JPH03243604A - Production of alpha-olefin polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having high stereoregularity in high yield by using a catalyst produced by compounding an organic Al compound with a solid prepared by contacting an Si compound and an organic Al compound to a solid component composed of a specific compound, a W compound and a component containing Ti, Mg and halogen. CONSTITUTION:The objective alpha-olefin polymer can be produced by polymerizing an alpha-olefin in contact with a polymerization catalyst produced by compounding (A) a solid catalyst component for Ziegler-type catalyst prepared by contacting (i) a solid component containing Ti, Mg and halogen as essential components, a compound of formula l (M is atom of element of group III to V of the periodic table; m is atomic valence of N; n is 1 to m; Ph is phenyl, etc.; X is H, O, halogen or 1-10C hydrocarbon group) and a W halide compound, (ii) a Si compound of formula II (R<1> is 3-20C hydrocarbon group; R<2> is R<1> or 1-20C hydrocarbon group; 1<=n<=3) and (iii) an organic Al compound with (B) an organic Al compound.

Description

[Detailed Description of the Invention] [Background of the Invention] Technical Field> The present invention provides a solid catalyst component for a Ziegler type catalyst, an α-olefin polymerization catalyst using the same, and a solid catalyst component for an olefin polymerization using the same. The present invention relates to a method for producing an α-olefin polymer.

When α-olefins are polymerized using the solid catalyst component according to the present invention as a transition metal component of a Ziegler-type catalyst, a polymer with high activity and excellent stereoregularity can be produced with less generation of by-product polymers. Is possible.

<Prior art> Conventionally proposed olefin polymerization catalysts consisting of a solid catalyst component obtained by contacting titanium, magnesium, and halogen with an organoaluminum compound have extremely high activity, but the stereoregularity of the product polymer is a problem. In such cases, it was necessary to use an electron-donating compound during polymerization.

However, such catalysts that use an electron-donating compound as the third component (external donor) have problems such as a decrease in the polymerization rate due to the reaction between the organoaluminum compound and the electron-donating compound, and problems with increasing the polymerization temperature. Since the above reaction is accelerated, it is difficult to control the performance of the product polymer, including the molecular weight of the product polymer, because it is difficult to increase the polymerization temperature and increase the amount of polymerization (increase production efficiency). There is a problem. Further, in order to maintain sufficient stereoregularity, a substantially large amount of the electron donating compound is required, so if the decatalyzing step is omitted, the odor caused by the electron donating compound will be audible.

Therefore, in order to solve the above problems, it is desired to develop a catalyst system that can produce highly stereoregular polymers with high catalytic yield without using an electron-donating compound as the third component (external donor). .

JP-A-58-138715 discloses a titanium composite (1) obtained by contacting tetravalent titanium, magnesium, halogen, and an electron donor without using an external donor;
An organosilicon compound (2) having an i-0-C bond,
The titanium composite is reacted in the presence of an organoaluminum compound, or the titanium composite is treated with an organoaluminum compound, and then the solid component obtained by reacting with the organosilicon compound is polymerized with a catalyst system formed from the organoaluminum. A method is disclosed.

However, although this proposal has made progress in resolving the above problems, it has limitations in terms of the performance of the resulting product polymer, as well as deterioration of the catalyst over time and the ratio of the amounts of titanium components and organoaluminum compounds used during polymerization. There are still many points that need to be improved, such as limitations.

According to the proposal of JP-A-62-187707, by using a special organoalkoxysilicon compound, restrictions on the amount of organoaluminum compound to be used during polymerization seem to be largely eliminated. However, when the purpose is to control the molecular weight or to produce a copolymer, it is not always possible to obtain a catalyst yield that allows the decatalyzing step to be omitted, and further improvements are desired.

JP-A-52-124084 proposes using alkoxyboron to widen the molecular weight distribution, but no improvement in activity has been obtained. Japanese Patent Publication No. 55-104303
, No. 56-26904, and No. 59-129204 propose the use of alkoxyline compounds. However, there is no proposal that phenoxy compounds are particularly superior, and improvement in activity is insufficient.

[Summary of the invention]

Summary> The present invention aims to provide a solution to the above problems. Therefore, the solid component for a Ziegler type catalyst according to the present invention is characterized in that it is obtained by bringing the following components (1), (if), and component (iii) into contact with each other.

Component (1) A solid component obtained by contacting the following components (A), Component (B), and titanium, Component (A): A solid component obtained by contacting titanium, magnesium, and halogen, Component (B): M(OPh)
n compound (here, M is an atom of group ⋯ to V of the periodic table, m is a number corresponding to the valence of M, n is an integer from 1 to m, and ph is a phenyl group or a substituted phenyl group) , X represents hydrogen, oxygen, halogen, a hydrocarbon residue having 1 to 10 carbon atoms, or an alkoxy group.) Titanium: Magnesium and halogen compound, component (1
1) A silicon compound composed of (here, R1 is a branched carbonized carbon having 3 to 20 carbon atoms (here, R1 is the same or different hydrocarbon residue having 1 to 20 carbon atoms, and R3 is a carbon number of 3 to 20 carbon atoms) Represents 1 to 12 hydrocarbon residues, where n is 1≦n≦3.) Component (iti) 6m aluminide 6 compound.

