HU215539B - Process for producing magnesium-di(3-substituted-phenoxid) - Google Patents

Abstract

FIELD OF THE INVENTION The present invention relates to a magnesia (3-halo-phenoxy) form for the production of vagagic magnesium (3- (1-8 carbon atoms) alkyphenyl oxide), having a high magnesium (1-8 carbon atoms) alkyd oxide for 3-halogen or 3- 1 carbon atoms. -8-charcoal) is reacted with an alkyloxy-pellet in the pellet phase and the liberated alkane is removed from the reaction mixture by distillation. ŕ

Description

The present invention relates to a process for the preparation of magnesium di (3-substituted phenoxide), more particularly magnesium di (3-halophenoxide) or magnesium di (3- (C 1 -C 8) alkoxyphenoxide). These compounds can be used as starting materials for the preparation of a solid catalyst component and an olefin polymerization catalyst containing it on a magnesium halide support.

It is known from EP-A-19,330 that solid olefin polymerization catalyst components can be prepared by halogenation of magnesium alkoxides or phenoxides with titanium tetrahalide in the presence of a liquid halogenated hydrocarbon and treatment of the halogenated reaction product with a tetravalent titanium compound. Comparative studies in the cited patent have shown that a second contact with titanium halide is essential for obtaining a favorable solid catalyst component, both in terms of polymer yield and polymer isotacticity.

U.S. Patent No. 4535 069 for the polymerization of olefins a catalyst to produce a starting MgR'R discloses ^two compounds of formula, wherein R ¹ and R ² is, inter alia, an aryloxy group of formula. There is no reference in the specification to compounds containing substituted aryloxy groups.

Surprisingly, the present invention, which is the subject of application P 9007130, has found that careful selection of the appropriate type and position of the substituent in the phenoxy moiety of the starting magnesium compound can provide favorable polymer yields and isotacticity, even if the second titanium halide is omitted. Favorable results seemed to be obtained when the phenoxy moiety at the 3-position contains an alkoxy or halo substituent while the 2-alkoxy, 4-alkoxy, 3-alkyl and 3,5-dialkyl substituents did not give satisfactory results. . In addition to saving one step of the process for producing the solid catalyst component, the process discussed also has the advantage of reducing the amount of titanium halide waste stream, thereby favorably affecting its processing and recycling.

A further advantage of the solid catalyst component prepared by the above process is that it has a lower decomposition rate compared to the solid components prepared from the unsubstituted magnesium phenoxide starting material. The phenomenon of catalyst decomposition was discussed by L. Luciani, Angew. Makromol. Chemie 94, 63-89, 14 and 15 (1981)].

Accordingly, there is a need for the preparation of magnesium di (3-halophenoxide) and magnesium di [3- (C 1 -C 8) alkoxyphenoxide] as starting materials for a solid catalyst component.

It is a further object of the present invention to provide a process for the preparation of a starting material of improved solid morphology, more particularly of narrow size distribution. To accomplish this object, the present invention provides a novel process for the preparation of magnesium di (3-halophenoxide) and magnesium di (3- (C 1 -C 8) alkoxyphenoxide).

The present invention relates to a process for the preparation of magnesium di (3-halogen phenoxide) or magnesium di [3- (C 1 -C 8) alkoxyphenoxide], wherein the magnesium di (C 1 -C 8) alkoxide is 3-halogen or (C8-C8) alkoxyphenol in the liquid phase and the liberated alkanol is removed from the reaction mixture by distillation.

The novel process of the present invention is based on the principle of ligand exchange according to the following schematic scheme:

Mg (OAlk) ₂ + 2HOPh Mg (OPh) ₂ + 2HOAlk where

Ph is 3-halophenyl or 3- (C 1 -C 8) alkoxyphenyl, and

Alk is typically C 1 -C 8 alkyl.

Preferably, the liquid phase is a liquid hydrocarbon which may be azeotroped with the alkanol to be removed. Preferred hydrocarbons are benzene, xylene, toluene, cumene, ethylbenzene, isopar E and petroleum ether.

In a preferred embodiment of the process of the invention, the starting material used is magnesium diethoxide, the alkanol to be removed is ethanol. Other magnesium alkoxides that may be used are isopropoxides, n-butoxides, isobutoxide and amyloxides.

The ligand exchange is carried out with stirring for a period of from 0.2 to 40 hours, usually from 10 to 20 hours. It is not necessary to use a starting magnesium compound of controlled morphology. Mg (OPh) _{2 of} controlled morphology (spherical) and narrow size distribution can be prepared by gradually and in controlled addition of the starting material Mg (OAlk.) ₂ with phenol and a suitable solvent, preferably an aromatic solvent such as toluene, ethylbenzene or xylene under reflux. One of the surprising features of the present invention is the production of Mg (OPh) _{2 of} controlled morphology.

The narrow particle size distribution of the monosubstituted magnesium phenoxide thus obtained is maintained during the synthesis of the solid catalyst component obtained therefrom. However, the improved morphology of the solid catalyst component is transferred to the olefin polymer morphology according to the well-known replication principle (see L. Luciani, supra). Improved polymer morphology is important to eliminate very fine powdery polymer particles and to increase reactor loading during the olefin polymerization process.

The catalysts prepared with the starting material according to the process of the invention are suitable for the polymerization of alkene, preferably 1-alkene such as butylene or more preferably propylene. The polymerization can be carried out by any conventional method, such as gas phase polymerization or slurry polymerization, using a liquid monomer or an inert hydrocarbon diluent as a liquid medium.

