JPS6026007A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce a highly stereoregular polyolefin in good yield per unit catalyst, by using a titanium catalyst component prepared by treating a magnesium halide as a support in the presence of oxygen and impregnating the treated support with a titanium halide. CONSTITUTION:A magnesium halide (e.g., anhydrous magnesium chloride) is ground in the presence of air or oxygen treated with a dehydrating agent such as molecular sieve and contacted with oxygen. The obtained magnesium halide (a support) and , if necessary, an oxygen-containing compound (e.g., carboxylate ester) are pulverized and brought into contact with a liquid titanium halide (e.g., titanium tetrahalide) to form a supported titanium catalyst component. An alpha- olefin is polymerized by using a catalyst comprising the above titanium catalyst component and an organoaluminum compound (e.g., diethylaluminum chloride).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses a special supported titanium halide catalyst in a method for polymerizing olefins using a catalyst consisting of a titanium halide catalyst supported on magnesium halide and an organoaluminum compound. Concerning how to use.

Since the method of using a catalyst consisting of a supported titanium fluoride catalyst and an organoaluminum compound as an olefin polymerization catalyst was proposed in Japanese Patent Publication No. 39-12105, many improved methods have been proposed. However, it is still insufficient in terms of catalyst performance, and in particular, the yield per catalyst is insufficient. It is necessary to add significant amounts of stabilizers to the resulting polymer.

As a result of conducting various inspections to improve catalyst performance, the present inventors discovered that it is possible to improve catalyst performance extremely easily by performing a special method, and have completed the present invention.

An object of the present invention is to provide a method for polymerizing olefins which has high activity and, when used in the polymerization of α-olefins, the resulting polyolefin has high stereoregularity.

The present invention relates to a method for polymerizing olefins using a catalyst consisting of a titanium halide catalyst supported on a magnesium halide and an organoaluminum compound. The present invention relates to a method for polymerizing an olefin, which is obtained by adhering titanium halide to magnesium halide treated in the presence of oxygen.

That is, in the production of olefin polymerization catalysts, the treatment is carried out in the presence of oxygen, which has until now been removed very strictly because it degrades performance. J.
The feature of the present invention is that q': is obtained.

Regarding the manufacturing method of the titanium halogenide catalyst supported in the present invention, it is sufficient that there is a step in which the halogenated magneuno comes into contact with oxygen in advance before contacting with the titanium halide, and various methods may be used. method can be adopted.

... Anhydrous magnesium chloride is used as the magnesium rogenide.

As the oxygen, pure oxygen or a mixture of air or the like can be used, but it can be treated with a dehydrating agent such as molecular sieves and then removed.

As a method for bringing magnesium chloride into contact with oxygen, for example, it is sufficient to first store magnesium chloride in the presence of oxygen, or to carry out the contact treatment with oxygen by crushing it in a suitable size in the presence of oxygen. It is.

By using the thus obtained magnesylanochloride which has been brought into contact with oxygen and applying a known method for producing a magnesium chloride supported catalyst, the supported catalyst used in the practice of the present invention is produced.

Specifically, for example, magnesium chloride and oxygen-containing compounds such as carboxylic esters, orthocarboxylic esters, ethers, and acetals, aromatic compounds such as benzene, toluene, xylene, and cumene, methylene chloride, dichloroethane, l-! J A method in which halogenated hydrocarbons such as chloroethane, chloropropane, and l-dichlorotoluenate are co-pulverized and then brought into contact with liquid titanium halide, in particular, oxygen-containing compounds are preferred in the polymerization of α-olefins. Also, during co-pulverization, At203.5i02
Of course, it is also possible to coexist oxides such as AtCIB, chlorides such as NaCl, CaCl, and the like. Furthermore, a method in which contact with titanium halide is repeatedly carried out, a method in which titanium halide is diluted, or a method in which titanium halide is complexed is used.

Alternatively, magnesium chloride that has been contacted with oxygen is solubilized in a hydrocarbon solvent or halogenated hydrocarbon solvent using alcohol or the like, and then T IC14, klct3
, by making it insolubilized in a solvent with a metal halide such as SIC14 or an organometallic compound such as alkylaluminiumuno, contacting it with the oxygen-containing compound listed above, and then treating it with a titanium halide catalyst. You can also get

In these cases, when the contact treatment of magnesium chloride and the organic compound is carried out by co-pulverization, it is also possible to carry out the contact with oxygen at the same time.

