JPS5821405A - Production of polyolefin - Google Patents

Abstract

PURPOSE:A reaction product of silicon oxide, magnesium compound or titanium compound is made to react with a specific silicon compound to prepare a solid component and it is combined with an organometallic compound to form a catalyst, which is used to produce the titled polymer which is bulky, containing a less amount of fine polymer particles and showing good processability. CONSTITUTION:The polymerization or copoymerization of an olefin is conducted by means of a catalyst that is composed of (A) an organometallic compound and a solid component obtained by reacting (B) a reaction product from (i) silicon oxide and/or aluminum oxide, (ii) magnesium halide and a compound of Me(OR)nXz-n (Me is element in groupI-IV of the periodic table; z is valency of Me; 0<n<=z; X is halogen; R is 1-20C hydrocarbon) and (iii) a titanium compound and/or vanadium compound, with (C) a compound of Si(OR')mX4-m (R' is 1-24C hydrocarbon; 0<=m<=4).

Description

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

Conventionally, in this type of technical field, many catalysts have been known in which compounds of transition metals such as Cj'' tan, vana, and dicum are supported on inorganic magnesium solids such as agnesium halide, magnesium oxide, and magnesium hydroxide. However, in these known techniques #C!, the bulk specific gravity of the obtained polymer is generally small, the average particle size is also relatively small, and the particle size distribution is generally wide, so there are many fine particulate powder parts, Improvements have been strongly desired in terms of productivity and slurry handling.Furthermore, when molding these polymers, problems such as generation of dust and reduction in efficiency during molding occur, so the above-mentioned bulk There was a strong desire to increase the specific gravity and reduce the particulate powder content.Furthermore, improvements were still needed in order to omit the pelletizing process, which has been increasing in demand in recent years, and to apply the powdered polymer directly to the processing machine. ing.

The present invention has been made through intensive research aimed at improving the above-mentioned drawbacks and obtaining a polymer that has a high bulk specific gravity, a large average particle size, a narrow particle size distribution, and a significantly reduced amount of fine particles. As a result, the present invention has been achieved.

By using the method of the present invention, the average particle size is larger,
A polyolefin with a narrow particle size distribution and a small amount of fine particles can be obtained with high activity, and the bulk specific gravity of the resulting polyolefin is high, which is very advantageous in terms of polymerization operations.Furthermore, it can be used not only as a pellet but also as a powder. However, it can be subjected to molding processing, and there are few troubles during molding processing, making it possible to produce polyolefins extremely advantageously.

Furthermore, the polymer obtained using the catalyst of the present invention has an extremely narrow molecular weight distribution, and is characterized in that the less ambiguous hexane extraction is, the less low polymers are produced. Therefore, when the polyolefin with a narrow molecule 1 distribution obtained by the method of the present invention is used for film, it has many advantages such as high strength, excellent transparency, and excellent anti-blocking and heat sealing properties. has.

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. I must say that is surprising.

The present invention will be specifically explained below. That is, the present invention provides method #C of polymerizing or copolymerizing an olefin using a solid catalyst component and an aiso metal compound as a catalyst, in which the solid catalyst component is (1) silicon oxide and/or aluminum oxide, (2) Magnesium halide and general formula M@(OR)
nXzl (ζζ, where ζζ is an element in group 1-W of the periodic table, 2 is the valence of the element Me, !l is 0 < n ≤ z, X is a helogen atom, and R is a hydrocarbon having 1 to 20 carbon atoms. A reaction product obtained by contacting and reacting (3) a titanium compound and/or a panadicum compound with a compound represented by (representing a residue) [Summer] General formula 81 (OR' ) rn The present invention relates to a method for producing a polyolefin characterized by comprising:

The silicon oxide used in the present invention is silica or a double oxide of silicon and at least one other metal from the periodic table of metals.

The aluminum oxide used in the present invention is a double oxide of alumina or aluminum and at least one other metal of Groups W to W of the periodic table.

