CS196270B2 - Catalyst for olefins polymerisation - Google Patents

Abstract

The invention relates to a catalyst for polymerization alkyl aluminum-containing monomers the compound and a brown solid mixture comprising Titanium tetrachloride. The object of the invention are mixtures of an organoaluminum compound and new The brown solid, which is porous, has a large surface and contains titanium β-chloride a a small amount of organic electron donor; are highly active and can be used for polymerization of α-olefins, especially propylene, into crystalline polymer products under normal conditions conditions solid, with high yields. Secondary low-molecular and especially amorphous polymeric (soluble) products are formed in small quantities.

Description

The present invention relates to a catalyst for the polymerization of monomers comprising an alkyl-aluminum compound and a brown solid mixture comprising β-titanium tetrachloride. The present invention provides mixtures of an organoaluminum compound and a new brown solid which is porous, has a large surface area and contains β-titanium chloride and a small amount of organic electron donor; they are highly active and can be used for the polymerization of α-olefins, in particular propylene, to crystalline polymer products solid under normal conditions, with high yields. Low-molecular and especially amorphous polymer (soluble) by-products are formed in small amounts.

In accordance with the invention, it has been found that a novel porous brown material with a high surface area, containing a β-crystalline form of titanium tetrachloride and a minor amount of organic electron donor such as ether, when used together with an organoaluminium compound for example, propylene. This brown solid, when used in admixture with an organoaluminium compound, in particular dihydrocarbylaluminum chloride, is particularly effective for propylene polymerization, since these mixtures exhibit exceptionally high polymerization rates and high catalyst yields, and compared to commercial activated titanium chloride with alumina. cause the formation of equal or lower amounts of soluble fractions (low molecular weight and especially amorphous polymeric components). The catalyst mixtures according to the invention can be further modified with additives which are able to reduce the soluble fraction to a substantially lower level without substantially affecting the yield relative to the catalyst. In addition, these catalyst mixtures, modified or unmodified, are sensitive to hydrogen used as a chain transfer agent to control the molecular weight of the polymer product, and can be used in slurry, block, or vapor phase polymerization.

Catalytic mixtures used for the polymerization of or-olefins, in particular propylene. are assessed from at least two aspects: in terms of their activity and yield relative to the catalyst, and their ability to form a highly crystalline polymer product with a minimum of low-molecular-weight and in particular amorphous polymer products. Many different factors influence the increase in activity and yield and the decrease in soluble fractions. One of them is the crystalline form of titanium tetrachloride in the organoaluminium compound titanium tetrachloride catalyst mixtures.

Four crystalline modifications are known

19B270

S titanium tetrachloride: a, β, γ and δ a in literature. the bending patterns measured by the powder method for at least the first three modifications are detailed. In the commercial polymerization of propylene, purple crystalline modifications, particularly the χ-form, were preferred, while the brown O-form was steadily rejected due to its activity and especially the high production of soluble fractions. However, U.S. Pat. No. 3,424,774 claims its use for cyclotrimerization of conjugated diolefinic substances.

Recently, South African Patent No. 721245 described a porous titanium tetrachloride with a large surface area based on violet titanium tetrachloride. When mixed with organoaluminium compounds, the catalyst is extremely active and produces high yields of polypropylene that are not transported by substantially increasing the soluble fraction,

U.S. Pat. No. 3,769,233 discloses a process for preparing a "catalyst consisting of violet TiCl 2 ... brown T 1 Cl 3, formed by reducing TiCl 2 at a temperature below about 100 ° C, by reacting brown T 1 Cl 3 with TiCl 3". The purpose is to convert the known low-surface-active brown form of T1Cl3 to one of the more potent violet forms, which are generally known for their higher polymerization rates and yields and higher stereospecifitosis,

US Patent No. 3058963 discloses polymerization using a "hydrocarbon-insoluble catalyst" produced by reacting, for example, TiCl 4 with an alkyl-aluminum compound in solution.

In U.S. Patent No. 3,116,274 ethers are used to enhance the stereospecificity of olefin polymerization. The preparation process comprises mixing ether, titanium tetrachloride. or vanadium. and alkylaluminum such as triethylaluminum or sesquichloride and reacting the resulting product with a promoter for use in polymerizing olefins.

