JP2514974B2 - Method for producing branched α-olefin polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a branched α-olefin polymer having a high-order regularity by a high activity and deashing-free polymerization method in a gas phase polymerization method. .

[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 the drawbacks of poor stereoregularity and rigidity, and poor polymerization activity.

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.
No. publication. However, although the branched α-olefin polymer obtained by the method described in the publication is excellent in stereoregularity and rigidity, it is desired to further improve the polymer yield (catalyst efficiency). It was

[Problems to be Solved by the Invention] The present invention has been made by recognizing that the conventional art in the production of a branched α-olefin polymer is in the above situation, and has a high stereoregularity. As a result of diligent studies on a method for producing a branched α-olefin polymer by a high activity and deashing-free polymerization method, (A) highly stereoregular titanium containing magnesium, titanium, halogen and an electron donor as essential components. In the presence of a catalyst formed from the catalyst component, the (B) organoaluminum compound catalyst component, and the (C) electron donor, branching is carried out at a position of 3 to 5 carbon atoms in the range of 5 to 10 carbon atoms. The above object can be achieved by polymerizing or copolymerizing the α-olefin or the branched α-olefin with the linear α-olefin having 2 to 20 carbon atoms by a gas phase polymerization method. Found that, we have reached the present invention.

[Means for Solving Problems] According to the present invention, (1) (A) a high-order ordered titanium catalyst component containing magnesium, tetravalent titanium, halogen and an electron donor as essential components, (B) In the presence of the catalyst formed from the organoaluminum compound catalyst component and (C) the electron donor, the number of carbon atoms is 5 to
A branched α-olefin having a range of 10 and having a branch at the position 3 or higher, or a branched α-olefin and a linear α-olefin having 2 to 20 carbon atoms are Polymerizing or copolymerizing by a single-stage polymerization or copolymerization process under the condition that the branched α-olefin forms a gas phase, (a) the number of carbon atoms is in the range of 5 to 10, and Three
80 to 100 mol% of repeating units derived from a branched α-olefin having a branch at position 6 or higher, and (b) a straight chain α- having 2 to 20 carbon atoms.
A process for producing a branched α-olefin polymer comprising 0 to 20 mol% of repeating units derived from an olefin is provided.

The highly stereoregular titanium catalyst component (A) used in the present invention contains magnesium, titanium, halogen and an electron donor 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) is preferably about 4 to about 100, more preferably about 6 to about 40, electron donor / titanium (mol). Ratio) is preferably about 0.2 to about 1
It is preferably in the range of 0, more preferably about 0.4 to about 6. Further, its specific surface area is preferably about 3 m ² / g or more, more preferably about 40 m ² / g or more, and further preferably about
100 m ² / g to about 8000 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 200μ, more preferably about 5 to about 100μ and a geometric standard deviation σg of the particle size distribution of preferably less than 2.1. It is 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. The preparation can be performed 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-50-1083
No. 85, No. 50-126590, No. 51-20297, No. 51-28189
No. 51, No. 51-64586, No. 51-92885, No. 51-136625,
52-87489, 52-100596, 52-14788, 52
-104593, 53-2580, 53-40093, 53-430
No. 94, No. 55-135102, No. 55-135103, No. 56-811
No. 56-11908, No. 56-18606, No. 58-83006,
58-138705, 58-138706, 58-138707,
58-138708, 58-138709, 58-138710, 58
It can be produced according to the method disclosed in, for example, No. 138715.

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

(1) A magnesium compound or a complex compound of a magnesium compound and an electron donor is crushed with or without crushing an electron donor in the presence or absence of a crushing aid or the like, and an electron donor and / or The solid obtained by pretreatment with a reaction aid such as an organoaluminum 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.

These titanium catalyst components (A) of (1) to (5)
In the preparation method of 1, when at least one of the magnesium compound and the titanium compound contains a halogen atom, it is not always necessary to use a halogenating agent such as a halogen-containing silicon compound or a halogenated organoaluminum compound. However, when neither the magnesium compound nor the titanium compound contains a halogen atom, the above halogenating agent is used.

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

Highly stereoregular titanium catalyst component (A) used in the present invention
Among the electron donors that are essential components in the above, diesters include dicarboxylic acid esters in which two carboxyl groups are bonded to one carbon atom or carboxyl groups in two adjacent carbon atoms, respectively. It is preferably a bound dicarboxylic acid ester. 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, itaconic acid; maleic acid; substituted maleic acid such as citraconic acid and dimethylmaleic acid; cyclopentane-1,1-dicarboxylic acid, cyclopentane-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, 1-
Alicyclic dicarboxylic acids such as 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-
A heterocyclic dicarboxylic acid such as dicarboxylic acid, pyrrole-2,3-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, indole-2,3-dicarboxylic acid; It can be illustrated.

