JPH0725837B2 - Branched α-olefin polymer composition and process for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a branched α-olefin polymer composition having excellent melt fluidity, moldability and melt tension, and a method for producing the same. .

More specifically, the present invention relates to a branched α having a carbon atom number in the range of 5 to 10 and having a branch at the position 3 or higher.
Two or more branched α-olefin systems consisting of olefin-derived repeating units (A) and straight-chain α-olefin-derived repeating units (B) having 2 to 20 carbon atoms. The present invention relates to a branched α-olefin polymer composition containing a polymer, which has excellent melt fluidity, good moldability, and excellent melt tension, and a method for producing the composition by a multistage polymerization process.

[Prior Art] Polymerization of branched α-olefin such as 4-methyl-1-pentene or 3-methyl-1-pentene in the presence of a stereoregular Ziegler polymerization catalyst of titanium trihalide such as TiCl _3. Alternatively, many attempts have been proposed in the past to produce a branched α-olefin polymer having excellent transparency and heat resistance by copolymerization. The branched α-olefin polymers obtained by the polymerization reaction using these titanium trihalide catalysts have a wide molecular weight distribution, excellent melt flowability and excellent moldability, but poor stereoregularity and rigidity. However, there is a drawback that the polymerization activity is also inferior.

The applicant examined a method for producing a branched α-olefin polymer using a conventional titanium trihalide catalyst, and formed a highly active titanium catalyst component, an organoaluminum compound catalyst component and an organosilicon compound catalyst component. It was found that an α-olefin polymer excellent in stereoregularity and rigidity can be obtained by adopting a method of polymerizing a branched α-olefin in the presence of a catalyst, which is disclosed in JP-A-59-206418. Proposed to. However, the branched α-olefin polymer obtained by the method described in the publication is excellent in stereoregularity and rigidity, but is further improved in physical properties such as melt fluidity, moldability and melt tension. There has been a demand for branched α-olefin polymers.

[Problems to be Solved by the Invention] Therefore, the present invention provides a repeating unit derived from a branched α-olefin having a carbon atom number in the range of 5 to 10 and having a branch at the position 3 or higher. Melt flow containing two or more kinds of a branched α-olefin polymer consisting of (A) and a repeating unit (B) derived from a linear α-olefin having 2 to 20 carbon atoms. Excellent in
A branched α-olefin polymer composition having good moldability and excellent melt tension, and (A) magnesium, Ti (O)
R) gX _4- g (R is a hydrocarbon group, X is a halogen, 0 ≦ g ≦
Titanium derived from the tetravalent titanium compound represented by 4),
The above composition by a multi-step polymerization process using a catalyst formed from a highly stereoregular titanium catalyst component containing halogen and an electron donor as essential components, (B) an organoaluminum compound catalyst component and (C) an electron donor. The purpose is to provide a manufacturing method of.

[Means for Solving the Problems] According to the present invention, the above-mentioned object is a branched α having a number of carbon atoms in the range of 5 to 10 and having a branch at the position 3 or higher.
-80 or more repeating units (A) derived from olefin
The repeating unit (B) derived from straight chain α-olefin having 100 mol% and the number of carbon atoms in the range of 2 to 20 is 0.
To 135 mol / g, the intrinsic viscosity [η] _H measured in decalin at 135 ° C is 5 to 30 dl / g.
A branched α-olefin polymer [I], and a repeating unit derived from a branched α-olefin having a number of carbon atoms in the range of 5 to 10 and having a branch at the position 3 or more. The repeating unit (B) derived from linear α-olefin having (A) 80 to 100 mol% and the number of carbon atoms in the range of 2 to 20 is substantially comprised from 0 to 20 mol%, Intrinsic viscosity [η] _L measured in decalin at 135 ° C is in the range of 1 to 10 dl / g and [η]
_A branched α-olefin polymer composition containing a branched α-olefin polymer [II] having an _H / [η] _L ratio in the range of 2 to 30, wherein the polymer [I] / The weight ratio of the polymer [II] is in the range of 1/99 to 60/40, the intrinsic viscosity [η] measured in decalin at 135 ° C is in the range of 1 to 20 dl / g, and 260 ° C.
Melt flow rate measured with a load of 5 kg at Melt flow rate measured at a load of 1 kg at 260 ° C against Is in the range of 10 to 30 and is achieved by a branched α-olefin polymer composition.

Further, the above object is derived from a tetravalent titanium compound represented by (A) magnesium, Ti (OR) gX _4- g (R is a hydrocarbon group, X is a halogen, 0 ≦ g ≦ 4) according to the present invention. A carbon atom in the presence of a catalyst formed from a highly stereoregular titanium catalyst component containing titanium, a halogen and an electron donor as essential components, (B) an organoaluminum compound catalyst component, and (C) an electron donor. The number is 5 or
A branched α-olefin having a branch in the range of 10 and at the 3-position or a branched α-olefin and a linear α-olefin having 2 to 20 carbon atoms in a multi-step manner. A method of polymerizing or copolymerizing in a polymerization step, wherein the intrinsic viscosity [η] _H measured in decalin at 135 ° C. is 5 to 30 dl in at least one polymerization step.
The amount of the branched α-olefin polymer [I] is in the range of 1/60% by weight of the branched α-olefin polymer composition in the range of 1 / g and is generated in the entire polymerization process. Intrinsic viscosity [η] measured in decalin at 135 ℃
_L is 1 to 10 dl / g, [η] _H / [η] _L is in the range of 2 to 30, and the branched α- produced in the whole polymerization step
By producing a branched α-olefin polymer [II] in the range of 99 to 40% by weight of the olefin polymer composition, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 1 to 20 dl / Melt flow rate in the range of g and measured at a load of 5 kg at 260 ° C Melt flow rate measured at a load of 1 kg against Is in the range of 10 to 30 and is achieved by a method for producing a branched α-olefin polymer composition.

Hereinafter, the present invention will be described in detail.

