JP3071477B2 - Olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

The present invention relates to a catalyst for olefin polymerization. More specifically, the present invention provides a catalyst component for olefin polymerization, which is highly active when applied to the polymerization of olefins and enables production of a polymer having a large particle size having high stereoregularity, and The present invention relates to an olefin polymerization catalyst comprising:

[0002]

2. Description of the Related Art Conventionally proposed olefin polymerization catalysts comprising a solid catalyst component containing titanium, magnesium and halogen as essential components and an organoaluminum compound exhibit high activity and high stereoregularity. Due to the insufficient average particle size of the resulting polymer, it was necessary to go through a granulation process at the final stage of the polymerization process. If this granulation process can be omitted, a significant increase in production efficiency can be achieved, so that production costs can be reduced.

[0003] In addition, in the polymerization without using a solvent, when a propylene block copolymer is produced, when the polymerization amount of the rubber component increases, the fluidity often deteriorates due to the adhesion of the polymer particles. It becomes a problem. This problem is considered to be improved if the polymer particles have a sufficient particle size. That this problem is improved means that it is possible to easily produce a block copolymer having a high rubbery copolymer content, which was conventionally considered to be extremely difficult or almost impossible to produce, That's what it means. Therefore, development of a catalyst system having high activity and high stereoregularity that provides polymer particles having a sufficient particle size to achieve the above object is desired.

In general, it is considered that a catalyst having a particle diameter commensurate with the production of a granular polymer having a large particle size is required. In the case of a catalyst containing a magnesium compound and a titanium compound as essential components, as one of the above-described ideas, a method of producing and starting with magnesium-containing particles having a sufficient particle size is known. For example, Japanese Patent Publication No. 61-45643 discloses a method in which a magnesium dihalide compound is melted and sprayed into a desired particle state for granulation.
No. 1 discloses that a melt comprising a magnesium dihalide and an alcohol is emulsified with an inert medium,
There is disclosed a method of cooling and solidifying it to obtain a desired particle state.

[0005] However, these proposals have a large cost burden on equipment and the obtained catalyst has a low activity per catalyst containing magnesium-containing particles having a sufficient particle size, so that it must be improved. There seems to be a point.

[0006] As another method, there is provided a method in which particles other than magnesium dihalide-containing particles to be a carrier having a sufficient particle size are separately prepared in advance, and a catalyst is supported on the particles to produce a catalyst having a desired particle size. And disclosed in, for example, JP-A-1-98604 and JP-A-2-97508. However, these catalysts also seem to have insufficient activity per catalyst including carrier particles.

[0007]

The problem to be solved by the present invention is to provide a solution to the above-mentioned problems in the prior art.

[0008]

[Summary of the Invention] [Summary] The purpose of the present invention is to provide a solution to the above points, and an attempt is made to achieve this object by using a specific catalyst-supporting carrier. Is what you do.

That is, the solid catalyst component for a Ziegler-type catalyst according to the present invention comprises the following components (A ₁ ) and (A ₂ )
Are obtained by contacting with each other.

Component (A ₁ ) The following components (a) and (b)
And (c) a contact product, (a) a pore size distribution measured by a porosimeter in the range of 75 to 10000 angstroms, a pore volume of 0.1 to 2.0 cc / g, and an average pore size. Is from 500 to 5000 angstroms and has a mean particle size of 50 to 3000 μm on a porous polymer carrier by the following formula (I)

[0011]

Embedded image (Where R ¹ is a hydrocarbon residue and n is a number of 2 or more) a component obtained by impregnating a polymer silicon compound having a structure represented by the following formula: (b) magnesium dihalide, (c) titanic acid Esters and / or polytitanates, Component (A ₂ ) A halogen compound of an element of Groups III to VI of the Periodic Table.

Further, the olefin polymerization catalyst according to the present invention is characterized by comprising a contact product of the following components (A) and (B). Component (A) A solid catalyst component for a Ziegler type catalyst obtained by contacting the following components (A ₁ ) and (A ₂ ), Component (A ₁ ) The following components (a), (b) and (c)
(A) the pore size distribution measured by a porosimeter is in the range of 75 to 10000 angstroms, the pore volume is 0.1 to 2.0 cc / g, and the average pore size is 500 to 5000. The following formula (I) is applied to a porous polymer carrier having an average particle diameter of 50 to 3000 μm, which is Angstrom.

[0013]

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(Where R ¹ is a hydrocarbon residue and n is a number of 2 or more) a component obtained by impregnating a polymer silicon compound having a structure represented by the following formula: (b) magnesium dihalide; ) Titanate and / or polytitanate, Component (A ₂ ) Halogen compounds of Group III to VI elements of the Periodic Table, Component (B) Organoaluminum compounds.

<Effect> The catalyst for olefin polymerization of the present invention has an improved catalyst-supporting state by previously impregnating a catalyst-supporting carrier with a polymer silicon compound, and has an activity and a three-dimensional structure per catalyst containing the carrier-supporting particles. A polymer having a sufficient particle size can be obtained without lowering the regular performance, and the problem of the known catalyst can be solved.

These features are extremely advantageous for industrial production and are important as features of the catalyst. The reason why such an effect is exhibited has not yet been elucidated yet, but since the catalyst-supporting porous carrier particles used in the present invention are previously impregnated with the polymer silicon compound, the carrier-supporting carrier particles have This is probably because magnesium dihalide-containing particles are adsorbed or precipitated over the whole.

