JP2883356B2 - Composition containing 3-methyl-1-butene polymer unit - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition containing a 3-methyl-1-butene polymer unit, a method for producing the same, and a transparent material containing the composition containing a 3-methyl-1-butene polymer unit. The present invention relates to a polypropylene composition having excellent properties.

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. It is also known that a polymer having high stereoregularity can be produced in a high yield by using it in the polymerization of olefins, especially propylene.

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, 3-methyl-1-butene is used as the olefin polymerization catalyst component. It is known that a propylene-based polymer having excellent transparency can be obtained by pre-polymerizing.

The present inventors have conducted further intensive studies based on the above findings, and found that a 3-methyl-1-butene polymer unit and a linear α-olefin polymer unit having 2 to 5 carbon atoms, in particular, propylene polymer A 3-methyl-1-butene-containing composition containing 10 to 90% by weight of a 3-methyl-1-butene polymer unit, wherein The molded article obtained from the polypropylene-based composition blended in a specific amount has very excellent transparency and has a high crystallization rate, and has completed the present invention.

SUMMARY OF THE INVENTION The present invention has been made in view of the prior art as described above, and has been developed in view of the above-mentioned conventional technology. An object of the present invention is to provide a butene polymer unit-containing composition, a method for producing the same, and a polypropylene-based composition containing the 3-methyl-1-butene polymer unit-containing composition.

SUMMARY OF THE INVENTION The composition containing a 3-methyl-1-butene polymer unit according to the present invention comprises [A] Ti (OR) _g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦ A solid titanium catalyst obtained by contacting a tetravalent titanium compound represented by 4), a non-reducing magnesium compound, and an electron donor, and comprising magnesium, titanium, a halogen and an electron donor as essential components A 3-methyl-1-butene polymer unit produced by using a component [B] an organoaluminum compound catalyst component, and if necessary, an olefin polymerization catalyst [I] formed from [C] an electron donor. And α-olefin polymer units having 2 to 5 carbon atoms, and the content of the 3-methyl-1-butene polymer unit is 30 to 90% by weight.

The method for producing a composition containing a 3-methyl-1-butene polymer unit according to the present invention comprises the following steps: [A] Ti (OR) _g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦ 4) a tetravalent titanium compound represented by the formula:
A solid titanium catalyst component obtained by contacting a magnesium compound having no reducibility with an electron donor and containing magnesium, titanium, halogen and an electron donor as essential components [B] a catalyst component of an organoaluminum compound and Accordingly, 3-methyl-1-butene is polymerized on the olefin polymerization catalyst [I] formed from the [C] electron donor, and if necessary, the above [B] organoaluminum compound catalyst component and [C] An electron donor is further added to polymerize a linear α-olefin having 2 to 5 carbon atoms, or a linear α-olefin having 2 to 5 carbon atoms is polymerized on the olefin polymerization catalyst [I], Then, if necessary, the [B] organoaluminum compound catalyst component and [C] electron donor are further added to polymerize 3-methyl-1-butene, Is 3
It is characterized in that the content of the 3-methyl-1-butene polymer unit in the composition containing the methyl-1-butene polymer unit is 30 to 90% by weight. The polypropylene-based composition according to the present invention comprises the above-mentioned 3-methyl-1-butene polymer unit-containing composition and polypropylene, and comprises 3-methyl-
It is characterized in that the content of 1-butene polymer unit is 10 to 10,000 ppm by weight. It comprises a 3-methyl-1-butene-containing composition and polypropylene, and is characterized in that the content of 3-methyl-1-butene polymer units is 10 to 10,000 ppm by weight.

A molded article such as a film or an injection molded article obtained from a polypropylene-based composition in which a specific amount of the 3-methyl-1-butene polymer unit-containing composition according to the present invention is blended,
Excellent transparency.

DETAILED DESCRIPTION OF THE INVENTION The composition containing a 3-methyl-1-butene polymer unit according to the present invention, a method for producing the same, and the 3-methyl-
The polypropylene composition containing the 1-butene polymer unit-containing composition will be specifically described.

The 3-methyl-1-butene polymer unit-containing composition according to the present invention comprises a 3-methyl-1-butene polymer unit and a linear α-olefin polymer unit having 2 to 5 carbon atoms, And the content of the 3-methyl-1-butene polymer unit is
It is 10 to 90% by weight, preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight.