Typical double oxides of silicon or aluminum and at least one other metal from Groups I to II of the periodic table include AI, O, .MgO, AI, 0.・OaO, AI, 0.
-810. , AI, O, .MgO-CaO.

AI, O, ・Mg()SiO,, AI, O, ・OuO,
AI,O,・F@,O,.

Mul, 0.・Nip, 8i0. - Various natural or synthetic composites and oxides such as MgO can be exemplified.

Here, the above formula is not a molecular formula, but only represents the composition, and the structure and component ratio of the multiple oxide used in the present invention are not particularly limited.
Naturally, the silicon oxide and/or aluminum oxide used in the present invention #C may adsorb a small amount of water without any problem, and may also be used without any problem even if it contains a small amount of impurities.

The magnesium 10-fluoride used in the present invention is substantially anhydrous, including magnesium heptafluoride,
Examples include magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred.

Further, in the present invention #C, these halide magnesium may be treated with an electron donor such as alcohol, ester, ketone, carboxylic acid, ether, amine, or phosphine.

The general formula used in the present invention is Me (OR) n For example, N* OR1Mg (OR) * eag(on)
x, 0a(OR)t+Z! 1(OR),, cd(
ou),, B(OR)1At(OR),, At(o
R), x, AI(OR)X,, 51(oa)4゜81(OR),
Examples include various O compounds such as oR)xlan(OR)4. Preferred specific examples of these include Mg(00*Hi)0Mg(oc, H,>al.

Mut(ooiis) B Alroo, H,),, AI
(On-0,H,), IAI(Ol-0,H,)1Al
(On-0,H,)1A1(Osec-0,H,),I
Ax(ot-o4■,), At(ocu,), at
, AI(00,H,), 01°AI(00,Hll)0
1. , AI(Ol-0,H,), 01. Al(Of
-0,H,)01,, 81(00,H,),,5
irOC, Hl), 01. 5I (00, H6).

Examples include compounds such as CI, 81rOO,H,)CI, and the like.

Magnesium halide, general formula Me (OR) nX
The reaction method with the compound represented by z-1 is not particularly limited.
~400℃, preferably 50-300℃ @ 5 minutes in the dark ~
The reaction may be carried out by mixing and heating for 10 hours, or may be carried out by co-pulverization.

In the present invention, a method using co-pulverization is particularly preferred.

The equipment used for co-pulverization is not limited to IC, but typically includes ball mills, vibration mills, rod mills, impact mills, etc., and those skilled in the art can easily determine conditions such as grinding temperature, grinding time, etc. depending on the grinding method. It is determined.

Generally, the grinding temperature is 0°C to 200°C, preferably Fi2
The temperature is 0°C to 100°C, and the grinding time is 0.5 to 50 hours.
Preferably it is 1 to 30 hours.

Of course, these operations should be performed in an inert gas atmosphere, and hot air should be avoided as much as possible.

Magnesicium halide and general formula M・rOR)nXz-
The reaction ratio with the compound represented by n is Mg:Me
(molar ratio) is 1:o, o1-10, preferably Q preferably 1:α
A range of 1 to 5 is desirable.

Examples of the titanium compound and/or vanadium compound used in the present invention include titanium and/or pacazicum halide, alkoxy halide, alkoxide halide oxide, etc. Preferred are valent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula 'l'il'0R)nX, -.

(Here, 8 represents an alkyl group having carbons a1 to 20, an aryl group f, or an aralkyl group, and X represents a hewagen atom.

