JP2795481B2 - Polypropylene injection molding - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a 3-methyl-1-butene polymer unit containing 3-methyl-1-butene polymer units which are densely blended in propylene polymer units. The present invention relates to a polypropylene injection molded article produced from the composition and a method for producing the same.

Technical Background of the Invention There have already been many proposals for a method for producing a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor as essential components, and such a solid titanium catalyst component having 3 or more carbon atoms has been proposed. It is also known that a polymer having high stereoregularity can be produced in a high yield by using an α-olefin, particularly a propylene polymer.

Further, when producing a propylene-based polymer using an olefin polymerization catalyst component comprising the solid titanium catalyst component and the organoaluminum compound catalyst component as described above,
Using the olefin polymerization catalyst component, 3-methyl-1-
It is known that propylene-based polymers having excellent properties can be obtained by prepolymerizing butene.

The present inventors have conducted further intensive studies based on the above findings, and found that the injection molding of the resin composition obtained as described above could not be achieved with conventional polypropylene. It has been found that an injection-molded article having excellent transparency can be obtained, and that the crystallization rate is increased by using such a composition, and the present invention has been achieved.

OBJECT OF THE INVENTION The present invention has been made in view of the prior art as described above, and an object of the present invention is to provide a polypropylene injection molded article having particularly excellent transparency.

SUMMARY OF THE INVENTION A polypropylene injection molded article according to the present invention comprises a 3-methyl-1-butene polymer unit and a propylene polymer unit, and the content of the 3-methyl-1-butene polymer unit is 10 to 10,000. It is characterized by being formed from a composition containing a 3-methyl-1-butene polymer unit in a weight ppm.

Further, the method for producing a polypropylene injection molded article according to the present invention comprises: [A] a liquid magnesium compound having no reducing property;
A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components obtained by reacting a liquid titanium compound in the presence of an electron donor [B] An organoaluminum compound catalyst component and a necessary component In the presence of a catalyst for olefin polymerization formed from [C] an electron donor,
Methyl-1-butene is prepolymerized, and then has 2 to 2 carbon atoms.
Pre-polymerizing a linear α-olefin of 5 or pre-polymerizing a linear α-olefin having 2 to 5 carbon atoms,
Then, using a prepolymerized catalyst component formed by prepolymerizing 3-methyl-1-butene and, if necessary, the above [B] organoaluminum compound catalyst component and [C] an electron donor, propylene is produced. 3-methyl-1-butene obtained by polymerizing, comprising a 3-methyl-1-butene polymer unit and a propylene polymer unit, and having a 3-methyl-butene polymer unit content of 10 to 10,000 ppm by weight. 1
-It is characterized in that a molded product is obtained by injection molding of the butene polymer unit-containing composition. Furthermore, the polypropylene injection molded article according to the present invention comprises: [A] a liquid magnesium compound having no reducing property;
A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components obtained by reacting a liquid titanium compound in the presence of an electron donor [B] An organoaluminum compound catalyst component and a necessary component In the presence of a catalyst for olefin polymerization formed from [C] an electron donor,
A prepolymerization catalyst formed by prepolymerizing methyl-1-butene and then prepolymerizing with a linear α-olefin having 2 to 5 carbon atoms, and optionally the above-mentioned [B] organoaluminum compound catalyst Using the component and the [C] electron donor, propylene is polymerized, or the olefin polymerization catalyst [I] is used to polymerize propylene.
5, a pre-polymerization catalyst component formed by polymerizing 3-methyl-1-butene and then the above-mentioned [B] organoaluminum compound catalyst component and [C] 3-methyl- obtained by polymerizing propylene with an electron donor
A 1-butene polymer unit, the α-olefin polymer unit and a propylene polymer unit, and 3-methyl-
It is characterized by being formed from a 3-methyl-1-butene polymer unit-containing composition having a 1-butene polymer unit content in the range of 10 to 10,000 ppm by weight.

The polypropylene injection molded article according to the present invention is a composition in which a specific amount of a 3-methyl-1-butene polymer unit and a propylene polymer unit are densely blended (in the present invention, such a composition is used). Is sometimes referred to as "composition containing a 3-methyl-1-butene polymer unit"), which is particularly excellent in transparency.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polypropylene injection molded article according to the present invention will be specifically described.

The polypropylene injection molded article according to the present invention is formed from a composition containing a 3-methyl-1-butene polymer unit.

The 3-methyl-1-butene polymer unit-containing composition in which the 3-methyl-1-butene polymer unit and the propylene polymer unit are densely blended is, for example, as described below. An example is a composition produced by polymerizing propylene using a prepolymerized catalyst obtained by performing prepolymerization of 3-methyl-1-butene using an olefin polymerization catalyst. The 3-methyl-1-butene polymer unit-containing composition used in the present invention includes, in addition to the above-mentioned composition containing a 3-methyl-1-butene polymer unit and a propylene polymer unit, A methyl-1-butene polymer unit and 2 carbon atoms
A composition in which an α-olefin polymer unit formed from linear α-olefins of Nos. 1 to 5 and a propylene polymer unit are in a state of being densely blended in the same manner as described above. Such densely blended 3-methyl-
In some cases, the 1-butene polymer unit-containing composition is
It is called a block copolymer of poly 3-methyl-1-butene and polypropylene or a block copolymer of poly 3-methyl-1-butene and polypropylene and a linear poly-α-olefin having 2 to 5 carbon atoms. Sometimes.

