JPS63159411A - Preparation of ethylene-olefin copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

As is known in the art, when ethylene and olefins are copolymerized, 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 so-called "solution polymerization" (generally at high temperature), which is carried out by dissolving the produced polymer in a solvent such as a hydrocarbon. The remaining one is so-called monopolymerization or "gas phase polymerization" in which polymerization is carried out while substantially forming polymer particles.

The latter polymerization method, ``vapor phase nitrogen'', is an excellent method for producing a copolymer because it does not use a solvent. However, "gas phase polymerization" has problems such as polymer adhesion, 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 the improvements have been made sufficiently.

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 ethylene and an olefin having 3 or more carbon atoms with a catalyst yarn made of a combination of the following components (A) and (B) under solvent-free conditions to produce polymers with a density of 900 to 900.
The present invention provides a method for producing an ethylene-olefin copolymer, characterized by obtaining an ethylene-olefin copolymer within the range of 0.945 r/ct11.

Component (A) A contact product of the following components (A1) to (A3), component (A,) containing ethylene, magnesium and halogen as essential components, 0 per gram of component (a). A component obtained by prepolymerizing 1 to 50 grams of olefin, Component (A2): A silicon compound having a Si-0-C bond, Component (A,): An organoaluminum compound, an organoaluminum compound.

Effects of the Invention The present invention can provide solutions to various problems that arise in "gas phase polymerization" when producing ethylene-olefin copolymers. i.e. polymer deposition,
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 leads to flatness in the film and a decrease in strength.

A further feature of the component of the present invention is that the component (A) itself has little adhesion. This is thought to lead to the improvement of the polymer adhesion and prevention of the formation of lumpy polymers.

Further, a feature of the production of the ethylene-α-olefin copolymer in the present invention is that the molecular weight of the polymer can be easily controlled. It is extremely important to completely control the molecular weight of this polymer in production; if this control is not carried out well, problems such as the above-mentioned polymer adhesion and formation of lumpy polymers will occur.

Another feature of the present invention is that a polymer with good polymer properties can be obtained. Looking at the bulk specific gravity of the polymer, which is one guideline, it is possible to have a polymer bulk specific gravity of 0.4 oy7a or more, and even 0.45. f 708 or higher is also possible.

The catalyst used in the present invention is a combination of component (A) and component (B), and the use of known electron-donating compounds (external donors) etc. in combination is prohibited to the extent that the effects of the present invention are not impaired. do not have.

Component (A) Component (A) consists of component (Aθ, component (A2) and component (A
3) is a contact product produced by contacting.

Component (A,) Component (A,) of the present invention is obtained by prepolymerizing component (a) with a certain amount of olefin.

Production of component (a) The solid component containing titanium, magnesium and halogen as essential components used in component (a) is a known solid component. For example, JP-A-53-45688, JP-A No. 53-45688;
No. 4-3894, No. 54-31092, No. 54-39
No. 483, No. 54-94591, No. 54-11848
No. 4, No. 54-131589, No. 55-75411, No. 55-90510, No. 55-90511, No. 5
No. 5-127405, No. 55-147507, No. 55
-155003, 56-18609, 56-7
No. 0005, No. 56-72001, No. 56-8690
No. 5, No. 56-90807, No. 56-155206, No. 57-3803, No. 57-34103, No. 57
-92007, 57-121003, 58-5
No. 309, No. 58-5310, No. 58-5311,
No. 58-8706, No. 58-27732, No. 58-
No. 32604, No. 58-32605, No. 58-677
No. 03, No. 58-117206, No. 58-12770
No. 8, No. 58-183708, No. 58-183709
No. 59-149905, 1 unit H59-14990
Those described in each publication No. 6 are used.

Magnesium compounds serving as magnesium sources for the catalyst used in the present invention include magnesium halide,
Examples include dialkoxymagnesium, alkoxymagnesilahalide, 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, and
represents a halogen, and n represents a number of O≦n≦4. ) can be mentioned. As a specific example, TiC
l4, Ti Br4, Ti (oc2H,) (J,'
ri(oc.

