JPH07173233A - Propylene-ethylene copolymer and its production - Google Patents

Abstract

PURPOSE:To provide a propylene-ethylene copolymer excellent in flexibility, clarity, and heat resistance. CONSTITUTION:A propylene-ethylene copolymer has a wt. average mol.wt. of 100,000-1,500,000, contains 5-60mol% ethylene units, and comprises 1-60wt.% polypropylene blocks having an intrinsic viscosity [eta] of 7dl/g or higher and a xylene-sol. content at room temp. of 0.5wt.% or lower and 40-99wt.% propylene-ethylene random copolymer blocks having an intrinisic viscosity of 0.5-7dl/g and a xylene-sol. content at room temp. of 50wt.% or higher.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a propylene-ethylene copolymer having excellent heat resistance, impact resistance and transparency.

[0002]

BACKGROUND OF THE INVENTION Since olefinic thermoplastic elastomers have excellent flexibility, low specific gravity and high weather resistance, various industrial parts including automobile parts such as bumpers, Widely used for home electric appliances. As these olefinic thermoplastic elastomers, ethylene propylene rubber (EPR) or ethylene propylene terpolymer (EPDM) and polypropylene resin are generally melt-kneaded in order to satisfy impact resistance and flexibility at low temperatures. In some cases, it is produced by a method of partially crosslinking before or after kneading.
Such a method is disclosed, for example, in JP-A-47-18943, JP-A-48-26838, JP-A-49-53938 and JP-A-49-53938.
4-1386. In addition, JP-A-61-2
In JP-A-64043, JP-A-2-140236 and JP-B-59-30736, a copolymer obtained by three-stage polymerization of propylene and ethylene having different ethylene contents, a propylene-ethylene copolymer and a diolefin are described. There is disclosed a method of increasing the heat resistance without impairing the flexibility by dynamically cross-linking the composition containing PP and a blend of PP, EPDM, EPR, divinylbenzene and the like. However, in this method, the respective polymers are produced in advance, and the productivity is poor by blending them next.Also, the transparency is poor because they are crosslinked and cannot be used for applications such as films and sheets, Furthermore, it has a problem that it is difficult to recycle.

On the other hand, in order to solve these problems, there has been proposed a method in which each component is polymerized stepwise in the same polymerization tank by using a multistage polymerization method. For example, JP-A-5
Nos. 5-80418 and 57-10611 are mentioned, but flexibility and heat resistance were insufficient. Japanese Patent Laid-Open No. Sho 57
In JP-61012-A, the improvement in tensile properties is insufficient, and at the same time, the polymerization temperature is low and a large temperature change is forced, so that stable production is difficult due to the problem of heat removal. Further, in JP-A-58-145718 and JP-A-58-71910, propylene, ethylene, 1-
Although a method in which heat resistance, impact resistance, and transparency are improved by three-stage polymerization of butene having different compositions is disclosed, it is insufficient as a product having a balanced physical property. As described above, the direct polymerization method is excellent in flexibility and transparency, as well as in manufacturing cost and recyclability, but has a problem that it lacks heat resistance and oil resistance.

As described above, the flexibility and transparency are good,
Moreover, development of an olefinic thermoplastic elastomer having good heat resistance has been desired.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polypropylene component having a specific viscosity and a propylene-ethylene copolymer component having a specific viscosity are used. The present invention has been completed by finding that a propylene ethylene block copolymer is an elastomer having good flexibility and transparency and high heat resistance. .

That is, the present invention relates to polypropylene components 1 to 6
A block copolymer containing 0 wt% and 40 to 99 wt% of a propylene ethylene random copolymer component, wherein the polypropylene component has an intrinsic viscosity [η] of 7 dl / g or more,
Further, the xylene-soluble component at room temperature is 5 wt% or less, the propylene ethylene random copolymer component has an intrinsic viscosity [η] of 0.5 to 7 dl / g, and the xylene-soluble component at room temperature is 50 wt. % Or more, and
It contains 5 to 60 mol% of ethylene-based monomer units, and has a weight average molecular weight of 100,000 to 1 for the entire copolymer.
It is a propylene-ethylene copolymer characterized by being 500,000.

