JPS63142008A - Production of ethylene-olefin copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer of specified density, by bringing ethylene and an olefin into contact with a specific catalytic system made up of organoaluminum compound, etc. to prevent developments of polymer attachment. bulk polymer, low melting point polymers of low molecular weight, etc. CONSTITUTION:The objective copolymer with a density 0.900-0.945g/cm<3> can be obtained by bringing ethylene and a >=3C olefin into contact, under a solventless condition, with a catalytic system consisting of a combination of (A) a product from contact of (i) a component derived from prepolymerization between a) a component containing, as the essential constituents, Ti, Mg and halogen (e.g., a component containing as the essential constituents, TiCl4 dialkoxymagnesium, fluorine, etc., and also containing SiCl4, etc.) and b) 0.1-50 (pref., 0.5-20)g par g the component a, of an olefin and (ii) an organoaluminum compound (e.g., trimethyl, aluminum) and (B) an organoaluminum compound.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing an ethylene copolymer by copolymerizing ethylene and an olefin having 3 or more carbon atoms under solvent-free conditions.

As has been known in the art, when ethylene is copolymerized with ethylene, the resulting copolymer has a lower polymer density than that of a homopolymer. Methods for producing copolymers of ethylene and olefins are broadly classified into two types. That is, one is the so-called "solution 1 reaction" (generally at high temperature), which is performed by dissolving the produced polymer in a solvent such as a hydrocarbon. The remaining one is the so-called "U-slurry polymerization" or "gas phase polymerization" which involves polymerization substantially with the formation of polymer particles.

The latter polymerization method, "gas phase polymerization," is an excellent method for producing a copolymer because it does not use a solvent. However, "gas phase polymerization" has problems such as polymer layer formation, formation of bulk polymers, and generation of low-melting-point, low-molecular-weight polymers. Regarding these problems,
Although some proposals have been made to improve this, it cannot be said that it has been significantly improved.

Prior art Prior art includes JP-A-55-52309 and JP-A-55-52309.
-54308, 55-58210, 58-12
Publications No. 2904 are cited.

These prior art techniques have the effect of improving the above-mentioned problems to some extent, but they are still inadequate from a practical point of view.

SUMMARY OF THE INVENTION The present invention involves contacting a catalyst system consisting of a combination of the following components and component (B) with ethylene and an olefin having 3 or more carbon atoms under solvent-free conditions to obtain a polymer density of 0.900-0.
The present invention provides a method for producing an ethylene-olefin copolymer, which is characterized by obtaining an ethylene-olefin copolymer having a molecular weight within the range of 945 f/-.

Ingredients Contact product of component (AI) and component (A2), component (A1), containing titanium, magnesium and nitrogen as essential components, to component (a) containing p0.0 per 1 gram of component (a).
A component obtained by prepolymerizing 1 to 50 grams of olefin. Component (A2): Organoaluminide; Component (B): Organoaluminum compound.

Effects of the Invention The present invention can provide solutions to various problems that arise in gas phase superimposition in producing ethylene-olefin copolymers. i.e. polymer attached layer,
The generation of lumpy polymers, low melting point low molecular weight polymers, etc. is prevented. Preventing polymer adhesion and generation of polymer lumps is extremely important for operational stability. Also, low melting point, low molecular weight polymers have a negative impact on the quality of the produced polymer. For example, this can lead to stickiness in the film and a decrease in strength.

Further, a feature of component (A) of the catalyst used in the present invention is that component (A) has little adhesion. It is thought that this leads to the above-mentioned improvement in polymer adhesion and prevention of the formation of lumpy polymers.

Further, in the present invention, it is possible to produce a polymer having a high polymer bulk specific gravity, specifically, 0.409/C
C or more, and it is also possible to make it more than 0.45 g/cc.

The catalyst used in the present invention is composed of a combination of component (B) and component (B), and may be used in combination with known electron-donating metals (external donors), etc., as long as the effects of the present invention are not impaired. .

Component (A) Component (A) is a contact product produced by contacting component (Aυ) and component (A2).

Component (A1) Component (A1) is obtained by prepolymerizing component (a) described below with a certain amount of olefin.