In such a composition, the 3-methyl-1-butene polymer unit and the α-olefin polymer unit having 2 to 5 carbon atoms are in a state of being densely blended.

Here, the composition in a state of being densely blended,
For example, as described below, 3-methyl-1-butene is polymerized using a highly active olefin polymerization catalyst,
Subsequently, it means a composition prepared by further polymerizing an α-olefin having 2 to 5 carbon atoms. That is,
A 3-methyl-1-butene polymer unit-containing composition produced by a so-called multistage polymerization using a specific high-activity catalyst as described above is an α-C 2-5 having essentially 2 to 5 carbon atoms which is hardly blended. A polymer unit derived from an olefin and a 3-methyl-1-butene polymer unit are in a state of being uniformly mixed at a molecular level. Simply melt-blending the conventionally used α-olefin polymer unit and 3-methyl-1-butene polymer unit does not achieve such a dense blend state, and the present invention does not provide a dense blend state. Such a blended state is a blended state achieved only by using a highly active catalyst for olefin polymerization.

Such densely blended compositions are sometimes referred to as block copolymers of poly 3-methyl-1-butene and C2-5 poly-α-olefins. However, the “block copolymer” used herein, that is, the composition containing a 3-methyl-1-butene polymer unit, is a block-like form of 3-methyl-1-butene in a strict sense.
It is not necessary to understand that the butene polymer unit and the linear α-olefin polymer unit having 2 to 5 carbon atoms are bonded.

Specific examples of the linear α-olefin having 2 to 5 carbon atoms used in the production of the 3-methyl-1-butene polymer unit-containing polymer used in the present invention include ethylene,
Propylene, 1-n-butene and 1-n-pentene are exemplified. Of these, ethylene and propylene are preferred, and propylene is particularly preferred. These α
The olefin may be used alone, and the olefin as a main component is at least 70 mol% or more, preferably 80 mol% or more.
It is also possible to use a mixture of two or more such that they contain at least 90 mol%, particularly preferably at least 90 mol%.

The 3-methyl-1-butene polymer unit may contain a polymer unit derived from an α-olefin having 1 to 10 carbon atoms of less than 10 mol%, preferably less than 5 mol%,
Preferably the 3-methyl-1-butene polymer units are present at 100 mol%.

Next, the method for producing the above-described composition containing a 3-methyl-1-butene polymer unit will be specifically described. It is manufactured using a 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 flow chart of a method for producing a 3-methyl-1-butene polymer unit-containing composition using the olefin polymerization catalyst according to the present invention.

The solid titanium catalyst component [A] used in the present invention 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 ) ₄ Ti (O 2 -ethylhexyl) ₄ and other tetraalkoxy titanium.

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.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a reducing magnesium compound and a non-reducing magnesium compound.

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 dimethylmagnesium,
Diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, dioctyl magnesium, didecyl magnesium, decyl butyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy Examples thereof include magnesium, ethylbutylmagnesium, and butylmagnesium halide. These magnesium compounds are:
It 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. The alkyl group in the magnesium compound described above may be branched or linear.

Specific examples of the non-reducing magnesium compound 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; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyoxymagne such as phenoxymagnesium and dimethylphenoxymagnesium Um; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. It may be contacted with a compound.

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. Examples of the substituted hydrocarbon group include a substituted hydrocarbon group containing a hetero atom such as N, O, or S. For example, —CO—C—, —COOR, —COOH, —OH, —SO ₃ H , -C
-N-C -, - and hydrocarbon group substituted with a structure such as 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 polyvalent carboxylic acid esters 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, dimethylmaleate, monooctylmaleate, diisooctylmaleate, diisobutylmaleate, butylmaleic acid Diisobutyl, diethyl butyl maleate, β
-Aliphatic polycarboxylates such as diisopropyl methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconic acid, dimethyl citraconic acid, 1,2-cyclohexanecarboxylic acid Diethyl, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, aliphatic polycarboxylates such as diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, Ethyl isobutyl phthalate, mono n-butyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, phthalic acid n- heptyl phthalate, di -
Aromatic polycarboxylic acid esters such as 2-ethylhexyl, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, and 3,4-flange Examples include esters derived from heterocyclic polycarboxylic acids such as carboxylic acids.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, and n-sebacate.
Octyl, di-2-ethylhexyl sebacate and the like,
Esters derived from long 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 are preferred, and diesters obtained by reacting phthalic acid with alcohols having 2 or more carbon atoms are particularly preferred.