The polymer having a sufficient particle size obtained by the present invention enables the omission of the granulation process from the post-polymerization treatment step in industrial production, and the rubbery copolymer in the production of the propylene block copolymer. The content ratio of the polymer can be increased.

[Specific description of the invention] [I] Olefin polymerization catalyst The olefin polymerization catalyst according to the present invention comprises a contact product of specific components (A) and (B).
Here, “consisting of” does not mean that the components are only those listed, and does not exclude the coexistence of a third component for the purpose.

<Component (A)> The component (A) of the catalyst of the present invention is a solid catalyst component for a Ziegler-type catalyst obtained by bringing the following components (A ₁ ) and (A ₂ ) into contact.
Here, "obtained by contacting" does not mean that the object is only the indicated one, but the coexistence of other suitable components (eg, optional components (details described later)) Do not eliminate.

<Component (A ₁ )> The component (A ₁ ) is a contact product of the following components (a), (b) and (c).
Details of the components (a) to (c) are as follows.

Component (a) Component (a) is used to prepare a specific compound, that is, a compound of the formula (I), on a porous polymer carrier which satisfies predetermined requirements for pore size distribution, pore volume, average pore size and average particle size. A polymer silicon compound having a structure represented by the following formula:

The porous polymer carrier used for the component (a) has a pore size distribution of 75 to 50 as measured by a porosimeter.
10,000 angstroms, preferably 100-10
2,000 angstroms, with a pore volume of 0.1-2.0 cc / g, preferably 0.5-1.5 cc / g.
g, the average pore size is from 500 to 5000 angstroms, preferably from 1000 to 4000 angstroms.

Angstroms. For those having a pore volume of 0.1 cc / g or less or (and) having an average pore diameter of 100 angstrom or less, the supported amount of the catalyst component is insufficient, and it is difficult to obtain a desired product. It is. The polymer carrier has an average particle size of 50 to 3000 μm, preferably 10 to 3000 μm.
0-1000 μm. here,
"Average particle size" is measured by Spica II manufactured by Nippon Avionics. If the polymer carrier has an excessively small particle size, it becomes difficult to produce a polymer having a large particle size. If the polymer carrier has an excessively large particle size, there is a problem that the catalytic activity is not sufficient.

As specific examples of the porous polymer carrier used for the component (a) of the present invention, first, from a chemical viewpoint,
(A) polystyrene, (b) polyacrylate, (c) polymethacrylate, (d) polyacrylonitrile, (e) polyvinyl chloride, and (f)
Examples include polyolefin-based ones. Specifically, for example, (a) styrene homopolymer or copolymer, for example, polystyrene, styrene-divinylbenzene copolymer, styrene-N, N'-alkylene dimethacrylamide copolymer, styrene-dimethacrylic acid Ethylene glycol copolymers, homopolymers or copolymers of esters of (b) acrylic acid (preferably lower alkyl esters), such as polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, Ethyl acrylate-divinylbenzene copolymer, (c) homopolymer or copolymer of methacrylic acid ester (preferably lower alkyl ester), for example, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polydimethacrylate Ethylene glycol methacrylate,
(D) acrylonitrile homopolymer or copolymer,
For example, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, (e) homopolymer or copolymer of other vinyl monomers, for example, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer And (f) homo- or copolymers of α-olefins (including ethylene) such as polyethylene, ethylene-methyl acrylate copolymer, and polypropylene.

Of these polymer carriers, preferred are polystyrene, polyvinyl chloride, poly α-olefin and polyacrylonitrile, and more preferred are styrene-divinylbenzene copolymer and polyvinyl chloride. Particularly preferred is a styrene-divinylbenzene copolymer.

According to the invention, these polymer carriers must have a certain porosity. If the porosity specified in the present invention is not realized during the formation or polymerization of the polymer, it must be imparted to the polymer by solvent extraction, grinding or other means. If desired, the porosity by extraction can be achieved "in situ" when the polymer silicon compound is loaded in the presence of an inert liquid medium (described later in detail) during impregnation with the liquid medium. You can also. Some specific examples of the polymer carrier having such a porosity can be found in those manufactured as chromatography carriers or ion exchange resins.

In the present invention, the porous polymer carrier is impregnated with a polymer silicon compound. The polymer silicon compound is a polymer silicon compound having a structure represented by the following formula (I).

[0028]

Embedded image (Where R ¹ is a hydrocarbon residue, preferably C ₁
To C ₁₂ , particularly preferably C _{1 to} C ₆ . n
Represents a number of 2 or more, preferably, from the viewpoint of handling, a number such that the viscosity of the polymer silicon compound becomes 1 to 100 centistokes.)

Examples of the polymer silicon compound having such a structure include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane, cyclohexylhydropolysiloxane, and the like.
Examples include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, and the like. In addition, the terminal structure of the hydropolysiloxane has no significant effect,
It is preferably blocked with an inert group such as an alkyl group.

The method of impregnating the porous carrier for supporting the catalyst with the polymer silicon compound may be any method as long as the effect of the present invention is recognized. In general, both are put in contact with each other. It is preferable to make contact under the following conditions. The contact temperature of both during the impregnation is about -50 to 200C, preferably 0 to 100C. As a method of impregnation, there is a method in which a polymer silicon compound and a porous carrier for supporting are coexistent, preferably in the presence of an inert liquid medium, brought into contact with stirring, and then only the inert liquid medium is removed. At this time, the amount of the polymer silicon compound used is about 10 to 200% by weight based on the weight of the porous carrier used,
Preferably, it is 30 to 100% by weight.