Further, the α-olefin polymerization catalyst according to the present invention is characterized by comprising the following component (A) and component (B).

Component (A) A solid catalyst component for a Ziegler type catalyst obtained by contacting components (i), (11) and component (iii) below.

Component (i) A solid component obtained by contacting the following components (A), Component (B), and titanium, A solid component obtained by contacting Component (A), titanium, magnesium, and halogen, Component (B): M(OPh)
n compound (where M is an atom from group ■ to ■ of the periodic table, m is a number corresponding to the valence of M, n is an integer from 1 to m, and ph is a phenyl group or substituted phenyl group) , X represents hydrogen, oxygen, halogen, a hydrocarbon residue having 1 to 10 carbon atoms, or an alkoxy group.) Titanium, magnesium and halogen compounds, components (1
1) A silicon compound composed of (here, R1 is a branched carbonized carbon having 3 to 20 carbon atoms (here, R1 is the same or different hydrocarbon residue having 1 to 20 carbon atoms, and R3 is a carbon number of 3 to 20 carbon atoms) Represents 1 to 12 hydrocarbon residues. n is 1≦n≦3.) Component (IJi) Organoaluminum compound.

Ingredient (B) Organoaluminum compound.

Further, the method for producing an α-olefin polymer according to the present invention includes:
The method is characterized in that an α-olefin is brought into contact with a polymerization catalyst consisting of the following components (A) and (B) to be polymerized.

Component (A) A solid catalyst component for a Ziegler type catalyst obtained by contacting the following components (i), (ii) and component (iii).

Component (i) A solid component obtained by contacting the following components (A), Component (B), and titanium, Component (A): A solid component obtained by contacting titanium, magnesium, and halogen, Component (B): M(OPh)
n compound (where M is an atom from Groups ■ to V of the periodic table, m is a number corresponding to the valence of M, n is an integer from 1 to m, and Ph is a phenyl group or substituted phenyl group) , X represents hydrogen, oxygen, halogen, a hydrocarbon residue having 1 to 10 carbon atoms, or an alkoxy group.) Titanium: magnesium and halogen compound, component (i
i) silicon compound (here, R1 is a branched carbonized carbon number of 3 to 20 carbon atoms (here, R1 is the same or different hydrocarbon residue of 1 to 20 carbon atoms, R3 is a carbon number of 3 to 20 carbon atoms) Represents 1 to 12 hydrocarbon residues. n is 1≦n≦3.) Component (iH) Organoaluminum compound.

Ingredient (B) Organoaluminum compound.

Effect> The solid catalyst component for Ziegler-type catalysts of the present invention and the α-olefin polymerization catalyst made of this solid catalyst component can be used without using an electron-donating compound (external donor) during polymerization.
Alternatively, it is possible to maintain high activity and stereoregularity of the polymer by using only a small amount, and it also solves the problems of known catalysts, such as suppressing the formation of non-quality components that cause stickiness of the film. It is something. The advantage of this polymerization catalyst can also be considered as an advantage of the method for producing an α-olefin polymer according to the present invention.

Such characteristics are extremely advantageous in industrial production and are important characteristics of catalysts.

The reason for this effect has not been sufficiently analyzed, or the halogenation and titanium extraction reactions by magnesium and halogen compounds are controlled, promoting halogenation while suppressing titanium extraction, resulting in high activity. It is thought that a catalyst is formed. Furthermore, by supporting a certain amount of the catalyst on the magnesium carrier, the polymerization rate may be increased. Therefore, it appears that the present invention has excellent effects that could not be expected from the known technology.

[Detailed description of the invention]

α-olefin polymerization catalyst> The α-olefin polymerization catalyst of the present invention contains a specific component (A
) and component (B).

Here, "consisting of" means that the ingredients are those listed (
That is, this does not mean that (A) and (B) are the only components, and the coexistence of a purposeful third component is not excluded.

Component (A) Component (A) of the catalyst of the present invention is a solid catalyst component for a Ziegler catalyst obtained by contacting the following components (i) to (Hi). Here, "obtained by contacting" means the listed components (i.e. (i) to (iii))
) does not mean only contact with
The purposeful coexistence of other components is not excluded.

Component (i) Component (i) is a solid component obtained by catalyzing the following components (a), (b) and (c). Here, "obtained by contacting" does not mean that the target is only the listed components (i.e., components (a), (b), and (c)), but other components for a purpose. does not exclude the coexistence of

Component (A) Component (A) is a solid component obtained by contacting titanium, magnesium and l\logen.