Next, a method for producing the 3-methyl-1-butene polymer unit-containing composition used for forming the polypropylene injection molded article according to the present invention will be specifically described.

The 3-methyl-1-butene polymer unit-containing composition can be produced, for example, using the following olefin polymerization catalyst.

The olefin polymerization catalyst used in the present invention is formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and, if necessary, an electron donor [C].

FIG. 1 shows an example of a flowchart of a method for producing a 3-methyl-1-butene-containing composition using the olefin polymerization catalyst as described above.

The solid titanium catalyst component [A] used in the present invention includes:
It is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such a solid titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below.

In the present invention, the titanium compound used for preparing the solid titanium catalyst component [A] includes, for example, Ti (OR)
_g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be exemplified.

More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti ( _{On-C 4 H 9) 2} Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On Monohalogenated trialkoxy titanium such as -C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H) _{9) 4 Ti (Oiso-C} 4 H 9) such as ₄ Ti (O @ 2- _{ethylhexyl) 4} tetraalkoxy titanium, and the like.

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for the preparation of the solid titanium catalyst component [A] include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond.

Specific examples of the magnesium compound having such a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, octyl magnesium, didecyl magnesium, decyl butyl magnesium, and ethyl butyl. Dialkyl magnesium such as magnesium; alkyl magnesium magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, aluminum magnesium chloride, and butyl magnesium halide; and alkyl alkoxy magnesium such as butyl ethoxy magnesium. . These magnesium compounds may be used alone, or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid. Further, the alkyl group in the magnesium compound described above may be branched or linear.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium and the like Alkoxy magnesium; magnesium magnesium such as magnesium laurate and magnesium stearate Such as phosphate salt can be mentioned.

These magnesium compounds having no reducibility may be compounds derived from the above-mentioned magnesium compounds having reducibility or compounds derived at the time of preparing the catalyst component. A magnesium compound having no reducing property,
In order to derive from a reducing magnesium compound,
For example, a reducing magnesium compound may be contacted with a compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, or an alcohol.

The magnesium compound is a complex compound, a complex compound of the above magnesium compound and another metal, or a mixture of another metal compound, in addition to the above-mentioned magnesium compound having a reducing property and a magnesium compound having no reducing property. You may. Also, magnesium metal can be used as a starting material. In addition, the above compound is
It may be a mixture of more than one species.

Any magnesium compound other than those described above can be used. In any case, some or all of them must be finally halogenated. Among these magnesium compounds, magnesium compounds having no reducibility are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

As the electron donor used for preparing the solid titanium catalyst component [A], preferably a polyvalent carboxylic acid ester is used, and specifically, a compound having a skeleton represented by the following formula is used.

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , R ⁶ is a hydrogen atom, a substituted or unsubstituted hydrocarbon group, R ³ , R ⁴ is a hydrogen atom, It is a substituted or unsubstituted hydrocarbon group. Preferably, at least one of R ³ and R ⁴ is a substituted or unsubstituted hydrocarbon group.
R ³ and R ⁴ may be connected to each other to form a cyclic structure. Here, as the substituted hydrocarbon group, N,
Examples include substituted hydrocarbon groups containing a different atom such as O and S, for example, -C-O-C-, -COOR, -COOH, -OH,
Substituted hydrocarbon groups having a structure such as —SO ₃ H, —C—N—C—, and —NH ₂ .

Among these, a diester in which at least one of R ¹ and R ² is derived from a dicarboxylic acid having an alkyl group having 2 or more carbon atoms is preferable.

Specific examples of the polyvalent carboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, butyl Diethyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyldiisobutylmalonate, diethyldinormalbutylmalonate, dimethyl maleate, monooctyl maleate,
Diisooctyl maleate, diisobutyl maleate,
Diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylates such as diethyl itaconate, diisobutyl itaconate, diisooctyl citrate, dimethyl citrate; diethyl 2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate, etc. Aliphatic polycarboxylic acid esters of monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono n-butyl phthalate, n-butyl ethyl phthalate, phthalate Di-n-propyl acid, diisopropyl phthalate, di-n-butyl phthalate,
Diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalate dicarboxylate, triethyl trimellitate, trimellitate Aromatic polycarboxylic acid esters such as dibutyl acid; esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid; and the like.

Other examples of polycarboxylic acid esters include long adducts such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. Esters derived from chain dicarboxylic acids can be mentioned.

Among these polycarboxylic acid esters, compounds having a skeleton represented by the aforementioned general formula are preferred, and more preferably phthalic acid, maleic acid, substituted malonic acid, and the like, and alcohols having 2 or more carbon atoms. Esters, phthalic anhydride and phthalic chloride are preferred, and diesters, phthalic anhydride and phthalic chloride obtained by reacting phthalic acid with an alcohol having 2 or more carbon atoms are particularly preferred.

As these polyvalent carboxylic esters, it is not always necessary to use the above-mentioned polyvalent carboxylic esters as starting materials, and for example, carboxylic acids and acid halides corresponding to the above-described esters, such as acid anhydrides, Using a compound capable of deriving these polyvalent carboxylic acid esters in the process of preparing the solid titanium catalyst component [A],
A polyvalent carboxylic acid ester may be generated at the stage of preparing the solid titanium catalyst component [A].