US. Patent No. ·. No. 3,058,9-70 discloses improving the stereospecificity of olefin polymerization using a catalyst component resulting from the reaction of, for example, chloride / titanium and diethylaluminium chloride in the temperature range of -20 to 40 ° C and subsequent maturation of the product at 40 to 150 ° C. . . ? ' · ..

It has now been found, despite all references, that a brown form of titanium tetrachloride can be prepared which is highly active, provides high yields and low solubility, and can be used as a catalyst component in the polymerization of .alpha.-olefins.

The present invention provides an olefin polymerization catalyst comprising an aluminum alkyl compound and a brown solid composition comprising titanium tetrachloride and up to 10 mol% of at least one organic electron donor selected from the group consisting of ethers, thioethers, thiols, ketones, esters. amides, amines, phosphines and stibines of hydrocarbons. ^U ®dená brown solid mixture has a surface area greater than 50 m ² / g and a pore volume greater than 0.10 cm ³ / g. . . .. ......

Said brown solid mixture is the subject of MS. No. 196,269 and can be prepared by the method disclosed in U.S. Pat. No. 196,271 and which comprises steps

a) reacting titanium tetrachloride and trihydrocarbylaluminum, dihydrocarbylaluminum chloride or bromide, at a molar ratio of the titanium compound to the aluminum compound of about 1: 3 to about 1: 0.5 at a temperature below about 0 ° C in the presence. Inert liquids dissolving titanium tetrachloride,

(b) increasing the temperature of the product of step i to less than about 100 ° C, cj reacting the solid product of step bj with at least one organic electron donor selected from the group consisting of ethers, thioethers, thiols, ketones, esters, amides, amines, phosphines and stibins; at a ratio of about 0.5 moles of donor per mole solids to about 5 moles per mole in the presence of an inert donor dissolving liquid and heating the product to a temperature greater than room temperature and less than about 80 ° C; from the group consisting of titanium halide, titanium tetraalkoxy halide, aluminum bromide, germanium chloride and silica, the acceptor being dissolved in an inert liquid, and

e) isolating a large surface porous brown solid containing β-titanium trichloride and up to 10 mol% of said organic electron donor from the step product

d). The resulting solid can be used with an organoaluminum compound, in particular a dialkylaluminum chloride, in the polymerization of α-olefins, especially propylene.

Described brown solid preferably has a BET surface area greater than 50 m ² / g, more preferably more than .80 m ² / g and most preferably more than 100 m ² / g. By color, X-ray powder diffraction patterns and the ratio of chloride to titanium, the inorganic portion of the brown solid is defined as essentially titanium tetrachloride in crystalline β modification. The porosity measurements of the brown solid show that it preferably has a pore volume greater than 0.10 cm ³ / g, more preferably above 0.15 cm ³ / g and most preferably above 0.20 cm ³ / g.

By determining the morphology of the brown solid by electron microscopy, it was found to be formed by irregularly shaped, somewhat round particles that appear to be clusters of even smaller particles.

Catalytic mixtures of an organoaluminum compound and a brown solid can be used in slurry, block, or vapor phase polymerization of N-olefins with excellent results.

Although the catalyst component and the organoaluminum compound are preferably used to polymerize propylene to achieve high crystallinity of polypropylene, they can also be used for other olefins having a terminal double bond of 2 to 10 carbon atoms, for example ethylene, 1-butene, 1-pentene, 4- methyl-1-pentene,. vinylcyclohexane etc. In addition.

The latter can be used for the preparation of end-block or purely block-type copolymers from propylene and other α-olefin or propylene and ethylene.

The polymerization conditions, i.e., temperature, pressure, and concentration, used for the catalyst compositions described herein are generally known to the art, or readily determined by one skilled in the art, for the polymerization of α-olefins.

