JPS5812888B2 - Method for manufacturing polyolefin - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for highly active polymerization of olefins.

More specifically, the present invention relates to a method for producing a polyolefin that can produce a highly stereoregular polymer in high yield when applied to the polymerization of an α-olefin having 3 or more carbon atoms.

Conventionally, in order to produce a highly stereoregular polymer of α-olefin having 3 or more carbon atoms, titanium tetrachloride was mixed with aluminum,
A combination catalyst system of titanium trichloride obtained by reduction with a reducing agent such as hydrogen or an organoaluminum compound and an organoaluminum compound is widely used.

It is also known that it is effective to add various electron donors to these catalyst systems in order to suppress the formation of non-quality polymers.

However, when the above catalyst system is used, the yield of polymer per unit catalyst is small, and as a result, the amount of catalyst residue remaining in the polymer cannot be ignored, so a step of removing the catalyst residue is required.

On the other hand, it is known that a complex containing at least magnesium, titanium, and a halogen is useful for the highly active polymerization of olefins. It is also known that they can be used in the highly stereoregular polymerization of

However, when the above-mentioned complex containing an electron donor is simply combined with an organometallic compound of a metal from Group 1 to Group 3 of the periodic table, it is difficult to polymerize an α-olefin having 3 or more carbon atoms in the presence of hydrogen. However, it is difficult to sufficiently reduce the production rate of non-quality polymers.

Various electron donors that were effective in suppressing the formation of non-quality polymers when using the titanium trichloride catalyst system,
Even when applied to the above-mentioned composite systems with different catalyst systems, the effects vary widely, and many have no effect at all, or do not show sufficient improvement effects to be industrially applicable.

Among them, organic acid esters showed excellent addition effects, and among them, aromatic carboxylic acid esters showed remarkable effects, but many other typical electron donors, such as ketones,
Altehydes, amines, alcohols, carboxylic acids, etc.
As mentioned above, the performance was inferior.

The present inventors extensively investigated many other additives in order to find ones with effects comparable to those of organic acid esters, and as a result, they discovered that acid anhydrides have similar effects. .

That is, according to the present invention, (a) a halogen compound obtained by contacting a magnesium compound, a titanium compound, and an electron donor with each other in any order;
Titanium (molar ratio) is greater than about 4, magnesium/titanium (molar ratio) is about 3 or more, electron donor/titanium (molar ratio)
is about 0.2 to about 6, and the specific surface area is about 40 m/
a complex containing at least magnesium, titanium, halogen, and an electron donor that is P or higher; (b) an organometallic compound of a metal from Group 1 to Group 3 of the periodic table; and (e) an acid anhydride. A method for producing a polyolefin (a term that includes copolymers) is provided, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst.

In the present invention, a composite containing at least magnesium, titanium, . The compound obtained by contacting is preferably one in which the halogen/titanium molar ratio contained in the composite exceeds about 4, and the titanium compound is not substantially eliminated by hexane washing at room temperature.

Although its chemical structure is unknown, it is thought that the magnesium and titanium atoms share a halogen and are strongly bonded to each other.

Further, depending on the manufacturing method, it may contain other metal atoms such as aluminum, silicon, tin, boron, germanium, calcium, and zinc, or an organic group based on an electron donor.

Furthermore, organic or inorganic inert diluents such as LiCl,
CaC03, BaCl2, Na2CO3, SrCl2
, B203 , Na2SQ4, AI203 , Si0
2, T102, NaB4o7, Cas(PO4)2,
CaSO,, AI 2 (804) 3, C a C l
2, Z n C 1 2, polyethylene, polypropylene, polystyrene, etc.

Various electron donors can be selected as the electron donor in the complex, but those containing organic acid esters or ethers are particularly preferred.

A good composite (a) is halogen/titanium (molar ratio)
is greater than about 4, preferably greater than or equal to about 5, more preferably greater than or equal to about 8, magnesium/titanium (molar ratio) is greater than about 3, preferably from about 5 to about 50, electron donor/titanium (
molar ratio) is about 0.2 to about 6, preferably about 0.4 to about 3, more preferably about 0.8 to about 2, and the specific surface area is about 40 m2/g or more, preferably about 1
00m2/g or more.