Production of component (a): Component (a) is a solid component containing titanium, magnesium and halogen as essential components, and is itself known.

As component (a), known examples include JP-A-53-456.
No. 88, No. 54-3894, No. 54-31092,
P2S5-39483, P2S54-94591, P2S5
No. 4-118484, No. 54-131589, 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. 456-72001, No. 56-86905 2)? il'J 56-90807
No. 456-155206, No. 57-3803, No. 57-34103, No. 57-92007+;-1 No. 5
No. 7-121003, No. 58-5309, No. 58-5
No. 310, No. 58-5311, No. 58-8706,
No. 58-27732, No. 58-32604, No. 58
-32605, 58-67703, 58-11
No. 7206, No. 58-127708, No. 58-183
No. 708, No. 58-183709, No. 59-1 '4
9905, 59-149906, etc. are used.

Magnesium compounds serving as the magnesium source for the catalyst used in the present invention include magnesium halide,
Examples include dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like.

In addition, the titanium compound serving as a titanium source has the general formula Ti (
OR") 4-nXn (here, R1 is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms,
X represents halogen, and n represents a number of 0≦n≦4. ) can be mentioned. As a specific example, 'l
'i Cl i Tj Br4, Ti (QC, H,) (IJ
sTi(QC.

Hs)z(llJz, Ti (0C2Hs)z (J,
TiC0-ncsHt)Cds,'pl(0-HC
4H@)Cjs, Ti (0-(I C4HJ
2 C's,'f'i (0CzHs) B T3,
T' (QC, H,) (oc4uJ z CJ %'
ri (0-nC4H1l)3ce,'l'i (0-
C,H,)CJ,Ti(OiC4H,)2CA! □、T
l (QC,t(,□)CI,,Tj (0C6HIB
)C1,'l't (0C2Hs)i % TI
(o-nCIJ(?)4,T'(0-nCj(J4,T
1 (0-ic4Hs) I Tl (0-HCaHta) I T
'(0-nC4H1l)4% Ti(OCf(2CH(
C2Hs)CaHJa, etc. Among these, especially
1'1C14 is preferred.

It is also possible to use a molecularized ornament obtained by reacting TIX' (where X' represents halogen) with an electron donor as described below. As a specific example, TiC14・CHjcoc
2H,,TtCJ4 @ CH,co2c,H,,'
pi (J4 a C6H.

No,, Ttα,・CHICOCI, Tiα4・C
,H,C0CJ,TlC14・C1H,CO□C2H'jiα4・αCOC,i−1,,1′1CIl,・
Examples include C,1(, O, etc.

The halogen source is usually supplied from the above-mentioned magnesium and/or titanium]-halogen compounds, but known halogen sources such as aluminum 710 halides, silicon halides, and phosphorus norogen compounds can be used as halogen sources. It can also be supplied from an agent.

The halogen contained in component (a) K@ may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred.

Component (a) of the catalyst used in the present invention includes, in addition to the above-mentioned essential components, siag, cn, 5icA! Silicon compounds such as methylhydrodiene polysiloxane, AI (Ois.

C5Hs)3, AlCll3, #Br3, AJ (0
C2H5)! , AJ(OCH3)2(?J and other aluminum compounds and B(OCH3)I B(QC,H,
It is also possible to use other components such as boron compounds such as ), B (OC,, Hs)s, which may remain in component (a) as components such as silicon, aluminum and boron.

Furthermore, component (a)'kW can also be produced using an electron donor as an internal donor.

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

More specifically, those having 1 to 1 carbon atoms, such as methanol, ethanol, furopanol, pentanol, hexanol, ocmenol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylpenzyl alcohol, etc.
Alcohols of 8; phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, flobylphenol, cumylphenol, nonylphenol, naphthol; acetone, methylethylketone, methylinophylphenol Ketones having 3 to 15 carbon atoms such as ketones, acetophenone, and benzophenone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, and ethyl acetate. , vinyl acetate, propyl acetate, octinoacetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, benzoate Methyl acid, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, anisic acid Methyl, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, r-butyrolact/, α-
Organic acid esters having 2 to 20 carbon atoms such as valerolactone, coumarin, phthalide, and ethylene carbonate; Inorganic acid esters such as silicate esters such as ethyl silicate, butyl silicate, and phenyltriethoxysilane; acetyl chloride, benzoyl Acid halides having 2 to 15 carbon atoms such as chloride, toluic acid chloride, anisyl chloride, phthaloyl chloride, and phthaloyl chloride; methyl ether, ethyl ether, isopropyl nityl, butyl ether, aluminum ether, tetrahydrofuran, anisole, diphenyl ether, etc. Carbon number 2 to 20
ethers; acetic acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine,
tribenzylamine, aniline, pyridine, picoline,
Amines such as tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile, and tolnitrile; and the like can be excluded. Two or more types of these electron donors can be used.

