JPS5930803A - Preparation of polyolefin - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having a high bulk specific gravity in good productivity without requiring the step of removing a catalyst, by polymerizing an olefin in the presence of a catalyst containing (A) a solid obtained by reacting a magnesium halide with a specific metallic compound, a silicon compound and a titanium compound in combination with (B) a reaction product obtained by reacting an organosilicon compound with an organometallic compound. CONSTITUTION:An olefin is polymerized or copolymerized with another alpha-olefin in the presence of a catalytic system containing (A) a solid substance obtained by reacting (i) a magnesium halide with (ii) a compound of formula I (Me is an element of Groups I -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), (iii) a compound of formula II (R' and R'' are 1-24C hydrocarbon; X is halogen; 0<=m<4; 0<n<=4; 0<m+n<=4) and (iv) a titanium compound and/or a vanadium compound in combination with (B) a reaction product obtained by reacting (v) a compound of formula III (R<1>-R<3> are 1-24C hydrocarbon, alkoxyl, H or halogen; R<4> is 1-24C hydrocarbon; 1<=q<=30) with (vi) 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 type of technical field, the
A catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide is known from Publication No. 05, and a catalyst in which magnesium halide and titanium tetrachloride are co-pulverized is known from Belgian Patent No. 742,112. It is being

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 method described in Japanese Patent Publication No. 39-12105 still has a low polymerization activity, while the method described in Belgian Patent No. 742,112 has a low polymerization activity. Although the temperature is considerably higher by 8 degrees, improvement is still desired.

In addition, in German Patent No. 2137872, the amount of fecal matter of magne-7cum halide is substantially reduced by co-pulverizing magne-sium halide, titanium tetrachloride, alumina, etc., but this is not a measure of productivity. No significant increase in activity per solid was observed, and a catalyst with even higher activity is desired.

However, in the production of polyolefin, it is desirable that the bulk specific gravity of the resulting polymer 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 @Kokukokoku Sho 39-12105, and the polymerization activity is low in the method described in Belgian Patent Publication No. ff'IJiJ742,112. However, the bulk specific gravity of the resulting polymer is low, and improvements are desired.

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 is related to the copolymerization method, and since the polymerization activity is extremely high, the 7mer partial pressure during polymerization is low, and the bulk specific gravity of the produced polymer is high, so the productivity can be increased as above, and the The amount of catalyst residue in the produced polymer is extremely small, and therefore the catalyst removal step can be omitted in the polyolefin production process, thereby simplifying the polymer treatment process and providing an extremely economical polyolefin AA method as a whole. .

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

Furthermore, the advantages of the present invention are that although the bulk specific gravity of the produced polymer is high in terms of particle size, there are few coarse particles and fine particles of 50μ or less, so continuous polymerization reaction is facilitated, and the polymer This facilitates the handling of polymer particles, such as centrifugation, S and powder transport in processing steps.

As an advantage of the present invention, the polyolefin obtained using the present catalyst has a high specific gravity as described above, and in order to obtain a polymer with a sterile melt index, the conventional pressure is required to be lower than the conventional pressure. Can be economical,
It can also be mentioned that it has a large effect on productivity.

In addition, when olefins are polymerized using the catalyst of the present invention, an advantage is that the olefin absorption rate decreases little with time, so 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 prong resistance.

The catalyst of the present invention has many of these characteristics and has fn
The present invention provides a novel catalyst system that improves the shortcomings of the prior art, and it must be said that it is surprising that these points can be easily achieved by using the catalyst of the present invention.

The present invention will be specifically explained below. That is, the present invention provides +11[I':l:tl) magnesium halide, (11) general formula Me(O)L) nX2-n
(Here, Me represents an element of Group I to Group II of the periodic table. However, 5tSTijd and V are excluded. R is an element with a carbon number of 1 to 2.
4 represents a hydrocarbon residue, and X represents a ) rogen atom.

