JPS5811509A - Preparation of polyolefin - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having a narrow distribution of molecular weight and improved anti-blocking properties at a low cost, by (co)polymerizing an olefin in the presence of a catalyst consisting of a solid component prepared by reacting a magnesium halide with a soecific metallic compound, and organosilicon compound and a titanium compound, etc. mixed with an organometallic compound. CONSTITUTION:An elefin is (co)polymerized in the presence of a catalyst prepared by mixing (A) a solid catalytic component obtained by reacting (A) a magnesium halide with (B) a compound expressed by the formula Me(OR)nXz-n (Me is represents an element of GroupsI-VIII in the periodic table except Si, Ti and V; R is 1-24C hydrocarbon; X is halogen; z is the valence of Me; 0<=n<=z), (C) a compound expressed by the formula R'mSi(OR'')nX4-m-n (R' and R'' are 1-24C hydrocarbon; 0<m<4; 0<n<4; 0<m+n<=4) and (D) a titanium, compound and/or vanadium compound with an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins using a novel polymerization catalyst.

Conventionally, in this kind of technical field, the special meeting
A catalyst in which a transition metal compound such as a titanium compound is supported on magnesium or halides is known from the 2005 newsletter, and furthermore, according to Belgian Patent No. 742,112, magnesium halide and titanium tetrachloride were co-pulverized. catalysts are known.

However, in the production of polyolefins, it is desirable for the catalyst activity to be as high as possible, and from this point of view, the polymerization activity is still low in the method described in JP-B-59-12105, and the polymerization activity is low in the method described in Belgian Patent No. 742.112. Although the level is higher than that of a monk, improvements are still desired.

Furthermore, in German Patent No. 2157872, the amount of magnesium halide used is substantially reduced by co-pulverizing magnesium halide, titanium tetrachloride, alumina, etc., but the amount of magnesium halide used is substantially reduced. No significant increase in activity was observed, and a catalyst with even higher activity is desired.

Further, in the production of polyolefin, it is desirable that the bulk specific gravity of the polymer produced be as high as possible from the viewpoint of productivity and slurry handling. From this point of view, the bulk specific gravity of the produced polymer is low and the polymerization activity is not satisfactory in the method described in the above-mentioned Japanese Patent Publication No. 39-12105, and the polymerization activity is high in the method of Belgian Patent No. 742,112. However, it has the disadvantage that the bulk specific gravity of the produced polymer is low, and it is desirable to use it.

The present invention improves the above-mentioned drawbacks, provides a method for producing a novel polymerization catalyst that can obtain a polymer with high polymerization activity and high bulk specific gravity in high yield, and allows continuous polymerization to be carried out extremely easily, as well as a method for producing the polymerization catalyst. Catalytic polymerization of olefins,
Or, it relates to a copolymerization method.Since the polymerization activity is extremely high, the monomer partial pressure during polymerization is low, and the bulk specific gravity of the produced polymer is high, so productivity can be improved. The amount of catalytic residue in the polyolefin L/7 is extremely small, and therefore the catalyst removal step can be omitted in the production process, simplifying the polymer treatment process and making the process of producing polyolefin L/7 extremely economical overall. This is what we provide.

In the method of the present invention, since the bulk specific gravity of the obtained polymer is large, the amount of polymer produced in each unit polymerization reactor is large.

One further advantage of the present invention is that although the bulk specific gravity is high -1 from the viewpoint of the particle size of the produced polymer, there are few coarse particles and fine particles of 50μ or less, so continuous polymerization reaction is facilitated, and far in the polymer processing process,
(b) The handling of polymer particles, such as separation and powder transportation, becomes easier.

Another advantage of the present invention is that the polyethylene obtained using the catalyst of the present invention has a high bulk specific gravity as described above, and in order to obtain a polymer with a desired mel index, K has a lower hydrogen concentration than in the conventional method. Therefore, the total pressure during polymerization can be made relatively small, and it can be said that it is economical and has a great effect on productivity.