As the inert liquid medium to coexist, an aliphatic or aromatic hydrocarbon such as hexane, heptane, and toluene is preferable.

Component (b) Component (b) is a magnesium dihalide, and specific examples include MgF ₂ , MgCl ₂ , MgBr ₂ , and Mgl ₂ . In addition, such a component (b)
Is known as a solid catalyst component of a Ziegler type catalyst for α-olefin polymerization, for example, from JP-A-58-127706. If necessary or consistent with the component (b) in the present invention, reference can be made to this known document.

Component (c) Component (c) is a titanate and / or polytitanate. In the present invention, the titanate, that is, the titanium alkoxide, is preferably a tetraalkoxide.

Specifically, as the titanate,
Esters with alcohols having about 1 to 16 carbon atoms, especially T
_{i (O-C 2 H 5} ) 4, Ti (O-nC 3 H 7) 4, T
i (O-nC ₄ H ₉ ) ₄ , Ti (O-nC ₅ H ₁₁ ) ₄ ,
Ti (O-nC ₆ H ₁₃ ) ₄ , Ti (O-nC
₇ H ₁₅ ) ₄ , Ti (OnC ₈ H ₁₇ ) ₄ , Ti (On)
_{C 10 H 21) 4, Ti} (O-nC 12 H 25) 4, etc., can be exemplified. Preferred are, Ti _(O-nC 4 H
₉ ) ₄ , Ti (O—C ₂ H ₅ ) _{4 and the} like.

The polytitanate is typically represented by the following formula.

[0036]

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(Wherein R ^{2 to} R ⁵ are the same or different hydrocarbon residues, and preferably each represents C ₂ to R ⁵ )
C _12, particularly preferably at the _C 4 _{~C 8,.} m indicates a number up to 20. Specific examples include normal butyl polytitanate (m = 2 to 20), normal hexyl polytitanate (m = 2 to 20), octyl polytitanate (m = 2 to 20), and the like.

The component (c) may be used together or within the group of these titanium compounds.

The component (c) is obtained by adding Si (OR ⁶ ) ₄ ,
Zr (OR ⁶ ) ₄ , B (OR ⁶ ) ₃ , Al (OR ⁶ ) ₃
Metal alkoxide (R ⁶ preferably has 1 to 1 carbon atoms)
An electron donor such as about 12 alkyl groups), alcohols, esters, and ethers may be used in combination. Electron donors such as alcohols, esters and ethers are those commonly used in Ziegler catalysts.

The component (c) is also known as a solid component of a Ziegler-type catalyst for α-olefin polymerization, for example, as disclosed in JP-A-58-127706. If necessary or consistent with the component (c) in the present invention, this known material can be referred to.

<Production of Component (A ₁ )> The above component (a)
The contact conditions of (c) to (c) can be arbitrary as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. As the contact method, it is preferable that the contact is performed by stirring in the presence or absence of an inert medium. As the inert medium used at this time, an aliphatic or aromatic hydrocarbon medium, a halohydrocarbon medium and the like can be mentioned.

Component (a) for producing component (A ₁ )
The contact method of (c) is optional as long as the effects of the present invention are recognized. For example, the following are specific examples. (B) Component (a) → Component (b) → Component (c), (b) Component (b) → Component (a) → Component (c), (c) Component (a) → ｛Component (b) + Component (c)｝.

The amount ratio of the components (a) to (c) can be arbitrary as long as the effect of the present invention is recognized, but the following range is generally preferred. The weight ratio of component (a) to component (b) is such that the weight ratio of component (b) is 10 to 200% by weight, preferably 50 to 100% by weight, based on the weight of component (a). Further, the quantitative ratio of component (c) to component (b) is
The atomic ratio of titanium to magnesium (titanium / magnesium) is in the range of 0.01 to 10, preferably 0.1 to 5.

The concentration of the component (b) with respect to the inert diluent is 50 g / liter or more, preferably 100 g / liter.
Liter to 1000 g / liter, particularly preferably 1
50 g / liter to 500 g / liter. The atomic ratio (silicon / titanium) of silicon of the component (a) to the titanium component constituting the component (c) is 0.0
It is in the range of 1 to 1000, preferably 0.1 to 100.

<Component (A ₂ )> The component (A ₂ ) is a halogen compound of an element from Groups III to VI of the periodic table. Specifically, for example, a halogen compound of titanium, a halogen compound of silicon, a halogen compound of phosphorus, a halogen compound of molybdenum, a halogen compound of tungsten, a halogen compound of aluminum, and a halogen compound of titanium or silicon is preferable. .

The halogen compound as the component (A ₂ )
Typically, all the valences of the halogenated element are filled with halogen (or different halogens), but the present invention is not necessarily limited to such. As a substituent other than halogen, for example, ＝ O
Groups, amino groups, C1-C20 hydrocarbon residues, C1-C20 alkoxide groups, and others. The component (A ₂ ) is preferably an inorganic halogen compound of an element of Groups III to VI of the periodic table.

<Optional Components> It has been mentioned above that the catalyst component for olefin polymerization according to the present invention, ie, component (A), does not exclude the coexistence of components other than the above-mentioned components (A ₁ ) and (A ₂ ). It is on the street. Representative examples of components that can coexist in the present invention include, for example, the following electron donors, silicon compounds, vinylsilane compounds, and organoaluminum compounds.

The electron donor electron donor (In this way electron donor added during the preparation of the transition metal component of the Ziegler type catalyst is sometimes called an internal donor.) Specific examples of the alcohols, Oxygen-containing electron donors such as phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, isocyanates And nitrogen-containing electron donors.