For cram schools, 0≦n≦4. ) is preferable,
Titanium tetrachloride, titanium tetrabromide, titanium tetrachloride, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium,
Monoethoxytrichloretane, dimethoxydichlorosilane, triethoxymonochlorotitanium, tetraethoxybutane, monoisopropoxytrichlorotitanium, diisopropoxymonochlorosilane, triisopropoxymonochlorosilane; tetrapropoxytitanium, monobutoxytrichlorotitanium, dibutoxy Examples include dichlorotitanium, monopentoxytrichlorosilane, heptanophenoxytrichlorothetane, diphenoxydichlorotitanium, triethoxymonochlorotitanium, canine triphenoxytitanium, and the like. As the silane compound of 31iIli, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide can be used with hydrogen, aluminum, and silane according to the periodicity law.
Examples include titanium trihalogenide obtained by reduction with an organometallic compound of group metal. Also, the general formula Ti(OR)m
Xa, 0m (wherein R represents an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and X represents 10 atoms) is O<m<4. ) indicated by Jlif
A trivalent silane compound obtained by reduction with a No. 1 compound of No. 5 can be mentioned. Examples of pakaji and cum compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, tetraethoxyvanadium, vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl, and triptoxybacadyl. Examples include pentavalent vanadium compounds such as vanadium trichloride, vanadium trichloride, and 3gfJ (nadicium) compounds such as vanadium triethoxide.

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/'f'1 molar ratio is 2/1 to α01/
A range of 1 is preferred.

General formula 8i(OR')mX used in the present invention cg,
-nl (where R' is a hydrocarbon residue such as an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms, and X is) 1
0 Gen atom is shown. Examples of the compound represented by m (0≦m≦4) include silicon tetrachloride, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono-n-butoxytrichloroa-cyclosilane, and monopentoxytrichlorosilane. , monooctoxytrichlorosilane, monosume aloxytrichlorosilane, monophenoxytrichlorosilane, monop
- methylphenokiditrichlorosilane, dimethoxydichlorosilane, dimethoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane,
Dioctoxydichlorocycne, 'Jrimethoxymonoca
Examples include rosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, triethoxymonochlorosilane, tetraethoxysilane, and tetralinepropoxysilane.

In the present invention, (1) silicon oxide and aluminum oxide (hereinafter abbreviated as components (2)-(1)), (2) magnesium helogonide and the general formula y・(OR
) n
is the valence of the element M@, 1 is O< n≦z, X is a herogen atom, and R is a hydrocarbon residue having 1 to 20 carbon atoms. (z)−(
2) R and (5) titanium compound R and/or vanadium compound (hereinafter abbreviated as components (x)-(3)) are brought into contact with each other and the reaction method #CFi Particular restrictions There isn't.

The contact order is component (I)-(1) and component [tech]-
After contacting (2), components (I)-(3) may be brought into contact, or components (1)-(1) and (zl-(3)) may be brought into contact with each other.
After contacting component (13-(2) and component CI)-(3), component (r)-(1) may be brought into contact. ) may be brought into contact with each other. In the present invention, component (z)-(1) and component
) is particularly preferably contacted with components (1]-(5).

Further, the contact method is not particularly limited, and any known method can be employed. In other words, when component (1)-(1) and fraction [technique]-(2) are brought into contact, component [technique]-(1)
and the contact product of component CI)-(3) and component (I)-(2
) or when contacting the contact product of component (rl-(2) with component (z')-(s>) and fraction (y)-(1), at a temperature of 0 to 200°C. CL5~5
Co-pulverization treatment may be performed for 0 hours, or mixed and heated in an organic solvent such as an inert hydrocarbon, alcohol, ether, ketone, or ester at a temperature of 50 to 300°C for 1 minute to 48 hours, and then A method of post-solvent removal may also be used, and component (z)-(1) and component (11-(3)
When contacting component Cx)-(1) and component
(2) and components (y)-(3) or when components (1)-(2) and component (zl-(3) are brought into contact with each other.
) at a temperature of 0 to 200°C.
The co-pulverization treatment may be carried out for 50 hours, or the unreacted titanium compound may be mixed and heated at a temperature of W-50 to 300°C for 5 minutes to 10 hours in the presence or absence of an inert solvent. And/or a method of removing the vanadium compound by rinsing with an inert solvent may be used.

The device for using component (2)-(2) used in the present invention is 101 to 59, preferably (11 to 2 g) for component (r)-(1>1r9c. Also, component (1)-(3)
It is preferable to adjust the equipment used so that the content of titanium and/or vanadium contained in the produced solid component is in the range of α5 to 20% by weight, and a well-balanced activity per titanium and/or vanadium and per solid. In order to obtain activity, a range of 1 to 10 multiple attacks is particularly desirable.