Ha), (J,, Ti(QC,H,), (J, T
i(0-nC3H,)(J8, Ti(Q-nC,
R9) C1s, rt (0-'C4Hg)2C12,
Ti (QC,R5)Br,,Ti (QC2H,)
(QC4H,)2C1%T+ (0-n C4H9)s
CI X Tl (0-CgHs) CI
, Ti(0-iC4H1l)2 CA'2,T
i (QC, H, □) C13, Ti (QC8H,)
C1,, T 1 (0CzHs) Ti (On C3
H7) iT+ (0-n C4H9)iTi (0-i
C4Ha)i, Ti(OncsH+s)< , Ti(
0-nC.

R57) I'l'i C0CH2CH(C2H5)C4
H9] There are 4 etc. Among these, 'riCA'4
is preferred.

Alternatively, a molecular compound obtained by reacting TlX4 (where X' represents a halogen) with an electron donor described later can also be used. As a specific example, TlC14・CH3COC2
H,,rlcg4- CH,Co2C2H,,Ticl
, 11 C, H5NO□, TiCl4・CH3C0C
J, Ti C14・C6H, C0CJ.

TxCl<・C6H3Co2C2H6, Ttcz,・C
Examples include H3COC2H, TiCl4.C, H,0, and the like.

The halogen source is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but there are also known halogen sources such as aluminum halides, silicon halides, and phosphorous halides.・Can also be supplied from a rogensing agent.

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

In addition to the above-mentioned essential components, the component (a) used in the present invention includes si
c! ! 4, CH35IC13, silicified figurines such as methylhydrodiene polysiloxane, Al (OisoC,
H,),,AlC11,AlBr3,Al(QC,H
,) 3, M (OCR,) 2C6 and other aluminized adducts and B (0CHs) s, B (IJc2H5
) 1, B (OCgHs ) z and other boron compounds may also be used, and these may remain in component (a) as components such as silicon, aluminum and boron.

Furthermore, component (a) t-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 organic or inorganic acids, ethers, and acid amides. , oxygen-containing electron donors such as 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, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc.
Alcohols of 8; phenol, cresol, xylenol, ethylphenol, flobylphenol, cumylphenol, nonylphenol, phenols having 6 to 25 carbon atoms which may have an alkyl group such as naphtholnato: acetone, methyl ethyl ketone, methyl imbutyl Ketones 1. Ketones having 3 to 15 carbon atoms such as acetophenone and benzophenone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propio/aldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, Vinyl acetate, propyl acetate, octyl acetate,
Cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate , butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate , diethyl hepthalate, diptyl phthalate, diheptyl phthalate, r-butyrolactone, α-
Organic acid esters having 2 to 20 carbon atoms such as valerolactone, coumarin 1, phthalide, and ethylene carbonate; Inorganic acid esters such as silicate esters such as ethyl silicate, butyl silicate, and phenyltriethoxysila; acetyl chloride , benzoyl chloride, toluic acid chloride,
Acids with 2 to 15 carbon atoms, such as anisyl chloride, phthaloyl chloride, phthaloyl chloride, etc. Ethers having 2 to 20 carbon atoms; Acetamides such as acetic acid amide, benzoic acid amide, toluic acid amide; Methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine Amines such as;
Nitriles such as acetonitrile, pe/dinitrile, tolnitrile; etc. can be mentioned. Two or more kinds of these electron donors can be used.

The quantitative ratio of the constituent components of this component (a) is such that the Ti/Mf atomic ratio is within the range of I
It is preferred that the y atomic ratio is in the range of 0.5 to 4 and that the optionally contained electron donor is not more than 510 moles per gram atom of MP, preferably in the range of 0.01-1 mole.

When silicon, aluminum and boron compounds are contained, the molar ratio of these compounds to the amount of the magnesium compound used is within the range of I x 10"" to 100, preferably I x 10-2 to 1 is within the range of

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

(a) A method of producing a magnesium halide suitable for activation and, if necessary, an electron donor and a titanium compound by simultaneously or gradually co-pulverizing or contacting them in a liquid state. This may be further brought into contact with a chlorogenating agent.

(b) Applying a halogenating agent, a reducing agent, etc. to the 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.