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. An oxygen-containing electron donor such as the above, a nitrogen-containing electron donor such as ammonia, amine, nitrile, and isocyanate can be used.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
1 to 1 carbon atoms such as isopropylbenzyl alcohol
18 alcohols; phenols, cresols, xylenols, ethylphenols, propylphenols, nonylphenols, cumylphenols, naphthols and the like having 6 to 20 carbon atoms which may have a lower alkyl group; acetone, methyl ethyl ketone, methyl isobutyl Ketones, acetophenones, benzophenones and other ketones having 3 to 15 carbon atoms; 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 P—O—O bond such as trimethyl phosphite and triethyl phosphite; And alkoxysilanes such as ethyl acid and diphenyldimethoxysilane.
Two or more 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,
After completion of the reaction, the product can be purified by thoroughly washing it with a liquid inert hydrocarbon. Inert liquid hydrocarbons used for this purpose include n-pentane, isopentane, n
-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 preparing the highly stereoregular titanium catalyst component (A) is a magnesium compound with or without reducing ability. Examples of the former are magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as 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 can be used, for example, in the form of a complex compound with organic aluminum or the like, and may be in a liquid state or a solid state. On the other hand, examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, magnesium ethoxy chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, Alkoxy magnesium halides such as octoxy magnesium chloride; aryloxy magnesium halides such as phenoxy magnesium chloride, methyl phenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkoxy magnesium; aryloxy such as phenoxy magnesium, dimethyl phenoxy magnesium Magnesium; magnesium laurate, and the like can be exemplified carboxylates of magnesium such as magnesium stearate. Further, the magnesium compound having no reducing ability, those derived from the magnesium compound having a reducing ability described above,
It may be 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, a mixture of two or more of these compounds may be used. 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).
R) gX _4-g (R is a hydrocarbon group, X is a halogen, 0 ≦ g ≦
A tetravalent titanium compound represented by 4) is suitable. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄
H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Tri (OisoC ₄ H ₉ ) Br ₃ and other trihalogenated alkoxytyranes; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (O
_{C 2 H 5) 2 Cl 2} , Ti (On-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl,
_{Ti (OC 2 H 5) 3} Cl, Ti (On-C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 Br
Trialkoxy titanium monohalogenated titanium; Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (On-C 4 H 9) such as tetra-alkoxy titanium such as ₄ can be exemplified. 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, a magnesium compound and an electron donor to be supported, and other electron donors which may be optionally used, for example, alcohol, phenol, monocarboxylic acid ester and the like. The amount of the silicon compound, the aluminum compound, etc. used varies depending on the preparation method and cannot be specified unconditionally, but for example, about 0.1 to about 10 mol of the electron donor to be supported and about 0.0 mol of the titanium compound per mol of the magnesium compound.
The ratio can be about 5 to about 1000 mol.

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

Examples of the component (B) include (i) an organoaluminum compound having at least one Al-carbon bond in the molecule,
For example, the general formula R ¹ mAl (OR ₂ ) nHpXq (wherein R ¹ and R ² are hydrocarbon groups containing carbon atoms, usually 1 to 15, preferably 1 to 4 and may be the same or different from each other. X is halogen, m is 0 <m ≦
3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦ q <3
Of the formula ( ¹ ) and (m + n + p + q = 3), and (ii) the general formula M ¹ AlR ¹ ₄ (where M ¹ is Li, Na, K, and R ¹ is the same as above). ) And a complex alkylated product of a Group I metal and aluminum.

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 an integer 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 <), and 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). Trialkylaluminums such as triethylaluminum and tributylaluminum; Tolualkenylaluminums such as triisoprenylaluminum; Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide. In addition to alkylaluminum sesquialkoxide, partially alkoxylated alkylaluminum having an average composition represented by ▲ R ¹ _2.5 ▼ Al (OR ² ) _0.5 ; diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, etc. Dialkyl aluminum halides; Ethyl aluminum sesquichloride, Butyl aluminum sesquichloride Alkyl aluminum sesquihalides such as chloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum hydride; Dialkylaluminum hydrides such as dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminium dihydride, etc. Other partially hydrogenated alkylaluminums; ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, Partial alkoxylation such as ethyl aluminum ethoxy bromide and Gen alkylaluminum.

Examples of the compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ ,
LiAl (C ₇ 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. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (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 aluminums described above 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 of metals belonging to Groups 1 to IV of the periodic table, and For example, salt.
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. In particular, 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 above 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, vinyltributoxysilane, 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.

Further, the amine having a large steric hindrance includes 2,2,6,6
-Tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, or derivatives thereof, tetramethylmethylenediamine and the like are particularly preferred.

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 gas phase polymerization method.

