and ethylene. The reaction ratio (weight ratio) of propylene and ethylene is usually 80/20 to
The reaction is carried out so as to produce a propylene / ethylene copolymer of 20/80, preferably 70/30 to 30/70. If the MFR is less than the above range, the dispersion of the propylene / ethylene copolymer produced in the second stage in the product becomes poor, and the moldability and the product appearance deteriorate. When the MFR exceeds the above range, the rigidity and impact resistance of the product are reduced. Further, when the reaction ratio of propylene and ethylene is out of the above range and propylene becomes excessive and is polymerized, the impact resistance is reduced. Also, when the amount of ethylene is excessive, a resin having reduced impact resistance can be obtained.

[0052] The amount ratio of propylene copolymer compositions of the present invention comprises the above-described first stage polymer and second stage polymer, the proportion of the crystalline propylene polymer of the first stage polymer is usually 70 to 97 %, Preferably 80 to 95% by weight, and the proportion of the propylene / ethylene copolymer in the second stage polymer is usually 3 to 30% by weight, preferably 5 to 20% by weight. The MFR ratio of the first-stage polymer and the second-stage polymer is usually 100 to 100,000, preferably 500 to 50,000, and the MFR ratio of the entire copolymer composition
FR is usually 5 to 200 g / 10 min, preferably 10 to 1 g.
50 g / 10 min, more preferably 20 to 100 g / 10
Minutes. When the proportion of the first-stage polymer is less than the above range, the rigidity of the product is reduced, and when it exceeds the above range, the impact resistance is reduced. When the proportion of the second-stage polymer is less than the above range, the impact resistance is reduced, and when it exceeds the above range, the rigidity is reduced. When the MFR ratio of the first-stage polymer and the second-stage polymer is less than the above range, rigidity, impact resistance, and moldability are all decreased. The properties and appearance of the product deteriorate. If the MFR of the entire copolymer composition is less than the above range, the moldability will deteriorate, and if it exceeds the above range, the impact resistance will decrease. In addition, in the multi-stage polymerization, particularly, a polymerization method using two steps has been described in detail.
It can be carried out before or after each polymerization step of the first and second polymerization steps, or by three or more polymerization steps in which another polymerization step is added between these polymerization steps.

[0053]

EXAMPLES The high-rigidity propylene copolymer composition of the present invention will be specifically described below with reference to examples and comparative examples. [I] Evaluation method MFR was measured according to JIS-K7210. The latter stage MFR was determined by the following equation. log (MFR of block copolymer)-(pre-stage polymerization ratio)
X log (first stage MFR) = (second stage polymerization ratio) x log (second stage MFR) I was determined as a ratio of insoluble matter by boiling n-heptane extraction. A heat stabilizer and a rust inhibitor were blended into the obtained powdery polymer, and each was pelletized by an extruder, and a test piece was molded by an injection molding machine.

The flexural modulus was measured according to JIS-K7203. Izod impact strength was measured according to JIS-K7110. A sheet having a drop weight impact strength of 2 × 80 × 120 mm was molded by an injection molding machine to obtain a test piece. The spiral flow was measured using a Meiki SJ type (in-line screw type) injection molding machine in a mold having a cross section of 2 mm x 8 mm under the following conditions. Molding temperature: 240 ° C. Injection pressure: 800 kg / cm ² Injection time: 6 seconds Mold temperature: 40 ° C. Injection rate: 50 g / sec Additives for granulation Irganox 1010 (manufactured by Ciba Geigy) 0.10% by weight calcium 0.10% by weight of aluminum stearate 0.10% by weight of aluminum hydroxy-di (tert-butylbenzoate)

[II] Experimental Example Example 1 (1) Preparation of Solid Catalyst Component 75 ml of purified heptane, 75 ml, was placed in a 500 ml glass three-necked flask (with a thermometer and a stirring bar) whose internal volume was replaced with nitrogen. Milliliter of titanium tetrabutoxide and 10 g of anhydrous magnesium chloride were added.
Thereafter, the temperature of the flask was raised to a temperature of 90 ° C., and the mixture was stirred at this temperature for 2 hours to completely dissolve the magnesium chloride. Next, the flask is cooled to a temperature of 40 ° C.
By adding 15 ml of methylhydrogenpolysiloxane, a magnesium chloride / titanium tetrabutoxide complex was precipitated. The precipitate was washed with purified heptane to obtain an off-white solid. 20 g of the precipitated solid obtained above was placed in a three-necked glass flask (with a thermometer and a stirrer) whose internal volume was replaced with nitrogen and was 300 ml.
65 ml of a heptane slurry containing
Next, 25 ml of a heptane solution containing 8.7 ml of silicon tetrachloride was added at room temperature over 30 minutes, and the mixture was further reacted at a temperature of 30 ° C. for 30 minutes and further reacted at a temperature of 90 ° C. for 1 hour. After the completion of the reaction, the reaction product was washed with purified heptane, 50 ml of a heptane solution containing 1.6 ml of phthaloyl chloride was added thereto, and the mixture was reacted at a temperature of 50 ° C. for 2 hours. Thereafter, the product was washed with purified heptane, 25 ml of titanium tetrachloride was further added, and reacted at a temperature of 90 ° C. for 2 hours. This was further washed with purified heptane to obtain a titanium-containing solid catalyst component. The titanium content in the titanium-containing solid catalyst component was 3.22% by weight.