The branched α-olefin polymer composition of the present invention contains two branched α-olefin polymers [I] and [II].

The branched α-olefin polymer [I] contained in the branched α-olefin polymer composition of the present invention has a carbon atom number in the range of 5 to 10 and has a position of 3 or more. The repeating unit (A) derived from a branched branched α-olefin has 80 to 100 mol%, preferably 90 to 100 mol%, more preferably 95 to 100 mol% and a carbon atom number of 2 to 20. The repeating unit (B) derived from a certain linear α-olefin becomes substantially in the range of 0 to 20 mol%, preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and the repeating unit in decalin at 135 ° C. The intrinsic viscosity [η] _H measured in 5 to 30 dl / g, preferably 6
To 30 dl / g, more preferably 8 to 30 dl / g, a branched α-olefin polymer.

The branched α-olefin polymer [II] contained in the branched α-olefin polymer composition of the present invention has a number of carbon atoms in the range of 5 to 10 and a position of 3 or more. The repeating unit (A) derived from a branched branched α-olefin has 80 to 100 mol%, preferably 90 to 100 mol%, more preferably 95 to 100 mol% and a carbon atom number of 2 to 20. The repeating unit (B) derived from a certain linear α-olefin becomes substantially in the range of 0 to 20 mol%, preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and the repeating unit in decalin at 135 ° C. The intrinsic viscosity [η] _L measured by 1 is 10 to 10 dl / g, preferably 1
To 8 dl / g, more preferably 1 to 6 dl / g and having a [η] _H / [η] _L ratio of 2 to 30, preferably 2
To 20 and more preferably 2 to 10 branched α
An olefin polymer.

In the branched α-olefin polymers [I] and [II], the repeating unit (A) derived from the branched α-olefin is less than 80 mol% and the repeating unit derived from the linear α-olefin. If it is more than 20 mol%, the branched α-olefin polymer composition containing the branched α-olefin polymers [I] and [II] will have poor heat resistance and rigidity.

The intrinsic viscosities [η] _H and [η] _L respectively represent the molecular weights of the branched α-olefin polymers [I] and [II] contained in the branched α-olefin polymer composition of the present invention. The ratio [η] _H / [η] _L is a measure of the molecular weight distribution, and these characteristic values are combined with other characteristic values to obtain the above-mentioned excellent properties of the present invention. It is useful for providing a branched α-olefin polymer composition.

Ratio [η] _H / [η] of the above intrinsic viscosity [η] _H and [η] _L
If the value of _L is smaller than 2, improvement in melt fluidity, moldability, melt tension, etc. cannot be expected. When it is larger than 30, the polymers [I] and [II] are uniformly mixed and it becomes difficult, and the heat resistance and mechanical properties are deteriorated.

In the branched α-olefin polymer composition, the weight ratio of the branched α-olefin polymers [I] and [II] is 1/99 to 60/40, preferably 2/98 to 50/50, More preferably, it is in the range of 5/90 to 50/50.

This characteristic value is a measure showing the molecular weight distribution of the branched α-olefin polymer composition of the present invention, and together with other characteristic values, the above-mentioned excellent properties can be obtained by using the above-mentioned branched α-olefin polymer composition. It serves to provide a polymer composition.

If the above weight ratio is less than 1/99, melt flowability, moldability,
No improvement in melt tension can be expected. The same applies when it is larger than 60/40.

The intrinsic viscosity [η] of the branched α-olefin polymer composition measured in decalin at 135 ° C. is 1 to 20 dl / g, preferably 1 to 15 dl / g, more preferably 1 to 10 dl.
It is in the range of / g. This characteristic value is a measure showing the molecular weight of the branched α-olefin polymer composition of the present invention, and together with other characteristic values, the above-mentioned excellent properties can be obtained by the above-mentioned branched α-olefin compound.
It serves to provide an olefin polymer composition.

When the intrinsic viscosity [η] is less than 1 dl / g, mechanical properties and the like are deteriorated. If it is higher than 20 dl / g, the moldability will deteriorate.

The branched α-olefin polymer composition of the present invention is generally used at 260-3
By extrusion granulation at a temperature of 40 ° C. and a residence time of 1 to 5 minutes Of the polymer composition adjusted to be 20 to 40 g / 10 min.
Melt flow rate measured at a load of 5 kg at 60 ° C Melt flow rate measured at a load of 1 kg at 260 ° C Is 10 to 30, preferably 12 to 30, and more preferably
It is in the range 12 to 25.

Ratio of the above melt flow rates Is a scale showing the molecular weight distribution of the branched α-olefin polymer composition of the present invention, and together with other characteristic values, the above-mentioned excellent properties are exhibited by the branched α-olefin polymer composition. Is useful to give to.

If the melt flow rate ratio is less than 10, the moldability will be poor. When it is larger than 30, mechanical properties and the like are deteriorated.

The molecular weight distribution (w / n) of the branched α-olefin polymer composition of the present invention determined by gel permeation chromatography (GPC) is 3 to 20, preferably 3.5 to 15, and particularly preferably 4 It is in the range of ~ 10.

This characteristic value in the branched α-olefin polymer composition of the present invention, together with other characteristic values, gives the branched α-olefin polymer composition the above-mentioned excellent properties. The w / n value was measured according to "Gel Permeation Chromatography" by Takeuchi, Maruzen.

(1) Using a standard polystyrene of known molecular weight (Toyo Soda (manufactured by Toyo Soda Co., Ltd.) monodisperse polystyrene), the molecular weight M and its GPC (Gel Permeation Chromatograph) count are measured, and the correlation diagram between the molecular weight M and EV (Elution Volume) is calibrated. A curve was created. The concentration at this time was 0.02 wt%.

(2) A GPC chromatograph of the sample was taken by GPC measurement, and the polystyrene-equivalent number average molecular weight n and weight average molecular weight w were calculated according to the above (1) to obtain the w / n value. The sample preparation conditions and GPC measurement conditions in that case are as follows.