2 represents the valence of Me, and n is Q, n≦2)
A compound represented by, Tll+) General formula R'm5i(0几)nX4-m
-n (here, 几', R' is a hydrocarbon residue having 1 to 24 carbon atoms, and X is a halogen atom. m, n are 0≦m<4゜0<n≦4.0<m+n≦ 4), B and (lv) a substance R'it' obtained by simmering a titanium compound S and/or a vanadium compound, a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group , hydrogen or nitrogen, 几4 has 1 to 24 carbon atoms
represents a hydrocarbon group. (q is 1≦q≦60), B and [■]: by a catalyst system consisting of a combination of an organometallic compound, or (2) [I
): (D magnesium halide, (11)
General formula Me (OR) n
and V are excluded. R is a hydrocarbon residue of carbon 61-24,
X represents a halogen atom.

2 represents the valence of Me, and n is O<n≦2)
A compound represented by, flll) General formula ratio 'm81(OR')nX, -m
-n (here) t' and R' represent a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. m, n are 0≦m, 4゜0<n≦4, O<m+n≦4); and (lv) a solid substance obtained by reacting an f-tan compound and/or a vanadium compound. , 8 and 几", R" represents a hydrocarbon residue having 1 to 24 carbon atoms, and represents a hydrocarbon group having 1 to 24 carbon atoms. q is 1≦q≦60) and (vl) a product obtained by reacting an organometallic compound.
Alternatively, the present invention relates to a method for producing a polyolefin, which involves copolymerization.

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

Examples of the compound represented by the general formula Me(OR)nX2-n (where Me, zS n and R are the above-defined H) used in the present invention include NaO, M
g(OR), ,Mg(oFL)x, 0a(OR), ,Z
n(OR),,Zn(OR)X.

0d(OR),,A1(0几),,AI(OR),X,
E(OR), B(OR), X, Ga(OR), ,Ge(
OR) 4.5n(OR),,P(on),,p(on
),,0r(OR),,Mn(ORh,Fe(OR)
,,Fe (OR) ,,Co (OR) ,,N
i (OR), and more preferable specific examples include Na0O, H,, N
a0O,H,,Mg(oon,),,Mg(00,H,
'),, Mg (o o * ua ) *, 0n(
00,H,'),,Zn(00,H,),,Zn(00
,H,)C1,AI(OOH,),,AI(00,H,
)l, Al(00,H6), C1,AI(00,,H,
),,AI(00,II,) 1lSAt(00,H,
),,B(00,H,),,B(0(E H)01,p
(oo H) , P (00H) , Fe (00
Examples include compounds such as a H*) m.

In the present invention, the general formula Mg(OR) nX, -
0, A1(0几)nxll-n and B(OR)nX,
Compounds represented by are preferred. Further, as the group, an alkyl group having 1 to 4 carbon atoms and a phenyl/I/ group are particularly preferable.

To this invention? The general formula a'5t(OR'
) -butoxysilane, monomethyltocy5ec-butoxysilane, monomethyltriisoproxy7rane, monomethyltripentoxysilane,
Monomethyltrioctoxysilane, monomethyltristearox7silane, monomethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, dimethyldiisobroboxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimene Termonoinobroboxysilane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monomethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane,
Monomethyljethoxymonochlorosilane, monomethyljethoxymonobromo7rane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxy7rane, monoethyltrimethoxysilane,
Monoethertriphenoxysilane, diethyldimethoxy7rane, diethyljethoxy7rane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyljethoxymonochlorosilane , monoethyldiphenoquine monochlorosilane, monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-
Butyltriethoxysilane, mono 5ec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyljethoxysilane, diphenylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxy Trichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenokiditrichlorosilane, monop-methylphenokiditrichlorosilane, methoxydichlorosilane, ethoxydichlorosilane, diynepropoxydichlorosilane,
Di-n-butoxydichlorosilane, dioctoxinchlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triinpropoxymonochlorosilane, trin-butoxymonochlorosilane, tri5ec-
Mention may be made of butoxymonochlorosilane, tetraethoxysilane, and tetraisopropoxysilane.