The polypropylene component in the propylene-ethylene copolymer of the present invention accounts for 1 to 1 of the total polymer.
Must be 60 wt%, preferably 3-40 wt
%. Further, the propylene ethylene random copolymer component (hereinafter, simply referred to as a random copolymer component) contains 5 to 60 mol%, preferably 8 to 50 mol% of a monomer unit based on ethylene, and the amount thereof is based on the whole polymer. Occupy 40 to 99 wt%, preferably 60 to 99 wt
Must be%. Polypropylene component is 60wt%
When it is more than 5% or when the content of the monomer unit based on ethylene in the random copolymer component is less than 5 mol%, the property as polypropylene becomes strong and sufficient flexibility and excellent impact resistance cannot be exhibited. On the other hand, the ethylene-based monomer unit in the random copolymer component is 60
When it exceeds mol%, the property as polyethylene becomes strong and the tensile impact strength and heat resistance become insufficient, which is not preferable.

The polypropylene component in the propylene-ethylene copolymer of the present invention has an intrinsic viscosity [η] of 7 dl / g or more, preferably 9 to 25 dl / g. If the intrinsic viscosity [η] is less than 7 dl / g, the effect of improving the heat resistance in the above ethylene composition is lowered, which is not preferable. The random copolymer component of the propylene-ethylene copolymer of the present invention has an intrinsic viscosity [η] of 0.5 to 7 dl.
/ G, preferably in the range of 1.0-5 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, heat resistance and impact resistance are insufficient, which is not preferable. The limiting viscosity in the present invention is 135 with tetralin as a solvent.
It is a value measured at ° C.

The polypropylene component in the propylene-ethylene copolymer of the present invention must have a xylene soluble component at room temperature of 5 wt% or less, preferably 0.1 to 3 wt%. This is because the polypropylene component has an extremely large molecular weight as described above and the polypropylene component has high crystallinity as described later. Therefore, xylene soluble component is 5 wt.
If it exceeds%, it is necessary to increase the proportion of the polypropylene component in the total polymer or to reduce the ethylene content in the random copolymer in order to maintain the heat resistance of the propylene-ethylene copolymer at a predetermined level. As a result, the impact resistance of all the copolymers is lowered. on the other hand,
The xylene-soluble component at room temperature in the random copolymer component must be 50 wt% or more, and further 60 to
100 wt% is preferable. This is because the random copolymer component needs to have amorphous or extremely low crystalline elastomeric properties. If the xylene-soluble component is less than 50 wt%, the crystallinity becomes too high, which is preferable. Absent.

The molecular weight of the propylene ethylene copolymer is
The weight average molecular weight (hereinafter abbreviated as Mw) is 100,000 to 1,500,000, and the range of 200 to 1,000,000 is more preferable in consideration of moldability. When the Mw exceeds the above range, the moldability is deteriorated and the desired physical properties cannot be obtained, which is not preferable. The propylene-ethylene copolymer of the present invention preferably has a molecular weight distribution (Mw / Mn) of 3 to 15. The weight average molecular weight in the present invention was measured by gel permeation chromatography (hereinafter abbreviated as GPC). The propylene-ethylene copolymer of the present invention may be obtained by any method, but the following method is particularly preferably adopted.

In the presence of a catalyst comprising the following components (A) titanium compound (B) organoaluminum compound and (C) electron donor, propylene is first polymerized in the first stage polymerization to obtain an intrinsic viscosity [η]. 7 wt / dl or more, and 5 wt% of xylene soluble component at room temperature
1 to 60 wt% of the total amount of polymerized polypropylene below
Then, in the second stage polymerization, propylene and ethylene are copolymerized to obtain an intrinsic viscosity [η] of 0.5 to 7d.
1 / g and 50w xylene soluble component at room temperature
t% or more, 5 to 6 monomer units based on ethylene
It is obtained by forming a propylene-ethylene random copolymer containing 0 mol% in an amount of 40 to 99 wt% of the total polymerization amount.

As the titanium compound which is the component (A) of the present invention, known titanium compounds and organoaluminum compounds used for the polymerization of olefins can be used without any limitation. As the titanium compound, α, β, γ, or δ-
Titanium trichloride can be used, among which, for example, JP-A-4
7-34478, 50-126590, 50.
-114394, 50-93888, 50-123.
09, 50-74594, 50-104191, 50-98489, 51-136625, 52-3.
The highly active titanium compound prepared by the method described in each of the publications of No. 0888 and 52-35283 is preferably used.

