JP2656573B2 - Catalyst component for α-olefin polymerization - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization. More specifically, the present invention provides a block copolymer mainly composed of a polymer of α-olefins, particularly propylene, using a catalyst obtained by subjecting a specific solid component to a prepolymerization in the presence of a specific organometallic compound. This makes it possible to advantageously produce the coalesced product under industrial conditions under stable polymerization conditions with little by-products.

2. Description of the Related Art Conventionally, in the presence of various types of stereospecific catalysts, a propylene crystalline homopolymer or copolymer (hereinafter, both are sometimes simply referred to as polypropylene) in the former stage.
To produce a rubbery copolymer of propylene by copolymerizing propylene and another α-olefin in the subsequent stage in the co-presence of the polypropylene, thereby maintaining the excellent rigidity of polypropylene and maintaining a low temperature. It is known to obtain compositions with improved impact resistance over time.

As a catalyst for producing such a block copolymer, a titanium trichloride type catalyst has conventionally been used,
Since the catalyst activity is low, a catalyst removal step, that is, a desorption step is required (Japanese Patent Publication Nos. 43-11230 and 44-16668).
No. 44-20612, No. 49-24593, JP-A-48-25781
No. 53-35789).

In recent years, a number of methods using a supported catalyst have been proposed as methods for greatly increasing the activity until the decontacting step becomes unnecessary (JP-A-52-98045, JP-A-53-88049, and JP-A-58-98049).
No. 83016).

The development of such a highly active catalyst has eliminated the decontact step and reduced the amount of by-products derived. However, on the other hand, the molecular weight distribution of the subsequent copolymer is small, so that the molecular weight distribution of the block copolymer is narrowed and the moldability during processing is deteriorated. There have been problems such as a sudden increase in the amount of the substance, an increase in powder adhesion, and an agglomeration or sticking of the polymer to cause an operation trouble.

For the purpose of resolving these problems, a method has been proposed in which an electron-donating compound is added at the start of the second-stage polymerization (JP-A-56-151713, JP-A-60-59139, and JP-A-61-69821).
No. 61-69822, No. 61-69823, No. 63-43915,
No. 63-165417).

However, to the knowledge of the present inventors, all of the molding processability, by-products, and polymer adhesion have not been satisfied.

[Summary of the Invention]

SUMMARY An object of the present invention is to improve the solid catalyst component as a result of improving the solid catalyst component. As a result, a solid catalyst obtained by subjecting a specific fixed component to prepolymerization using a specific organometallic compound is obtained. It is intended to achieve this goal by the use of components.

That is, the α-olefin polymerization catalyst component according to the present invention comprises α component in the presence of component (II) in the solid component (I) comprising the following component (A) and component (B) and optionally further component (C). Contacting the olefin, the α
The olefin is present in an amount of from 0.01 to 1 gram per solid component (I);
It is obtained by polymerizing 100 grams.

Solid Component (I) Component (A) A solid component essentially containing tetravalent titanium, magnesium and halogen.

Component (B) R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ is a branched carbonized carbon atom in which the carbon atom adjacent to the silicon atom, ie, the α-position carbon atom, is secondary or tertiary) A hydrogen residue, R ² represents a hydrocarbon residue which is the same as or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number satisfying 1 ≦ n ≦ 3.) Component (C) Period Organometallic compounds of Group I to III metals.

Component (II) An organomagnesium or organolithium compound.

Effect By producing a propylene block copolymer using the α-olefin polymerization catalyst component according to the present invention, it is possible to obtain a copolymer having high rigidity and high impact strength with few by-products.

Further, according to the present invention, even when the weight of the rubbery copolymer is increased (for example, 30% by weight or more), the adhesiveness of the polymer particles is small, and the operation trouble which has been conventionally regarded as a problem is solved. Can be solved.

[Specific description of the invention]

Solid Component I The solid component I of the present invention comprises the specific component (A) and the component (B), and optionally further comprises the component (C). Here, "consisting of" does not mean that the components are only those indicated (ie, (A) and (B) or components (A), (B) and (C)). , As long as the improvement effect by undergoing prepolymerization in the presence of component II is not impaired,
It means that additional components (eg, titanium halide) may be included.

Although a polymer having sufficient activity, bulk density and stereoregularity can be obtained by combining the components (A) and (B), if the physical properties are insufficient, the component (C) is further used. You can see improvements.

