JPH0488003A - Polymerization method for branched α-olefins - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for polymerizing branched α-olefins, and more particularly to α-olefins having a branch at the 3-position and having 6 or more carbon atoms. The present invention relates to a polymerization method.

TECHNICAL BACKGROUND OF THE INVENTION Olefin polymers such as polyethylene and polypropylene are the most commonly used polymers. However, since it has a lower melting point (Tm) and glass transition point (Tg) than the same thermoplastic resins as polyester and polycarbonate, its use in applications requiring heat resistance is restricted.

By the way, it is generally known that the melting point of an isotactic polymer of a branched α-olefin increases as the degree of branching increases or as the position of branching approaches a carbon-carbon double bond. In particular, isotactic polymers of α-olefins having a branch at the 3-position exhibit a high melting point and are industrially useful as materials with excellent heat resistance.

For this reason, many attempts have been made to polymerize branched α-olefins using Ziegler catalysts to produce olefin polymers with excellent heat resistance. However, in the polymerization of such branched α-olefins, the polymerization activity is lower than that in the polymerization of straight-chain α-olefins, and especially in α-olefins having a branch at the 3-position, there is a remarkable tendency for the activity to decrease. As a method to improve such points, for example, Japanese Patent Application Laid-Open No. 182305/1982 and Japanese Patent Application Laid-Open No. 58-8
Publication No. 708, Japanese Unexamined Patent Publication No. 5! IJ-232103 and the like are disclosed. According to these methods, a polymerization activity several times higher than that of the conventional methods has been obtained, but it is still desired to develop a method that can polymerize branched α-olefins with an even higher polymerization activity.

Purpose of the Invention The present invention has been made in view of the above-mentioned prior art, and an object of the present invention is to provide a method for polymerizing an α-olefin having a branch at the 3-position with high polymerization activity. There is.

Summary of the Invention The method for polymerizing a branched α-olefin according to the present invention comprises [A]
Magnesium, titanium, halogen and electron donor (a
) in the presence of a polymerization catalyst formed from a titanium catalyst component as an essential component, [B] an organometallic compound catalyst component, and [C] an electron donor (c) a catalyst component, having a branch at the 3-position, It is characterized by polymerizing a branched α-olefin having 6 or more carbon atoms.

According to the method for polymerizing branched α-olefins according to the present invention,
An α-olefin polymer having a branch at the 3-position and having excellent heat resistance can be obtained with high polymerization activity.

DETAILED DESCRIPTION OF THE INVENTION The method for polymerizing a branched α-olefin according to the present invention will be specifically described below.

In the present invention, the word "polymerization" is not limited to homopolymerization, but may also be used to include copolymerization.
Furthermore, the term "polymer" is sometimes used to include not only homopolymers but also copolymers.

The polymerization catalyst used in the method for polymerizing a branched α-olefin according to the present invention includes: [A] a titanium catalyst component containing magnesium, titanium, halogen, and an electron donor (a) as essential components; [B]
It is formed from an organometallic compound catalyst component and a [C] electron donor (c) catalyst component.

The titanium catalyst component [A] used in the present invention includes magnesium, titanium, halogen, and an electron donor (a).
Contains as an essential ingredient. Such a titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound, and an electron donor (a).

In the present invention, the magnesium compound used in the preparation of the titanium catalyst component [A,] includes a magnesium compound having reducing ability and a magnesium compound not having reducing ability.

Here, as a magnesium compound having reducing ability,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride,
Butyl magnesium chloride, hexyl magnesium chloride,
Examples include amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium hydride.

Specific examples of magnesium compounds that do not have reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride.

Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride: nitoxymagnesium, isopropoxymagnesium,
butoxymagnesium, n-octoxymagnesium,
Alkoxymagnesium such as 2-ethylhexoxymagnesium: Examples include phenoxymagnesium, dimethylphenoxymagnesium, aryloxymagnesium laurate, magnesium stearate, and magnesium carboxylates.