The suspension polymerization of propylene with a brown catalyst component carried out in a glass bottle shows that the polymer has a distinct brown color during the formation and until cessation of the polymerization, which differs from the purple to pink coloration which occurs when, for the same type of polymerization, The polypropylene produced by using the brown catalyst component in the bulk polypropylene is exclusively composed of opaque particles. The same is true for the polypropylene produced with the brown catalyst component in suspension. In block polymerizations of propylene. using a brown catalyst component and R2AICI, it was found that about three-quarters of the fraction designated herein as hexane extractable could be removed by simply suspending the powder product in hexanes for 70 hours at 70 ° C.

The soluble or extensible moiety may further be limited by modifying the catalyst mixture with at least one modifier, such as, for example, a (La) / amine, preferably a spherically hindered cyclophyl ^- amine, amine oxide, ether, organic. phosphorethane, polyether, for example diglyme and the like. Mixtures of alkyl tin sulfides such as bis- (tributyl) tin sulfide with an amine, an amine oxide or an organic phosphite or a mixture of hydrogen sulfide with an amine, an amine oxide or an organic phosphite can also be used to further reduce the soluble fraction of Isp. The latter mixtures are ex. The solubilization of the solubles is particularly suitable since they have only a slight effect on the polymer yield.

DETAILED DESCRIPTION OF THE INVENTION The invention is described with reference to the following examples, which are intended to be illustrative only, but are not intended to be limiting to the scope of the present invention. /b·-.·;

Water and other polar substances were removed from all solvents and polymerization media prior to use.

Powder X-ray diffraction measurements were performed with materials in sealed glass tubes in a conventional manner using a diffractometer. The porosity measurements were performed on a high pressure mercury porosimeter (420 MPa) from the American Instrument Company, Silver Springe, Md.

Surface measurements were performed using the single point BET method using a mixture of 10% nitrogen and 90% helium. The sample was pre-treated at room temperature for about 1 hour with a slow stream of the gas mixture, then cooled to liquid nitrogen for about 45 minutes to adsorb nitrogen and finally warmed to room temperature and the desorbed gas composition was measured by a thermal conductivity detector.

Chemical analyzes were performed by dissolving the weighed catalyst samples in methanol or water acidified with sulfuric acid. Aliquots of this solution were used to determine titanium and aluminum by atomic absorption and chlorine by Volhard titration. Ether was determined by neutralizing methanolic solutions or extracting aqueous solutions with hexane and injecting the obtained samples into a gas chromatograph column calibrated with standard solutions containing the relevant ether.

The brown catalytic component described herein forms a purple solution upon dissolution in dilute sulfuric acid and a blue solution upon dissolution in MeOH-H2SO4.

Suspension rates are grams of crystalline polymer (total polymer minus soluble fraction) per gram of brown solid (calculated as TiCl 3) per hour of polymerization. Block rates are grams of total polymer per gram of brown solid (calculated as TiCl 3) per hour of polymerization.

The weights indicated are those of the brown solid used. In calculating the moles of the brown solid, the small organic content was generally neglected.

He did

A 3'00 ml round-bottom flask was charged with 24.6 ml dry hexane and 12.5 ml titanium tetrachloride. The flask and its contents are protected by a layer of dry nitrogen throughout the preparation. The solution was stirred with a magnetic stirrer and cooled with an ice bath maintained at 1 ° C. 74.8 ml of diethylaluminum chloride in hexane (24.4 wt.% Diethylaluminum chloride, solution density 0.739 g / cm ³ ) was added dropwise to the titanium tetrachloride solution over three hours. After the addition of the alkyl is complete, the suspension is stirred for 15 minutes at -1 ° C, fitted with a condenser and then heated to 65 ° C over 1 hour. The suspension was then stirred at 65 ° C for 1 hour. After cooling to room temperature, the solid was washed with five 42 mL portions of dry hexane: decanting at the last wash was performed at 65 ° C.

The solid was decanted, 144 ml dry hexane and 21.3 ml isopentyl ether were added and the suspension was stirred at 35 ° C for 1 hour. The solid was then washed with five 42 ml portions of dry hexane by decantation.