Component (A) The component (A) is a solid component containing tetravalent titanium, magnesium and halogen as essential components. Here, "contains as an essential component" means that it may contain other suitable elements in addition to the three components listed,
It indicates that each of these elements may be present as any purposeful compound, and that these elements may be present as interconnected.

Known solid components can be used. For example, JP-A-53-45688, JP-A-54-3894, and JP-A-54-31092.
No. 54-39483, No. 54-94591, No. 54-118484,
No. 54-131589, No. 55-75411, No. 55-90510, No. 55
-90511, 55-127405, 55-147507, 55-1
No. 55003, No. 56-18609, No. 56-70005, No. 56-72001
Nos. 56-86905, 56-90807, 56-155206,
No. 57-3803, No. 57-34103, No. 57-92007, No. 57-
No. 121003, No. 58-5309, No. 58-5310, No. 58-531
No. 58-8706, No. 58-27732, No. 58-32604, No.
58-32605, 58-67703, 58-117206, 58-
127708, 58-183708, 58-183709, 59-14
Nos. 9905 and 59-149906 are used.

Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate. Among these magnesium compounds, magnesium halide is preferred.

The titanium compound serving as a titanium source is represented by the general formula Ti (OR
^{4) _4-n} X _n (where R ⁴ is a hydrocarbon residue, preferably of the order of 1 to 10 carbon atoms, X is a halogen,
n shows the number of 0 <= n <= 4. )). Specific _{examples, TiCl 4, TiBr 4, Ti} (OC 2 H 5) Cl 3, Ti (OC 2 H 5) 2 Cl 2, Ti (OC 2 H 5) 3 Cl, Ti (O-iC 3 H 7 _{) Cl 3, Ti (O-} nC 4 H 9) Cl 3, Ti (O-nC 4 H 9) 2 Cl 2, Ti (OC 2 H 5) Br 3, Ti (CO 2 H 5) (OC 4 H _{9) 2 Cl, Ti (O} -nC 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-iC 4 H 9) 2 Cl 2, Ti (OC 5 H 11) Cl _{3, Ti (OC 6 H 13} ) Cl 3, Ti (OC 2 H 5) 4, Ti (O-nC 3 H 7) 4, Ti (O-nC 4 H 9) 4, Ti (O-iC 4 H ₉ ) ₄ , Ti (O-nC ₆ H ₁₃ ) ₄ , Ti (O-nC ₈ H ₁₇ ) ₄ , Ti [OCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] _{4 and the} like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (where X ′ represents halogen) can also be used. Specific _{examples, TiCl 4 · CH 3 COC 2} H 5, TiCl 4 · CH 3 CO 2 C 2 H 5, TiCl 4 · C 6 H 5 NO 2, TiCl 4 · CH 3 COCl, TiCl 4 · C 6 H _{5 COCl, TiCl 4 · C 6} H 5 COCl, TiCl 4 · C 6 H 5 CO 2 C 2 H 5, TiCl 4 · ClCOC 2 H 5, TiCl 4 · C 4 H 4 O and the like.

Among these titanium compounds, preferred are TiCl
₄ , Ti (OEt) ₄ , Ti (OBu) ₄ , Ti (OBu) Cl _{3 and the} like.

The halogen source is magnesium and / or
It is usually supplied from a halogen compound of titanium, but it can also be supplied from a known halogenating agent such as a halide of aluminum, a halide of silicon, and a halide of phosphorus.

The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

The solid component used in the present invention includes SiCl
_4, CH ₃ SiCl _3, silicon compounds such as methylhydrodiene _{polysiloxane, Al (OiC 3 H 7)} 3, AlCl 3, AlBr 3, Al (OC 2 H 5) 3, Al (OCH 3) , such as ₂ Cl Aluminum compound, B (OC ₆ H ₅ ) ₃
It is also possible to use other components such as a boron compound, etc., and these may remain in the solid component as components such as silicon, aluminum, and iodine.

Furthermore, when producing this solid component, it can also be produced using an electron donor as a so-called internal donor.