In the present invention, preliminary polymerization may be carried out before carrying out the polymerization or copolymerization by the gas phase polymerization method.

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, a hydrocarbon formed by using a catalyst formed from the component (A), at least a part of the component (B) and at least a part of the component (C) is used. In the medium, the branched α-olefins are added in an amount of about 1 to about 10 per 1 mmol of titanium in the component (A).
It is preferable to carry out the polymerization or copolymerization in the presence of a branched α-olefin prepolymerization catalyst formed by prepolymerizing at a rate of 00 g. By carrying out this prepolymerization treatment, a powder polymer having a high density can be obtained in the gas phase polymerization to be carried out later, so that the powder property is also good, and the polymer yield per unit catalyst is also large and the stereoregularity is high. There is also an advantage that the functional 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. Therefore, as the polymerization medium, an inert hydrocarbon, for example, butane, pentane, hexane, heptane, octane, decane, dodecane, an aliphatic hydrocarbon such as kerosene, cyclopentane, an alicyclic hydrocarbon such as cyclohexane is used. preferable.

In the pre-polymerization, for example, the titanium catalyst component (A) is converted into titanium atom per hydrocarbon medium of about 0.
5 to about 100 millimoles, particularly about 1 to about 10 millimoles, the organoaluminum compound catalyst component (B) is 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 produced prepolymer does not dissolve in the hydrocarbon medium, and although it varies depending on the kind of the hydrocarbon medium, for example, about -20 to about + 70 ° C,
A preferred range is from about 0 ° to about 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 gas phase 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 polymerized by a gas phase method using a catalyst obtained by prepolymerizing α-olefin as described above.

The prepolymerized catalyst exhibits a greater polymerization activity in the gas phase polymerization process of the present invention, and the stereoregularity of the obtained branched α-olefin polymer is improved.

In the polymerization step of the present invention, the catalyst is used in an inert solvent or in the absence of a solvent and has 5 to 10 carbon atoms.
A branched α-olefin having a branch in the range of 10 and at the position 3 or more, or a branched α-olefin and a linear α-olefin having a carbon number of 2 to 20. Polymerization or copolymerization is carried out under the condition that α-olefin forms a gas phase to form a branched α-olefin polymer. In the gas phase polymerization step, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 30 dl / g, preferably 0.7 to 20 dl / g, more preferably 1 to 10 dl / g.
To produce a branched α-olefin polymer in the range.

The repeating unit (A) derived from the branched α-olefin in the branched α-olefin polymer produced in the polymerization step is 80 to 100 mol% and the repeating unit derived from the linear α-olefin ( Polymerization or copolymerization is carried out in such a proportion that B) is 0 to 20 mol%.

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

The concentration of each catalyst component in the polymerization product liquid in the polymerization vessel in the gas phase polymerization step is about 0.001 to about 0.1 mmol, preferably about 0.001 to about 0.1 mmol of the treated catalyst in terms of titanium atom per polymerization volume. It is preferably adjusted to about 0.05 millimol and the Al / Ti (atomic ratio) of the polymerization system is about 1 to about 1000, preferably about 2 to about 1000. Therefore, the organoaluminum compound catalyst component (B) can be additionally used if necessary. In the polymerization system, hydrogen is added for the purpose of controlling molecular weight, molecular weight distribution, etc.
An electron donor, a halogenated hydrocarbon and the like may coexist.

In the method of the present invention, the temperature of the gas phase polymerization is within a temperature range in which the gas phase polymerization is possible, and is about 0 ° C. or higher, more preferably about
A range of 30 to about 200 ° C is preferred. Further, the polymerization pressure is recommended to be, for example, atmospheric pressure to about 200 kg / cm ² , and particularly atmospheric pressure to about 100 kg / cm ² . Then, it is preferable to set the polymerization time such that the amount of the polymer produced is about 5000 g or more, particularly about 10,000 g or more per 1 mmol of titanium in the titanium catalyst component.

In the gas phase polymerization step, polymerization or copolymerization of the branched α-olefin or the branched α-olefin with the linear α-olefin is carried out in the absence or presence of an inert medium. It is particularly preferred to carry out in the presence of a medium amount of branched .alpha.-olefin. As the inert medium, those specifically exemplified below can be used.

The number of carbon atoms which can be used in the present invention is 5 to
3-methyl-1-pentene as a branched α-olefin in the range of 10 and having a branch at the position 3 or higher,
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
-Pentene, 3-ethyl-pentene, vinylcyclohexane can be mentioned. 4-Methyl-1-pentene is preferred.

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

Examples of the inert medium that can be used in the gas phase polymerization step for forming the branched α-olefin polymer include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, and kerosene. Alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloroethane, methylene chloride and chlorobenzene; and mixtures thereof. Of these, the use of aliphatic hydrocarbons is particularly desirable.

