Components and catalysts for the polymerization of olefins

<td> +</td><td>(12) LETTERS (19) NO (id 178153 row B (5i) Int Cl⁶ C 08 F 4/654, 10/00</td>

NORWAY

The Board of Industrial Law Protection

<td>(21) Application no (22) Starting day (24) Race day (41) Alm. avail. (44) Explanation date</td><td>911238 (86) Int. Entering day and 26.03.91 application number 26.03.91 (85) Continuation Day 01.10.91 (30) Priority 30.03.90, IT, 19891/90 10/23/95</td>

<td>(71) Patent applicant (72) Inventor</td><td>Himont Inc, PO Box 15439, Wilmington, DE 19850-5439, US Enrico Albizzati, Arona, IT Giampiero Morini, Voghera (Pavia), IT Umberto Giannini, Milan, IT Luisa Barino, Novara, IT Raimondo Scordamaglia, Milan, IT Pier Camillo Barbe ', Ferrara, IT Luciano Noristi, Ferrara, IT</td>

<td>(74) Agent</td><td>Tandbergs Patentkontor AS, Oslo</td>

<td>(54) Designation</td><td>Catalysts for polymerization of olefins</td>

(56) Published publications GB 966025, US 4397763

<td>(57) Summary</td><td>Catalyst for polymerization of olefins, comprising the reaction product of (a) an Al-alkyl compound, (b) an ether containing two or more ether groups and at least one heteroatom selected from the group consisting of N, P, S, Si, non-ether-O and halogen atoms, or at least one double bond, or both at least one heteroatom and at least one double bond, and (c) a solid catalyst component comprising an magnesium dihalide in active form; on which is deposited a titanium halide or alkoxy halide and an electron donor compound, of which at least 70 mole% can be extracted from the solid with Al triethyl, and wherein the solid catalyst component, after extraction, has a surface area greater than 20 m²/ G. A more detailed description of particularly useful catalyst components according to paragraph (c) is given.</td>

The present invention relates to catalysts for polymerization of olefins. The catalysts are especially used in the polymerization of CH₂= CHR olefins, wherein R is a C 1 -C 6 alkyl radical, an aryl radical, preferably phenyl, or a hydrogen atom.

Catalysts comprising titanium compounds carried on magnesium halides in active form are well known in the art. Catalysts are described e.g. in US 4,278,718. Although these have high activity both in polymerization of ethylene and α-olefins, such as propylene, they do not have sufficient stereospecificity. This is enhanced by the addition of an electron donor compound to the solid component comprising the titanium compound (US 4,554,713).

Further improvements have been achieved using both an electron donor compound added to the solid component (internal donor) and one added to the Al-alkyl compound (external donor; US 4,107,414).

High performance, expressed as both activity and stereospecificity, is achieved with the catalysts described in European Patent No. 0045977. The solid component of the catalysts comprises an active magnesium halide on which a titanium halide (TiCl₄) and an electron donor compound selected from particular groups of carboxylic acid esters, of which representative examples are the phthalates. The cocatalyst used is an Al-alkyl compound added to a silicon compound containing at least one Si-OR bond (R = hydrocarbyl radical).

US 4,522,930 discloses catalysts wherein the solid catalyst component is characterized in that it contains an electron donor compound, of which at least 70 mole% can be extracted with Al-triethyl under standard extraction conditions and after extraction has a surface area of ​​at least 20 m²/ G.

These catalysts comprise, as a cocatalyst, an Al trialkyl compound to which is added an electron donor compound which does not undergo complex-forming reactions with Al triethyl which can be detected by potentiometric titration under special reaction conditions. Examples of said electron donor compounds are silicon compounds having Si-OR bonds where R is a hydrocarbyl radical;

2,2,6,6-tetramethylpiperidine, 2,2,5,5-tetramethylpyrolidine, Al-diethyl-2,2,6,6-tetramethylpiperidine and Al-dichloromonophenoxy.

In published European patent applications 0361494 and 0362705, ethers are disclosed which have special reaction and structural properties and are suitable for the preparation of catalysts and catalyst components for polymerization of the aforementioned olefins.

Now, a new group of ethers has unexpectedly been found useful in the preparation of highly active and stereospecific catalysts and catalyst components for polymerizing these olefins.