The most preferred component (I)-(1) in the present invention #c, (
The order and method of contacting [E]-(2) and (X)-(S) are as follows.

That is, first, using a solvent in which the reaction product of the component (r)-(2) magnesium halide and the compound represented by the general formula M@(OR), X, -n is dissolved, the component is dissolved in the solvent. The reaction between (z]-(1) and component CI)-(2) is from 0 to
The reaction is carried out at 300°C, preferably 10 to 200°C, most preferably 20 to 100°C, for 1 minute to 48 hours, preferably 2 minutes to 10 hours. As the solvent, alcohol, tetrahydrofuran, ethyl acetate, etc. are preferably used. .

At this time, the contact ratio of component (1)-(1) and fraction (I)-(2) is 1 component (1)-(1) to 1 fraction (I)-(2).
(2) 0.01 to 5 g, preferably α1 to 2 g.

After the reaction, the solvent was removed and the component (I'J-(1) and component [
A contact product of I]-(2) is obtained.

Next, the titanium compound and/or metal vanadate of component (z)-(3) is added to the contact product of component (x)-(1) and component (x)-(2), such as hexanoate or heptane. Heating and mixing in the presence of an active solvent at a temperature of 20 to 300°C, preferably 50 to 150°C for 5 minutes to 10 hours,
The contact product of fractions (1)-(1) and components (z)-(2) is made to support butane compound feces and/or metal vanadate. At this time, the use of components (1) to (3) to be used depends on the position of the titanium compound and/or vanadium compound contained in the produced solid component, 4t o, s ~ 20 overlapping ≦
It is used in a stacked type or in a stack of 1 to 10 stacks. After the reaction is completed, unreacted titanium compounds and/or metal vanadides are removed by washing the Ziegler catalyst several times with a solvent inert to the Ziegler catalyst, and then evaporated under reduced pressure to obtain a solid powder.

Component (z)-(1) thus obtained, component (z) J2
) and (z]-(3) reaction product (hereinafter referred to as component (r
)), then the general formula 81 (OR' )n
The solid catalyst component of the present invention is obtained by reacting with a compound represented by 1x6 (hereinafter abbreviated as component number 0).

There are no particular restrictions on the method of reaction between the component [technique] and the component [summer], and the reaction may be carried out by co-pulverization.
The reaction may also be carried out in the presence or absence of an inert solvent. The reaction at this time is desirably carried out under heating at a temperature of 20 to 400°C, preferably 50 to 300°C, for 5 minutes to 20 hours.

The reaction ratio of component [I] and component (II) is component (I) 1
00 g, the component [π] is 105 to 50, preferably α1 to sag.

As the organometallic compound used in the present invention, organometallic compounds of Group 1-W of the periodic table, which are known as components of Tegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula R□mu11R, mu IX, Rmu IX, SR, Al
Organoaluminum compounds of OR, RAt(OR) ) or general formula R, Zn
(However, R is an alkyl group having 1 to 20 carbon atoms and may be the same or different.) It is an organic zinc compound represented by triesteraluminum, triisopropylaluminium, tri-isopropylaluminium, tri-isopropylaluminum, Includes 5ee-butylaluminum, tri-tert-butylaluminum, trihexyla I minicum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum sesquichloride, and mixtures thereof. . The amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 100100 times the amount of the titanium compound and/or vanadium compound.

In the present invention, the organometallic compound component can also be preferably used as a mixture or addition compound of the organometallic compound and an organic acid ester.

At this time, when the organometallic compound and the organic acid ester are used as a mixture, the organic acid ester is usually α1 to 1 mol, preferably α2 to (1 mol) per mol of the organometallic compound.
Use 5 moles. When used as an addition compound of an organometallic compound and an organic acid ester, it is preferable that the organometallic compound:organic acid ester ratio is 2:1 to 1:2.

