JPS58117205A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer excellent in stereoregularity, etc. in good, operability, by polymerizing an olefin with the aid of a catalyst system comprising an organoaluminum compound and a solid catalytic component containing a titanium component supported on a specified Mg compound. CONSTITUTION:A tetravalent titanium halide compound (e.g., titanium tetraaholoride) is brought into contact with a magnesium compound (e.g., magnesium chloride) liquefied with a phosphine oxide of the formula, wherein R<1>, R<2> and R<3> are 1-20C hydrocarbyls (e.g, trimethylphosphine oxide) or with a solid magnesium compound precipitated from the liquefied magnesium compound. Then, an olefin (e.g., propylene) is polymerized with the aid of a catalyst system comprising the produced solid catalytic component and an organoaluminum compound (e.g., triethylaluminum) to obtain the purpose olefin polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing olefin polymers (including copolymers) using a Ziegler-Natsuta type catalyst. More specifically, the present invention relates to a method for producing an olefin polymer using a catalyst system basically consisting of a solid catalyst component in which a titanium component is supported on an Mg compound and an organoaluminium compound.

Prior Art There have already been many proposals regarding methods for producing solid catalyst components in which a tetravalent titanium compound is supported on a magnesium compound.

One of the characteristics of this solid catalyst component is that it has extremely high olefin polymerization activity.

For the polymerization of α-olefins having 3 or more carbon atoms, stereoregularity of the resulting polymer can be improved by incorporating a specific electron donor (for example, a carboxylic acid ester, especially an aromatic carboxylic acid ester) into the solid catalyst component. It is also known that (II) can be improved.

When using Mg compound gold, which itself is insoluble or poorly soluble in an inert solvent, as a manufacturing method for a solid catalyst component, it is ground in contact with an electron donor using a grinder, or it is ground in an inert solvent. A common method is to bring the magnesium compound into contact with the necessary reagents in the form of a slurry. In particular, in order to obtain high II polymers of α-olefins in high yields, solids that include the step of co-pulverizing the magnesium compound and various reagents are commonly used. Catalyst manufacturing method is preferred O Handling and pulverizing the solid itself is a complicated operation, and the solid catalyst component manufactured by the manufacturing method that requires a large amount of co-pulverization process as described above is difficult to handle and crush. There is a drawback that it is difficult to control the particle size and particle size distribution of the olefin polymer produced using it. As a method of liquefying and using magnesium compounds that are insoluble or dissolvable in inert solvents for the purpose of improving
-40293). Another proposal is to liquefy a magnesium compound with an alcohol, an aldehyde, an amine, or a carboxylic acid.

In the above proposal for liquefying a magnesium compound,
The rate at which the magnesium compound liquefies is slow, the amount of liquefying agent used is large, the viscosity of the liquefied product is high and it is difficult to handle, or the solid product precipitated from the liquid oxide is It has defects such as low polymerization performance (polymerization activity and II) and is not satisfactory.

In order to compensate for the above drawbacks when preparing a solid catalyst component by liquefying a magnesium compound, the applicant has developed a method of liquefying a magnesium compound with a phosphorus compound having a C-0-P or C-N-P bond. I proposed (I ¥1 request 1984-1)
17461).

Although this proposal greatly improves the drawbacks of the conventional method, it is difficult to reuse the phosphorus compound used to liquefy the magnesium compound, which complicates the solid catalyst manufacturing process and increases the cost. There was a drawback.

Purpose The present invention has improved the above-mentioned drawbacks, and has high activity when used in the polymerization of olefins, a small decrease in activity over time, uniform particle size, and carbon atoms with a carbon number of 3 or more. It is an object of the present invention to provide a new catalyst system capable of obtaining a high II in the polymerization of olefins and of obtaining a polymer with a high bulk density.

Abstract In order to achieve the above objective, as a result of intensive research, we found that A halogen compound of titanium (M) and the general formula R"R" R
″p=.

Phosphine oxyto (here gl, R2
, R8 is a hydrocarbon residue having 1 to 20 carbon atoms, and each may be the same or different), or solid magnesium precipitated from the liquefied magnesium compound. It has been found that the above object can be easily achieved when an olefin is polymerized using a catalyst system consisting basically of a solid catalyst component obtained by contacting a solid catalyst component with a compound B, and an organoaluminum compound. First of all, when using phosphine oxide as a liquefaction agent for magnesium compounds, in addition to making it possible to make the magnesium compound into a liquid compound that is easy to handle by using only a small amount of the phosphorus compound, Compounds can be easily recovered and reused.