Here, "obtained by contacting" means that in addition to the three listed components, other elements may be included for a purpose;
This indicates that each of these elements may be present in any suitable compound, and that these elements may also be present in combination with one another. The solid components, including titanium, magnesium and halogens, are themselves known. For example, JP-A-53-
No. 45688, No. 54-3894, No. 54-3109
No. 2, No. 54-39483, No. 5494591, No. 54-118484, No. 54131589, No. 55
-75411, 55-90510, 55-90
No. 511, No. 55-127405, No. 55-1475
No. 07, No. 55-155003, No. 56-18609
No. 56-70005, No. 56-72001, No. 56-86905, No. 56-90807, No. 56-
No. 155206, No. 57-3803, No. 57-341
No. 03, No. 57-92007, No. 57-121003
No. 58-5309, No. 58-5310, No. 58
-5311, 58-8706, 58-2773
No. 2, No. 58-32604, No. 58-32605,
No. 58-67703, No. 58-117206, No. 5
No. 8-127708, No. 58-183708, No. 58
-183709, 59-149905, 59-
No. 149906, No. 60-130607, No. 61-5
No. 5104, No. 61-204204, No. 62-508
No. 62-15209, No. 62-20507, No. 62-184005, No. 62-236805, No. 6
Those described in JP-A-1-139601, JP-A-1-215806, etc. are used.

Further, examples include those treated with tungsten or molybdenum compounds.

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

In addition, the titanium compound serving as a titanium source has the general formula Ti(O
R)

) can be mentioned.

Specific examples include T I C14, T h B r 4
, Ti(OC2H5)C13, Ti(OC2H5)2C12, T1(OC2H5)3CI.

Tl(O-jC3H7)C13, Tl(0-nC4H9)C13, Tl(O-nC4H9)2C12, Tl(OC2H5) B'3, Ti(OCH)
(OC4H9)2C115 T L (On C4H9) 3 CI, T i (0
-C6H5) CI 3, Ti(0-1C4H9)2C
12, Tl (OC5Htt) C' 3, Tl (OC6H
13) C13, T1 (OC2H5) 4, Ti (On C3H7) 4, T r (On C4H9) 4, Ti (Os C4H9) 4, Ti (0-nC6H,3) 4, Ti (0-nC8H17) 4, Tl[OCHCH(C2H5)C4H9]4 and the like.

Further, a molecular compound obtained by reacting TiX'4 (herein, X' represents a halogen) with an electron donor described later can also be used. As a specific example, T ICl 4・CH3
COC2H5, T i Cl 4 ・CH3CO2C2H
5, T ICl 4・C6H5NO2, T r CI −CH3COCl 1T iC14・
C6H5COCl, TiCl4・C6H5CO2C2H5, TiC1・
Examples include CICOC2H5 and TiCl4C4H40.

Among these titanium compounds, preferred are T L
C14, T l (OE t ) 4, Ti (O
Bu) Ti (OBu)C10 etc. 4.

As a halogen source, the above-mentioned magnesium and/or
It is usually supplied from a titanium halide compound, but it can also be supplied from known halogenating agents such as aluminum halides, silicon halides, and phosphorous halides.

Halogens contained in catalyst components include fluorine, chlorine, bromine,
It may be iodine or a mixture thereof, with chlorine being particularly preferred.

In addition to the above-mentioned essential components, the solid components used in the present invention include Si
Silicon compounds such as CI CH3S iCl B, polymeric silicon compounds such as methylhydrodiene polysiloxane, A I (OL C3H7) 3, A
I CI A I B r 3, Al (OC2
H5) 3.3ゝ Aluminum compounds such as Al (OCH3)2C1 and B(OCH3)3, B(OC2H5)3, B(OC6H
5) It is also possible to use other components such as boron compounds such as No. 3, and there is no problem with these remaining in the solid component as components such as silicon, aluminum, and boron.

Furthermore, when producing this solid component, it is also possible to produce it using an electron donor as an internal donor.

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

More specifically, (a) methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol and the like having 1 to 18 carbon atoms; alcohols, (b) phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone ,
Ketones having 3 to 15 carbon atoms such as methyl isobutyl ketone, acetophenone and benzophenone; (d) Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; (e) Methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, benzoic acid Methyl, 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 ethoxybenzoate, diethyl phthalate, dibutyl phthalate, dihebutyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 20 carbon atoms such as ethylene carbonate, (h) inorganic acid esters such as silicate esters such as ethyl silicate, butyl silicate, phenyltriethoxysilane, (g) acetyl chloride, benzoyl Chloride, toluic acid chloride, anisyl chloride, phthaloyl chloride, isophthaloyl isochloride, etc. having 2 to 1 carbon atoms
5 acid halides, (thi) ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, (
) Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (x) methylamine, ethylamine,
Examples include amines such as diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, and nitriles such as (l)acetonitrile, benzonitrile, and tolnitrile. Two or more types of these electron donors can be used. Preferred among these are organic acid esters and organic acid halides, and particularly preferred are cellosolve acetate, phthalic esters, and phthalic halides.

The amount of each of the above components used may be arbitrary as long as the effects of the present invention are observed, but numerically, it is preferably within the following range.

The amount of the titanium compound to be used is preferably within the range of 1.times.10@-4 to 1000, preferably within the range of 0.01 to 10, in molar ratio to the amount of the magnesium compound used. When using a compound for this purpose as a halogen source, the amount used should be determined regardless of whether the titanium compound and/or magnesium compound contains a halogen.
I×1 in molar ratio to the amount of magnesium used
It is within the range of 0-2 to 1000, preferably 0.1 to 100.

The amount of silicon, aluminum and boron compounds used is
1 in molar ratio to the amount of magnesium compound used above.
x10-3 to 100, preferably 0.01 to 1.