Examples of the titanium compound S and/or vanadium compound used in the present invention include titanium and/or vanadium halide, alkoxy halide, alkoxide, halide oxide, and the like. As the titanium compound, a titanium compound of 41if [i and a titanium compound of 3 ryo are suitable, and specifically as a titanium compound of 4 strokes, the general formula 'I'i (O 几) PX4-p (here 几 is represents an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms, X represents a herogen atom, p is 0≦
p≦4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium,
Triethoxymonochlorotitanium, tetraethoxytitanium, monoimprofoxytrichlorotitanium, diisoproboxydichlorotechn, triinobropoquine monochlorotetane, tetrainopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium , heptanophenoxytrichlorothetane, diphenoxydichloroticune, triphenoxymonochlorotitanium, tetraphenoxytitanium, and the like. 5IiIli titanium compounds include trihalogens obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of metals from groups I to II of the periodic table. Examples include titanium oxide. Also, the general formula Ti(oa) rx4
-r (here, R represents an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms; X represents a herogen atom; r represents O<r<4); Examples include trivalent titanium compounds obtained by reducing logogenated alkoxyditane with organometallic compounds of metals in groups 1 to 1 of the periodic table. Examples of vanadium compounds include vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vacanium tetraiodide, and detraethoxypacadium, as well as vanadium oxytrichloride, ethoquine dichlorvanadyl, triethoxybacadyl, and tributoxyvanadyl. Examples include vanadium compounds such as vanadium trichloride, vanadium trichloride, and vanadium triethoxide.

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. The V/Ti molar ratio at this time is preferably in the range of 2/1 to 0.01/1.

General formula R'81(OR')X4 used in general formula CI) used in the present invention
Compounds represented by mn-rrl-n and R'rnS i (0′)nX4
Examples include chain-like and semi-cyclic polysiloxanes in which the repeating unit obtained by condensation of -m-n to obtain R' is represented by +StO+.

(1) Magnesium halide according to the present invention, (1)
A compound represented by the general formula Me(OR)X, n
A compound represented by z −n (till i7'5t(oR') The method is not limited in terms of loading, and is carried out at a temperature of 20 to 400°C, preferably 50 to 300°C, in the presence or absence of an inert solvent.
A method of reacting by contacting under heating for usually 5 minutes to 20 hours, a method of reacting by co-pulverization treatment,
Alternatively, the reaction may be carried out by appropriately combining these methods. There is also no particular restriction on the reaction order of components (1) to (1v).

The inert solvent is not particularly limited, and hydrocarbon compounds S and/or derivatives thereof that do not normally inactivate the Tegler type catalyst can be used. Specific examples of these include propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, various aliphatic saturated hydrocarbons such as cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and ethanol and diethyl. Examples include alcohols, ethers, and esters such as ether, tetrahydrofuran, ether acetate, and ether benzoate.

When reacting by co-pulverization, the equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and the grinding temperature, grinding time, etc. is easily determined by those skilled in the art. Generally, the grinding temperature is 0 to 200°C, preferably 20'C to 100°C, and the grinding time is 0.5 to 50 hours, preferably 1 to 3
It is 0 hours. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible.

Magnesium halide and general formula Me(OR)X
The mixing ratio of the compound 4 with the formula n z -n is given by the general formula Me (0 liters)
Even if the amount of the compound represented by
0, preferably in the range of 110.01 to 1/1, most preferably in the range of 110.05 to 1105, for the production of highly active catalysts.

Magnesium halide and general formula 14' 5i (OR
')nX4. The mixing ratio with the compound represented by -n is the amount of the compound represented by the general formula R' 5t (OR') First, the Mg/Si molar ratio is in the range of 110.01 to 1/1, preferably 170.05 to 1105.

The amount of titanium compound 8 and/or vanadium compound is most preferably adjusted so that titanium and/or vanadicum contained in catalyst component CI) is within the range of 0.5 to 20%, which provides a good balance. In order to obtain an activity per titanium and/or pacadium, and an activity per solid, a range of 1 to 10% by weight is particularly desirable.

In the present invention, the addition effect cannot be expected if the amount of the general formula 1 used for l is too large or too small, and α1 to 100 mol, preferably within the range of 0.3 to 20 mol.

In accordance with the third aspect of the present invention, it is also preferably employed to use the catalyst component [1] thus obtained as supported on an oxide of a metal of Groups I to II of the periodic table.