When preparing the solid titanium catalyst component [A], an electron donor other than the polyvalent carboxylic acid ester can be used. Examples of the electron donor other than the polyvalent carboxylic acid that can be used in the present invention include: As described below, alcohols, amines, amides, ethers, ketones, nitriles, phosphines, stippins, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, Acid halides, aldehydes, alcoholates, organosilicon compounds such as alkoxy (aryloxy) silanes, organic acids and I of the Periodic Table
Examples include amides and salts of metals belonging to groups IV to IV.

The solid titanium catalyst component [A] can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium) into contact with an electron donor and a titanium compound. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum.

The method for producing the solid titanium catalyst component [A] will be briefly described below with several examples.

(1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and / or a reaction assistant such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once.

(2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium complex.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A solid obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. In this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

(9) magnesium compound and alkoxytitanium and / or
Or a method in which a catalyst component in a hydrocarbon solution containing at least an electron donor such as an alcohol or an ether is reacted with a halogen-containing compound such as a titanium compound and / or a halogen-containing silicon compound. A method in which an electron donor represented by a phthalic acid diester as described above coexists.

Among the methods for preparing the solid titanium catalyst component [A] described in the above (1) to (9), a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a method using a titanium compound When used, a method using a halogenated hydrocarbon is preferred.

The amount of each of the above components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. In an amount of 5 moles, preferably 0.05-2 moles, the titanium compound is about 0.01-500
It is preferably used in an amount of 0.05 to 300 moles.

The solid titanium catalyst component [A] thus obtained
Contains magnesium, titanium, halogen and an electron donor as essential components.

In this solid titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100.
Wherein the electron donor / titanium (molar ratio) is about 0.1 to 1
0, preferably about 0.2 to about 6, and magnesium / titanium (atomic ratio) of about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [A] contains magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 30 m ² / g.
Or more, preferably about 60 to 1000 m ² / g, more preferably about
100-800 m ² / g.

Such a solid titanium catalyst component [A] can be used alone, but also includes, for example, a silicon compound,
It can be used after being diluted with an inorganic compound or an organic compound such as an aluminum compound or polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity.

For a method of preparing such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-126590.
No. 51-20297, No. 51-28189, No. 51
No. 64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52-100596, No. 52-1
No. 47688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-43
No. 094, No. 55-135102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-119
No. 08, No. 56-18606, No. 58-83006,
JP-A-58-138705, JP-A-58-138706, JP-A-58-138707
JP-A-58-138708, JP-A-58-138709,
Nos. 58-138710, 58-138715, 60-23404
No. 61-21109, No. 61-37802, No. 61
And -37803.

As the organoaluminum compound catalyst component [B], a compound having at least one Al-carbon bond in the molecule can be used. Examples of such a compound include: (i) a compound represented by the general formula R ¹ _m Al (OR ² ) _{n Hp} X _q (wherein R ¹ and R ² each usually have 1 to 15 carbon atoms, preferably 1 to X is a hydrocarbon group containing four, and may be the same or different from each other, and X represents a halogen atom;
<M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
A number of q <3, moreover organic aluminum compound represented by a is) m + n + p + q = 3, a (ii) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, K, R ¹ Are the same as those described above), and a complex alkylated product of a Group 1 metal and aluminum.

As the organoaluminum compound belonging to the above (i), the following compounds can be exemplified.

General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.5
≦ m ≦ 3), a general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above; X is a halogen, m is preferably 0 <m <3); and a general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above; m is preferably 2 ≦ m <3); and a general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² is the same as above, X is halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

Specific examples of the aluminum compound belonging to (i) include: trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; ; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide formula R ¹ _2.5 Al (OR ²⁾ partially alkoxylated alkyl aluminum having an average composition represented _0.5 like; diethylaluminum chloride, Dialkylaluminum halides such as dibutylaluminum chloride and diethylaluminum bromide; Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; Alkyl aluminum halides such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum Dialkylaluminum hydrides such as hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride and alkylaluminum dihydride such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethyl Partial access to aluminum ethoxy bromide Kokishi reduction and halogenated alkylaluminum can be exemplified.

Examples of the compound similar to (i) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, Methyl aluminoxane and the like can be mentioned.

Examples of the compound belonging to (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more aluminum compounds described above are bonded.

In the present invention, when producing an olefin polymerization catalyst, an electron donor [C] can be used as necessary.

Examples of such electron donor [C] include oxygen-containing electrons such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxysilanes. Donor; Nitrogen-containing electron donor such as ammonia, amine, nitrile, isocyanate; or polyvalent carboxylic acid ester as described above.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; C3-C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; acetaldehyde, propiona Aldehydes having 2 to 15 carbon atoms such as aldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate Propyl acetate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, Diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethyl phthalate Organic acid esters having 2 to 30 carbon atoms such as xyl, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride Acid halides; ethers and diethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, epoxy-p-menthane; acetate amide, benzoic acid amide; Acid amides such as toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; acetonitrile Nitriles such as toluene, benzonitrile and tolylnitrile; and acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

Further, as the electron donor [C], an organosilicon compound represented by the following general formula [Ia] can also be used.

_{R n Si (OR ') 4} -n ... [I a] [ wherein, R and R' is a hydrocarbon group, 0 <n <
4] Specific examples of the organosilicon compound represented by the above general formula [Ia] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t -Butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amyldimethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, Bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmeth Rudiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyl Trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-
Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane,
Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltrimethylsilane Allyloxy silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like are used.