These magnesium compounds without reducing ability may be compounds derived from the above-mentioned magnesium compounds having reducing ability or compounds derived during preparation of the catalyst component. In order to derive a magnesium compound that does not have reducing ability from a magnesium compound that has reducing ability, for example, a magnesium compound that has reducing ability is mixed with a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. All you have to do is bring it into contact with a compound.

In addition, magnesium compounds include the above-mentioned magnesium compounds with reducing ability and magnesium compounds without reducing ability, as well as complex compounds, composite compounds, or mixtures of the above-mentioned magnesium compounds with other metals, or other metal compounds. You can. Furthermore, a mixture of two or more of the above compounds may be used.

Among these magnesium compounds, magnesium compounds without reducing ability are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, allyloxymagnesium chloride,
Allyloxymagnesium chloride is preferably used.

In the present invention, the titanium compound used for preparing the titanium catalyst component [A] is, for example, Ti(OR).
A tetravalent titanium compound represented by gX4-g (R is a hydrocarbon group, X is a halogen atom, 0≦g≦4) can be mentioned. More specifically, titanium tetrahalides such as TiCl4, TiBr4, Trr4: T+(OCH3)C13, Ti(OC2H5)C13, Ti(On-C4Hs)C13, T'(OC2H5)Br3 , T1(0-iso-C4H9)Br3, etc., trihalogenated alkoxytitanium Ti(OCH3)2CI2, Ti(OC2H5)2CI2, T! Dihalogenated dialkoxytitaniums such as (On-C4H9)2C12, Ti(OC2H5)2B T2; Ti(OCH3)3Cl, Ti(OC2H5)3Cl, Ti(on-c4H9)3cl.

T! (OC2Hs) Monohalogenated l-realkoxytitanium with s B r.

Examples include tetraalkoxy titanium such as Ti(OCH3)4, Ti(○C2H3)4, Ti(On-C4H9)4, Ti(○-1so-C4H9)4, Tl(0-2~ethylhexyl)4, etc. I can do it.

Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds may be diluted with hydrocarbon compounds or halogenated hydrocarbon compounds.

In the present invention, examples of the electron donor (a) used in the preparation of the titanium catalyst component [A] include diesters and diester-forming compounds.

The diester, which is an essential component in the highly active titanium catalyst component [A], is an ester of a dicarboxylic acid in which two carboxyl groups are bonded to one carbon atom or a diester in which two carboxyl groups are bonded to two adjacent carbon atoms. Preferably, it is an ester of a dicarboxylic acid to which the group is attached. Examples of dicarboxylic acids in such esters of dicarboxylic acids include malonic acid, substituted malonic acid, succinic acid, substituted succinic acid, maleic acid, substituted maleic acid, fumaric acid, substituted fumaric acid, and one alicyclic acid. Alicyclic dicarboxylic acid in which two carboxyl groups are bonded to two carbon atoms, alicyclic dicarboxylic acid in which carboxyl groups are bonded to each of two adjacent carbon atoms forming an alicyclic ring, and aromatic acid having a carboxyl group in the ortho position. Examples include esters of dicarboxylic acids such as group dicarboxylic acids and heterocyclic dicarboxylic acids having carboxyl groups on two adjacent carbon atoms forming a heterocycle.

More specific examples of the above dicarboxylic acids include the following dicarboxylic acids.

Malonic acid.

Substituted malonic acids with methylmalonic acid, ethylmalonic acid, isopropylmalonic acid, allylmalonic acid, phenylmalonic acid, etc.

Succinic acid: methylsuccinic acid, dimethylsuccinic acid, ethylsuccinic acid,
Substituted succinic acids such as methylethylsuccinic acid and itaconic acid. Substituted maleic acids such as dicarboxylic maleic acid and dimethylmaleic acid.