The oxides of groups ■ to ■ of the periodic table to be used are those of group I of the periodic table.
Not only oxides of group F to II metals alone but also deoxidized products of these metals may be used, and of course, mixtures thereof may be used. Specific examples of these metal oxides include Mg
O1OaO1ZnO1BaO18i0. ,SnO,,A
I, O,, MgO・Al, O,1, Sin, ・AI,
O,, MgO・SiO,, MgO-0aOAl, O,,
At, 0.・OaO etc. can be expressed as V++, but especially 5to2, AI, O,, 8i0.・AI, 08,
MgO・AI, 0. is preferred.

The method of supporting the catalyst component CI] on the oxide of metal of groups ① to ① of the periodic table is not particularly limited.
), component (11), component (B) and component (1v) are added, heated to react, and then the liquid phase is removed; The raw material obtained by co-pulverizing components (1), S and (11) in advance is added to the mixture and reacted with a heated knife, after which the liquid phase is removed and an inert solvent is added. Preferred examples include a method in which the components (machi and lv) are reacted by heating.

As the organometallic compound used in the present invention, organometallic compounds belonging to Groups I to II of the periodic law known as components of Tegler's catalyst can be used, but organic aluminum compounds 3 and organozinc compounds are particularly preferred. Specific examples include the general formula R, lAl, )t, AiX, JLAIX,, R
, AloftSRAI (OR)X g and 几, AI,
X, an organoaluminum compound (where 几 is an alkyl group or an aryl group having 1 to 20 carbon atoms, There are organozinc compounds represented by the following alkyl groups (which may be the same or different), including triethylaluminum, triethylaluminum,
Tri-isobrobyl aluminum, tri-isobrobyl aluminum, tri-5ec-butyl aluminum, tri-ter
t-butylaluminum, trihexylaluminum,
Specific examples include triethylaluminum, diethylaluminium chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc 8, and mixtures thereof. In addition, together with these organometallic compounds, benzoic acid ether, 0- or p-
Organic carboxylic acid esters such as toluic acid ether and p-ethyl anisate can also be used in combination. The dosage of organometallic compound is not particularly limited, but is usually 0.1 to 1 gram per titanium compound and/or vanadium compound.
It can be used 001000 times.

R'' may be used by reacting the compound with the above-mentioned organometallic compound.The reaction ratio at this time is according to the general formula 500-
The range is 1:1, more preferably 1:100 to 1
:2 range.

The amount of the product obtained is such that the sl:Ti (mole ratio) is 0.1:1 to the titanium compound in catalyst component CI).
A range of 100:1 is preferred, and a range of Ojl to 20:1 is more preferred.

Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization, or gas phase polymerization, and it can be particularly preferably used for gas phase polymerization 8 and slurry polymerization. The polymerization reaction is carried out in the same manner as an ordinary olefin polymerization reaction using a Tegler type catalyst. That is, all anti-L6 reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for olefin are a temperature of 20 to 120°C, preferably 50 to 100°C, and a pressure of normal pressure to 7.5°C.
0 to 97cm”, preferably 2 to 6Q kg 7c
It is m. The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the molecular weight can be effectively controlled 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 can be applied to the polymerization of all olefins that can be mounted on a Ziegler catalyst, and is particularly suitable for the polymerization of carbon a2-1
α-olefins of 2 are preferred, such as homopolymerization of α-olefins such as ethylene, propylene, butene-1, hexene-1,4-)f-pentene-1, octene-1, and ethylene and propylene, ethylene and butene-1, Ethylene and hexene-1, ethylene and 4-meth)L
It is suitably used in the copolymerization of /pentene-1, ethylene and octene-1, propylene and butene-1, and the copolymerization of ethylene and other α-olefins of 244 or more classes.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, etheridenorporene, cyclopentadiene, and the like.

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

Example 1 (a) Preparation of solid catalyst fraction (I) 10 g of commercially available anhydrous magnesium chloride and aluminum triethoxide were placed in a stainless steel pot with an internal volume of 400 frLt containing 25 stainless steel balls with a diameter of 172 inches. 2.39, tetraethoxy 7
Run 3.29.8 and 2.5 g of titanium tetrachloride were added and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere.

