JPS6341509A - Method for gaseous phase polymerization of olefin or such - Google Patents

Abstract

PURPOSE:To obtain a polymer having high stereoregularity without reducing catalytic activity even in the absence of an electron donative compound in polymerization, by using a specific solid component as a solid acid component for Ziegler catalyst in a gaseous phase polymerization. CONSTITUTION:First, (A) a solid component comprising Ti, Mg and a halogen as essential components is brought into contact with (B) a silicon compound shown by formula R<1>R<2>3-nSi(OR)n (R<1> is branched chain hydrocarbon residue; R<2> is R<1> or other hydrocarbon residue; R<3> is hydrocarbon ; n 1-3) preferably 0-100 deg.C to give a solid catalytic component. Then an olefin is polymerized in a gas phase in the presence of a catalyst consisting of the solid catalytic component and an organoaluminum compound at 50-90 deg.C. The component A, for example, is obtained by bringing a magnesium halide and an electron donor to a Ti-containing compound. A compound shown by the formula may be cited as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for gas phase polymerization of olefins. More specifically, by using the solid component of the Ziegler catalyst as a specific solid component in the gas phase polymerization method, high polymerization activity and stereoregularity can be achieved regardless of the presence or absence of an electron-donating compound (external donor) during polymerization. A polymer with excellent properties can be obtained.

Prior Art Conventionally, the polymerization of olefins includes slurry polymerization using an inert solvent, solution polymerization, liquid phase bulk polymerization using the monomer itself as a solvent, gas phase polymerization using no solvent, and the like. In the former case, such as slurry polymerization using a solvent, operations other than polymerization such as separation of the polymer and solvent, drying of the polymer, recovery and purification of the solvent are required.

On the other hand, in the latter gas phase polymerization, operations other than the former polymerization are
tl is almost unnecessary, which is extremely advantageous in terms of the production cost of the polymer.

However, in gas phase polymerization, polymerization stability has conventionally been insufficient, making it difficult to perform stable operation and obtain polymers of high quality.

In addition, in order to omit the above-mentioned post-treatment step after polymer production in gas phase polymerization, a so-called "highly active catalyst" is required.

In recent years, a catalyst component in which a titanium compound is supported on a magnesium compound has been developed as a highly active catalyst. These catalyst components certainly have higher activity than conventional Ziegler catalysts, but when producing polymers of olefins with 3 or more carbon atoms, their stereoregularity often decreases, making them impractical for practical use. It's often not the point.

Therefore, various methods have been investigated to improve the stereoregularity of polymers. Among them, in addition to solid catalyst components and organoaluminum compounds, silicon compounds, amines, It is effective to use electron-donating compounds such as alcohols (for example,
No. 5-127408, No. 56-41206, No. 58-
83006 publications, etc.).

Catalyst systems using these wc3 additives are somewhat effective in slurry polymerization using solvents, but
In gas phase polymerization the effectiveness is greatly reduced. If you want to get the best effect, you need to increase the amount used. However, when the amount used increases, the catalyst activity decreases, the color of the polymer increases,
Leads to worsening odor levels.

Therefore, in gas phase polymerization, there is currently a need to develop a catalyst system that can produce highly stereoregular polymers of olefins having 3 or more carbon atoms without the use of a third additive. be.

Summary of the invention The present invention aims to provide a solution to the above problems,
The present invention was completed by studying various catalyst components.

That is, the present invention provides a method for polymerizing olefins in a gas phase in the presence of a catalyst, wherein the catalyst comprises the following components (A) and (I3). It provides legality.

Component (N Component (1): A solid component containing titanium, magnesium and halogen as essential components, and Component (ii) General 2 R'R'', n5i (OR3)
A silicon compound represented by n (where t is a branched hydrocarbon residue, B2 is a hydrocarbon residue that is the same as or different from R1, B3 is a hydrocarbon residue, and n represents a number of 1≦n≦3). , a solid component obtained by contacting Component (B) an organoaluminum compound.

Effects of the Invention When olefins (olefins having 3 or more carbon atoms in lrf) are subjected to gas phase polymerization using the catalyst system of the present invention, a highly active polymer with high stereoregularity can be obtained.

In general, in gas phase polymerization, since no solvent is used, the contact efficiency between each catalyst component is poor, resulting in less catalytic activity and lower stereoregularity than in stripe-one-foo polymerization. There is. In contrast, the catalyst system of the present invention has high catalytic activity and high stereoregularity because it does not use a third additive.