[Sample Preparation] (a) A sample was dispensed into an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to be 0.1 wt%.

(B) Anti-aging agent 2, in the Erlenmeyer flask containing the sample,
6-di-tert-butyl-p-cresol was added at 0.05 wt% with respect to the polymer solution.

(C) The Erlenmeyer flask was heated to 140 ° C. and stirred for about 30 minutes to dissolve it.

(D) The solution was applied to GPC.

[GPC measurement conditions] The measurement was performed under the following conditions.

(A) Equipment Waters (150C-ALC / GPC) (b) Column Toyo Soda (GMH type) (c) Sample amount 400 μl (d) Temperature 140 ° C (e) Flow rate 1 ml / min Branching α of the present invention The crystallinity of the olefin polymer composition measured by X-ray diffractometry is in the range 0.5 to 60%, preferably 0.5 to 50%. This characteristic value is a measure indicating that the branched α-olefin polymer composition of the present invention is excellent in rigidity and tensile properties, and together with other characteristic values, the above-mentioned excellent properties are branched α. -Useful for providing olefin polymer compositions. Crystallinity
It was described by X-ray diffraction measurement of a 1.5 mm pressed sheet.

The branched α-olefin polymer composition of the present invention has a n-decane-soluble content at 10 ° C. in the range of 0.1 to 20% by weight,
It is preferably in the range of 0.5 to 10% by weight. The n-decane-soluble content of the branched α-olefin polymer composition of the present invention at 10 ° C was measured according to the following method. That is, after dissolving 1 g of polymer in 1000 ml of n-decane,
It was cooled to 10 ° C. and left at 10 ° C. for 1 hour to precipitate a highly crystalline component. The soluble portion was collected by filtration, the solvent was removed and weighed to obtain the n-decane-soluble content (wt%).

The branched α-olefin polymer composition of the present invention described above can be produced by the following method.

First, the catalyst used in the production of the branched α-olefin polymer composition of the present invention will be described.

The highly active titanium catalyst component (A) used in the present invention is a tetravalent titanium compound represented by magnesium, Ti (OR) gX _4- g (R is a hydrocarbon group, X is a halogen, and 0≤g≤4). It contains titanium, a halogen, and an electron donor derived from the above as essential components. As such a titanium catalyst component (A), magnesium / titanium (atomic ratio) is preferably about 2
To about 100, more preferably about 4 to about 70, halogen / titanium (atomic ratio) preferably about 4 to about 100,
More preferably about 6 to about 40, and the electron donor / titanium (molar ratio) is preferably in the range of about 0.2 to about 10, more preferably about 0.4 to about 6. or,
Its specific surface area is preferably about 3 m ² / g or more, more preferably about 40 m ² / g or more, even more preferably about 100 m ² / g to about 800 m ² / g.

Such a titanium catalyst component (A) generally does not substantially eliminate the titanium compound by simple means such as washing with hexane at room temperature. Regardless of the starting magnesium compound used in the catalyst preparation, the X-ray spectrum shows amorphousness with respect to the magnesium compound, or is preferably much more amorphous than that of a usual commercial product of magnesium dihalide. It is in a broken state.

In addition to the above-mentioned essential components, the titanium catalyst component (A) may contain other elements, metals, functional groups, etc. as long as the catalyst performance is not significantly deteriorated. Further, it may be diluted with an organic or inorganic diluent. Other elements, metals,
When it contains a diluent or the like, it may affect the specific surface area or the amorphous property, and in that case, when such other components are removed, the specific surface area value as described above is exhibited and It is preferably amorphous.

The titanium catalyst component (A) also has an average particle size of preferably about 1 to about 200 μ, more preferably about 5 to about 100 μ and a geometric standard deviation σ of the particle size distribution.
It is preferable that g is less than 2.1, and more preferably 1.95 or less. Further, it is preferable that the shape is a regular shape such as a true sphere, an ellipsoid, or a granule.

In order to produce the titanium catalyst component (A), a magnesium compound (or magnesium metal), a titanium compound and an electron donor or an electron donor-forming compound (compound forming an electron donor) are used, and another reaction reagent is used. Alternatively, it is preferable to adopt a method of bringing them into contact with each other without using them. Its preparation is
It can be carried out in the same manner as the conventionally known method for preparing a highly active titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components. For example, JP-A-50-108385
No. 50, No. 50-126590, No. 51-20297, No. 51-28189,
51-64586, 51-92885, 51-136625, 52
-87489, 52-100596, 52-147688, 52-1
04593, 53-2580, 53-40093, 53-43094
No. 55, No. 55-135102, No. 55-135103, No. 56-811,
56-11908, 56-18606, 58-83006, 58
-138705, 58-138706, 58-138707, 58-
138708, 58-138709, 58-138710, 58-13
It can be manufactured according to the method disclosed in No. 8715.

Several examples of methods for producing these titanium catalyst components (A) will be briefly described below.

(1) The magnesium compound or the complex compound of the magnesium compound and the electron donor is crushed with or without crushing in the presence or absence of an electron donor, a crushing aid, etc., and an electron donor and / or an organic compound. A solid obtained by pretreatment with a reaction aid such as an aluminum compound or a halogen-containing silicon compound or without pretreatment is reacted with a titanium compound forming a liquid phase under the reaction conditions. However, the electron donor is used at least once.

(2) A liquid titanium compound having no reducing ability is reacted with a liquid titanium compound in the presence of an electron donor to precipitate a solid titanium complex.

(3) The compound obtained in (2) is further reacted with a titanium compound.

(4) An electron donor and a titanium compound are further reacted with those obtained in (1) and (2).

(5) A magnesium compound or a complex compound of a magnesium compound and an electron donor is pulverized in the presence or absence of an electron donor, a pulverization aid or the like, and in the presence of a titanium compound to obtain an electron donor and / or The solid obtained with or without pretreatment with a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound is treated with halogen or a halogen compound or an aromatic hydrocarbon. However, the electron donor is used at least once.