Cyclopentane-1,1-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,6-dicarboxylic acid,
Alicyclic dicarboxylic acids such as cyclohexene-3,4-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, nadic acid, methylnadic acid, ■-allylcyclohexane-3,4-dicarboxylic acid, phthalic acid, naphthalene-1 , 2-dicarboxylic acid, aromatic dicarboxylic acids such as naphthalene-2,3-dicarboxylic acid, furan-3,4-dicarboxylic acid, 4,5-dihydrofuran-2,3-dicarboxylic acid, benzopyran-3,4-dicarboxylic acid acids, heterocyclic dicarboxylic acids such as pyrrole-2,3-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, indole-2,3-dicarboxylic acid.

At least one of the alcohol components of the dicarboxylic acid ester preferably has 2 or more carbon atoms, particularly 3 or more carbon atoms, and both alcohol components preferably have 2 or more carbon atoms, particularly preferably 3 or more carbon atoms. For example, diethyl ester, diisopropyl ester, moro-propyl ester, moro-butyl ester, diisobutyl ester, di-tert-butyl ester, diisoamyl ester, dirowhexyl ester, di-2-ethylhexyl ester, moro-octyl ester, diisodecyl ester of the above-mentioned dicarboxylic acids. Examples include ester, ethyl n-butyl ester, and the like.

The electron donor (a) used in the present invention includes not only diesters or diester-forming compounds as described above, but also alcohols, phenols, aldehydes, ketones,
Ethers, carboxylic acids, carboxylic anhydrides, carbonic esters, monoesters, amines, etc. can also be used.

The titanium catalyst component [A] according to the present invention can be obtained by contacting the above magnesium compound, titanium compound, and electron donor (a), or can be prepared by contacting magnesium, titanium, halogen, and electron donor (a). It can be carried out in the same manner as the preparation of conventionally known titanium catalyst components having as an essential component.

For example, JP-A-50-108385, JP-A-501
No. 26590, No. 51-20297, No. 51
-28189 Publication, Publication No. 51-64586, Publication No. 5
No. 1-92885, No. 51-136625,
No. 52-87489, No. 52100596, No. 52-147688, No. 52-104593
Publication No. 53-2580, Publication No. 53-40093
No. 53-43094, No. 55-1351
Publication No. 02, Publication No. 55135103, Publication No. 55-15
No. 2710, No. 56-811, No. 56-11
Publication No. 908, Publication No. 56-18606, Publication No. 58-8
No. 3006, No. 58-138705, No. 58
No. 138706, No. 58-138707, No. 58-138708, No. 58-138709, No. 58-138710, No. 58-13871
Publication No. 5, Publication No. 60-23404, Publication No. 60-195
No. 108, No. 61-21109, No. 61-3
It can be prepared according to the methods disclosed in Japanese Patent No. 7802, Japanese Patent No. 61-37803, and the like. In addition, in the above-mentioned contact, it may be brought into contact in the presence of other reaction reagents such as silicon, phosphorus, and aluminum.

Several examples of methods for preparing these titanium catalyst components [A] will be briefly described below.

(1) A method in which a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor (a) is reacted with a titanium compound in a liquid phase. In this reaction, each component may be pretreated with an electron donor (a) and/or a reaction aid such as an organometallic compound or a halogen-containing silicon compound. In this method, the electron donor (a) is used at least once.

(2) a liquid magnesium compound that does not have reducing properties;
A method of precipitating a solid magnesium-titanium complex by reacting a liquid titanium compound in the presence of an electron donor (a).

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

(4) A method in which the reaction product obtained in (1) or (2) is further reacted with an electron donor (a,) and a titanium compound.

(5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor (a) in the presence of a titanium compound is mixed with a halogen, a halogen compound, or an aromatic hydrocarbon. How to handle it. In this method, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor (a) may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor (a) may be pulverized in the presence of a titanium compound, then pretreated with a reaction aid, and then treated with a halogen or the like.