(c) A method of producing a catalyst by reacting an organomagnesium compound such as a Grignard reagent with a halogenating agent, a reducing agent, etc., and then contacting this with an electron donor and a titanium compound as necessary.

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

The component (AI) used in the present invention is the above component (a)
It is obtained by prepolymerizing a certain amount of olefin. Prepolymerization is carried out using a catalyst system consisting of the above component (a) and an organoaluminum compound. Known organoaluminum compounds can be used here.

As a specific example, R” s -n AJI collapse or,
R33-mAl(OR') (Here, R2 and R3 are hydrocarbon residues or hydrogen having about 1 to 20 carbon atoms, which may be the same or different, R4 is a hydrocarbon residue, and X is) ・Rogen, n
and m are each expressed as O≦n (3, O<m<3). Specifically, (a) trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum,
Trioctyl aluminum, tridecyl aluminum,
trialkylaluminum, such as (b) alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, (c) diethylaluminumno-hydride, diisobutylaluminum hydride, etc. Examples include aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminium phenoxide.

In addition to these organoaluminum compounds (a) to), other organometallic compounds such as R:, -aAJ(OR')a
1≦a≦3, R5 and R6 are hydrocarbon residues having a carbon number of 1 to 208 degrees and which may be the same or different. ) can also be used in combination with an alkyl aluminum alkoxide. 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. Examples include combination use.

Prepolymerization conditions may be arbitrary as long as the effects of the present invention are observed, but the following conditions are generally preferred. The polymerization temperature is 0 to 80°C, preferably 10 to 60°C. The amount of polymerization is 0 per gram of component (a).
．． It is preferred to polymerize 1 to 50 grams of olefin, more preferably 5 to 20 grams of olefin.

If the amount of prepolymerization is too small, it will be difficult to obtain the desired effect of the present invention, and if it is too large, problems such as a decrease in catalytic activity will occur. Use of organoaluminum compound during prepolymerization] # is A for the titanium component in component (a).
l/Ti (molar ratio) from 0.1 to 100, preferably from 1 to
It is 10. The olefins specially used for prepolymerization are:
Ethylene, propylene, butene-1, hexene-1,4
-Methyl-pentelium 1, etc., and mixtures thereof can also be used.

Component (A2) Component (A2) is a silicide compound having a 5L-O-C bond.

Any silicon compound having a 3i -0-C bond can be used as long as the effects of the present invention are observed! Generally, the general formula a74-ns+ (OR')
n (Here, R' is a hydrocarbon residue having about 1 to 20 carbon atoms, preferably about 1 to io), and R8 is a hydrocarbon residue having about 1 to 20 carbon atoms, preferably about 1 to 10 carbon atoms.
It is a hydrocarbon residue of a certain degree. ) is preferred.

Specific examples include <cH3)si<ocHx>3, (C
H3) 5! (QC!H5)! , (C2HI)2Si
(OCH4)z, (nC5Hu)Si (0CHs
) s, (C2H4) Sl (QC, Hs) x, (
n -Cto H2+)Si(0C2H3)s,
(CF(2=CH)Si(QC)(3),,C/(CH
2) 3Si (OCHji, Si (0CH3) 4, (
C2H5)2S 1 (QC2H5) 2, (C17H
35) Si(0CH1),,Si(OC2H3)
4, (C6H5) Sl (0CR3) s, (C6H
5) 2Sl (OCH3)2, (C6H5) (CH3)
8 dishes (0Ci(s)2, (C=Hs)3
t (OC2H5)3, (C5Hs)2S
t (OC2H5) 2, NC(CH2) 2 S r
(OC2H5)s, (C5Hs) (CHJ Sl
(0C2H5) 2, (n-C3H7) Si(QC
2F(,),,(CH3)Si(0C3Ht),
, (C61 (, CH2) disorder CH.

S i (0CHs) * C1z, (CHa)3C
-81(OCf(,)3,(CH,),C-8i(QC
,H,),,CH30Hs Acid component A3) Component () is an organoaluminum compound. The organoaluminum compound of component (A,) used in the present invention is the same as the one that can be used when producing the component (A□), and is used when producing component (A,) and component (As) i. The resulting organoaluminum compounds may be the same or different.