More specifically, (a) C 1 to C 1
8, alcohols such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol; Good phenols having 6 to 25 carbon atoms, such as phenol, cresol, xylenol,
(C) C2 to C15 ketones such as ethylphenol, propylphenol, cumylphenol, nonylphenol, and naphthol; and (D) C2 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone. Aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and the like;
To 20 organic acid esters such as methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, chloroacetic acid Methyl, ethyl dichloroacetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate,
Benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-
(F) inorganic acid esters such as valerolactone, coumarin, phthalide, ethylene carbonate and the like, for example, silicate esters such as ethyl silicate, butyl silicate and phenyltriethoxysilane, and (g) acid halides having 2 to 15 carbon atoms. ,
(H) ethers having 2 to 20 carbon atoms, such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthaloyl chloride, and the like, for example, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether; (Li) acid amides such as tetrahydrofuran, anisole and diphenyl ether; (nu) amines such as acetate amide, benzoic acid amide and toluic acid amide;
For example, methylamine, ethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
(R) nitriles such as aniline, pyridine, picoline, and tetramethylethylenediamine; and nitriles such as acetonitrile, benzonitrile, and tolunitrile. Two or more of these electron donors can be used.

Among these, preferred are organic acid esters and acid halides, and particularly preferred are phthalic acid esters, cellosolve acetate and phthalic acid halides.

Silicon Compound Next, a silicon compound is used. In the present invention, the general formula R ⁷ _p X _q Si (OR ⁸ ) _4-pq (where R ⁷ is a hydrocarbon residue and R ⁸ is R ⁷ is the same or different hydrocarbon residue as X, X is halogen, p and q are respectively 0 ≦ p ≦ 3 and 0 ≦ q ≦ 3, and 0 ≦ p + q ≦ 3). Is a silicon compound. R ⁷ and R ⁸ are each preferably about 1 to 20, preferably 1 to 10, hydrocarbon residues.
X is preferably chlorine at least in terms of economy.

Specific examples of such a silicon compound include:
(CH ₃ ) Si (OCH ₃ ) ₃ , (CH ₃ ) Si (OC
_{2 H 5) 3, (C} 2 H 5) 2 Si (OCH 3) 3, (n
—C ₆ H ₁₁ ) Si (OCH ₃ ) ₃ , (C ₂ H ₅ ) Si
_{(OC 2 H 5) 3,} (n-C 10 H 21) Si (OC
_{2 H 5) 3, (CH} 2 = CH) Si (OCH 3) 3, C
1 (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , Si (OCH ₃ )
₄ , Si (OC ₂ H ₅ ) ₃ Cl, (C ₂ H ₅ ) ₂ Si
(OC ₂ H ₅ ) ₂ , (C ₁₇ H ₃₅ ) Si (OCH ₃ ) ₃ ,
Si (OC ₂ H ₅ ) ₄ , (C ₆ H ₅ ) Si (OCH ₃ )
_{3, Si (OCH 3) 2} Cl 2, (C 6 H 5) 2 Si
(OCH ₃ ) ₂ , (C ₆ H ₅ ) (CH ₃ ) Si (OCH
₃ ) ₂ , (C ₆ H ₅ ) Si (OC ₂ H ₅ ) ₃ , (C ₆ H
₅ ) ₂ Si (OC ₂ H ₅ ) ₂ , NC (CH ₂ ) ₂ Si
(OC ₂ H ₅ ) ₃ , (C ₆ H ₅ ) (CH ₃ ) Si (OC
_{2 H 5) 2, (n} -C 3 H 7) Si (OC 2 H 5) 3,
(CH ₃ ) Si (OC ₃ H ₇ ) ₃ , (C ₆ H ₅ ) (CH
₂ ) Si (OC ₂ H ₅ ) ₃ ,

[0053]

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[0054]

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[0055]

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[0056]

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(CH ₃ ) ₃ CSi (CH ₃ ) (OC
H ₃ ) ₂ , (CH ₃ ) ₃ CSi (HC (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 ) CH-Si (CH ₃ )
(OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) Si (O
CH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (CH ₃ )
(OCH ₃ ) ₂ , C ₂ H ₅ C (CH ₃ ) ₂ Si (C
H 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 ) _{3 and the} like.

Of these, preferred are those in which the carbon at the α-position of R ⁷ is a secondary or tertiary branched-chain hydrocarbon residue having 3 to 20 carbon atoms, and particularly the carbon at the α-position of R ⁷ is a tertiary carbon. Which is a silicon compound having a branched chain hydrocarbon residue having 4 to 10 carbon atoms.

Specific examples of the vinylsilane compound include monosilane (S
at least one hydrogen atom in iH ₄ ) is vinyl (CH
₂ = CH-), and some of the remaining hydrogen atoms are halogen (preferably Cl), alkyl (preferably having 1 to 12 carbons), alkoxy (preferably 1 to 12 carbons). ), Aryl (preferably phenyl) and others, more specifically CH ₂ ＣＨCH—SiH ₃ , CH
_{2 = CH-SiH 2 (CH} 3), CH 2 = CH-SiH
_{(CH 3) 2, CH 2} = CH-Si (CH 3) 3, CH
₂ ＣＨCH—SiCl ₃ , CH ₂ ＣＨCH—SiCl ₂ (C
H ₃ ), CH ₂ ＣＨCH—SiCl (CH ₃ ) H, CH ₂
ＣＨCH—SiCl (C ₂ H ₅ ) ₂ , CH ₂ ＣＨCH—Si
_{(C 2 H 5) 3,} CH 2 = CH-Si (CH 3) (C 2
_{H 5) 2, CH 2 =} CH-Si (C 6 H 5) (CH 3)
₂ , CH ₂ ＣＨCH—Si (CH ₃ ) ₂ (C ₆ H ₄ C
_{H 3), CH 2 = CH} -Si (OCH 3) 3, CH 2 =
CH—Si (OC ₂ H ₅ ) ₃ , CH ₂ ＳｉCH—Si (C
_{2 H 5) (OCH 3)} 2, CH 2 = CH-Si (OC 2
H _{5) 2} H,