Thus, with the present invention, there is provided a catalyst for polymerization of olefins, comprising the reaction product of:

a) an Al-alkyl compound,

b) an ether containing two or more ether groups, and

c) a solid catalyst component comprising an magnesium dihalide in active form to which is deposited a titanium halide or alkoxy halide and an electron donor compound, of which at least 70 mol% can be extracted from the solid with Al triethyl, and wherein the solid catalyst component, after extraction , has a surface area greater than 20 m²/ G.

The catalyst is characterized in that the ether (b) contains at least one heteroatom selected from N, P, S, Si, non-ether-0 and halogen atoms, or at least one double bond, or both at least one heteroatom and at least one double bond, provided that the ether is not an ether-alcohol compound.

In fact, the ethers used in the invention, together with Al-alkyl compounds and in combination with solid catalyst components having properties as described in US 4,522,930, form highly active and stereospecific catalysts. The ethers used in the invention have a special structure and, when present in solid catalyst components comprising a titanium halide or alkoxy halide supported on an magnesium halide in active form, can also provide highly active and stereospecific catalysts even without the use of electron donor compounds added to the Al-alkyl compound.

The ethers used in the invention contain two or more ether groups and at least one heteroatom selected from N, S, P, Si, non-ether-O and halogen atoms, or at least one double bond, or contain both at least one heteroatom as defined above and at least one double bond.

Representative ethers which are particularly useful when present in the solid catalyst component to form highly active and stereospecific catalysts, even without the use of additional electron donor compounds added to the Al-alkyl compound, are 1,3-dieters of the formula

X

IN

R_x - 0 - CH₂ - C-CH₂ - 0-R_z

Y where

R_x and R₂ are the same or different and are hydrocarbon radicals having 1-6 carbon atoms, optionally unsaturated and / or containing halogen atoms;

X is a hydrocarbon radical having 1-18 carbon atoms containing at least one heteroatom not directly bonded to the central carbon atom (in 2-position) of the 1,3-diethyl molecules, wherein the heteroatom is selected from N, S, P, Si, non-ether-0 and halogen atoms, or X is a halogen atom or a heteroatom-containing group in which one heteroatom is bonded directly to the central carbon atom of the 1,3-diethler of the formula above and selected from -NR'R, -SO₂R ', -SOR', -OP (OR ') (OR), -OP (O) (OR') (OR), -Si (R'R)_o(OR ')_n and -OSi (R'R) '(OR')_n, wherein R ', R, R' are hydrocarbon radicals, optionally unsaturated, having 1 to 18 carbon atoms, and R 'and R together may, for NR'R, also form a cyclic structure, and R' or R, or both, can for Si (R'R)_n(0R ')_n and -OSi (R'R)_m(0R ')_n also be hydrogen or halogen, m and n are numbers from 0 to 3, and m + n = 3; or X is an R^IVhydrocarbyl group having 1-18 carbon atoms containing at least one double bond and optionally containing one or more heteroatoms selected from N, S, P and Si, non-ether-O and halogen atoms;

Y is X when X is halogen, Si (R'R)_m(0R ')_n or R^IVradical, or Y is a hydrogen or an R^v-hydrocarbon radical containing 1-18 carbon atoms;

X and Y may also be bonded together to form an R^WEhydrocarbon radical having 1-18 carbon atoms and optionally containing heteroatoms selected from halogen, non-ether-0 and N, S, P and Si, with R^WE optionally also bonded to the central carbon atom via a double bond.

Representative examples of 1,3 diets containing halogen atoms are:

2-Isopropyl-2-trifluoromethyl-1,3-dimethoxypropane, 2-isopropyl-2-trifluoromethyl-1,3-diethoxypropane, 2-isopropyl-2-trifluoromethyl-1,3-dibutoxypropane, 2-isobutyl-2- trifluoromethyl-1,3-dimethoxypropane;

2- (2-chloro-n-propyl) -2-n-propyl-1,3-dimethoxypropane,

2- (chloroneopentyl) -2-methyl-1,3-dimethoxypropane,

2- (4-chloro-3,3-dimethylbutyl) -2-ethyl-l, 3-dimethoxypropane;