The organic acid ester used at this time has 1 to 1 carbon atoms.
It is an ester of 24 saturated or unsaturated monobasic or dibasic organic carboxylic acids and an alcohol having 1 to 30 carbon atoms. Specific #C is medel formate, ethyl acetate,
Amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, dityl stearate, methyl benzoate, allyl benzoate, n-propyl benzoate, di-propyl benzoate, butyl benzoate, hexyl benzoate , cyclopentyl benzoate, cyclobenzoate, gycyl, benzoin
Phenyl, 4-tolyl benzoate, methyl salicylate,
Ether naritate, methyl p-oxybenzoate, ether p-oxybenzoate, phenyl naritate, cyclohexyl p-oxybenzoate, benzyl naritate, diyl α-resorucinate, ethyl anisate, ether anisate , phenyl anisate, benzyl anisate, nitrous 0-methoxybenzoate, methyl p-ethoxybenzoate, p-
) Methyl tolyate, P-) Ether tolyate, p-) Phenyl tolyate, o-Tolyl ether, m-) Nityl tolyate, Methyl p-aminobenzoate/p-7 minobenzoate, Benzoic acid Examples include vinyl acid, allyl benzoate, benzyl benzoate, methyl f″7toate, difJ/ naphthoate, and the like.

Among these, particularly preferred are benzoic acid, and alkyl esters of p-toluic acid or p-anisic acid, with methyl esters and ethyl esters of these being particularly preferred.

Polymerization of olefins using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization.

In particular, the catalyst of the present invention can be suitably used for gas phase polymerization, and the polymerization reaction is carried out in the same manner as an olefin polymerization reaction using a normal Tegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for the olefin are 20 to 120°C, preferably 5°C.
The temperature is 0 to 100℃, and the pressure is normal pressure to 70J9/
Wound 1, preferably 2 to 6'r: 1119/(Ja) The temperature of 0 molecules can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst. Of course, using the catalyst of the present invention, two-step or more multi-step polymerization reactions with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problems. .

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with a t-glycan catalyst.
α-olefins such as ethylene, propylene, 1-butene, hexene-1,4-methylpentene-1, etc. are preferred; It is suitably used in the copolymerization of hexene-1, propylene and 1-butene, and the copolymerization with other α-olefins of 2al or higher.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 14-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like.

Examples are given below, but these are for illustrative purposes only and the invention is not limited thereto.

Practical example t (1) Production of solid catalyst component 10 g of commercially available anhydrous magnesium chloride and 4.2 g of aluminum triethoxide are placed in a 400-inch stainless steel pot containing 25 stainless steel balls with a diameter of 172 inches. under nitrogen atmosphere.
Pole milling was performed at room temperature for 16 hours to obtain a reaction product. A 3-tube flask equipped with a stirrer, a reflux condenser, and a reflux condenser was purged with nitrogen, and 59 g of the above reaction product and SSO, (Fuji Davison, Na952) 5F calcined at 600°C were charged into the 3-tubular flask, and then tetrahydro 7 run was added. After adding 1Q (lst) and reacting at 60°C for 2 hours, it was dried under reduced pressure at 120°C to remove tetrahydrofuran. Next, 50 ee of hexane was added and stirred, and titanium tetrachloride was added. under refluxing hexane
After a period of reaction, a solid powder (mu) was obtained. The titanium content in each solid powder (mu) obtained was 40 m9.

The solid powder obtained above was placed in 50 kg of hexane, then 1 g Lt of tetraethoxysilane was added, and the mixture was reacted for 2 hours under refluxing hexane to obtain a solid catalyst component.

(b) Gas-phase polymerization A stainless steel autoclave was used as the gas-phase polymerization apparatus, and a blower was used for one flow. A loop was made with a moderator and a dry tube, and the temperature of the autoclave was adjusted by pouring hot water into the jacket.

In an autoclave adjusted to 80°C, the above solid catalyst component was added at 250 μ/hr, and jd and triether aluminum were added at 5 hr.
It was supplied at a rate of 0 mmol/hr, and the putene-17 ethylene ratio (molar ratio) in the gas phase of the autoclave was adjusted to α27
Polymerization was carried out by supplying C and hydrogen at 17% of the total pressure while supplying each gas and circulating the gas in the system using a blower.

