JPS63159407A - Polymerization of ethylene and alpha-olefin - Google Patents

Abstract

PURPOSE:To polymerize ethylene and alpha-olefin, wherein the production cost of the catalyst is reduced and the catalyst exhibits an excellent activity, by polymerizing ethylene and alpha-olefin in the presence of a specified supported Ti catalyst. CONSTITUTION:1g of a carrier obtained by pulverizing a complex of Mg, a halogen and an electron-donating compound or of an electron-donating compound and an electron-accepting compound together and 20ml or TiCl4 are heated at 80 deg.C in a (halogenated) hydrocarbon solvent for 2hr, after which the resultant is washed with a large amount of n-heptane to give a supported Ti ingredient A which supports TiCl4 in an amount of 3-5 times by weight of the standard amount. Ethylene and alpha-olefin are polymerized in the presence of a catalyst consisting of the ingredient A, an organoaluminum compound B and, if necessary, an electron-donating compound or an electron-accepting compound C at -50-200 deg.C under normal pressure to 200kg/cm<2>G.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for copolymerizing ethylene and α-olefin, and more specifically to a method for copolymerizing ethylene and α-olefin using a Ti-based carrier catalyst component prepared by a special method. The present invention relates to a polymerization method.

[Prior Art] The use of polyolefin polymerization catalysts is shifting from the conventional Ziegler-Nanta catalysts to high-performance carrier catalysts that combine a carrier catalyst component in which a transition metal compound is supported on a carrier and an organometallic compound.

Supported catalysts are highly desirable catalysts due to their high performance, but in order to improve their performance, the catalyst manufacturing process becomes complicated and a large amount of auxiliary raw materials are used. This results in a very expensive catalyst, which is not economical.

As one of the typical methods for producing a supported catalyst component, a simple method of co-pulverizing magnesium chloride, a titanium compound and, if necessary, an electron donor compound and the like is known, but this method is not sufficient in terms of performance. Another method is
-1405, there is a method in which magnesium chloride is brought into contact with various compounds, then heated with a large amount of titanium tetrachloride, and further washed with an inert solvent. Although the performance of this catalyst is good, it requires the use of a very large amount of titanium tetrachloride, and also requires a large amount of equipment and utilities to recover and reuse the large amount of titanium tetrachloride and the washing solvent. As a result, the production cost of the catalyst becomes very high, and improvements have been desired.

[Problems to be Solved by the Invention] The object of the present invention is to relate to a supported catalyst component used in the polymerization of ethylene and α-olefin, and the conventional supported catalyst component requires a large amount of titanium tetrachloride. In contrast, it is possible to obtain an effective supported catalyst component using a small amount of titanium tetrachloride, thereby significantly reducing the manufacturing cost of the catalyst.

[Means for Solving the Problems] The inventors of the present invention have arrived at the present invention as a result of intensive studies aimed at reducing the manufacturing cost of catalysts. That is, the present invention provides a method for producing ethylene and α- In the method for producing olefins, the carrier-type titanium component (a) is a carrier containing magnesium, a halogen, and an electron-donating compound or a complex of an electron-donating compound and an electron acceptor as essential components (
A), and the amount of titanium tetrachloride used when contacting this carrier (A) with titanium tetrachloride in a hydrocarbon solvent or halogenated hydrocarbon solvent is 20 ml of titanium tetrachloride per 1 g of the carrier (A). Based on the amount of supported titanium tetrachloride obtained by heating with titanium at 80 ° C. for 2 hours and washing with a large amount of n-heptane, the amount of titanium tetrachloride is 0.3 to 5 times the weight of this standard amount. A method for polymerizing ethylene and α-olefins.

The present invention is characterized by the carrier-type titanium component (a), which is prepared as follows. First, a carrier (A) containing magnesium, a halogen, and an electron-donating compound or a complex with an electron-donating compound or an electron-accepting compound as essential components is prepared. This is not particularly limited as long as the above components are essential components, and a known carrier such as a halogen-containing magnesium compound such as magnesium cybaride or magnesium alkoxy halide, an electron-donating compound, or a complex of this with an electron-accepting compound. It is prepared by co-grinding or contacting with the addition of. The halogen-containing magnesium compound is preferably magnesium dichloride, magnesium cybaride, or a compound containing these as a main component.
1. Cj! Magnesium chlorinated with a halogenating agent such as
, CI, , a product obtained by reacting an organic Mg compound with an electron donor such as an alcohol, or a product obtained by reacting a magnesium dialkoxide with a halogenating agent, etc. is also used.