Examples of electron donors (internal donors) that can be used for producing the solid component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acids. Examples thereof include oxygen-containing electron donors such as anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

More specifically, (a) a compound having 1 carbon atom such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol;
To 18 alcohols, (b) phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethyl phenol, propyl phenol, cumyl phenol, nonyl phenol, naphthol, (c) acetone C3-C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; (d) C2-C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; (E) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, ethyl acetate cellosolve, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, stearyl Ethyl, chloroacetic acid methyl,
Ethyl dichloroacetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, ethyl benzoate cellosolve, propyl benzoate, butyl benzoate, octyl benzoate,
Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, Diheptyl phthalate,
γ-butyrolactone, α-valerolactone, coumarin,
Organic acid esters having 2 to 20 carbon atoms, such as phthalide and ethylene carbonate, and (f) silicates or silanes such as ethyl silicate, butyl silicate, phenyltriethoxysilane, diphenyldimethoxysilane, and tert-butylmethyldimethoxysilane Silicon halides such as (g) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, phthaloyl isochloride and the like;
(H) Ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; (ii) acid amides such as acetic amide, benzoic amide and toluic amide Kind,
(Nu) methylamine, ethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
Examples thereof include amines such as aniline, pyridine, picoline, and tetramethylethylenediamine; and nitriles such as (ル) acetonitrile, benzonitrile, and trinitrile. Two or more of these electron donors can be used. Among these, preferred are organic acid esters, acid halides and silicon compounds, and particularly preferred are ethyl acetate cellosolve, phthalic esters, phthalic halides and organic alkoxysilicons.

The use amount of each of the above components can be arbitrary as long as the effects of the present invention are recognized, but generally, the following ranges are preferable.

The amount of the titanium compound used is preferably in the range of 1 × 10 ^{−4 to} 1000, and more preferably in the range of 0.01 to 10, in terms of a molar ratio to the amount of the magnesium compound used. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio to the amount of magnesium used, regardless of whether or not the titanium compound and / or the magnesium compound contains halogen. ^It is preferably in the range of ^{-2 to} 1000, and more preferably in the range of 0.1 to 100. The amount of the silicon, aluminum and boron compounds used as the optional components is preferably in the range of 1 × 10 ^{−3 to} 100, more preferably 0.01 to 1, in a molar ratio with respect to the amount of the magnesium compound. Is within.

The amount of the electron donating compound used is preferably in the range of 1 × 10 ⁻³ to 10 and more preferably in the range of 0.01 to 5 in terms of a molar ratio with respect to the amount of the magnesium compound.

The component (A) is produced, for example, by the following production method using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor.

(A) A method in which a magnesium halide is brought into contact with an electron donor, if necessary, and a titanium-containing compound.

(B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, and a titanium-halogen-containing compound are brought into contact therewith.

(C) A method of contacting a titanium halide and / or a silicon halide with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, a compound represented by the following formula is suitable.

(Where R represents a hydrocarbon residue having about 1 to 10 carbon atoms, and n represents a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes). Empolysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, cyclohexylhydrogenpolysiloxane , Etc. are preferred.

(D) A method in which a magnesium compound is dissolved in a titanium tetraalkoxide and an electron donor, and the solid component precipitated with a halogenating agent or a titanium halide compound is brought into contact with the titanium compound.

(E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, and the like, and then, if necessary, contacted with an electron donor and a titanium compound.

(F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor.

Component (B) Component (B) is a compound represented by the general formula R ¹ R ² _3- nSi (OR ³ ) _n (where R ¹ is a carbon atom adjacent to a silicon atom, ie, α
- position carbon atoms, the branched chain hydrocarbon residue which is but secondary or tertiary, the R ² is R ¹ identical or different hydrocarbon residues, R ³ is a hydrocarbon residue, n represents 1 ≦ n ≦ 3, respectively).

Here, R ¹ is preferably an alkyl group, a cycloalkyl group or an aryl group (for example, a phenyl group or a methyl-substituted phenyl group) from a carbon atom adjacent to a silicon atom. In particular, those having a tertiary carbon atom bonded to a silicon atom are preferred. The carbon number of R ¹ is usually 3 to 20, preferably 4 to 10.

R ² is usually a branched or straight-chain aliphatic hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms. R ³ is usually an aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group having 1 to 4 carbon atoms.

Specific examples of the silicon compound as the component (B) are as follows.

(CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H _{5) 2, (C 2 H} 5) 3 CSi (CH 3) (OCH 3) 2, (CH 3) (C 2 H 5) CHSi (CH 3) (OCH 3) 2, (C 2 H 5) ( CH ₃ ) ₂ CSi (CH ₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (OCH ₃ ) _{3 , (CH 3) 3 CSi (} OC 2 H 5) 3, (C 2 H 5) 3 CSi (OC 2 H 5) 3, (CH 3) (C 2 H 5) CHSi (OCH 3), (C 2 H ₅ ) (CH ₃ ) ₂ CSi (OCH ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OC ₂ H ₅ ) ₃ , Component (C) Component (C) is an organometallic compound of a metal belonging to Groups I to III of the periodic table. As the metal, lithium, sodium,
Potassium, magnesium, zinc and aluminum are typical. The organic group to be directly connected to these metals to form an organometallic compound is an alkyl group (about 1 to 10 carbon atoms).
And phenyl or lower alkyl substituted phenyl groups are typical. The valence of these metals must be at least one of which must be filled with such organic groups, while the remaining valences are of other groups, for example alkoxy groups (1 carbon atoms).
To about 10), and may be filled with a halogen atom or the like.

Specific examples of such an organometallic compound include organic lithium compounds such as methyllithium, n-butyllithium, and tert-butyllithium, organic zinc compounds such as diethylzinc and di-n-butylzinc, dibutylmagnesium, and butyl. Examples thereof include organic magnesium compounds such as ethyl magnesium and butyl magnesium bromide, and organic aluminum compounds such as trimethyl aluminum, triethyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, and diethyl aluminum ethoxide. . Of these, organoaluminum compounds are preferred.

Component II Component II is an organolithium or organomagnesium compound. With respect to the groups to be bonded to lithium and magnesium, the statements made above for component (C) apply.

Specific examples of such an organometallic compound include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, diethylmagnesium, and di-n-butyllithium.
-Butylmagnesium, di-n-hexylmagnesium,
Examples thereof include butylethylmagnesium, hexylethylmagnesium, butylmagnesium bromide, tert-butylmagnesium bromide, and n-butylmagnesium ethoxide.

Prepolymerization The solid component (I) and the component (II) are contacted with an α-olefin, and the α-olefin is polymerized in an amount of 0.01 to 100 g per 1 g of the solid component (I).
An olefin polymerization catalyst component is obtained. As the α-olefin used in this polymerization, that is, prepolymerization, ethylene, propylene, 1-butene, 1-hexene, 1-octene, butadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methylpentene -1,3-methylbutene-
1, styrene, p-methylstyrene, divinylbenzene and the like are used. Further, these olefins may be used in a plurality of steps or coexistence. The temperature during the prepolymerization is arbitrary, but is preferably from -20 ° C to 70 ° C, more preferably from 0 ° C to 50 ° C.

The quantitative ratio of the solid component (I) to the component (II) is arbitrary,
Preferably, the component (II) is used in an amount of 0.01 to 100 times, more preferably 0.1 to 100 times, based on 1 mol of titanium in the solid component (I).
Use 10-fold molar.

The prepolymerization is generally carried out in an inert solvent, but may be carried out in a liquid monomer or a gaseous monomer. It is also possible to coexist with hydrogen for controlling the molecular weight.

Utilization of Catalyst Component / Olefin Polymerization Catalyst Formation The solid catalyst component according to the present invention described above provides a useful catalyst for α-olefin polymerization by combining it with an organoaluminum compound as a polymerization activator.

As the organic aluminum compound, those known as those used for Ziegler-Natta type catalysts, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide And methylalumoxane. It is also possible to use a combination of two or more of these.

Olefin Polymerization While such catalysts can be widely used for the polymerization of α-olefins, it is the block copolymerization of propylene that can particularly benefit from the catalyst components of the present invention.

Block copolymerization of propylene is known, and the polymerization step comprises at least two stages, a first stage polymerization and a second stage polymerization.

(Pre-Stage Polymerization) In the pre-stage polymerization, propylene alone or a propylene / ethylene mixture is supplied to a polymerization system having the above-mentioned catalyst and polymerized in one or more stages to produce a propylene homopolymer or ethylene content of 7% by weight or less, preferably 0.5% by weight or less of a propylene / ethylene copolymer
This is a step of forming an amount corresponding to about 95% by weight, preferably 50 to 90% by weight.

If the ethylene content in the propylene / ethylene copolymer exceeds 7% by weight in the first-stage polymerization, the bulk density of the final copolymer decreases, and the amount of by-products of the low-crystalline polymer greatly increases. On the other hand, when the polymerization ratio is less than the lower limit of the above range, the amount of by-product of the low crystalline polymer also increases. On the other hand, when the polymerization ratio exceeds the upper limit of the above range, the effect of improving the impact resistance, which is the purpose of the block copolymer, does not appear, and the effect of improving the spiral flow, which is an effect unique to the catalyst component of the present invention, does not appear. .