Further, a titanium compound supported on a carrier such as magnesium chloride can also be preferably used. For example,
JP-A-56-155206 and JP-A-56-13680
6, the same 57-34103, the same 58-8706, the same 58-
83006, 58-138708, 58-1837.
09, ibid. 59-206408, ibid. 59-219311,
60-1208, 60-81209, 60-18
6508, 60-192708, 61-21130.
9, 61-271304, 62-15209, 6
2-11706, 62-72702, 62-104
A titanium compound supported on a carrier such as magnesium chloride prepared by the method shown in 810 etc. is used.

As the organoaluminum compound which is the component (B) of the present invention, those which are generally used in combination with a titanium compound for the polymerization of olefins can be used without any limitation. For example, alkylaluminum halides such as diethylaluminum chloride, ethylaluminum sesquichloride and ethylaluminum dichloride, trialkylaluminums such as triethylaluminum and triisobutylaluminum, alkylaluminum hydrides such as diethylaluminum hydride and alkylaluminums such as alkylaluminoxane are used. These can be exemplified, and these organoaluminum compounds can be used alone or in combination of two or more kinds.

In the present invention, it is preferable to carry out the prepolymerization of the olefin in the presence of the titanium compound and the organoaluminum compound. The amount of the organoaluminum compound used in the prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 20 in terms of Al / Ti (molar ratio) with respect to the titanium atom of the titanium compound.

Examples of olefins used in the prepolymerization include propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, and the like. These can be used alone or in combination.

It is also possible to employ a method in which the same or different olefins are prepolymerized in multiple stages. The polymerization amount of the above olefin is 0.1 to 1 per 1 g of the titanium compound.
It is preferably 00 g, more preferably 0.5 to 50 g.

For the prepolymerization, it is usually preferable to apply solution polymerization, and as the solvent, hydrocarbons such as hexane, heptane, cyclohexane and toluene can be used alone or in combination.

When carrying out the prepolymerization, an electron donor may be added. As the electron donor used, known compounds used for polymerization of olefins can be used without any limitation. Specific examples include ethers, amines, amides, esters, sulfur compounds, phosphorus compounds, nitrile compounds, carboxylic acids, organic silicon compounds and halogen compounds.

Other conditions in the prepolymerization, for example,
Temperature, pressure, time, unless the effect of the present invention is impaired,
It is not particularly limited and may be determined as appropriate. After completion of the prepolymerization, it is preferable to wash the produced titanium-containing polyolefin with the above hydrocarbon solvent.

After the preliminary polymerization, main polymerization is carried out. In the main polymerization, propylene is polymerized in the first stage polymerization, and then random copolymerization of propylene and ethylene is performed in the second stage polymerization. In the first-stage propylene polymerization, an organoaluminum compound is added,
This may be the same as or different from the organoaluminum compound used in the prepolymerization. The amount of the organic aluminum compound used is Al / Ti with respect to the titanium atom of the titanium compound.
The (molar ratio) is preferably in the range of 1 to 5000, more preferably 1 to 500.

The polymerization ratio of propylene is 1 to 60 wt% with respect to the total amount of polymerization, and may be appropriately determined according to the physical properties of the desired propylene-ethylene copolymer. That is, when flexibility and transparency are required, it is preferable that the amount of propylene polymerized is smaller, and when a substance having higher strength and hardness is required, the amount of polymerization may be increased.

The polymerization conditions for propylene are 0 to 0.
100 ° C., generally 40 to 80 ° C. is preferred. The polymerization may be any of slurry polymerization using propylene itself as a solvent, gas phase polymerization, solution polymerization and the like, and it is also possible to carry out the polymerization in two or more stages under different conditions.