As these polyvalent carboxylic esters, it is not always necessary to use the above-described polyvalent carboxylic esters as starting materials, and for example, using a carboxylic acid, an acid halide, or an acid anhydride corresponding to the above-described ester, The compound capable of deriving the polycarboxylic acid ester in the preparation process of the titanium catalyst component [A] may be used to generate the polycarboxylic acid ester in the preparation stage of the solid titanium catalyst component [A].

Particularly preferred compounds include phthalic acid, phthalic anhydride, phthalic chloride and the like.

Examples of the electron donor other than the polyvalent carboxylic acid that can be used when preparing the solid titanium-based catalyst [A] include alcohols, amines, amides, ethers, ketones, and nitriles as described below. , Phosphines, stippins, arsines, phosphoramides, esters,
Organosilicon compounds such as thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, and members of Groups I to IV of the Periodic Table Examples thereof include metal amides and salts.

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 of reacting a hydrocarbon solution containing at least an electron donor such as an alcohol or an ether with a halogen-containing compound such as a titanium compound and / or a halogen-containing silicon compound. A method of coexisting an electron donor represented by

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 In this case, a method using a halogenated hydrocarbon is preferable.

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. For example, the amount of the electron donor is about 0.01 to 5 per mole of the magnesium compound. Moles, preferably 0.05 to 2 moles, and the titanium compound is used in an amount of about 0.01 to 500 moles, preferably 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], halogen /
The titanium (atomic ratio) is about 4-200, preferably about 5-100, and the electron donor / titanium (molar ratio) is about 0.1-1.
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 a 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
~800m is a ² / g.

Such a solid titanium catalyst component [A] may be used alone, or may be used after being diluted with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound, or a 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
-37803, and the like.

As the organoaluminum compound catalyst component [B], a compound having at least one Al-carbon bond in the molecule can be used. Such compounds include, for example, (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;
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0
≦ q <a number of 3, moreover organic aluminum compound represented by m + n + p + q = a 3), a (ii) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, K, R ¹ is the same as described above), and a complex alkylated product of a Group 1 metal and aluminum, and the like.

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

As the aluminum compound belonging to (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, partially alkoxylated alkyl aluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _{0.5 and the} like; diethyl aluminum chloride, dibutyl Dialkyl aluminum halides such as aluminum chloride and diethyl aluminum bromide; ethyl aluminum sesquichlor Alkylaluminum sesquihalides such as chloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; diethylaluminum Dialkyl aluminum hydrides such as hydride and dibutyl aluminum hydride; other partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride and alkyl aluminum dihydride such as propyl aluminum dihydride; ethyl aluminum ethoxycyclolide, butyl aluminum butoxycyclolide, ethyl Partially alkoxy, such as aluminum ethoxy bromide And the like, and halogenated alkyl aluminum.

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, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , 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 an electron donor [C] include alcohols, phenols, ketones, and the like. Aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, nitriles, nitrogen-containing electron donors such as isocyanates, or the above Such polycarboxylic acid esters can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol,
Octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol,
Alcohols having 1 to 18 carbon atoms such as isopropylbenzyl alcohol; 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol. Phenols;
C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, 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, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate Phenyl acid,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-hexyl cyclohexenecarboxylate,
Diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, di-2-ethylhexyl phthalate, γ
An organic acid ester having 2 to 30 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; an acid halide having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride Methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether,
Ethers and diethers having 2 to 20 carbon atoms such as 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; nitriles such as acetonitrile, benzonitrile, tolunitrile; Acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride are used.

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

^{_{R n Si (OR ') 4}} -n ... [I] [ wherein, R and R' is a hydrocarbon group, 0 <n <a 4 organic represented by the general formula above [I] As the silicon compound, specifically, trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-
Butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bism-tolyldimethoxysilane, bis-p-tolyldimethoxysilane,
Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-
Chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-amino Propyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxy Silane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy (allyloxy) silane, vinyl tris (β-methoxyethoxysilane) Vinyltriacetoxysilane, dimethyl tetraethoxy disiloxane is 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 [II] can be used.