In addition, the X-ray spectrum of the composite may show inferior properties regardless of the presence of the starting magnesium compound, or it may be in a highly amorphous state compared to that of ordinary commercially available magnesium dihalides. It is desirable that there be.

As an example of the means for producing the composite (a), for example, Japanese Patent Application Publication No. 1983-1.08385, Japanese Patent Application Publication No. 126590
No., JP-A-51-20297, JP-A-51-2818
No. 9, Japanese Patent Application Publication No. 1-64586, Japanese Patent Application Publication No. 1977-13
No. 6625, JP-A-52-87489, JP-A-52-
100596, JP-A-52-104593, JP-A-52-147688, JP-A-52-151691, JP-A-53-2580, and the like.

Typical methods disclosed in these documents involve at least one of a magnesium compound (or magnesium metal), an electron donor, and a titanium compound.

As electron donors, water, alcohol, phenols,
Oxygen-containing electron donors such as ketones, aldehydes, carboxylic acids, esters, ethers, and acid amides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates can be used.

More specifically, methanol, ethanol, furopanol, pentanol, hexanol, i-octanol, dodecanol, octatecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
1 carbon number such as isopropylbenzyl alcohol (・
18 alcohols, phenol, cresol, xylenofur, ethylphenol, flobylphenol,
Phenols having 6 to 15 carbon atoms that may have a lower alkyl group such as cumylphenol and naphthol; 3 to 1 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and penzophenone.
5 ketones, aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate,
Vinyl acetate, probyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, benzoic acid Ethyl, probyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, 0-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 18 carbon atoms such as ethylene carbonate, 2 to 1 carbon atoms such as acetyl chloride, penzyl chloride, toluic acid chloride, anisyl chloride, etc.
5 acid halides, methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, methylamine, ethylamine, Amine oils such as diethylamine, tributylamine, piperidine, tripendylamine, aniline, hyridine, picoline, and tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, and tolnitrile, and aluminum, silicon, and tin that have these functional groups in their molecules. Compounds such as the following can be mentioned.

Two or more types of these electron donors can be used.

The magnesium compound used for catalyst preparation is preferably a compound containing a halogen and/or an organic group.

Specific examples of these include magnesium dihalide,
Examples include alkoxy halides, hydroxyhalides, hydroxyhalides, dialkoxides, diallyloxides, alkoxyallyloxides, aryl halides, alkyl halides, aryl halides, dialkyl compounds, diaryl compounds, and alkyl alkoxides.

These may be present in the form of adducts with the electron donor.

It may also be a composite compound containing other metals such as aluminum, tin, silicon, germanium, zinc, and boron.

For example, metal halides such as aluminum, alkyl compounds, alkoxy halides, allyloxy halides,
It may also be a composite compound of an alkoxide, allyloxide, etc. and the above-mentioned magnesium compound.

Alternatively, it may be a complex compound in which phosphorus, boron, etc. are bonded to magnesium metal via oxygen.

Of course, these may be a mixture of two or more.

The above-exemplified compounds can usually be represented by a simple chemical formula, but depending on the manufacturing method of the magnesium compound, they may not be represented by a simple formula, and these are usually considered to be a mixture of the above compounds.

For example, a method in which magnesium metal is reacted with alcohol or phenol in the presence of halosilane, phosphorus oxychloride, or thionyl chloride, or a Grignard reagent is decomposed with heat or with a compound having a hydroxyl group, carbonyl group, ester bond, ether bond, etc. Compounds obtained by methods such as
Depending on the amount of reaction reagent used and the extent of the reaction, the product may be considered as a mixture of various compounds, and these can of course be used in the present invention.

Various methods are known for producing the above-mentioned magnesium compound, and any of these methods may be used.

The magnesium compound may also be pretreated prior to use.

For example, there is a method of separating the solid component by dissolving it alone or together with other metal compounds in ether or acetone, and then evaporating the solvent or introducing it into an inert solvent.

Alternatively, one or more magnesium compounds and other metal compounds may be mechanically pulverized in advance.