[0060]

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[0061]

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(CH ₂ ＣＨCH) —Si (CH ₃ ) ₂ —O
_{-Si (CH 3) 2 (CH} = CH 2), (CH 2 = C
H) ₂ SiCl ₂ , (CH ₂ ＣＨCH) ₂ Si (CH ₃ )
₂ etc. can be illustrated. Of these, vinyl silane containing no oxygen is preferable, and vinyl alkyl silane is more preferable.

[0063] Specific examples of the organoaluminum compound organoaluminum compound, R 9 _^3-t A
lX _t or _{^{R 10 3-u Al (OR}} 11) u ( wherein R
⁹ and R ¹⁰ may have the same or different carbon number of 1 to 2
About 0 hydrocarbon residue or hydrogen atom, R ¹¹ is a hydrocarbon residue, X is halogen, t and u are each 0 ≦ t <
3, 0 <u <3. ).

Specific examples of such an organoaluminum compound include (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum,
Trialkyl aluminum, such as trialkyl aluminum, (ii) diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, etc., alkyl aluminum halide, (c) diethyl aluminum hydride, diisobutyl aluminum hydride, ( D) Aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide. Preferred among these are triethylaluminum and triisobutylaluminum.

These organoaluminum compounds (a) to (d) may be replaced with another organometallic compound such as R ¹² _3-v Al
(OR ¹³ ) _v (where v is 1 ≦ v ≦ 3 and R ¹²
And R ¹³ may be the same or different and have 1 to 20 carbon atoms.
Hydrocarbon residues. )) Can also be used in combination. For example, a combination of triethylaluminum and diethylaluminum ethoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and ethylaluminum diethoxide, triethylaluminum and diethylaluminum ethoxide and diethylaluminum chloride Are used in combination.

<Production of Component (A)> Component (A) is a solid catalyst component obtained by bringing component (A ₁ ) and component (A ₂ ) into contact with each other. The contact conditions of the component (A ₁ ) and the component (A ₂ ) may be any conditions as long as the effects of the present invention are recognized, but generally the following conditions are preferred. The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. In the contact method, the contact is usually performed by stirring in the presence of an inert medium. Examples of the inert medium used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons.

The contact ratio between the components (A ₁ ) and (A ₂ ) and the optional component is arbitrary as long as the effect of the present invention is recognized, but the following range is generally preferred. Ingredient (A
The amount ratio of _2), (molar ratio relative to component a is the component of A ₁₎ (b) (component (A ₂₎ component / component (b)) at 0.1 to 10 mole ratio, preferably 0 It is from 0.5 to 5 molar ratio, particularly preferably from 1 to 3 molar ratio.

When the electron donor is used as an optional component, the amount of the electron donor used is 1 × 10 ⁻³ to 10 and preferably 0.01 to 10 in a molar ratio to the amount of the component (b).
~ 5.

When the silicon compound is used as an optional component, the amount of the silicon compound used is 0.01 to 1000 in terms of the atomic ratio of silicon of the silicon compound to the titanium component constituting the component (A ₁ ) (silicon / titanium). , Preferably in the range of 0.1 to 100.

When the vinylsilane compound is used as an optional component, the amount of the vinylsilane compound used is determined by the component (A)
The atomic ratio (silicon / titanium) of silicon in the vinylsilane compound to the titanium component constituting ₁ ) is 0.001.
１０００1000, preferably 0.01-300.

When the organic aluminum compound is used as an optional component, the amount of the organic aluminum compound used is as follows:
The atomic ratio (aluminum / titanium) of aluminum in the organoaluminum compound to the titanium component constituting component (A ₁ ) is 0.01 to 100, preferably 0.1 to 100.
-30.

<Component (B)> The component (B) is an organoaluminum compound. Specific examples of the organoaluminum compound as the component (B) can be found in the above-mentioned examples of the organoaluminum compound used as an optional component in producing the component (A). Preferred as the component (B) are trialkylaluminums such as triethylaluminum and triisobutylaluminum. The amount of component (B) used is such that the ratio of component (B) / component (A) is in the range of 0.01 to 1,000, preferably 0.1 to 100, by weight.

[II] Use / Polymerization of Catalyst <General Description> The catalyst according to the present invention can be applied not only to ordinary slurry polymerization but also to liquid phase solventless polymerization substantially using no solvent. It is also applicable to solution polymerization or gas phase polymerization. Further, the present invention is also applicable to a system in which continuous polymerization, batch polymerization or preliminary polymerization is performed. As the polymerization solvent in the case of slurry polymerization, hexane, heptane, pentane,
A single or mixture of saturated aliphatic or aromatic hydrocarbons such as cyclohexane, benzene, and toluene is used. The polymerization temperature is from room temperature to about 200 ° C, preferably 50 ° C.
重合 150 ° C. and the polymerization pressure is atmospheric pressure〜300 kg / cm ²
Degree, preferably atmospheric pressure to 50 kg / cm ² , and hydrogen may be used as a molecular weight regulator at that time.