Second, the time required to liquefy the magnesium compound is short. Third, the liquefied magnesium compound has a relatively low viscosity and is easy to handle.

Fourth, the solid product obtained by contacting the liquefied magnesium compound with the titanium(t)halogen compound itself has a high Learn about the performance of catalyst components.

Furthermore, even when using a solid magnesium compound precipitated by a method other than contacting a liquid magnesium compound with a titanium (1) halide, the solid magnesium compound and titanium (transfer) may be used.
A single contact with the halogen compound can provide a sufficiently high performance solid catalyst component.

These things are important for streamlining the solid catalyst component manufacturing process.
A solid catalyst component can be produced very advantageously, easily and at low cost.

Fifth, when polymerizing olefins using the catalyst system of the present invention, the activity is high with little decrease over time, and
When the olefin is an a-olefin having 3 or more carbon atoms, the resulting polymer has a high II content, so that the catalyst removal step and the atactic polymer extraction step are unnecessary.

Sixthly, since the polymer produced using the catalyst system of the present invention has a high bulk density, the amount of polymer produced per unit volume of the polymerizer is large and the molding machine has good penetration.

Seventh, the catalyst system of the present invention has extremely high activity not only in the homopolymerization or copolymerization of olefins, but also in the copolymerization of olefins and polyenes, and has unsaturated groups in the main chain or side chain. A highly reactive copolymer can be obtained in high yield.

Eighthly, even if the catalyst system of the present invention is used to carry out monopolymerization or copolymerization of olefins, or copolymerization of olefins and polyenes in the presence of hydrogen, there is little decrease in polymerization activity and II.

It is a well-known fact that the solid catalyst component having many of these characteristics is derived from the above-mentioned magnesium compound liquefied with phosphine oxide, and that once used phosphine oxide can be easily recovered and reused. No, I should say it's surprising.

DETAILED DESCRIPTION OF THE INVENTION 1) Phosphine oxyto Phosphine oxyto for liquefying the magnesium compound used in the present invention is represented by the general formula %. Here, R1, R2 and R3 have 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 1 to 15 carbon atoms.
The hydrogen atoms of these hydrocarbon residues are substituted with nitrogen, alkoxy groups, etc. Also, R1, R2 and R3 may be the same or different.

Specific examples of these phosphine oxides are shown below. F-n-butylphosphine oxyto, tri-butylphosphine oxyto, tri-n-butylphosphine oxyto, tripentylphosphine oxyto, trihexylphosphine oxyto, trioctylphosphine oxyto, tris(2-ethylhexyl)phosphine oxyto, tridodecylphosphine oxide, tri7-chlorohexylphosphine oxide, triphenylphosphine oxide, dibutylphenylphosphine oxide, etc.

Among these, trimethylphosphine oxide, triethylphosphine oxide, tri-n-7' lovylphosphine oxide, trimy propylphosphine oxide,
Tri-n-butylphosphine oxide and tri-butylphosphine oxide are preferred, and tri-butylphosphine oxide is particularly preferred. The amount of these phosphine oxides to be used depends on the type of magnesium compound described below. Although not uniform, it is usually used in an amount of 0.1 to 20 mol, preferably O, S to 10 mol, particularly preferably 1 to 10 mol, per mol of the magnesium compound.

When the magnesium compound is magnesium halide such as magnesium chloride, it is 1 to 10 mol, and when it is a magnesium salt of carboxylic acid or alkoxymagnesylam,
Preference is given to using ~10 mol of phosphine oxide per mole of magnesium compound.

Moreover, one type of phosphine oxyto may be used, or two or more types may be used in combination. By using two or more kinds in combination, the solubility of the magnesium compound increases or the viscosity of the liquefied magnesium compound decreases, so that the total amount of phosphorus compounds used may be reduced.

2) Magnesium Compound The magnesium compound to be liquefied for use in the present invention is a solid or semisolid magnesium compound that is insoluble or soluble in an inert solvent, or a liquid magnesium compound with extremely high viscosity. When using a magnesium compound having a C-Mg bond, the C-Mg bond is decomposed in advance or during the preparation process of the solid catalyst component to form a compound without a C-Mg bond.