Among these magnesium compounds, preferred are magnesium dihalide, allyloxychloride, allyloxide, or composite compounds of these with aluminum, silicon, etc. More specifically, MgCl2, MgBr2,
MgI2, MgF2, MgCl (QC6H5), Mg
(QC a H5 )2, MgC1(QC3H,2-C
H3), Mg(OC6H4- 2-CH3)2, (MgCl2)x-(Al (OR), CI3-,)y
, (MgCl2)X(Sl(OP)mCl4-m), (
However, R is a hydrocarbon group such as an alkyl group or an aryl group,
m or n R's may be the same or different.

0≦n≦3, 0≦m≦4, x and y are positive numbers], etc.

Particularly preferred is MgCl2 or complexes or complexes thereof.

There are various titanium compounds, but they usually have the formula Ti(OR
)gX4-(R is a hydrocarbon group, X is a halogen, 0≦g≦
The tetravalent titanium compound shown in 4) is suitable.

More specifically, titanium tetrahalides such as TiCl, TiBr4, Ti14; Ti(OCH3)Cl3,
Ti(QC2us)Cl3, Ti(OnC4H9)Cl
3 Trihalogenated alkoxy titanium such as Ti(OisoC4H9)Br3: Ti(OCR3)2Cl2, Ti(
OC2H5)2CI2, TI(OnC4H9)CI2,
Dihalogenated alkoxytitanium such as Ti(OC2H5)2Br2; Ti(OCH3)3Cl, TI(OC2Hs)3Cl, TI(OnC4H9)3C
Examples include monohalogenated trialkoxytitanium such as Ti(OC2H5)3Br; Ti(OCH3) and trialkoxytitanium such as Ti(OC2H5)4.

Among these, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred.

There are various ways of reacting the magnesium compound (or magnesium metal), electron donor, and titanium compound as described above, and representative examples are shown below.

CI] A method in which a magnesium compound and an electron donor are reacted, and then a titanium compound is reacted.

(I-a) Method of 5CI) involving co-milling of a magnesium compound and an electron donor.

The electron donor added at the time of co-pulverization does not need to be in a free state, and may be present in advance in the form of an adduct with the magnesium compound.

Alternatively, during co-pulverization, the organic or inorganic inert diluent, halogenating agent such as a silicon halogen compound, polysiloxane, other silicon compounds, compounds such as aluminum, germanium, tin, etc. may be contained in the composite. Although such an additional component or a part of the titanium compound may be present, the electron donor may be present in the form of an adduct (complex compound) of such a compound.

The amount of electron donor used is preferably about 0.005 to about 10 mol, more preferably about 0.01 to about 1 mol, per 1 mol of the magnesium compound.

For co-grinding, for example, a rotary ball mill, a vibrating ball mill,
Equipment such as an impact mill can be used.

Taking a rotary ball mill as an example, stainless steel (SUS3
2) made of stainless steel (SUS32) with a diameter of 15 mm in a ball mill cylinder with an internal volume of 800 ml and an internal diameter of 100 mm.
Accommodates 100 balls and can handle 20 to 40 objects
When it is 1, co-pulverization is preferably carried out at a rotational speed of 125 rpm for at least 24 hours, more preferably for at least 48 hours.

The temperature of the pulverization process is usually about room temperature to 100°C.

In order to react the co-pulverized material and the titanium compound, the amount of the titanium compound in the liquid phase, with or without using an inert solvent, is about 0.05 mol or more, preferably about 0.1 to about 1 mol, per 1 mol of the magnesium compound. It is preferable to adopt a method of suspending and contacting the co-pulverized material in 50 moles.

The reaction temperature is preferably room temperature to about 200° C. and the reaction time is preferably about 5 minutes to 5 hours, but it is of course possible to carry out the reaction under conditions outside this range.

After the reaction is completed, the temperature is high, for example about 60 to about 150°C.
It is preferable to isolate the product by hot filtration in the vicinity, and further wash it well with an inert solvent before subjecting it to polymerization.

(I-b) A method that does not involve co-pulverization of a magnesium compound and an electron donor.

Usually, the magnesium compound and the electron donor are reacted in an inert solvent, or the magnesium compound is dissolved or suspended in a liquid electron donor.

Of course, an embodiment may be adopted in which magnesium metal is used as a starting material and is reacted with an electron donor while producing a magnesium compound.