In addition, when ethylene is polymerized using the catalyst of the present invention, there is little decrease in the ethylene absorption rate over time, so another advantage is that the polymerization can be carried out for a long time with a small amount of catalyst.

Furthermore, the polymer obtained using the catalyst of the present invention has an extremely narrow molecular weight distribution and is characterized by extremely low by-products of low polymers, such as a small amount of hexane extraction. Therefore, it is possible to obtain a product of good quality, such as film grade, which has excellent anti-blocking properties.

The catalyst of the present invention provides a novel catalyst system that has many of these features and improves on the drawbacks of the prior art described above, and the use of the catalyst of the present invention makes these issues easier to overcome. I must say it is amazing what can be achieved.

The present invention will be specifically explained below. That is, the present invention provides: +1) JSHke: magnesium/chloride (21 general formula M
e(OR), group, X represents a halogen atom, 2 represents the valence of M, and n is 0 (n
≦2), att member prime number 1~
24 hydrocarbon residues, and X represents a halogen atom. m,
n is a compound represented by O (m (4* O The invention consists in a method for producing polyolein by polymerizing or copolymerizing olefin using a wrinkled solid catalyst component and an organometallic compound as a catalyst.

The magnesium halide used in the present invention is substantially anhydrous and includes magnesium heptadide, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred.

General formula M・(OR)fiX used in the present invention, =1(
, where Me, z, n and mouse are as defined above), for example, NaOR
1Mg(OR), , Mg(OR)X.

0e(OR), , an(OR)4 , P(OR), ,
Cr(OR),,1in(OR)w,i+'e(OR
)1% re(OR)8% Co(OR)1%N1(O
R), and more preferable specific examples include Na0C, II, , Na0C
,H,,Mg(OCR,4,Mg(oc,4)*
-Mg(OCsHJwCm(QC,H,)so,Zn
(OCwHs)m, Zn(QC,H,)C&A
n(OCQI)l-muJ(OCwHs)s,muj(
OetHs)sCl.

AI(Ochi-)i A11(OCaH,)i A#(OC@
l1g)IB (Gel II)I, 11 (Q
Cs Hs )w C1,p<oc@H@)s,P
Examples include metal compounds such as (OchiIs)s and Fe (OCaHe).

In the present invention, in particular, for the general formula Mg(OR)n,
#(OR)HXs-n and B(Oll)nX,-
, , are preferred. In addition, a is particularly preferably an alkyl group having 1 to 4 carbon atoms and 7-denyl i/M.

X represents a halogen atom, such as a hydrocarbon residue such as an alkyl group, an aryl group, or an aralkyl group.

m, n are O(m (4* 0 (n (4-0(ti
Examples of compounds represented by (+m≦4) include monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltriethoxysilane, monomethyltrih-butoxysilane, monomethyltriinopropoxysilane, and monomethyltripentoxysilane. , methyltrioctoxysilane, monomethyltristearoin, monomethyltriphenol, dimethyldimethoxysilane, dimethylshed, disilane, dimethyldiisogloboxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethyl Monoethoxysilane, trimethylmonoisopropoxysilane,
Trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monoethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyljethoxymonochlorosilane, monomethyljethoxymonobromosilane, monomethyldiphenosilane, dimethylmonoethoxymonochlorosilane , monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriisoprop-boxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilatylmonophenoxysilane, mono ethyldimethoxymonochlorosilane,
Monoethyljethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, monoispropyltrimethoxysilane, mono-n-butyltrimethoxysilane, 7-n-butyltriethoxysilane, mono-5ec-butyltriethoxysilane, monophenyltriethoxysilane , diphenyljethoxysilane, and diphenylmonoethoxymonochlorotetrasilane.

Examples of the titanium compound and/or vanadium compound used in the present invention include halides, alkoxyhalides, alkoxides, and halogenated oxides of titanium and/or panadicum. As the titanium compound, a tetravalent titanium compound and a pentavalent titanium compound are suitable. Specifically, the tetravalent titanium compound has the general formula 〒1(OR)EIX, n (where 8 is a carbon number of 1 to 1). 24 alkyl group, aryl group or aralkyl group, X represents a halogen atom, n is 0≦n≦4), and titanium tetrachloride, titanium tetrabromide, and tetraiodide are preferable. Titanium, monomethoxytrichlorotitanium, dimethoxycyclotidan, trimethoxytichlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, senoisoproboxytrichlorotitanium, diiso Propoxydichlorotitanium.

Triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, heptanophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium can be mentioned. Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of periodic ceramic groups 1 to 1 metals. can be mentioned. Also, the general formula Ti(OR)In-m (where 8 represents an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms,
indicates a halogen atom. A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by O (m (4)) with an organometallic compound of a metal from Group 1 of the Periodic Table of Elements may be mentioned.Vanadium Examples of compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium; pentavalent vanadium compounds such as vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl, and triptoxyvanadyl; trivalent vanadium compounds such as vanadium compounds, vanadium trichloride, and vanadium trichloride.

In the present invention, tetravalent titanium compounds are most preferred.

In order to make the present invention even more effective, titanium compounds and vanadium compounds are often used in combination. At this time, the V/'I'' i molar ratio is 2/1 to Q, 01
The range of /1 is preferable. In the present invention, (1) magnesium halide, (2)
There is no particular restriction on the method for obtaining the solid catalyst component of the present invention by reacting a compound represented by the general formula Me(oa)nx, -n with (4) a titanium compound and/or a vanadium compound. In the presence or absence of a solvent at a temperature of 20-400°C, preferably 50-400°C! s
K
You may react more. There is no particular restriction on the reaction order of components +1) to (4); the four components may be reacted at the same time, the three components may be reacted and then another component may be reacted, or the two components may be reacted. After reacting, the other two components may be reacted, or after reacting the two components, the next one component may be reacted, and then the remaining one component may be reacted. The solvent is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include proton, butane.

Various aliphatic saturated hydrocarbons such as pentane, hexane, heptane, octane, benzene, toluene, xine/cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, Benshomon Examples include alcohols such as ethyl acid, ethers, and esters.

Magnesium halide and general formula Me(OR)nX,
The mixing ratio with the compound represented by n is based on the general formula M・(O
R) If the amount of the compound represented by Hxz-n is too small or, conversely, if the amount of K is too large, the polymerization activity tends to decrease.
%/20, preferably in the range of 1/α01 to 1/1, most preferably 1/Q, in the range of 05 to 1/α5 for the production of highly active catalysts.

In the present invention, [, general formula Rms s < OR) nX6
．． If the amount of the compound or substance represented by n-0 is too large or too small, no effect can be expected, and it is usually halogenated! It is within the range of α1 to 50f, preferably 0.5 to top, relative to 100PK of magnesium.

Moreover, it is most preferable to adjust the amount of the titanium compound and/or vanadium compound so that the amount of titanium and/or vanadium contained in the solid catalyst component produced is within the range of 0.5 to 20% by weight. In order to obtain the activity of titanium/and/or vanadium and the activity of solid stroke, a range of 1 to 1011 is particularly desirable.

The equipment used for co-grinding is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and conditions such as mixing order, grinding time, and grinding temperature are particularly limited depending on the grinding method. This is a conflict that can be easily determined by painters rather than by artists. Normally 0℃~200
℃, preferably at a temperature of 20℃ to 100℃ for 0.5 hours to
It is desirable to co-mill for 50 hours. Of course, the co-grinding operation should be carried out in an inert gas atmosphere and moisture should be avoided as much as possible.

As the organometallic compound used in the present invention, organometallic compounds belonging to Groups 1 to 2 of the periodic table, which are known as components of Ziegler's catalyst, can be used, but in particular organoaluminum compounds and compounds with the general formula "s Al, R" can be used. @ A IX,
RA IXh, iL*A#OR.