In the present invention, dl, a U-bearing titanium catalyst obtained by the above method and an organoaluminium, such as triethylaluminum,
tripropyl aluminum, tributyl aluminum,
l-realkylaluminum such as tripropylaluminum and trihexylaluminum, diethylaluminum noride, dipropylaluminumorhamnolide,
Among sialgyl aluminum halides such as dibutyl aluminum halide, diethylaluminum nolide, and dibutyl aluminum halide, sialgyl aluminum chloride can be used alone or in mixtures or in combination to polymerize olefins, and α-olefins. In the polymerization of the carboxylic acid ester, a carboxylic acid ester is used.

Examples of the olefin in the present invention include ethylene and α-olefins such as ethylene, propylene, butene, and hexene, and homopolymerization or copolymerization thereof can be performed.

By applying the method of the present invention, it is possible to produce polyolefins with high activity per catalyst, which is industrially valuable.

EXAMPLES The present invention will be explained in more detail below with reference to Examples.

Example 1 a) Production of a covalent titanium halide catalyst Charge each pot of the mill in 207 dry air and grind for 1-2 hours.

Next, tetraethoxysilane rne was charged into each bot in dry air and pulverized at 30° C. for 40 hours. Next, the co-pulverized product was taken out in dry nitrogen, placed in a 200 ml round bottom flask that had been sufficiently purged with dry nitrogen, and 30 me/l of titanium tetrachloride and 30 me of luene were added, followed by stirring at 80°C for 1 hour. Leave to stand, remove the supernatant, and add 3 titanium tetrachloride (1 me/l□Luene: 1
0 ml was added, stirred at 80°C for 1 hour, and then left standing to remove the supernatant. Then once] 0 0 m7! n-
The operation of washing the solid portion with hebutane a1 was repeated seven times to obtain a solid catalyst slurry. A sample of a portion of the solid catalyst was analyzed and found to contain 2.5% Ti. It contained 4 wt qb gold.

1) Polymerization reaction Prepare an autoclave with an internal volume of 5 tons that has been thoroughly dried and replaced with nitrogen. Thoroughly dried and replaced with nitrogen 200
ml flask, put 50 ml of dry n-hebutane purged with nitrogen, and add 0.1 ml of diethylaluminum chloride.
．． 2 8 me) Methyl ruylate 0.0 6 me,
0.08 mg of l-ethylaluminum and 30 mfl of the solid catalyst obtained in 1 were added and the mixed catalyst slurry was charged into the above autoclave, and then 1.5 kg of propylene was added.
Charge 0.6Nt of hydrogen and heat the autoclave to an internal temperature of 75
Polymerization was carried out at ℃ for 1 hour. After the polymerization reaction, unreacted propylene was discharged and the polypropylene powder was taken out and heated at 60℃ for 1 hour.
After drying for 0 hours, it was weighed, and the intrinsic viscosity (hereinafter abbreviated as η) was determined with a tetralin solution at 135°C. The results are shown in the table.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the pulverization and co-pulverization of magnesium chloride were carried out in dry nitrogen. The results are shown in the table.

Example 2 The same procedure as in Example 1 was performed except that magnesium chloride was crushed in dry air and co-pulverized in dry nitrogen.
, shown in the table.

Examples 3 to 5 Comparative Examples 2 and 3 The same procedure as in Example 1 was carried out except that the co-pulverized material and oxygen source shown in the table were used (Examples 3 to 5), except that the co-pulverized material shown in the table was used. 1: Same procedure as Comparative Example 1 (Comparative Examples 2 and 3) The results are shown in the table.

Claims (1)

[Scope of Claims] 1) In a method for polymerizing an olefin using a catalyst comprising a titanium halide catalyst supported on magnesium halide and an organoaluminum compound, a titanium halide catalyst supported on magnesium halide; is obtained by supporting titanium halide on magnesium halide which has been previously treated in the presence of oxygen. 2) The method according to claim 1, wherein the magnesium halide is magnesium chloride. 3) Claim 1, wherein the titanium halide catalyst is obtained by treating magnesium halide treated in the presence of oxygen with an organic compound containing a C-0 bond, and then supporting titanium halide. Method described. 4) The titanium halide catalyst is obtained by contacting magnesium halide with a compound containing a C-0 bond in the presence of oxygen, and then supporting the titanium halide with titanium halide. The method described in Section 1.