Among these preparation methods, it is preferable to use a liquid titanium halide in the catalyst preparation, or to use a halogenated hydrocarbon after or when using a titanium compound.

Examples of the electron donor used in the above preparation include diester or diester-forming compounds, alcohols, phenols, aldehydes, ketones, ethers, carboxylic acids, carboxylic acid anhydrides, carbonic acid esters, monoesters, amines, and other electron donors. be able to.

Among the electron donors which are essential components in the high activity titanium catalyst component (A) used in the present invention, the diester is 1
It is preferably an ester of a dicarboxylic acid having two carboxyl groups bonded to one carbon atom or an ester of a dicarboxylic acid having a carboxyl group bonded to two adjacent carbon atoms. Examples of the dicarboxylic acid in the ester of such dicarboxylic acid include malonic acid, substituted malonic acid, succinic acid, substituted succinic acid, maleic acid, substituted maleic acid, fumaric acid, substituted fumaric acid, and one that forms an alicyclic ring. Alicyclic dicarboxylic acid having two carboxyl groups bonded to each carbon atom, alicyclic dicarboxylic acid having a carboxyl group bonded to two adjacent carbon atoms forming an alicyclic ring, and aromatic having a carboxyl group at the ortho position Examples thereof include group dicarboxylic acids and dicarboxylic acid esters such as heterocyclic dicarboxylic acids having a carboxyl group at two adjacent carbon atoms forming a heterocycle.

More specific examples of the dicarboxylic acid include malonic acid; substituted malonic acids such as methylmalonic acid, ethylmalonic acid, isopropylmalonic acid, allyl malonic acid, and phenylmalonic acid; succinic acid; methylsuccinic acid.
Substituted succinic acid such as dimethylsuccinic acid, ethylsuccinic acid, methylethylsuccinic acid and itaconic acid; maleic acid; substituted maleic acid such as citraconic acid and dimethylmaleic acid; cyclopentane-1,1-dicarboxylic acid, cycoumaropentan-1 , 2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,6-dicarboxylic acid, cyclohexene-3,4-dicarboxylic acid, cyclohexene-
4,5-dicarboxylic acid, nadic acid, methyl nadic acid,
Alicyclic dicarboxylic acids such as 1-allylcyclohexane-3,4-dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid; furan-3, 4-dicarboxylic acid, 4,5-
Dihydrofuran-2,3-dicarboxylic acid, benzopyran-
3,4-Cicarboxylic acid, pyrrole-2,3-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, indole-2,3-dicarboxylic acid, indole-2,3-dicarboxylic acid Examples thereof include dicarboxylic acids such as heterocyclic dicarboxylic acids such as acids.

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

Examples of electron donors other than diesters that can be used to prepare the titanium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and alkoxysilanes of acid anhydrides. And oxygen-containing electron donors such as, and nitrogen-containing electron donors such as ammine, amine, nitrile and isocyanate can be used.

More specifically, it has 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol and isopropylbenzyl alcohol.
Alcohols of 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; acetone, methylethylketone, methylisobutylketone C3 to C15 ketones such as acetophenone and benzophenone; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
Aldehydes having 2 to 15 carbon atoms such as tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, chloroacetic acid. Methyl, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, toluyl Ethyl acid, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
γ-butyrolactone, δ-valerolactone, coumarin,
C2 to C30 organic acid esters such as phthalide and ethylene carbonate; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether , Butyl ether, isoamyl ether, tetrahydrofuran, anisole,
C2-C20 ethers such as diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, Amines such as picoline, tetramethylmethylenediamine and tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile and tolunitrile; Organophosphorus compounds having a poo bond such as trimethyl phosphite and triethyl phosphite; And alkoxysilanes such as ethyl acid and diphenyldimethoxysilane.
Two or more kinds of these electron donors can be used.

The electron donors that are preferably contained in the titanium catalyst component (A) include organic acid or inorganic acid esters, alkoxy (aryloxy) silane compounds, ethers, ketones, tertiary amines, acid halides, acid anhydrides. Organic acid esters and alkoxy (aryloxy) silane compounds are particularly preferable because they do not have active hydrogen, and among these, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms, malonic acid, substituted malonic acid, substituted amber. Particularly preferred are esters of dicarboxylic acids such as acids, maleic acid, substituted maleic acids, 1,2-cyclohexanedicarboxylic acid and phthalic acid with alcohols having 2 or more carbon atoms. Of course, these electron donors do not necessarily have to be used as raw materials when preparing the titanium catalyst, and may be used as other compounds that can be converted into these electron donors and converted into these electron donors during the catalyst preparation process.

The titanium catalyst component obtained by the various methods as exemplified above can be purified by sufficiently washing with a liquid inert hydrocarbon after the reaction. As the inert liquid hydrocarbon used for this purpose, n-pentane, isopentane, n-pentane,
Hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene,
Aliphatic hydrocarbons such as liquid paraffin; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, cymene; Chlorobenzene, dichloroethane Such halogenated hydrocarbons or mixtures thereof can be exemplified.

The magnesium compound used for the preparation of the (A) highly active titanium catalyst component is a magnesium compound with or without reducing ability. As an example of the former, a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond, for example, dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium,
Didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium,
Butyl magnesium halide and the like.
These magnesium compounds may be used in the form of complex compounds with, for example, organic aluminum, and may be in a liquid state or a solid state. On the other hand, as the magnesium compound having no reducing ability, magnesium chloride,
Magnesium halides such as magnesium bromide, magnesium iodide, magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride; phenoxy magnesium chloride, methylphenoxy Allyloxy magnesium halides such as magnesium chloride; alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium; phenoxy magnesium, dimethyl phenoxy magnesium, etc. Allyloxy magnesium; like magnesium laurate, magnesium stearate Such as carboxylic acid salts of magnesium can be exemplified. Further, the magnesium compound having no reducing ability may be one derived from the above-mentioned magnesium compound having reducing ability or one derived at the time of preparation of the catalyst component. Further, the magnesium compound may be a complex compound with another metal, a double compound, or a mixture with another metal compound. Further, it may be a mixture of two or more of these compounds. Among these, preferred magnesium compounds are compounds having no reducing ability, and particularly preferred are halogen-containing magnesium compounds, especially magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride.