In the case of slurry polymerization, the amount of component (A) used is preferably in the range of 0.001 to 0.1 g, component (A) / liter solvent.

The α-olefins to be polymerized with the catalyst of the present invention are represented by the general formula R ¹⁴ —CH ＝ CH ₂ (where R ¹⁴ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, May be included.). Specifically, ethylene, propylene, butene-1, pentene-
There are olefins such as 1, hexene-1,4-methylpentene-1. Preferred are ethylene and propylene. In addition to the homopolymerization of these α-olefins, copolymerizations, for example up to 50% by weight, preferably up to 20% by weight thereof, of the above-mentioned olefins can be carried out, and 30% by weight relative to propylene. Copolymerization with up to percent of the above olefins, especially ethylene, can be performed. Copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefin, etc.) can also be performed.

According to the present invention, a polymer having a good particle size, for example, a polymer having an average particle size of about 0.5 to 5 mm can be produced as a product of the polymerization step.

<Block copolymerization> The catalyst according to the present invention comprises:
Although it can be used for various polymerizations of various α-olefins as described above, the catalyst of the present invention which can immediately obtain a granular polymer as a product of the polymerization process produces a rubbery polymer “in situ”. As described above, it is particularly useful in the case of block copolymerization for producing a thermoplastic elastomer.

This type of block copolymerization of α-olefins, preferably block copolymerization of ethylene and propylene, is usually carried out by gas phase polymerization substantially without using a solvent. Therefore, the copolymerization step in the gas phase polymerization carried out in the presence of the catalyst component of the present invention comprises at least two steps, step (1) and step (2).
Any of the steps (1) and (2) may be performed first, but it is industrially advantageous to perform the steps in this order ((1) → (2)). Both steps are performed in the substantial absence of a solvent. In any case, in both steps, the subsequent step is carried out in the presence of at least a part of the product of the preceding step according to a conventional method for producing a block copolymer.

Formation of Catalyst The catalyst of the present invention is formed by bringing the catalyst components (A) and (B) into contact with each other, either temporarily or stepwise, inside or outside the polymerization system. A catalyst may be added in each step, and in particular, the latter step can be carried out by adding component (B).

Polymerization Step (1) In the polymerization step (1), propylene alone or propylene /
The ethylene mixture is supplied to a polymerization system having the catalyst components (A) and (B) and polymerized in one or more stages to form a propylene homopolymer or an ethylene content of 7% by weight or less,
Preferably, 0.5% by weight or less of the propylene / ethylene copolymer is formed in an amount corresponding to 20 to 80% by weight of the total polymerization amount.

When the ethylene content in the propylene / ethylene copolymer exceeds 7% by weight in the polymerization step (1), the bulk density of the final copolymer decreases, and the amount of by-product of the low-crystalline polymer significantly increases. Increase. 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.

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

Polymerization Step (2) In the polymerization step (2), the propylene / ethylene mixture is polymerized in one stage or in multiple stages, and the polymerization ratio (weight ratio) of propylene / ethylene is 70/30 to 30/70. This is the step of obtaining a rubbery copolymer of propylene (however, the amount of polymerization in this step is an amount corresponding to 80 to 20% by weight of the total amount of polymerization).

In the polymerization step (2), other comonomers may coexist. For example, 1-butene, 1-pentene, 1
Α-olefins such as -hexene can be used.

The polymerization temperature in the polymerization step (2) is from 30 to 90.
° C, preferably 50-80 ° C. The polymerization pressure is usually in the range of 1 to 50 kg / cm ² G.

When the process proceeds from the polymerization step (1) to the polymerization step (2), it is preferable to purge the propylene gas or the propylene / ethylene mixed gas and the hydrogen gas and then proceed to the next step.

In the polymerization step (2), a molecular weight regulator may or may not be used according to the purpose.

The propylene copolymer to be produced by carrying out the above-mentioned polymerization has a rubbery copolymer (xylene-soluble content at 20 ° C.) content of 20 to 70% by weight, preferably 35 to 6% by weight.
0% by weight.

[0089]

EXAMPLES <Example 1> [Production of component (A)] In a flask sufficiently purged with nitrogen,
100 ml of dehydrated and deoxygenated n-heptane are introduced,
15 ml of methylhydropolysiloxane (of 20 centistokes), and then “Chromosorb 103” (manufactured by Johns Manville, fully nitrogen-substituted) (average particle size 21
0 μm porous cross-linked polystyrene beads. As a result of porosimetry, this product has a pore size distribution of 400 to 700.
0 angstrom, pore volume (cc / g) 0.87cc
/ G, average pore size was 2,000 Å)
After stirring at 30 ° C. for 2 hours, n-heptane is evaporated with nitrogen gas to prepare a methylhydropolysiloxane-impregnated porous carrier in advance (preparation of component (a)).

Separately, a flask was sufficiently purged with nitrogen, and 25 ml of dehydrated and deoxygenated n-heptane, 5 g of MgCl ₂ , and 40 g of Ti (OnC ₄ H ₉ ) ₄ were prepared.
ml was introduced and reacted at 95 ° C. for 1 hour. After the reaction, 4
The temperature was lowered to 0 ° C., 10 g of component (a) prepared in advance (porous cross-linked polystyrene beads impregnated with methylhydropolysiloxane) was introduced, and reacted for 3 hours.
The resulting solid component was washed with n-heptane.