SiR ¹ R ² _m (OR ³ ) _3-m ... [II] 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 a cyclopentyl group having an alkyl group Wherein R ³ is a hydrocarbon group, and m is 0 ≦ m ≦ 2. In the above formula [I], R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and as R ¹ , in addition to the cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group And a cyclopentyl group having an alkyl group such as a 2,3-dimethylcyclopentyl group.

In the formula [I], R ² is any one of an alkyl group, a cyclopentyl group and a cyclopentyl group having an alkyl group, and examples of R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. group, alkyl groups 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 equation [I], R ³ is a hydrocarbon group, R ³
Examples thereof include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

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]. In the present invention, 3-methyl-1-butene is polymerized using this olefin polymerization catalyst, and then, if necessary, the above [B] organoaluminum compound catalyst component and [C] electron donor are further added. A linear α-olefin having 2 to 5 carbon atoms is polymerized, or a linear α-olefin having 2 to 5 carbon atoms is polymerized, and if necessary, the above [B] organoaluminum compound catalyst component and [ C] An electron donor is further added to polymerize 3-methyl-1-butene, and the resulting composition containing 3-methyl-1-butene polymer units contains 3-methyl-1-butene polymer units. By setting the content to 10 to 90% by weight, a composition containing a 3-methyl-1-butene polymer unit is produced.

In the present invention, the 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.

Suspension polymerization can be performed in an inert hydrocarbon medium.

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, etc. 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. Further, the polymerization can be carried out using the monomer itself as a solvent or in a state substantially without a solvent.

In the polymerization method of the present invention, the solid titanium catalyst component [A] is usually converted into Ti atoms per polymerization volume,
It is used in an amount of about 0.001-0.5 mmol, preferably about 0.005-0.1 mmol. Further, the organoaluminum compound catalyst component [B] is added to 1 mol of titanium atoms in the polymerization system.
The metal atom in the organoaluminum compound catalyst component is generally used in an amount of about 1 to 2000 mol, preferably about 5 to 500 mol. Further, the electron donor [C]
Metal atom 1 in organoaluminum compound catalyst component [B]
Usually, about 0.001 to 10 mol, preferably about 0.01
２2 mol, particularly preferably about 0.05-1 mol.

 During the polymerization, hydrogen can also be used.

The polymerization temperature is usually about 0 to 200 ° C, preferably about 10 to 1
At 00 ° C., the pressure is usually set at normal pressure to 100 kg / cm ² , preferably about normal pressure to 40 kg / cm ² . In the polymerization method of the present invention, the polymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system.

Next, the polypropylene-based composition according to the present invention will be described. The polypropylene-based composition comprises the above-described composition containing a 3-methyl-1-butene polymer unit and polypropylene, and comprises 3-methyl-1 The content of butene polymer units is 10 to 10,000 ppm by weight, preferably 100 to 100 ppm;
It is 3,000 ppm by weight, particularly preferably 100 to 1,000 ppm by weight.

As the polypropylene used in the present invention, conventionally known polypropylenes can be widely used. For example, the polypropylene used in the present invention includes homopolypropylene, random polypropylene, and block polypropylene. Here, examples of the random polypropylene include a random copolymer of propylene and ethylene and / or butene-1.
Examples of the block polypropylene include, for example, a mixed composition comprising a homopolypropylene or a random polypropylene and a propylene / ethylene copolymer or an ethylene / hexene-1 copolymer.

Various stabilizers can be added to the composition of the present invention.

It is preferable that a phenolic stabilizer is added to the composition according to the present invention, since a molded article having excellent heat stability and transparency is obtained. Particularly, a phenolic stabilizer and an organic phosphite stabilizer are added. Is preferable because a film excellent in heat stability and transparency can be obtained.