The amount of electron donor used is preferably about 0.01 to about 10 mol, more preferably about 0.05 to about 6 mol, per 1 mol of the magnesium compound.

It is sufficient to carry out the reaction for about 5 minutes to 5 hours at a reaction temperature of room temperature to about 200°C.

After the reaction is completed, the reactant can be isolated by filtration, evaporation, etc., and washing with an inert solvent.

The reaction between the reactant and the titanium compound can be carried out in the same manner as the method explained in (I-a).

(I-c) A method in which a reaction product of a magnesium compound and an electron donor is reacted with a compound selected from an organoaluminium compound, a silicon compound, or a tin compound, and then reacted with a titanium compound.

This method is a special embodiment of method (I-b).

In general, the complexes obtained by the method (I-a) have high performance, but some of the complexes obtained by the method (I-b) are (I
- There are some methods that are inferior in performance to that of (a).

For such materials, it is very effective to adopt the present method in which the organoaluminum compound or the like is reacted in advance before the reaction with the titanium compound.

Organoaluminides used in this process: compounds include trialkylaluminum, dialkylaluminum hydride, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, dialkylaluminum, alkoxide or phenoxide, alkylaluminum alkoxyhalide or phenoxy Examples include halides and mixtures thereof, among which dialkylaluminum halites, alkyl aluminum ses. Preferred are dihalides, alkylaluminum dihalides and mixtures thereof.

Examples of these include trialkylaluminum, triisobutylaluminum, diethylaluminium hydride, dibutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum bromide, ethylaluminum sesquichloride, diethylaluminum ethoxide, ethylaluminum ethoxychloride, ethylaluminum dichloride,
Examples include butylaluminum dichloride.

Silicon or tin compounds, such as halogen compounds or organic compounds, have one or more halogen or hydrocarbon groups directly bonded to silicon or tin, and also contain hydrogen alkoxy groups, phenoxy groups, etc. Good too.

Specific examples include silicon tetrahalide, silicon tetraalkyl, silicon alkyl halide, silicon alkyl hydride, tin tetrahalide, tin dihalide, tin alkyl halide, and tin hydrogenated halide. Among them, it is preferable to use silicon tetrachloride or tin tetrachloride.

An inert solvent may be used in the reaction between the magnesium compound/electron donor reactant and the organoaluminum compound.

These compounds, per mol of magnesium compound,
Preferably, about 0.1 to about 20 moles are used, more preferably about 0.5 to about 10 moles.

The reaction is usually carried out preferably at a temperature of about room temperature to about 100° C. for about 5 minutes to about 5 hours.

After completion of the reaction, it is preferable to wash thoroughly with an inert solvent and then react with a titanium compound.

The reaction between this reactant and a titanium compound can be carried out according to the method described in (I-a).

(■) A method of simultaneously reacting a magnesium compound, an electron donor, and a titanium compound.

(■) A method of reacting a titanium compound, an electron donor reactant, and a magnesium compound.

The above method is a typical method, and many variations are possible.

(1) Method of CI) in which an electron donor is present when reacting a titanium compound.

(2) A method in which an organic or inorganic inert diluent or a compound such as silicon, aluminum, germanium, or tin mentioned above is present during the reaction, a method in which it acts before the reaction, a method in which it acts in the middle of each reaction, a method in which it acts in the middle of each reaction, or a method in which it acts after the reaction. How to make it work.

A representative example of this is the method (I-C), but these reagents can be used at any point in the above-mentioned methods.

For example, a method in which a halogenating agent such as SiCl4 is applied to the compound obtained by each method of (2-a) (I) (■) (■).

(3) A method in which a titanium compound is applied two or more times.

(3-a) [■] A method of reacting a titanium compound and an electron donor with the reaction product obtained by the method on pages.

(3-b) A method of reacting a titanium compound, an organoaluminum compound, and an electron donor with the reaction product obtained by the methods of (I) to (■).

In addition to the above methods, changing the order of addition of reaction reagents,
Numerous variations are possible by carrying out multiple reactions and by incorporating other additional reaction reagents.