Among them, trimethylmethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane,
Phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-
Preferred are tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyldiethoxysilane.

Further, as the electron donor [C], an organosilicon compound represented by the following general formula [IIa] can be used.

SiR ¹ R ² _m (OR ³ ) _3-m ... [IIa] wherein R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is an alkyl group, a cyclopentyl group and cyclopentyl having an alkyl group A group selected from the group consisting of groups, R ³ is a hydrocarbon group, and m is 0 ≦ m ≦ 2. In the above formula [IIa], R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and specifically as R ¹ , besides the clopentyl group, for example, 2
And cyclopentyl groups having an alkyl group such as -methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group.

In the formula [IIa], R ² is any one of an alkyl group, a cyclopentyl group and a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, an alkyl group such as hexyl, or cyclopentyl group having an exemplified cyclopentyl group and an alkyl group as R ¹ can be exemplified similarly.

Further, in the formula [IIa], R ³ is a hydrocarbon group,
As R ³ , for example, an alkyl group, a cycloalkyl group,
And hydrocarbon groups such as aryl groups and aralkyl groups.

Among these, it is preferable to use an organosilicon compound in which R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, particularly a methyl group or an ethyl group.

Specific examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane and dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxy Silane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldi Chill silane, mono-alkoxysilanes such as cyclopentyl dimethylethoxysilane, and the like.

As the electron donor [C], the above-mentioned organic carboxylic acid esters and organic silicon compounds are preferable, and the organic silicon compounds are particularly preferable.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and, if necessary, the electron donor [C]. I have.

In the present invention, in the presence of this olefin polymerization catalyst,
A pre-polymerization catalyst component formed by pre-polymerizing 3-methyl-1-butene, and if necessary, the above-mentioned [B]
By polymerizing propylene using the organoaluminum compound catalyst component and the [C] electron donor, a composition containing a 3-methyl-1-butene polymer unit is obtained.

At this time, 3-methyl-1-butene has a content of the 3-methyl-1-butene polymer unit in the composition of 10 to 1000.
The prepolymerization is carried out in such an amount that it becomes 0 ppm.

3-Methyl-1-butene is the component [A], [B]
It is desirable that the polymer is prepolymerized in an amount of 0.1 to 100 g, preferably 0.5 to 50 g, more preferably 1 to 10 g, per 1 g of the solid portion in the olefin polymerization catalyst formed from the components and, if necessary, the component [C]. When preliminarily polymerizing 3-methyl-1-butene, a small amount of an α-olefin other than 3-methyl-1-butene may be copolymerized, and the copolymerization amount is preferably within 20 mol%, preferably Is within 10 mol%,
Particularly preferably, it is within 5 mol%.

In particular, in the present invention, the content of the 3-methyl-1-butene polymer unit in the composition is preferably from 100 to 3
By performing the prepolymerization in an amount such that the amount falls within the range of 000 ppm by weight, more preferably 100 to 1000 ppm by weight, a composition capable of forming a film having more excellent transparency is formed.

In the present invention, 3-methyl-
Before or after performing the prepolymerization operation using 1-butene, the prepolymerization operation can be performed using a linear α-olefin having 2 to 5 carbon atoms. In this case α
-As the olefin, ethylene, propylene, n-butene-1, n-pentene-1 and the like can be used. These α-olefins may be used alone or in combination. Of the above-mentioned α-olefins, it is particularly preferable to carry out the prepolymerization using propylene or ethylene.

In the present invention, when preparing the prepolymerized catalyst component,
Together with methyl-1-butene, the linear α-
Since olefin is used, polymer particles having a small fine powder and a high bulk specific gravity can be obtained. In the present invention,
Particularly when ethylene is used as the α-olefin,
A film having excellent blocking resistance can be obtained from an olefin polymer using the obtained prepolymerized catalyst component.

In the α-olefin thus prepolymerized, the prepolymerization amount of the α-olefin polymer unit formed by the prepolymerization is 0.1 to 100 per 1 g of the solid titanium catalyst.
0 g, preferably 1 to 500 g, and more preferably 2 to 200 g.

In the prepolymerization as described above, the concentration of the catalyst in the reaction system may be equal to or higher than the concentration of the catalyst in the main polymerization.

That is, the solid titanium catalyst component [A] in the prepolymerization is usually 0.001 to 200 mmol, preferably 0.1 to 1 in terms of titanium atoms per hydrocarbon solvent described below.
It is used in an amount of 00 mmol, particularly preferably 1-500 mmol.

The organoaluminum catalyst component [B] is used usually in an amount of 0.1 to 500 mol, preferably 1 to 100 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A].

The electron donor [C] is used as needed. When the electron donor [C] is used, the electron donor [C]
Is usually 0.1 to 100 mol, preferably 1 to 50 mol, per 1 mol of titanium atom in the solid titanium catalyst component [A],
Particularly preferably, it is used in an amount of 1 to 10 mol.

In the prepolymerization, 3-methyl-1-butene and an α-olefin having 2 to 5 carbon atoms are used in the presence of a catalyst as described above.
It is preferable to carry out the polymerization under mild conditions in an inert hydrocarbon medium or in a monomer solvent.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. However, the prepolymerization can be carried out in place of the above-mentioned inert hydrocarbon medium, or by using the monomer itself as a solvent together with the inert hydrocarbon medium. Can also.