Nezumi 41 (OR)X*! He-me 11t It is an alkyl group having 1 to 20 carbon atoms, and the two groups may be the same or different. Tori 5ea
-Butylaluminum, trit@rt-butylaluminum, trihexylalunnium, trioctylaluminum, diethylaluminum chloride, diinoprobylaluminum chloride, ethylaluminum methacrylate, diethylzinc, and mixtures thereof. It will be done. In addition, organic carboxylic acid esters such as ethyl benzoate, ethyl 0- or I)-)ruylate, and ethyl p-earthate can also be used in combination with these organometallic compounds. The amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 11 to IQQQmo 1 times the amount of the titanium compound and/or metal vanadate.

In addition, in the present invention, the solid catalyst component KIIl of the present invention
klEf) General formula R, A#X, a*H,, RAN(O
R) It is also preferable to use the compound after reacting it with an organoaluminum compound containing a metal compound represented by X or B, Al*Xm. At this time, the amount of the /10-gen-containing organic pluronium compound to be used is such that the molar ratio of the /10-gen-containing organic arginium compound:titanium compound and/or metal vanadide is 1:101 to 100, preferably 1; α! It is 1-50. There is no particular restriction on the method of this reaction; for example, the reaction may be carried out in the presence of an inert hydrocarbon, or the reaction may be carried out by co-milling treatment in the absence of a solvent.゛Reaction temperature is 0
The temperature range is preferably from 100°C to 100°C, and the reaction time is 5
Preferably from minutes to 10 hours.

Tonoyo 51C, when a solid material obtained by reacting the solid catalyst component of the present invention with organic aluminum containing No. 10 Ge/I is used as a catalyst component, the catalyst activity is improved and the molecular weight distribution of the resulting polymer You get something narrower. In this case, as the organometallic compound to be combined with the catalyst component, various compounds can be used as described above, but particularly preferred are organic alelectronium compounds represented by the general formula -I.

Polymerization of olefins using the catalyst of the present invention can be carried out by slurry polymerization, S-liquid polymerization or gas phase polymerization.
4? The polymerization reaction, which can be suitably used in gas phase polymerization, is carried out in the same machine as the olefin polymerization reaction using a usual Ziegler catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons in a state substantially free of oxygen, water, etc. The polymerization conditions for the olefin include a temperature of 20 to 120°C, preferably 50 to 10°C.
The temperature is 0° C. and the pressure is normal pressure to 701 tp/ai, preferably 2 to 406 tp/aII. Although the molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any hindrance.

The method of the present invention is applicable to the polymerization of olefins that can be polymerized with TIG 2-catalysts.

41 is preferably an α-olefin having a vertical prime number of 2 to 12, such as ethylene, propylene, 1-butene-hexane-
α- such as 1,4-methylpentene-1, octene-1
Single heavy metal olefins and ethylene and propylene,
Ethylene and 1-butene, ethylene and hemium-1, ethylene and 4-methylpentene-1, ethylene and octene-1
It is suitably used in the copolymerization of 1,propylene and 1-butene, and the copolymerization of ethylene and other α-olefins having two or more chains.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of the geno compounds used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, etc. can be mentioned.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Preparation of m catalyst components Two stainless steel balls having h inch diameter
5; 10 tons of commercially available anhydrous magnesium chloride, 2.5 F of arunic triethoxide, and 2.5 f of titanium tetrachloride were placed in a stainless steel pot with an internal volume of 400 mm.
Ball charging was performed at room temperature for 16 hours under a nitrogen atmosphere. Then monomethyltriethoxysila: /2
．． ,．． Added 5ft.

Ball milling was further carried out for 16 hours.

Pole-kiri pufferfish 41. The obtained solid catalyst component IPK was 3
A stainless steel autoclave was used as the heavy metal vapor phase polymerization apparatus, and a loop was created using a blower (1 flow rate) and a dry cyclone.

The temperature of the autoclave was maintained at v1m11 by flowing hot water through the jacket.

The above solid catalyst component t'50jf/br and triethylaluminum v were placed in an autoclave heated to 80°C Kl1.
The butene-17 ethylene ratio (molar ratio) vcL2 in the gas phase of the autoclave was supplied at a rate of 5 inertmol/hr.
zK, further gas was supplied while adjusting the hydrogen to 15% of the total pressure, and the gas YWr in the makuuchi was circulated using a puller to maintain the total pressure v10IIP/a11・GK and J5KL'C1 was performed. . The produced ethylene copolymer has a bulk specific gravity α37. Melt index (Ml)1
1. The density was α92o2. Also, the catalyst activity was extremely high at 528,000f copolymer/gTj.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but it was found that the inner walls and one stirrer were completely clean with no polymer adhering to them.