Solid catalyst component obtained after ball milling [1] 19
contained 351n9 titanium.

(b) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower 1 flow rate regulator and a dry cyclone, and the temperature of the autoclave was regulated by flowing hot water into the jacket.

The above-mentioned solid catalyst component CI) was fed into an autoclave adjusted to 80°C at a rate of 50'l'9/hr and monomethyltriethoxysilane α22ml/t. Each gas was supplied while adjusting the hydrogen ratio (molar ratio) to 0.28 and hydrogen to 17% of the total pressure, and the gases in the system were circulated using a blower to bring the total pressure to 10%. Polymerization was carried out while maintaining the temperature at 9/cm-Q. The produced ethylene copolymer has a bulk specific gravity of 065 and a melt index (MI) of 1.
0, and the density was 0.9217.

The catalytic activity was 294,000 copolymer/ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner wall and the stirrer were clean with no polymer attached at all.

This copolymer was prepared with a melt index MI of . Melt index MI□ measured at □6 and load 10JC9.

F. expressed as a ratio of几. Value (F.)L. =M1
10/MI t, □6) was 6.7, and the molecular weight distribution was extremely narrow.

In addition, a film of this copolymer was boiled in chitin for 10 min.
When extracted over time, the amount of hequinane extracted was large. 5w
t%, and the amount extracted was extremely small.

Comparative Example 1 Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that monomethyltriethoxysilane was not added. The produced ethylene copolymer has a bulk specific gravity of 060 and a density IJ (0.9210
, and the melt index was t3.

Also, the catalyst activity is 310,000g copolymer/gT
It was i.

Still, the r. ratio. The value was 73, and when the film was extracted in boiling chitin for 10 hours, the amount of hequinane extracted was 16 wt%.

Example 2 20 g of ethanol 10-1 anhydrous magnesium chloride and 4.6 g of triethoxypolone were added to a 300ee Mitsuro flask equipped with a magnetic induction stirrer, and the mixture was reacted under reflux for 6 hours. After the reaction was completed, 150 mj of n-~quinane was added to form a precipitate, and after the mixture was allowed to stand still, the supernatant liquid was removed.
Makabe drying was performed at 200°C to obtain a white dry powder.

Contents: 25 stainless steel poles with a diameter of 1/2 inch [In a 400-inch stainless steel pot, put the above white powder 112, jetoxydiethylsilane & Og2, and 2.4 titanium tetrachloride under a nitrogen atmosphere, Ball milling was performed at room temperature for 16 hours. 59■ for 31g of solid catalyst component Cl obtained after ball milling
contained titanium.

Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example f111, except that the solid catalyst component CI) was fed at a rate of 5 [1 mV/hr]. The produced ethylene copolymer has a bulk specific gravity of 0.33 and a degree of 0.922.
0, melt index t2.

Further, the catalyst activity was extremely high at 340,000 g mutual benefit $/g Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Furthermore, the F. R. The value was 6.9, and when the film was extracted in boiling chitin for 10 hours, the amount of hechitin extracted was 0. It was 8 wt%, and the amount extracted was extremely small.

Example In the ball mill pot described in Example 1, anhydrous magnesium chloride 109, ;) ethoxymagnesium 3.19j+!
After adding 2.99 g of IKA titanium chloride and bono milling for 5 hours at room temperature under a nitrogen atmosphere, 3.8 g of methyltriethoxysilane was added and pole milling was performed for an additional 12 hours. Solid catalyst component (1
mN9 contained 37W9 titanium.

The above solid catalyst component CI) was fed at a rate of 501 n9/hr, and a mixture of 1 mol of triethylaluminum and 0.1 mol of tetraethoxysilane was simmered at 85°C for 2 hours, resulting in 5 mmol/hr in terms of aluminum.
Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1, except that the feed was carried out at a rate of 1 hour. The produced ethylene copolymer has a bulk specific gravity of 0.34 and a density of 0.92.
15, and the melt index was 0.95.

The catalyst activity is 258,000g copolymer/g'I
'i, which showed extremely high activity.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and the stirrer were clean with no polymer attached at all.