The temperature at the time of the prepolymerization may be a temperature at which the resulting prepolymer is not substantially dissolved in the hydrocarbon medium, and is usually -20 to + 100 ° C, preferably -20 to + 80 ° C.
° C, more preferably within the range of 0 to + 40 ° C.

Further, the prepolymerization can be carried out while using a molecular weight modifier such as hydrogen gas.

The prepolymerization can be performed in a batch system or a continuous system. Further, both the batch system and the continuous system can be performed in combination. For example, after preliminarily polymerizing 3-methyl-1-butene is carried out in a batch system, the polymer of α-olefin can be carried out in a continuous system.

Thus, by preliminarily polymerizing 3-methyl-1-butene and the above-mentioned α-olefin using the above-mentioned olefin polymerization catalyst, 3-methyl-1-butene is formed around the solid portion in the olefin polymerization catalyst. A prepolymerization catalyst having a methyl-1-bun polymer unit and an α-olefin polymer unit (that is, an olefin polymerization catalyst subjected to a prepolymerization treatment) is formed. The 3-methyl-1-butene polymer unit-containing composition used in the present invention is obtained by polymerizing at least propylene using the prepolymerized catalyst obtained as described above. For example, it is obtained by copolymerizing propylene homopolymer or propylene with an α-olefin having 2 to 10 carbon atoms other than propylene.

The main polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization, suspension polymerization and monomer solvent polymerization or a gas phase polymerization method.

For example, suspension polymerization can be performed in an inert hydrocarbon medium.

Examples of the inert hydrocarbon medium used in this case include the aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and mixtures thereof exemplified in the above-described prepolymerization. Can be. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Further, as in the case of the prepolymerization, the monomer itself can be used as a solvent, and the main polymerization can be carried out in a substantially solvent-free state.

In the main polymerization, the solid titanium catalyst component [A]
In terms of Ti atom per polymerization volume, usually about 0.001 to
It is used in an amount of 0.5 mmol, preferably about 0.005 to 0.1 mmol. Although the organoaluminum compound catalyst component [B] is used as needed, the metal atom in the organoaluminum compound catalyst component is usually about 1 to 1 mole of titanium atom in the reaction system of the main polymerization. It is desirable that it be used in an amount such that it is 2000 moles, preferably about 5 to 500 moles. Further, the electron donor [C] is used as needed, and is usually about 0.001 to 10 mol, preferably about 0.01 to 2 mol, per 1 mol of metal atom in the organoaluminum compound catalyst component [B]. Especially preferably about 0.
It is desirable to use it in such an amount that it becomes 05 to 1 mol.

In the case of the main polymerization, a molecular weight modifier such as hydrogen gas may be used.

The main polymerization temperature is usually about 0 to 200 ° C, preferably about 10 ° C.
At 〜100 ° C., the pressure is usually set at normal pressure to 100 kg / cm ² , preferably about normal pressure to 40 kg / cm ² .

The main polymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system.

The 3-methyl-1-butene polymer unit-containing composition formed as described above contains 3-methyl-butene as described above.
The 1-butene polymer unit is contained in an amount within the range of 10 to 10,000 ppm, preferably within the range of 100 to 3000 ppm, more preferably within the range of 100 to 1000 ppm by weight.

When the polypropylene composition in which the composition containing the 3-methyl-1-butene polymer unit is blended in the amount described above is injection-molded into a desired shape, an injection-molded article having excellent transparency can be obtained. .

In addition, conventionally known conditions can be adopted as injection molding conditions for obtaining an injection-molded product by injection-molding the above-mentioned polypropylene-based composition.

Further, the polypropylene-based composition in which the composition containing the 3-methyl-1-butene polymer unit is blended in the above-described amount has a high crystallization rate, and therefore can shorten the injection molding cycle.

The molding temperature in this case may be at least the temperature at which the 3-methyl-1-butene polymer unit-containing composition is in a molten state, but is usually 190 to 300 ° C, preferably 210 to 280 ° C. It is desirable to heat and shape the object.

3-methyl-1 prepared by simply mixing conventional poly-3-methyl-1-butene and polypropylene or the like
The composition containing the butene polymer is poly-3-methyl-
1-butene and polypropylene and the like are not densely blended to a state where both are mixed at a molecular level like the 3-methyl-1-butene polymer unit-containing composition used in the present invention, When such a conventional composition is used, it has been difficult to produce an injection molded article having high transparency. In the present invention, 3-methyl-1-
By using the butene polymer unit composition, the spherulite size of the propylene-based polymer is reduced, and the transparency of the injection-molded product obtained because the crystallization rate of the propylene polymer unit is increased is improved. It is thought that.

That is, by using the 3-methyl-1-butene polymer unit-containing composition, the spherulite size of the propylene-based polymer is reduced and the crystallization speed is remarkably improved. The injection-molded article of the present invention having a high ratio is obtained. In contrast, poly-3-methyl-
In a composition obtained by a conventional method of simply melt-blending 1-butene and polypropylene, etc., the mixed state of poly-3-methyl-1-butene and polypropylene, etc., is better as the two are closer to each other at the molecular level. In addition, injection molded articles having excellent transparency cannot be obtained.

At the time of injection molding, various stabilizers can be added to the polypropylene composition.

