JPS59115308A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To eliminate a prepolymerization step from the production of an olefin polymer and to improve the performance of a supported catalyst component, by contacting an olefin with a specified catalyst system comprising a titanium- containing solid catalyst component and an organoaluminum compound. CONSTITUTION:In polymerizing an olefin by contacting it with a catalyst system comprising a titanium-containing solid catalyst component (component A) and an organoaluminum compound (component B); component A should meet the following requirements: (1) component A be the one which is prepared by treating a solid composition containing magnesium, titanium, and a halogen as components with both an organoaluminum compound of the formula and an electron-donating compound in the presence of an olefin, and washing the solid composition with an inert solvent, and (2) the treatment of the solid composition with the organoaluminum compound and the electron-donating compound be conducted under the following conditions: (a) the ratio of the organoaluminum compound to the solid composition is 0.1-50 (in terms of an Al/Ti atomic ratio), and (b) the ratio of the electron-donating compound to the organoaluminum compound is 0.01-1.0 (in mol/atom ratio).

Description

BACKGROUND 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 provides a titanium-containing solid catalyst component (component A) obtained by treating a solid composition containing magnesium, titanium, and halogen as essential components with an organoaluminum compound and an electron donor, and then washing the composition, and The present invention relates to a method for producing olefin polymers using a catalyst system consisting essentially of an organic aluminum compound (component B) and an organoaluminum compound (component B).

Prior art A method for polymerizing olefins using a solid composition in which a tetravalent titanium compound is supported or composited on a magnesium compound as a solid catalyst component of a Ziegler-Natsuta type catalyst is known. At the dawn of time, many proposals have been made regarding the production method of . One of the characteristics of this supported catalyst component is that it has extremely high olefin polymerization activity. oh(
It is also known that the stereoregularity (II) of the resulting polymer can be improved by incorporating a specific electron donor (for example, an aromatic carzenate ester) into the supported catalyst component.

Although these supported catalyst components have a fairly high industrial potential in terms of polymerization activity, II, bulk density, etc., they are not sufficient for application to rational processes based on roofing, no deashing, and no extraction. There wasn't. Furthermore, the supported catalyst component is uneconomical due to the large amount of organoaluminum compound that must be combined with it, the activity during polymerization decreases markedly over time, and the supported catalyst component lacks storage stability. There was a problem that preliminary polymerization was required.

As a solution to the above problem, JP-A-56-136806
and No. 57-74307, each of which has 0 proposals.

The method described in JP-A-56-136806 is intended to improve storage stability by treating a supported catalyst component with an organoaluminum compound and a small amount of olefin and then drying it. However, in this proposal, since olefin is used as a processing component, the volume of the processing product is high (and the dried powder of the product has poor fluidity, making it inconvenient to handle. If the amount of olefin was reduced, the II and bulk density of the polymer would decrease.

On the other hand, the proposal in JP-A No. 57-74307 is to treat the supported catalyst component with an organoaluminum compound in the absence of an olefin, thereby omitting preliminary polymerization, reducing the amount of the organoaluminum compound used in the main polymerization, and increasing the activity. The aim is to improve the material's performance, weight, bulk density, etc. This method has the disadvantage that although the above effects are enjoyed immediately after treatment, the activity and II decrease with time after treatment (the decrease in activity is particularly significant).

Summary of the Invention The present invention solves the above-mentioned drawbacks in improving the performance (activity, II, bulk density) of supported catalyst components of Ziegler-Natsuta type catalysts, omitting prepolymerization, reducing the decline in polymerization activity over time, and stability over time after treatment. This goal is achieved by manufacturing supported catalyst components in a particular manner.

Therefore, in the method for producing an olefin polymer according to the present invention, in the method of polymerizing an olefin by bringing it into contact with a catalyst system basically consisting of a titanium-containing solid catalyst component (component A) and an organoaluminum compound (component B), It is characterized in that component A is as follows.