The weight ratio of the components of this component (a) is Ti/M? The atomic ratio is within the range of I
It is preferable that the y atomic ratio is within the range of 0.5 to 4, and the optionally contained electron donor/my molar ratio is within the range of 1 or less.

When silicon, aluminum and boron compounds are contained, the molar ratio of these compounds to the amount of the above-mentioned magnesium compound used is in the range of I x 10-'' to 100, preferably in the range of l x 10 to l. It is within.

Component (a) of the catalyst used in the method of the present invention can be produced by a known method, but the following production method is particularly preferred.

(a) Activated magnesium halide and, if necessary, an electron donor and a titanium compound at the same time or Fi
A method of manufacturing by gradually co-pulverizing or contacting in a liquid state. A halogenating agent may be further brought into contact with this.

(b) Applying an electron donor as necessary to the precipitate obtained by reacting a halogenating agent, a reducing agent, etc. to a magnesium compound in a homogeneous state in the presence or absence of an electron donor; A method for producing a catalyst by contacting titanium compounds.

(A method for producing tM by reacting an organomagnesium compound vlJ such as a Grignard reagent with a halogenating agent, a reducing agent, etc., and then contacting it with an electron donor and a titanium compound as necessary.

B) A method for producing a catalyst by contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor.

Production of component (A1): The component (A1) of the catalyst used in the present invention is the above component (
It is obtained by prepolymerizing a certain amount of olefin to a). The preliminary N-association is carried out using a catalyst system consisting of the above component (a) and an organoaluminum compound.

Any organic aluminum compound can be used here.

Specific examples include R23-nAIXn塘 or R”3--
hl(OR')m (Here, R2 and R3 are hydrocarbon residues having about 1 to 20 carbon atoms or hydrogen, which may be the same or different, R'id hydrocarbon residue, X is halogen, +1 and m Each fL is expressed by 0≦n (3,0 (m (the number 3)).Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, Trialkylaluminum such as trioctylaluminum, tridecylaluminum, (b) Alkylaluminum halide such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) Diethylaluminum hydride, diisobutyl aluminum hydride, to)
Examples include aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminium phenoxide.

These organoaluminum compounds (a) to (c) may contain other organometallic compounds, such as IC' 3-anr (Of also 6) a (l≦a≦3, R5 and R6 may be the same or different). It is also possible to use an alkyl aluminum alkoxide represented by (which is a hydrocarbon residue having a carbon number of 1 to 208 degrees) 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.

Preliminary loading conditions are arbitrary as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The polymerization temperature is 0 to 80°C, preferably 10 to 60°C.
It is.

The amount of polymerization is 0.1 to 5 per gram of component (a).
It is preferred to polymerize 0 grams of olefin, more preferably 0.5 to 20 grams of olefin. If the amount of prepolymerization is too small, the desired effect of the present invention cannot be obtained, and if it is too large, problems such as a decrease in catalyst activity will occur.

The amount of the organoaluminum compound used during prepolymerization is 0.1 to 100, preferably 1 to 10, in terms of Al/Ti (mole ratio), based on the titanium component in component (a). Examples of the olefin used in the prepolymerization include ethylene, phlopylene, butene-1, hexene-1,4-methyl-pentene-1, and mixtures thereof may also be used. Preliminary polymerization can also be carried out in the presence of hydrogen.