In addition, the F, R, and I values of this copolymer were 67, and when the film was extracted in boiling hexane for 10 hours, the amount extracted by hexane was 0.4 wt%, which was an extremely small amount extracted at °C. .

Example 4 In the ball mill pot described in Example 1, 10 g of anhydrous magnesium chloride and 2.1 g of triethoxyphosphorus (p(obt)s) were added.
9 and ball milled at room temperature under a nitrogen atmosphere for 3 hours. After that, further add tetrane propoxysilane 4.
5, add X and 3.09 g of titanium tetrachloride and perform pole milling again for 16 hours. 1 g of solid catalyst component [I] obtained after pole milling contained 57vn9 of titanium.

The above solid catalyst component CI) was fed at a rate of 50 m9/hr, and ethylene and Continuous gas phase polymerization of butene-1 was carried out. The produced ethylene copolymer has a bulk specific gravity of 0.35, a density of 0.9218,
The melt index was t1.

Further, the catalyst activity was extremely high at 270.0009 copolymer/gTi.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner wall 3 and the stirrer were clean with no polymer attached to them.

In addition, the F, R, values of this copolymer were 7.0, and when the film was extracted in boiling chitin for 10 hours, the hexane extraction amount was 0.9 W t%, which was an extremely small extraction amount. Ta.

Example 5 Into the ball mill bottle described in Example 1, 1a of anhydrous mug chloride, 3.5 g of jetoxyzinc, and 2.89 g of diisobropoquine dichlorokatan were added, and under a nitrogen atmosphere,
After performing ball milling at room temperature for 16 hours, 3.89 g of triethoxymonochlorosilane was further added and ball milling was performed for 7 hours. 1 g of the solid catalyst component [1:] obtained after ball milling contained 28 μg of titanium.

Feed the solid catalyst component (I) at a rate of 50 μ/hr,
Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that tetraethoxysilane was fed at a rate of 0.25 mmol/hr instead of monomethylethoxysilane.

The produced ethylene copolymer had a bulk specific gravity of 0.39, a solubility of 0.9224, and a melt index of 1.2.

In addition, the catalytic activity is 330.0009 copolymer/g'l'i
The activity was extremely high.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Further, the F, R, and values of this copolymer were zO, and when the film was extracted in boiling hexane for 10 hours, the amount extracted by hexane was α7wt%, which was an extremely small amount extracted at °C.

The autoclave equipped with an induction stirrer manufactured by Stenle Nutair in Example 2 was purged with nitrogen, and 1,000 fnt of hexane was added thereto, and 1 ml and a half of triethylaluminum, 1 mmol of tetraethoxysilane α, and the solid catalyst component (I) obtained in Example 1 were added. ) was added and the temperature was raised to 85°C while stirring. By injecting nitrogen, the system was reduced to 2 to 97 cm',
(Adjust J K, then add hydrogen until the total pressure is 5PC9/Cm
・Put the autoclave in until the pressure reaches G, and then add ethylene until the total pressure reaches 10 kg 7 cm"・G to start polymerization. Polymerization was carried out for 1 hour while maintaining the pressure of the autoclave at 10 to 9/C♂・G. After completion of polymerization, the polymer streaks were transferred to a beaker, hexane was removed under reduced pressure, and melt index to, density 0.9631, bulk specific gravity 0.
38 pieces of white polyethylene were obtained. Catalytic activity is 6
6.300 polyethylene/g Ti-hr-0, H4 pressure, 25209 polyethylene/g solid/hr-C,H, pressure.

In addition, the values of F and It of the obtained polyethylene are Z5
The molecular weight distribution is extremely narrow compared to Comparative Example 2.
The amount of hexane extracted was 0.2 wt%.

Comparative Example 2 Polymerization was carried out for 1 hour in the same manner as in Example 6, except that tetraethoxysilane was not added, and a white product with a melt index of 14, a density of 1 degree of 0.9637, and a specific gravity of o of 35 was obtained. 134 g of polyethylene was obtained. Catalytic activity is 76.5009 polyethylene/gTLhr・OlH
, pressure, 26809-boriethe l/7/g solid hr-0
, I'l, was.