(1) Component A is obtained by treating a solid composition containing magnesium, titanium and halogen as essential components with an organoaluminum compound of the formula HmRnAIX3- (m+n) and an electron donor compound in the absence of an olefin. (In the above formula, R represents a hydrocarbon residue having 1 to 20 carbon atoms, X represents a halogen, and m and n represent 0≦m<3 and 0 < n ≦ 3 and 2 < m +'
The number satisfies n≦3. (2) The treatment of the above solid composition with an organoaluminum compound and an electron donor is performed under the following conditions.

b) Amount of organoaluminum compound/amount of solid composition 20, 1
~50 (Al/Ti atomic ratio) (b) Electron donor amount compound/organoaluminum compound amount = 0.01 to 1.
0 (mole/atomic ratio) effect The method of the present invention can enjoy many effects as follows.

(b) Improved activity (b) Improved II times c) Improved bulk density) No deterioration in performance even after long-term storage after treatment e) No need for prepolymerization (f) Reduced activity decline over time during polymerization Many of these effects However, it is difficult to easily infer from the conventionally known facts that the supported catalyst component can be obtained by treating it in the coexistence of an organoaluminum compound and an electron donor compound and then washing it, and it is truly surprising. be.

The titanium-containing catalyst component of the Ziegler-Natsume type catalyst used in the process of the present invention is obtained by subjecting a specific solid composition to a specific treatment.

Solid Composition This solid composition contains magnesium, titanium and halogen as essential components. Here, "consisting of essential components" means that in addition to these three components, other auxiliary components may be included as long as they do not interfere with achieving the objective of the present invention. Examples of such auxiliary components include electron donor compounds.

The composition of this solid composition is arbitrary as long as the object of the present invention is achieved, but generally 'rt O, 1 to 10 inches (by weight; the same applies hereinafter), preferably 0.5 to 8 inches, more preferably is 1.0-6.0%, Mg 5-50%,
Preferably 10-40%, more preferably 10-30%
10 to 80% halogen, preferably 80% to 80%, more preferably 30% to 75%, electron donor (if used) 1% to 30%, preferably 5% to 2%, more preferably 7% to 15% It is. Furthermore, the Mg/Ti atomic ratio is 3~
200, preferably 5-100, particularly preferably 7-5
0. The halogen/Ti atomic ratio is 10-100, preferably 15-80, electron donor (if used)/Tf (
mole/atomic ratio) is 0.05-2, preferably 0.1-1
, more preferably from 0.3 to 0.9.

The halogen is preferably chlorine.

Such a solid composition is essentially the same as the supported catalyst component as described above, and can be used as one produced by a conventionally known method. Among these, a magnesium compound, particularly a magnesium halide, Especially magnesium chloride, with certain solubilizing agents, for example alcohols such as ethanol, butanol, octatool, amines such as trimethylamine, triethylamine, trimethylamine, titanates such as tetra-n-propyl titanate, tetra-n-butyl titanate. phosphoric acid esters such as tributyl phosphate, trihexyl phosphate, trioctyl phosphate, especially titanates,
and then precipitated by adding a halogen compound of titanium, such as a titanium halide, especially titanium tetrachloride, or an electron donor compound (if used), for example selected from the exemplified compounds listed below, or It is preferable to precipitate a magnesium compound-containing solid from the magnesium compound-containing solution before bringing it into contact with the halogen compound of titanium, and then bring it into contact with the halogen compound of titanium. The above titanium may be treated with a halogen compound.

Preferred examples of such solid compositions include Japanese Patent Application Laid-open No. 5
Publication No. 4-40293, Japanese Patent Application No. 117461/1983,
Examples include supported catalyst components produced by the methods described in the specifications of No. 56-130728, No. 56-130729, No. 56-211577, and No. 57-65606. Particularly preferred solid compositions for use in the present invention are JP-A No. 54-40293 and Japanese Patent Application No. 56-40293.
No. 130728, No. 56-130729, No. 57-6
This is a supported catalyst component prepared from Kaio V-Komali as described in No. 5606.

The most distinctive feature of the invention is the solid composition sound,
The process consists of treating with an organoaluminum compound and an electron donor compound in the absence of an olefin, and thoroughly washing with an inert mortar after the treatment.

If olefin is present during processing, the target olefin polymer will have a lower density and bulk density.
Finn's presence must be avoided.

If an electron donor compound is not used at the time of treatment, the catalyst performance (especially activity) will drop significantly during storage after treatment, making it impractical, so it is essential to use an electron donor compound at the time of treatment. .

Furthermore, in the present invention, cleaning after treatment is essential. Although some of the objectives of the present invention can be achieved without washing, it cannot be said that the reduction in catalyst performance deterioration during storage is sufficient, and the improvement in II is small. and II both improve.