□The produced polyurethane copolymer has a bulk specific gravity α42, a melt index (XI), a density Ifα920B, and is 15.
The powder had an average particle size of 750μ with no particles smaller than 0μ.

Comparative Example 1 The following gas phase polymerization was carried out using the apparatus described in Example 1.

80°C WCAtJ1. The solid powder (M) obtained in Example 1 was placed in an autoclave at 2501119/hr, M
and triethylaluminum at a rate of 50 mmol/hr, and butene-17 in the autoclave gas phase.
#C141 so that the ethylene ratio (mole ratio) is 0.25 fC and the total pressure of hydrogen is 155 g! Polymerization was carried out at a total pressure of 10j9/csl by supplying each gas while adjusting the temperature and circulating the gas in the system using a blower. The produced ethylene copolymer has a specific gravity α of 41, a melt index (MI) of 12, and a density of 150μ for L9210.
The powder had an average particle size of 700μ with no particles below.

The catalyst activity is 112,000g copolymer/g'l'i
Met.

The F, R, values of this copolymer were Z6, and the molecular temperature distribution was broader than that of Example HC.

In addition, a film of this copolymer was boiled in chitin for 10 min.
When time-extracted, the amount of hexane extracted was t 1 wt%
Met.

Example 2 (a) Production of solid catalyst component 10 g of anhydrous magnesium chloride and 4.29 g of tetraethoxysilane were placed in the ball mill pot described in Example IC, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. . The above reaction product 59 and 8i0, which was calcined at 600°C, were placed in a 3-tube flask as in Example 1.
5 g of tetrahydro 7ran was added, and then 100 ml of tetrahydro 7ran was added and reacted at 60°C for 2 hours, followed by drying under reduced pressure at 120°C to remove tetrahydr 7ran. Next, 50 ee of hexane was added and stirred. Titanium chloride was added and reacted for 2 hours under reflux of hexane to obtain a solid powder (B). Obtained solid powder (B) 19
The content of titanium inside was @If140119.

The solid powder (n) obtained above was placed in hexane (50), then tetraethoxysilane (1) was added, and the mixture was reacted for 2 hours under reflux of hexane to obtain a solid catalyst component.

(b) Gas phase polymerization The following gas phase polymerization was carried out using the apparatus described in Example 1.

The above solid catalyst component was supplied at a rate of 250"9/hr% and triethylaluminum at a rate of 50 mmol/hr to an autoclave held at 80° C. Polymerization was carried out by supplying each gas while adjusting α281C and hydrogen to 17 times the total pressure, and circulating the gas in the system using a blower.

The produced polyethylene copolymer has a bulk specific gravity α38, a melt index (Ml) tl, a density If (19250''?',
The powder had an average particle size of 750μ with no particles smaller than 150μ.

Moreover, the catalytic activity is 1. Do, 000g copolymer/g'I'
It was i.

The van value of the copolymer was 7.2, and when a film of this copolymer was extracted in boiling chitin for 10 hours, the amount of hexane extracted was α8vt%.

Comparative Example 2 The following gas phase polymerization was carried out using the apparatus described in Example 1.

The solid powder (B) obtained in Actual Example 1 was placed in an autoclave containing 80" CIC 11 at 250 μ/hr and Toriet.
Aluminum A was supplied at a rate of 50 mmol/hr, and the butene-1/triene ratio in the autoclave gas phase (
The molar ratio) was 0.28C, and each gas was supplied while adjusting Cm so that the total pressure of hydrogen was 15≦, and the gases in the system were circulated using a blower to bring the total pressure to 10J9/CI+.
Polymerization was carried out using The produced polyethylene copolymer has a bulk specific gravity of α38, a melt index (MI) of 180, and an average particle size of 75 without any particles smaller than 150μ.
It was a powder of 0μ.

In addition, the catalytic activity is 120.0 GOg copolymer/g'l'l
Met.

The F and R values of this copolymer were 8.0, and the molecular distribution was wider than that of Example 2C.

