CS196271B2 - Method of producing the catalytic component - Google Patents

Description

The invention relates to a process for the production of a novel brown colored solid composition containing β-titanate chloride, which is useful in admixture with an organoaluminum compound to polymerize monomers. It is an object of the present invention to provide a process for producing a new brown solid composition which is porous, has a large surface area and contains n-titanium chloride and a small amount of organic electron donor. Its mixtures with an organoaluminium compound are highly active and can be used for polymers of α-olefins, especially 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, high surface area brown material containing a β-crystalline form of titanium tetrachloride and a minor amount of organic electron donor, e.g. ether, is highly effective in α-olefin polymerization for example propylene. This brown solid, when used in admixture with an organoaluminum compound, in particular dihydrocarbylaluminum chloride, is particularly effective for propylene polymerization since these mixtures exhibit exceptionally high polymerization rates and high catalyst yields, and 19 8 2 71 compared to commercial chloride. titanium activated aluminum causes the formation of equal or lower amounts of soluble fractions (low molecular weight and especially amorphous polymeric components). Further, the catalyst compositions of the present invention may be modified with additives which are capable of lowering the soluble fraction to a substantially lower level without substantially affecting the yield relative to the catalyst. Moreover, these catalyst mixtures are modified or modified. unmodified, hydrogen sensitive, 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. .. "

The catalyst mixtures used for the polymerization of α-olefins, in particular propylene, are assessed from at least two aspects: in terms of their activity and catalyst-related yield and their ability to form a highly crystalline polymer product with a minimum of low-molecular and especially 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 of titanium tetrachloride are known: a, β, γ and <S, and the bending patterns measured by the powder method for at least the first three modifications are detailed in the literature. In the commercial polymerization of propylene, purple crystalline modifications, especially the χ-form, were preferred, while the brown (3-form) was steadily rejected due to its activity and particularly the high production of soluble fractions. for cyclotrimerization of conjugated diolefinic substances.

Recently, South African Patent No. 721,245 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, which are not accompanied by a substantial increase in the soluble fraction.

U.S. Patent No. 3,769,233 discloses a process for preparing a "catalyst consisting of violet TiCl 2 ... from brown TiCl 2, formed by reducing TiCl 4 at a temperature below about 100 ° C, by reacting brown TiCl 3 with TiCl 3". The purpose is to convert the known brown form of small surface T1Cl3 to one of the more potent violet forms, which are generally known for their higher polymerization rates and yields and higher stereospecificity.

U.S. Patent No. 3,058,963 discloses polymerization using a "hydrocarbon-insoluble catalyst component" produced by the reaction of, for example, TiCk with an alkyl-aluminum compound in solution.

In U.S. Pat. No. 3,116,274, ethers are used to increase the polymerization half-life of the olefins: The preparation process comprises mixing ethers of titanium tetrachloride or vanadium tetrachloride alkylaluminium, for example triethylaluminum or sesquichloride, and reacting the resulting product. with a promoter * for use in the polymerization of α-olefins.

U.S. Patent No. 3,058,970 discloses improving the stereospecificity of olefin polymerization by using a catalyst component resulting from the reaction of, for example, tetrachloride and diethylaluminum chloride, at temperatures ranging from -20 ° C to about 20 ° C and subsequent aging at 40 ° C to 150 ° C. - · ». · Τ · τ ’·

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 α-olefins.

It is an object of the present invention to provide a process for producing a brown catalyst component which comprises:

(a) reacting titanium tetrachloride and tri-hydrocarbylaluminum, dihydrocarbylaluminum bromide or dihydrocarbylaluminum chloride in a molar ratio of 1 mole of titanium compound to 0.5 to 3 moles of aluminum compound at a temperature below 0 ° C in the presence of an inert liquid solvent for titanium tetrachloride; the temperature of the product of step a) is raised to less than 100 ° C, c) at least one organic electron donor selected from the group consisting of ethers, thioethers, thiols, is introduced into the brown solid of step b) in the presence of an inert liquid solvent for an organic electron donor; . ketones, esters, amides, amines, phosphines and stibines of hydrocarbons, in a molar ratio of 0.5 to 5 moles of electron donor per mole of titanium compound in the brown solid from step b),

d) the product of step c) is heated to a temperature between room temperature and 80 ° C,

e) treating the brown solid from step dj at a temperature of 40 ° C to 100 ° C with a solution of electron-donor titanium halide, titanium alkoxy halide, aluminum bromide, germanium chloride or silicon tetrachloride, in an inert liquid at temperature, time and concentration; wherein the electron ¹ acceptor is dissolved in an inert liquid and at such a molar ratio of electronceptor to titanium contained in the brown solid from step dj that allows the conversion of the brown solid from step d) to a brown solid having a surface area greater than 50 m ² / g and pore volume greater than 0,10 cm ³ / ga

f) from step e), a polymerization catalyst is obtained. a component containing brown β-titanium tetrachloride containing up to 10 mol% of at least one of said organic electron donors having a surface area greater than 50 m ² / g and a pore volume greater than 0.10 cm ³ / g.