In addition, the F and R values of the obtained polyethylene were 83,
The amount of hexane extracted was 0.6 wt%.

Example 7 The solid catalyst component (I) obtained in Example 1 was added to 501+19
/hr, and the product obtained by reacting triethylaluminum and monomethicyto9-ethoxysilane at a composition (molar ratio) of 5+0.22 at room temperature for 2 hours was fed at a rate of 5 mmol/hr in terms of aluminum. Implementation row 1
Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as above. The produced ethylene copolymer has a bulk ratio ii0
．． 34, density α9214, melt index 0.93
Met.

Further, the catalyst activity was extremely high at 501,000 copolymer/gTi.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

Further, the F, R, values of this copolymer were 68, and when the film was extracted in boiling chitin for 10 hours, the amount of hexane extracted was 0.6 wt%, which was extremely small.

Example 2 Commercially available anhydrous magnesium chloride 109H and aluminum triethoxide 4.27% were placed in a stainless steel pot with an internal volume of 400 cm containing 25 stainless steel poles with a diameter of 1/2 inch, and the temperature was kept at room temperature under a nitrogen atmosphere. Ball milling was carried out for 16 hours to obtain a reaction product. A 3-throated flask equipped with a stirrer, a reflux condenser, and a reflux condenser was purged with nitrogen, and the above reaction product 2.59X and 810. (i!
Davison, NA 952) 5G+ was added, and then tetrahydrofuran 100- was added, and the mixture was reacted at 60°C for 2 hours, followed by drying under reduced pressure at 120°C to remove tetrahydrofuran. Next, 50 cc of hexane was added and stirred, and then 11-titanium tetrachloride was added and reacted for 2 hours using a hequinane reflux filter to obtain a solid powder (A). The content of titanium in 1 g of the obtained solid powder (A) is 37 m
It was y.

The solid powder (A) obtained above was placed in 50 tons of hexane, and then tetraethoxysilane 2- was added and reacted for 2 hours under refluxing hexane to obtain a solid catalyst component.

The above solid catalyst component was used at 150rn9/hr, and the triethyl aluminum and tetraethoxysilane were used at AI/5i=20.
Continuous gas phase polymerization was carried out in the same manner as in Example 1, except that the reaction product obtained by reacting at 85° C. for 15 hours at a molar ratio of 5 mmol/hr was fed as AI at a rate of 5 mmol/hr. The produced ethylene copolymer has a bulk specific gravity of 0.38 and a density of 1. f
The melt index was 0.9213.

In addition, the catalytic activity is 543.000 Ii copolymer/g
It had extremely high activity as Ti.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but no polymer adhered to the inner wall 8 or the stirrer, and the copolymer was clean. was 6.9, and when the film was extracted in boiling chitin for 10 hours, the amount of hexane extracted was 0.8 wt%, which was an extremely small amount.

Example 9 10 g of anhydrous magnesium chloride and 4.27 g of jetoxymagnesium were placed in the ball mill pot described in Example 1, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product. Into the 3 flask described in Example 8, 2.5 ml of the above reaction product, 0.5 ml of Si calcined at 600°C were added, and then 1 ml of tetrahydrofuran was added.
After adding 00 g ILt and reacting at 60°C for 2 hours, drying was performed under reduced pressure at 120°C to remove tetrahydrofuran. Next, 50 cc of hexane was added and stirred, and then titanium tetrachloride was added and reacted for 2 hours under refluxing hexane to obtain a solid powder (E). The content of titanium in 1 g of the obtained solid powder (B) was 56 m9.

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

Continuous gas phase polymerization was carried out in the same manner as in Example 8 except that the solid catalyst component was fed at a rate of 150 .mu./hr. The produced ethylene copolymer has a bulk specific gravity of 0.41 and a density of 0.
．． 9203, and the melt index was 0.8. Further, the catalyst activity was extremely high at 49,000 gTi/gTi.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

In addition, the P and R values of this copolymer were 6.9, and when the film was extracted in boiling chitin for 10 hours, the amount of hexane extracted was 1.0 wt%, which was extremely small. Ta.