As the electron-donating compound, known electron-donating compounds used in Ziegler catalysts containing O, P, N, S, St, etc. are used. Further, these electron-donating compounds or complexes of these and electron-accepting compounds can be used. Examples of electron-donating compounds include ethers, ketones, esters, organic acid halides, organic acid anhydrides, aldehydes, and
Examples include class amines, phosphites, phosphoric acid amides, nitriles, thioethers, alkoxysilanes, carboxylic acid orthoesters, and complexes of these with electron-accepting compounds such as aluminum halides and titanium tetrachloride can be used. . Specifically, diphenyl ether, acetophenone, ethyl benzoate, diisobutyl fuculate, methyl toluate, T-butyrolactone, benzoyl chloride, benzoic acid-N,N-diethylamide, triptylamine, benzonitrile, ethyl benzoate/aluminum chloride complex. , diphenyl ether/chloride 7L/
Examples include minium complex, phenyltriethoxysilane, tetraethoxysilane, triethyl orthoacetate, polysiloxane, and 2,2,6,6-titramethylpiperidine.

The carrier (A) is prepared by co-pulverizing a complex of the above-mentioned components containing magnesium and halogen as essential components and an electron-donating compound or an electron-accepting compound, or by bringing them into contact in an inert solvent. ^) Also includes those in which halogenated hydrocarbons, hydrocarbons, aluminum chloride, iron chloride, silicon tetrachloride, and various other components other than the above-mentioned essential components are added.

The support (A) and titanium tetrachloride are then brought into contact in the presence of an inert solvent such as a hydrocarbon compound or a halogenated hydrocarbon compound. The support (A) and titanium tetrachloride are brought into contact at room temperature to 200°C, preferably from 40°C to 150°C in the presence of a hydrocarbon compound or a halogenated hydrocarbon compound.
Contact for several minutes to 10 hours at a temperature of .

As the hydrocarbon compound or halogenated hydrocarbon compound, aliphatic, alicyclic, aromatic hydrocarbon compounds or their halogen derivatives are used, such as n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, ethylene. Dichloride, chlorobenzene, etc. are used.

In the present invention, the amount of titanium tetrachloride used for the carrier (A) is 201 titanium tetrachloride per 1 g of the carrier (A) at 80°C.
The amount of supported titanium tetrachloride obtained by heating for 2 hours at a temperature of
)], 0.3 to 5 times by weight, preferably 0.5 to 5 times
By using 3 times by weight, more preferably 0.7 to 2 times by weight of titanium tetrachloride, the carrier-type titanium component (a) used in the present invention can be prepared. In this case, it is also possible to contact the carrier (A) and titanium tetrachloride in the presence of a hydrocarbon compound or a halogenated hydrocarbon compound, and then wash the unreacted titanium tetrachloride with a solvent before use. It can also be used without washing, which is another feature of the present invention.

(b) Organoaluminum compounds used together with the carrier-type titanium component (a) obtained by the above method include compounds in which an organic group is directly bonded to aluminum, such as alkylaluminum compounds, alkylaluminum alkoxides, alkylaluminum hydrides, and alkyl aluminum compounds. Examples of aluminum halides include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-1so-butylaluminum, trioctylaluminum, diethylaluminum hydride, diethylaluminium chloride, diethylaluminium iodide, diethylaluminum bromide, diethylaluminum chloride. , diethylaluminium ethoxide, diethylaluminum phenoxide, imprenyl aluminum, and Et, ^10AI
Examples thereof include Et2, EhAI-N-AIEh, etc., and it is particularly preferable to use a mixture thereof, for example a mixture of triethylaluminum and diethylaluminum monochloride.

The usage ratio of (a) carrier type titanium component and (b) organoaluminum compound is 1 titanium atom contained in (a)
The amount of (b) is 0.5 to 500 mol, preferably 1 to 200 mol, per gram atom.

(c) A complex with an electron-donating compound or an electron-accepting compound added as necessary in the method of the present invention is (a) the same electron-donating compound used during production or a complex of this with an electron-accepting compound. Examples of these include the same compounds as used in (a), and particularly preferred are methyl toluate, phenyltrimethoxysilane, and ethyl benzoate/aluminum chloride complex.