Details of the processing conditions are as follows.

(k) Slurry Concentration Solid compositions are usually processed in a dispersed state in an inert solvent. In this case, the inert solvent is preferably one selected from those exemplified below as a cleaning solvent, and is preferably a solvent for the treating agent, that is, the organoaluminum compound and the electron donor compound.

The slurry concentration of the solid composition to be treated is usually 10 to 50,000 in terms of titanium atoms contained in the solid composition.
0 mg/liter, preferably 20-20.00
0mg/l/l/, particularly preferably 50-10,
000 mg/liter. A concentration lower than 10 mg/liter is not preferable because the improvement in catalytic activity is small and the bulk density is lowered. 50,0
If the concentration is higher than 0.00 mg/liter, it becomes difficult to stir and remove the reaction heat, or it may stick to the reactor, making it difficult to obtain a solid catalyst component with homogeneous properties. This is not desirable as it becomes difficult.

(b) Organoaluminum compound The organoaluminum compound that can be used in the treatment of the present invention is represented by the general formula HmRnAIX3-(m+n). Here, R has 1 to 20 carbon atoms, preferably 1-1
5, particularly preferably 2 to 12 hydrocarbon residues, X represents a halogen, preferably chlorine, m and n each satisfy 0≦m<3.0<n≦3, and 2 m+n
The number satisfies ≦3.

Preferred examples of these organoaluminum compounds include triethylaluminum, triisobutylaluminum, triisoprenylaluminum, tridodecylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, a mixture of triethylaluminum and diethylaluminum chloride, and triisobutylaluminum. and diethylaluminium chloride. These organoaluminum compounds may be used alone or in combination of two or more. Among these, particularly preferred examples are triethylaluminum and triisobutylaluminum.

(c) At/Ti ratio When the solid composition is treated with an organoaluminum compound and an electron donor compound, the ratio of the organoaluminum compound to titanium contained in the solid composition (AI/Ti atomic ratio) is:
0.1-50, preferably 0.3-20, particularly preferably 0.5-10. It is. If this ratio is too small, sufficient effects cannot be obtained. Moreover, if this ratio exceeds the above range, it is not only uneconomical but also undesirable because there may be a decrease in activity, especially II.

B) Electron Donor Compounds Electron donor compounds that can be used in the process of the present invention are compounds containing O, N or (and) P, and do not contain active hydrogen. Specifically, ethers, ketones, aldehydes, oxygen-containing compounds such as carboxylic acid esters, tertiary amines, nitriles,
Nitrogen-containing compounds such as incyanates, amineoxy F:'', phosphorus-containing compounds such as phosphoric acid esters, phosphite esters, phosphines, phosphine oxytos,
Examples include metal acid esters such as silicate esters.

More specifically, those having 2 carbon atoms such as diethyl ether, diisoamyl ether, tetrahydrofuran, anisole, etc.
~2o ethers, acetone, methyl ethyl ketone,
3 to 2 carbon atoms such as acetophenone and benzophenone
Ketones, aldehydes with 2 to 20 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, diethyl carbonate, ethyl formate, ethyl acetate, butyl butyrate, ethyl acrylate, ethyl methacrylate, croton ethyl acid, ethyl cyclohexanecarzenate, methyl benzoate, ethyl benzoate, butyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate,
Cardanic acid esters having 2 to 20 carbon atoms such as ethyl toluate, amyl toluate, methyl anisate, ethyl anisate, dimethyl phthalate, diethyl phthalate, ethyl naphthoate, γ-butyrolactone, trimethylamine, triethylamine, tributylamine , dimethylaniline, methyldiphenylamine, etc. having 3 to 2 carbon atoms
Tertiary amines, 2 to 1 carbon acids such as acetonitrile, zolobionitrile, benzonitrile, naphthonitrile
Nitriles of No. 5, incyanates having 2 to 15 carbon atoms such as benzoisocyanate, toluisocyanate, and naphthoisocyanate, amine oxides having 3 to 15 carbon atoms such as trimethylamine oxide, triethylamine oxide, and dimethylaniline oxide, triethyl phosphate,
Phosphate esters such as tributyl phosphate, triphenyl phosphate, diethyl phenylphosphonate, diphenyl ethylphosphonate, ethyl diphenylphosphinate, triethyl phosphite, trisulfite, triphenyl phosphite, arsenite esters such as diethylphenylphosphonite and ethyldiphenylphosphinite;
Phosphine such as triethylphosphine and triphenylphosphine, phosphine oxyto such as tributylphosphine oxyto and triphenylphosphine oxyto, tetraethyl silicate, tetrabutyl silicate,
Examples include silicic acid esters such as phenyltriethoxysilane.