The amount of the electron-donating compound to be used is within the range of 1X10' to 10, preferably 0.01 to 5, in molar ratio to the amount of the above-mentioned magnesium compound used.

The solid component of component (a) can be manufactured by a known method using the above-mentioned titanium source, magnesium source, and halogen source, and if necessary, other components such as an electron donor. For example, the following manufacturing method is preferable. .

(a) A method of bringing magnesium halide and, if necessary, an electron donor and a titanium-containing compound into contact.

(b) A method of treating alumina or magnesia with a phosphorus halide compound and contacting it with a magnesium halide, an electron donor, a titanium halogen-containing compound, or a tungsten-containing compound.

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

As this polymeric silicon compound, those represented by the following formula are suitable.

1←5i-0← (Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, n
indicates a degree of polymerization such that the viscosity of this polymeric silicon compound is about 1 to 100 centistics. ) Among these, methylhydrogenborinoxane, 1,3,5,7-titramethylcyclotetranoxane, 1,3,5,79-pentamethylcyclopentasiloxane, ethylhydrogenpolysiloxane, phenylhydro Diene polysiloxane, cyclohexylhydrodiene polysiloxane, etc. are preferred.

(d) In the solid component obtained by the production method of (c) above,
Method of contacting electron donors.

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

(F) A method in which an organomagnesium compound such as a Grignard reagent is allowed to react with a halosaponizing agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact with the compound, if necessary.

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

In this way, a solid component (a) containing titanium, magnesium and halogen as essential components is obtained.

Component (B) Component (B) is a compound represented by the general formula M(OPh) Xm-n. Here, M is an atom from group ① to V of the periodic table, m is a number corresponding to the valence of M, n is an integer from 1 to m, ph is a phenyl group or a substituted phenyl group, and X is hydrogen. , oxygen, halogen, from 1 carbon number]O
hydrocarbon residues or alkoxy groups.

M in component (b) is preferably boron, aluminum, silicon, titanium, zirconium, phosphorus and vanadium, and the substituent of the substituted phenyl group as pH is preferably lower alkyl. Further, the halogen as X is preferably chlorine, bromine, and iodine, the hydrocarbon residue (C1 to C1o) as X is preferably an alkyl group, a phenyl group, or a lower alkyl-substituted phenyl group, and the alkoxy group as X has a carbon number of 1 to 8 are preferred. Therefore, such component (b) of the present invention
Preferred specific examples include (a) boron compounds such as triphenyl borate, tri(0-cresyl) borate, diphenyl borate, and ethyldiphenoxyboron;
(b) Aluminum compounds such as aluminum triphenoxide, ethylaluminum diphenoxide, diethylaluminum phenoxide, (c) Silane compounds such as tetraphenoxysilane, ethyltriphenoxysilane, diphenyldiphenoxysilane, (d) Tetraphenoxytitanium, triphenoxysilane, etc. Titanium compounds such as cytitanium chloride and biscyclopentagenyl titanium diphenoxide, (e) zirconium compounds such as tetraphenoxyzirconium and diphenoxyzirconium dichloride, (f) triphenyl phosphite, diphenyl phosphite,
Examples include phosphorus compounds such as triphenyl phosphate, tricresyl phosphite, and diphenyl phenyl phosphite, and vanadium compounds such as (tri)triphenoquine vanadium, oxyvanadium tonofe, and tuxito. Among these, compounds all having phenoxy groups, such as triphenyl borate, tetraphenoxysilane, and triphenyl phosphite, are preferred.

Titanium Titanium is a magnesium and halokene compound. The tungsten forming such titanium can be of any valence. Further, the halogen may be any of fluorine, chlorine, bromine, and iodine, and among these, the latter three are typical. Specifically, tungsten hexachloride, tungsten pentachloride, tungsten tetrachloride, tungsten dichloride, tungsten ookuda, tungsten pentabromide, tungsten tribromide, tungsten tetraiodide, tungsten diodide, oxytungsten tetrachloride, Examples include oxytungsten chloride. Among these, tungsten hexachloride, tungsten pentachloride, tungsten chloride, etc. are preferred.

Preparation of component (i) Component (1) is a solid component obtained by contacting the above components (a) to c). The amount of each component to be used is arbitrary as long as the effect of the present invention is recognized, but numerically it is preferably within the following range.

The amount of component (b) used is within the range of 1X10' to 1000, preferably 1X10-3 to 10, based on the amount of magnesium compound used as component (a). The amount of titanium used is 0.01 to 1001, preferably 0.01 to 1,001 in molar ratio to the titanium compound in component (a). The range is from 1 to 30.

There are no particular restrictions on the order and number of contacts of components (a), (b), and (c), but examples include (b) a method of reacting components (a) and component (b) and then bringing them into contact with titanium; (
(b) A method of adding and reacting a mixture of component (B) and titanium to component (A); (b) A method of bringing component (A) into contact with titanium and then contacting component (B); (to)
A method of bringing components (a), (b), and (c) into contact at the same time,
Nato is fried.