Procedural amendment April 1, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 138455, filed in 19822, Name of the invention: Process for producing polyolefins3, Person making the amendment Relationship with the case Patent applicant name (444) Nippon Oil Co., Ltd. 6, Scope of claims and detailed description of the invention in the specification subject to amendment 7
, Contents of the amendment (1) The scope of the claims will be amended on a separate sheet.

(2) The details will be amended as follows.

(3) Delete all "P(OR)5" on page 13, line 5 of the details.

(1) CI): (i) Magnesium halide, (ii) General formula MeCOR>nX, -, (Here, Me represents an element of Groups I to II of the periodic law. However,
Excludes Si, Ti and V. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents gold. 2 represents all the valences of Me, n is 0 and n≦2), (iii) a compound represented by the general formula RJiCOR"TenX4-
---． (Here R'.

R" is a hydrocarbon residue t having 1 to 24 carbon atoms, and X is a halogen atom. Usually, n is 0≦m<4.0<n≦4, usually +n≦4) compound, and Ov
) represents a solid substance obtained by reacting a titanium compound and/or a vanadium compound, or a halogen; H4 represents a hydrocarbon residue having 1 to 24 carbon atoms; q is 1≦q≦30), and [■]: Polymerization of olefin using a catalyst system consisting of all organometallic compounds,
Alternatively, a method for producing a polyolefin characterized by copolymerization.

(2) [1]: (i) Magnesium halide, (11) General formula Mg(OR), -¥, -n (where,
'Me represents an element of Group I to Group II of the periodic table. However, S
i, Ti and V are excluded. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a rogen atom. 2 represents the valence of Mg, n is O (n≦2), (1j) a compound represented by the general formula R'J s (07?'')nX4
-rn-n (here, R'IR" has 1 to 24 carbon atoms
The hydrocarbon residues k and X represent halogen atoms. m, n are 0≦m<4, 0<n≦4, O<m+n≦4); and Gv) a solid substance obtained by reacting a titanium compound and/or a vanadium compound; H4 represents a carbon atom or a halogen, and H4 represents a hydrocarbon having 1 to 24 carbon atoms. q is 1≦q≦30) and (vD) is characterized in that it polymerizes or copolymerizes olefins using a catalyst system formed by combining a product obtained by reacting an organometallic compound. A method for producing polyolefin.

Claims (1)

[Claims] (1) [I): (1) Magnesium halide, (II) General formula Me(OR)nX2-n (here, Me represents an element of Group I to Group II of the periodic table. However,
St, Tie and V are excluded. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. 2 represents the valence of Me, n is 0 and n≦2), (III) a compound represented by the general formula a, 4st(o几')
nX4-ml-n 'where R', R' is carbon E!
11 to 24 hydrocarbon residues, and X represents a halogen atom. m and n are 0≦m<4, o<n≦4, O<m+n≦
4), solid substance 1 obtained by reacting g and (1v) titanium compound g and/or palfium compound, I R1 is a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group ,
It represents hydrogen or halogen, and 4 represents a hydrocarbon group having 1 to 24 carbon atoms. q is 1≦q≦30), B and [■]: Olefin is polymerized by a catalyst system consisting of a combination of organometallic compounds,
Alternatively, a method for producing a polyolefin characterized by copolymerization. +2) CI ) : (1) Magnesium halide, (11) General formula Me(O几)X (Here, M
e represents an element of group ■ to group ■ of the periodic table. However, 81, T.I.
Excludes N and V. R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. 2 represents the valence of Me, and n is 0 and n≦2). X represents a halogen atom, and m and n are 0≦m<4.0<n≦4.
0<m+n≦4), B and (lvl) A solid substance obtained by reacting a 5-thane compound 2 and/or a vanadicum compound, g and 几 are hydrocarbons having 1 to 24 carbon atoms a residue, an alkoxy group, hydrogen or a halogen; R' represents a hydrocarbon group having 1 to 24 carbon atoms; q is 1≦q≦60); and (vl) an organometallic compound. Polymerizes olefins using a catalyst system that combines the products obtained by the reaction.
Alternatively, a method for producing a polyolefin comprising copolymerization.