JPH0372643B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for storing solid catalyst components for α-olefin polymerization. The solid catalyst component for α-olefin polymerization, which has magnesium, titanium, halogen, and an electron donor as essential constituents, is sensitive to light. In particular, when the solid catalyst component is in powder form, its catalytic performance is significantly reduced by exposure to light.
This is a unique phenomenon observed only in the above-mentioned solid catalyst component. In fact, solid catalyst components based on titanium trichloride, which are currently widely used industrially, retain their catalytic performance over long periods of time even when exposed to light. The present invention provides a method for storing a solid catalyst component for α-olefin polymerization containing magnesium, titanium, halogen, and an electron donor as essential components, and the gist thereof is to irradiate light in an inert gas atmosphere. The purpose is to store the solid catalyst component in a blocked state. The solid catalyst component for α-olefin polymerization in the present invention contains magnesium, titanium, halogen, and an electron donor as essential components. The solid catalyst component is disclosed in, for example, JP-A-56-45909, JP-A-56-55405, JP-A-56-76411, JP-A-56-163102, filed by the present applicant.
No. 57-18706, No. 57-25306, No. 57-
Publication No. 25307, Publication No. 57-83510, Patent Application 1983-
It can be prepared by the method described in the specification of No. 26102, or by a method of co-pulverizing magnesium halide, titanium halide, and an electron donor such as ester, ether, or amine. These solid catalyst components are used in combination with organoaluminum compounds as polymerization catalysts for ethylene, propylene, butene-1, hexene-1, and octene-1. Specific examples of the inert gas include nitrogen, argon, helium, and the like. In the present invention, the solid catalyst component is stored in a light-blocked state, for example, in a glass container, plastic container, ceramic container, or metal container that does not substantially transmit light. If a glass or plastic container is used, it is necessary to cover the outer wall with a black sealant or to paint the container itself in a color that is substantially opaque to light. The solid catalyst component may be stored suspended in an inert organic solvent such as heptane, hexane, toluene, benzene, cyclohexane, or a highly viscous substance such as mineral oil or warisene, or may be stored as a dry powder. It's okay. Next, Examples and Comparative Examples will be shown. In the following, polymerization activity is the yield (g) of polypropylene per 1 g of solid catalyst component per 1 hour of polymerization time, and HI is the yield (g) of polypropylene obtained by extracting polypropylene produced in the polymerization reaction with boiling n-heptane for 24 hours. % by weight of the solid polymer treated relative to the untreated polymer. Examples 1 to 5 and Comparative Examples 1 to 4 (1) Preparation of solid catalyst component: 15 mmol of anhydrous aluminum chloride was added to 40 mmol of toluene.
ml and then methyltriethoxysilane 15
After adding 1 mmol of the mixture and reacting at 25° C. for 0.5 hour with stirring, the temperature was raised to 60° C. and the reaction was continued for 1 hour. After the reaction mixture was cooled to -5° C., 18 ml of diisoamyl ether containing 27 mmol of n-butylmagnesium chloride was added dropwise to the reaction mixture over 0.5 hours while stirring. The temperature of the reaction system is -5
It was kept at ℃. After the dropwise addition was completed, the temperature was raised to 30°C and the reaction was continued for 1 hour. The precipitated solid was separated and washed with toluene. 4.90 g of the obtained solid was suspended in 25 ml of toluene, and 150 mmol of titanium tetrachloride was added to this suspension. The temperature was raised to 90°C and the solid and titanium tetrachloride were brought into contact for 1 hour with stirring. . At the same temperature, the titanium-containing solid was separated and washed with n-heptane and then toluene. 4.10 g of the titanium-containing solid was suspended in 25 ml of toluene, and 6.5 mmol of ethyl benzoate was added to this suspension, which was kept at 90° C. for 1 hour with stirring. The ester treated solid was separated at the same temperature and washed with n-heptane and then toluene. Suspend the ester-treated solid in 25 ml of toluene,
Add 150 mmol of titanium tetrachloride to this suspension,
The ester-treated solid was brought into contact with titanium tetrachloride for 1 hour at 90°C with stirring. The obtained solid catalyst component was separated at the same temperature and washed with n-heptane. The titanium content of the solid catalyst component was 2.7% by weight. (2) Storage of solid catalyst component: The solid catalyst component was placed in a brown eggplant flask and dried under vacuum (1 mmHg) at room temperature for 4 hours.
Next, a predetermined amount of the solid catalyst component was collected into a transparent glass tube in a dry box under an inert gas atmosphere by flowing nitrogen, and the tube was sealed to form an ampoule. Four of the glass ampoules were covered with aluminum foil, and the remaining four were stored indoors for a predetermined number of days. (3) Polymerization: A glass ampoule containing a solid catalyst component (8.4 mg as solid catalyst component) was placed in an autoclave with an internal volume of 1 and equipped with a stirrer, and then the air in the autoclave was replaced with nitrogen. 6.6 ml of an n-heptane solution containing 0.12 mmol of methyl p-tolylate and then 1.7 ml of an n-heptane solution containing 0.47 mmol of triethylaluminum were charged into the autoclave. After this, 600 ml of liquid propylene was introduced into the autoclave and the autoclave was shaken. After raising the temperature of the contents of the autoclave to 65℃, stirring was started to crush the glass ampoule, and the temperature was increased to 65℃.
Propylene was polymerized for 1 hour. After the polymerization reaction was completed, unreacted propylene was released, glass fragments were removed, and the resulting polypropylene was dried under reduced pressure at 50°C for 20 hours. The polymerization results are shown in Table 1.

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Claims (1)

[Claims] 1 α-olefin polymerization characterized in that a solid catalyst component for α-olefin polymerization containing magnesium, titanium, halogen, and an electron donor as essential constituents is stored in an inert gas atmosphere in a state where light is blocked. Storage method of solid catalyst components for use.