Examples of these magnesium compounds include the general formula b
A compound represented by ig Xn(OR') , n is a number of 0≦n≦2), a reaction product of magnesium oxyhalide and an aluminum halogen compound, or a reaction product of this reaction product and a siloxane compound.

Specific examples of these magnesium compounds include:
Magnesium halides such as magnesium chloride, magnesium bromide, and magnesium iodide; alkoxy magnesium chlorides such as methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride, 2-ethylhexyloxymagnesium chloride, and desyloxymagnesium chloride; Magnesium halide, phenoxymagnesium chloride,)
IJ O-+ magnesium chloride, nonylphenyloxymagnesium chloride, etc. - roxymagnesium halide, methoxymagnesium, ethoxymagnesium, butoxymagnesium, octoxymagnesium, 2
- Magnesium alkoxides such as ethylhexyloxymagnesium, magnesium alkoxides such as phenoxymagnesium, tritetraxymagnesium, nonylphenyloxymagnesium 4, magnesium carboxylates such as magnesium acetate, magnesium butyrate, magnesium lafricate, magnesium stearate, etc. and reaction products of magnesium oxychloride and ethylaluminum dichloride. Among these, preferred magnesium compounds include magnesium chloride, alkoxymagnesium chloride, aryloxymagnesium chloride, and magnesium alkoxychloride, with magnesium chloride being particularly preferred.

These magnesium compounds may be used alone or in combination of two or more, and the magnesium compounds may be in the form of complex compounds or double salts with other compounds.

Note that the magnesium compound used in the present invention is C-Mg
It may be a magnesium compound derived from a bound metal-containing organomagnesium and containing no C-Mg bond. For example, Grignard reagents, dialkylmagnesiums, or the general formula Ha Mg fi R'p R'q Xr Ys where M is aluminum, zinc, boron, or
IJium atom, R5%R' represents a hydrocarbon residue, X and Y represent an alkoxy group, a siloxy group, a secondary amino group,
a1β)O,p.

q%r%S≧0, p+q1r1s toma -1-2β,
m is the valence of M), alcohols, phenols, carboxylic acids, chlorine, hydrogen chloride, silicon tetrachloride, methyltrichlorosilane,
Examples include products obtained by reacting halogenating agents such as tin tetrachloride.

3) Halogen compound of titanium (M) The halogen compound of titanium (M) used in the production of the solid catalyst component in the present invention has the general formula Ti (OR')
It is expressed as tXa-1. Here, R7 has 1 to 20 carbon atoms
X represents a halogen atom selected from chlorine, bromine, and iodine, and t represents 0≦A(4
Specific examples of these titanium-membered halogen compounds are as follows. Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytrichlorotitanium, ethoxytrichlorotitanium, butoxytrichlorotitanium, dimethoxydichlorotitanium, dimethoxydichlorotitanium, triethoxychlorotitanium, trimethylsiloxytitanium trichloride, etc.

Among these, titanium tetrachloride and alkoxytrichlorotitanium are preferred, and titanium tetrachloride is especially preferred.

4) Method for Preparing Solid Catalyst Component The solid catalyst component of the present invention is: 0) Liquid magnesium compound liquefied with the above-mentioned specific phosphorus compound. It is produced by a method basically consisting of contacting the liquefied liquid magnesium-containing food of (a) with a 710-gen compound of titanium (trans). A method of contact is preferred.

Liquefaction of Magnesium Compounds The term "liquefaction" of magnesium compounds as used in the present invention includes not only becoming a liquid itself, but also becoming a solution in a solvent. It also includes the case where it is made into a homogeneous solution.

The solution may be completely dissolved or may contain a colloidal or semi-dissolved substance that is slightly cloudy.

Even if the magnesium compound itself is soluble in a solvent, the liquefaction of the present invention reduces the viscosity, allows processing at high concentrations, and allows the preparation of high-performance catalysts. The present invention can also be applied to such cases.