Production of component ■ (component (Al), component (A,) and component (
The component (A) used in the present invention is the component (Aυ, contact of the component (A)).
A2) and component (A,) are brought into contact. These contacts can be exemplified in the following order.

(1) Component (A1) → Component (A2) → Component (A,)
(2) Component (A1) → Component (A, ) → Component (A2) (3
) component (A1) → (mixture of component (A2) and component (A, )) (A) component (A1) → (component (A2) and component (
Mixture of A3) → component (A,) Among these, it is preferable to contact in the order of (1).

These contact conditions may be arbitrary as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The contact temperature is 0 to 100°C, preferably 20 to 80°C. The contacting method is generally preferably carried out under stirring, and an inert solvent such as n
- Hydrocarbons such as hexane, n-hebutane, impentane, n-octane, n-tecane, benzene, toluene, xylene, cyclohexane, l,2-dichloroethylene,
It can also be carried out in the presence of halohydrocarbons such as n-butyl chloride, n-butyl bromide, chlorobenzene, dichlorobenzene, and the like.

The usage ratio of component (A□), component (A2) and component (A,) is 3i/Ti (atomic ratio ) is 0.01
-100, preferably 0.1-10.

In addition, the amount of component (A,) used is AI1/T5 (M child ratio)
may be within the range of 0.1 to 1000, preferably 1 to 1
It is within the range of 00.

Component (B) Component (B) is an organoaluminum compound. component(
The organoaluminum compounds used as ingredients are the same as those that can be used in the production of component (A,)''fr, and in the production of component (B), component (A,), and component (AI). All organic aluminum compounds used may be the same or different.

The use of these organometallic compounds -#L is not particularly limited, but it is preferably within the range of 0.5 to 1000 in weight ratio to the solid catalyst component (A) of the present invention.

Copolymerization of ethylene and olefin Olefin Specific examples of olefins having 3 or more carbon atoms to be copolymerized with ethylene using the catalyst of the present invention include propylene, butene-11pentene-1, hexene-1,4-/thylpentene-1, and heptene. -1, octene-1, decene-
1, etc. 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 between 1 mole percent and 50 mole percent.

Polymerization Conditions Copolymerization is carried out under solvent-free conditions. The process according to the invention is therefore carried out in the gas phase polymerization mode in the absence of a hydrocarbon solvent. As the polymerization apparatus to be used, any type such as a fluidized bed type or a stirred tank type can be used. Polymerization temperature is 30-95
℃, preferably 70-90℃, polymerization pressure 1-1o
kr/c+4. Preferably, 3 to 35 kf/- is appropriate. Further, hydrogen can be used as an auxiliary molecular weight regulator.

The resulting copolymer The ethylene-olefin copolymer produced according to the present invention has a polymer density of 0.900 to 0.9452/-1.
Usually it is 0.910 to 0.935 f/-.

Experimental Examples Example 1 (1) 20 ml of dehydrated and deoxidized fen-hebutane was introduced into a flask with an inner diameter of 1Ocrn in which the synthesized light component of component (a) was replaced with nitrogen, and then 1 mol of MyC120, TI (On C4
0.2 mol of H,)4 was introduced, and the mixture was reacted at 95°C for 1 hour. The diameter of the stirring blade used at that time was 9 cm. 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-heptane, a portion was taken out, and the average particle diameter was measured by the gradient method and found to be 28.2 microns.

The solid components described above were introduced into a fully purified flask.

44.4 ml of TiCA' and 12 ml of methylhydrogen polysiloxane were completely mixed with 50 ml of n-hebutane, 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).

(2) Preparation of component (a) ['J1 go ([min (Al) G'
) Synthesis') In a stainless steel cracked autoclave with an internal volume of 1.5 liters and a stirring and temperature control device,
Lightly dehydrated and deoxidized Wa-hebutane '15QO
ml, and then 4.5 grams of triethylaluminum Ramula and 4.5 grams of component (a) Is synthesized above were introduced, respectively. The temperature was set at 50° C., hydrogen gas was introduced at a partial pressure of 1 kp/aA, and then ethylene was introduced at a partial pressure of 1 kg/cd. Thereafter, polymerization was carried out at 50°C for 1 hour. After the polymerization was completed, unreacted gas was purged, and the mixture was thoroughly washed with n-hebutane to obtain a component (A). The amount of preliminary polymerization was 9.5 grams per gram of component (a).