In the polymerization of propylene, an electron donor which is the component (C) can be added in order to improve the stereoregularity of the resulting polymer. As the electron donor to be used, a known electron donor used for conventional olefin polymerization can be used without any limitation. Specifically, alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol; phenol,
Phenols such as cresol and xylenol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; aldehydes such as acetaldehyde, propionaldehyde and benzaldehyde; methyl acetate, ethyl acetate, vinyl acetate, methyl propionate, propionic acid Organic acid esters such as ethyl, methyl butyrate, ethyl butyrate, ethyl valerate, ethyl stearate, ethyl acrylate, methyl methacrylate, ethyl benzoate, ethyl phthalate; ethyl silicate, dicyclopentyldimethoxysilane, phenyltriethoxy Silicic acid esters such as silane, ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, anisole; amides such as acetic acid amide and benzoic acid amide; 2,2 6,6-tetramethylpiperidine, 2,4,6-amines such as trimethyl pyridine; acetonitrile, nitriles such as benzonitrile; Other sulfur-containing electron donor; may be mentioned phosphorus-containing electron donor. Among them, organic acid esters such as methyl methacrylate and butyl acetate; ketones such as methyl isobutyl ketone;
Silicic acid esters such as dicyclopentyldimethoxysilane are preferably used.

The amount of hydrogen added may be appropriately determined in consideration of the physical properties of the desired propylene-ethylene copolymer, in consideration of the polymerization ratio of the polypropylene component and the intrinsic viscosity of the polypropylene produced, but more effective It is preferable not to add hydrogen in order to increase the temperature.

Next, random copolymerization of propylene and ethylene, which is a second stage polymerization, is carried out in the presence of a molecular weight modifier, an organoaluminum compound and an electron donor which is the component (C). As the molecular weight regulator, known ones can be used without any limitation, but hydrogen, which is most widely used, is preferable.

As the organoaluminum compound, an alkylaluminum alkoxide other than those mentioned above can be preferably used. Specifically, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum n-butoxide, diethyl aluminum isobutoxide, diethyl aluminum t-butoxide, diethyl aluminum octoxide,
Diethyl aluminum phenoxide, ethyl aluminum sesquiethoxide, ethyl aluminum diethoxide, ethyl aluminum chloride monoethoxide, ethyl aluminum bromide monoethoxide, diethyl aluminum phenoxide, diethyl aluminum (2,6-dimethylphenoxide), diethyl aluminum (2. 6-diisobutylphenoxide), diethylaluminum (2,6-di-t-butylphenoxide), diethylaluminum (2,6-diphenylphenoxide), ethylaluminum di (2,6-di-t-).
Butylphenoxide), ethyl aluminum di (2,6)
-Di-t-butyl-4-methylphenoxide) and the like.

The electron donor used in the second-stage polymerization of the present invention may be the same as the electron donor used in the above-mentioned first-stage polymerization.

The addition amount of the organoaluminum compound and the electron donor used in the second stage polymerization is 0.01 to 10, more preferably 0. 0, based on the organoaluminum compound used in the first stage polymerization. 1-1 (molar ratio)
On the other hand, the electron donor is 0.001-1 with respect to the organoaluminum compound used in the second stage polymerization.
The range of 0, more preferably 0.001 to 1 (molar ratio) is preferable.

The polymerization ratio of the random copolymer component is 40 to 99 wt% with respect to the total amount of polymerization, and may be appropriately determined according to the desired physical properties of the propylene-ethylene copolymer.

The random copolymerization of propylene and ethylene may be any of gas phase polymerization, slurry polymerization, solution polymerization and the like. However, since the polymerization rate and the amount of residual aluminum in the obtained copolymer can be reduced, propylene is used. Slurry polymerization using itself as a solvent is preferably used. In this case, a small amount of inert hydrocarbon may be contained in order to dilute the catalyst component in addition to the propylene solvent.

In random copolymerization of propylene and ethylene, hydrogen is allowed to coexist as a molecular weight regulator, but the gas phase gas concentrations of propylene, ethylene and hydrogen are such that the composition of propylene and ethylene of the resulting copolymer is 40 respectively.
˜95 mol% and 5 to 60 mol%, and the intrinsic viscosity [η] of the obtained copolymer is 0.5 to 7 d.
97.5 / 2 / 0.5-42.5 / so that it becomes 1 / g
It may be appropriately determined within the range of 42.5 / 15 (molar ratio). The polymerization temperature is preferably 0 to 100 ° C, more preferably 40 to 80 ° C. Further, a method in which the polymerization is carried out in two or more steps under different conditions, for example, a method in which a low ethylene composition is carried out in the first step and then a high ethylene composition is carried out in the second step, or a hydrogen concentration is changed in the first and second steps Can also be adopted. The polymerization time may be appropriately determined from the polymerization temperature and the amount of polymerization. The propylene ethylene copolymer obtained in the present invention, without decomposition by peroxide,
Molded articles having various shapes can be obtained by various molding methods such as injection molding, extrusion molding and press molding.