Melt index ME measured by method of kA8TM-DI238-65T at 190'C, load 2.14KP"C', @sl-t load 10mm, ゛F, R, value (ν.

R, zMl, 4+/M1m, t*) was 7.1te&'), and the molecular weight distribution was extremely narrow.

When extracted in xane for 10 hours, the amount of hexane extracted was t1wt%, which was extremely small.

Comparative Example 1 Monomethyltriethoxysilane 2.5 in Example 1
A solid catalyst component was synthesized in the same manner as in Example 1, except that f'll was not added.

The solid catalyst component 1P contained 45M9 titanium.

Continuous gas phase polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component was fed at a rate of 5011 v/hr. The produced ethylene copolymer has a bulk specific gravity of a34. Density α9201. The melt index was t1.

Also, what about the catalytic activity? i15,000P copolymer/gTj.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but it was found that some polymer had adhered to the inner wall and the stirrer.

Further, the F and R values of this copolymer were 8.3, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 4.0 wt%.

Example 2 Ethanol 11WL1. Anhydrous magnesium chloride 20),) ethoxyboron 46P, and 6ft of monomethyltriethoxysilane were added, and the mixture was reacted under reflux for 3 hours. After the reaction is complete.

15011j't of n-hexane was added to form a precipitate IR, and after the mixture was allowed to stand still, the supernatant liquid was removed.

A white dry powder Y was obtained by vacuum drying at 200°C.

Two stainless steel balls with a diameter of 1 inch
5; 12P% of the above white powder and 25% of titanium tetrachloride were placed in a stainless steel pot with an internal volume of 40011j.
Ball tVing was carried out at room temperature for 16 hours under a nitrogen atmosphere in PY. The solid catalyst component IPK obtained after the ball construction contained 58111F titanium. The above solid catalyst component! Continuous gas phase polymerization was carried out in the same manner as in Example 1 except that the feed rate was 50 Wv/hr. The produced ethylene copolymer has a bulk specific gravity α34. Density α9
215. The melt index was t1. Further, the catalyst activity was extremely high at 584,000P copolymer/gTi.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but no polymer was found on the inner Il# and the stirrer.

It was beautiful.

Moreover, the F, R, values of this copolymer were Z5, and when the film was taken out in boiling hexane at 101$1M),
The amount of hexane extracted was 12w1%, and the amount of extraction valve was extremely small.

Example 3 Implementation In a ball mill bottle as described above, anhydrous magnesium chloride IQP, jetoxymagnesium &, 1f, monomethyljethoxymonocone OH95) were added. Pole erection was carried out at room temperature for 16 hours in a bulk atmosphere containing IP and titanium tetrachloride 25PY. The solid catalyst component IP obtained after ball-ring contained 541v of titanium.

Continuous gas phase polymerization was carried out in the same manner as in Example 1, except that the solid catalyst component was fed at a rate of v50/hr. The produced ethylene copolymer has a bulk specific gravity α57. Density α?
199. The melt index was t1.

Further, the catalyst activity was extremely high at 51 soooP copolymer/gT1.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but no polymer was found on the inner wall or the stirrer.

It was beautiful.

Further, the Fl value of this copolymer was 7.5, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 14w1%, and the fk extraction valve was extremely small.

Example 4 Anhydrous magnesium chloride 10), ) lithoxy next to (P (011!t)s)
)11 P- and titanium tetrachloride 2 were placed in an stv and ball milled at room temperature for 16 hours under a nitrogen atmosphere.

Next, I added 2.5 tk of Nanabu's dirutriethoxysilane and spent another 5 hours building the ball. The solid catalyst component 1fK obtained after ball milling contained 38% of titanium.