(3) Production of component particles (contact of component (A, ), component (A2), and component (A3)) Into a flask that had been replaced with nitrogen in the light, 100 milliliters of sufficiently purified n-hebutane was introduced, 1 ml of component (A,)'i1o duram and phenyltriethoxysilane (component (A2)) prepared above were added to 4 people and brought into contact with each other at 70° C. for 2 hours.

After the contact was completed, it was washed with Ll-hebutane.

Subsequently, triethylaluminum (, [min (Aj)
) 2.0 g was introduced and reacted at 70°C for 2 hours.

After the reaction was completed, the mixture was washed with n-hebutane to separate the components.

When we examined the amount of adhered ingredients, we found that ingredient (A) 1
The weight was 0.02 grams. (Hereinafter, this amount of adhesion will be abbreviated as K).

The amount of adhesion was measured as follows.

A fixed amount (approximately 10 grams) of component (A) was introduced into a glass flask and shaken for 10 minutes. Thereafter, component (A) was taken out from the flask, and the amount of nitrogen attached was measured.

(A) Polymerization of ethylene Using the apparatus for gas phase polymerization disclosed in Example 1 described in JP-A-57-73011, fully purified polyethylene powder was charged into the apparatus, and then triethyl 100 mg of aluminum, component (A) synthesized above
*1 O5 and IJ grams were introduced respectively. Then,
Hydrogen gas was introduced at 1.2 kp/m, the temperature was raised to 85°C, introduction of an ethylene-butene-1 mixed gas containing 10 body M% of butene-1 was started, and the total pressure was 9 kf/cI at 4185°C.
．． Polymerization was carried out for 5 hours.

The result was 148 grams of polymer, MFR=0
．． 43 t/10 min, polymer bulk specific gravity = 0.47 f/c
C, polymer density = 0.920 f/cry, and when examining the amount of bulk polymer (hereinafter abbreviated as P) and the amount of polymer adhesion in the polymerization tank (hereinafter abbreviated as Kp), it was found that 1 gram of normal polymer Atashi 0.0 each
0.02 grams and 0.001 grams.

Comparison Examples 1 to 3 In the production of component (A) in Example 1, when component (A2) and component (A,) were not used, or when only one of component (A2) or component (A,) was used. In each case, the respective components were prepared and polymerized under exactly the same conditions as in Example 1. The results are shown in Table IK.

Examples 2 to 7 In the production of component (A) in Example 1, the compounds shown in Table 2 were used as component (A,) and component (A,), and the components (A2) and (A,) were The polymerization of ethylene was carried out in the same manner as in Example 1 except that the contact conditions were as shown in Table 2, and then the respective components (A) obtained were used. The results are shown in Table-3.

(Leaving space below) Example 8 (1) Production of component (a) 75 ml of thoroughly degassed and purified n-hebutane was placed in a 1 liter flask that had been purged with nitrogen, and anhydrous MtC12 (in a ball mill) was added to the flask. 10 grams of
10 milliliters of was introduced and the reaction was carried out at 70°C for 30 minutes. Next, a mixture of 5.4 ml of n-butanol and 5.4 ml of n-hebutane was introduced from a spray nozzle in 10 seconds to form droplets of 210 microns, and the mixture was reacted at 70° C. for 1 hour. There, TtC
I! Introduce 4 to 2.3 mm and 70℃.
The reaction was carried out for 1 hour. Next, 9 mm IJ IJ liter of methylhydrodiene polysiloxane was introduced, and 70 mm
The reaction was carried out at ℃ for 2 hours. After the reaction was completed, the average particle size of component (a) was measured and found to be 16 microns.

(2) Prepolymerization of component (a) (synthesis of component (A1)) In the prepolymerization condition of Example 1, 8.6 g of triisobutylaluminium was used instead of triethylaluminum, and the temperature was 50°C. Prepolymerization was carried out in the same manner as in Example 1, except that the temperature was changed from .degree. C. to 65.degree. C. and the polymerization time was changed to 6 is minutes. The amount of prepolymerization is 1 gram of component (a),
It was 4 grams.