In the present invention, there are various titanium compounds used for preparing the titanium catalyst component (A). For example, Ti (OR)
gX _4- g (R is a hydrocarbon group, X is a halogen, 0 ≦ g ≦ 4)
A tetravalent titanium compound represented by is preferable. 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 ₅ ).
Cl, Ti (OC ₂ H ₅ ) Br ₃ , Tri (OisoC ₄ H ₅ ) Br ₃ and other trihalogenated alkoxy titanium; 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 alkoxy titanium such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti
Monohalogenated trialkoxy titanium such as (OC ₂ H ₅ ) ₃ Cl, Ti (On-C ₄ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ).
Examples thereof include tetraalkoxytitanium such as ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti (On-C ₄ H ₉ ) ₄ . Of these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be diluted with a hydrocarbon, a halogen hydrocarbon or the like.

In the preparation of the titanium catalyst component (A), a titanium compound,
The magnesium compound and the electron donor to be supported, and other electron donors that may be optionally used, such as alcohol, phenol, monocarboxylic acid ester, silicon compound, aluminum compound, etc. It depends on the method and cannot be specified unconditionally, but for example, about 0.1 to about 10 moles of electron donor and about 0.05 to about 1 mole of titanium compound per mole of magnesium compound.
The ratio can be about 000 mol.

In the present invention, the combination catalyst of the highly active titanium catalyst component (A) obtained as described above, the organoaluminum compound catalyst component (B) and the electron donor (C) is used.

As the component (B), (i) at least 1 in the molecule
Organoaluminum compounds having a number of Al-carbon bonds, such as the general formula R ¹ mAl (OR ² ) nHpXq (where R ¹ and R ² are carbon atoms, usually 1 to 15, preferably 1 to 4 carbon atoms). The hydrogen groups may be the same or different, X is halogen, and m is 0 <m ≦.
3, 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3). (Ii) General formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, a K, R ¹ is as defined above), and the like alkylated complex of a group 1 metal and aluminum represented by.

Examples of the organoaluminum compound belonging to (i) above include the following. The general formula R ¹ mAl (OR ² ) ₃ −m (wherein R ¹ and R ² are as defined above, m is preferably 1.5
It is a number of ≦ m ≦ 3. ), The general formula R ¹ mAlX ₃ -m (where R ¹ is the same as above, X is a halogen, and m is preferably 0 <m <3), the general formula R ¹ mAlH ₃ -m (where R is ¹ is the same as above, m is preferably 2 ≦ m <3), the general formula R ¹ mAl (OR ² ) nXq (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).

The following compounds can be illustrated as an example of the aluminum compound which belongs to (i). Triethylaluminum,
Trialkyl aluminums such as tributyl aluminum; Tolualkenyl aluminums such as triisoprenyl aluminum; Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide, dibutyl aluminum butoxide; Alkyl such as ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide Besides aluminum sesquialkoxide, partially alkoxylated alkylaluminum having an average composition represented by ▲ R ¹ _2.5 ▼ Al (OR ² ) _0.5, etc .; such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide Dialkyl aluminum halides; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum Alkyl aluminum sesquihalides such as umsesquibromide; partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum hydride, dibutyl aluminum hydride Such as dialkyl aluminum hydride; ethyl aluminum dihydride, propyl aluminum dihydride, etc. alkyl aluminum dihydride, etc., other partially hydrogenated alkyl aluminum; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy Partially alkoxylated and halogenated alkyls such as bromide Aluminum.

Examples of the compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ ,
LiAl (C ₂ H _{15) 4} etc. can be exemplified.

Further, a compound similar to (i) may be an organoaluminum compound in which two or more aluminums are bound via an oxygen atom or a nitrogen atom. As such a compound,
For example _{(C 2 H 5) 2 AlOAl} (C 2 H 5) 2, (C 4 H 9) 2 AlOAl (C 4 H 9) 2, Can be exemplified.

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminums are bonded.

In the present invention, the electron donor (C) used as a catalyst component includes amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoramides, esters, thioethers. , Thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids and amides and salts of metals belonging to Groups 1 to 4 of the periodic table And so on.
Salts can also be formed in situ by the reaction of an organic acid with an organometallic compound used as catalyst component (B). Specific examples thereof can be selected from those exemplified above as the electron donor contained in the titanium catalyst component (A). Good results are obtained with organic acid esters, alkoxy (aryloxy) silane compounds, ethers, ketones, acid anhydrides, amines and the like. Particularly when the electron donor in the titanium catalyst component (A) is a monocarboxylic acid ester, the electron donor as the component (C) is preferably an alkyl ester of an aromatic carboxylic acid.

Further, when the electron donor in the titanium catalyst component (A) is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms as exemplified above as preferable ones, the general formula RnSi
(OR ¹ ) _4- n (wherein R and R ¹ are hydrocarbon groups, O ≦ n <4)
It is preferable to use an alkoxy (aryloxy) silane compound represented by and an amine having a large steric hindrance as the component (C). Specific examples of the alkoxy (aryloxy) silane compound include trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane , Γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriethoxysilane Isopropoxysilane, vinyltryptoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy (allylo
xy) silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, and the like, and especially trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, triethylmethoxysilane,
Tri-n-propylmethoxysilane, tri-iso-propylmethoxysilane, triphenylmethoxysilane and the like are preferable.

The amine having a large steric hindrance is 2,2,6,6-
Tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, derivatives thereof, tetramethylmethylenediamine and the like are particularly preferable.