[Examples] Next, the method of the present invention will be specifically described with reference to Examples.

Example 1 <Preparation of titanium catalyst component (a)> Beef-free magnesium chloride 4.76 kg (50 mol), decane 25
And 2-ethylhexyl alcohol 23.4 (150mol)
Was heated at 130 ° C for 2 hours to form a uniform solution, 1.11 kg (7.5 mol) of furanic anhydride was added to this solution, and the mixture was stirred and mixed at 130 ° C for an additional 1 hour to give phthalic anhydride. Dissolve in. The homogeneous solution thus obtained was cooled to room temperature, and then titanium tetrachloride 200 (1
(800 mol) is added dropwise to the whole solution over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C over 4 hours, and when it reached 110 ° C, diisobutyl phthalate 2.6
8 (12.5 mol) is added and the mixture is maintained at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, a solid portion was collected by filtration, the solid portion was resuspended in 200 TiCl ₄ , and then the reaction was conducted again 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,
A part of this is dried for the purpose of examining the catalyst composition. The composition of the titanium catalyst component [A] thus obtained is titanium.
3.1 wt%, chlorine 56.0 wt%, magnesium 17.0 wt%
And diisobutyl phthalate were 20.9% by weight.

<Preliminary Polymerization> 20 reactors equipped with a stirrer are charged with 20 n-hexane, 1 mol of triethylaluminum, 200 mol of trimethylmethoxysilane, and 100 mol of titanium catalyst component in terms of titanium atoms. While maintaining the temperature at 25 ° C, 3.0 kg of 4-methyl-1-pentane was added over 30 minutes, and the reaction was continued at 25 ° C for 30 minutes. The reaction was filtered through a glass filter, washed 3 times with a total of 30 n-hexane and suspended in 20 n-hexane. Prepolymerization amount is 1 mg of titanium atom per atom
It was 30 g. Trimethylmethoxysilane was used as the organosilicon compound in the prepolymerization, and diphenyldimethoxysilane was used in the polymerization, and the prepolymerization and the polymerization were performed in the same manner as in Example 1. The results are shown in Table 1.

<Polymerization> Polymerization reaction was carried out using a fluidized bed polymerization reactor having a diameter of 340 mm and a reaction part volume of 65. The fluidized bed polymerization reactor was continuously spray-supplied from a catalyst supply nozzle as a mixture consisting of the prepolymerization catalyst in an amount shown in Table 1 and N ₂ gas of 300 N / H, and triethylaluminum of 100 mmol.
/ H and trimethylmethoxysilane 100mmol / H continuously supplied, 4-methyl-1-pentene at a rate of 1kg / H and hydrogen at a rate of 0.10N / H. A gas phase polymerization reaction was carried out. The temperature during the gas phase polymerization reaction is 100 ° C, the pressure is 2.5 kg / cm ² G, and the gas superficial velocity is 40 c.
The prepolymerization catalyst feed rate was controlled as shown in Table 1 so that the amount of the 4-methyl-1-pentene polymer produced was 1 kg / H. The polymer was withdrawn so that the volume of the reaction part was constant. The gas discharged from the upper part of the reaction bed was cooled to 40 ° C. by a cooler and then circulated in the lower part of the reactor.

Examples 2 and 3 Using the titanium catalyst component prepared in Example 1, prepolymerization was carried out in the same manner as in Example 1 except that the organosilicon compound was changed, and the results are shown in Table 1.

Examples 4 and 5 Polymerization The same fluidized bed polymerization reactor as in Example 1 was used to carry out the polymerization reaction. 1-Hexene or 1-decene as a comonomer was continuously fed to the fluidized bed reactor at a rate of 300 g / H, and other conditions were the same as in Example 1.

 The results are shown in Table 2.

[Brief description of drawings]

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

Claims (1)

(57) [Claims] 1. A highly stereoregular titanium catalyst component containing (A) magnesium, tetravalent titanium, halogen and an electron donor as essential components, (B) an organoaluminum compound catalyst component, and (C) an electron donor. In the presence of the catalyst formed, it has 5 to 5 carbon atoms.
A branched α-olefin having a range of 10 and having a branch at the position 3 or higher, or a branched α-olefin and a linear α-olefin having 2 to 20 carbon atoms are Polymerizing or copolymerizing by a single-stage polymerization or copolymerization process under the condition that the branched α-olefin forms a gas phase, (a) the number of carbon atoms is in the range of 5 to 10, and Three
80 to 100 mol% of repeating units derived from a branched α-olefin having a branch at position 6 or higher, and (b) a straight chain α- having 2 to 20 carbon atoms.
A process for producing a branched α-olefin polymer comprising 0 to 20 mol% of repeating units derived from an olefin.