Note that examples of the reaction aid include organometallic compounds and halogen-containing silicon compounds.

Note that in this method, the electron donor (a) 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 contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor (a) and a titanium compound.

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

(9) Magnesium compound and alkoxytitanium and/or electron donor (a) such as alcohol or ether
) and a halogen-containing compound such as a titanium compound and/or a halogen-containing silicon compound.

(10) A method in which a non-reducing liquid magnesium compound and an organometallic compound are reacted to precipitate a solid magnesium-aluminum complex, and then a titanium compound is reacted.

Among the methods for preparing the titanium catalyst component [A] listed in (1) to αO) above, methods (1) to (4) and QO) are preferably used.

In preparing the titanium catalyst component [A], the amounts of the magnesium compound, titanium compound, and electron donor (a) used are:
For example, the electron donor (a) is about 0.1 to 10 mol per mol of the magnesium compound, and about 0.05 to 100 mol of the titanium compound.
Preferably, it is used in an amount of 0 mol.

The titanium catalyst component [A] thus obtained contains magnesium, titanium, halogen, and an electron donor (a).
Contains as an essential ingredient.

In the titanium catalyst component [A], the halogen/titanium (atomic ratio) is about 4 to 100, preferably about 6 to 40,
Electron donor (a)/titanium (molar ratio) is approximately 0.2 to IO
1 preferably about 0.4 to about 6, and the magnesium/titanium (atomic ratio) is about 2 to 100, preferably about 4 to 70.
It is desirable that

In addition, this titanium catalyst component [AI contains magnesium halide with a small crystal size compared to commercially available magnesium halides, and usually has a specific surface area of about 3 d/g or more, preferably about 40 ITIl/g or more, more preferably about It is 100 to 800 i/g.

Since the titanium catalyst component [AI] is integrated with the above components to form the catalyst component, its composition is not substantially changed by hexane washing. Titanium catalyst component It is preferable that the material exhibits a highly amorphous state.

In addition to the essential components listed below, the titanium catalyst component [A,] may contain other elements, metals, functional groups, electron donors, etc., under conditions that do not deteriorate the catalyst performance. It may be further diluted with an organic or inorganic diluent.If the inclusion of other elements, metals, diluents, etc. may affect the specific surface area or quality, It is preferable that when such other components are removed, the material exhibits the above-mentioned specific surface area value and exhibits poor quality.

In the present invention, a polymerization catalyst formed from the titanium catalyst components [AI], an organometallic compound [B], and an electron donor [C] as described above is used.

As such an organometallic compound [B], an organometallic compound of a metal from Group 1 to Group 2 of the periodic table is used, and specifically, the following compounds are used.

(]) R'□AI(OR2). H, ,0
<m≦3, n is O≦n<3, p is 0≦p<3, q is 0≦
q<3, and m+n+p+q=3).

(2) A complex alkylated product of a Group Ⅰ metal and aluminum represented by M'A IR4 (wherein Ml is Li, Na, or Ni, and R1 is the same as above).

(3) R’R2M2 (In the formula, R1 and R2 are the same as above.

M2 is Mg5Zn or Cd)
Dialkyl compounds of group or group II.

As the organometallic compound belonging to the above (1), the following compounds can be exemplified.

General formula R1□Al (OR2) 3-0 (wherein, R1 and R2 are the same as above. m is preferably 1.5≦m≦3
), general formula R', AlI3-m (in the formula, R1 is the same as above; In the formula, R1 is the same as above. m is preferably 2≦m<3
), general formula R', AI (OR2) nXQ (where R1
and R2 are the same as above. X is halogen, 0<m≦3.
0≦n<3.0≦q<3, and m+n+q−=3)
Examples include compounds represented by:

More specifically, the aluminum compounds belonging to (1) include trialkylaluminum such as triethylaluminum and 1-butylaluminum; trialkenylaluminum such as triisoprenylaluminum; diethylaluminum ethoxide, dibutylaluminum butoxide, etc. Dialkyl aluminum alkoxide; Alkylaluminum sesquialkoxide such as ethyl aluminum sesgiethoxide, butyl aluminum sesquibutoxide, R1□5A1 (○R2). Partially alkoxylated aluminum alkyls having an average composition of Alkyl aluminum sesquihalides with sesquipromide.