2- (p-chloromethylphenyl) -2-isobutyl-1,3-dimethoxypropane,

2- (p-chloromethylphenyl) -2-isobutyl-l, 3-diethoxypropane,

2- (4-klorsykloheksyl) -2-isobutyl-l, 3-dimethoxypropane;

2- (4-chlorocyclohexyl) -2-isobutyl-1,3-diethoxypropane,

2- (4-chlorocyclohexyl) -2-isobutyl-1,3-dibutoxypropane,

2,2-bis- (4-chlorocyclohexyl) -1,3-dimethoxypropane,

2- (2-chloromethyl-2-propenyl) -2-isobutyl-l, 3-dimethoxypropane;

- (bromineopentyl) -2-methyl-1,3-dimethoxypropane,

2- (bromineopentyl) -2-ethyl-1,3-dimethoxypropane,

2- (jodneopentyl) -2-ethyl-l, 3-dimethoxypropane;

2- (chloromethyl) -2-isobutyl-l, 3-dimethoxypropane;

- (chloromethyl) -2-isobutyl-1,3-diethoxypropane,

2- (3-chloro-2-methyl-2-propenyl) -2-propyl-1,3-dimethoxypropane,

2,2-bis- (4-chlorocyclohexylmethyl) -1,3-dimethoxypropane,

1,1-bis- (methoxymethyl) -4-chloro-decahydronaphthalene,

1,1-bis- (methoxymethyl) -6-chloro-tetrahydronaphthalene,

1,1-bis- (methoxymethyl) -2-isopropyl-5-chlorocyclohexane,

2,2-bis (methoxymethyl) -5-chloro-bicyclo- [2.2.1] -heptane,

2-chloro-2-ethyl-l, 3-dimethoxypropane;

2-chloro-2-ethyl-l, 3-diethoxypropane,

2-bromo-2-ethyl-1,3-dimethoxypropane;

2-chloro-2-n-propyl-l, 3-dimethoxypropane;

2-chloro-2-n-propyl-l, 3-diethoxypropane,

2-chloro-2-n-propyl-3-dibutoksypropan,

2-bromo-2-n-propyl-l, 3-dimethoxypropane;

2-bromo-2-n-propyl-l, 3-diethoxypropane,

2-chloro-2-n-butyl-l, 3-dimethoxypropane;

2-chloro-2-i-butbutyl-1,3-dimethoxypropane,

2-chloro-2-isobutyl-l, 3-diethoxypropane,

2-chloro-2-isoamyl-l, 3-dimethoxypropane;

2-chloro-2-isoamyl-l, 3-diethoxypropane,

2-chloro-2-neopentyl-l, 3-dimethoxypropane;

2-chloro-2-cyclohexyl-1,3-dimethoxypropane;

2-chloro-2-phenyl-l, 3-dimethoxypropane;

2,2-dichloro-1,3-dimethoxypropane,

2-chloro-2-phenyl-1,3-diethoxypropane,

2-bromo-2-phenyl-1,3-dimethoxypropane,

2-chloro-2-trifluoromethyl-1,3-dimethoxypropane;

2-chloro-2- (chloroneopentyl) -1,3-dimethoxypropane,

2-chloro-2- (4-klorsykloheksyl) -1,3-dimethoxypropane;

2-chloro-2-chloromethyl-l, 3-dimethoxypropane;

2-chloro-2- (p-chlorophenyl) -1,3-dimethoxypropane.

Examples representative of 1,3-diets containing heteroatoms different from halogens are:

2-trimethylsilyl-1,3-dimethoxypropane;

2- (2-trimethylsilylethyl) -1,3-dimethoxypropane;

2-trimethylsilyl-2-ety1-1,3-dimethoxypropane;

1- methyl-2-trimethylsilyl-2-ethyl-1,3-dimethoxypropane,

2-triphenylsilyl-1,3-dimethoxypropane,

2,2-bis- (p-trimethylsilyl-phenyl) -1,3-dimethoxypropane,

2- (4- [1-silolanyl] -butyl) -2-ethyl-1,3-dimethoxypropane,

2,2-bis- (trimethylsilylmethyl) -1,3-dimethoxypropane,

2- (4-N, N-diisobutylaminobutyl) -2-ethyl-1,3-dimethoxypropane,

2- (1-piperidyl) -2-propyl-l, 3-dimethoxypropane;