Another advantage of the present invention is that the polymer has good properties and a high bulk density. Although it depends on the manufacturing method of component (A) described later, O-4s t
It is also possible to achieve a bulk density of Q, 50t/a or more, or in some cases, Q, 50t/a or more.

Yet another advantage is the improved odor level of the polymerized polymer when using the catalyst system of the present invention. The cause of this is still not well understood, but
One reason is thought to be that no third additive is used.

Detailed Description of the Invention (Catalyst) The catalyst used in the present invention consists of component (A) and component (2).

Component (7i0) Component (A) is a solid component [component (i)] containing titanium, magnesium and halogen as essential components and -] general 2R'R--rI5i (OR3)n (however, R1
is a branched hydrocarbon residue, a hydrocarbon residue that is the same as or different from R2UR'', ■ is a hydrocarbon residue, n is 1≦n
It is a solid component obtained by contacting a silicon compound [component (ii)) represented by a number of ≦3].

The component (+) may contain titanium, magnesium, and halogen as essential components, and even if each of the above three components is included independently, it may also contain a compound such as titanium halide or magnesium halide, or an additive. It may be included in the form of objects.

Specific examples of this component (1) include, for example, JP-A-53
-45688, 54-3894, 54-310
No. 92, No. 54-39483, No. 54-94591, No. 54-118484, No. 54-131589,
No. 55-75411S No. 55-90510, No. 55
-90511, 55-127405, 55 1
．． 47507 Shiju, 55 155003 Bow-1 56
- No. 18609, No. 56 70005) No. 56 72
No. 001, No. 56-86905, No. 56 90807
No. 56-155206, No. 57-3803 Shiba No. 57-34103, No. 57-92007, No. 57-
No. 121003, No. 58-5309, No. 58-531
0 sun, No. 58 5311, No. 58-8706, No. 5
No. 8-27732, No. 58-32604S-11 No. 58
-32605, 58-67703, 58-11
720 (No. 3, No. 58-127708, No. 58-18
3708 size, 58-1.83709, 59-14
Examples of prior art include Publications No. 9905 and No. 59-149906.

In addition to the above-mentioned essential components, the component (1) used in the present invention may also include silicon, aluminum, boron, etc.
It is also possible that these components remain in component (1).

A specific example of the method for producing component (1) will be described below.

(a) A method in which magnesium halogenide, an electron donor, and a titanium-containing compound are brought into contact, and if necessary, treated with a specific solvent.

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

(c) A method of contacting a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymeric silicon compound with an electron donor, a titanium...halogen compound, and/or a silicon halogen compound, if necessary.

2) 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.

(e) A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact with the organomagnesium compound.

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

Magnesium compounds used to produce the above component (1) include magnesium noride, dialkoxymagnesium, alkoxymagnesium halide,
Examples include magnesium oxynoride, dialkylmagnesium, magnesium oxide, magnesium hydroxide, and magnesium carboxylate.

In addition, the titanium compound used for producing component (1) has the general formula Ti (OR)4-m
(Here, R4 is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, and X).
represents a number of 0≦n≦4). Specific examples are 'h C1a, T I B r
4, Ti (0CZH &) Cl3, Ti (0CzH
s)z Ctz, Ti(OCzl(s)actsTi(
0-ic3Hy) (J3, Ti(0-nc4H9)at
3, Ti (0-nC4us) 2 at2, Ti (0C
2H5) Brs, Ti(OC2Hsχ0Cd(o)z
(J, Ti(0-nc4Hs)aCtXTi(0-Cs
Hs) CLs, Ti(0-icn&)zCt2, Ti
(0CsHn) C13, Ti (0CaHts) a
t3, Ti (OC2H3)4, Ti(0-nc31(
r)4, Ti (0-n C4Hll)4, Ti(0-
iC4H9)4, Ti(0-nc6Hx3)n, Ti(
0-ncaH17) a, sealed (OCHzCH (CzHs)
Cd(o)< etc.

Alternatively, a molecular compound obtained by reacting TiX'4 (where X' represents . . . rogene) with an electron-donating compound may be used.