Partially halogenated alkylaluminum hydrides such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, dialkylaluminum hydrides such as dibutylaluminum hydride; ethylaluminum dicdride, provil Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as aluminum dihydride.

Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxypromide.

Compounds belonging to (2) above include LiAl (c2H5) 4, L! AI (c7HI5)4 and the like can be mentioned.

Compounds similar to (1) include organometallic compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (c2H5) 2AIOAl (c2H6)2. , (c
4H,) 2A, 1OAl (c4H8)2, (c2H
5) 2AINA, l (c2H5)2C2H.

Examples include methylaluminoxane.

Among these, the above-mentioned alkylaluminum compounds having two or more aluminum atoms and l-realkylaluminum compounds are preferably used.

The [C] electron donor (c) used in the present invention will be explained. [C] As the electron donor (c), an organosilicon compound represented by the following general formula [N] can be used.

R' n5i(ORb)4-n...[I](
In the formula, R" and Rh are hydrocarbon groups, and
) Specifically, the organosilicon compound represented by the above general formula [I] includes trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyljethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis-o-tolyl Dimethoxysilanthine silane, bis p-tolyldimethoxysilane, bis p-tolyljethoxysilanyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Vinyltrimethoxysilane, methyltriethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ
-Chlorpropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilanetriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane,
Phenyltriethoxysilane, aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyl)-butoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2 - norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β
-methoxyethoxysilane), vinyltriacetoxysilane, and dimethyltetraethoxydisiloxane.

Furthermore, as the electron donor (c), the following general formula [
An organosilicon compound represented by ]I] can also be used.

SiR'R'm(OR')3-m +++ [II]
(In the formula, Ro is a cyclopentyl group or a cyclopentyl group having an alkyl group, Rd is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, and R'' is a hydrocarbon group. , m is 0≦m≦2.) In the above formula [IIal, Ro is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
In addition to the cyclopentyl group, o can include a cyclopentyl group having an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, or a 2,3-dimethylcyclopentyl group.

Further, in formula [II], R' is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and Rd is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. , an alkyl group such as a hexyl group, or a cyclopentyl group having a cyclopentyl group and an argyl group exemplified as Ro.

Further, in formula [II], Ro is a hydrocarbon group,
Examples of Ro include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis(2methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane, nitricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, Examples include monoalkoxysilanes such as dicyclopentyl ethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

In the present invention, in the presence of a polymerization catalyst formed from the titanium catalyst component [A], an organometallic compound [B], and an electron donor [C], a carbon An α-olefin having a number of 6 or more is polymerized. As such a branched α-olefin, a branched α-olefin having 6 or more carbon atoms is used, and specifically, for example, 3,3-dimethyl-butene-1,3-methyl-1-pentene, 3 -ethyl-1-pentene, 3-methyl-1-hexene, 3-
Examples include ethyl-1-hexene, 3.5-dimethyl-1-hexene, hexene for 3.5.5-)limethyl, vinylcyclopentane, and vinylcyclohexane.

Among these, 3-ethyl-1-pentene, 3-
Ethyl-1-hexene is preferably used. These branched α-olefins can be used alone or in combination.

In the polymerization, a polymerization catalyst prepared by prepolymerizing the branched α-olefin described above may be used.