In the present invention, the above-mentioned catalyst is used in the present invention to provide a branched α-olefin having carbon atoms in the range of 5 to 10 and having a branch at the position 3 or more, or the branched α-olefin and the carbon atom. Linear α-olefins having a number in the range of 2 to 20 are polymerized or copolymerized by a multistage polymerization process.

In the present invention, prepolymerization may be carried out before carrying out polymerization or copolymerization in a multistage polymerization process.

In the present invention, in the presence of the catalyst formed from the above (A), (B) and (C), the branched α-olefin is polymerized or the branched α-olefin and the linear α-olefin are combined. Prior to that, at least a part of the component (A) and at least a part of the component (B) are used for branching in a hydrocarbon catalyst. It is preferable that the α-olefins are prepolymerized at a ratio of about 1 to about 1000 g per 1 mmol of titanium in the component (A). By carrying out this preliminary polymerization treatment, a powder polymer having a high density can be obtained in the slurry polymerization which will be carried out later, so that the slurry properties are good and there is an advantage that a high concentration operation can be carried out. Further, there are advantages that the polymer yield per unit catalyst is large and the stereoregular polymer can be produced at a high rate.

The branched α-olefin used in the prepolymerization is an α-olefin having a number of carbon atoms in the range of 5 to 10 and having a branch at the position 3 or higher, and the branched α-olefin used in the main polymerization described later. Olefin can be similarly exemplified. The prepolymerization is preferably carried out under relatively mild conditions and under conditions in which the prepolymer does not dissolve in the polymerization medium. For this reason, it is preferable to use an inert hydrocarbon as a polymerization catalyst, for example, an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and an alicyclic hydrocarbon such as cyclopentane and cyclohexane. preferable.

In the prepolymerization, for example, per 1 hydrocarbon medium,
The titanium catalyst component (A) is converted to titanium atoms in an amount of about 0.5 to about 100 mmol, particularly about 1 to about 10 mmol, and the organoaluminum compound catalyst component (B) is converted to Al / Ti.
(Atomic ratio) is about 1 to about 100, especially about 2 to about 8
It is preferable that the electron donor (C) is used in an amount of about 0.01 to about 2 moles, and particularly about 0.01 to about 1 mole per mole of the component (B).

The polymerization amount of the branched α-olefin to be prepolymerized is
About 1 to about 1000 per 1 mmol of titanium in the component (A)
g, preferably in the range of about 3 to about 500 g. In order to carry out the above-mentioned amount of polymerization, it is usually sufficient to use a predetermined amount of the branched α-olefin. In addition, the concentration of the branched α-olefin in the prepolymerization is the same as that of the hydrocarbon medium 1.
It is preferably about 1 mol or less, particularly about 0.5 mol or less.

The prepolymerization is preferably carried out at a temperature at which the resulting prepolymer does not dissolve in the hydrocarbon medium, and although it varies depending on the type of the hydrocarbon medium, it is, for example, about -20 to about + 70 ° C, preferably about 0 ° to about An example is the range of 50 ° C.

In the present invention, the polymerization of the branched .alpha.-olefin or the copolymerization of the branched .alpha.-olefin with the linear .alpha.-olefin is carried out by a multi-step polymerization method using a catalyst subjected to a prepolymerization treatment. At this time, the component (B) and / or the component (C) may be additionally used. Preferably,
The component (B) is about 1 to about 1000 mol per mol of titanium,
In particular about 10 to about 1000 moles, component (C) about 0.005 to about 2 moles per mole of component (B), especially about 0.01
It is advisable to additionally use 1 to about 1 mol.

In the present invention, the raw material olefin can be multi-stage polymerized by using the catalyst obtained by prepolymerizing α-olefin as described above.

The prepolymerized catalyst exhibits greater polymerization activity in the multi-step polymerization process of the present invention, and the stereoregularity of the obtained branched α-olefin polymer composition is improved. The branched α-olefin polymer composition obtained in the present invention has better stereoregularity and higher rigidity than that obtained using a TiCl ₃ catalyst.

In the polymerization step of at least one step of the present invention, the above catalyst is used in an inert solvent or in the absence of a solvent so that the number of carbon atoms is in the range of 5 to 10 and the branching is carried out at the position 3 or higher. A branched α-olefin or a branched α-olefin and a straight chain α having 2 to 20 carbon atoms
The intrinsic viscosity [η] _H measured in decalin at 135 ° C. by polymerizing or copolymerizing olefins is 5 to 30 dl / g, preferably 6 to 30 dl / g, more preferably 8 to 30 dl.
A branched α-olefin polymer [I] in the range of / g is produced.

In another at least one stage of the polymerization process of the present invention,
Branched α-olefins having 5 to 10 carbon atoms in the presence of hydrogen in the presence of hydrogen in an inert solvent or in the absence of a solvent and having a branch at the 3-position or more. Alternatively, the branched α-olefin and the number of carbon atoms are 2
A linear α-olefin in the range of 20 to 20 is polymerized or copolymerized and the intrinsic viscosity [η] _L measured in decalin at 135 ° C. is 1 to 10 dl / g, preferably 1 to 8 dl / g.
g, more preferably a branched α-within the range of 1 to 6 dl / g
An olefin polymer [II] is formed.

In the polymerization step, the branched α-olefin and the linear α
-Olefin is a repeating unit derived from the branched α-olefin in the branched α-olefin polymer composition of the present invention, wherein the repeating unit (A) derived from the branched α-olefin is from 80 to 100 mol% and the linear α-olefin. Unit (B) is 0 to 20 mol%
Polymerization or copolymerization is performed in such a ratio that

Such a ratio depends on the type of α-olefin used, the catalyst, the reaction conditions, etc., but can be easily determined by a simple experiment.