Liquefaction of a magnesium compound with a phosphorus compound is carried out at -50 to 300°C in the presence or absence of an inert solvent.
Preferably -25°C to 200°C, more preferably -50°C
~170°C for 1 minute to 20 hours, preferably 10 minutes to 15 hours
This is achieved by contacting the two for a period of time, preferably 30 minutes to 10 hours. The amount of phosphorus compound used at this time is not uniform depending on the type of phosphorus compound and magnesium compound, but it is usually O0! ~2σ moles, preferably 0.5
~10 mol, particularly preferably 1 to 10 mol.

In the process of liquefying a magnesium compound, or after liquefaction, it may be used for various purposes, such as improving polymerization activity, 1. L
improvement of polymer bulk density, improvement of titanium content in the solid catalyst component, improvement of polymer shape and particle size distribution control,
Various compounds can be added for purposes such as controlling the molecular weight distribution of the polymer and improving the solubility of the magnesium compound.

By adding these additives, a single effect may be obtained, or a combined effect of two or more may be obtained.

For example, mainly 1. For the purpose of improving L, known electron donors used for this purpose, specifically organic carboxylic acid esters, ethers, tertiary amines, phosphines, phosphates, phosphites, phosphorus, etc. Acid amides, acid halides, acid amides, etc. are used, among them methyl benzoate, ethyl benzoate, butyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, methyl anisate, Aromatic carboxylic acid esters such as ethyl anisate and ethyl hydroxybenzoate, α-branched carboxylic acid esters such as ethyl α-phenylbutyrate, and aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride, and anisic acid chloride are preferred. Of these, aromatic carboxylic acid esters are particularly preferred. In order to improve the solubility of the magnesium compound and the shape of the polymer, ethers such as diptyl ether, diynamyl ether, tetrahydro7rane, ethylene oxide, propylene oxide, shrimp chlornidoline, and phenylglycidyl ether, tetraalkyl titanates, Metal alkoxides or alkoxides such as tetraaryl titanate, tetraalkyl silicate, tetraaryl silicate, tetraalkoxytin, tetraaryloxytin, trialkylborate, triarylborate, aluminum alkoxide, aluminum alkoxide, and alcohols are used, among others. Preference is given to using rutitanate in tetraal, propylene oxide and epichlorohydrin, especially epichlorohydrin. A metal alkoxide or a metal oxide may be effective in improving the bulk density and II of the polymer and controlling the molecular weight distribution. The amount of these additives used varies depending on the purpose and is not uniform, but is usually 0.001 to 6 mol per mol of the magnesium compound, preferably o
, o o s - 2 mol, and preferably 0.001 - 1 mol per mo of phosphorus compound, preferably o, o o s -
It is 1 mole.

Examples of inert solvents that may be used during or after liquefying a magnesium compound include aliphatic hydrocarbons such as hexane, heptane, and deca-7; alicyclic hydrocarbons such as cyclobencune and cyclohexane; Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and /10-generated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and dichlorobenzenato. These inert solvents can be selected depending on the solubility of the contact product between the magnesium compound and the phosphorus compound.

The role of the inert solvent is to reduce the viscosity of the liquefied magnesium compound, maintain the liquid state at low temperatures, improve the dispersibility of various reagents, and precipitate the magnesium-containing solid described later.
In the step (2) of contacting with a rogen compound, there is an effect of extracting compounds that may be disadvantageous in the polymerization of olefins.

One embodiment of the method for producing a solid catalyst component according to the present invention is a method basically consisting of a step of contacting the above-mentioned liquid magnesium compound and a titanium (trans)halogen compound.

Any method can be used as the cough contact method.

For example, a method of adding an appropriate amount of a liquid magnesium compound to a titanium compound, a method of adding an appropriate amount of a titanium halogen compound to a liquid magnesium compound, and a method of adding an appropriate amount of a halogen compound of titanium to a liquid magnesium compound, or adding a liquid magnesium compound to an inert solvent. The contact temperature and time vary depending on the composition of the liquid magnesium compound, but the temperature is usually -
The temperature is 80 to +250°C, preferably about -60 to +100°C, and after adding each component or both components, the temperature is at room temperature to
30 minutes to 1 at 200℃, preferably about 50 to 150℃
It is common to keep the mixture in contact for about 0 hours, preferably for about 1 to 5 hours.6◎ Contacting appropriate amounts is not only important for removing reaction heat and preventing coarse or fine solid precipitation, but also for
Catalytic performance of the nine solid catalyst components obtained (polymerization activity, polymer II, bulk density, particle size and particle size distribution, particle shape, etc.)
It is important to improve the

The amount of the titanium (trans)halogen compound used in this contact is usually 0.5 mol or more, preferably 1.0 to 200 mol, more preferably 2.0 to 100 mol, per 1 mol of the magnesium compound. , and the amount is equivalent to 1 mol or more, preferably 3 to 100 mol, per 1 mol of the phosphorus compound.