Component (N) Component (if) is represented by the general formula (where R1 is a branched carbonized chain having 3 to 20 carbon atoms (here, a hydrocarbon residue having 1 to 20 carbon atoms that is the same as or different from R1), R3 represents a hydrocarbon residue having 1 to 12 carbon atoms, and n is a number satisfying 1≦n≦3.

Ru.

Here, R1 is preferably branched from the carbon atom adjacent to the silicon atom. In that case, the branching group may be an alkyl group, a cycloalkyl group or an aryl group (for example,
A phenyl group or a methyl-substituted phenyl group) is preferable. More preferably, R1 is such that the carbon atom adjacent to the silicon atom, that is, the α-position carbon atom, is secondary or tertiary.
Particularly preferred is a carbon atom in which the carbon atom bonded to the silicon atom is tertiary. R
The number of carbon atoms in 1 is 3 to 20, preferably 3 to 12. R
2 is usually a branched or linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. R3 is an aliphatic hydrocarbon group, preferably having 1 to 4 carbon atoms
It is usually a chain aliphatic hydrocarbon group.

Specific examples of component (11) are shown below.

(CH) C-81 (QCH) , (CH) C-9
t(OCH) , 33 252 2
53 32 (CH3) 30-8iku0CH
3) 3, (C113)30-8i (oc2H5)
3. Component (Ni) Component (iii) is an organic aluminum compound.

As the organoaluminum compound of component (ii), component (
Compounds similar to those described as B) (details described later) can be used. Specific examples of preferable organoaluminum compounds used as component (iii) include (
b) Trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, (
b) Alkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, isobutylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) diethylaluminum hydride, etc. alkyl aluminum hydride, (d) diethyl aluminum ethoxide,
Alkylaluminum alkoxides such as diethylaluminum phenoxide, (e)methylaluminoxane,
Examples include alumoxanes such as ethyl aluminoxane and isobutylaluminoxane. These can be used alone or in a mixture of two or more. It can also be mixed with organometallic compounds such as butyllithium, butylethylmagnesium, diethylzinc, titanocene dimethyl, etc., or used as a complex.

Preparation of Component (A)> The contacting method and usage amount of components O) to (jO) may be arbitrary as long as the effects of the present invention are observed, but numerically the following conditions are preferable.

The quantitative ratio of component (i) to component (if) is the atomic ratio of silicon in component (11) to the titanium component constituting component (1) (silicon/titanium) of 0.01 to 1000. Preferably it is in the range of 0.1 to 100. Ingredients (Iio ingredients (
The quantitative ratio to i) is the aluminum/titanium atomic ratio of the organoaluminum compound of 0.01 to 1000. Preferably 0. The range is from 1 to 300.

The order of contacting components (i) to 1li) is not particularly limited, but for example, (a) a method of bringing component (i) into contact with component (ii) and then contacting component (Iii), and (b) a method of contacting component (ii) with component (I). (i) and component (iii) are brought into contact, and then component (11
), (c) a method of bringing the two components (11) into contact with the component (i);
li) A method of contacting a material that has been brought into contact with component (i) in advance, (d) Components (1), (it) and (lit)
There are methods of contacting both at the same time. Note that there is no problem in performing a cleaning process between each process.

The contact temperature is about -50 to 200°C, preferably 0 to 1
It is about 00℃. Examples of the contact method include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a media stirring pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons, and polysiloxanes.

During these contacts, other components other than components (1) to (ill), such as methylhydrodiene polysiloxane, ethyl borate, aluminum triisopropoxide, aluminum trichloride, may be used as long as the effects of the present invention are not impaired. , silicon tetrachloride, tetravalent titanium compound,
It is also possible to coexist a trivalent titanium compound or the like.

It is also possible to use ethylenically unsaturated compounds such as olefins and diene compounds as an optional component during or after the preparation of component (A) of the present invention. Specific examples of such ethylenically unsaturated compounds include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-butene,
Pentene, 2-pentene, 2-methyl-1-butene, 3-
Methyl 1-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-
Pentene, 4-methyl-1-pentene, 2-methyl-2
-Pentene, 3-methyl-2-pentene, 4-methyl-
2-pentene, 2-ethyl-1-butene, 2.3-dimethyl-1-butene, 3.3-dimethyl-1-butene, 2
, 3-dimethyl-2-butene, 1-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1
nonene, 1-decene, 1-undecene, 1-dodecane,
1-tridecane, 1-tetradecane, 1-pentadecane,
1-hexadecane, 1-heptadecane, 1-octadecane, 1-nonadecane, styrene, α-methylstyrene,
Divinylbenzene, 1,3-butadiene, isoprene,
Hexadiene, 1.4-hexadiene, 1.5-hexadiene, 1.3-pentadiene, 1.4-pentadiene, 2.3-pentadiene, 2,6-octadiene, ci
s-2, trans4-hexadiene, trans 2
゜trans 4-hexadiene, 1.2-heptadiene, 1.4-heptadiene, 1,5-hebutadiene, 1
．． 6-heptadiene, 2,4-hebutadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-
Cyclohexadiene, cyclopentadiene, 1,3-cyclohebutadiene, 1,3-butadiene, 4-methyl-
Examples include 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, and 1,13-tetradecadiene. These usually polymerize if they are brought into contact with component (A) together with an organoaluminium compound if necessary, and therefore component (A) produced in this way is considered to have undergone so-called prepolymerization. Become.