Among these examples, cardanic acid esters and phosphoric acid esters are preferred, and cardanic acid esters are particularly preferred. Among carboxylic acid esters, aromatic power) V
Most preferred are boronic acid esters. Suitable examples of aromatic carzenate esters include lower alkyl esters such as benzoic acid, lower alkyl-substituted rhozoic acid, and lower alkoxy group-substituted benzoic acid. Here, lower means one having 1 to 5 carbon atoms. Optimal aromatic CalNy
Examples of ll esters include methyl benzoate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, and the like.

(e) Electron donor compound/Al ratio The amount of the electron donor compound used in the treatment of the present invention is such that the electron donor/organoaluminum compound ratio (mol/Al atomic ratio) is 0.01 to 1.0; Preferably 0.05-0. −
8, particularly preferably 0.1 to 0.7.

If the amount of the electron donor compound used is too small, the storage stability after treatment will be poor, and if it is too large, the activity and II will be reduced.

(f) Inert Solvent As mentioned above, in the process of the present invention, the solid composition is used in the form of a slurry in an inert solvent. Although the organoaluminum compound and the electron donor compound can be used without being diluted, they are usually used after being diluted with an inert solvent. After this step, the slurry concentration after treatment (before cleaning) is
The content should be 1 to 50,000 mg/liter in terms of titanium atoms (as described above).

The inert solvent used in this treatment is a solvent that does not adversely affect the polymerization performance of the supported catalyst component, and is usually a hydrocarbon. For example, hexane, heftane, tecan,
Kerosene, benzene, toluene, xylene, etc. are preferably used, and among them, hexane, hezotane, and toluene are preferably used.

(g) Contact order There is no particular restriction on the contact order of each component during treatment. Specifically, for example, (a) a method of adding an organoaluminum compound and then an electron donor compound to a slurry of a solid composition; (b) a method of adding an electron donor compound to a solid composition slurry and then adding an organoaluminum compound; How to add (
c) There are methods such as adding a mixture of an organoaluminum compound and an electron donor compound that have been brought into contact with each other to the solid composition slurry, but method (C) is preferably used.

In the case of (c), the effect of the present invention may be weakened due to a secondary reaction between the organoaluminium compound and the electron donor compound. A stick used for contact with objects is preferable.

(b) Processing temperature and time The processing temperature and time are usually 40 to 150°C for about 1 second to
About 10 hours, preferably about 5 seconds at -10~ioo''C
About 5 hours, particularly preferably about 1 minute to about 1 hour at -5 to 80''C.

(Single force cleaning In the present invention, cleaning after treatment is essential. The same type of inert solvent as used in the above-mentioned treatment is used as the cleaning solvent, but saturated aliphatic hydrocarbons such as hexane and hezotane are particularly preferred. .

It is desirable that the washing be carried out until substantially no titanium and aluminum are detected in the washing liquid. for example,
1.100ml of 1g of solid composition used for treatment
Wash with hebutane 3 to 10 times.

By this washing, the storage stability of the produced solid barrier component (1) and the catalytic performance (II) are further improved compared to those without washing. The reason for this is not clear, but
This is thought to be due to the fact that unnecessary organoaluminum compounds and electron donor compounds are washed away, and trace amounts of soluble or extremely small titanium components are also removed.

Polymerization of Olefin (a) Organoaluminum Compound In the present invention, the solid catalyst component is combined with an organoaluminum compound and subjected to olefin polymerization.

As the organic aluminum compound, those represented by the following formula are preferable.