In this contact step (including the heat treatment step), the solid catalyst component is precipitated. The precipitate can be separated from the liquid phase, washed with an inert solvent, especially a hydrocarbon in the final stage, and then subjected to olefin polymerization. In the present invention, this precipitate is further treated with titanium (
Its major feature is that it can enjoy sufficiently high catalytic performance even without contacting with the halogen compound of titanium (g), but it is of course also possible to use it for olefin polymerization after contacting it with the halogen compound of titanium (trans). It is.

Another embodiment of the method for producing a solid catalyst component according to the present invention is a method in which a solid magnesium compound precipitated from a liquefied magnesium compound is brought into contact with a halogen compound of titanium. The method for precipitating the magnesium compound is not particularly limited, and any method such as precipitation by temperature control, precipitation by concentration control, precipitation by contact with a non-solvent or a precipitating agent can be used.

Examples of the precipitating agent include the above-mentioned titanium (conversion)/10 compound, silicon tetrachloride, methyl trichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, trichlorosilane and other silicon compounds, tin tetrachloride,
tin 7-rogen compounds such as butyl trichloride,
Germanium tetrachloride, germanium compounds such as methyltrichlorogermanium nato, boron halogen compounds such as boron trichloride, aluminum trichloride, trimethylsiloxyaluminum dichloride, 7-aluminum dichloride, ethylaluminum dichloride, ethylaluminum sesquichloride, etc. Examples include I-rogen compounds of O-aluminum, etc.
It should not be limited to these.

When using a precipitating agent, the amount varies depending on the type and amount of the phosphorus compound contained in the liquefied magnesium compound, but usually 0.1 mol or more of the precipitating agent per 1 mol of the phosphorus compound, Preferably 0.5 to 200 moles are used. In this case, the inert solvent may or may not be used. There is no particular restriction on the precipitation temperature, and it is usually -80~
A temperature in the range H of +250°C, preferably -60°C to +200°C is chosen.

The precipitated solid magnesium compound is brought into contact with a titanium halogen compound, with or without washing with an inert solvent. The use of an inert solvent is optional at this time as well. There is no particular restriction on the method of contacting the precipitated solid magnesium compound with the halogen compound of titanium (P/).

For example, a method of adding a solid magnesium compound in powder or slurry form to a titanium (trans) compound, or conversely, a method of adding a titanium (trans) compound to a powder or slurry of a solid magnesium compound; Alternatively, a method of adding appropriate amounts of both can be used in the present invention. The contact temperature and time are usually -SO~
+250°C, preferably about -60 to 106°C,
After addition of each component, temperature is between room temperature and 200°C, preferably 50°C.
~150℃ for 30 minutes to 10 hours, preferably 1
~5 hours is normal.

The amount of the titanium compound used is usually 0.5 mol or more, preferably 1.0 to 200 mol, more preferably 2.0 to 1 mol, per 1 mol of the solid magnesium compound.
00 moles.

After contacting the magnesium compound with the titanium (trans) compound,
After separating the produced solid from the liquid phase and washing it with an inert solvent, especially a hydrocarbon in the final stage, it can be subjected to olefin polymerization.

Although it is of course possible to further treat this produced solid with a titanium (trans)halogen compound, sufficiently high catalytic performance can be enjoyed without re-treatment.

In the above-mentioned two embodiments of the solid catalyst component manufacturing method of the present invention, components other than the essential components, such as the magnesium compound, phosphorus compound, and titanium (conversion) compound, may be added optionally, and there is no particular restriction on the timing of addition. For example, the electron donor may be added in the step of liquefying a magnesium compound with a phosphorus compound, or in the step of precipitation of a magnesium compound, or in the step of liquefying a magnesium compound with a phosphorus compound, or in the step of precipitation of a magnesium compound,
It may be added at any step of contacting the compound. When producing a high II polymer of a-olefin, a high-performance catalyst can often be obtained by adding the magnesium compound in the liquefaction step or precipitation step.