2- (1-piperidyl-2-isopropyl-1,3-dimethoxypropane,

2- (1-piperidyl) -2-n-isobutyl-l, 3-dimethoxypropane;

2- (1-piperidyl) -2-n-propyl-1,3-diethoxypropane,

2- (1-piperidyl) -2-n-propyl-1,3-dibutoxypropane,

2- (2,6-Dimethyl-l-piperidyl) -2-n-propyl-l, 3-dimethoxypropane;

2- (4-N, N-bis- [trimethylsilyl] -aminobutyl) -2-propyl-1,3-dimethoxypropane,

2-trimethylsilyloxy-2-n-propyl-l, 3-dimethoxypropane;

2-trimethylsilyloxy-2-n-propyl-l, 3-diethoxypropane,

2-trimethylsilyloxy-2-n-propyl-3-dibutoksypropan,

2-trimethylsilyloxy-2-isopropyl-l, 3-dimethoxypropane;

2-trimethylsilyloxy-2-isopropyl-l, 3-diethoxypropane,

2-trimethylsilyloxy-2-isobutyl-1,3-dimethoxypropane;

2-trimethylsilyloxy-2-isobutyl-l, 3-diethoxypropane,

2-trimethylsilyloxy-2-isoamyl-l, 3-dimethoxypropane;

2-trimethylsilyloxy-2-isoamyl-l, 3-diethoxypropane,

2-benzoyloxy-2-n-propy1-1,3-dimethoxypropane;

2-benzoyloxy-2-n-propyl-1,3-dimethoxypropane, 2-benzoyloxy-2-isobutyl-1,3-dimethoxypropane, 2-trimethylsilyl-2-n-propyl-1,3-dimethoxypropane,

2-pivaloxy-2-n-propyl-1,3-dimethoxypropane,

2-t-butylmercapto-2-ethyl-l, 3-dimethoxypropane;

2,2-bis- (p-diphenylphosphine phenyl) -1,3-dimethoxypropane,

2,2-bis- (p-pivaloxyphenyl) -1,3-dimethoxypropane,

2- (3-N, N-diphenylaminopropyl) -2-n-propyl-1,3-dimethoxypropane,

2-ethyl-2-methoxysulfonyl-l, 3-dimethoxypropane;

2-isopropyl-2-ethylsulfonyl-1,3-dimethoxypropane;

1,1-bis- (methoxymethyl) -1-ethyl-diphenylphosphite,

1,1-bis- (methoxymethyl) -1-ethyl-diphenylphosphate.

Examples representative of 1-3 ethers containing unsaturation are:

2- (1-ethyl-propylidenyl) -1,3-dimethoxypropane,

2- (1-ethyl-isobutylidenyl) -1,3-dimethoxypropane,

2- (1-phenyl-isobutylidenyl) -1,3-dimethoxypropane,

2- (1-propyl-isoamylidenyl) -1,3-dimethoxypropane,

2- (1-propyl-butylidenyl) -1,3-dimethoxypropane;

2- (alpha-phenyl-benzylidenyl) -1,3-dimethoxypropane;

2-isoamylidenyl-1,3-dimethoxypropane;

2- (2-norbornylidenyl) -1,3-dimethoxypropane,

2- (1-isoamyl-isoamylidenyl) -1,3-dimethoxypropane;

2-isobutyl-2- (3,3-dimethylallyl) -1,3-dimethoxypropane, 2-2-bis- (3,3-dimethylallyl) -1,3-dimethoxypropane,

2-i-butbutyl-2- (2-methyl-2-butenyl) -1,3-dimethoxypropane,

2-isopropyl-2- (5-norbornene-2-yl) -1,3-dimethoxypropane;

2-isoamyl-2-crotyl-1,3-dimethoxypropane,

cyclopentyl idenyl -1,3-dimethoxypropane,

2-isopropyl-2-cinnamyl-l, 3-dimethoxypropane;