(3) Preparation of component (A) In the same manner as in Example 1, the same Ka
50 ml of diluted n-heptane was introduced, and 1.5 g of the component (Ax) prepared above and 1.5 g of tri-n-hexylaluminum were introduced.
The contact was carried out for 1 hour at ℃. Next, 1.3 ml of phenyltriethoxysilane'i was introduced and the mixture was heated at 80°C for 2 hours.
Allowed time to react. After the reaction was completed, the components were washed with n-hebutane to concentrate the components. K=0.03 grams.

(A) Ethylene-propylene copolymerization In the polymerization of Example 1, 200 milligrams of triimbutylaluminum was used instead of triethylaluminum as the organic aluminum, and the components obtained above (
A) Example 1 and (b) were repeated except that instead of the 61 mg ethylene-butene-1V gas mixture, an ethylene-propylene mixed gas containing 8% by volume of propylene was used. As a result, 201 grams of polymer were obtained, M F R = 2, 1 t 7
10 minutes, polymer bulk specific gravity = 0.40 f/CL, polymer density = 0.919 f/cd, P = 0.003,
KJ) = 0.002, K = 0.03.

Example 9 (1) Production of component (al) Component (a) was produced in the same manner as in Example 1 except for the following changes in the production of component (a) in Example 1. Si on the siloxane base
1.0.25 mol of C was used. Also TiCJ, 4.
4 milliliters of Ti and 12 milliliters of methylhydrodiene polysiloxane were reacted with Ti (J47.5 milliliters was used at 90°C for 3 hours. After the reaction was completed, the mixture was washed with n-heptane, and the components were <11). And so.

(2) Prepolymerization of component (a) Under the prepolymerization conditions of Example 1, component (a) obtained above was
), and prepolymerization was carried out in the same manner as in Example 1, except for the following changes. Using a mixture of 4.3 grams of triisobutylaluminum and 3.7 grams of ethylsesquialuminum in triethylaluminum glue, the polymerization temperature was increased from 50°C to 70°C, and the polymerization time was 25°C.
It was a minute. As a result, the amount of prepolymerization was 5.7 grams per gram of component (a).

(3) Creation of component (A) In the same manner as in Example 1, add b to a flask purified by optical spectroscopy.
100 milliliters of diluted n-hebutane was introduced, 10 grams of the component (At) k prepared above, 1.2 milliliters of phenyltriethoxysilane, and 2.5 grams of triethylaluminum were introduced, and the mixture was contacted at 85° C. for 1 hour. I let it happen. After the reaction was completed, the components were washed with n-hebutane to concentrate the components. K=0.025 grams.

(A) Ethylene-butene-1 copolymer At the 1% condition of Example 1, (C2H5) s A1
Polymerization was carried out under the same conditions as in Example 1, except that the amount used was 50 milligrams and the sweetened component was 67 milligrams. As a result, 256 grams of polymer were obtained, MFR = 1.4 P710 min, polymer bulk density = 0.40 t/cc, polymer density = 0.9
19 f/cj, P=0.004, Kp=0.
It was 003.

5j! Examples 10-11 and Comparative Examples 4 to 5 Example 1 <! : Ethylene-butene-1 was prepolymerized in the same way, except that the obtained components αθ were used.
Copolymerization was also carried out in the same manner as in Example 1. Table 2 shows the results.
Shown below.

(p), bottom margin)

[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) A catalyst system consisting of a combination of the following components (A) and (B) is brought into contact with ethylene and an olefin having 3 or more carbon atoms under solvent-free conditions, and the polymer density is 0.900 to 0.
．． 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 components (A_1) to (A_3),
Component (A_1): Component (a) 1 is added to component (a) containing titanium, magnesium and halogen as essential components.
A component obtained by prepolymerizing 0.1 to 50 grams of olefin per gram.Component (A_2): A silicon compound having a Si-O-C bond.Component (A_3): An organoaluminum compound.Component (B) An organoaluminum compound.