SU549087A3 - Method for producing polyimine type aluminum compounds - Google Patents

Description

one

This invention relates to a process for the preparation of polyimine-type aluminum compounds which can be used for the polymerization of unsaturated compounds.

A known method for producing aluminum compounds of the polyimine type, containing holoid or hydrogen atoms, is bound to the aluminum atom 1.

The compounds, when used as components of catalytic systems in conjunction with transition metal derivatives in the polymerization of conjugated diene compounds, promote polymerization to a higher degree than with other catalytic systems, while the side effects are eliminated. cyclization of polymer chains. This makes it possible to obtain a polymer with less consumption of derivatives of transition metals.

The aim of the invention is to improve the catalytic properties of aluminum compounds of the polyimine type in polymerization reactions.

Aluminum compounds according to the proposed method obsh, her formula

AU (NR) ftHiIj

wherein R is a radical of an aliphatic, aromatic, or cycloaliphatic hydrocarbon;

H is a hydride hydrogen atom;

Y is a halogen atom;

K is between 2 and 50, the ratio

, (i + j),, a.

The proposed aluminum compounds are prepared by conducting a batch reaction with polyimine compounds of composition

- -AIX-NR - and (X-A1NR) (XYA1) y (NHR) y

where X and Y are the same or different and represent a hydrogen hydride atom and / or halogen atoms directly bonded to an aluminum atom;

ha - is an integer less than or equal to 10;

Y is an integer greater than 0;

R is a radical of an aliphatic, aromatic or cycloaliphatic hydrocarbon, and silk or alkaline earth metal allanates or complex compounds of aluminum hydride.

When starting materials are used, hydrogen evolution can occur and / or an alkali metal halide is released.

The reaction readily proceeds at temperatures of ~ 70 ° C, preferably at pressures equal to the vapor pressure of the solvent in which the reaction takes place, at the operating temperature.

Solvents belonging to the class of ethers can be used, for example, dimethyl ether, diethyl ether, methyl ethyl ether, cyclic ethers or mixtures thereof with hydrocarbons or only hydrocarbons. The resulting compounds are useful components of catalytic systems for the polymerization of compounds containing at least one olefinic unsaturation, together with a transition metal compound.

Example 1.26 mmol of lithium aluminine hydride in ether solution (1M) is added in 5 minutes to 176 mg. polyiminoalane atom (in terms of A1), dissolved in 300 ml of a mixture of ether and heptane (30% diethyl ether) at a ratio of C1A1 0.26, NA1 0.97, and the addition is carried out at 45 ° C and moving. Such conditions are maintained for 4 hours, after which the entire mixture is filtered through a sintered glass filter. All operations are carried out in an inert and anhydrous atmosphere.

The filtrate is distilled in vacuo to remove diethyl ether and heptane is added.

The solution according to the analysis has the composition

AliHi, 25No, 9Clo, i

Example 2 20 mmol of sodium aluminum hydride suspended in diethyl ether are added to 187 mmol of polyiminoalane (in terms of A1) dissolved in 300 ml of a mixture of ether and hexane (30% diethyl ether,) at a ratio of C1-A1 0, 26; N-A1: 0.97, and the addition is carried out with movement and at a temperature of 45 ° C. The whole reaction mixture was kept in these fields for 4 hours, then filtered through sodium chloride.

The filtrate was distilled in vacuo to remove diethyl ether and heptane (and not hexane) was added. The solution, according to the analysis, has the following composition; mol / l:

A1 0.724; N 0.602; H 0.864; C1 0.85.

Example 3. 25 mmol of sodium hydride are added with stirring and a temperature of 45 ° C to 180 mg-atom of polyimipoalane (calculated as A1) dissolved in 300 ml of a mixture of diethyl ether and heptane, at a ratio of C1: A1 0.25, N: A1 0.86.

The whole reaction mixture was kept under the above conditions for 4 hours, after which it was cooled, filtered through a sintered glass filter.

The filtrate is distilled in vacuo to remove diethyl ether and heptane is added. The solution according to the analysis has the following composition, mol / l: A1 0.95; N 0.84; C1 0.10; H 1.10, which corresponds to

AliNo.seHi.ieClo ,.

Claims (4)

1. A method of producing aluminum compounds of the polyimine type, characterized in that, in order to increase their catalytic activity in the polymerization process, the composition of the aluminum compounds of the polyimine type is reacted - -A X-NR- - “and (X-AlNR) (XYAl) K (NHR) y, where X and Y are the same or different and represent a hydrogen atom and / or a halogen atom directly bonded to an aluminum atom; integer; , integer; R is an aliphatic, aromatic, cycloaliphatic radical, and alkali or alkaline earth metal alanates or complex compounds of aluminum hydride. 2. A method according to claim 1, characterized in that the reaction is carried out at a temperature of from 0 to 70 ° C. 3. Method according to c. 1., - is different from the fact that the reaction is carried out in the presence of ethers, hydrocarbons or their mixtures. 4. A method according to claim 1, characterized in that the reaction is carried out at a pressure equal to the vapor pressure of the solvent at the operating temperature. Sources of information taken into account in the examination 1. The patent of France No. 2075698, cl. COBd 1/00, 08.10.71 (prototype).