The polymerization temperature of the first-stage polymerization is 30 to 95 ° C, preferably 50 to 85 ° C.
° C., a degree, polymerization pressure is usually in the range of 1~50kg / cm ² G. In the first-stage polymerization, it is preferable to control the MFR using a molecular weight modifier such as hydrogen to increase the melt fluidity of the final copolymer.

(Second-stage polymerization) The second-stage polymerization is performed after the first-stage polymerization.
The ethylene content is further introduced to increase the ethylene content to 20 to 10
0% by weight, preferably 30 to 100% by weight, more preferably 30% by weight.
This is a step in which about 70% by weight of a propylene / ethylene copolymer is obtained in one or more stages. In this step, it is desirable to form an amount corresponding to 5 to 70% by weight, preferably 10 to 50% by weight of the total polymer amount.

In the latter stage polymerization, other comonomers may coexist.
For example, α-olefins such as 1-butene, 1-pentene and 1-hexene can be used.

The polymerization temperature of the second-stage polymerization is 30 to 90 ° C., preferably 50 to 80 ° C.
Degrees Celsius. The polymerization pressure is usually in the range of 1 to 50 kg / cm ² G.

When moving from the first-stage polymerization to the second-stage polymerization, it is preferable to purge the propylene gas or the propylene / ethylene mixed gas and the hydrogen gas before moving to the next step. Further, if necessary, a catalyst, particularly an organoaluminum compound, can be added.

In the second-stage polymerization, the molecular weight regulator may or may not be used depending on the purpose.

(Polymerization mode) The method for producing such a propylene block copolymer is as follows.
It can be carried out by any of batch, continuous and semi-batch methods. At this time, a method in which polymerization is performed in an inert hydrocarbon solvent such as heptane, a method in which polymerization is performed using the monomer itself as a medium, and a method in which polymerization is performed in a gaseous monomer without using a medium Further, there is a method of performing polymerization by combining these.

Further, for the purpose of increasing the molecular weight of the rubber to be produced in the latter polymerization step, an electron donating compound or an organometallic compound can be added during the latter polymerization.

Experimental Examples Example 1 [Production of solid component (I)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then MgCl ₂ was added thereto.
0.4 mol and 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours.
The resulting solid component was washed with n-heptane.

Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Subsequently, 0.4 ml of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane. Then, phthalic acid chloride was added to 25 ml of n-heptane.
0.024 mol was mixed, introduced into the flask at 70 ° C./30 minutes, and reacted at 90 ° C. for 1 hour.

After the completion of the reaction, the resultant was washed with n-heptane. Then SiCl ₄
20 ml was introduced and reacted at 80 ° C. for 6 hours.
After the completion of the reaction, the resultant was sufficiently washed with n-heptane. This (component (A)) had a titanium content of 1.21% by weight.

50 ml of fully purified n-heptane is introduced into a flask sufficiently purged with nitrogen, 5 g of the above-obtained component is introduced, and then (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ )
₂ Introduce 1.6 ml of (Component (B)) and then add TiC
l ₄ 0.52 ml addition of triethylaluminum (component (C)) 3.0 grams respectively introduced, 2 at 30 ° C.
Contact for an hour. After the contact was completed, the solid was sufficiently washed with n-heptane to obtain a solid component (I). The titanium content in solid component (I) was 3.64 weight percent.

[Preliminary polymerization / Production of polymerization catalyst component]

400 ml of dehydrated and deoxygenated n-heptane was placed in a 1.5 liter stirred autoclave sufficiently purged with nitrogen.
After the system was cooled to 15 ° C., 0.4 g of n-butyllithium as the component (II) and the solid component (I) were added.
4 g was introduced, and propylene was fed at a rate of 8 g / Hr for 0.5 hour to perform prepolymerization. After completion of the propylene feed, residual pressure polymerization was performed for 10 minutes. After the completion, the resultant was washed twice with n-heptane to obtain a desired polymerization catalyst component. On 4 g of this polymerization catalyst component, 3.72 g of polymer was obtained, and thus 7.72 g of the polymerization catalyst component of the present invention was obtained.