Specific examples Toshiteha, T1c/4・CH3COC2H5, T
i at < -CH3CO2C2H5, TiCl4・C
6H5N02, Ti C1<-C) T3COC1, TH
14.Ca) (sCOCl-1Tic/Lt.C6Hs
COzCzHs,'nc14ΦCIC0CzHs,T
Six types of Xct4, C4H40, etc. are obtained.

Also, electron donating compounds can be used when producing component (i). Electron-donating compounds that can be used to produce the solid component (1) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Oxygen-containing electron donors such as nitrites, nitrogen-containing electron donors such as ammonia, amines, nitriles, isocyanates, and the like can be exemplified.

More specifically, those having 1 to 1 carbon atoms, such as methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc.
8 alcohols; phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, naphthol; acetone, methyl ether ketone, methyl isobutyl Ketone, acetophenone, benzophenone, etc. with 3 carbon atoms
to 15 ketones: acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
Aldehydes having 2 to 15 carbon atoms such as tolualdehyde and nandoldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate,
Ethyl valerate, needle stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, phthalic acid Diptyl, dihebutyl phthalate, γ-butyrolactone, α
- Organic acid esters having 2 to 20 carbon atoms such as valerolactone, coumarin, phthalide, and ethylene carbonate; Inorganic acid esters such as silicic acid esters such as ethyl silicate, butyl silicate, and phenyltriethoxysilane; acetyl chloride, C2-C15 acid halides such as benzoyl chloride, toluyl chloride, anisyl chloride, phthaloyl chloride, iso-phthaloyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, aluminum ether, tetrahydrofuran, anisole, diphenyl ether, etc. Carbon number 2 or 2
Ethers of o; acetic acid amides such as acetamide, benzoic acid amide, and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine Nitriles such as acetonitrile, benzonitrile, tolnitrile, etc. can be mentioned. It is also possible to use two or more of these in combination.

The amount of each component to be used in producing component (i) 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 as a titanium source is within the range of 1 x 10 to 1000, preferably within the range of 0.01 to 10, in molar ratio to the magnesium compound as a magnesium source, and 1 x 1 of the halogen is used.
Similarly, the molar ratio to the magnesium compound is within the range of 0.1 to 100, preferably within the range of 1 to 50.

In addition, when using an electron donating compound as an optional component, the molar ratio is 1 x 10 to 1 to the magnesium compound.
within the range of 0.00, preferably within the range of 0.01 to 10.

As the catalyst component (i) used in the present invention, the solid component obtained as described above can be used as it is, or the solid component can be prepolymerized by contacting it with an olefin in the presence of an organoaluminum compound. It can also be used as

When component (i) is prepolymerized, this component (
There are no particular restrictions on the conditions for prepolymerization of olefins for producing 1), but numerically the following conditions are preferable. The polymerization temperature is 0 to 80°C, preferably 10 to 6°C.
It is 0°C. The amount of polymerization is 0 per gram of solid component.
．． It is preferred to polymerize 0.001 to 50 grams of olefins, more preferably 0.1 to 10 grams.

Generally known organic aluminum components can be used during prepolymerization.

Specific examples include At(C2H3)3, AL(isoc
tHe)s, At(CsHn)3. , u(CsHly
)s) I'J-(CtoHzx)s, At(C2Hs
)2ct, AL(isoc4H9)2Ct, AA(
CzHs)2H.

At(isoc+H9)2H1M(CzHs)z(OC
2Hs) etc.

Among these, AA(Cs+Hs)a, AL
(is.

C4H,)3. Further, a combination of trialkylaluminum and alkyl aluminum halide, a combination of trialkylaluminum trialkyl aluminum halide and alkyl aluminum ethoxide, etc. are also effective.

To give a specific example, AL(CzHs)3 and AA(C2R5
) Combination of two, Aj (1soc4H9)3 and At, (
1socnH*) combination of zC/=, kl (C2R5)
s and Aj (C2H3) 1.5 (also 1.5 combination,
AA(CzHs)3 and AA(CzHs)zc2 h A
The combined use of 2(C2Hs)2(OC2Hs), etc. may be mentioned.

The amount of organoaluminum component used during prepolymerization is M/Ti (molar ratio) relative to the Ti component in the solid component.
and is 1 to 20, preferably 2 to 10.

In addition to these, alcohol, ester,
Known electron donors such as ketones can also be added.