In the prepolymerization, the branched α-olefin in component [A] is converted into the branched α-olefin in component [A] using at least a portion of the acid component [A], [B] acid component and at least a portion of the acid component [C]. It is carried out at a rate of about 1 to 1000 g per millimole of titanium. By performing this prepolymerization treatment, branching α to be performed later
- In the main polymerization of olefins, it is possible to obtain a powdered polymer with a large bulk density. In addition, the properties of the slurry in the main polymerization are also good, which has the advantage of allowing high concentration polymerization.

Furthermore, the polymer yield per unit catalyst is large, and a polymer with high stereoregularity can be obtained at a high yield.

The branched α-olefin used in the prepolymerization may be the same as or different from the branched α-olefin used in the main polymerization described above. The prepolymerization is preferably carried out by adding the branched α-olefin and the above catalyst components to an inert hydrocarbon medium under relatively mild conditions and under conditions in which the prepolymer is not dissolved in the polymerization medium.

Specifically, the inert hydrocarbon medium used in this case includes propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, didiclopentane, cyclohexane, and methylcyclopentane. and alicyclic hydrocarbons; or mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Incidentally, the prepolymerization can be carried out using the branched α-olefin itself as a solvent, or the prepolymerization can be carried out substantially in the absence of a solvent.

The concentration of the titanium catalyst component [A] in the prepolymerization is usually 0.5 to 100 mol (in terms of titanium atoms), preferably about 1 to 10 mmol, per 1.12 mmol of the above-mentioned inert hydrocarbon medium. It is preferable to do so. In addition, the organometallic compound [B] is different from the titanium catalyst component [A] in terms of AI/
Ti (atomic ratio) is about 1 to 100, preferably about 2 to 20
It is desirable to use the amount of electron donor [C] acid component,
Approximately 0.01 to 2 per mole of organometallic compound [B] component
It is preferred to use amounts of molar, preferably 0.02 to 1 molar.

In the prepolymerization, a branched α-olefin is mixed with a titanium catalyst component [A
] It is preferred to polymerize about 1000 g, preferably about 3 to 100 g, per millimole of titanium in the titanium. The concentration of branched α-olefin in the prepolymerization is determined by the hydrocarbon medium IIl
It is preferred that the amount is less than about 1 mole, preferably less than 0.5 mole.

If the amount of prepolymerization is too large, the production efficiency of the branched α-olefin polymer may decrease. The prepolymerization is preferably carried out at a temperature at which the prepolymer to be produced does not dissolve in the hydrocarbon medium, which varies depending on the hydrocarbon medium, but is usually about -20 to 70°C, preferably about 0 to 50°C. is desirable.

Incidentally, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Prepolymerization can be carried out batchwise or continuously.

When copolymerizing an α-olefin having a branch at the 3-position as described above, any α-olefin other than the α-olefin having a branch at the 3-position may be used as a copolymerization component. .

For example, ethylene, propylene, 1-butene, 1-pentene, ■-hexene, ■-octene, ■-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene, 4-methyl-1-pentene, etc. may be mentioned. In such a copolymerization, the content of α-olefin having a branch at the 3-position in the copolymer is about 8
It is preferable to use the copolymerized component in an amount of 0 mol % or more, preferably about 90 mol % or more.

It is preferable that the main polymerization is carried out in the reaction form of suspension polymerization.

At this time, the above-mentioned α-olefin itself may be used as the polymerization medium, or the above-mentioned inert hydrocarbon may also be used.

In the present invention, the polymerization temperature of the branched α-olefin may be within a range that allows suspension polymerization, and although it varies depending on the type of polymerization medium, it is usually about 20 to 100°C, preferably about 30 to 80°C. is preferred.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted and a polymer with a high melt flow rate can be obtained.

In the polymerization method of the present invention, polymerization can be carried out in any of the batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The branched α-olefin polymer thus obtained may be a homopolymer, a random copolymer, a block copolymer, or the like.

The branched α-olefin polymer obtained as described above exhibits excellent heat resistance, but among these, 3-ethyl-
Particularly preferred are 1-pentene polymer and 3-ethyl-1-hexene polymer.