HU 215 539 Β

The invention is illustrated by the following examples.

a) A reactor equipped with a propeller stirrer and a Dean and Stark apparatus was charged with 280 g of 100-140 petroleum ether and 25.6 g (206.2 mmol) of 3-methoxyphenol. The mixture was heated to 80 ° C and 11.5 g (100.5 mmol) of Mg (OEt) ₂ was added, causing an exothermic reaction. The mixture is heated to reflux and the ethanol / petroleum ether mixture is distilled until ethanol is no longer present in the distillate. The total weight of the distillate was 108 g [= 1.07 g / mmol Mg (OEt) ₂ µl. After cooling, the solid was separated by filtration from the mother liquor, washed twice with petroleum ether and dried under flowing nitrogen.

Analysis (GLC and volumetric) shows a 2.05 / 1 ratio of 3-methoxyphenol / Mg, residual ethoxide is negligible or absent (below GLC detection limit).

b) A 500 cm ³ reactor was equipped with an anchor stirrer and Dean and Stark equipment, filled with 400 cm ^{3 of} toluene or ethyl benzene and 27 cm ³ (250 mmol) of 3-methoxyphenol. Stirring was started and the mixture was heated to reflux and distillation started. 11.44 g (100 mmol) of Mg (OEt) ₂ were then added in five portions of 2.3 g. Further details are added after the first addition only when the initial concentration of ethanol in the distillate is reduced by 90%. The total volume of the reaction mixture is kept constant by the addition of toluene. After the final addition, the distillation is continued until ethanol is no longer detectable in the distillate. The total weight of the distillate was 1085 g [= 10.84 g / mmol Mg (OEt) ₂ ]. The mixture was cooled to 80 ° C, the stirring was stopped, and after the solid had settled, the mother liquor was decanted. The product was washed four times (200 cm ³ at 80 ° C) with isooctane and dried under a stream of nitrogen (25 ° C). Scanning electron microscopy showed spherical particles to form.

The following examples illustrate the suitability of the compounds of the present invention for the preparation of an olefin polymerization catalyst. In the comparative examples, the substituted 3-substituted magnesium diphenoxide uses the 2-substituted and 4-substituted derivatives, respectively.

A) 6.76 g (25 mmol) of magnesium di (3-methoxyphenoxide) at 20 ° C in 13.72 cm ³ (125 mmol) of titanium tetrachloride, 0.63 cm ³ (4.4 mmol) of ethyl benzoate. and 61.28 cm ^{3 of} monochlorobenzene. The stirred mixture was heated to 100 ° C for 20 minutes and maintained at this temperature for 1 hour. The liquid phase was removed by high temperature filtration and the resulting solid catalyst component was washed six times with 75 cm ³ portions of iso-octane at 30-36 ° C. The solid catalyst component (Component A) contains magnesium and chlorine in a ratio of at least 1: 1.75 atoms.

B) The whole of Compound A obtained in Example A is suspended in 13.72 cm ³ (125 mmol) of titanium tetrachloride and 61.28 cm ^{3 of} monochlorobenzene at 100 ° C and the suspension is kept at this temperature for 0.5 hour. agitated. The solid was separated from the reaction mixture and washed six times with isooctane to give

Component B) is obtained.

C) (Comparative example)

Example A except that magnesium di (2-methoxyphenoxide) was used instead of magnesium di (3-methoxyphenoxide). Magnesium di (2-methoxyphenoxide) is prepared by reacting magnesium diethoxide with 2-methoxyphenol according to the procedure described in Example b). The solid thus obtained was obtained

This is called component C).

D) (Comparative example)

The procedure of Example A was followed except that magnesium di (4-methoxyphenoxide) was used instead of magnesium di (3-methoxyphenoxide). Magnesium di (4-methoxyphenoxide) is prepared by reacting magnesium diethoxide with 4-methoxyphenol according to the procedure described in Example b). The solid thus obtained was obtained

This is called component D).

E) Propylene is polymerized by a liquid medium process under the following conditions:

At a temperature of 700 ° C for 1 hour, a molar ratio of TEA / Ti of 80: 1, a molar ratio of DEAC / Ti of 20: 1, a ratio of TEA / PEEB of 1.8: 1, and a hydrogen concentration of 1-1.5% by volume. (TEA = triethylaluminum, DEAC = diethylaluminum chloride, PEEB = ethyl p-ethoxybenzoate).

The table shows the density (BD), yield and xylene soluble content (XS) of the polymers obtained in the polymerization experiments using components A, B, C and D.

component polypropylene mining Kg / g XS crowd% BD g / cm ³ THE) 41.5 3.2 0.39 B) 50.0 3.6 0.40 C) * 6.2 7.4 0.29 D) * 22.4 5.5 0.30

* = Comparative example

Claims (2)

PATIENT INDIVIDUAL POINTS A process for the preparation of magnesium di (3-halophenoxide) or magnesium di [3- (1-8C) alkoxyphenoxide], characterized in that magnesium di (C1-C8) alkoxide is 3-halogen or 3 C 1-8 alkoxyphenol is reacted in a liquid phase at a molar ratio of greater than 1: 1 and the liberated alkanol is removed from the reaction mixture by distillation. Process according to claim 1, characterized in that magnesium dioxide is used as the magnesium di (1-8C) alkoxide.