To the decanted solid was added 70.8 mL of a 20.3% (v / v) stock solution of titanium tetrachloride in hexane (46.3 mL titanium tetrachloride plus 181.8 mL hexane). The suspension was stirred at 62-65 ° C for 2 hours and cooled to room temperature. The solid was washed with five 42 mL portions of dry hexane and decanted at the last wash at 65 ° C. Decant the solid and add 50 mL of dry hexane. 1.0 ml of the final suspension contains 0.295 g of brown solid.

The powder X-ray diffraction pattern, measured for a dry brown colored solid, exhibits peaks corresponding to

5.8 w, 5.4 s, 2.89 w, 2.77 s b, 2.15 m, 1.96 w, 1.78 m-s b, 1.48 w, vb, 1.14 vvw.

By measuring the surface of the dry brown solid, a value of about 106 m ² / g was obtained.

Analysis of the brown solid showed 22.5% titanium, 0.6% aluminum, 59.8% chlorine, and 10.0% isopentyl ether.

Example 2

Place in a 50 ml round-bottomed flask

49.2 ml dry hexane and 25 ml titanium tetrachloride. The flask and its contents are protected by a layer of dry nitrogen during preparation. The solution was slowly stirred with a magnetic stirrer and cooled in an ice bath at -1 ° C. Add dropwise over 3 hours

149.6 ml of diethylaluminum chloride in hexane (24.4 wt.% Diethylaluminum chloride, solution density 0.739 g / cm ³ ). After the addition of the alkyl is complete, the suspension is stirred slowly at -1 ° C for 15 minutes, equipped with a condenser and hours heated to 65 ° C. the suspension is stirred slowly for 1 hour at 65 ⁰ C. After cooling to room temperature the solid was washed with five 84 ml portions of dry hexane, decanting the last wash is carried out at 65 ° C.

The solid was decanted, 288 mL hexane and 42.6 mL isopentyl ether were added and the suspension was stirred slowly at 35 ° C for 1 hour. The solid was then washed with five 84 ml portions of dry hexane and the resulting slurry was divided into four equal portions.

One portion was decanted and 54.5 ml of a 13% (v / v) solution of titanium tetrachloride in hexane was added to the solid. The suspension was stirred slowly at 65 ° C for 2 hours and cooled to room temperature. The solid was washed with five 25 ml portions of dry hexane; decantation at the last wash is performed at 65 ° C. Decant the solid and add another 50 mL of hexane. 1.0 ml of the final suspension contains 0.141 g of brown solid.

The powder X-ray diffraction pattern, measured for a dry brown solid, has peaks corresponding to 5.8 w, 5.4 s,

2.75 bs, 2.14 m, 2.00 m-s, 1.96 w, 1.77 bs,

1.52 w, 1.49 vw, 1.13 vw,

Analysis of the brown solid gave 26.6% titanium, 0.6% aluminum, 58.2% chlorine, and 9.5% isopentyl ether. Example 3

The procedure is the same as in Example 2 except that after the suspension is divided into 4 equal portions, one portion is decanted and 35.4 ml of a 20.3% (v / v) titanium tetrachloride solution in hexane is added to the solid. The suspension was stirred slowly at 65 ° C for 105 minutes and cooled to room temperature. The solid was washed with five 25 µL of dry hexane; decantation at the last wash is performed at 65 ° C. Decant the solid and add 50 mL of hexanes. 1.0 ml of the final suspension contains 0.158. g of brown solid.

The X-ray powder diffraction pattern, measured for a dry brown solid, has peaks corresponding to 5.9 vw, 5.4 s,

2.9 w, 2.75 b m, 2.12 / m, 1.99 m-s, 1.95 w,

1.77 w and 1.48 w.

Analysis of the brown solid gave 26.2% titanium, 0.7 aluminum, 59.4% chlorine, and 6.3% isopropyl ether.