The plasticized solid can be used with an organoaluminum compound, especially a dialkylaluminum chloride, in the polymerization of n-olefins, especially propylene.

The described brown solid preferably has a BET surface area greater than 50 m ² / g, more preferably greater than 80 m ² / g and most preferably greater 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 the 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 a snake 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.

In a preferred embodiment, the brown solid is produced as described below.

For the preparative and wash steps of the preparation of the brown catalyst component, it is suitable to use any substantially inert liquid medium. Alkanes such as pentane, hexane, cyclohexane and the like and halogenated compounds such as chlorobenzene and chloraicanes can be used after purification to remove water and other polar constituents such as alcohols, mercaptans, etc.

6 2 ⁵ 7 ί environments using lower alkanes and most preferably hexane.

For the initial preparative step, titanium tetrachloride reduction, a trihydrocarbylaluminum or dihydrocarbylaluminum halide is preferred, more preferably dihydrocarbylaluminum chloride may be used, and most preferably a lower alkyl dialkylaluminium chloride such as dlethylaluminum chloride is used. By lower alkyl is meant an alkyl radical of one to about eight carbon atoms.

It is most advantageous to keep the temperature of the reduction below 0 ° C during the slow mixing of the titanium tetrachloride and the organoaluminum compound and to maintain the same temperature for some time thereafter. Preferably, the mixing is accompanied by shaking. More preferably, temperatures between -30 ° C and 0 ° C are used, and most preferably between -10 ° C and 0 ° C.

The slurry resulting from the reduction is then briefly heated to a temperature of up to 100 ° C, more preferably up to 80 ° C. The term "briefly" means more than a few minutes and less than a few hours.

The amount of organoaluminum compound used varies with the amount of titanium tetrachloride used and is preferably in the range of 3 moles of organoaluminum compound per mole of chloride to 0.5 moles per mole. More preferably, the molar ratio is from 2: h to 0.5: 1 and most preferably from 1.5: 1 to 0.75: 1.

The solid formed by reduction, which is essentially a small surface area titanium tetrachloride containing a small amount of organoaluminum compounds, is preferably separated and briefly washed and the resulting product is treated in an inert liquid medium with at least one organic electron donor such as ether, thioether, thiol a ketone, ester, amide, amine, phosphine or slot. Preferably said at least one donor is an ether, thtoester, thiol or ketone, and more preferably said donor is at least one ether such as n-butyl, isobutyl, cyclohexyl, isopentyl or octyl ether and the like, or an ether with mixed organic groups , such as isobutylisopentyl ether, isopentylphenyl ether, etc. Most preferably said donor is formed from at least one lower alkyl ether, such as isopentylethyl ether. a mixture of isopentyl n-butyl ether. By lower alkyl is meant alkyl groups of two to about eight carbon atoms. Generally, the electron donor reactants are added at a temperature close to room temperature and the product formed is heated to a temperature between room temperature and 80 ° C. More preferably, the heating is performed at a temperature in the range of 30 to 70 ° C, and most preferably from 35 to 50 ° C. - ···! '

The amount of said organic electron donor added to the separated and washed solid from the first stage is preferably from 0.5 mol of donor per mole of titanium contained in the solid to 5 moles per mole. More preferably, the electron donor is in the range of about 2 moles of titanium contained in the solid to about 0.75 moles per mole, and most preferably the molar ratio is between 1.5: 1 and 0.9: 1. 1.

The heating time in the described step is preferably from about 10 minutes to several hours, more preferably from 15 minutes to 2 hours.

After the described reaction with at least one electron donor, the solid product of the second reaction step is preferably separated and washed with an inert liquid.

The second stage solid product, which is a substantially brown form of small surface titanium tetrachloride containing small amounts of organoaluminium compounds and a donor, is then reacted with an electron acceptor for several minutes to several hours, preferably 15 minutes to several hours, in contact with an inert liquid. environment. The temperature range of this heating is between about ambient temperature and 100 ° C, preferably between 30 and 80 ° C, and more preferably between 40 and 70 ° C.