RlaAl(OR2)bXc(1) (wherein, R1 and R2 are hydrocarbon residues having 1 to 2 carbon atoms, preferably 1 to 10 carbon atoms, and may be the same or different from each other. X is fluorine, chlorine represents a halogen atom or a hydrogen atom selected from , bromine, and iodine.alb and C represent O<a≦3.0≦b<3°, 0≦c(
A positive number that satisfies 3, and a 4- b + c
= 3) This organoaluminum compound is a complex compound with a metal compound of Group 1 or Group 1I of the periodic table, or a compound of these with water, alcohol, a primary or secondary amine, sulfuric acid, a sulfurized aqueous bed, or a halogen. Although it can be used in the form of a reaction product with aluminum chloride, it is preferable to use it as the organoaluminum compound itself represented by the above formula.

Specific examples of the organoaluminum compound represented by the above formula are as follows. (a) Trimethylaluminum, triethylaluminum, 1J-n-propylaluminum, treatypropylaluminum, )IJ-n
- trihydrocarbylaluminum, such as butylaluminum, tri-l-ditylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, triimprenylaluminum,
(b) dihydrocarbylaluminum halites such as diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, di-butylaluminum chloride 1, dibutylaluminum chloride, diethylaluminum bromide, (3) Dihydrocarbyl aluminum hydride such as diethylaluminum hydride and diethylaluminum chloride; (c) Hydrocarbyl aluminum sesquihalide such as ethyl aluminum sesquichloride and butyl aluminum sesquichloride; (C) Ethyl aluminum dichloride, probyl aluminum dichloride, butyl aluminum Hydrocarbylaluminum civalides such as dichloride, dihydrocarbylaluminum alkoxy tomos (aryloxides, etc.) such as diethylaluminium ethoxide, diethylaluminum (2,6-di-tert-butyl) phenoxy P, etc. These may be one type or two types. The above may be used in combination.

Examples of metal compounds of Group 1 or Group 1I of the periodic table that may be used in combination with the organoaluminum compound represented by the above formula include organic alkali metal compounds such as ethyllithium, zotyllithium, and phenyllithium, and diethylmagnesium. , ethylditylmagnesium,
Examples include organic alkaline earth metal compounds such as butylmagnesium chloride F'-, and organic compounds of Group I metals such as diethylzinc and diptylcadmium.

Among the organoaluminum compounds represented by the above formula, trihydrocarbyl aluminum, dihydrocarbyl aluminum hydride, P1 hydrocarbyl aluminum halide, or mixtures thereof are particularly preferred.

The amount of organoaluminum compound used is usually 1 to 1,000 mol per gram atom of titanium in the solid catalyst component.
Preferably 5 to 800 mol, particularly preferably 10 to 50 mol
It is 0 mole.

Organoaluminum compounds can also be used in the form of adducts or reactants with electron donor compounds. The electron donor compound used in the process of the present invention may be Among these, aromatic carboxylic acid esters are particularly preferred in order to obtain high II polyα-olefins.

The amount of the electron donor compound to be used is usually 0.01 to 1 mol, preferably 0.01 to 1 mol, preferably 0.01 to 1 mol, preferably 0.
05 to 0.8 mol, more preferably 0.08 to 0.6
It is a mole.

(b) Olefin The olefins used in the polymerization of the present invention are ethylene and α-monoolefins, especially α-monoolefins having 3 or more carbon atoms. These can be used either in homopolymerization or in mutual random and/or block copolymerization. Specific examples of α-monoolefins include zoropyrene,
Examples include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-butene.

In copolymerization, butadiene, inzolene, bi'')'V
Conjugated dienes such as 7, cyclic polyenes such as 4-vinylcyclohexene, ethylidenenorzernene, dicyclopentadiene, vinylnorzernene, flopenylnorzernene, 1,4-hexadiene, 4-methyl-1,4 Comonomers of polyenes such as non-conjugated linear polyenes such as -hexadiene, 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, and 3-methyl-1,5-hexadiene It can be done. Among these, choosing non-conjugated linear polyenes, especially 4-methyl-1,4-hexadiene and/or 5-methyl-1,4-hexadiene as a comonomer, is important because it reduces polymerization activity. This is a preferred combination of monomers because it is easy to control the molecular weight using H2.

(c) Olefin polymerization In the present invention, there are no particular limitations on the olefin polymerization method, conditions, and polyolefin molecular weight control method, and conventionally known methods and conditions can be used. Namely, there are gas phase methods in which the monomers are kept substantially in the gas phase without using a liquid medium, slurry methods and solution methods that use liquid media, and monomers in a liquid state and other liquid media. Any method such as a liquid phase bulk method that does not use substantially any of these methods can be used. The polymerization conditions are also the usual conditions used for polymerization using a Ziegler-Natsuta catalyst. That is, at 0 to 300 °C, preferably 20 to 250 °C, especially 50 to 200 °C, normal pressure to 500 kg/am%
The polymerization can be carried out preferably under a pressure of 2 to 100 kg/cm 2 .