The olefins used in the prepolymerization conditions include ethylene,
Propylene, 1-butene, 1-hexene, 4-methyl-
Examples include pentene-1. It is also possible to coexist with a prepolymerization condition element.

A component obtained by prepolymerizing a solid component containing titanium, magnesium, and halogen as essential components by contacting it with an olefin in the presence of an organoaluminum compound (
1) is obtained.

Component (ii) to be brought into contact with the above component (1) to produce component (A) of the catalyst used in the method of the present invention has the general formula R1R7n5i(OR3)n (wherein R1 is a branched chain R2 is the same or different hydrocarbon residue as R1, R3 is a hydrocarbon residue, and n is a number of 1≦n≦3.

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.
It is a carbon atom of class.

Particularly preferred are those in which the carbon atom bonded to the silicon atom is tertiary. The carbon number of R is usually 3 to 20, preferably 4 to 10. De is usually a branched or linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. R3 is usually an aliphatic hydrocarbon group, preferably a chain aliphatic hydrocarbon group having 1 to 4 carbon atoms.

Specific examples of the silicon compound of component 01) are shown below.

CF(s CT(3CH
3Ct, (a (CHa)3C-8i(OCJ(3h, (CI(3)3
C-8i (OC2H5)3C■ (3CIT3 etc.

The contact conditions of the above component (1) (either prepolymerized or non-prepolymerized) and component (11) are as follows:
Although any conditions may be used as long as the effects of the present invention are recognized, numerically, the following conditions are preferable.

The contact temperature is about -50 to 200°C, preferably 0 to 100°C. 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, hydrogen halitide, polysiloxane, and the like.

Regardless of the presence or absence of prepolymerization of component (i), the quantitative ratio of component (1) to component (11) is the atomic ratio of silicon in component (11) to the titanium component constituting component (1) (silicon/titanium). may be within the range of 0.01 to 1000, preferably 0
．． It is within the range of 1-100.

Component (Caterization 8)) is an organoaluminum compound. Specific examples include R-nAtXn spanning, Rf3-rn A1.
(OR')m (here, R5 and R6 are hydrocarbon residues or hydrogen atoms having about 1 to 20 carbon atoms, which may be the same or different)
R7 is a hydrocarbon residue, XFi halogen, and n and m are each represented by O<n (3, O<rn<3).

Specifically, (a) trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, ←) diethylaluminium monochloride, diisobutylaluminum monochloride, Alkylaluminum halides such as ethylaluminum sesquichloride and ethylaluminum dichloride; (iii) diethylaluminum hydride and diisobutylaluminum hydride; and aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide.

Other organometallic compounds may be added to these organoaluminum compounds (a) to (c), such as beard-aAZ(OR9)a(1
≦a≦3, R8 and R9 are hydrocarbon residues having about 1 to 20 carbon atoms, which may be the same or different.) Alkylaluminum alkoxides represented by the following formula can also be used in combination.

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.

(Polymerization) The polymerization method in the present invention is gas phase polymerization. The polymerization method may be any method such as continuous polymerization, batch polymerization, multistage polymerization, etc.

The polymerization temperature is from room temperature to about 100°C, preferably from 50 to 90°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time.

The ratio of the amounts used of component (A) and component (13) may be arbitrary as long as the effects of the present invention are observed, but numerically it is preferably within the following range. Component C for component (A)
The weight ratio of B) [component (B)/component (A)] is 0.1 to 1
000, preferably within the range of 1-100.

The polymerization pressure ranges from normal pressure to about SOW/*, and in order to remove the heat of polymerization, a liquid easily volatile hydrocarbon such as propane or butane may be supplied and vaporized in the polymerization zone.

(Olefins) The olefins used in the method of the present invention have the general formula R-C
It is represented by H=CI'Lt (where R is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and may have a branching group). Specifically, ethylene, propylene, butene-1, pentene-1, hexene-1,
There are olefins such as 4-methylpentene-1. Preferred are ethylene and propylene.

In the case of these polymerizations, it is possible to carry out copolymerizations with up to 50 weight percent, preferably 20 weight percent, of the above olefins, based on ethylene, and up to 30 weight percent of the above olefins, in particular with ethylene, based on propylene. can be copolymerized.

Further, in addition to the above-mentioned olefins, copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefins) can also be carried out.