The electracceptor is preferably composed of a Lewis acid soluble in an inert liquid medium such as titanium halide, titanium tetraalkoxy halide, aluminum bromide, germanium chloride, silicon tetrachloride and other halides of elements of periodic groups IV.B, IV.A and VA More preferably the electronceptor is chloride titanium tetrachloride, germanium chloride or silicon tetrachloride, and most preferably titanium tetrachloride.

The reaction of the solid from the second stage with the electron acceptor in solution is preferably carried out in a molar ratio of acceptor to titanium contained in the solid of 10: 1 to 0.5: 1. More preferably, the molar ratio is from 5: 1 to 0.5: 1, and most preferably from 3: 1 to 1: 1. It is important here not to use too much electron-acceptor solution. A 5 to 30 wt.% Solution is preferred, more preferably the lower limit is about 10 wt.%.

The brown solid product of the third reaction step is then separated, preferably washed, and used in conjunction with an organoaluminum compound such as an aluminum trialkyl or dialkylaluminum halide, preferably a dialkylaluminum chloride, to polymerize α-olefins. Lower alkyl dialkylaluminium chloride is preferably used.

The invention is described in connection with the following examples, which are illustrative only. Alternatives, modifications, and variations that will be apparent to those skilled in the art from the examples are within the scope of the invention.

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

Powder x-ray error measurements were performed with materials in sealed glass tubes in a conventional manner using a diffractometer. Porosity measurements were performed on a high pressure mercury porosimeter (420 MPa) from Ame196271 ricah Instrument Company, Silver Springs,

Md.

Surface measurements were performed by a one-hour 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 measured by 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 catalyst 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 polymers (total polymer minus soluble fraction) per gram of brown solid (calculated as TiCl 2) per hour of polymerization. Block rates are grams of total polymer per gram of brown solid (calculated as TiCl 2) per hour of polymerization.

The weights in the Example column and the weights are the weights of the brown solid used. In calculating the moles of the brown solid, the small organic content was generally neglected.

Example 1

Place in a 300 ml round-bottomed flask

24.6 ml dry hexane and 12.5 ml titanium tetrachloride. Flask and its contents They are protected by a layer of dry nitrogen throughout the preparation. The solution was stirred with a magnetic stirrer and cooled in an ice bath maintained at -1 ° C. To the titanium tetrachloride solution was added dropwise over 3 hours

74.8 ml of diethylaluminum chloride in hexane (24.4 wt% diethylaluminum chloride, solution density 0.739 g / cm ³ ). After addition of the alkyl, the suspension was stirred at -1 ° C for 15 minutes, evaporated 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: decantation 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% (w / w) 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. The solid is decanted ^; and 50 ml of dry hexane are added. 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 substance, has peaks corresponding to 5.8 w, 5.4 s, 2.89 w, -2.77 sb, · 15 m, 1.96 w, 1.78 ms, 1.48 w vb, 1.14 vvw ..

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

Analysis of the brown colored 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. Flask a; 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 diethylaluminium chlorides in hexane (24.4% by weight of diethylaluminium chloride, solution density 0.739 g / cm ³ ) After the addition of the alkyl is complete, the suspension is stirred slowly at 11 ^° C for 15 min. heated to 65 ° C. The suspension was then stirred at 65 ° C for 1 hour / slowly. After cooling to room temperature, the solid was washed with five 84 ml portions of dry hexane; decantation at the last wash is performed at 65 ° C.

The solid was decanted, 288 ml of hexane and 42.6 ml of isopentylether 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.

Decant one portion and add 54.5 ml of a 13% (w / w) solution of titanium tetrachloride in hexane to the solid. The suspension was stirred slowly at 65 ° C for 2 hours and cooled to room temperature. The solid is washed with five. 25 ml portions of dry hexane; decantation at the last wash was 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 a brown solid.

The powder X-ray diffraction pattern, measured for a dry brown solid, exhibits peaks of 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, w.

Analysis of brown solids were obtained

10 values of 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 slurrying into 4 equal parts: one part is decanted and 35.4 ml of a 20.3% (w / w) 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 ml portions of dry hexane, decanting at the last wash at 65 ° C. Decant the solid and add 50 mL of hexane. 1.0 ml of the final suspension contains 0.158 g of brown solid.

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

2.9 w, 2.75 bs, 2.12 m, 1.99 m-s, 1.95 w,

1.77 w and 1.48 w.

Analysis of a brown solid were obtained 26,2 _0/0 Ti, 0.7% Al, 59.4% Cl and 6.3% isopentyletheru.