2-i-butbutyl-2- (3-methyl-2-pentenyl) -1,3-dimethoxypropane,

2,2-bis- (3-cyclohexenylmethyl) -1,3-dimethoxypropane,

2.2-bis- (methoxymethyl) norbornene,

2,3-bis (methoxymethyl) norbornene,

2-isobutyl-2- (1-methylpropenyl) -1,3-dimethoxypropane, 1-allyl-2,2-dimethyl-1,3-dimethoxypropane,

2.2-di in sobutyl-1-methoxy-3-allyloxypropane,

2- (1-propyl-isoamylidenyl) -l-methoxy-3-allyloksypropan,

1- (methylpropenyl) -2,2-dimethyl-1,3-dimethoxypropane,

2- (1-methyl-ethylidenyl) -1,3-dimethoxypropane, 1- 2- (1-isopropyl-isobutylidenyl) -1,3-dimethoxypropane,

2- (1-t-butyl-isobutylidenyl) -1,3-dimethoxypropane,

2- (Dicyclohexyl-methylidenyl) -1,3-dimethoxypropane,

2- (1l sopropyl-1-soxylidenyl) -1,3-dimethoxypropane,

2- (1-cyclohexyl-isobutylidenyl) -1,3-dimethoxypropane, 2- (1-ethyl-neopentylidenyl) -1,3-dimethoxypropane,

2- (1-cyclohexyl-n-propylidenyl) -1,3-dimethoxypropane,

2- (α-cyclohexyl-benzylidenyl) -1,3-dimethoxypropane,

2- (1-methyl-neopentylidenyl) -1,3-dimethoxypropane.

Examples representative of 1,3-dieters containing 20 heteroatoms and unsaturations are:

2-isopropyl-2- (6-chloro-5,5-dimethyl-2-hexenyl) -1,3-dimethoxypropane;

2-isopropyl-2- (3-chloroallyl) -1,3-dimethoxypropane;

2-isobutyl-2- (5-p-trifluoromethylphenyl) -2-pentenyl-1,3-dimethocyclopropane,

2-methyl-2- (3-chloro-2,2-dimetylpropylidenyl) -1,3-dimethoxypropane;

2 isopropy1-2- (4-diisobutylamino-2-butenyl) -1,3-dimethoxypropane;

2-allyl-2-pyridyl-l, 3-dimethoxypropane;

2-isopropyl-2- (4-trimetylsylyl-2-butenyl) -1,3-dimethoxypropane.

Other examples of usable ethers are:

1-chloromethyl-l, 2,2-trimethyl-l, 2-dimethoxyethane,

2,2-diisobutyl-1-methoxy-3- (2-chloroethoxy) -propane, 1- (3-chloro-2-methyl-2-propenyl) -2,2-diisobutyl-1,3-dimethoxypropane,

1- (3-chloropropyl) -2,2-diisobutyl-1,3-dimethoxypropane, 1-chloro-2,2-diisopropyl-1,3-dimethoxypropane,

1,3-dichloro-2-isobutyl-1,3-dimethoxypropane, 1-methyl-2-chloro-2-isopropyl-1,3-dimethoxypropane,

1-chloro-2,2-diisopropyl-1,3-dimethoxypropane,

2-chloro-2-ethyl-1-methoxy-3- (2-chloroethoxy) -propane, 2-chloro-2-n-propyl-1-methoxy-3- (2-chloroethoxy) -propane,

2-chloro-2-phenyl-1-methoxy-3- (2-chloroethoxy) -propane, 2-chloro-2-ethyl-1,3-bis- (2-chloroethoxy) -propane, 2-chloro-2- n-propyl-1,3-bis- (2-chloroethoxy) -propane, 2-chloro-2-phenyl-1,3-bis- (2-chloroethoxy) -propane,

1,3-dichloro-2-isobutyl-1,3-diethoxypropane,

1,3-dichloro-2-isobutyl-1,3-dibutoxypropane,

1,4-dimethoxy-cis-2-butene,

1- allyl-1,2,2-trimethyl-1,2-dimethoxyethane,

2,3-bis- (3-cyclohexenyl) -1,4-dimethoxybutane,

2,3-bis- (3-cyclohexenyl) -1,4-diethoxybutane.

The compounds used in the invention are prepared according to methods known in the literature. For example, 2-chloro-2-alkyl-1,3-dialkoxypropanes can be synthesized according to the procedure described in Chemical Abstracts, volume 65 (1966) 3727c.