[0033]

According to the present invention, an olefinic thermoplastic elastomer having good heat resistance can be obtained without impairing flexibility and transparency. Further, since the decomposition step with peroxide is not performed, odors and the like derived from decomposition residues are eliminated,
A high quality copolymer can be produced.

[0034]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The physical properties in the examples are measured by the following methods.

Intrinsic viscosity (hereinafter abbreviated as [η]): Measured at 135 ° C. in a tetralin solvent.

[Η] _P ... Indicates the intrinsic viscosity of the polymer produced in the first step.

[Η] _EP shows the intrinsic viscosity of the polymer polymerized in the second stage.

[Η] _T ... Shows the intrinsic viscosity of all polymers.

[Η] _EP is a value calculated by the following method.

[0041]

[Chemical 1]

Room temperature xylene solubles: 1 g of polymer p-
The mixture was added to 100 ml of xylene, heated to 135 ° C. with stirring, further stirred for 30 minutes, completely dissolved to form a uniform solution, cooled to room temperature, and allowed to stand at room temperature for another 24 hours. After filtration by suction filtration, the filtrate was evaporated to dryness and the weight of the remaining polymer was determined.

Weight average molecular weight: GPC manufactured by Waters
The measurement was performed at -135 ° C using o-dichlorobenzene as a solvent, using -150C. The column used is S manufactured by Showa Denko
It is a HODEX UT806L.

Ethylene content: The ethylene content was measured using infrared absorption spectrum.

Flexural modulus: J120SAI manufactured by Japan Steel Works
12.7mm × 12.7mm × by I type injection molding machine
A 3.1 mm test piece was prepared and tested in accordance with JIS K7203.

Vicat softening temperature: A test piece for measuring flexural modulus was used in accordance with JIS K7206.

Hardness: A test piece was prepared according to JIS K7215 and measured using an A type tester.

Izod impact strength: JIS K7110
It was measured according to.

Internal haze: After granulating a mixture in which an antioxidant and a heat stabilizer are added to a polymer, a T die is attached to an extruder, and a sheet having a thickness of 0.5 mm is formed at a molten resin temperature of 230 ° C., A test piece was prepared. After coating liquid paraffin on both sides of the test piece, haze was measured according to JIS K7150 to evaluate transparency.

Example 1 (Preliminary Polymerization) A glass autoclave reactor having an internal volume of 1 liter equipped with a stirrer was sufficiently replaced with nitrogen gas, and
400 ml of hexane was added. Then diethyl aluminum chloride 14.5 mmol, diethylene glycol dimethoxide 0.18 mmol and ethyl iodide 1
8.1 mmol was added and the reactor temperature was kept at 15 ° C. Titanium trichloride (Marubeni Solvay Chemical Co., Ltd.) 18.1m
After adding mol, propylene was continuously introduced into the reactor for 30 minutes such that the amount of propylene was 3 g per 1 g of the catalyst. After stopping the supply of propylene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing polypropylene was analyzed. As a result, 2.9 g of propylene was polymerized per 1 g of the catalyst. Subsequently, 1-butene was continuously introduced into the reactor for 90 minutes so that the amount of 1-butene was 10 g per 1 g of the catalyst. The temperature during this period was kept at 15 ° C. After stopping the supply of 1-butene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing poly (propylene-1-butene) copolymer was washed 5 times with purified hexane. As a result of the analysis, 14.6 g of the polymer was produced per 1 g of the catalyst.