In the polypropylene injection molding of the present invention, when a phenolic stabilizer is blended, an injection molded article having excellent heat stability and transparency is obtained, and thus a phenolic stabilizer and an organic phosphite stabilizer are particularly preferred. It is preferable that the compound is blended, because an injection molded article having particularly excellent heat stability and transparency can be obtained.

Further, in the polypropylene injection molded article of the present invention,
When the higher fatty acid metal salt is blended, the thermal stability of the resin at the time of molding is improved, the moldability is improved, and troubles due to rust and corrosion of the molding machine due to the halogen gas due to the catalyst are suppressed. I can do it. Particularly, when the higher fatty acid metal salt is used in combination with the phenol-based stabilizer and / or the organic phosphite-based stabilizer as the stabilizer, excellent synergistic effects are obtained in moldability, transparency and heat resistance of the obtained injection molded article. Is preferably achieved. Examples of phenolic stabilizers include, specifically, 2,6-di-t
-Butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-diphenol -T-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t -Butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrene Cresol, dl-α-tocophenol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-t-butylphenol) ), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-thiobis (4-methyl -6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2 '-Ethylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 1,1,3-tris (2-methyl-4-hydroxyphenol) −5-
t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5- Di-t-
Butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4-4hydroxyphenyl) propionate], N, N'-hexamethylenebis (3 , 5-di-t-butyl-
4-4 hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzyldiphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4)
-T-4butylbenzyl) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2) , 6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, bis (ethyl 3,3,5-di-tert-butyl-4-hydroxybenzylphosphonate) calcium, bis ( Ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel, bis [3,3-bis (3-t-butyl-4-hydroxyphenyl) butyric acid] glycol Ether, N, N'-bis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2' Ogizamidobisu [ethyl-3- (3,5-di -t
-Butyl-4-hydroxyphenyl) propionate], bis [2-t-butyl-4-methyl-6- (3-t-
Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- (β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl] -2, 4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3,5-di-t-butyl-4-)
Hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane, and β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester.

As the above-mentioned phenolic stabilizer, β- (3,5-di-t-
When an alkyl ester of (butyl-4-hydroxyphenyl) propionic acid is used, an alkyl ester having 18 or less carbon atoms is particularly preferably used.

Also in the molecule Or A phenolic stabilizer having a structure represented by the following formula is preferred.

However, in the above formulas, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms, R ³ carbons 1
Represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R ₄ has an alkyl group having 1 to 22 carbon atoms or the following structure.

(Here, m + n = 3, n = 0, 1, 2, 3) (Where R ₅ : It is. ) Among them, 2,6-di-tert-butyl-4-methyl-p-cresol, stearyl-β- (4-hydroxy-3,5-di-tert-butylphenol) propionate, 2,2′-ethylidenebis (4,6-di-tert-butylphenol), tetrakis [methylene-3- (3,5-di-t
[ert-butyl-4-hydroxyphenyl) propionate] methane is preferred.

These phenolic stabilizers can be used alone or as a mixture.

Examples of the phosphite-based stabilizer include trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite. Diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris ( Butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4,4'-isopropylidene-diphenolalkylphosphite (Where alkyl is about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl)- 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, tetra (tridecyl) -4,4'-butylidenebis (3
-Methyl-6-t-butylphenol) diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octyl) Phenyl) bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)]
1,6-hexaneol diphosphite, hexatridecyl-1,1,3-tris (2-methyl-4
-Hydroxy-5-t-butylphenol) diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, tris (1,3-distearoyloxyisopropyl)
Phosphite, 9,10-dihydro-9-phosphaphenanthrene-10-
Oxide, tetrakis (2,4-di-t-butylphenyl) 4,4'-
Biphenylenediphosphonite and the like can be mentioned.

Among these, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediene Hoofite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred.

Further, a phosphite-based stabilizer derived from pentaerythritol represented by the following formula can also be used.

In the above formulas (1) and (2), R ¹ and R ² represent an alkyl group.

Such organic phosphite-based stabilizers can be used alone or in combination.

Examples of higher fatty acid metal salts include alkali metal salts, alkaline earth metal salts, and other metal salts of saturated or unsaturated carboxylic acids having 12 to 40 carbon atoms. Further, the saturated or unsaturated carboxylic acid having 12 to 40 carbon atoms may have a substituent such as a hydroxyl group. Specifically, examples of saturated or unsaturated carboxylic acids having 12 to 40 carbon atoms include stearic acid, oleic acid, lauric acid, capric acid, arachidonic acid, palmitic acid, behenic acid and 12-hydroxystearic acid, montanic acid Higher fatty acids such as acids; and examples of metals which form salts by reacting with these higher fatty acids include alkaline earth metal salts such as magnesium, calcium and barium, and alkali metals such as sodium, potassium and lithium. Metals and cadmium, zinc and lead can be mentioned.

Specific examples of higher fatty acid salts include magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium arachidonate, behenin Barium acid, zinc stearate, zinc oleate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate,
Examples include potassium laurate and calcium 12-hydroxystearate, sodium montanate, calcium montanate, zinc montanate, and the like.

Among these higher aliphatic metal salts, especially those having 12 to
Zinc salts of 35 saturated fatty acids are particularly preferred.

Such higher fatty acid metal salts can be used alone or in combination.