The proportion of the electron-donating compound or the complex of this and the electron-accepting compound used is 5 mol or less, preferably 1 mol or less, per 1 mol of the organoaluminum compound in the carrier-type titanium component (a).

The catalyst according to the present invention is composed of ethylene and general 2 GHz C1l-R.
(However, R represents a hydrocarbon group having 1 to 12 carbon atoms.) This is a method for polymerizing an α-olefin.

α-olefins include propylene, butene-1, pentene-1, hexene-12 octene-1, decene-1,
Examples include 4-methylpentene-1, styrene, 4-vinylcyclohexene, polymerization or copolymerization of these α-olefins and ethylene, and dicyclopentadiene, 1,4-hexadiene, ethylidene norbornene, etc. Copolymerization with polyenes can also be carried out in the present invention.

The copolymerization reaction can be carried out by a known method related to olefin polymerization, such as random polymerization, block polymerization, etc.

The polymerization reaction can be carried out in solution, slurry or gas phase;
In the case of solution or slurry polymerization, inert solvents such as propane, butane, hexane, heptane, benzene,
Polymerization can be carried out in the presence of toluene, xylene, etc., or in the case of propylene, butene-1, etc., bulk polymerization can be carried out using the monomer itself as a solvent.

In the case of slurry polymerization or gas phase polymerization, in order to improve the properties of the polymer, it may be prepolymerized with ethylene and/or α-olefin before polymerization. Prepolymerization is generally performed at a slower rate than normal polymerization. It is preferable to polymerize with

The polymerization reaction is carried out batchwise or continuously, at a temperature of -50°C to 250°C, preferably 0°C to 200°C, and a pressure of normal pressure to 20 (1 Kg/cd G, preferably 2 to 1
00Kg/+ffl G, and the molecular weight of the resulting polymer can be controlled by adding hydrogen, dialkylzinc, or alkyl halide.

[Example] Next, the present invention will be described using reference examples, examples, and comparative examples.

Reference Example 1 (1) Preparation of carrier (A,) 20 g of anhydrous magnesium chloride, 2 ml of ethyl benzoate, and 2 m It of diphenyl ether were placed in a vibrating mill pot with an internal volume of about 1 containing 3 kg of steel balls with a diameter of 12III11.

Add 2 m6 of carbon tetrachloride and grind for 24 hours to obtain a carrier (A1).

(2) Supporting TiCl4 on carrier (A1) (supporting conditions (a)) 10 g of carrier (A) prepared in (1) and 200 nl of titanium tetrachloride were placed in a 200 ml round bottom flask purged with N2, and heated at a temperature of 80°C. It reacted for 2 hours.

After removing the supernatant liquid by decantation, 200 ml of n-heptane was added and stirred at 80°C for 15 minutes, followed by washing 10 times to remove the supernatant liquid by decantation, and titanium tetrachloride was added to the carrier (A1). carried it.

A portion of the slurry was dried under reduced pressure at 60'C for 30 minutes and the titanium content was measured, and it was found to contain 1.80 wt% titanium. This is 7.43 as titanium tetrachloride.
Corresponds to @t%.

Example 1 To 10 g of the carrier (A+) shown in Reference Example 1, 0.743 g of titanium tetrachloride and 100 Ill of n-heptane were added.
By heating at 00° C. for 2 hours, a carrier-type titanium component (a) was obtained without washing with n-heptane. A portion of the slurry in this carrier-type titanium component (a) was heated at 60°C under reduced pressure for 30 minutes.
After drying for a minute and measuring the titanium content, it was t, 55w.
The titanium tetrachloride used contained 91.% of titanium.
It was found that 7% was supported on the carrier (A).

Next, propylene was polymerized using this carrier-type titanium component (a).

In a N-substituted autoclave with an internal volume of 21 cm, ljl of n-heptane, 0.1 g of carrier-type titanium component (a), 0.2 ml of triethylaluminum, and 0.07 ml of methyl ruylate. Diethylaluminium o, o8IIll
was added, the gas phase of the autoclave was replaced with propylene, hydrogen was added at a partial pressure of 0.2 kg/-, and the pressure was increased to 3 kg/CIIG with propylene.

The internal temperature in the autoclave was raised to 70°C over 5 minutes, and then the propylene pressure was 5K at 70°C.

Propylene was replenished so that the concentration was /cdG, and polymerization was carried out for 1.5 hours.

After the polymerization was completed, the autoclave was cooled, and the contents were taken out and filtered to obtain 383 g of polypropylene powder. On the other hand, the filtrate was evaporated to obtain 6.0 g of non-quality polypropylene.

The bulk specific gravity of the obtained polypropylene powder is 0.45
g/ml, intrinsic viscosity number 1.72 dl/g (135℃
Tetralin), boiling n-peptane extraction residue (powder) was 97.1X.

The activity of the catalyst in this polymerization reaction was 2593 g/g-, < 1
Ivy144Kg/g-Ti, hr, the amount of polymer obtained was 3890g/g (I.

It was 216Kg/g-Ti. In addition, the ratio of boiling n-peptane extraction residue to the total polymer (total 11) was 95.6.
It was 2.

Comparative Example 1 Table 1 shows the results of polymerization carried out under the same conditions as in Example 1, except that the catalyst carrying titanium tetrachloride on carrier (a+)C shown in Reference Example 1 was used as is.

Comparing Example 1 and Comparative Example 1, almost the same polymerization results were obtained. The benefits are great.

Example 2 50ml of n-heptane was placed in an autoclave with an internal volume of 61ml in an Nt atmosphere. 0.1 ml of triisobutyl was added to 0.1 g of carrier-type titanium component (a) prepared in Example 1, the gas phase was replaced with n-butane, 1.5 kg of n-butane was charged, and hydrogen and ethylene were added. were added to 5 g at partial pressure, respectively, and the temperature was raised to 95° C. for 10 minutes. After raising the temperature to 95°C, ethylene was added to bring the pressure to 25 kg/eIIIG and polymerization was continued for 2 hours.

After polymerization, the contents are taken out and polyethylene 1230
I got g. The intrinsic viscosity of the obtained polyethylene was 1.43.
, and the bulk specific gravity was 0.45 g/ml.

Comparative Example 2 Ethylene polymerization was carried out under exactly the same conditions as in Example 2, except that the catalyst in which titanium tetrachloride was supported on the carrier (A1) shown in Reference Example 1 was used as it was.

The results are shown in Table 2.

Comparing the results of Example 2 and Comparative Example 2, it was found that similar results were obtained, and unlike the method of Example 2, titanium tetrachloride can be greatly reduced, and washing can be omitted, which has industrial advantages. big.

c. Effects of the present invention] By using the carrier-type titanium component (a) according to the present invention, the manufacturing cost of the catalyst can be significantly reduced, and when used in the polymerization method of ethylene and α-olefin, it exhibits excellent catalytic activity. .

Patent applicant Mitsui Toatsu Kagaku Co., Ltd. Procedural Authorization (spontaneous) December 7, 1985 Director General of the Patent Office Kunio Ogawa 1, Indication of the case 1986 Patent Application No. 306209 2, Title of the invention Polymerization method of ethylene and α-olefin 3, relationship with the amended case Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (31
2) Mitsui Toatsu Chemical Co., Ltd. 4. The number of inventions increased by the amendment: 0 5. The list of attached documents in the application subject to the amendment, the brief description of drawings in the specification and the drawing 6, the content of the amendment ( 1) Accurate application and (2) Contents of amendments to the specification and (
1) Accurate application Attachment (2) Contents of amendments to the specification On page 19, line 5 of the specification, between “Exhibits excellent catalytic activity when used” and “Patent applicant Mitsui Toatsu Chemical Co., Ltd.” A note to add the following words:

[Brief explanation of the drawing]

FIG. 1 is a flow chart diagram of the Ziegler catalyst according to the present invention. (2) Attach the drawings as shown in Figure 1.

Claims (1)

[Scope of Claims] Ethylene and In the method for producing α-olefins, the carrier-type titanium component (a) is a carrier containing magnesium, a halogen, and an electron-donating compound or a complex of an electron-donating compound and an electron acceptor as essential components (
A), and when this carrier (A) is brought into contact with titanium tetrachloride in a hydrocarbon solvent or a halogenated hydrocarbon solvent, the amount of titanium tetrachloride used is 2 per 1 g of the carrier (A).
After heating with 0ml of titanium tetrachloride at 80℃ for 2 hours,
Ethylene and α-olefin characterized in that the amount of supported titanium tetrachloride obtained by washing with a large amount of n-heptane is 0.3 to 5 times the weight of the standard amount. polymerization method.