The number of carbon atoms which can be used in the present invention is 5 to 10
As a branched α-olefin having a branch at the position 3 or higher and a 3-methyl-1-pentene, 4
-Methyl-1-pentene, 3-methyl-1-butene, 3,
3-dimethyl-1-butene, 4,4-dimethyl-1-hexene, 3-methyl-1-hexene, 4,4-dimethyl-1-
Mention may be made of pentene, 3-ethyl-pentene, vinylcyclohexane. 4-Methyl-1-pentene is preferred.

The number of carbon atoms which can be used in the present invention is 2 to 20
As linear α-olefin in the range of, ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
Examples thereof include 1-octene, 1-decene, 1-dodecene and the like. Particularly, straight chain α-olefin having 6 to 14 carbon atoms such as 1-hexene, 1-octene, 1-decene, 1-dodecene is preferable.

Examples of the inert medium that can be used in the polymerization step for producing the branched α-olefin polymers [I] and [II] include propane, butane, pentane,
Hexane, heptane, octane, decane, kerosene and other aliphatic hydrocarbons; cyclopentane, cyclohexane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloroethane, methylene chloride,
Examples thereof include halogenated hydrocarbons such as chlorobenzene; or a mixture thereof. Of these, the use of aliphatic hydrocarbons is particularly desirable.

The concentration of each catalyst component in the polymerization product liquid in the polymerization vessel in each polymerization step is about 0.001 to about 0.1 mmol, preferably about 0.001 to about 0.05, in terms of titanium atom of the treated catalyst per 1 polymerization volume. And the polymerization system Al /
The Ti (atomic ratio) is preferably adjusted to about 1 to about 1000, preferably about 2 to about 1000. Therefore, if necessary, an organoaluminum compound catalyst component (B)
Can be used additionally. In the polymerization system, hydrogen, an electron donor,
Halogenated hydrocarbon and the like may coexist.

The polymer temperature is within a temperature range in which slurry polymerization, solution polymerization or gas phase polymerization is possible, and about 0 ° C or higher, more preferably about 30
The preferred range is from about 200 ° C. The polymerization pressure is
For example, a range of atmospheric pressure to about 200 kg / cm ² , especially atmospheric pressure to about 100 kg / cm ² is recommended. The amount of polymer produced is about 50 per 1 mmol of titanium in the titanium catalyst component.
It is preferable to set the polymerization time such that the polymerization time is 00 g or more, particularly about 10,000 g or more.

The branched α-olefin polymer composition obtained by the present invention is excellent in melt flowability as compared with the branched α-olefin polymer and the branched α-olefin polymer composition obtained by a conventional method, Good moldability and excellent melt tension.

Therefore, the branched α-olefin polymer composition obtained by the present invention can be formed into a film by a molding method such as extrusion molding, blow molding, injection molding, press molding, or vacuum molding.
It can be formed into a sheet, a hollow container, and various other products, and can be used for various purposes.

Example 1 <Preparation of titanium catalyst component (a)> 4.76 g (50 mmol) anhydrous magnesium chloride, 25 ml decane and 23.4 ml (150 mmol) 2-ethylhexyl alcohol.
Was heated at 130 ° C for 2 hours to form a uniform solution, and 1.11 g (7.5 mmol) of phthalic anhydride was added to this solution.
Stir-mixing is further performed at 0 ° C. for 1 hour to dissolve phthalic anhydride in the homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride kept at -20 ° C.
The total amount is dropped into 200 ml (1.8 mol) over 1 hour. After the charging is completed, the temperature of this mixed solution is 110 for 4 hours.
The temperature was raised to ℃, and when it reached 110 ℃, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, the solid portion was collected by filtration, the solid portion was resuspended in 200 ml of TiCl ₄ , and then the reaction was again carried out at 110 ° C. for 2 hours by heating. After completion of the reaction, the solid portion is again collected by heating, and the solid portion is thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound is detected in the washing liquid. The titanium catalyst component (a) synthesized by the above production method is stored as a hexane slurry, and a part of this is dried for the purpose of examining the catalyst composition. The titanium catalyst component (a) thus obtained had a composition of 3.1% by weight of titanium, 56.0% by weight of chlorine and 1% of magnesium.
It was 7.0% by weight and 20.9% by weight of diisobutyl phthalate.

<Preliminary Polymerization> A 1000 ml flask was charged with 500 ml of n-decane, 5 mmol of triethylaluminum, 1 mmol of trimethylmethoxysilane, and 0.5 mmol of titanium catalyst component (a) in terms of titanium atoms. While maintaining the temperature at 20 ° C, 150 g of 4-
Methyl-1-pentene was added over 1 hour and the reaction was further continued at 20 ° C. for 2 hours. Furthermore, 10 g of 3-methyl-1-pentene was added all at once, and the reaction was carried out at 20 ° C. for 2 hours. The reaction was filtered through a glass filter and resuspended in 500 ml n-decane. The amount of prepolymerization was 300 g per 1 mmol of titanium.

<Polymerization> Dehydration was carried out in 17 SUS reaction kettles that had been sufficiently replaced with nitrogen, and 14 replaced with nitrogen, 4-methyl-1-pentene, 270 ml of 1-decene, 10 mmol of triethylaluminum, 10 mmol of trimethylmethoxysilane, and titanium atoms. Converted to 0.02 mmol
The prepolymerized component of was added and polymerized at 50 ° C. for 2 hours. Here, a part of the polymerization slurry was extracted, and the amount of the polymer excluding the solvent-soluble polymer produced at this stage and the molecular weight were determined. As a result, the polymer [I] _H 13.5 dl / g [I] Is titanium 1 mmol
It was found that the amount produced was 31,600 g per unit. Subsequently, hydrogen was added until the partial pressure reached 2 atm, and the mixture was further added at 50 ° C for 6
Polymerization was carried out for a period of time (while the polymer [II] was formed). After stopping the polymerization by adding a small amount of isobutyl alcohol, it was cooled to room temperature, the solvent was removed by a centrifuge,
After vacuum drying, 2,940 g of a white powdery polymer was obtained. Thus, [η] of the polymer excluding the solvent-soluble polymer finally obtained was 6.42 dl / g, and the amount produced was 147,000 g per 1 mmol of titanium. Therefore, the polymer obtained by the main polymerization reaction is composed of the polymer [I] _H 13.5 dl / g of polymer [I] and the polymer [II] _L 3.97 dl / g of [II],
And the weight ratio of [II] was found to be 21.5 / 88.5. The polymer obtained is extruded and granulated under the conditions of a resin temperature of about 280 ° C and a residence time of about 2 minutes after mixing an appropriate amount of an antioxidant. Was adjusted to about 30g / 10min. The results of measuring the physical properties of the polymer are shown in Table 1. In the following examples and comparative examples, the physical properties were measured after MFR adjustment under the same conditions.