These ethylenically unsaturated compounds are thought to polymerize during the preparation of component (A), and therefore the amount used is 0.01 to 100% of component (A) before use.
twice the weight, preferably 0.1 to 10 times the weight.

Ingredient (B) Component (B) is an organoaluminum compound.

Specific examples include R3-nAIXn or 6
7-5 RAl(OR) (here R and R6 are 3-a
m is a hydrocarbon residue or hydrogen atom with about 1 to 20 carbon atoms, which may be the same or different, R7 is a hydrocarbon residue with about 1 to 20 carbon atoms, X is halogen, n and m are each 0≦
The numbers are n<3 and O<m<3. ). Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum,
Trialkylaluminum such as trihexylaluminum, trioctylaluminum, tridecylaluminum, (b) diethylaluminum monochloride,
Alkylaluminum halides, such as diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c)
Alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, alumoxanes such as (di)methylalumoxane, ethylalumoxane, and isobutylalumoxane, (
e) Aluminum alkoxides such as diethylaluminium ethoxide and diethylaluminium phenoquinide;
etc.

These (a) to (d) aluminum compounds may contain other organometallic compounds, for example, R and R9 may be the same or different and have a carbon number of 1 to 2.
There are about 0 hydrocarbon residues. ) can also be used in combination with an alkyl aluminum alcokindra represented by. For example, combinations of triethylaluminum and diethylaluminium ethoxide, combinations of diethylaluminum monochloride and diethylaluminum ethoxide, combinations of ethylaluminum dichloride and ethylaluminum jetoxide, and combinations of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride. Can be used in combination.

The amount of component (B) used is component (B)/component (A) in weight ratio.
) is 0.01 to 1000, preferably 0.1 to 100,
is within the range of

Third component (optional component) The α-olefin polymerization catalyst of the present invention has a specific component (A
) and component (B).

Here, "consisting of" means that the ingredients are those listed (
That is, as mentioned above, this does not mean that there are only component (A) and component (B)), and the coexistence of a purposeful third component is not excluded.

Typical examples of such purposeful third components include electron-donating compounds such as ethers, esters,
Examples include amines, inorganic alkoxy compounds, and others.

Specifically, (a) ethers, such as diphenyldimethoxymethane, eucalyptol, 25-dimethylhexahydrofuran, etc.; (b) esters, such as ethyl benzoate, ethyl p-toluate, p-)methyl toluate; Kasa's organic carboxylic acid esters, (iii) amines, such as 2, 26.6. Tetramethylpiperidine, 2,6-dimethylbiperidine, di-tertbutylamine, diisobutylmethylamine, (d) Inorganic alkoxy compounds such as triethyl borate, trimethyl borate, triethyl phosphite, phenyldiethoxysilin, tris (diphenylmethoxy)aluminum, bis(diphenylmethoxy)aluminumethyl, ethyl silicate, phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, diisobutyldimethoxysilane,
Examples include di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, phenylisopropyldimethoxysilane, norbornylmethyldimethoxysilane, diphenylmethylmonomethoxysilane, and diphenylisopropylmonomethoxysilane.

The amount of these third components to be used may be arbitrary as long as the effects of the present invention are recognized, but it is preferably within the following numerical range. The molar ratio to the titanium component in component (A) is in the range of 0.01 to 300, preferably 0.1 to 100.

Formation of Catalyst> The catalyst according to the present invention is composed of components (A) and (B), and such a catalyst is prepared by polymerizing both components and optionally a third component in a polymerization tank or by polymerizing the components (A) and (B). It can be formed by contacting the polymer in the presence of the olefin to be polymerized, or in the presence of the olefin to be polymerized outside the polymerization tank, sometimes in stages or in parts over several times.

There are no particular restrictions on the method of supplying components (A) and (B) to the contact location, but they may be dispersed in an aliphatic hydrocarbon solvent such as hexane or heptane and added separately to the polymerization tank, or Usually, they are brought into contact with each other in advance and then added to the polymerization tank. Component (A) is a component (B) in a solid state.
) may be added to the polymerization tank separately.

Polymerization of olefin:/> The catalyst of the present invention can be applied not only to ordinary slurry polymerization, but also to liquid-phase solventless polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. also applies. It is also applicable to continuous polymerization, batch polymerization or preliminary polymerization. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures. The polymerization temperature is from room temperature to about 200°C, preferably from 50 to 150°C,
Hydrogen can then be used as an auxiliary molecular weight regulator. At the time of slurry polymerization, the amount of component (A) used is preferably within the range of 0.0001 to 0.1 g of component (A)/liter of solvent.

The olefins polymerized with the catalyst 7 system of the present invention have the general formula R-
CH-CH2 (here R is a hydrogen atom or a carbon number of 1 to 1
0 hydrocarbon residues, and may have a branched group. ). Specifically, ethylene, propylene, butene-1, pentene-1, hexene-1,4-
There are olefins such as methylpentene-1. Preferred are ethylene and propylene. In the case of these polymerizations, up to 50 weight percent, preferably up to 20 weight percent, based on ethylene, of the above-mentioned olefins can be copolymerized, and up to 30 weight percent, based on propylene.
up to weight percent of the above olefins, especially ethylene,
can be copolymerized with Copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefins, etc.) can also be carried out.