Then, 25 ml of n-heptane was introduced, and S
6 ml of iCl ₄ was added dropwise at 30 ° C. over 30 minutes and 90 ° C.
For 2 hours, and the resulting solid component was washed with n-heptane. Then, 25 ml of n-heptane was introduced, and 0.43 ml of phthalic acid chloride was added dropwise at 90 ° C. over 30 minutes, reacted at 90 ° C. for 1 hour, and washed with n-heptane after completion of the reaction.

Then, 10 ml of SiCl ₄ was introduced at 30 ° C. and reacted at 100 ° C. for 4 hours. After the reaction, n-
Washed with heptane. What was not carried in the cross-linked polystyrene beads was removed at this time to obtain component (A).

[Polymerization of Propylene] In a 1.5-liter stainless steel autoclave having a stirring and temperature control device, 500 ml of sufficiently dehydrated and deoxygenated n-heptane, and triethyl aluminum 125 as a component (B), were added. 100 milligrams of the above-prepared component (A) and then 60 milliliters of hydrogen were introduced, the temperature was increased and the pressure was increased, and the polymerization pressure was 5 kg / cmG.
Polymerization was performed under the conditions of polymerization temperature = 75 ° C. and polymerization time = 2 hours. After completion of the polymerization, the obtained polymer slurry was separated by filtration, and the polymer was dried. As a result, 68.6 g of a polymer was obtained.

The filtrate yielded 0.15 grams of polymer. From the boiling heptane extraction test, all products I.I. I (hereinafter abbreviated as TII) was 99.1 weight percent. MFR = 2.5 g / 10 min, polymer bulk specific gravity = 0.32 g / cc. The polymer average particle size was 1.2 mm (the polymer average particle size was measured by Spica II manufactured by Nippon Avionics Co., Ltd. (the same applies to the following examples)).

<Example 2> [Production of component (A)] In a flask sufficiently purged with nitrogen,
100 ml of dehydrated and deoxygenated n-heptane are introduced,
15 ml of methylhydropolysiloxane (of 20 centistokes), followed by "Chromosorb 101" (J.
As a result of a porosimeter measurement, a porous polymer composed of a copolymer of styrene and divinylbenzene having a pore size of 100 to 7000 angstroms and a pore volume (cc / g) of 0.88 cc / g, having an average pore diameter of 1500 angstroms), stirring at 30 ° C. for 2 hours, and evaporating n-heptane with nitrogen gas to prepare a porous carrier impregnated with methylhydropolysiloxane (component). Preparation of (a)).

Separately, a flask was sufficiently purged with nitrogen, and 25 ml of dehydrated and deoxygenated n-heptane, 5 g of MgCl ₂ , and 40 g of Ti (OnC ₄ H ₉ ) ₄ were prepared.
ml was introduced and reacted at 95 ° C. for 1 hour. After the reaction, 4
The temperature was lowered to 0 ° C., and the previously prepared component (a) (a porous polymer made of a copolymer of styrene and divinylbenzene impregnated with methylhydropolysiloxane) was added to 1
0 g was introduced and reacted for 3 hours. The generated solid component is represented by n
-Washed with heptane.

Then, 25 ml of n-heptane was introduced and S
6 ml of iCl ₄ was added dropwise at 30 ° C. over 30 minutes, and 90 ° C.
And react for 2 hours. The resulting solid component was washed with n-heptane. Then, 25 ml of n-heptane was introduced,
0.43 ml of phthalic acid chloride was added dropwise at 90 ° C. over 30 minutes, reacted at 90 ° C. for 1 hour, and washed with n-heptane after completion of the reaction.

Then, 10 ml of SiCl ₄ was introduced at 30 ° C. and reacted at 100 ° C. for 4 hours. After the reaction, n-
Washed with heptane.

Next, 0.5 ml of trimethyl-vinylsilane was introduced as a vinylsilane compound, and (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ was added as a silicon compound in 0.1 ml.
5 ml was introduced, and then 1.7 g of triethyl-aluminum was introduced as an organoaluminum, followed by contact at 30 ° C. for 2 hours. After the completion of the contact, the resultant was sufficiently washed with n-heptane, and those not supported on the crosslinked polystyrene beads were removed at this time to obtain Component (A).

[Polymerization Polymerization] The same conditions as in the polymerization of propylene in Example 1 were carried out. As a result, 125.0
g of polymer were obtained, and all products I.I. I = 99.1 weight percent, MFR = 1.3 g / 10 min, polymer bulk specific gravity = 0.32 g / cc, average particle size 2 mm.

<Comparative Example 1> In the preparation of the component (A) of Example 2, instead of "Chromosorb 101" impregnated with a polymer silicon compound (methylhydropolysiloxane), no contact was made with the polymer silicon compound ( Not impregnated), fully substituted with nitrogen
Component (A) was produced in exactly the same manner except that "1" was used. The polymerization of propylene was performed in exactly the same manner.

As a result, 55.44 g of a polymer was obtained. I = 99.0 weight percent, MFR =
2.0 g / 10 min, polymer bulk specific gravity = 0.25 g / cc,
The average particle size was 1.8 mm.

Example 3 In Example 2, when preparing component (a), instead of treating 30 g of Chromosolve 101 with 15 ml of methylhydropolysiloxane (of 20 centistokes), 7.5 ml of methyl 30 g of "Chromosorb 101" hydropolysiloxane
Was impregnated. Component (A) was produced in exactly the same manner as in Example 2 except for the amount of the polymer silicon compound impregnated in component (a). The polymerization of propylene was performed in exactly the same manner. As a result, 87.0 g of a polymer were obtained, and all products I.I. I = 99.1 weight percent, MFR = 1.6
g / 10 min, polymer bulk specific gravity = 0.30 g / cc, average particle size 1.9 mm.