The composition of the solid catalyst component thus obtained was Ti
0.1 to 10% (wt%; the same applies hereinafter), preferably 0.
5 to 8%, more preferably 1 to 7%, 5 to 50%,
Preferably 10-40%, more preferably 10-30%
%, C/, 10-80%, preferably 20-80%, more preferably 30-75%, Po, 0001-5%,
Preferably 0.005-2%, more preferably 0.0
01-1%.

Further, the Mg/Ti atomic ratio is 3 to 200, preferably p/
'ri atomic ratio is 0.0001 to 5, preferably o, o
o s~2, particularly preferably 0.001~1, P/M
g atomic ratio (electron-donating substances other than phosphine oxide,
For example, phosphates, carboxylic esters, amides,
Ethers, amines, etc. also have a solid content of 0.4, preferably 0.
02 to 0.4, particularly preferably 0.05 to 0.3@5) Organoaluminum compound In the present invention, the organic aluminum compound used in the polymerization of olefin in combination with the solid catalyst component-containing organoaluminum compound. As an aluminum compound, general formula (1)% formula% (
1) Organoaluminum compound represented by (here, R11
and R9 has 1 to 20 carbon atoms. Preferably, 1 to 10 swelling hydrogen residues may be the same or different from each other. x A halogen atom selected from fluorine, chlorine, bromine, and iodine or water * [Represents a child. X%'/s Z is 0 (x≦
3.0≦y (3,0≦V (a positive number that satisfies 3,
Moreover, x y + z = 3), or composite compounds of these with metal compounds of group Ⅰ or group 4 of the periodic table, or combinations of these with water, alcohol, primary or secondary amines, sulfuric acid, hydrogen sulfide, Although a reaction product with aluminum halide can be used, an organoaluminum compound represented by formula (1) is preferred.

Specific examples of the organoaluminum compound represented by formula (1) are as follows. trimethylaluminum,
triethylaluminum, ')IJ-n-propylaluminum, treaty propylaluminum, tri-n
- trihydrocarbylaluminum such as butylaluminum, treatybutylaluminum, tri5ec-butylaluminum, trihexylaluminum, trioctylaluminum, triisoprenylaluminum, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butyl Aluminum chloride, di-butylaluminum chloride, G-5
Dihydrocarbyl aluminum halides such as ec-butylaluminum chloride, diethylaluminium blonde, diethylaluminium hydride, diptylaluminium hydride Table: Hydrocarbyl aluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum hydrocarbylaluminum cybarides such as dichloride, propylaluminum dichloride and butylaluminum dichloride; dihydrocarbylaluminum alkoxides such as diethylaluminum methoxide and diethylaluminum (2,6-di-1-butyl) phenoxide; and a9Q oxide.

The periodic table that can be used in combination with the organoaluminum compound represented by formula (1)! Examples of group or Group 1 metal compounds include organic alkali metal compounds such as ethyllithium, butyllithium, and phenyllithium, organic alkaline earth metal compounds such as diethylmagnesium, ethylbutylmagnesium, and butylmagnesium chloride, diethylzinc, and dibutylcadmium. etc. 1st
Examples include group metallized organic compounds.

Among the organoaluminum compounds represented by formula (1), trihydrocarbyl aluminum, dihydrocarbyl aluminum hydride, hydrocarbyl aluminum halide, or a mixture thereof is particularly preferably used.

The amount of the organoaluminum compound used is usually 1 to 1.000 mol, preferably 5 to 800 mol, particularly preferably 10 to 500 mol, per 1 gram atom of titanium in the solid catalyst component.
It is a mole.