[Experiment example]

Example-1 [Production of component (A)] Dehydrated and deoxidized n in a flask that was sufficiently purged with nitrogen.
- introducing 200 ml of hebutane, then MgC
0.1 mol of l2, 0.1 mol of Ti(0-nC4H9)4. 2 mol was introduced and the reaction was carried out at 95°C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, then 12 ml of methylhydropolysiloxane (20 centistoke) was introduced, and 3
Allowed time to react. The solid component produced was washed with n-hebutane. Next, 50 milliliters of n-hebutane purified in the same manner as above was introduced into a flask that had been sufficiently purged with nitrogen.
0.03 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, add S to 25 ml of n-hebutane.
05 moles of iC140 were mixed and introduced into a flask at 30°C for 30 minutes, followed by reaction at 70°C for 3 hours. After the reaction was completed, it was washed with n-hebutane.

Next, 0.003 mol of phthaloyl chloride was mixed with 25 ml of n-hebutane, and the mixture was introduced into a flask at 90°C for 30 minutes, and reacted at 95°C for 1 hour. After the reaction was completed, component (a) was obtained by washing with n-hebutane. Next, add 1.0 ml (3 mL) of triphenyl phosphite (component).
, 2 mmol) and 0 tungsten hexachloride (titanium)
．． 6 grams and 80 milliliters of n-hebutane were introduced and reacted at 90°C for 3 hours. After the reaction was completed, the solid component (1) was obtained by thoroughly washing with n-hebutane. Component (i) contained 0.92 weight percent titanium.

Next, add 88% of n-hebutane to a flask that has been sufficiently purged with nitrogen.
0 milliliter, 4 grams of component (1) obtained above, then 3 3 of (CH) C51(CH)(OCH3)2 as component (ii).
3 2.2 mmol, 1.71 grams (1
5 mmol) was added dropwise over 30 minutes at 15°C. After the dropwise addition was completed, the temperature was raised to 30° C., and each component was brought into contact with each other for 2 hours. After the contact was completed, the product was sufficiently washed with n-hebutane to obtain component (A).

This component (A) contained titanium in an amount of 0.89 FI percent.

[Polymerization of propylene]

In a 1.5 liter stainless steel autoclave equipped with stirring and temperature control, 500 milliliters of thoroughly dehydrated and deoxygenated n-hebutane were added to the ingredients (
125 mg of triethylaluminum as B);
And 15 milligrams of the catalyst component (A) synthesized above was introduced. Next, 60 milliliters of H2 was introduced, the temperature and pressure were increased, and polymerization was carried out under the conditions of a polymerization pressure of 5 kg/cd G, a polymerization temperature of -75°C, and a polymerization time of -2 hours. After the polymerization was completed, the resulting polymer slurry was separated by filtration, and the polymer was dried.

As a result, 215.6 grams of polymer was obtained. Also, 0.68 grams of polymer was recovered from the filtrate. Therefore, the activity per catalyst is 14,400 grams of polymer/gram of solid catalyst, and the activity per titanium atom is 166×10
'gram polymer/gram titanium. The polymer had an MFR of 1.33 grams/10 minutes and a bulk specific gravity of 0.433. Further, the polymer density of the sheet obtained by press molding was measured using a density gradient tube, and the result was 0.9070 g/milliliter.

Example-2 [Production of component (A)] 0.5 ml (1.6 mmol) of triphenyl phosphite and 80 ml of n-hebutane were introduced into component (A) obtained in Example-1. , then the temperature was raised to 90°C, and 1
Allowed time to react. After the reaction was completed, the temperature was lowered to 30°C, 0.5g of tungsten hexachloride was introduced, and the temperature was increased to 90°C again.
The temperature was raised to 0.degree. C., and the mixture was reacted for 2 hours. After the reaction was completed, solid component (i) was obtained by thoroughly washing with n-hebutane. This component (1) contained 1.01% by weight of titanium.

All Example-1 except for using the obtained solid component (1)
Component (if) and component (iii) were contacted under the same conditions as . This component (A) contained 0.95% by weight of titanium.

[Polymerization of propylene]

Polymerization was carried out using the above component (A) under the same conditions as in Example-1. The results are shown in Table-1.

Comparative Examples-1, 2, 3, 4 Component (A) was used under the same conditions as Example-1 except that component (B), titanium, component (Ii), or component (lii) was not used in Example-1. and carried out the polymerization of propylene. The results are shown in Table-1.

Comparative Example 5 Using the catalyst obtained in Comparative Example 3, polymerization was carried out under the same conditions as in Example 1 except that 26.8 milligrams of diphenyldimethoxysilane was used during propylene polymerization.

The results are shown in Table-1.

Examples 3 to 6 and Comparative Examples 6 to 8 Component (A
) and polymerized propylene. The results are shown in Table-2.

