JPS5930805A - Method for storing catalytic component for polymerizing alpha-olefin - Google Patents

Abstract

PURPOSE:To prevent the deterioration in the catalytic ability of the titled catalytic component, by storing the solid catalytic component for polymerizing an alpha-olefin consisting of magnesium, titanium, a halogen and an electron donor in an atmosphere of an inert gas under conditions of shielded light. CONSTITUTION:A solid catalytic component for polymerizing an alpha-olefin consisting of magnesium, titanium, a halogen and an electron donor as essential components is stored in an atmosphere of an inert gas, e.g. helium, under conditions of shielded light by sealing the components with the inert gas in a light- untransmissible vessel, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for storing solid catalyst components for alpha-olefin polymerization.

The solid catalyst component for α-olefin polymerization has four essential components: magnesium, titanium, halogen, and an electron donor.
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, which essentially consists of magnesium, titanium, halogen, and an electron donor. 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 is
The four essential components are magnesium, titanium, nitrogen, and an electron donor.

The solid catalyst component is described, for example, in Japanese Patent Application Laid-open Nos. 56-45909 and 56-554'05 filed by the same applicant.
No. 56-76411.

No. 56-76411, No. 57-18706, No. 57-8510, No. 57-25307, No. 57-83510.

It can be prepared by the method described in Japanese Patent Application No. 56-26102, or by the method of co-pulverizing magnesium halide, titanium halide, and an electron donor such as ester, ether, or amine. Can be done. These solid catalyst components are combined with organoaluminum compounds to produce ethylene, propylene, butene-1, hexene-1
Used as a polymerization catalyst for +octene-1.

Specific examples of inert gases include nitrogen and argon.

Examples include helium.

In the present invention, the solid catalyst component is stored in a light-blocking state, for example, in a glass container that does not substantially transmit light.
Store in plastic, ceramic, or metal containers. When using glass or plastic containers,
Either the outer wall must be coated with a black sealant, or the container itself must be painted 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 petrolatum, or as a dry powder. You can.

Next, Examples and Comparative Examples will be shown. 9 In the following, polymerization activity is the yield (fI) of polypropylene per hour of polymerization time per solid catalyst component 17, and H,1, is the amount of polypropylene produced in one polymerization reaction extracted with boiling n-hbutane for 24 hours. It is the weight percent of the solid polymer obtained by treatment relative to the polymer before treatment.

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 ml of toluene.
Then, 15 mmol of methyltriethoxysilane was added, and the mixture was reacted at 25°C for 0.5 hour while stirring, and then the temperature was raised to 60°C, and the reaction was continued for 1 hour.

After the reaction product mixture was cooled to -5°C, it was heated to n-
18 ml of diisoamyl ether containing 27 mmol of butylmagnesium chloride were added dropwise to the reaction mixture over a period of 0.5 hours. What is the temperature of the reaction system?

It was kept at -5°C. 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.

The obtained solid 4.9 Or was suspended in 25 ml of toluene, 150 mmol of titanium tetrachloride was added to this suspension, the temperature was raised to 90°C, and the hedron and titanium tetrachloride were mixed for 1 hour with stirring. brought into contact. At the same temperature, the titanium-containing solid was separated with P and washed with n-hebutane and then toluene.

4.10 r of the titanium-containing solid were suspended in 25 tnl of toluene, 6.5 mmoles of ethyl benzoate were added to this suspension and kept at 90°C for 1 hour with stirring.

The ester-treated solid was separated at the same temperature and washed with n-hebutane and then toluene.

The ester treated solid was suspended in 25 ml of toluene.

To this suspension was added 150 mmoles of titanium tetrachloride, and the ester-treated solid was brought into contact with the titanium tetrachloride at 90° C. for 1 hour with stirring. The obtained solid catalyst component was subjected to F separation at the same temperature and washed with n-hebutane.

The titanium content of the solid catalyst component was 2.7% by weight.

(2) Storage of solid catalyst component: The solid catalyst component was taken into a brown eggplant flask and dried under vacuum (1, nr) at room temperature for 4 hours.

Next, a predetermined amount of the solid catalyst component was taken out into a transparent glass tube in a dry box, and the cheap was melt-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 (8.47 ng as a solid catalyst component) was placed in an autoclave with an internal volume of 1 ton equipped with a stirrer, and then the air in the autoclave was replaced with nitrogen.

p-) 6.6 ml of n-heptane solution containing 0.12 mmol of methyl lylate + then 1.7 ml of n-heptane solution containing 0.47 mmol of triethylaluminum
1 was placed in an autoclave.

After this, 600 rttl of liquid propylene was introduced into the autoclave and the autoclave was shaken.

After heating the autoclave contents to 65°C.

Start stirring and crush the glass ampoule.

Propylene was polymerized for 1 hour at 65°C.

After the polymerization reaction is complete, unreacted propylene is released.

Remove the glass fragments and heat the resulting polypropylene to 50'C.
It was dried under reduced pressure for 20 hours.

The polymerization results are shown in Table 1.

Chapter 1 Table

Claims (1)

[Claims] α-olefin polymerization characterized by storing a solid catalyst component for α-olefin polymerization, which has four essential components of magnesium, titanium, halogen, and an electron donor, in an inert gas atmosphere and in a state where light is blocked. Storage method for solid catalyst components.