Organoaluminum (IJ compounds can also be used in the form of adducts or reactants with an electron donor. In this case, the electron donor may be used by forming an adduct or a reactant with an organoaluminum compound in advance, The adduct or reactant may be formed in the polymerization vessel by adding them individually to the polymerization vessel.In addition to the phosphorus compound used in the present invention, the electron donor may also include the phosphorus compound described in the section on liquefaction of the magnesium compound. Examples of electron donors include: Among these, aromatic carboxylic acid esters are preferably used to obtain a high I'I polyolefin.The amount of electron donor used is usually 1 mole of the organoaluminum compound. 0.01 to 1 mole, preferably 0.05 to 0.8 mole, more preferably 0.01 to 1 mole.
6) Olefin The olefin used in the polymerization of the present invention is ethylene and a-monoolefins having 3 or more carbon atoms, especially α-monoolefins. These can be used in homopolymerization or mutual 27 dam and/or block copolymerization. Specific examples of the a-monoolefin include propylene, l-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, etc. Examples include cyclic polyenes such as butadiene, isoprene, bihelylene ft cD conjugated dienes, 4-vinylcyclohexene, ethylidene norbornene, dicyclopene-containing diene, vinylnorbornene, propenylnorbornene, 1,4-hexadiene, 4-1+1.4 -hexadiene, 5-/-)-1,4-hexadiene, 2
-Methyl-1,5-hexadiene, 3-methyl-1,5
- Polyenes such as non-conjugated linear polyenes such as hexadiene can be used as comonomers. Among these, when non-conjugated linear polyenes, especially 4-methyl-1,4-hexadiene and/or 5-methyl-1,4-hexadiene are selected as comonomers, the color changes due to a decrease in polymerization activity. This is a preferable combination of monomers since it has a small amount of carbon dioxide and the molecular weight can be easily controlled by H2.

7) Polymerization of olefin In the present invention, there are no particular restrictions on the method and conditions for polymerizing olefin, and the method for controlling the molecular weight of polyolefin, and conventionally known methods and conditions can be used. Namely, there are the gas phase method, which does not use a liquid medium and keeps the monomers substantially in the gas phase, the slurry method and solution method, which uses a liquid medium, and the monomers which are kept in a liquid state and other liquid media. It is also possible to use a method such as a liquid phase bulk method that does not substantially use the method.

The polymerization conditions are also the usual conditions that are carried out using a Ziegz-Natsume catalyst. That is, at a temperature of 0 to 300°C, preferably 20 to 250°C, especially 50 to 200°C, and a temperature of normal pressure to 5°C.
ob/j, preferably under a pressure of 2 to 100 Kf/-.In the present invention, when an α-olefin having 3 or more carbon atoms is used as the main monomer olefin, a high II poly! - can be obtained in high yield, and there is little decrease in activity and I-activity during molecular weight control.

Furthermore, in the method according to the present invention, the produced polymer has good diameter and particle size distribution, and is extremely easy to handle.

8) Experimental Examples In order to demonstrate the present invention more specifically, examples will be given and explained below.

In this experimental example, CY(Ti) is the polymer yield obtained from 1 t of titanium atoms (4/f-Ti'), and CY(SC) is the polymer yield obtained from 91 f of solid catalyst acid (rf/l-
8G), L 1. (A) d Proportion (%) of residue extracted with boiling n-hebutane for 6 hours in powdered polymer, T
BD
is polymer bulk density Cf/ml>, MI is ASTM D
Polymer melting index measured by No.-1238 (
f/10 minutes).

Example 1 When 22.99 g of trilobylphosphine oxide was added at room temperature to a slurry consisting of 5 t of anhydrous magnesium chloride and 50 su of toluene, the temperature rose to 40° C. and a homogeneous solution was obtained in about 15 minutes. .

2.4 d of ethyl benzoate was added to this solution, and the mixture was stirred at 80° C. for 1 hour. The obtained solution was added dropwise over 30 minutes to a solution consisting of 100% titanium tetrachloride and 100% toluene kept at -20°C, and then the temperature was raised to 90°C over 3 hours.
The mixture was stirred at 90° C. for 4 hours to obtain a red-colored slurry. The solid product was separated from the liquid phase by filtration and washed with toluene 100 m
The slurry was washed with 100% hebutane three times and three times with 100% hebutane to obtain a slurry containing a pale yellow solid catalyst component. This solid catalyst component contains 4.13% titanium, 16.9% magnesium,
It contained 63.6% chlorine, 0.15% phosphorus, and 13.1% benzoic acid ester. Therefore, Mg/Ti
Atomic ratio is 8.06, P/Ti atomic ratio is 0.04
4,'ri atomic ratio is 20.8.