Example 4

The procedure is the same as in Example 1 except that after washing the solid with five 42 ml portions of dry hexane by decantation, 35.4 ml of a 20.3% (w / w solution of titanium tetrachloride in hexane) is added to the solid. The solid was washed with five 25 ml portions of dry hexane, decanted at the last wash at 65 DEG C. The solid was decanted and 50 ml of hexane was added. 0.158 g of a brown solid, Example 5

The procedure is the same as in Example 4, except that the titanium chloride isopentyl ether complex is treated with a 40% (wt. Solution of germanium chloride in hexane).

Propylene polymerizations are carried out in a cylinder at 2.8 atp and 70 ° C for two hours cycles with the following amounts of brown catalyst component, 1.0 mL 24) 4% (w / w diethylaluminum chloride and 200 mL hexane as polymerization medium).

TABLE I

Example #, Weight (gj Speed (g / g / hr) 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 AATiCb (Stauffer Chemical Company) was used instead of brown titanium tetrachloride.

Example7

The polymerizations are carried out at 71 ° C for about 1 hour in a 3.8 liter rector 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 titanite chloride, BTS and Coll in a molar ratio of 2.8 / 1.0 (0.014) / 0.027.

TABLE II

Example # Weight (g) Speed (g / g / hr) Soluble fraction (%) 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 1.8 **, ***. * 0.4 628 2.6 * 0.4 401 4.6 ***

* AATIC, Stauffer Chemical Company.

** Molar ratio of diethylaluminum chloride, titanium tetrachloride, BTS and Coll

2.8 / 1 / 0.028 / 0.054.

* * * Four-hour cycles.

198271

12

Example 8 for 2 hours at 71 ° C under propylene pressure

3.22 MPa and with a small amount of hydrogen. IN

Liquid phase propylene polymerization (0.3 ml of 24.4% (w / w) was used for each cycle) was carried out in a filter reactor after a solution of diethyl aluminum 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

* AATiCb, Stauffer Chemical Company.

** 0.0025 ml BTS and 0.00125 Coll.

*** 0.32 ml of a 24.4% (w / w) solution of diethyl aluminum chloride in hexane.

Example 1 9

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 is added. 247 ml of 24.4% diethyl aluminum chloride (0.739 g / ml) was added over 3 hours. The resulting suspension was warmed to room temperature, heated at 65 ° C for 1 hour, and washed to determine the concentration of the suspension.

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 2 hours, the resulting brown solid was washed with hexane and aliquots of the slurry were used in the polymerization.

He did

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 diethyl aluminum chloride.

2. 144 ml of hexane and 20.1 ml of benzylisopentyl ether were added to the washed solid from step 1. The mixture was stirred for 2 hours.

3. To the solid of step 2, add

60.4 ml of a 11.9% (v / v) solution of titanium tetrachloride in hexane.

Example 11

Example 10 is repeated except that 79.5 ml is used in step 3. The reaction is repeated. 9.04% (v / v) titanium tetrachloride solution in hexane.

Example 12.

A stock solution of the brown catalyst component is prepared as in Example 9 with the following exceptions:

1. 196.8 ml of hexane and 100 ml of titanium tetrachloride are cooled to 0 ° C and added

594.8 ml of a 25% Et2AlCl solution. To the washed and decanted solid was added 400 mL hexane.

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

3. To the washed solid from step 2, 56 ml of hexane and 14.2 ml of titanium tetrachloride are added.

Example 13

A brown catalyst stock solution was prepared as in Example 12 except that 15.4 mL of isobutyl vinyl ether was used in place of isopentyl and n-butyl ether.

Ex. 1 and d. 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.

Example5

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.

Example number

TABLE IV

Speed (g / g / hodj Soluble fraction (%)

The comparison is made with a brown catalyst component containing isopentyl ether, prepared similarly to Examples 1-4, having a rate of 178 and a soluble fraction of 1.3%.

3.2

Example 1 6

The following suspension polymerizations were carried out as in Example 15 except that about 0.08 g of the brown catalyst component and 1 ml of a 25% Et 2 AlCl solution were used and neither BTS nor Coli was used.

Example #

TABLE V Speed (g / g / hr)

Soluble fraction (%)

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

20.3

21.5 4,2

17.2

15.5

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

* rate 165, soluble fraction 6.1 ** rate 157, soluble fraction 5.8 *** rate 170, soluble fraction 5.4.