Further, when a higher fatty acid metal salt is added to the composition according to the present invention, the thermal stability of the resin at the time of molding is improved, the moldability is improved, and a molding machine using halogen gas due to the catalyst is improved. Problems associated with rusting and corrosion can be suppressed. Particularly when the higher fatty acid metal salt is used in combination with the phenol-based stabilizer and / or the organic phosphite-based stabilizer, which are the above-mentioned stabilizers, an excellent synergistic effect is achieved in moldability, transparency and heat resistance of the obtained molded article. Is preferred.

Specific examples of the phenolic stabilizer include, specifically, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-dicyclohexyl- 4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2, 6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl-2-ethyl-6-tert-octylphenol, 2-isobutyl-4-ethyl-5 t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, dl-α-tocophenol, t-butylhydroquino 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-hydroxy-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 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, and 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 fatty acid 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.

The polypropylene-based composition in which the composition containing the 3-methyl-1-butene polymer unit is blended in the amount described above is, for example, formed into a film, or when molded into a desired shape by injection molding, A molded article having excellent transparency can be obtained, and the stretched film has excellent transparency. This is considered to be because the 3-methyl-1-butene polymer unit blended in the polypropylene-based composition reduces the spherulite size of the propylene-based polymer.

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

Effects of the Invention A molded product such as a film or an injection molded product obtained from a polypropylene-based composition in which the 3-methyl-1-butene polymer unit-containing composition according to the present invention is blended in a specific amount,
It is excellent in transparency, and the stretched film is excellent in transparency.

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 Ti catalyst component [A]] 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 m of decane
l and 2-ethylhexyl alcohol 35.1ml (225mmo
l) was heated at 130 ° C. for 2 hours to form a homogeneous solution. Then, 1.67 g (11.3 mmol) of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour. Was dissolved in the homogeneous solution. After cooling the thus obtained homogeneous solution to room temperature, the whole solution was dropped into 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C over 1 hour. After the charging is completed, the temperature of the mixed solution is set to 4
The temperature was raised to 110 ° C. over time, and when the temperature reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl terephthalate was added,
From this, stirring was maintained at the same temperature for 2 hours. After the completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and this solid portion was 275 ml.
Was re-suspended in TiCl ₄ and heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing solution. The solid Ti catalyst component [A] synthesized by the above-mentioned production method was stored as a hexane slurry, and a part thereof was dried for the purpose of examining the catalyst composition. The composition of the solid Ti catalyst component [A] thus obtained has a composition of titanium 2.6
% By weight, 58% by weight of chlorine, 18% by weight of magnesium and 12.4% by weight of diisobutyl phthalate.

[Polymerization] Purified hexane 65 in a 2 l autoclave purged with nitrogen
After charging 0 ml and cooling the mixture to 0 ° C., 100 mmol of triethylaluminum, 300 g of 3-methyl-1-butene, 100 mmol of trimethylmethoxysilane and 10 mmol of the above-mentioned titanium catalyst component [A] were charged in 10 mmol in terms of titanium atoms. The autoclave was sealed, and polymerization was carried out at 20 ° C. for 6 hours with stirring. After completion of the polymerization, the reaction mixture was taken out under a nitrogen atmosphere, and then the liquid part was removed to isolate a solid part, which was reslurried in decane. The polymerization amount of 3-methyl-1-butene is a catalyst
The weight was 13 g per g.

Next, 4 l of purified n-decane was added to a 6-liter glass reactor equipped with a stirrer sufficiently purged with nitrogen, and then heated to 60 ° C.
A mixed gas of propylene and hydrogen containing 0.83% by volume of hydrogen was supplied while bubbling into n-decane. 360 mmol of triethylaluminum, 36 m
After adding mol of cyclohexylmethyldimethoxysilane and 7.2 mmol of the above titanium catalyst component [A] in terms of titanium atom, propylene was polymerized at 60 ° C. for 0.5 hour. When 0.5 hour had passed after the addition of the catalyst, about 5 ml of isopropyl alcohol was added to terminate the polymerization, and at the same time, the supply gas was switched to nitrogen. N- containing the resulting polymer
The decane suspension was filtered, and the solid polymer was sufficiently washed with n-hexane, and then dried under reduced pressure at 80 ° C. The yield of the obtained polymer was 650 g, and the MI was 12.0 g / 10 minutes. Therefore, the content of 3-methyl-1-butene polymer units in this polymer was 40% by weight.