The compounding ratio of the phenolic stabilizer is 0.01 to 10% by weight, preferably 0.02 to 0.5% by weight, particularly preferably 0.03 to 0.2% by weight, based on the molding raw material resin, and the compounding ratio of the organic phosphite-based stabilizer is the same. 0.01 to 1.0% by weight, preferably 0.02 to 0.5% by weight, particularly preferably 0.03 to 0.2% by weight.
% By weight, and the mixing ratio of the higher fatty acid metal salt is also 0.1%.
It is from 0.01 to 1.0% by weight, preferably from 0.02 to 0.5% by weight, particularly preferably from 0.03 to 0.2% by weight.

Effect of the Invention Since the polypropylene injection molded article according to the present invention is formed from the composition containing a 3-methyl-1-butene polymer unit, it is particularly excellent in transparency.

Moreover, by using the composition containing a 3-methyl-1-butene polymer unit, the crystallization rate of the resin is increased, so that an injection molded article having excellent transparency can be manufactured in a short time.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Solid Titanium Catalyst Component [A] Anhydrous magnesium chloride 7.14 kg, decane 37.5 and 2
-Ethylhexyl alcohol 35.1 was heated and reacted at 140 ° C for 4 hours to obtain a homogeneous solution. Thereafter, 1.67 kg of phthalic anhydride was added to the solvent, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above-mentioned homogeneous solution.

After cooling the thus obtained homogeneous solution to room temperature, the whole solution was dropped into titanium tetrachloride 200 kept at -20 ° C over 3 hours. After the dropwise addition, the temperature of the resulting solution was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., 5.03 of diisobutyl phthalate was added.

Stir at the above temperature for another 2 hours. After the completion of the reaction for 2 hours, a solid portion was collected by filtration under hot conditions, and the solid portion was collected for 275 hours.
Was re-suspended in TiCl ₄ and heated again at 110 ° C. for 2 hours.

After the completion of the reaction, a solid portion was collected again by hot filtration and washed with hexane. This washing was performed until no titanium compound was detected in the washing solution.

The solid titanium catalyst component [A] synthesized as described above was obtained as a hexane slurry. A part of the catalyst was collected and dried. When the dried product was analyzed, the composition of the solid titanium catalyst component [A] obtained as described above was determined to be 2.4% by weight of titanium, 59% by weight of chlorine, 18% by weight of magnesium, and 11.6% by weight of diisobutyl phthalate.
% By weight.

[Preliminary polymerization] Purified hexane 100, triethylaluminum 10 mol, trimethyltrimethoxysilane 10 mol, 1 mol of the titanium catalyst component [A] in terms of titanium atom and 3-methyl-1-butene were placed in a nitrogen-purged reactor. After the addition of 20 kg, the suspension was kept at 20 ° C. with stirring for 5 hours to carry out prepolymerization of 3-methyl-1-butene. As a result of the analysis, the prepolymerized amount of the 3-methyl-1-butene polymer unit was 7.2 g / g of the catalyst solid portion. Then, the stirring was stopped, the solid portion was allowed to settle, and the supernatant was removed. After washing twice with hexane, the total volume was adjusted to 120, 3 mol of triethylaluminum was added, and then propylene was supplied at a rate of 2130 Nl / hour for 1.5 hours to perform prepolymerization of propylene. Meanwhile, the prepolymerization temperature was maintained at 15 to 20 ° C. After the supply of propylene was completed, the reactor was closed, polymerization of the remaining propylene was performed for 30 minutes, and the mixture was washed twice with hexane. As a result of the analysis, the propylene polymer unit prepolymerization amount was 2.7 g / g of the catalyst solid portion.

[Polymerization] Using a polymerization vessel having an internal capacity of 250, random polymerization of propylene and ethylene was continuously performed. Polymerization pressure is 5kg / cm
^{At 2} G, the polymerization temperature was controlled at 70 ° C. The catalyst component is based on a rate of 0.24 mmol / hour in terms of titanium atom based on the above titanium catalyst component obtained by prepolymerizing propylene and 3-methyl-1-butene with 16 mmol / hour of triethylaluminum, 1.6 mmol / hour of dicyclohexyldimethoxysilane. Were continuously fed. The supply amounts of hydrogen and ethylene were adjusted so that the hydrogen / propylene ratio in the gas phase portion of the polymerization reactor was about 0.07 mol / mol and the ethylene / propylene ratio was about 0.03 mol / mol.

The production rate of the obtained polypropylene is about 6 kg / average
It was time. MFR of the obtained polypropylene is 7.0 g / 10
And the ethylene content was 4.7 mol%, and the content of the 3-methyl-1-butene polymer unit in the polypropylene was 600 ppm by weight.

Examples 2 to 3 In Example 1, the content of the 3-methyl-1-butene polymer unit was changed to 210 ppm by weight (Example 2) and 420 ppm by weight by changing the ratio of polypropylene per solid catalyst by adjusting the residence time. (Example 3) Polypropylene which was the same was produced.

[Production of Injection Molded Article] 100 parts by weight of the obtained composition containing a 3-methyl-1-butene polymer unit was added with calcium stearate as a stabilizer.
0.1 parts by weight and Irganox 1010 (Ciba Geiger Co., Ltd.)
Antioxidant, tetrakis [methylene-3 (3,5'-
Di-tert-butylhydroxyphenylpropionate]
After adding 0.1 parts by weight of methane) and mixing using a Henschel mixer, the mixture was heated to 200 ° C. using a 65 mm diameter extruder to form granules.

Using an injection molding machine with a diameter of 30 mm, the obtained pellets were injection molded at a resin temperature of 220 ° C. and a mold temperature of 50 ° C.
A thick square plate was obtained.