Component (A2) Component (A2) of the catalyst used in the present invention is an organoaluminum compound. As this organoaluminum compound, the same compound as that used in producing the above-mentioned component (A2) can be used, but a more preferable result is a compound of the general formula R
:A7 and R1-1AA+Xx (here, R7 is hydrogen or a hydrocarbon residue having about 1 to 10 carbon atoms, R11 is a hydrocarbon residue having about 1 to 10 carbon atoms, and i is 1≦i<
3, and X represents a halogen). For example, AIC
CxHs)x and AJ(C'2H5)2 C'% Al
(i C<He)s and AJ (CtHs)2 C1%
Al (i C4Hv)zH and AI! (CtHs)
2 C1, AI (C2Ha) 2 H and hl (C
.

R5) Brz Al(n-CiHl2)j and A12 (
CzHa)s C13, AA'(n-C1, H2□)j
(!: hlcc2Hs) C1z, AI! (02B2)
, and Al2cc2Hs)sClj, AI(C2H5)s
and AJ(n-CsH+t)s and AI(CtHs)z
Examples include C1, etc.

Production of component: Component (A) of the catalyst used in the method of the present invention is obtained by contacting component (A1) and component (A2) described above.

The contact conditions may be any conditions that provide the effects of the present invention, but the following conditions are generally preferred.

The contact temperature is 0 to 100°C, preferably ld20 to 8
It is 0°C. The contacting method is generally preferably carried out under stirring, and may be carried out in the presence of an inert solvent such as a hydrocarbon or a halohydrocarbon. Specific examples of these hydrocarbons include tehahexane, heptane, toluene, and cyclohexane, and specific examples of halogenated hydrocarbons include n-butyl chloride, 1,2-dichloroethylene, carbon tetrachloride, and chlorobenzene. The usage ratio of A1) and component (A2) is 0°01 to 100 in terms of Al/Ti (molar ratio) to the titanium constituting component (at)i.
It may be within the range of 0, preferably within the range of Zoo.

Component (B) Component (B) Fi is an organoaluminum compound, which can be selected from those shown as specific examples as organoaluminum compounds that can be used in the production of component (A1). This organoaluminum compound as component (B) may be the same or different from the organoaluminum compound used in the production of component (A1), and may be the same or different from the organoaluminum compound used as component (A2). It's okay.

The amount of these organometallated fractions to be used is not particularly limited, but the weight ratio to the solid catalyst component (A) of the present invention is 0.
It is preferably within the range of 5 to 1000.

Copolymerization of ethylene and olefin (olefin) Specific examples of olefins having 3 or more carbon atoms to be copolymerized with ethylene using the catalyst used in the method of the present invention include propylene, butene-11 pentene-1, hexene-1,4 -methyl-pentene-1, heptene-11 octene-1%7 sen-1, and the like. Preferred olefins are those having 3 to 10 carbon atoms. It is also possible to use mixtures of the above olefins.

The amount of olefin to be used relative to ethylene varies depending on the required polymer density, but is generally from 1 mole percent to 50 mole percent.

(Polymerization conditions) Copolymerization is performed under solvent-free conditions. The process of the invention is therefore carried out in the gas phase polymerization mode in the absence of carbonized limescale solvent. The polymerization equipment used is fluidized bed type, stirred seed type,
[Hydrogen can also be used as an auxiliary].

(Produced copolymer) The ethylene-olefin copolymer produced according to the present invention has a polymer density of 0.900 to 0.945 t/i,
Usually it is 0.910 to 0.93597 m.

Experimental Examples Example 1 [Threat of component (a)] 20 milliliters of dehydrated and deoxygenated n-hebutane was introduced into a flask with an inner diameter of 10 (7) which was purged with nitrogen, and then MP, 720.1 mol, Ti(0-nC.

H9) 0.2 mol of 4t was introduced and reacted at 95°C for 1 hour. The diameter of the stirring blade used at that time was 9 crn. After the reaction was completed, the temperature was lowered to 40° C., 15 ml of methylhydrodiene polysiloxane was introduced, and the reaction was carried out for 3 hours at a stirring speed of 2 Or, p, m.

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 28.2 microns.

The solid components described above were introduced into an optically purified flask.

50 ml of n-hebutane, 44.4 ml of TicA and 1 ml of methylhydrogen polysiloxane
Two milliliters of the mixture was mixed together, introduced into a flask at 30°C, and reacted at 70°C for 2 hours. After the reaction was completed, it was washed with n-hebutane to obtain component (a).