Experimental Examples Example 1 [Production of component (i)] 100 ml of dehydrated and deoxygenated n-hebutane was introduced into a flask with an inner diameter of 10 crn that was sufficiently purged with nitrogen, and then 20.1 mol of MgCl, Ti(O-nC4H
9) 0.2 mol of 4 was introduced and reacted at 95°C for 1 hour. After the reaction was completed, the temperature was lowered to 40° C., 15 ml of methylhydrodiene polysiloxane was introduced, and the reaction was allowed to proceed for 3 hours at a stirring speed of 20 rpm. After the reaction was completed, the produced solid component was washed with n-hebutane, a portion of which was taken out, and the average particle size was measured by a sedimentation method and found to be 24.5 microns.

Then, 75 milliliters of n-hebutane was introduced into the thoroughly purified flask, and the solid component was reduced to 0.00 milliliters in terms of dog atoms.
Then, 40.1 moles of 5ict were mixed with 25 ml of n-hebutane, and the mixture was introduced into the flask at 30°C for 30 minutes, and reacted at 90°C for 3 hours. Next, add 0 7-talyl chloride to 25 ml of n-hebutane.
．． 006 moles were mixed and introduced at 90°C for 30 minutes,
The reaction was carried out at 90°C for 1 hour. After the reaction was completed, it was washed with n-hebutane. Next, 425 mm+) liters of TiCt was introduced and reacted at 110° C. for 3 hours. After the reaction was completed, it was thoroughly washed with n-hebutane. A portion was taken out and the titanium content was measured and found to be 2.56% by weight.

Then internal volume 1.5 with stirring and temperature control device
500 milliliters of sufficiently dehydrated and deoxygenated n-hebutane, 2.1 grams of triethylaluminum, and 10 grams of the solid component obtained above were each introduced into a 1 J bottle stainless steel stirring tank. The temperature inside the stirring tank is set to 20
℃, propylene was introduced at a constant rate, and propylene polymerization was carried out for 30 minutes. After the polymerization was completed, it was thoroughly washed with n-hebutane. When a portion was taken out and the amount of propylene polymerized was examined, it was found to be 0.99 grams of propylene per gram of solid component. The solid component thus obtained was used as component (t) below.

[Production of component (c)]

Into a flask that had been sufficiently purged with nitrogen, 50 milliliters of sufficiently purified n-hebutane was introduced, and then 5 grams of component (i) obtained above was introduced, and the components (iD as a silicon compound, Hs CHs CH3 26 and was brought into contact for 2 hours at 30°C. After the contact was completed, the mixture was thoroughly washed with n-hebutane, and the component (A) was prepared.

[Gas phase polymerization of propylene]

Using the gas phase polymerization apparatus disclosed in Example 1 described in JP-A-57-73011, sufficiently purified polypropylene powder was charged into the apparatus, and then 100 mg of triethylaluminum and the above-mentioned 20 milligrams of each ingredient was introduced. Next, 500 milliliters of hydrogen gas was introduced, introduction of propylene was started at 75°C, and polymerization was carried out for 3 hours at a total pressure of 7 kg/cr 1175°C.

The result was 197 grams of polymer.

This polymer had MFR = 2.39/10 min, polymer bulk specific gravity = o, 4 s t /cc, and the smell of the polymer was found to be 2nd grade with almost no odor according to a sensory test. Also, 1, I = 99.0 weight percent.

The odor test method is to put 20g of the produced polymer powder into an Erlenmeyer flask, heat it at 80℃ for 2 hours, and evaluate it in 5 grades from odorless grade 1 to grade 5 in a sensory test using the sense of smell of 5 panelists. The students were divided into classes.

1. Measurements were made by extracting the resulting polymer powder with boiling hebutane for 6 hours.

Comparative Example 1 [Manufacture of component mass] Under the catalyst component production conditions of Example 1, component (1) and component (11) were not brought into contact and component (1) was used as it was as a component mass.

[Polymerization of propylene]

Polymerization of propylene was carried out in the same manner as in Example 1, except that the catalyst component (A) was changed to that produced above under the polymerization conditions of Example 1, and 21.4 milligrams of diphenyldimethoxysilane was further used as the third component. Ta.

As a result, 127 grams of polymer were obtained, MFR = 5
．． 1 y/1o min, polymer bulk specific gravity = 0.44t/cr
,,The odor of the polymer is quite strong and quaternary, 1,I
= 98.5 weight percent.