Ethers containing unsaturations can be synthesized by the Wittig reaction based on the dialkoxy ketones and corresponding phosphorylides (obtained by the reaction of triphenylphosphine and alkyl halides).

1,3-dieters containing halogens on the hydrocarbon substituents in the 2-position can be synthesized by reacting 1,3-dieters with unsaturations in the hydrocarbon substituents in

2 position, and the corresponding hydrogen halides.

Ethers containing heteroatoms other than halogen can also be prepared according to known methods described in the literature; eg. For example, the 2-alkyl-2- (trialkylsilyloxy) -1,3-dialkoxypropanes can be synthesized by reaction between the 2-hydroxyalkyl-1,3-dialkoxypropanes (obtained by reaction of a dialkoxyacetone and a Grignard) with the corresponding chlorotrialkylsilanes.

As already stated, the electron donor compounds can be used with Al-alkyl compounds to form, in combination with the catalyst components described in US 4,522,930, highly active and stereospecific catalysts.

The catalyst components disclosed in US 4,522,930 contain a titanium compound containing at least one Ti-halogen bond and an electron donor compound, of which at least 70 mol% is extractable with Al-triethyl under standard extraction conditions. After extraction, the solid has a surface area (BET) of at least 20 m²/ g and usually between 100 and 300 m^z/ G.

Electron donor compounds which can be used in the preparation of the catalyst components disclosed in US 4,522,930 include ethers, ketones, lactones, compounds containing N, P and / or S atoms and particular types of esters. In addition to the esters of US 4,522,930, the group of esters described in EP 0045977 may also be used.

Especially suitable are phthalic acid esters such as diisobutyl, dioctyl and diphenyl phthalate, benzyl butyl phthalate, malonic acid esters such as diisobutyl and diethyl malonate, alkyl and aryl pivalates, alkyl, cycloalkyl and aryl maleate, alkyl and aryl carbonate, diisobutyl and aryl carbonate, such as diis succinic esters such as mono- and diethyl succinate. Phthalic acid esters are preferred.

The preparation of catalyst components is carried out by various processes. The preparation methods set forth below may also be used for the preparation of catalyst components containing electron donor compounds different from the ethers used in the invention, such as those described in US 4,522,930, for example.

For example, the magnesium halide (used in anhydrous state containing less than 1% water), the titanium compound, and the ether compound are ground together under conditions where the magnesium halide is activated. The milled product is then treated one or more times with excess TiCl₄ at temperatures of 80 ° to 135 ° C, and then washed repeatedly with a hydrocarbon (hexane) until no chloride ions are in the wash.

According to another method, the anhydrous magnesium halide is pre-activated by known methods and then reacted with excess TiCl₄ containing the ether compound in solution. In this case, the operation also takes place at a temperature of 80 ° to 135^eC. Optionally, TiCl₄- repeated treatment and the solid washed with hexane or heptane to eliminate traces of unreacted TiCl₄.

According to another method, an MgCl₂* nROH adduct (especially in the form of spheroidal particles) where n is usually from 1 to 3 and ROH is ethanol, butanol, isobutanol, reacted with excess TiCl₄ containing the ether compound in solution. The temperature is usually from 80 to 120 ° C. After the reaction, the solid is reacted again with TiCl₄, and then separated and washed with a hydrocarbon until no chloride ions are present in the wash.

According to yet another method, magnesium alkoxides and alkoxy halides (the alkoxy halides can be prepared specifically according to US 4,220,554) are reacted with excess TiCl₄ containing the electron-donor compound in solution, by reaction under the same conditions already described.

According to another method, magnesium halide complexes with titanium alkoxides (MgCl₂"2Ti (OC₄H₉)₄The complex is a typical example) reacted in hydrocarbon solution with excess TiCl₄ containing the ether compound in solution; the solid product which is separated is reacted again with excess TiCl₄, and is then separated and washed with hexane. The reaction with TiCl₄ is carried out at a temperature of 80 to 120 ° C.

According to an alternative embodiment, MgCl₂-the titanium alkoxide complex reacted in hydrocarbon solution with methylhydropolysiloxane. The solid product is separated and reacted at 50 ° C with silicon tetrachloride containing the ether compound in solution. The resulting solid is then reacted with excess TiCl₄ at 80-120 ° C.