[Threat of component (A1)] Content 1Ji1.517 with stirring and temperature control device
Into a stainless steel lined autoclave of a tube, 500 milliliters of fully dehydrated and deoxygenated n-hebutane was introduced, followed by 4.5 grams of triethylaluminum and 15 grams of component (a) mentioned above. . Set the temperature to 50℃ and add hydrogen gas at a partial pressure of 1/
Ethylene was introduced at a partial pressure of lkF/- through cds, and the mixture was heated at 50° C. for 1 hour. After finishing the weighting, unreacted gas was purged, and the component (A
1). The amount of component (a) in the prepolymerization chamber was 99.5 grams per gram.

[Production of component (A)] In a flask that had been replaced with nitrogen, an n-
Take 100ml of hebutane, add 10g of the ingredient (A1) left behind in the upper d pipe, and add AJ as ingredient (A2).
Add 1.0 g of (C2H5) s and heat at 30°C for 2
Contacted for an hour. After the contact was completed, the product was optically washed with n-hebutane to obtain component (A).

When the amount of the obtained component (A) adhered to the wall of a glass flask was examined, it was found to be 0.2 grams per gram of component (A) (hereinafter, this amount of adhered material will be abbreviated as K).

The amount of adhesion was measured as follows. - Feet! (approximately lθ grams) of component (A) was introduced into a glass flask, shaken for 10 minutes, and then the component (A) was removed from the flask.
We measured wit with 9 out.

[Ethylene! Sweet

Using the apparatus for gas phase polymerization disclosed in Example 1 described in JP-A-57-73011, optically purified polyethylene powder' was charged into the apparatus, and then component (B )
100 milligrams of triethylaluminum and 105 milligrams of component (A) synthesized above were introduced. Next, hydrogen gas was introduced at 1.2 mm/d, and the history [8
At 5°C, an ethylene-butene-1 mixed gas containing butene-1'iil O form y<1 was introduced, and the total pressure was 9 kf.
/cIi for 2.5 hours at 85°C.

As a result, 193 grams of polymer was obtained, with M F R” 1.6 W/10 min, polymer bulk density = 0.44 f/cc, polymer density = 0
．． 921P/cII4.

When the amount of bulk polymer and f of polymer adhesion in the polymerization tank were investigated, they were 0.002 g and 0.0 Ol g, respectively, per 1 g of normal polymer (hereinafter abbreviated as P and Kp).

Comparative Example 1 In the production of the component powder in Example 1, component (Az) was not used, and component (Al)'ft was used as it was as component (A). Polymerization was also carried out under exactly the same conditions as in Example 1. As a result, 174 grams of polymer was obtained, M1=”R=2.6?/10 min, polymer bulk ratio [=
0.40 f/cc, polymer density [= 0.923
r/cd, p=0.015, Kp=0.01
7, K=0.16.

Examples 2 to 7 The same procedure as in Example 1 was carried out except that the compound shown in Table 1 was used as component (A2) and the reaction conditions were used to produce the component powder in Example 1, and ethylene polymerization was also obtained. The same procedure as in Example 1 was carried out except that component (A) t- was used. The results are shown in Table-2.

(Leaving space below) Example 8 [Production of component (a)] Into a 1-liter flask that had been purged with nitrogen, 75 ml of thoroughly degassed n-hebutane was added, and anhydrous MS' (, ”10 grams of J2 (pulverized for 24 hours in a ball mill) and Ti (O-nC4H9
) 4k'' milliliter was introduced and reacted at 70°C for 30 minutes.Next, a mixture of 5.4 milliliters of n-butanol and 5.4 milliliters of n-hebutane was added.
Spray nozzle so that the a droplet is 0 micron, 91
The mixture was introduced for 0 seconds and reacted at 70°C for 1 hour. There,
TiC/44t-2,3 Mi 171J Tsutle introduced, 7
The reaction was carried out at 0°C for 1 hour. Next, 9 milliliters of methylhydrodiene polysiloxane was introduced and reacted at 70°C for 2 hours.

After the reaction was completed, the average particle size of component (a) was measured and found to be 1
It was 6 microns.