The properties of the obtained square plate were measured and evaluated according to the evaluation methods described below.

Comparative Example 1 In the same manner as in Example 1 except that 3 mol of triethylaluminum and 1 mol of titanium catalyst component [A] were used in terms of titanium atom, and only propylene was prepolymerized to prepare a prepolymerized catalyst. It went to.

[Evaluation Method of Square Plate] (1) Haze Measured according to ASTM D1003.

(2) Initial flexural modulus The transverse Young's modulus of the film was measured with an Instron tensile tester at a tensile speed of 50 mm / min according to JIS K6781.

 Table 1 shows the results of Examples 1 to 3 and Comparative Example 1.

Example 4 A solid titanium catalyst component [A] was prepared in the same manner as in Example 1.

[Preliminary polymerization] Purified hexane 100, triethylaluminum 10 mol, trimethyltrimethoxysilane 10 mol, 1 mol of the titanium catalyst component [A] in terms of titanium atom and 10 kg of 3-methyl-1-butene were placed in a nitrogen-purged reactor. Is added, the suspension is kept at 20 ° C. while stirring for 3 hours,
Prepolymerization of 3-methyl-1-butene was performed. As a result of the analysis, the prepolymerized amount of the 3-methyl-1-butene polymer unit was 3.9 g / g of the catalyst solid portion. Then, the stirring was stopped, the solid portion was allowed to settle, and the supernatant was removed. 2 in hexane
After washing twice, the total volume was adjusted to 120, 3 mol of triethylaluminum was added, and ethylene was supplied at a rate of 3150 Nl / hour for 2 hours to carry out prepolymerization of ethylene. Meanwhile, the prepolymerization temperature was maintained at 15 to 20 ° C. After the supply of ethylene was completed, the reactor was closed, polymerization of residual ethylene was carried out for 30 minutes, and the resultant was washed twice with hexane.
As a result of the analysis, the amount of prepolymerization with ethylene was 2.8 g / g solid catalyst part.

[Polymerization] Propylene was polymerized in the same manner as in Example 1. As a result, the content of poly-3-methyl-1-butene in the produced polypropylene was 260 ppm. A film was prepared in the same manner as in Example 1, and the film was evaluated.

 Table 2 shows the results.

[Brief description of the drawings]

FIG. 1 is a flowchart showing the production of the composition containing a 3-methyl-1-butene polymer unit used in the present invention.

Continuing from the front page (72) Inventor Masaya Yamada 3 Chikusa Beach, Ichihara-shi, Chiba Mitsui Oil Chemical Industry Co., Ltd. References JP-A-1-217014 (JP, A) JP-A-1-3111106 (JP, A) JP-A-2-265905 (JP, A) JP-A-2-283704 (JP, A) 1-126306 (JP, A) JP-A-1-156305 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 10/00-10/14 C08F 110/00-110 / 14 C08F 210/00-210/18 C08L 23/00-23/36 C08F 4/60-4/70

Claims (2)

(57) [Claims] [A] A magnesium, a titanium, a halogen and an electron donor obtained by reacting a liquid magnesium compound having no reducing property with a liquid titanium compound in the presence of an electron donor are essential. In the presence of a solid titanium catalyst component [B], an organoaluminum compound catalyst component and, if necessary, [C] an olefin polymerization catalyst [I] formed from an electron donor, 3-methyl-1- Butene is pre-polymerized and then a linear α-olefin having 2 to 5 carbon atoms is pre-polymerized, or a linear α-olefin having 2 to 5 carbon atoms is pre-polymerized and then 3-methyl-1- Using a prepolymerized catalyst component formed by prepolymerizing butene and, if necessary, the above [B] organoaluminum compound catalyst component and [C] electron donor, propylene Obtained by the polymerization, 3-methyl-1 and a butene polymer unit and a propylene polymer units, and 3-methyl -
Production of a polypropylene outgoing molded article, characterized in that a molded article is obtained by injection molding a 3-methyl-1-butene polymer unit-containing composition having a 1-butene polymer unit content of 10 to 10,000 ppm by weight. Method. 2. [A] Magnesium, titanium, a halogen and an electron donor obtained by reacting a liquid magnesium compound having no reducing property with a liquid titanium compound in the presence of an electron donor are essential. In the presence of a solid titanium catalyst component [B], an organoaluminum compound catalyst component and, if necessary, [C] an olefin polymerization catalyst [I] formed from an electron donor, 3-methyl-1- A prepolymerization catalyst component formed by prepolymerizing butene and then preliminarily polymerizing a linear α-olefin having 2 to 5 carbon atoms, and if necessary, the above [B] organoaluminum compound catalyst component and [C] Propylene is polymerized using an electron donor or a compound having 2 carbon atoms in the presence of the olefin polymerization catalyst [I].
To 5 linear α-olefins are prepolymerized and then 3
Propylene is polymerized using a pre-polymerization catalyst component formed by pre-polymerization of -methyl-1-butene and, if necessary, the [B] organoaluminum compound catalyst component and [C] electron donor. Obtained by
3-methyl-1-butene polymer unit, containing the α-olefin polymer unit and propylene polymer unit, and the content of 3-methyl-1-butene polymer unit is 10 to 1000.
A polypropylene injection molded article formed from a composition containing a 3-methyl-1-butene polymer unit in the range of 0 ppm by weight.