In addition, the film of this coelectric composite was boiled in chitin for 10
The time of extraction is 2. Owt%
Met.

Actual example 3 (1) Production of solid catalyst component In the ball mill pot described in Example IC, add 109z of anhydrous magnesium chloride and 4.2 g of aluminum triethoxide.
was added to obtain nitride. EXAMPLE HC 81 was calcined with 5 g of the above reaction product and 6GO''C in a 3 flask as described in HC.
Add 0.5 m of ethyl acetate, then add 100 m of ethyl acetate.
After reacting at 60"C for 2 hours, drying was performed under reduced pressure at 120"C to remove ethyl acetate.

Next, 50 ee of hexane was added and stirred, and then titanium tetrachloride was added and reacted for 2 hours under reflux of hexane to obtain a solid powder (0). Obtained solid powder (c) 1
The acid content of titanium in the sample was 40,119.

The solid powder (0) obtained above was placed in hexane 5o-, then tetraethoxysilane a5m was added, and the mixture was reacted for 3 hours under refluxing hexane to obtain a solid catalyst component.

(b) Gas phase polymerization The following gas phase polymerization was carried out using the apparatus described in Example 1.

The above solid catalyst component was supplied at a rate of 250''9/hr* and triether aluminum at a rate of 50!lIn1el/hr to an autoclave adjusted at 80'CC, and the butene-17 ethylene ratio (mol) in the gas phase of the autoclave was ratio)
#C to α27 and hydrogen to 17% of the total pressure.
#14 Each gas was supplied while adjusting the system, and the gases in the system were circulated using a blower to carry out polymerization. The produced ditrene copolymer had a bulk specific gravity [139, a melt index (ax) ts, a close jet α of 9200, and was a powder with an average particle size of 600μ with no particles smaller than 150μ.

Moreover, the catalyst activity failed at 90,000q copolymer/gTj.

Of Jin's copolymer! , R1 value was z5, and when this copolymer was extracted in fill M-comb, +11' chitin for 10 hours, the extraction pupil of this copolymer was α9vt%.

Practical example 4 (a) Production of solid catalyst component 10 g of anhydrous magnesium chloride and 4.1 g of tetraethoxypolone were placed in the ball mill pot described in Example 1, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. Ta. Example 1 Into a 3 flask described in fc, 5 samples of C material during the above reaction and S10 calcined at 600°C were added.
, 5g was added, and then tetrahydro7ran 100- was added and reacted at 60°C for 2 hours, followed by drying under reduced pressure at 120°C to remove tetrahydro7ran.
After 50 ee of hexane was added and stirred, silane tetrachloride was added and reacted for 2 hours under refluxing hexane to obtain a solid powder (D). The acid content of titanium in each solid powder (D) obtained was 4Q''19.

The solid powder (D) obtained above was placed in hexane (50), then tetraethoxysilane (1) was added, and the mixture was reacted for 2 hours under refluxing hexane to obtain a solid catalyst component.

(b) Gas phase polymerization The following gas phase polymerization was carried out using the apparatus described in Example 1.

The above solid catalyst component was supplied at a rate of 250sI9/hrS and triethylaluminum at a rate of 50 mmol/hr to an autoclave heated at 80°C #CMl1, and the butene-1/ethylene ratio (mole ratio) in the autoclave gas phase was
α27C, and hydrogen to be 17% of the total pressure Ic
Polymerization was carried out by supplying each gas while adjusting it and circulating the gas within the system using a blower. The produced ethylene copolymer has a bulk specific gravity α42 and a melt index (
XI) 15, dense α9205 powder with an average particle size of 500μ with no particles smaller than 44μ.

In addition, the catalyst activity is 7 to 000g copolymer/g'f'i
Met.

This copolymer! , the R0 value Fi was 74, and the quinan extraction pupil was α9wt% when a film of this copolymer was extracted in boiling chitin for 10 hours.