[Production of Film] 3-Methyl-1-butene polymerization obtained in this manner
0.10 parts by weight of the composition containing the body unit and Irgano as a stabilizer
x1010 (Antioxidant manufactured by Ciba Geigy, Tetrakis [me
Tylene-8 (3 ', 5'-di-tert-butylhydro
0.1 parts by weight of [xyphenyl) propionate] methane,
0.1 parts by weight of calcium stearate, erucamide 0.1
Parts by weight, silica (Syloid 224 manufactured by Fuji Devison Chemical Co., Ltd.)
) 0.1 parts by weight, with a melt index of 6.5 g / 10 minutes
Addition to propylene homopolymer with 98.2% heptane extraction residue
After mixing with Henschel mixer, 65mmφ extruder
It was granulated into pellets.

Next, the obtained pellets were melt-extruded at a resin temperature of 240 ° C. by a 65 mmφT die film forming machine and cooled by a roll at 30 ° C. to obtain a 25 μm unstretched film.

Examples 2-3 The amount of the 3-methyl-1-butene polymer unit-containing composition in Example 1 was 0.05 part by weight (Example 2) and 0.1 part by weight.
An unstretched film was prepared in the same manner as in Example 1 except that the amount was changed to 15 parts by weight (Example 3).

Example 4 Using the Ti catalyst component [A] prepared in Example 1, polymerization was carried out as follows.

[Polymerization] Purified n-decane was placed in a nitrogen-substituted 2 l autoclave.
After charging 650 ml and cooling it to 0 ° C., 100 mmol of triethylaluminum, 300 g of 3-methyl-1-butene,
After 100 mmol of trimethylmethoxysilane and 10 mmol of the titanium catalyst component [A] were charged in terms of titanium atoms, the autoclave was closed, and polymerization was carried out at 20 ° C. for 6 hours with stirring. After completion of the weight, the reaction mixture was taken out, the liquid part was removed, the solid part was isolated, and this was reslurried in decane. The polymerization amount of 3-methyl-1-butene is 13 / g of catalyst.
g.

Next, 4 l of purified n-decane was added to a 6-liter glass reactor equipped with a stirrer sufficiently purged with nitrogen, and then heated to 60 ° C.
A mixed gas of ethylene and hydrogen containing 50% by volume of hydrogen
Supplied with bubbling in decane. After the addition of 360 mmol of triethylaluminum and 7.2 mmol of the above titanium catalyst component [A] in terms of titanium atoms under the supply of the mixed gas, ethylene was polymerized at 60 ° C. for 1.0 hour. When 1.0 hour had passed after the addition of the catalyst, about 5 ml of isopropyl alcohol was added to stop the polymerization, and at the same time, the supply gas was switched to nitrogen. N- containing the resulting polymer
The decane suspension was filtered, the solid polymer was sufficiently washed with n-hexane, and then dried at 80 ° C under reduced pressure. The yield of the obtained polymer was 450 g, and the MI was 8.0 g / 10 minutes. Therefore, the content of the 3-methyl-1-butene polymer unit in this polymer was 60% by weight.

[Production of Film] An unstretched film having a thickness of about 25 μm was prepared in the same manner as in Example 1 except that the amount of the 3-methyl-1-butene polymer unit-containing composition thus obtained was changed to 0.05 part by weight. A film was obtained.

Example 5 Using the Ti catalyst component [A] prepared in Example 1, polymerization was carried out as follows.

[Polymerization] Purified n-decane was placed in a nitrogen-substituted 2 l autoclave.
After charging 650 ml and cooling it to 0 ° C., 100 mmol of triethylaluminum, 300 g of 3-methyl-1-butene,
After 100 mmol of trimethylmethoxysilane and 10 mmol of the titanium catalyst component [A] were charged in terms of titanium atoms, the autoclave was closed, and polymerization was carried out at 20 ° C. for 6 hours with stirring. After completion of the weight, the reaction mixture was taken out, the liquid part was removed, the solid part was isolated, and this was reslurried in decane. The polymerization amount of 3-methyl-1-butene is 13 / g of catalyst.
g.