(Main Polymerization) A stainless steel autoclave reactor having an internal volume of 2 liter equipped with a stirrer was sufficiently replaced with nitrogen gas, then 1 liter of liquid propylene and 1.1 mmol of diethylaluminum chloride were added, and the inside of the reactor was charged. The temperature was raised to 55 ° C. The titanium-containing polymer obtained by the preliminary polymerization was used as titanium trichloride, and 0.14 mmol was added under a nitrogen gas atmosphere. After homopolymerization of propylene at 55 ° C. for 30 minutes, 0.33 mmol of diethylaluminum sesquiethoxide and 0.
055 mmol was added, and then the introduction of hydrogen and ethylene was started, ethylene gas concentration was supplied at 7 mol% and hydrogen gas concentration was supplied at 2 mol%, and propylene and ethylene were polymerized at 55 ° C. for 120 minutes. After the completion of the polymerization, unreacted propylene, ethylene and hydrogen were removed, and then treated with propylene oxide and water to obtain a propylene-ethylene copolymer. The results are shown in Tables 1 and 2.

Examples 2 to 9 Except that the polymerization temperature, the polymerization time, the ethylene concentration and hydrogen concentration in the gas phase, and the amount of alkylaluminum alkoxide or electron donor added in Example 1 were changed to those shown in Table 1. The same operation as in Example 1 was performed. The results are shown in Tables 1 and 2.

Example 10 (Preparation of Titanium Component) Preparation of titanium component was carried out according to JP-A-58.
It was carried out according to the method of Example 1 of JP-A-83006.
The solid titanium compound thus obtained was analyzed and found to have titanium 2.1.
wt%, chlorine 57.0 wt%, magnesium 18.0w
t% and diisobutyl phthalate 21.9 wt%.

(Preliminary Polymerization) A glass autoclave reactor having an internal volume of 1 liter equipped with a stirrer was sufficiently replaced with nitrogen gas, and then 400 ml of hexane was added. Triethylaluminum 50mmo keeping reactor temperature at 15 ℃
1, 10 mmol of diphenyldimethoxysilane, 50 mmol of ethyl iodide, and 5 mmol of a solid titanium catalyst component in terms of titanium atom were added. Propylene was continuously introduced into the reactor for 1 hour such that the amount of propylene was 3 g per 1 g of the catalyst. After stopping the supply of propylene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing polypropylene was analyzed. As a result, 3.0 g of propylene was polymerized per 1 g of the catalyst.

(Main Polymerization) A stainless steel autoclave reactor having an internal volume of 2 liters equipped with a stirrer was sufficiently replaced with nitrogen gas, and then 1 liter of liquid propylene, 0.5 mmol of triethylaluminum and 0.5 mmol of diphenyldimethoxysilane. And add 55 ° C inside the reactor.
After the temperature was raised to 0.002, 0.002 mmol of the titanium-containing polymer obtained by the preliminary polymerization in terms of titanium atom was added under a nitrogen gas atmosphere. After homopolymerization of propylene for 30 minutes at 55 ° C., the introduction of hydrogen and ethylene was subsequently begun,
Ethylene gas concentration 7mol%, hydrogen gas concentration 2mo
It was supplied so that it would be 1%, and propylene and ethylene were polymerized at 55 ° C. for 120 minutes. After the completion of the polymerization, unreacted propylene, ethylene and hydrogen were removed, and then treated with propylene oxide and water to obtain a propylene-ethylene copolymer. The results are shown in Tables 1 and 2.

Comparative Example 1 The same operation as in Example 1 was carried out except that hydrogen was not added during random copolymerization of propylene ethylene. 1,3-bis (t
-Butylperoxyisopropyl) benzene, an antioxidant and a heat stabilizer were added, and the mixture was granulated and injection molded. The results are shown in Table 1.
And shown in Table 2.

Comparative Example 2 A polymer polymerized in the same manner as in Comparative Example 1 was granulated and injection-molded by adding an antioxidant and a heat stabilizer without adding an organic peroxide. The results are shown in Tables 1 and 2.

Comparative Examples 3 and 4 A polypropylene component and a random copolymer component were separately produced, and an antioxidant and a heat stabilizer were added to the obtained polymer and dry blended, followed by granulation and injection molding.
As the random copolymer component, a polymer obtained by performing only the second-stage polymerization in Example 1 and decomposed with the peroxide used in Comparative Example 1 was used. In Comparative Example 3, 5 wt% of polypropylene component was added, and in Comparative Example 4, 20 wt% of polypropylene component was added. The results are shown in Table 2.