However, whichever method is adopted, the complex (a
It is desirable that the mutual ratios, surface areas, and X-ray spectra of halogen, titanium, magnesium, and electron donors in ) are within the ranges or states described above.

Electron donors preferably contained in the complex (a) are those that do not have active hydrogen, such as esters, ethers, ketones, tertiary amines, acid halides, and acid anhydrides;
Organic acid esters or ethers are particularly preferred, and aromatic carboxylic acid esters and alkyl-containing ethers are particularly preferred.

Representative examples of suitable aromatic carboxylic acid esters include lower alkyl esters such as benzoic acid, lower alkylbenzoic acid, and lower alkoxybenzoic acid.

The term "lower" herein means a compound having 1 to 4 carbon atoms, with 1 or 2 carbon atoms being particularly preferred.

Suitable alkyl group-containing ethers are ethers having 4 to 20 carbon atoms, such as diisoamyl ether and dibutyl ether.

Organometallic compounds of metals from Groups 1 to 3 of the periodic table (b
) have a hydrocarbon group directly bonded to a metal, such as alkyl aluminum compounds, alkyl aluminum alkoxides, alkyl aluminum hydrides, alkyl aluminum halides, dialkyl zinc, dialkyl mak'
Examples include nesium.

A preferred compound among these is At (C21{3)
3, AI (CH3)3, A l (C3 H7)
s, AI (C, H9) 3, AI (C12H25
)s trialkyl or trialkenyl aluminum, (C2H5)2AIOA1 (C2H5)2, (
C4H9)2AI0Al(C4H9)2, (C2H5)
Alkylaluminum compounds with a structure in which many A1 atoms are linked via oxygen or nitrogen atoms such as (C2H5)2, (C2H5)2AIH, (C4H
9) Dialkyl aluminum hydrides such as 2A IH, dialkyl aluminum halides such as (C2H5)2AICI, (C2H5)2AII, (C4H9)2AIC1, (C2H5)2A1 (OC2H5), (C2H5)2A l (OCaH5) The most preferred dialkylaluminum alkoxide or phenoxide is trialkylaluminum.

An acid anhydride is used as the catalyst (C) component.

Typical examples include acetic anhydride, propionic anhydride, n-butyric anhydride, iso-butyric anhydride, monochloroacetic anhydride,
Acid anhydrides of aliphatic monocarboxylic acids having 2 to 18 carbon atoms such as trifluoroacetic anhydride, caproic anhydride, lauric anhydride, stearic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, methylsuccinic anhydride, dimethylsuccinic anhydride,
Anhydrides of aliphatic polycarboxylic acids having 4 to 22 carbon atoms, such as ethylsuccinic anhydride, butylsuccinic anhydride, octylsuccinic anhydride, stearylsuccinic anhydride, methylglutaric anhydride, hexahydrofucric anhydride, and anhydride acid, carbon number 8 to 1, such as methylnadic anhydride
0 alicyclic carboxylic acid anhydride, acetobenzoic anhydride, aceto1-ruic anhydride, benzoic anhydride, toluic anhydride, phthalic anhydride, trimellitic anhydride with 9 carbon atoms
to 15 aromatic carboxylic acid anhydrides.

Among these, aromatic carboxylic acid anhydrides are preferred.

Next, anhydrides of aliphatic monocarboxylic acids are preferred, although they tend to have slightly lower polymerization activity.

These acid anhydrides can also be used as electron donors when producing composite (a).

These acid anhydrides may be used in the form of addition reaction products or substitution reaction products with the organometallic compound (b).

A preferred method of use is to replace the inside of the polymerization system with an olefin monomer, then add the acid anhydride and organometallic compound (b), and then add the titanium catalyst (composite) (a). There is no problem even if the acid anhydride and the organometallic compound (b) are brought into contact with each other and then charged into the polymerization system.

Olefins used in polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc., and these can be subjected not only to homopolymerization but also to random copolymerization and block copolymerization.

Further, during copolymerization, a polyunsaturated compound such as a conjugated diene or a non-conjugated diene can be selected as a copolymerization component.

In particular, when used in the polymerization of α-olefins having 3 or more carbon atoms, polymers with high stereoregularity can be obtained in high yields.

Polymerization can be carried out in either liquid phase or gas phase.