Comparative Example 1 Branched α-olefins and linear α-similar to Example 1
Using olefin, the same catalyst components as in Example 1 were further added, and hydrogen was added until the partial pressure reached 0.7 atm, and the temperature was 50 ° C.
Polymerization was carried out for 6.5 hours. Thus, 1 mmol of titanium is 193,
000 g of polymer was obtained. Table 1 shows the results of measuring the physical properties of the polymer.
It was shown to.

Examples 2 to 5 Except that the hydrogen partial pressure and the polymerization time to be added at the time of the polymerization of the first stage (forming the polymer [I]) and the latter stage (forming the polymer [II]) are as shown in Table 1. The same procedure as in Example 1 was performed. The results of polymerization and the results of measuring physical properties are shown in Table 1.

Examples 6,7 No linear α-olefin was used in Example 1,
Furthermore, Example 1 was repeated except that the polymerization temperature, hydrogen partial pressure, and polymerization time in the first-stage and second-stage polymerizations were as shown in Table 1.
I went the same way. Table 1 shows the results of polymerization and the measurement of physical properties.
It was shown to.

Examples 8 and 9 The linear partial α-olefin was used only in the latter stage, and the hydrogen partial pressure and the polymerization time in each of the first and second polymerization stages are shown in Table 1.
Polymerization was performed in the same manner as in Example 1 except that the above was performed. The results of the polymerization and the results of measuring the physical properties are shown in Table 1.

Comparative Examples 2 to 5 The procedure of Example 1 was repeated, except that the amount of linear α-olefin used, the hydrogen partial pressure, the polymerization temperature, and the polymerization time in each polymerization stage were changed as shown in Table 1. The results of the polymerization and the results of measuring the physical properties are shown in Table 1.

Examples 10 and 11 Polymerization was carried out in the same manner as in Example 1 except that 1-hexene and 1-tetradecene were used as the linear α-olefins in the amounts shown in Table 1, respectively. The polymerization results are shown in Table 1.

ADVANTAGES OF THE INVENTION According to the present invention, a branched α-olefin polymer composition having excellent melt fluidity, good moldability, and excellent melt tension and a multi-step polymerization process using a highly active catalyst can be used. A method of making the composition is obtained.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for preparing the catalyst according to the present invention.

Claims (2)

[Claims] 1. 80 to 100 mol% of a repeating unit (A) derived from a branched α-olefin having a carbon atom number of 5 to 10 and having a branch at the position 3 or more and a carbon atom. 0 to 20 mol% of repeating units (B) derived from linear α-olefin having a number in the range of 2 to 20
Of the branched α-olefin polymer [I] having an intrinsic viscosity [η] _H measured in decalin at 135 ° C. of 5 to 30 dl / g, and a carbon number of 5 80 to 100 mol% of the repeating unit (A) derived from a branched α-olefin having a branch in the 3-position or more and a range of 2 to 20 carbon atoms. The repeating unit (B) derived from the chain α-olefin is substantially in the range of 0 to 20 mol%, and the intrinsic viscosity [η] _L measured in decalin at 135 ° C. is in the range of 1 to 10 dl / g. And [η] _H /
[Η] A branched α-olefin polymer [II] having an _L ratio in the range of 2 to 30, wherein the polymer [I] / the The polymerization ratio of the polymer [II] is in the range of 1/99 to 60/40, and the intrinsic viscosity [η] measured in decalin at 135 ° C is in the range of 1 to 20 dl / g and 260 ° C.
Melt flow rate measured with a load of 5 kg at Melt flow rate measured at a load of 1 kg at 260 ° C against Is in the range of 10 to 30. A branched α-olefin polymer composition. 2. (A) magnesium, Ti (OR) gX _4- g (R
Is a hydrocarbon group, X is halogen, titanium derived from a tetravalent titanium compound represented by 0 ≦ g ≦ 4), a highly stereoregular titanium catalyst component containing halogen and an electron donor as essential components, (B) In the presence of a catalyst formed from an organoaluminum compound catalyst component and (C) an electron donor, the number of carbon atoms is 5 to
A branched α-olephine in the range of 10 and having a branch at the position 3 or higher, or a branched α-olefin and a linear α-olefin having a number of carbon atoms in the range of 2 to 20 in multiple stages. A method of polymerizing or copolymerizing in a polymerization step, wherein the intrinsic viscosity [η] _H measured in decalin at 135 ° C. is 5 to 30 dl in at least one polymerization step.
The amount of the branched α-olefin polymer [I] is in the range of 1/60% by weight of the branched α-olefin polymer composition in the range of 1 / g and generated in the entire polymerization process. Intrinsic viscosity [η] measured in decalin at 135 ℃
_L is 1 to 10 dl / g, [η] _H / [η] _L ratio is in the range of 2 to 30, and 99 to 40% by weight of the branched α-olefin polymer composition produced in the whole polymerization process. By producing a branched α-olefin polymer [II] in the range of 10 ° C., the intrinsic viscosity [η] measured in decalin at 135 ° C. is 1
Melt flow rate measured at 260 ° C with a load of 5 kg Melt flow rate measured at a load of 1 kg at 260 ° C against A process for producing a branched α-olefin polymer composition having a ratio of 10 to 30.