Comparative Examples 5 and 6 A polypropylene component obtained by polymerizing only the first stage polymerization of Example 1 at a hydrogen concentration of 2 mol% and a random copolymer obtained by performing only the second stage polymerization of Example 1. After the blended components were dry blended, they were granulated and injection molded. The results are shown in Table 2.

Comparative Example 7 The same procedure as in Example 1 was carried out except that hydrogen was added during the first stage polymerization in Example 1. An antioxidant and a heat stabilizer were added to the obtained polymer, followed by granulation and injection molding. The results are shown in Tables 1 and 2.

[0061]

[Table 1]

[0062]

[Table 2]

[Procedure amendment]

[Submission date] January 11, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

The polypropylene component in the propylene-ethylene copolymer of the present invention must have a xylene soluble component at room temperature of 5 wt% or less, preferably 0.1 to 3 wt%. This is because the polypropylene component has an extremely large molecular weight as described above and the polypropylene component has high crystallinity as described later. Therefore, xylene soluble component is 5 wt.
If it exceeds%, it is necessary to increase the proportion of the polypropylene component in the total polymer or to reduce the ethylene content in the random copolymer in order to maintain the heat resistance of the propylene-ethylene copolymer at a predetermined level. As a result, the impact resistance of all the copolymers is lowered. on the other hand,
The xylene-soluble component at room temperature in the random copolymer component must be 50 wt% or more, and further 60 to
100 wt% is preferable. This is because the random copolymer component must have an amorphous or extremely low crystalline elastomeric property , and if the xylene-soluble component is less than 50 wt%, the crystallinity becomes too high, which is preferable. Absent.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

Further, a titanium compound supported on a carrier such as magnesium chloride can also be preferably used. For example, JP-A-56-155206 and JP-A-56-136.
806, 57-34103, 58-8706, 5
8-83006, 58-138708, 58-18
3709, 59-206408, 59-21931.
1, the same 60-1208, the same 60-81209, the same 60-
186508, 60-192708, 61-211
309, 61-271304, 62-15209,
62-11706, 62-72702, 62-1
A titanium compound supported on a carrier such as magnesium chloride prepared by the method shown in No. 04810 is used.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

Internal haze: After granulating a mixture in which an antioxidant and a heat stabilizer are added to a polymer, a T die is attached to an extruder, and a sheet having a thickness of 0.5 mm is formed at a molten resin temperature of 230 ° C., A test piece was prepared. After coating liquid paraffin on both surfaces of the test piece, haze was measured to evaluate transparency. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 30, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a flow chart showing a typical polymerization procedure in the present invention.

[Procedure Amendment 2]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 1

[Correction method] Added

[Correction content]

[Figure 1]

Claims (2)

[Claims] 1. A polypropylene component of 1 to 60 wt% and a propylene ethylene random copolymer component of 40 to 99 wt.
%, The polypropylene component has an intrinsic viscosity [η] of 7 dl / g or more, and the xylene soluble component at room temperature is 5 wt% or less, and the propylene ethylene random copolymer component is It has an intrinsic viscosity [η] of 0.5 to 7 dl / g, a xylene-soluble component at room temperature of 50 wt% or more, and further contains 5 to 60 mol% of an ethylene-based monomer unit. A propylene-ethylene copolymer having a weight average molecular weight of 100,000 to 1,500,000 as the whole polymer. 2. In the presence of a catalyst comprising the following components (A) titanium compound (B) organoaluminum compound and (C) electron donor, propylene is first polymerized in the first stage polymerization to obtain an intrinsic viscosity [η ] Is 7 dl / g or more, and the component soluble in xylene at room temperature is 5 wt%
1 to 60 wt% of the total amount of polymerized polypropylene below
Then, in the second stage polymerization, propylene and ethylene are copolymerized to obtain an intrinsic viscosity [η] of 0.5 to 7d.
1 / g and 50w xylene soluble component at room temperature
t% or more, 5 to 6 monomer units based on ethylene
The method for producing a propylene-ethylene copolymer according to claim 1, wherein the propylene-ethylene random copolymer containing 0 mol% is produced in an amount of 40 to 99 wt% of the total polymerization amount.