Finally, it is possible to react with the excess TiCl₄ containing the ether compound in solution, porous resins such as partially cross-linked styrene divinylbenzene resins in the form of spherical particles, or inorganic porous oxides such as silica and alumina impregnated with solutions of Mg compounds or complexes soluble in organic solvents.

Porous resins which can be used are described in EP 344 755. The reaction with TiCl₄ is performed at 0-120 ° C. After separation of the excess of T1C1₄, the reaction is repeated and the solid is then washed with a hydrocarbon solvent.

The molar ratio of MgCl₂ and the electron donor compound used in the above reactions is usually from 2: 1 to 12: 1.

The electron donor compound is usually bound to the magnesium halide in amounts from 5 to 20 mole%.

However, in the case of components supported on porous resins and inorganic oxides, the molar ratio of elephantron donor to magnesium is different, i.e., usually from 0.1 to 1.

The Mg / Ti ratio of the catalyst components is usually from 30: 1 to 4: 1. The ratio is different in components carried on porous resins or inorganic oxides, and is usually from 10: 1 to 2: 1.

Titanium compounds which can be used in the preparation of catalyst components are halides and alkoxy halides. Titanium tetrachloride is the preferred compound. Satisfactory results are also obtained with titanium trihalides, especially TiCl₃HR, TiCl₃ARA, and with alkoxy halides such as TiCl₃OR where R is a phenyl radical.

The preparations given above lead to the formation of magnesium halide in active form. The preparations which lead to the formation of magnesium halide in active form based on magnesium compounds different from magnesium halides are well known in the literature. Examples of the preparation of catalyst components which lead to the formation of magnesium halides in active form and can be used in the preparation of catalysts of the invention are described in the following US patents: 4,335,015, 4,547,476, 4,647,550, 4,393,182, 4,780,443. , 4 771 024.

The active form of magnesium halides in the catalyst components is probable by the fact that the X-ray diffraction spectrum of the catalyst component no longer shows the principal intensity reflection that appears in the spectrum of non-activated magnesium halides (having a surface area less than 3 m²/ g), and instead a halo with the maximum intensity shift relative to the position of the maximum intensity reflection appears, or the maximum intensity reflection is less intense, giving a half peak width at least 30% greater than that of the main intensity reflection appearing in the spectrum for it. non-activated magnesium halide.

The most active forms of magnesium halide are those where the X-ray spectrum of the solid catalyst component shows a halo.

Among the magnesium halides, the magnesium chloride is the preferred compound. For the most active forms of magnesium chloride, the X-ray spectrum of the catalyst component shows a halo instead of the reflection, which is located in the spectrum of the chloride at an interplanar distance of 2.56 Å.

Solid catalyst components, by reaction with Al-alkyl compounds, form catalysts which can be used in polymerization of CH₂= CHR olefins wherein R is hydrogen, or an alkyl radical of 1-6 carbon atoms, or an aryl, preferably a phenyl, or mixtures of said olefins and / or mixtures thereof with diolefins having at least one olefinic unsaturation in the α-position.

In the case of polymerization of CH₂= CHR olefins wherein R is hydrogen or an alkyl radical of 1-8 carbon atoms, or aryl, and especially when the olefin is propylene, the Al-alkyl compounds used are selected from Al-trialkyls such as Al-trimethyl, Al-triethyl, Al -triisobutyl, Al-tri-n-butyl and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other via O or N atoms, or SO₄- and SO₃-groups.

Examples of these compounds are:

(C₂H₅)₂A1-O-A1 (C₂H₅)₂ (C₂H₅)₂A1-N-A1 (C₂H_s)₂ c₆h₅ (C₂H₅)₂- A1-SO₄-A1 (C₂H₅)₂ ch₃

C₃(Al-O-)_nAl (CH₃)₂ ch₃ (Al-O-)_n where n is a number from 1 to 20.

It can also be used A1R₂OR 'compounds where R' is a C₆-C₁₂-aryl radical substituted at the 2 and / or 6 position with a C₁-C₆-alkyl radical which is linear or branched, and R is an alkyl radical of 1-8 carbon atoms, and A1-R₂H compounds where R is as defined above.