Effects of the Invention According to the present invention, the polymer yield per unit titanium is high;
Furthermore, the production ratio of polymers with high stereoregularity is also high.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 <Preparation of titanium catalyst component [A]> Anhydrous magnesium chloride 4.76 g (50 mmol), decane 25 m (! and 2-ethylhexyl alcohol 2
After heating and reacting 3.4 ml (150 mmol) at 130°C for 2 hours to make a homogeneous solution, 1.11 g (7.5 mmol) of phthalic anhydride was added to this solution, and the mixture was heated at 130°C.
Stirring and mixing was continued for an additional hour at C to dissolve phthalic anhydride into the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped into titanium tetrachloride 20 (llynl (1.8 mol)) maintained at -20°C over 1 hour. After the addition, the temperature of this mixed solution was raised to 110°C over 4 hours, and when it reached 110°C, diisobutyl phthalate-1□2.68yJ (1
2.5 mmol) was added thereto and the mixture was kept at the same temperature for 2 hours with stirring. After the 2-hour reaction, the solid portion is collected by hot filtration, and after resuspending the solid portion in 200 me TiC14, the reaction is heated again at 110° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, and 1
Wash thoroughly with 10'C decane and hexane until no free titanium compound is detected in the washing solution. The titanium catalyst component [A] prepared as described above is stored as a hexane slurry, and a portion of it is dried for the purpose of examining the catalyst composition. The composition of the titanium catalyst component [A] thus obtained was 3.1% by weight of titanium and 5% by weight of chlorine.
6.0% by weight, 17.0% by weight of magnesium, and 1.20.9% by weight of diisobutyl phthalate.

<Polymerization> 100 m in a 200 m1 glass polymerization vessel under nitrogen atmosphere
1 of 3-ethyl-1-pentene, 1 mmol of triethylaluminum and 1 mmol of trimethylmethoxysilane were added. Next, the temperature was raised to 50°C while flowing hydrogen so that the H2 partial pressure in the polymerization vessel became 0.1 atm, and O, t
Millimole of titanium catalyst component [A] was added and stirred for 3 hours. Add 10ml of isopropanol to this slurry solution, react at 60'C for 1 hour, filter, and then add 60ml of isopropanol.
Washed with n-hexane/isopropanol (9/L volume ratio) at 0'C.

7.84 g of polymerized powder was obtained. The powder yield per mmol of Ti was 78.4 g/mmol T1.

Examples 2 to 10 Copolymers were obtained in the same manner as in Example 1 except for using the comonomers listed in Table 1.

Table 1 shows these polymerization results.

Example 11 A polymer was obtained in the same manner as in Example 1 except that 3-ethyl-1-hexene was used as the branched α-olefin. The polymerization results are shown in Table 1.

Comparative Examples 1 to 5 Using the monomers or comonomers listed in Table 1, using 2.5 mmol of titanium trichloride (manufactured by Toho Titanium ■, TAC-131) and 5 mmol of diethylaluminium chloride as catalysts, Polymerization temperature 80°C
Polymerization was carried out in the same manner as <Polymerization> of Example 1 except that 1 hydrogen was not used to obtain a polymer or copolymer.

Table 1 shows these polymerization results.

Claims (3)

[Claims] (1) [A] A titanium catalyst component consisting of magnesium, titanium, halogen, and an electron donor (a) as essential components, [B] an organometallic compound catalyst component, and [C] an electron donor (c) a catalyst component. A method for polymerizing a branched α-olefin, which comprises polymerizing a branched α-olefin having a branch at the 3-position and having 6 or more carbon atoms in the presence of a polymerization catalyst. (2) The method for polymerizing a branched α-olefin according to claim 1, wherein the branched α-olefin is 3-ethyl-1-pentene or 3-ethyl-1-hexene. (3) A branched α-olefin polymer obtained by the polymerization method according to claim 1 or 2.