When carried out in a liquid phase, an inert solvent such as hexane, heptane or kerosene may be used as the reaction medium, but the olefin itself may also be used as the reaction medium.

In the case of liquid phase polymerization, the concentration of the composite (a) component in the polymerization system per liter of liquid phase is 0,001 to 0.5 mmol per liter of solvent, based on titanium atoms, and the concentration of the organometallic compound is 0.5 mmol per liter of solvent, based on metal atoms. 01 to 50 mm as standard
l is preferred.

The amount of organometallic compound (b) used is the same as that of the metal atom and (a).
The ratio of titanium atoms in the components is preferably 1/1 to 100
0/], more preferably 1/1 to 200/].

In addition, the amount of acid anhydride (c) used is 1 of the metal of the organometallic compound.
It is preferably 0.001 to 1 mol, more preferably 0.01 to 1 mol, per atom.

The olefin polymerization reaction using the catalyst of the present invention can be carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst.

That is, all reactions are conducted in a state where oxygen, moisture, etc. are substantially excluded.

When using a suitable inert solvent, for example an aliphatic hydrocarbon such as hexane, hebutane or kerosene, the polymerization is carried out by charging a catalyst and an olefin, and optionally a diolefin.

The temperature for olefin polymerization is usually selected from 20 to 200°C, preferably from 50 to 150°C.

The polymerization is preferably carried out under pressure, from normal pressure to 50 kg/cm2, especially from 2 to 20 kg/cm2.
It is preferable to carry out the process under moderate pressure.

When carrying out olefin polymerization using this catalyst system, the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, but it is most effective to add hydrogen to the polymerization system.

By employing the method of the present invention, a polymer having a large melt index and high stereoregularity can be produced in high yield.

Example 1 20 g anhydrous magnesium chloride, 6. 0 ml of ethyl benzoate and 3.0 ml of methylpolysiloxane (viscosity 20c,e, (25°C)) were mixed in a nitrogen atmosphere with a diameter of 1
5mm stainless steel (SUS-32) ball 2.
800ml internal volume that accommodates 8 kg, internal diameter 100m
The sample was placed in a ball mill container made of stainless steel (SUS-32) and left in contact for 24 hours at an impact acceleration of 7°C.

The obtained solid treated product 102 was suspended in 100 ml of titanium tetrachloride, and after contact at 80° C. with stirring for 2 hours, the solid component was collected by filtration, and free titanium tetrachloride was no longer detected in the washing liquid. After thoroughly washing with purified hexane until dry,
Obtain a titanium composite.

Titanium 3.0% by weight, chlorine 58.2% by weight in terms of atoms,
Magnesium 18.0% by weight, ethyl benzoate 15.5%
Including weight %.

Moreover, its specific surface area is 180 m/g.

After replacing an autoclave with an internal volume of 2 liters with propylene, 750 ml of hexane from which oxygen and moisture had been sufficiently removed, 4.5 mmol of triethylaluminum, and 1.5 mmol of phthalic anhydride were added.
5 mmol, and 0.5 mmol of the titanium complex in the previous section in terms of titanium atoms. Charge 0.3 mmol.

After sealing the system, 250 ml of hydrogen was charged and the temperature started to rise.
When the polymerization system reaches 60° C., propylene is introduced and polymerization is started at a total pressure of 8 kg/cm 2 .

After polymerization was carried out at 60°C for 6 hours, the introduction of propylene was stopped, the inside of the autoclave was cooled to room temperature, and the resulting solid was filtered and dried to yield white powdery polypropylene 335.
Get 1'.

The extraction residue rate by boiling n-hegukun was 949%, its apparent density was 0.31 g/ml, and its melt index was 27.

On the other hand, 13.4 g of a solvent-soluble polymer was obtained by concentrating the liquid phase.

Example 2 Commercially available anhydrous magnesium chloride 9.5 g (0.1 mol)
was suspended in 0.3 liters of kerosene, and 23.3 m of it was suspended at room temperature.
l (0.4 mol) of ethanol and 143 ml (0
．． 1 mol) of ethyl benzoate was added and stirred for 1 hour.