Example 4 j /

The procedure is the same as in Example 1 except that after washing the foams with five 42 ml portions of dry hexap by decanting, 35.4 ml of a 20.3% (v / v) solution of titanium tetrachloride in hexane is added to the solid. The suspension was stirred slowly at 65 ° C for 105 minutes and cooled to room temperature. The solid was washed with five 25 ml portions of dry hexane, decanting at the last wash at 65 ° C. The solid was added and 50 ml of hexane was added. 1.0 ml of the final suspension contains 0.158 g of brown solid. Example 5

The procedure is the same as in Example 4 except that the titanic chloride-isopentyl ether complex is treated with a 40% (v / v) solution of gernianidium chloride in hexane. Example 6

Propylene polymerizations were carried out in a pressurized bottle at 0.28 MPa and 70 ° C for two hours cycles with the following amounts of brown catalyst component, 1.0 mL of 24.4% (w / w) diethylaluminum chloride, and 200 mL of hexane as polymerization medium.

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TABLE I

Example Weight (g) Speed g / g / h Soluble fraction%

1 0,0875 253 10.9 1 0,0875 219 2,5 * 4 0.0754 213 5.4 2 0,0843 165 6.0 5 0,099 106 19.6 3 0,0948 195 5.7 ** 0,2 65 6.0 ** 0,2 35 2,2 *

* In these polymerizations, 0.008 ml of bis (tributyl) tin sulphide (BTS) and 0.004 ml of 2,4,6-collidine (Coll) were added.

** In these cases, commercially available AATiCls (Stauffer Chemical Company) was used instead of brown titanium tetrachloride.

Example 7

The polymerizations are carried out at 71 ° C for about 1 hour in a 3.8 liter reactor at a propylene pressure of greater than 1.75 MPa and a low hydrogen partial pressure using

1200 ml hexane as polymerization medium. The catalyst used is diethylaluminum chloride, brown titanium tetrachloride, BTS and Coll in a molar ratio of 2.8 / 1.0 (0.014) / 0.027.

TABLE II

Example Weight (g) Speed (g / g / li) Soluble fraction i (%) 3 0.1 2002 2.1 ** 4 0.1 2170 4.2 4 0.1 2226 2.5 4 0.1 2320 1.5 ** 3 0.1 1215 β β * * *** 4 0.1 1422 4.4 *** 4 0.1 1583 16 ## * * # * 0.4 628 2.6 * 0.4 401 4.6 ***

* AATiCls, Stauffer Chemical Company.

** Molar ratio of diethylaluminum chloride to titanium tetrachloride, BTS and Coll 2.8 / 1 / 0.028 / 0.054.

*** Four-hour cycles.

Example 2 hours at 71 ° C under propylene pressure

3.22 MPa and with a small amount of hydrogen. IN

Liquid phase propylene polymerizations (0.3 ml of 24.4% (w / w) are used in each cycle) are carried out in a pound reactor after a solution of diethylaluminum chloride in hexane.

TABLE III

Example Speed (g / g / h) Soluble fraction (%) Extractable fraction and quantity (g) (%)

4 0.03 3084 4.8 11.0 4 0.03 3187 1.6 4.6 ** 2 0,021 2390 1.3 4.2 ** 4 0,028 2322 0.9 2,7 **, # 0.05 1186 4.3 6.8 0.05 797 3.3 3.8

* AAT1Cl3, Stauffer Chemical Company ** 0.0025 ml BTS and 0.00125 Coll *** 0.32 ml of a 24.4% (w / w) solution of diethylaluminum chloride in hexane.

1θ Β27Ο

Example9

A brown catalyst stock solution was prepared by adding 80 mL hexane and 40 mL titanium tetrachloride to a 500 mL flask and cooling to 0 ° C. To this solution was added 247 ml of 24.4% (w / w) diethylaluminum chloride (0.739 g / ml) over 3 hours. The resulting suspension was warmed to room temperature, heated at 65 ° C for 1 hour, and washed. The concentration of the suspension is determined.

ml of the latter suspension (about 6 g of solid) is placed in a 200 ml flask, decanted and 40 ml of hexane are added. Then, 8.8 ml of octyl ether was added and the suspension was heated at 35 ° C for 1 hour. The product was washed with hexane.

The solid was decanted from the latter slurry to which 12 ml hexane and 4 ml titanium tetrachloride were added. The mixture was then heated at 65 ° C for one hour, the resulting brown solid was washed with hexane and aliquots of the slurry were used in the polymerization.