Example 4 Production of Component (A) Component (A) was produced in exactly the same manner as in Example 2.

[Copolymerization of Propylene] A polymer obtained by replacing the inside of a polymerization tank of a 1.5-liter stainless steel autoclave having a stirring and temperature control device with sufficiently purified nitrogen, and then sufficiently dehydrating and deoxygenating the polymer. 30 grams of carrier were added. Next, 50 mg of triethylaluminum of the component (B) and 200 mg of the component (A) synthesized above were introduced. In the first polymerization step (1), after introducing 60 ml of hydrogen, the temperature was adjusted to 75 ° C., and propylene was fed into the polymerization layer through a gas amount counter so as to maintain propylene at 9 kg / cm ² G.

The rotation speed of the polymerization tank was 350 rpm.
Met. When the polymerization amount reaches 80 g (measured by a counter), the introduction of propylene is stopped, and propylene and residual hydrogen gas in the polymerization tank are purged until the pressure becomes atmospheric pressure. Thereafter, the temperature was raised to 70 ° C., and 100 ml of H ₂ was added to start the polymerization step (2). In the second stage polymerization, a mixed gas in which propylene and ethylene were mixed at a molar ratio of 1: 1 was fed so that the pressure in the polymerization tank was maintained at 5 kg / cm ² G.

When the polymerization amount of the copolymer of propylene and ethylene reached about 80 g (determined by a counter), the introduction of the mixed gas of propylene and ethylene was stopped to terminate the copolymerization.

When the monomer was purged and the polymer was taken out, 153 g of a copolymer was obtained. MF of formed polymer
R is 2.5 g / 10 min, and the polymer bulk density (B.
D) was 0.38 (g / cc), the average particle size was 1.8 mm, and the polymer falling speed was 5.0 seconds. The weight of the rubbery copolymer was 48.2 weight percent. The polymer falling speed means the time required for 50 grams of polymer to fall.

<Example 5> [Production of component (A)] 25 g of n-heptane was added to 5 g of MgCl ₂ which was component (b) in Example 2.
Was introduced by adding 10 ml of n-heptane to 5 g of MgCl _2.
The component (A) was produced in exactly the same manner except that the concentration of MgCl ₂ was increased to 500 g / liter.

[Polymerization of propylene] The polymerization was carried out in exactly the same manner as in Example 2. As a result, 109.4 g of a polymer was obtained. All products of this I = 99.0 weight percent, MFR = 1.7 g / 10 min, polymer bulk specific gravity = 0.
33 g / cc and an average particle size of 1.8 mm.

<Comparative Examples 2 and 3> In Comparative Example 1, the component (A) was prepared by using a homopoly powder (Comparative Example 2) and silica (Comparative Example 3) instead of “Chromosorb 101” as the porous carrier. ) Was carried out in exactly the same manner as above. The polymerization of propylene was carried out in the same manner. The results are shown in Table 1 together with the results of Example 2 and Comparative Example 1.

[0112]

[Table 1]

[0113]

According to the olefin polymerization catalyst of the present invention, a polymer having a sufficient particle diameter can be obtained without reducing the activity and steric order performance per catalyst including the carrier particles for supporting. Polymers with a diameter enable the omission of the granulation process from industrial productivity, post-polymerization processing steps, and
The fact that the content of the rubbery copolymer can be increased during the production of the propylene block copolymer is as described above in the section of "Means for Solving the Problems".

[Brief description of the drawings]

FIG. 1 is a flowchart for assisting understanding of the technical contents of the present invention relating to a Ziegler catalyst.

Claims (2)

(57) [Claims] 1. A solid catalyst component for a Ziegler-type catalyst, which is obtained by contacting the following components (A ₁ ) and (A ₂ ). Component (A ₁ ) The following components (a), (b) and (c)
(A) the pore size distribution measured by a porosimeter is in the range of 75 to 10000 angstroms, the pore volume is 0.1 to 2.0 cc / g, and the average pore size is 500 to 5000. Angstrom, a porous polymer carrier having an average particle size of 50 to 3000 μm was added to the following formula (I): (Where R ¹ is a hydrocarbon residue and n is a number of 2 or more) a component obtained by impregnating a polymer silicon compound having a structure represented by the following formula: (b) magnesium dihalide, (c) titanic acid Esters and / or polytitanates, Component (A ₂ ) A halogen compound of an element of Groups III to VI of the Periodic Table. 2. A catalyst for olefin polymerization, comprising a contact product of the following components (A) and (B). Component (A) A solid catalyst component for a Ziegler type catalyst obtained by contacting the following components (A ₁ ) and (A ₂ ), Component (A ₁ ) The following components (a), (b) and (c)
(A) the pore size distribution measured by a porosimeter is in the range of 75 to 10000 angstroms, the pore volume is 0.1 to 2.0 cc / g, and the average pore size is 500 to 5000. Angstrom, a porous polymer carrier having an average particle size of 50 to 3000 μm, was added to the following formula (I): (Where R ¹ is a hydrocarbon residue and n is a number of 2 or more) a component obtained by impregnating a polymer silicon compound having a structure represented by the following formula: (b) magnesium dihalide, (c) titanic acid ester and (or) polytitanate ester, component (a ₂₎ periodic table halogen compound of a III to VI group elements, components (B) an organoaluminum compound.