[Ingredient 2) Sweet acid] Under the prepolymerization conditions of Example 1, 8.6 grams of triisobutylaluminum was used in the triethylaluminum paste, the temperature was changed from 50°C to 65°C, and the polymerization time was changed to 15 minutes. Prepolymerization was carried out in the same manner as in Example 1 except for the following. The amount of prepolymerization is 06.4 per gram of component (a).
It was grams.

[Manufacture of component (A)]

In the production of component (A) in Example 1, (C2H4)s
Ad glue 9 (n - C, H, 2), AI 2.
Component (A) was prepared in the same manner as in Example 1 except that 6 grams was used.

[Ethylene-propylene (7) cojl) In the polymerization of Example 1, 200 mg of triisobutylaluminum was used instead of triethylaluminum as the organic aluminum of component ω), and the component (A) obtained above was
Polymerization was carried out in the same manner as in Example 1, except that an ethylene-propylene mixed gas containing 1 mg of ethylene-butene-1 was used instead of the ethylene-butene-1 mixed gas. As a result, 2
01 grams of polymer was obtained, M F R = 2.1
9710 minutes, polymer bulk specific gravity = 0.40? /C
C, polymer density = 0.919 y/cd, p = o, o
03, Kp = 0.002, K = 0.03.

Example 9 [Synthesis of component (a)] In the production of component (a) in Example 1, component (a) was created in the same manner as in Example 1, except for the following changes. Methylhydrodienepolysiloxane glue 5r
0.25 mol of CI was used. Also TiC/44.
4 milliliters of Ti (J) and 12 milliliters of methylhydrodienepolysiloxane were reacted at 90°C for 3 hours using 47.5 milliliters of Ti (J4). After the reaction was completed, the mixture was washed with n-heptane and the component (a) did.

[Synthesis of component (A1)] Preliminary polymerization was carried out in the same manner as in Example 1, except that the prepolymerization conditions of Example 1 were changed as follows. Instead of triethylaluminum, a mixture of 4.3 g of triisobutylaluminum and 3.7 g of ethylsesquialuminum was used, the polymerization temperature was varied from 50°C to 70°C, and the polymerization time was 25 minutes. As a result, the total amount of Preliminary 1 was 5.7 grams per gram of component (a).

[Creation of ingredient (A)]

In creating component (A) of Example 1, (CzHs)x
The same procedure as in Example 1 was conducted except that a mixture of 0.7 g of (1CaHe)3hi and 4 g of (C2Hs) ik12C130 was used as a component of Az.

[Polymerization of ethylene]

Under the polymerization conditions of Example 1, the amount of (CzHs)nAz used was 50 mg, and component (A) synthesized above.
Polymerization was carried out under the same conditions as in Example 1 except that the amount was changed to 67 mm IJ grams. 256 grams of polymer were obtained, MFR = 1.4 r/10 min, polymer bulk density = 0
．． 40t/hiro, polymer density = 0.919ri/72)'
= 0.004, Kp = 0.003.

Examples 10 to 11 and Comparative Examples 2 to 3 Prepolymerization was carried out in the same manner as in Example 1, except that the preliminary ML conditions of Example 1 were changed as shown in Table 3. ) and use this to obtain the component (
A was sweetened. Furthermore, ethylene-butene-1 co-injection was carried out in the same manner as in Example 1, except that this component (A) was used. The results are shown in Table-2.

(Margin below)

[Brief explanation of the drawing]

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

Claims (1)

[Claims] (1) Ethylene and an olefin having 3 or more carbon atoms are brought into contact with a catalyst system consisting of a combination of the following components (A) and (B) under solvent-free conditions, and the polymer density is 0.900 to 0.90.
A method for producing an ethylene-olefin copolymer, characterized by obtaining an ethylene-olefin copolymer within a range of 945 g/cm^3. Component (A) A contact product of the following component (A_1) and component (A_2),
Component (A_1) A component obtained by prepolymerizing 0.1 to 50 grams of olefin per 1 gram of component (a) to component (a) containing titanium, magnesium, and halogen as essential components, Component (A_2) Organoaluminum compound . Component (B) Organoaluminum compound.