In the present invention, when an α-olefin having 3 or more carbon atoms is sometimes used as the main monomer olefin, a high II polymer can be obtained in high yield, and there is little decrease in activity and II when controlling the molecular weight with H2. .

Further, in the method according to the present invention, the production, particle size and particle size distribution of 71J-mer are good, and handling is extremely easy.

EXAMPLES In order to further specifically demonstrate the present invention, experimental examples will be given and explained below.

(kg/g -S C), II (A) is the percentage of the residue extracted with boiling n-hebutane for 6 hours in the powdered polymer (%
), T'-II is the percentage of boiling n-heptane extraction (6 hours) residue (% L
BD is polymer bulk density (g/ml), MI is AST
Each represents the melt viscosity index (g/10 min) of the polymer measured by MD-1238.

Manufacturing example 1 of solid composition: 5 g of commercially available anhydrous magnesium chloride was mixed with 5 ml of toluene.
To this slurry was added 37.4 g of tetra-n-butyl titanate, and the mixture was heated at 90° C. for 2 hours to obtain a uniform bath liquid containing magnesium. A solution in which 1.5 g of ethyl benzoate was added to this solution and 9 g of titanium tetrachloride were added.
and a solution prepared by dissolving 25 ml of K in toluene were simultaneously added dropwise over 1 hour into 35 ml of toluene that was kept at 20°C and stirred. A solid precipitates out as it is added dropwise. After completion of the dropwise addition, the mixture was aged at a heated temperature for 1 hour, and then allowed to stand still, and 2/3 of the supernatant was extracted.

Next, 80 ml of toluene and 69 g of titanium tetrachloride were added in this order to the remaining slurry, and the mixture was stirred at 80°C for 2 hours. Remove the supernatant by decantation and add toluene Zo
Washed twice with 0 ml. 69 g of titanium tetrachloride was added to the slurry obtained by () and heated at 80°C for 2 hours.
After repeating the washing operation two more times, the Hezota 710
A solid composition was obtained by washing 10 times with 0 ml. This solid composition contains 4,1.4% Ti (% by weight).

Same below), Mg 17.6%, benzoic acid x f le 1
It contained 0.4% and 5.7% of chlorine b.

Example 1 (a) Preparation of solid catalyst component A In 50 ml of heptane, 114 mg of triethylaluminum and p-toluyl (Jll ethyl 49.2 mg) were added at 0°C.
mg in this order, stirred for 5 minutes, and heated to 20°C.
40 ml of the solid composition slurry prepared in Production Example 1 (containing 48 mg of titanium) was added, and the mixture was heated to
The mixture was stirred for 10 minutes, left to stand, the supernatant was removed by decantation, and the mixture was washed five times with 100 ml of heptane to obtain solid catalyst component A. This solid catalyst component contained 4.07% titanium.

(b) Polymerization of zoropylene 500 ml of heptane in a 1 liter autoclave at 20°C under a propylene atmosphere, 95.4 mg of ethylaluminum, 51.7 mg of ethylaluminum sesquichloride, 41.0 ml of ethyl p-toluate.
1 mg N and an amount equivalent to 0.4 mg of the solid catalyst component A in terms of titanium atoms were added in this order,
Charge hydrogen gas in an amount equivalent to 180 ml in standard conditions, and pressurize propylene gas to bring the total pressure to 1 k.
After prepolymerizing at 20°C for 15 minutes while maintaining g/Cm, the temperature was raised to 70°C, and propylene was press-injected to bring the total pressure to 7k.
Main polymerization was carried out for 2 hours while maintaining the g/am. The autoclave was opened and the solid polymer was separated by filtration, while the P solution was concentrated to recover the soluble polymer. The results are shown in Table 1.

Example 2 Using the solid catalyst component A obtained in Example 1, propylene polymerization was repeated according to the method of Example 1 without prepolymerization. The results are shown in Table IK.