Example 10

A brown catalyst stock solution was prepared as in Example 9, with the following exceptions:

1. Cool 24.6 ml of hexane and 12.5 ml of titanium tetrachloride to 0 ° C and add 74.8 ml of diethylaluminum chloride.

2. 144 ml of hexane and 20 ml of benzylisopentyl ether are added to the washed solid from 1..

3. Add 60.4 ml of a 11.9% (w / w) solution of titanium tetrachloride in hexane to the solid of 2.

Example 11

Example 10 is repeated except that 79.5 ml of a 9.04% (w / w) solution of titanium tetrachloride in hexane is used in step 3.

Example 1 a d 12

A brown catalyst stock solution was prepared as in Example 9 with the following exceptions;

1. 196.8 ml of hexane and 100 ml of titanium tetrachloride were cooled to 0 ° C and 594.8 ml of a 25% Et 2 AlCl solution was added. To the washed and decanted solid was added 400 mL hexane.

2. To 50 ml of the suspension from 1. is added 181 ml of hexane, 14.2 ml of isopentyl ether and 5.9 ml of n-butyl ether.

3. 56 ml of hexane and 14.2 ml of titanium tetrachloride are added to the washed solid from 2. Example 13

A stock solution of the brown catalyst component is prepared as in Example 12 except that 15.4 ml of isobutyl vinyl ether is used instead of isopentyl and n-butyl ether.

Example 14

A brown catalyst stock solution was prepared as in Example 12 except that 11.8 ml of anisole was used instead of isopentyl and n-butyl ether.

Example 15

The following suspension polymerizations were carried out at 70 ° C and propylene pressure of 0.28 MPa for 2 hours in cylinders using 80 mg of the brown solid of Example 9, 182 mg of Et 2 AlCl, 9.5 mg of BTS and 3.7 mg of Coll.

TABLE IV Example Speed (g / g / h) Solubility (%) The comparison is carried out with a brown isopentyl ether-containing catalyst component prepared similar to Example 1 to 4 and having a rate of 178 and soluble. share

1.3%.

Example 16 uses about 0.08 g of the brown catalyst component and 1 ml of a 25% Et 2 AlCl solution and is not used

Subsequent suspension polymerization was either BTS or Coll. as described in Example 15, except that they are

Example

TABLE V Speed (g / g / h)

Soluble fraction (%)

10 * 68.5 11 * 51.7 12 *** 161 13** 58 14 ** 65

20.3

21.5 4,2

17.2

15.5

10 * * 27®

The comparison is carried out in each case with a brown catalyst component containing Isopentylether, prepared similarly to Examples 1 to 4.

* rate 165, solubility 6.1, ** rate 157, solubility 5.8, *** rate 170, solubility 5.4.

Example 17

The following suspension polymerizations were carried out as in Example 16 except that 0.008 ml BTS and 0.004 ml Coll.

Example

TABLE VI Speed (g / g / h)

Soluble fraction (%)

159 1,2

55 11,6

7.2 Comparison for 12, 13 and 14 is carried out with a brown isopentyl ether-containing catalyst component, prepared similarly to Examples 1-4, having a rate and soluble fraction of 178 and 1%, respectively. 164 and 1.2 ° / o, respectively. 164 and 1.2%.

Example 18

The brown catalyst component was produced by the procedure of Example 1 with the following amounts of reagents:

1. 196.8 ml hexane

100 ml titanium tetrachloride

598.4 ml Et 2 AlCl

336 ml hexane for each wash,

2. 1152 ml hexane

170 ml Isopentylether

336 ml hexane at each wash,

3. 448 ml of hexane added separately from

113.6 ml of titanium tetrachloride

338 ml hexane each time wash.

The resulting brown solid has a surface area of 147 m ² / g and a pore volume of 0.197 cm ³ / g. Analysis yielded 26.8% Ti, 58.5% Cl, 0.36% Al and 6.41% isopentylether. The powder X-ray diffraction pattern has peaks corresponding to 5.9 m, 5.4 s,

2.75 vs br, 2.13 w, 1.98 m, 1.94 w, 1.77 m br,

1.72 w, 1.47 w br, 1.23 w, 1.13 w br,

Example 19

A brown catalyst component is produced as in Example 18. The resulting brown solid has a surface area of 101 m ² / g and a pore volume of 0.193 cm ³ / g. Values were obtained by analysis

26.8% Ti, 60.0% Cl, 0.38% Al and 8.26% isopentylether.