Example 17

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

TABLE VI

Example No. Speed (g / g / hodj Soluble fraction (%)

159 1,2

55 11,6. 7.2 Comparison for 12, 13, 14 is carried out with a brown isopentyl ether-containing catalyst component produced similarly to Examples 1-4 which it has. rate and soluble fraction of 178 and 1%, respectively. 164 and 1.2%, respectively, 164 and 1.2%.

Example 18

The brown catalyst component was prepared as described in 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 at each wash

2.1152 ml hexane

170 ml isopentyl ether

336 ml hexane at each wash

3,448 ml of hexane added separately from

113.6 ml titanium tetrachloride 336 ml hexane with each wash

The resulting brown solid has a surface

147 m ² / g and pore volume 0.197 cm ³ / g. Analysis yielded 26.0% Ti, 58.5 why. Cl, 0.36% Al and 6.41% isopentyl ether. The powder X-ray diffraction pattern has peaks corresponding to 5.9 m. 5.4 s,

2.75 in 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 was prepared as in Example 18. The resulting brown solid had 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, 0.36% Al and 6.26% isopentyl ether.

Example. 2 0

A brown catalyst component was prepared as in Example 19, except that isopentyl ether 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 / g.

Example 21

The propylene polymerizations were carried out as in Example 6.

TABLE VII

Example No. Weight (gj. Speed (g / g / h) Soluble stage (%}

18 0.08 0.08 19 Dec 0.08 0.08 20 May 0.08 0.08

259 5.0 263 3.9 264 5.7 240 5.2 173 6.4 168 1.4

0.008 ml BTS and 0.004 ml Coll.

Example 22

The propylene polymerizations were carried out as in Example 8.

TABLE VIII

Example. ...... 'Weight (gj *** Speed (g / g / hodj Extractable fraction _______ (%)

0.05 * * 3065 3.6

0.05 ** 2276 3.8

0.05 * 1766 2.9

0.05 ** 1393 2.8 * 2-hour cycle ** 4-hour cycle ***. a brown solid / Et 3 AlCl / BTS / Coll ratio of 1.0 / 3.0 / 0.03 / 0.06 was used.

Claims (10)

SUBJECT A process for producing a catalyst component of a brown color, characterized in that: (a) reacting titanium tetrachloride and trihydrocarbylaluminum, dihydrocarbylaluminum bromide or dihydrocarbylaluminum chloride in a molar ratio of 1 mole titanium compound to 0.5 to 3 moles of aluminum compound at a temperature below 0 ° C in the presence of an inert liquid titanium tetrachloride to form a brown solid; b) the temperature of the product of step a) is raised to less than 100 ° C, i.e. at least one organic electrondonor selected from the group consisting of ethers, thioethers is introduced into the brown solid of step b) in the presence of an inert liquid solvent for the organic electron donor; thiols, ketones, esters, amides, amines, phosphines and stibins of hydrocarbons, in a molar ratio of 0.5 to 5 moles of electron donor per mole of titanium compound in the brown solid from step bj, dj the product of step cj is heated to a temperature between room temperature and 80 ° C e) treating the brown solid from step dj at a temperature of 40 ° C to 100 ° G with a solution of an electronceptor such as titanium tetrahalide, titanium alkoxy halide, aluminum bromide, germanium chloride or silicon tetrachloride in an inert liquid at temperature, time and concentration; wherein the electronceptor is dissolved in an inert liquid and at such a molar ratio of electronceptor to titanium contained in the brown solid from step d) that allows Severography, n. YNALEZU converting a brown solid from step d ·] to a brown solid having a surface area greater than 50 m ² / g and a pore volume greater than 0.10 cm ⁵ / g and fj from step ej yields a solid polymerization catalyst component containing brown β titanium chloride having up to 10 mole% of at least one of said organic electron donors having a surface area greater than 50 m ² / g and a pore volume greater than 0.10 cm ³ / g. 2. Process according to claim 1, characterized in that, as trihydrocarbylaluminium, dihydrocarbylaluminum chloride or bromide, the process is carried out. using dl (lower alkyl) aluminum chloride. 3. The method of claim 2 wherein the organic electron donor is selected from the group consisting of ethers. , 4. The method of claim 2 wherein the organic electron donor is a single compound, namely an ether. 5. The method of claim 3, wherein the electracceptor is titanium tetrachloride. 6. The method of claim 4, wherein the electracceptor is titanium tetrachloride. 7. The process of claim 5 wherein the ethers are lower alkyl ethers. 8. The process of claim 6 wherein the ether is a lower alkyl ether. 9. The process of claim 7 wherein the lower alkyl ethers are isopentyl ether and n-butyl ether. 10. The process of claim 8 wherein the lower alkyl ether is isopentyl ether.