Example 5 (a) Production of solid catalyst component 10 g of anhydrous magnesium chloride and 4.2 g of jetoxymagnesium were placed in the ball mill pot described in Example 11C, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a reaction product. Ta. Into the 3 flask described in Example 1, 5 g of the above reaction product and 8
i0,59 and then tetrahydro7 run 100-
was added and reacted at 60°C for 2 hours, then at 120°C.
Drying under reduced pressure was carried out to remove tetrahydrofuran.
Next, 50 cc of hexane was added and stirred, and then 11% of titanium tetranomide was added and reacted for 2 hours under refluxing hexane to obtain a solid powder (B). Obtained solid powder (E)
The titanium content 1i in the sample was 40m9.

The solid powder (1) obtained above was placed in 50 kg of hexane, then 1 gt of tetraethoxysilane was added, and the mixture was reacted for 2 hours under refluxing hexane to obtain a solid catalyst component.

(b) Gas phase polymerization The following gas phase polymerization was carried out using the apparatus il#c described in Example 1.

250119/hr% of the solid catalyst component and 50 mmol/hr of triethylaluminum were continuously supplied to an autoclave adjusted to 80°C, and the butene-1/ethylene ratio (molar ratio) in the gas phase of the autoclave was set to 0.
Step 27: Further, each gas was supplied while adjusting hydrogen to 17% of the total pressure, and the gases in the system were circulated using a blower to carry out polymerization.

The produced ethylene copolymer had a bulk specific gravity of 0.40 and a melt index (MI) of [15, f! ! The powder had an average particle size of 600μ with no particles smaller than 100μ at α9250.

In addition, the catalytic activity is 100.0009 copolymer/gTl”C
'It's four.

This copolymer! , the R0 value was Z5, and when a film of this copolymer was extracted in boiling chitin for 10 hours, the hexane extraction density was [L4vt%].

Procedural amendment September 4, 1980 Commissioner of the Patent Office Shima 1) Haruki Tono1, Indication of the case 1982 Patent Application No. 1185322, Name of the invention Process for producing polyolefin 3, Person making the amendment Related: Name of patent applicant (444) Nippon Oil Co., Ltd. 4, Agent 6, Contents of amendment (1) The specification (the same applies hereinafter) amends "less" to "less" on page 4, line 5.

(2) Correct "ethyleneto" in line 9 of page 24 to "ethylene and".

(3) Insert Yodo's text between lines 6 and 7 on page 27.

"Also, the catalyst activity was 100,000 f copolymer/Ti. This copolymer was
F, which is expressed as the ratio of the melt index M1216 measured at 190°C and a load of 2.16Kf and the melt index M110 measured at a load of 10Kg, according to the method of T.
, R, value (F, R, = MI 2.16/Ml 10 )
was 7.2, and the molecular weight distribution was extremely narrow.

In addition, a film of this copolymer was prepared in boiling hexane for 10
When time-extracted, the amount of hexane extracted was 0.8 wt%, which was extremely small. ” Procedural amendment March 26, 1980 Commissioner of the Patent Office Shima 1) Indication of the Haruki Tonori case 1982 Patent Application No. 118532 2 Title of the invention Process for producing polyolefin 7 3. Case of the person making the amendment Relationship between Patent applicant name (444) Contents of amendment in Column 6 of Detailed Description of the Invention in the specification of Nippon Oil Co., Ltd. (1) "Example 1" in the fourth line from the bottom on page 30 of the specification is changed to "Example 1" 2”.

(2) Correct “tetraethoxybone” t “triethoxyboron” on page 34, line 1 of the specification@

Claims (1)

[Claims] In method #C of polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst, the solid catalyst component is (1) (1) silicon oxide puyo and/or aluminum oxide Things, (2) ^σgenka mug sheep shikumu and general style lid・(OR)
,
is the valence of the element gM, n is O x n≦zs, X is a herogen atom, and B is a hydrocarbon residue having 1 to 20 carbon atoms), and (3) A reaction product obtained by contacting a titanium compound g and/or a vanadium compound with a phase "!
~24 hydrocarbon residues, X represents 10 gene atoms, m
is 0≦−≦4).