Example 20

A brown catalyst component was prepared as in Example 19 except that the isopentylether was distilled over sodium prior to use. The resulting brown solid has a surface area of 89 m ² / g and a pore volume of 0.188 cm ³ / g.

Example 21

The polymerization of propylene is carried out as in Example 6.

TABLE VII

Example Weight (gj Speed (g / g / h) Soluble fraction (%)

18 0.08 0.08 259 263 5.0 3.9 19 Dec 0.08 264 5.7 0.08 240 5.2 20 May 0.08 173 8.4 0,08 *. 168 1.4

* 0.008 ml BTS and 0.004 ml Coll.

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1S 16

Example 2

The propylene polymerizations were carried out as in Example 8.

TABLE VIII

Example Weight (g) *

0.05 *

............ 0.05 ** '0.05 *

0.05 ** * 2-hour cycle ** 4-hour cycle

Speed (g / g / hj Extractable fraction (%)

3065 3.6 2276 3.8 1766 2.9 1393 2.8

*** Brown / Etz ratio used

Claims (19)

SUBJECT An olefin polymerization catalyst comprising an alkyl-aluminum compound and a brown solid mixture containing β-titanium tetrachloride and up to 10 mol% of at least one organic electron donor selected from the group consisting of ethers, thioethers, thiols, ketones, esters, amides, amines , phosphines and stibins of hydrocarbons, said brown solid mixture having a surface area greater than 50 m ² / g and a pore volume greater than 0.10 cm ³ / g. 2. The catalyst of claim 1 wherein the organic electron donor is selected from the group consisting of ethers. 3. The catalyst of claim 1 wherein the organic electron donor is a single compound, namely an ether. 4. The catalyst of claim 2 wherein the ethers are lower alkyl ethers. 5. The catalyst of claim 3 wherein the ether is a lower alkyl ether. 6. The catalyst of claim 4 wherein the lower ethers are isopentyl ether and n-butyl ether. 7. The catalyst of claim 5 wherein the lower alkyl ether is isopentyl ether. 8. The catalyst of claim 2 comprising dialkylaluminum chloride and said solid mixture, wherein the ethers are lower alkyl ethers. 9. The catalyst of claim 3 comprising dialkylaluminum chloride and said brown solid mixture, wherein the ether is a lower alkyl ether. 10. The catalyst of claim 4 comprising dialkylaluminum chloride and said brown solid mixture, wherein the lower alkyl ethers are isopentyl ether and n-butyl ether. 11. Catalyst according to claim 5, characterized by YNALEZ by containing dialkylaluminum chloride and said brown solid mixture, wherein the lower alkyl ether is isopentyl ether. 12. Catalyst according to claim 4, characterized in that: The composition according to claim 1, wherein the brown solid mixture has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 cm ³ / g. 13. The catalyst of claim 5, wherein the brown solid mixture has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 cm ³ / g. 14. The catalyst of claim 6 wherein the brown solid mixture has a surface area greater than 80 m &^lt; ^{2 >} / g and a pore volume greater than 0.15 cm < ³ > / g. 15. The catalyst of claim 7 wherein the brown solid mixture has a surface area greater than 80 m &^lt; ^{2 >} / g and a pore volume greater than 0.15 cm < ³ > / g. 16. The catalyst of claim 4 comprising a dialkylaluminum chloride and wherein the brown solid mixture has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 cm ³ / g. 17. Catalyst according to claim 5, characterized in that it contains dialkylaluminum chloride and that the brown solid mixture has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 cm ³ / g. 18th catalyst according to Claim 6, characterized in that it comprises a dialkylaluminum halide, and the brown mixture peivná has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 CIN ³ / g. 19. The catalyst of claim 7 comprising a dialkylaluminum chloride and wherein the brown solid mixture has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 cm ³ / g.