(Propylene copolymerization)

After sufficiently replacing the inside of a 1.5-liter stirred autoclave with propylene, 500 ml of sufficiently dehydrated and deoxygenated n-heptane was introduced, and 20 mg of the above-mentioned polymerization catalyst component (including 39.4 mg polymer), triethyl aluminum 50 milligrams were introduced under a propylene atmosphere.

In the first-stage polymerization, after introducing 270 ml of hydrogen, the temperature was raised to 70 ° C., and propylene was introduced at a constant rate of 0.917 g / min. After 3 hours, the introduction of propylene was stopped, and the polymerization was stopped.
Continued at 75 ° C. When the pressure reached ² kgcm ² gauge, 1/10 sampling was performed as an intermediate sample. Further, after purging the gas phase to 0.2 kg / cm ² gauge,
33 g / min and ethylene were introduced at a constant rate of 0.200 g / min at 65 ° C. for 1.5 hours.

After the completion of the polymerization, the gas phase was purged, and the slurry was filtered and dried to obtain 162.2 g of a polymer. On the other hand, the filtrate was dried to obtain 3.37 g of a low-crystalline polymer as a by-product. The MFR of the resulting polymer was 5.52 grams / 10 minutes and the bulk density was 0.464 g / cc. The MFR of the polymer obtained by drying the intermediate sample was 18.9 g / 10 minutes. The angle of repose of the powder polymer was 32.7 degrees. The yield of this polymerization is 9200 g / polymer / g-solid catalyst.

Example 2 [Production of a catalyst component for polymerization] The same operation as in Example 1 was carried out except that the amount of n-butyllithium used as the component (III) in Example 1 was changed to 0.24 g. On 4 g of the obtained catalyst component for polymerization, 4.12 g of the polymer was obtained, and thus 8.12 g of the catalyst component of the present invention was obtained.

(Propylene copolymerization)

Polymerization was carried out under the same conditions as in Example 1 except that the polymerization catalyst was changed. The results were as shown in Table 1.

Example 3 17 mg of the catalyst component for polymerization obtained in Example 2 (3 mg
Polymerization was carried out under the same conditions as in Example 1 except that 4.5 mg of polymer), 125 mg of triethylaluminum and 200 ml of hydrogen were used. The results were as shown in Table 1.

Comparative Example 1 [Production of Catalyst Component for Polymerization] Using 4 g of the solid component (I) obtained in Example 1,
Preliminary polymerization was carried out under the same conditions as in Example 1 except that 0.6 g of triethylaluminum was used instead of component (II). On 4 g of the obtained catalyst component for polymerization, 4.2 g of the polymer was obtained, and thus 8.2 g of the catalyst component of the present invention was obtained.

(Propylene copolymerization)

Polymerization was carried out under the same conditions as in Example 1 except that the catalyst component for polymerization was 17 mg (containing 34.9 mg of polymer), 125 mg of triethylaluminum and 200 ml of hydrogen. The results were as shown in Table 1.

Examples 4, 5, 6, 7 and Comparative Example 2 [Preparation of Catalyst Component for Polymerization] Except that 4 g of the solid component I of Example 1 was used and the compounds shown in Table 2 were used as the component II, all of the examples were used. Preliminary polymerization was performed under the same conditions as in Example 1. The results were as shown in Table-2.

(Propylene copolymerization)

Polymerization was carried out under the same conditions as in Example 1. The results are shown in Table
As shown in FIG.

Example 8 [Preparation of solid component I] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask sufficiently purged with nitrogen, and then MgCl ₂ was added thereto.
0.4 mol and 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours.
The resulting solid component was washed with n-heptane.

Next, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms. Subsequently, 0.4 ml of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, the resultant was washed with n-heptane.

Then, 0.55 g of diphenylmethanol was dissolved in 25 ml of toluene, introduced into a flask at 50 ° C./30 minutes, reacted at 90 ° C. for 3 hours, and washed with n-heptane after completion of the reaction. Then add 25ml of TiCl ₄ and 90 ℃
For 2 hours. After removing the supernatant, additional TiCl
25 ml of ₄ was added and reacted at 90 ° C. for 2 hours. After the completion of the reaction, the resultant was washed with n-heptane. After the washing was completed, 0.14 ml (1 mM) of 2-ethoxyethyl acetate was added, and reacted at 90 ° C. for 2 hours. After completion of the reaction, the resultant was washed with heptane.
Then, 0.43 ml of TiCl ₄ and (CH ₃ ) ₃ CSi (C
1.06 ml of H ₃ ) (OCH ₃ ) ₂ and then 2.4 g of triethylaluminum were introduced at 30 ° C., and the reaction was carried out for 2 hours. After completion of the reaction, heptane washing was performed to obtain a target solid component (I). The titanium content in the solid component (I) was 4.36% by weight.