Examples 2 to 4 [Production of component (E)] In the production of component (A) in Example 1, the same amount of the compound shown in Table 1 as component (jl) [based on the molar ratio (silicon /Titanium = 3) was used, but the same method as in Example 1 was used to produce the component.

[Polymerization of propylene]

Under the polymerization conditions of Example 1, component (B) shown in Table 1
Polymerization was carried out in the same manner as in Example 1, except that the type and/or amount used and the polymerization temperature were changed.

The results are shown in Table-1.

(Leaving space below) Example 5 [Production of component (i)] 75 ml of thoroughly degassed and purified n-hebutane was placed in a 1-liter flask that had been purged with nitrogen, and 10 grams of MgCl2 and Ti (0 -ncgHe)i was introduced in an amount of 10 ml and reacted at 70°C for 30 minutes. Next, a mixture of 5.4 ml of n-hebutane and 5.4 ml of n-butanol was introduced from the spray nozzle in 7 seconds to form droplets of 180 microns.
The reaction was carried out at 0°C for 1 hour.

Next, 17.4 milliliters of SiC/4 was introduced at 30°C for 1 hour, and the mixture was reacted at 90°C for 2 hours. After the reaction is complete,
Washed with n-hebutane. Next, 0.014 mol of diheptyl phthalate was mixed with 25 ml of n-hebutane, and the mixture was introduced at 70°C for 0.5 hours, followed by reaction at 90°C for 1 hour. After the reaction was completed, it was washed with n-hebutane. Then T
475 milliliters of iCt was introduced and the reaction was carried out at 110°C for 3 hours.

After the reaction was completed, it was washed with n-heptane to obtain component (1).

[Manufacture of ingredient prisoners]

50 milliliters of sufficiently purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and then 3 grams of component (1) obtained above were added, followed by the silicon compound of component (11). 5H3CH3 and was brought into contact at 50°C for 2 hours. After the contact was completed, the product was thoroughly washed with n-hebutane to obtain component (A).

[Polymerization of propylene]

Propylene was used in the same manner as in Example 1, except that the polymerization conditions of Example 1 were changed to 300 mg of triisobutylaluminum instead of triethylaluminum, the amount of component (c) used was changed to 20 mg, and the polymerization temperature was changed to 70°C. Polymerization was carried out.

The result was 188 grams of polymer.

This polymer has an MFR of 2.9 t/1o, a polymer bulk density of 0.39 t/ct, and a polymer odor of 3.
1. I = 97.1 weight percent.

Comparative Example 2 [Manufacture of Component Container] Under the manufacturing conditions of Example 5, component (1) was not used and component (1) was used as it was as component (A).

[Polymerization of propylene]

Polymerization was carried out under the same conditions as in Example 5 except that the components obtained above were used. As a result, 137 grams of polymer was obtained, which had MFR=2x, 4y/1a min, polymer bulk density=o, a4t/engine, and 1. I=s
It was 1.4 weight percent.

Examples 6 to 7 [Production of component (1)] In the production of component (i) in Example 1, 40.06 mol of 5ict was used instead of TiCt4, and the reaction time was 6
Component (1) was produced in the same manner as in Example 1, except that the time was changed.

[Manufacture of component (A)]

In the production of component (A) in Example 1, the component obtained above (
Component (A) was produced in the same manner as in Example 1, except that the compounds shown in Table 2 were used as i) and component (11).

[Polymerization of propylene]

Polymerization of propylene was carried out under the same conditions as in Example 1, except that the components obtained above were used. The results are shown in Section 2.

(Margin below)

[Brief explanation of drawings]

FIG. 1 is intended to assist in understanding the technical content of the present invention regarding Ziegler catalysts.

Claims (1)

[Claims] (1) A method for polymerizing olefins in a gas phase in the presence of a catalyst, wherein the catalyst comprises the following components (A) and (B). ¥Component (A)¥ Component (i): A solid component containing titanium, magnesium and halogen as essential components, and Component (ii): General formula R^1R^2_3_-_nSi(
OR^3)_n (where, R^1 is a branched hydrocarbon residue, R^2 is the same or different hydrocarbon residue as R^1, R^3 is a hydrocarbon residue, and n is 1≦ A solid component obtained by contacting a silicon compound represented by n≦3), ¥Component (B)¥ Organoaluminum compound.