Comparative Example 1 Polymerization of propylene was carried out according to the method of Example 1, using the solid composition prepared in Preparation Example 1 instead of solid catalyst component A without carrying out the treatment according to the invention. The results are shown in Table 1.

Comparative Example 2 Example 2 was prepared by using the solid composition prepared in Preparation Example 1 in place of the homologous catalyst component A without carrying out the treatment according to the present invention.
I went back. The results are shown in Table 1.

Example 3 Example 1 was repeated except that the propylene polymerization was changed to 6 hours. The results are shown in Table 1.

Comparative Example 3 Example 3 was repeated using the solid composition prepared in Preparation Example 1 instead of solid catalyst component A without the treatment according to the invention. The results are shown in Table 1.

Example 4 Example IC The prepared slurry of solid catalyst component A was stored at room temperature for 40 days, and then propylene polymerization was carried out by the method of Example 1. The results are shown in Table 1.

Comparative Example 4 The solid composition was treated in the same manner as in Example 1 except that the solid composition was treated with p-) ethyl rulylate, and the slurry was stored at room temperature for 40 days before propylene polymerization was carried out in Example 1. It was carried out using the method. The results are shown in Table 1.

Comparative Example 5 Example 1 was repeated, except that the treatment of the solid composition was not washed with hebutane. The results are shown in Table 1.

Comparative Example 6 In the treatment of the solid composition of Example 1, 0.4 ml of solid composition slurry, 1.14 ml of ethylaluminum
Example 1 was repeated in the same manner except that 1.64 mg of ethyl ruylate (T1 concentration during treatment 9.6 mg/I) was used. The results are shown in Table 1.

Example 5 Example 1 was repeated by replacing 114 mg of triethylaluminum with 198 mg of triisobutylaluminum and replacing 49.2 mg of ethyl p-)rulyate with 45.1 mg of ethyl benzoate. Results are shown in Table 1.The T1 content of the solid catalyst component A obtained by the modification treatment was 4.09.

Example 6 The amount of p-)ethyl ruylate used during modification treatment was 82.1
Example 1 was repeated in place of mg. The results are shown in Table 1. The T'i content of solid catalyst component A was 4.05 mg.

Comparative Example 7 Example 1 was repeated with 500 mg of propylene present during the modification treatment. The results are shown in Table 1.

Analysis of Results A comparison between Example 1 and Comparative Example 1 shows that the activity, T-II and BD are significantly improved by the modification treatment of the present invention.

From the comparison between Example 2 and Comparative Example 2, it can be seen that by the modification treatment of the present invention, the catalyst can be used for practical purposes without undergoing prepolymerization.

A comparison between Example 3 and Comparative Example 3 shows that the persistence of polymerization activity is improved by the modification treatment of the present invention.

A comparison between Example 4 and Comparative Example 4 shows that unless an electron donor compound is present during the treatment, the catalyst performance (activity, T-II, BD) after the modification treatment deteriorates significantly over time, making it unsuitable for practical use. It turns out that there isn't.

Comparative Example 5 and Comparative Example 6 show that the effects of the present invention cannot be enjoyed unless washing is performed after the modification treatment, and unless the Tigk degree during the modification treatment is 10 mg/liter or more.

Comparative Example 7 shows that the effects of the present invention cannot be achieved if olefins coexist during the modification treatment.

Applicant's agent Kiyoshi Inomata

Claims (1)

[Claims] A method of polymerizing an olefin by bringing it into contact with a hornworm medium basically consisting of a titanium-containing solid catalyst component (component A) and an organoaluminum compound (component B).
A method for producing an olefin polymer, characterized in that is as follows. (1) Component A is a solid composition containing magnesium, titanium, and nitrogen as essential components, and an organoaluminum compound of the formula (nIRnA1x3-(m+n)) and an electron donor compound in the absence of an olefin. After processing,
The product must have been washed with an inert solvent (in the above formula, R represents a hydrocarbon residue having 1 to 1 carbon atoms, and X represents rogene), m and n are 06m, 3, and (2) The above solid composition is treated with an organoaluminum compound and an electron donor under the following conditions. To be. (a) Amount of organoaluminum compound/amount of solid composition = 0.
1-50 (Al/Ti atomic ratio) (b) Amount of electron donor compound/amount of organoaluminum compound = 0.01-1.
0 (mol/atomic ratio)