Next, 4 l of purified n-decane was added to a 6-liter glass reactor equipped with a stirrer sufficiently purged with nitrogen, and then heated to 60 ° C.
A mixed gas of propylene and hydrogen containing 0.83% by volume of hydrogen was supplied while bubbling into n-decane. 360 mmol of triethylaluminum, 36 m
After adding mol of cyclohexylmethyldimethoxysilane and 7.2 mmol of the above titanium catalyst component [A] in terms of titanium atom, propylene was polymerized at 60 ° C. for 0.3 hours. About 0.3 hour after the addition of the catalyst, about 5 ml of isopropyl alcohol was added to terminate the polymerization, and at the same time, the supply gas was switched to nitrogen. N- containing the resulting polymer
The decane suspension was filtered, the solid polymer was sufficiently washed with n-hexane, and then dried at 80 ° C under reduced pressure. The yield of the obtained polymer was 430 g, and the MI was 7.4 g / 10 minutes. Therefore, the content of the 3-methyl-1-butene polymer unit in this polymer was 60% by weight.

[Production of film] Except that the compounding amount of the thus obtained 3-methyl-1-butene polymer unit-containing composition was 0.05 parts by weight,
A film having a thickness of about 25 μm was obtained in the same manner as in Example 1.

The film properties were measured according to ASTM D 100 for haze.
3. Gross was performed according to ASTM D 523. The measurement of the LSI value was performed using an LSI tester manufactured by Toyo Seiki.

 The evaluation results are described below.

Comparative Example 1 is different from Example 1 in that 3-methyl-
It is an experimental result at the time of performing without adding the 1-butene polymer unit containing composition.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing the production of the poly-3-methyl-1-butene polymer unit-containing composition according to the present invention.

Continuing on the front page (72) Inventor Masaya Yamada 3 Chikusa Beach, Ichihara City, Chiba Prefecture Mitsui Oil Chemical Industry Co., Ltd. (72) Inventor Masanobu Ishiyama 3 Chikaga Coast, Ichihara City, Chiba Prefecture Mitsui Oil Chemical Industry Co., Ltd. (56 References JP-A-3-28208 (JP, A) JP-A-3-28246 (JP, A) JP-A 1-229056 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C08L 23/00-23/36

Claims (3)

(57) [Claims] [A] Ti (OR) _g X _4-g (R is a hydrocarbon group, X
Is obtained by contacting a halogen atom, a tetravalent titanium compound represented by 0 ≦ g ≦ 4), a non-reducing magnesium compound, and an electron donor, to obtain magnesium, titanium, a halogen and an electron donor. 3-methyl produced using a solid titanium catalyst component contained as an essential component, [B] an organoaluminum compound catalyst component, and, if necessary, [C] an olefin polymerization catalyst [I] formed from an electron donor. -1-butene polymer unit and linear α-olefin polymer unit having 2 to 5 carbon atoms, and the content of 3-methyl-1-butene polymer unit is 30 to 90% by weight. A composition containing a 3-methyl-1-butene polymer unit. 2. [A] Ti (OR) _g X _4-g (R is a hydrocarbon group, X
Is obtained by contacting a halogen atom, a tetravalent titanium compound represented by 0 ≦ g ≦ 4), a non-reducing magnesium compound, and an electron donor, to obtain magnesium, titanium, a halogen and an electron donor. 3-methyl-1-butene is added to the solid titanium catalyst component, [B] the organoaluminum compound catalyst component, and [C] the olefin polymerization catalyst [I] formed from the electron donor as necessary. And then, if necessary, further adding the above [B] organoaluminum compound catalyst component and [C] an electron donor to polymerize a linear α-olefin having 2 to 5 carbon atoms, or The catalyst [I] is polymerized with a linear α-olefin having 2 to 5 carbon atoms, and then, if necessary, the above [B] organoaluminum compound catalyst component and C] The addition of an electron donor to polymerize 3-methyl-1-butene, and the resulting 3-methyl-1-butene polymer unit-containing composition contains a 3-methyl-1-butene polymer unit. Characterized in that the amount is 30 to 90% by weight,
A method for producing a 1-butene polymer unit-containing composition. 3. A composition comprising the 3-methyl-1-butene polymer unit-containing composition according to claim 1 and polypropylene, wherein the content of the 3-methyl-1-butene polymer unit is 10 to 10,000 ppm by weight. A polypropylene-based composition, characterized in that: