JPH0425285B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of using a special supported titanium halide catalyst in a method of polymerizing olefin using a catalyst consisting of a titanium halide catalyst supported on magnesium halide and an organoaluminum compound. . Japanese Patent Publication No. 39-12105 describes a method using a catalyst consisting of a supported titanium halide catalyst and an organoaluminum compound as a polymerization catalyst for olefins.
Many improved methods have been proposed since the method was first proposed in the publication. However, the improvement in catalyst performance is still insufficient, and in particular, in order to produce products without removing catalyst residues, when used in the polymerization of a-olefin, a considerable amount of It is necessary to add stabilizers. As a result of various studies on improving 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 a-olefins, provides a polyolefin with high stereoregularity. The present invention provides a method for polymerizing olefins using a catalyst consisting of a titanium halide catalyst supported on magnesium halide and an organoaluminum compound, in which the titanium halide catalyst supported on magnesium halide reacts with oxygen and water. The present invention relates to a method for polymerizing an olefin, which is obtained by supporting titanium tetrachloride on magnesium halide treated in the presence of olefin. That is, in the production of olefin polymerization catalysts, oxygen and water, which have been conventionally removed extremely strictly because they degrade performance, are intentionally present to obtain the catalyst, and the present invention provides a catalyst. It has the characteristics of Regarding the production method of the supported titanium halide catalyst in the present invention, it is sufficient that the process includes a step in which magnesium halide is brought into contact with oxygen and water before contacting with titanium tetrachloride; Various methods can be adopted. As the magnesium halide, anhydrous or magnesium chloride containing a small amount of water is preferably used. The oxygen can be pure oxygen or a mixture such as air. When water is added at the same time, water can be added to oxygen or air, or it can be added in liquid form if dry oxygen or air is used. When using magnesium chloride hydrate as the magnesium halide, there is no need to further add water, and the preferable amount of water present is
It is 0.1wt~16wt%. The contact treatment of magnesium chloride with oxygen and water is carried out by storing it in the presence of oxygen and water or by grinding it in the presence of oxygen or water, preferably by grinding it in the presence of oxygen or water. For example, it can be done by twisting it. A supported catalyst is produced by applying a known method for producing a supported magnesium chloride catalyst using the magnesium chloride that has been contacted with oxygen and water thus obtained. For example, oxygenated compounds such as magnesium chloride and carboxylic acid esters, orthocarboxylic acid esters, ethers, and acetals, aromatic compounds such as benzene, toluene, xylene, and cumene, and halogens such as methylene chloride, dichloroethane, trichloroethane, chloropropane, and trichlorotoluene. Oxygen-containing compounds are preferred in the method of co-pulverizing carbonized hydrocarbons and then contacting them with liquid titanium tetrachloride, especially in the polymerization of a-olefins.
Also, during co-pulverization, oxides such as Al ₂ O ₃ and SiO ₂ ,
Of course, it is also possible to coexist chlorides such as AlCl ₃ , NaCl, and CaCl ₂ . Further, a method of repeatedly catalyzing titanium tetrachloride, a method of diluting titanium tetrachloride, a method of using titanium tetrachloride after complexing, etc. are used. Another method is to solubilize magnesium chloride that has been contacted with oxygen and water in a hydrocarbon solvent or halogenated hydrocarbon solvent using alcohol or the like, and then to make it insolubilized in the solvent using a metal halide or the like. Furthermore, it can also be obtained by treatment with the oxygen-containing compound listed above and then treatment with a titanium tetrachloride catalyst. When carrying out a contact treatment of magnesium chloride and an organic compound by co-pulverization, it is also possible to carry out contact with oxygen and water at the same time. In the present invention, the supported titanium catalyst obtained by the above method and an organic aluminum such as triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum,
Among trialkylaluminum halides such as trihexylaluminum, diethylaluminum halide, dipropylaluminum halide, dibutylaluminum halide, dipentylaluminum halide, and dihexylaluminum halide, dialkylaluminum chloride may be used alone, in mixtures, or in combination. used in the polymerization of olefins. In addition, when polymerizing a-olefin,
Known stereoregularity improvers such as carboxylic esters, orthocarboxylic esters, ethers, and phosphoric esters are used. Examples of the olefin in the present invention include ethylene and a-olefin such as ethylene, propylene, butene, and hexene, which are used for homopolymerization or copolymerization thereof. By applying the method of the present invention, it becomes possible to produce polyolefin with high activity per catalyst, which is industrially valuable. EXAMPLES The present invention will be explained in more detail with reference to Examples below. Example 1 (a) Production of supported titanium halide catalyst A vibratory mill equipped with two crushing pots each containing 80 rigid balls with an internal volume of 600 ml and a diameter of 12 mm was prepared, and 20 g of commercially available magnesium chloride (moisture content) was placed in each crushing pot. 0.05wt%) and 0.1ml of pure water in dry air,
Grind for 2 hours. Next, 2 ml of tetraethoxysilane and 3 ml of 1,2-dichloroethane were charged into the above pot in dry air, and the mixture was pulverized at 30 DEG C. for 40 hours. Next, the co-pulverized product was taken out in dry nitrogen, and 10 g was placed in a 200 ml round bottom flask that had been sufficiently purged with dry nitrogen. 30 ml of titanium tetrachloride/30 ml of toluene were added, stirred at 80°C for 1 hour, and then left to stand to supernatant. was removed, 30 ml of titanium tetrachloride/30 ml of toluene were added, and the mixture was stirred for 1 hour at 80°C, then left to stand and the supernatant was removed. Then,
The operation of washing the solid portion with 100 ml of n-heptane was repeated seven times to obtain a solid catalyst slurry. When a part of the solid catalyst was sampled and analyzed,
It contained 2.6wt% Ti. (b) Polymerization reaction Prepare an autoclave with an internal volume of 5 that has been thoroughly dried and purged with nitrogen. Thoroughly dried and replaced with nitrogen
In a 200 ml flask, add 50 ml of dried n-heptane and diethylaluminium chloride, purged with nitrogen.
0.128ml, methyl toluate 0.06ml, triethylaluminum 0.08ml, and the solid catalyst obtained in a)
The mixed catalyst slurry containing 30 mg of the catalyst was charged into the above autoclave, and then 1.5 kg of propylene and hydrogen were added.
Charge 0.6Nl and heat the autoclave until the internal temperature is 75
Polymerization was carried out at ℃ for 1 hour. After the polymerization reaction, unreacted propylene was discharged, the polypropylene powder was taken out, dried at 60°C for 10 hours, weighed, and the intrinsic viscosity number (hereinafter η abbreviated) was determined with a tetralin solution at 135°C. The extraction residue rate (extracted with a Soxhlet extractor for 6 hours was stopped, calculated as extraction residue polymer weight/pre-extraction polymer weight x 100%, abbreviated as below) and bulk specific gravity were determined. The results are shown in the table. Comparative Example 1 Magnesium chloride was ground and co-ground in the same manner as in Example 1, except that the grinding and co-grinding were carried out in dry nitrogen without adding water. The results are shown in the table. Example 2 Magnesium chloride was pulverized in dry air and co-pulverized in dry nitrogen in the same manner as in Example 1. The results are shown in the table. Examples 3 to 5 Comparative Examples 2 and 3 The same procedure as Example 1 was carried out except that the co-pulverized material, oxygen source, and amount of water shown in the table were used (Examples 3 to 5).
5) The same procedure as Comparative Example 1 was carried out except that the co-pulverized material shown in the table was used (Comparative Examples 2 and 3), and the results are shown in the table. 【table】

[Brief explanation of drawings]

FIG. 1 is a flowchart to aid in understanding the present invention.

Claims (1)

[Claims] 1 In a method of polymerizing olefin using a catalyst consisting of a titanium halide catalyst supported on magnesium halide and an organoaluminum compound, the titanium halide catalyst supported on magnesium halide is polymerized in the presence of oxygen and water. A method for polymerizing an olefin, characterized in that the olefin is obtained by supporting titanium tetrachloride on magnesium halide treated with.