(2) Production of Propylene Copolymer Composition After sufficiently replacing the inside of a stirred autoclave having an internal volume of 200 liters with propylene, dehydrated and deoxygenated n-
60 liters of heptane were introduced, and 15.0 g of triethylaluminum, 3.0 g of the above-mentioned titanium-containing solid catalyst component and 4.3 g of tert-butylmethyldimethoxysilane were added at 70 ° C.
And introduced under a propylene atmosphere. In the first-stage polymerization, after heating the autoclave to a temperature of 75 ° C., propylene was added at 9 kph while keeping the hydrogen concentration at 13% (volume).
Started by introduction at a speed of g / hour.
After 228 minutes, the introduction of propylene was stopped, and the polymerization was continued for 75 minutes.
C. for 90 minutes. Purging was performed until propylene in the gas phase became 0.2 kg / cm ² G. Then, n
4.9 g of butanol are added and the autoclave is
After cooling to a temperature of ° C., the second stage polymerization was carried out by feeding at a feed rate of 2.58 kg / hour of propylene and 1.72 kg / hour of ethylene for 53 minutes. The slurry thus obtained was filtered and dried to obtain a powdery propylene copolymer composition.

Table 1 shows the results of the polymerization. The physical properties of the obtained propylene copolymer composition were measured according to the evaluation methods described above, and the results are shown in Table 2. The weight ratio of the produced polymer in the first-stage polymerization and the second-stage polymerization in Table 1 is obtained by dissolving the block copolymer in boiling xylene
The component precipitated at the stage of cooling to 3 ° C. was defined as a first-stage polymer, and the dissolved component was defined as a second-stage polymer. The reaction ratio (weight ratio) between propylene and ethylene in the second stage polymerization is as follows:
The fractionated dried product of the above-mentioned component dissolved at 23 ° C. in xylene was determined by IR measurement. Further, the MF of the first stage polymer
R, I. I and density were determined by sampling and measuring a small amount at the end of the first-stage polymerization.

Examples 2 to 4 and Comparative Examples 1 to 5 The procedure of Example 1 was repeated except that the polymerization conditions of Example 1 were changed to the conditions shown in Table 1. Table 2 shows the results.

COMPARATIVE EXAMPLE 6 After sufficiently replacing the inside of a stirring type autoclave having an internal volume of 200 liters with propylene, dehydration and deoxygenation of n-
60 liters of heptane were introduced, and 50.8 g of diethylaluminum monochloride and 12.7 g of a titanium trichloride catalyst manufactured by Marubeni Solvay were introduced at a temperature of 65 ° C. in a propylene atmosphere. In the first stage polymerization, the autoclave was
After the temperature was raised to 0 ° C., the hydrogen concentration was increased to 9.5% at that temperature.
And started by introducing propylene at a speed of 9 kg / h. Stopping the introduction of 228 minutes after propylene, after it continued further 90 minutes the polymerization at a temperature of 70 ° C., the gas phase propylene 0.6 kg / cm ² G
Purged until Next, the autoclave was heated to 60 ° C.
, And the second stage polymerization was carried out by feeding at a feed rate of 2.58 kg / hour of propylene and 1.72 kg / hour of ethylene for 53 minutes. The slurry thus obtained was filtered and dried to obtain a powdery propylene copolymer composition. Table 1 shows the polymerization results. The physical properties of the obtained propylene copolymer composition were measured according to the evaluation methods described above, and the results are shown in Table 2.

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[Table 1]

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[Table 2]

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As described above, the high-rigidity propylene copolymer composition of the present invention has an excellent balance of mechanical strength, particularly, a balance of rigidity and impact resistance, and has good moldability, thinness and light weight. It is very useful as a resin for injection molding or extrusion molding.

Continuation of the front page (72) Inventor Yoshihiro Fukushima 1 Toho-cho, Yokkaichi-shi, Mie Pref. Yokkaichi Research Institute, Mitsubishi Yuka Co., Ltd. (56) References JP-A-61-252218 (JP, A) JP-A-4 -279617 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 297/08 C08F 4/642

Claims (1)

(57) [Claims] 1. A propylene copolymer composition produced by a catalyst comprising a supported titanium-containing solid catalyst component and an organoaluminum compound component in at least two stages of a first stage and a second stage. The first-stage polymer has an MFR of 50 to 200 g / 10
, Boiling heptane-insoluble matter is 97% by weight or more, and density is 0.1%.
9070 g / cm ³ or more, a crystalline propylene polymer occupying 70 to 97% by weight of the total polymer, and the second stage polymer has an MFR of 0.001 to 1.0 g.
/ 10 minutes, the reaction ratio (weight ratio) of propylene and ethylene is 80/20 to 20/80, and 3 to 30% by weight of the whole polymer.
Is a propylene / ethylene copolymer, and the MFR of the entire copolymer composition is 5 to 200 g / 10 minutes,
The first stage polymer and the second stage polymer have an MFR ratio of 500 to 5
A high-rigidity propylene copolymer composition having a molecular weight of 000.