(Production of catalyst component for polymerization)

Preliminary polymerization was carried out under the same conditions as in Example 1 except that 4 g of the solid component was used. There were 4.00 g of the polymer on 4 g of the obtained catalyst component for polymerization, and a total of 8.0 g was recovered.

(Propylene copolymerization)

Polymerization was carried out under the same conditions as in Example 1 except that the above-mentioned polymerization catalyst component was used. The results were as shown in Table-3.

Example 9 introduces n- heptane 200 ml of dehydrated and deoxygenated was thoroughly purged with nitrogen flask Production of the solid component (I)], then MgCl ₂
0.4 mol and 0.8 mol of Ti (O-nC ₄ H ₉ ) ₄ were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (of 20 centistokes) was introduced and reacted for 3 hours.
The resulting solid component was washed with n-heptane.

Then, 50 ml of n-heptane purified in the same manner as above was introduced into a flask sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atoms.

Next, 0.96 mol of SiCl ₄ was fed all at once at 15 ° C., and reacted at 15 ° C. for 2 hours. Next, the whole was heated to 90 ° C. and reacted for further 2 hours. After the completion of the reaction, the resultant was washed with n-heptane. Next, 0.06 mol of tert-butylmethyldimethoxysilane was fed and reacted at 15 ° C. for 1 hour. After completion of the reaction, n-heptane washing was performed to obtain a solid component (I). This solid component contained 4.88% by weight of titanium and 15.4% by weight of tert-butylmethyldimethoxysilane.

(Production of catalyst component for polymerization)

400 ml of dehydrated and deoxygenated n-heptane was placed in a 1.5 liter stirred autoclave sufficiently purged with nitrogen.
After the system was cooled to 15 ° C., 0.8 g of n-butyllithium as the component (II) and 12 g of the solid component (I) were introduced, and propylene was fed at 16 g / Hr for 0.5 hour. Prepolymerization was performed. After completion of the propylene feed, residual pressure polymerization was performed for 10 minutes. After the completion, the resultant was washed twice with n-heptane to obtain a desired polymerization catalyst component. There were 7.2 grams of polymer on 12 grams of this polymerization catalyst component, for a total of 19.2 grams.

(Propylene copolymerization)

Polymerization was carried out under the same conditions as in Example 1 except that 25 milligrams of the above-mentioned polymerization catalyst component (containing 40 milligrams of polymer), 125 milligrams of triethylaluminum, and 200 milliliters of hydrogen were introduced. The results were as shown in Table-3.

In these tables, the estimated MFR of the EPR unit is obtained by the following equation.

A is the amount of the produced polymer, a1 is the amount of the _first- stage polymerization (estimated from the amount of the feed monomer, the amount of the solvent dissolved, and the remaining amount of the gas phase)
a ₂ is the second-stage polymerization amount (estimated), MFR-P is of the produced polymer MF
R and MFR-1 indicate the MFR of the intermediate sample after completion of the previous stage, respectively.

[Brief description of the drawings]

FIG. 1 is to assist in understanding the technical contents of the present invention relating to the Ziegler catalyst.

Claims (1)

(57) [Claims] 1. An α-olefin is brought into contact with the following component (A), component (B) and, if necessary, fixed component (I) comprising component (C) in the presence of component (II). -Olefin is added to 0.1 g per 1 gram of fixed component (I).
Characterized by being obtained by polymerization of from 01 to 100 grams, α-
Catalyst component for olefin polymerization. Solid Component (I) Component (A) A solid component essentially containing tetravalent titanium, magnesium and halogen. Component (B) R ¹ R ² _3-n Si (OR ³ ) _n (where R ¹ is a branched carbonized carbon atom in which the carbon atom adjacent to the silicon atom, ie, the α-position carbon atom, is secondary or tertiary) R ² represents a hydrocarbon residue which is the same as or different from R ¹ , R ³ represents a hydrocarbon residue, and n represents a number satisfying 1 ≦ n ≦ 3. . Component (C) An organometallic compound of a metal of Groups I to III of the periodic table. Component (II) An organomagnesium or organolithium compound.