Heptane 5 in a 1 t autoclave under a propylene atmosphere
00W/) ethyl aluminum + (TEA) 143”
fxl)) 62.0 wg of methyl Aylate and an amount equivalent to 0.419 VC of the solid catalyst component in terms of Ti atoms were added in this order, and 200 d of hydrogen gas was added in terms of standard conditions, and the mixture was stirred for 70 minutes. The temperature was raised to 0.degree. C., and propylene gas was injected to maintain the total pressure at 9 Kf/cjG, and polymerization was carried out for 2 hours. The resulting slurry was filtered to obtain 189t of powdered polypropylene. This powdered polypropylene was extracted with boiling n-hebutane for 6 hours, and when filtered, the extracted residue was 97%
．． I lost at 8%. MI is 1.8f/10min, BD is 0.
It was 40. In addition, from the F solution of the polymerization slurry, 1.6
The amorphous polypropylene of F was recovered, i.e., CY(
Ti) is 477Kf/f-Ti, CY(SC) is 1
9.7 first/1-8C, 1, L (A) is 97.8%, T-
II is 97.0%.

Examples 2 to 4 Example 1 was repeated nine times using various phosphine oxides in place of tri-n-butylphosphine oxide in twice the molar amount relative to anhydrous magnesium chloride.

Table 1 shows the composition of the solid catalyst component, and Table 2 shows the propylene polymerization results.

Examples 5 to 8 In the production of solid catalyst components, ethyl benzoate was not used, or more or in place of ethyl benzoate, various carboxylic acid esters were used at 0.3 mol per 1 mol of magnesium chloride. Example it was repeated.

Polymerization of propylene was carried out in the same manner as in Example 1.

The results are shown in Table 3.

Example 1O Conducted using the solid catalyst component obtained in Example 1, replacing TEA with triisobutylaluminum (TIBA) 182 cape and ethylaluminum dichloride 45319, and replacing the amount of 1)-) methyl ruylate with 44q. Polymerization of propylene was carried out according to the method of Example 1. Yield of powdered polypropylene 267 f.

Amorphous polypropylene recovered from ν liquid 1.7t%CY
(Ti) 672 KIF/t-Ti, CY
(Good), 27.8 o/f-ta, 1.1. (A) 97
．． 6%, T -1,1,97,0%, BDo, 40, M
I 2.1 t was 710 minutes.

Example 11 Solution F and toluene washing solution 1 from the production of the solid catalyst component in Example 1 were collected, added dropwise to 3 L of water under water cooling, and stirred at 50° C. for 1 hour. Separate the layers and add 10% sulfuric acid to the organic layer twice.
After washing with an aqueous sodium bicarbonate solution five times and further with water five times, it was dried with molecular sieves. This organic layer was concentrated to 70m by distillation. This concentrate contains tree n
It contained 19.9 f of -butylphosphine oxide and 1.3 f of ethyl benzoate. That is, 87% of tri-n-butylphosphine oxide was recovered.

Add tri-n-butylphosphine oxide 3 to this concentrated solution.
．． O2 and ethyl benzoate 11F were added, and 5f of anhydrous magnesium chloride was added at room temperature to obtain a homogeneous solution. Contacting this solution with titanium tetrachloride was carried out in the same manner as in Example 1,
A solid catalyst component having a Ti content of 4.01% was obtained.

Using this solid catalyst component, propylene was polymerized according to the method of Example 1, and powdered polypropylene 191
f. 1.7 tons of amorphous polypropylene were obtained. CY (T
i) Iti, 482Ce/IF-Ti, CY
(SC) 19.8 Kg/t-FIC. Also, 1.1. (A) is 97.4%, T -1,1, is 9
6.5%, BD is 0.41 f/R1% MI is 1.5
f/10 minutes.

Example 12

Claims (1)

[Claims] A: a halogen compound of titanium (W), and a compound of the general formula R' R
"R" p-. Phosphine oxyto (here, R1, R3
, R1 is a hydrocarbon residue having 1 to 20 carbon atoms, each of which may be the same or different), or a solid state precipitated from the liquefied magnesium compound. A method for producing an olefin polymer, which comprises polymerizing an olefin using a catalyst system basically consisting of a solid catalyst component obtained by contacting a magnesium compound with B an organic aluminum compound.