The Al-alkyl compound is used in such amounts that the Al / Ti ratio is usually from 1 to 1000.

In the case of polymerization of propylene and similar α-olefins, the trialkyl compounds may be used in admixture with Al-alkyl halides such as AlEt₂Cl and Al₂a₃Cl₃.

The above-mentioned Al-alkyl compounds are used when the ether compound is used as an external donor, ie it is added to the Al-alkyl compound. As already stated, the solid component in this case contains an electron donor compound having the properties set forth in US 4,522,930 and EP 0045977.

Polymerization of olefins is carried out according to known methods in liquid phase comprising the monomer or monomers, or a solution thereof, in an aliphatic or aromatic hydrocarbon solvent or in gas phase, or even by a combination of liquid phase and gas phase polymerization steps.

(Co) the polymerization temperature is usually from 0 ° C to 150 ° C; especially from 60 ° C to 100 ° C. The design takes place under atmospheric pressure or higher. The catalysts can be contacted in advance with small amounts of olefins (prepolymerization). Pre-polymerization improves both the catalyst performance and the morphology of the polymers. The prepolymerization is carried out by holding the catalyst in slurry in a hydrocarbon solvent (hexane, heptane, etc.) and it is polymerized at a temperature between room temperature and 60 ° C, giving polymer amounts usually from 0.5 to 3 times the catalyst weight. It can also be carried out in liquid propylene under the temperature conditions set forth above, thus producing polymer amounts which can reach 100 g / ml. g of catalyst component.

In the case of stereoregular polymerization of olefins, if an electron donor compound is added to the Al-alkyl, the ratio of Al-alkyl to electron-donor compound is usually from 5: 1 to 100: 1.

Example 1

1000 ml n-heptane, 5 mmol A1 (C₂H₅)₃, 30 mg of catalyst component and 1 mmol of 2- (2-chloro-n-propyl) -2-n-propyl-1,3-dimethoxypropane are introduced into a 2000 ml stainless steel autoclave equipped with anchor tubes under propylene flow at 25 ° C.

The autoclave is closed and after the pressure is brought to 1 atm, hydrogen overpressure of 0.2 atm is applied. The contents are then heated to 70 ° C and the total pressure is brought up to 7 atm. with propylene.

The polymerization is carried out for two hours while the monomer is fed continuously. The polymer thus obtained is filtered off. The polymer remaining in the filtrate is precipitated with methanol, dried in vacuo and taken into account in determining the total n-heptane extraction residue. A polymer yield equal to 8000 g of PP / g catalyst component is obtained and the polymer has an isotactic index of 92.

The catalyst component used was prepared by the following method.

225 ml of TiCl₄ is introduced at 0 ° C into a 500 ml reactor equipped with filtration partition. Within 15 minutes, 10.1 g (54 mmol) of microspheroidal adduct MgCl is added, with stirring.₂-2,1C₂H₅OH obtained by the method described in Example 1 of US 4,469,648.

After the addition is complete, bring the temperature to 40 ° C and introduce 9 mmoles of diisobutyl phthalate. The temperature is then brought to 100 ° C in one hour. The reaction is allowed to proceed for two hours, after which T1C1₄ is removed by filtration. Another 200 ml of TiCl₄ is introduced and the contents are allowed to react at 120 ° C for one hour, and then filtered and washed at 60 ° C with n-heptane until chloride ions are no longer present in the filtrate.

Example 2

By operating under the conditions of Example 1, but using 1 mmol of 2- (1-methyl-neopentylidene) -1,3-dimethoxypropane instead of 2- (2-chloro-n-propyl) -2-n-propyl-1 , 3-dimethoxypropane, obtains a polymer having an isotactic index of 95 and with a yield equal to 10,000 g PP / g catalyst component.

Example 3

By operating under the conditions of Example 1, but using 1 mmol of 2- (n-propyl-2-trimethylsilyloxy)

1,3-dimethoxypropane instead of 2- (2-chloro-n-propyl) -2-n-propyl

1.3-dimethoxypropane, a polymer is obtained having an isotactic index of 93.9 and with a yield equal to 4,300 g PP / g catalyst component.