Next, 24.2 ml of diethylaluminum chloride (0.
2 mol) was added dropwise at room temperature and stirred for 1 hour.

After taking the solid part of the product and thoroughly washing it with kerosene, suspending the solid in 0.3 liters of kerosene containing 30 ml of titanium tetrachloride,
The reaction was carried out at 80°C for 2 hours.

After the reaction is completed, the supernatant is removed by decantation, and the solid is thoroughly washed with fresh kerosene to obtain a titanium composite.

Contains 35% by weight of titanium, 59.3% by weight of chlorine, 19.3% by weight of magnesium, and 14.7% by weight of ethyl benzoate in terms of atoms.

Further, its specific surface area is 175 m2/g.

0.05 mmol of the above titanium complex in terms of titanium atoms
Propylene polymerization was carried out in the same manner as in Example 1 except that 327.4 g of white powdery polypropylene was obtained.

The extraction residue with boiling n-heptane is 95.0%, the apparent density is 0.32 g/ml, and the melt index is 36.

Meanwhile, 11.7 g of solvent-soluble polymer was obtained by concentrating the liquid phase.
get.

Examples 3 to 8 Using the titanium composite synthesized in Example 1, propylene polymerization was carried out in the same manner except that phthalic anhydride was replaced with another acid anhydride.

The results are shown in Table 1.

Example 9 Commercially available Mg (OCH3) 28.6 S' (0.
1 mol) was suspended in 0.3 liters of kerosene, 10.6 ml (0.1 mol) of O-cresol was added, and the mixture was reacted at 80°C for 1 hour.

At the same temperature, 7.2 ml (0.05 mol) of ethyl benzoate
was added and the reaction was further continued for 1 hour.

Cool to 60℃ and add 42.9ml of SiCl (0.02
5 mol) was added dropwise over 30 minutes, and the mixture was reacted at 60°C for 1 hour.

After cooling, the solid part of the product was taken and thoroughly washed with kerosene.The solid was suspended in 300 ml of titanium tetrachloride and heated at 130°C for 2 hours.
Allowed time to react.

After the reaction is completed, the supernatant is removed by decantation, and the solid is thoroughly washed with fresh kerosene to obtain a titanium composite.

It contained 4.1% by weight of titanium, 54% by weight of chlorine, 167% by weight of magnesium, and 11.3% by weight of ethyl benzoate, and had a specific surface area of 160 m2/g.

The above titanium composite is 0.03 mm in terms of titanium atoms.
When propylene polymerization was carried out in the same manner as in Example 1 except that 0.01 was used, white powdery polypropylene 296.
Obtain 2g.

The extraction residue with boiling n-hebutane is 951%, the apparent density is 0.30 g/ml, and the melt index is 36.

On the other hand, a solvent-soluble polymer 12.07 is obtained by concentrating the liquid phase.

Example 10 A titanium composite was obtained by contacting both components in the same manner as in Example 1, except that 20 g of anhydrous magnesium chloride and 6.5 wLl of isoamyl ether were used.

It contained 2.1% by weight of titanium and 69% by weight of chlorine in terms of atoms, and its specific surface area was 130 m2/g.

The above titanium complex is 0.03 mmol in terms of titanium atoms.
Propylene polymerization was carried out in the same manner as in Example 1 except that 325.3 g of white powder polypropylene was obtained.
get.

The extraction residue with boiling n-hebutane is 933%, the apparent density is 0.35 g/ml, and the melt index is 40.

On the other hand, solvent-soluble polymer 9.9 is obtained by concentrating the liquid phase.

Claims (1)

[Scope of Claims] 1(a) The halogen/titanium (molar ratio) obtained by contacting a magnesium compound, a titanium compound, and an electron donor with each other in any order is greater than about 4, and the magnesium/titanium (molar ratio) is about 3 or more, the electron donor/titanium (molar ratio) is about 0.2 to about 6, and the specific surface area is about 40 m
2/g or more of a complex containing at least magnesium, titanium, halogen, and an electron donor; (b) an organometallic compound of a metal from Group 1 to Group 3 of the periodic table; and (e) an acid anhydride. 1. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst. 2. The method according to claim 1, wherein the electron donor in 2(a) is an organic acid ester or ether.