Continuous gas phase polymerization was carried out in the same manner as in Example 1 except that the above solid catalyst component was fed at g5QWv/llr.

The produced ethylene copolymer has a bulk specific gravity α40 and a density α
9208. The melt index was α92.

The catalyst activity was extremely high at 454,000 P copolymer/gTl.After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but there was no polymer attached to the inner wall or stirrer. figure.

It was beautiful.

Moreover, the F, R, values of this copolymer are 7.5, and Q s
7 i” ' k # jl f in he 1011 in y
When extracted between i, the amount of hexane extracted was 15w1%,
There were very few extraction valves.

Example 11f15 The ball millbot described in Example 1 was charged with 10 p of anhydrous magnesium chloride, zinc & 5F in a shed, and 2.8 Pt' diisopropoxydicyclotetratitanium, and subjected to ball milling at room temperature for 16 hours under a nitrogen atmosphere. Next, add 2.4 f' of monoethyltriethoxy Vyn and add 5 more 'kamaru'.
I made a time ball-ken ring. One ton of solid catalyst component obtained after ball-ring contained 30 mounds of titanium.

Continuous gas phase polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component was fed at a rate of t'501111 p/hr. The produced ethylene copolymer has a bulk specific gravity α58.
Density α9205. The melt index was t2.

In addition, the catalyst activity was extremely high at 378,000 P copolymer/gT.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but no polymer was found on the inner wall or the stirrer.

It was beautiful.

Further, the F and R values of this copolymer were 15, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 15 wt%, which was extremely small.

Example 6 A 2J stainless steel L111 autoclave equipped with a stirrer was purged with nitrogen, 1000-g of hexane was added, 1 mol of triethylaluminum and 10 #t' of the solid catalyst component obtained in Example 1 were added, and the temperature was raised to 90°C with stirring. It was warm.

The vapor pressure of hexane is 211 p/awl-GK, but hydrogen is added until the total pressure is 4.8 KP/d-GK.
Next, ethylene was charged until the total pressure was 1011/d・GK, and the autoclave pressure v1 was increased starting with heavy metal Y:WIa.
04/am! - Polymerization was carried out for 1 hour while maintaining GK. After polymerization, transfer the polymer to a slurry beaker.
Remove hexane under reduced pressure and melt index tS.

Density α? 651. White polyethylene 1 with bulk specific gravity α56
98P'j=obtained. Catalytic activity is 105,800? Poly Z
f 1 / n / gTi -hr -C snow H4 pressure,
4800t polyethylene/Pli 1 body, hr, C1H4
It was pressure.

In addition, the F and R values of the obtained polyethylene are &2,
The molecular weight distribution was extremely narrow compared to Comparative Example 2, and the amount of hexane extracted was (L20 ft%).

Comparative Example 2 Using the solid catalyst component 10111' used in Comparative Example 1, heavy metal heating was performed for 1 hour in the same manner as in Example 6, and the melt index was t7. ! ! degree α9655° bulk specific gravity α! IO white polyethylene 145P was obtained. Catalytic activity is 6197
0F Polytechnical Chile y/gT Todoroki, br, c@H4 pressure, 2,7
90F polyethylene/? Solid, h y * C 嘗84
It was pressure.

In addition, the Fl value of the obtained polyethylene was 9.5; h9
．． The amount of hemeisan extracted was 2 wt%. Patent applicant: Nippon Oil Co., Ltd.

Claims (1)

[Scope of Claims] A method for polymerizing or copolymerizing olefins using a solid catalyst component and an organometallic compound as a catalyst, in which the solid catalyst component comprises (1) a halogenated Mac screw l) A, (21 general formula M
e (OR) Carp
Excludes. R is a hydrocarbon residue having 1 to 24 carbon atoms, and X is)
10 Gen atoms are shown. 2 represents the valence of Me, n
is a metal compound represented by Q (n≦2), (3) general formula Rm8i (OR) 1 person -m-n (where -o(
A method for producing a polyolefin, comprising a substance obtained by reacting a compound represented by n (410 (m+n≦4) and (4) a titanium compound and/or a vanadium compound.