Example 7 and Comparative Example-9 [Propylene/ethylene block copolymerization] Internal volume 1.
After sufficiently replacing the inside of a 5-liter stirring autoclave with propylene, 500 milliliters of n-hebutane that had been sufficiently dehydrated and deoxidized was introduced, and 17.9 milligrams of component (A) obtained in Example-1 was added, or 24.4 milligrams of component (A) obtained in Comparative Example-1 and 125 milligrams of triethylaluminum were introduced under a propylene atmosphere.

After introducing 200 milliliters of hydrogen into the reaction system, the temperature was raised to 75° 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 continued at 75°C.

When the pressure reached 2 kg/ciG, 1/10 sample was taken as an intermediate sample. Furthermore, the gas phase part is 0.2k
After purging to g/cjG, 0.025 mmol of methyl borate (B(OCH3)3) was introduced as a third component. Then propylene duram/min, each at a constant rate of 65
The introduction was carried out for 1.5 hours at ℃. After the introduction, the polymerization was continued, and when the pressure reached 1.0 kg/cdG, the gas phase was purged to stop the polymerization. The results are shown in Table-3.

0.133 g/min of ethylene, 2,004 g/min of ethylene,

[Brief explanation of drawings]

Figure 1 shows Techniques of the present invention regarding Ziegler catalysts This is to help understand the details of the procedure.

Claims (1)

[Scope of Claims] 1. A solid catalyst component for a Ziegler type catalyst, which is obtained by contacting components (i), (ii), and (iii) below. ¥Component (i)¥ A solid component obtained by contacting the following components (A), Component (B) and Component (C), Component (A): A solid component containing titanium, magnesium and halogen as essential components, Component (b): A compound represented by M(OPh)_nX_m_-_n (where M is an atom of group III to V of the periodic table, m is a number corresponding to the valence of M, and n is 1 to m Ph represents a phenyl group or a substituted phenyl group, and X represents hydrogen, oxygen, halogen, a hydrocarbon residue having 1 to 10 carbon atoms, or an alkoxy group.) Component (c): tungsten halogen compound, ¥ component(
ii) Silicon compound represented by ￥ R^1R^2_3_-_nSi(OR^3)_n (where R^1 is a branched hydrocarbon residue having 3 to 20 carbon atoms, and R^2 is R^ R^3 represents a hydrocarbon residue having 1 to 20 carbon atoms that is the same as or different from 1, and R^3 represents a hydrocarbon residue having 1 to 12 carbon atoms. n is 1≦n≦3.) ¥ component (iii )￥ Organoaluminium compounds. 2. A catalyst for α-olefin polymerization, characterized by comprising the following components (A) and (B). ¥Component (A)¥ A solid catalyst component for a Ziegler type catalyst obtained by contacting the following components (i), (ii) and component (iii). ¥Component (i)¥ A solid component obtained by contacting the following components (A), Component (B) and Component (C), Component (A): A solid component containing titanium, magnesium and halogen as essential components, Component (b): A compound represented by M(OPh)_nX_m_-_n (where M is an atom of group III to V of the periodic table, m is a number corresponding to the valence of M, and n is 1 to m Ph represents a phenyl group or a substituted phenyl group, X represents hydrogen, oxygen, halogen, a hydrocarbon residue having 1 to 10 carbon atoms, or an alkoxy group.) Component (c): tungsten halogen compound, ¥ component(
ii) Silicon compound represented by ￥ R^1R^2_3_-_nSi(OR^3)_n (where R^1 is a branched hydrocarbon residue having 3 to 20 carbon atoms, and R^2 is R^ R^3 represents a hydrocarbon residue having 1 to 20 carbon atoms that is the same as or different from 1, and R^3 represents a hydrocarbon residue having 1 to 12 carbon atoms. n is 1≦n≦3.) ¥ component (iii )￥ Organoaluminium compounds. ¥Component (B)¥ Organoaluminum compound. 3. A method for producing an α-olefin polymer, which comprises bringing an α-olefin into contact with a polymerization catalyst consisting of the following components (A) and (B) to polymerize it. ¥Component (A)¥ A solid catalyst component for a Ziegler type catalyst obtained by contacting the following components (i), (ii) and component (iii). ¥Component (i)¥ A solid component obtained by contacting the following components (A), Component (B) and Component (C), Component (A): A solid component containing titanium, magnesium and halogen as essential components, Component (b): A compound represented by M(OPh)_nX_m_-_n (where M is an atom of group III to V of the periodic table, m is a number corresponding to the valence of M, and n is 1 to m Ph represents a phenyl group or a substituted phenyl group, and X represents hydrogen, oxygen, halogen, a hydrocarbon residue having 1 to 10 carbon atoms, or an alkoxy group.) Component (c): tungsten halogen compound, ¥ component(
ii) Silicon compound represented by ￥ R^1R^2_3_-_nSi(OR^3)_n (where R^1 is a branched hydrocarbon residue having 3 to 20 carbon atoms, and R^2 is R^ R^3 represents a hydrocarbon residue having 1 to 20 carbon atoms that is the same as or different from 1, and R^3 represents a hydrocarbon residue having 1 to 12 carbon atoms. n is 1≦n≦3.) ¥ component (iii )￥ Organoaluminium compounds. ¥Component (B)¥ Organoaluminum compound.