CS196269B2 - Brown solid mixture - Google Patents

Description

. The invention relates to a novel brown-colored composition comprising β-titanium tetrachloride, which is useful in admixture with an organoaluminum compound to polymerize monomers. The subject of the invention is a new brown solid composition which is porous, has a large surface area and contains β-titanium chloride and a small amount of organic electron donor. Its mixtures with an organoaluminum compound are highly active and can be used to polymerize n-olefins, especially propylene, into 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 comprising a β-crystalline form of titanium tetrachloride and a minor amount of organic electron donor, e.g. ether, when used together with an organoaluminum compound -. 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 ₂ as compared to commercial. The aluminum-activated titanium tetrachloride causes the formation of equal or lower amounts of soluble fractions (low molecular weight and especially amorphous polymeric components). The catalyst compositions of the invention may further be. modified additives capable of lowering 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 polymerization, vapor phase tendency,

The catalytic mixtures used for the polymerization of 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 weight 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 catalyst mixtures based on organoaluminium compounds and titanium tetrachloride. '

19B269

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

Recently, South African Patent No. 721,245 has described a porous titanium tetrachloride having a large active surface based on violet α-titanium chloride. 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 3 ... from brown TiCl 3, formed by reducing TiCl 3 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 the low active surface Tiob 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 reacting, for example, TiCl 4 with an alkyl-aluminum compound in solution.

In U.S. Patent No. 3,116,274 ethers are used to increase the stereospecificity of olefin polymerization. The preparation process comprises mixing ether, titanium (IV) chloride or vanadium (II) chloride and an alkyl aluminum such as triethylaluminum or sesquichloride and reacting the resulting product with a promoter for use in the polymerization of α-olefins.

U.S. Pat. No. 3,058,970 discloses improving the stereospecificity of olefin polymerization by using a catalyst component resulting from the reaction of, for example, titanium tetrachloride 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 in literature, 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.

The present invention provides a brown solid composition suitable as a catalyst component for the polymerization of olefins, in particular propylene, containing titanium β-chloride and up to 10 mole percent of at least one organic electron donor selected from the group consisting of ethers, thioethers, thiols, ketones, esters, amides, amines, phosphines and stannins of hydrocarbons. This brown solid mixture, consisting predominantly of β-titanate chloride, has a surface area above 50 · m ² / g and a pore volume greater than 0.10 cm ³ / g.

The brown solid composition according to the invention can be prepared by the method of the art. No. 196,271 and which comprises the steps of (a) reacting titanium tetrachloride and tri-hydrocarbyl aluminum, dihydrocarbylaluminum chloride or bromide in a molar ratio of titanium compound to aluminum compound of about 1: 3 to about 1: 0.5 at a temperature below about 0 ° C in the presence of inert titanium tetrachloride dissolving liquids; (b) increasing the temperature of the step product (even to less than about 100 ° C; (cj reaction of the step product solid (bj with at least one organic electron donor selected from the group consisting of ethers, thioethers, thiols, ketones, esters, amides, amines, phosphines) and stibins of hydrocarbons, at a ratio of about 0.5 mole 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 above room temperature and below about 80 ° C; and (e) isolating a porous brown, high surface area solid containing β- titanium tetrachloride and up to 10 mol% of said organic electrondonorus, from the product of step (dj). The resulting solid can be used with an organo-clay compound, especially a dialkylaluminum chloride, in the polymerization of α-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 chloride 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 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.

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

That. water and other polar substances were removed before use. .

The powder X-ray diffraction measurements were. performed with the materials in the sealed glass tubes in a conventional manner using a diffractometer. The porosity measurements were performed on a high pressure mercury porosimeter (412 MPa) from the American Instrument Company, Silver Springs, Md.

Active surface measurements were performed using the single point BET method using a 10% nitrogen-90% helium mixture. The sample was pre-treated at room temperature for about 1 hour with a slow stream of said 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 not spraying the obtained samples onto a gas chromatograph column calibrated with standard solutions containing the appropriate 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 polymer (total polymer minus soluble fraction) per gram of brown solid (calculated as TlCls) 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 are the weights of the brown excipient used. In calculating the moles of the brown solid, the low organic content was generally neglected.

Example 1

24.6 ml of dry hexane and 12.5 ml of titanium tetrachloride are introduced into a 300 ml round bottom flask. 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 in an ice bath maintained at -1 ° C. 74.8 ml of diethylaluminum chloride in hexane (24.4% by weight of dieithylaluminum chloride, solution density 0.739 g / cm ³ ) was added dropwise over three hours to the titanium tetrachloride solution. 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 for 2 hours at 62 to 65 ^at C and then cooled to room temperature. The solid was washed with five 42 ml portions of dry hexane with decantation 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 1 a d 2

A 50 ml round bottom flask was charged with 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% diethylaluminum chloride, solution density 0.739 g / cm ³ ). After completion of the addition of the alkyl, the suspension was stirred slowly at -1 ° C for 15 minutes, equipped with a condenser and then heated to 65 ° C over 1 hour. The suspension was then stirred slowly at 65 ° C for 1 hour. 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 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.

Decant one portion and add 54.5 ml of a 13% (v / v) 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 was washed with five 25 ml portions of dry hexane; decantation at the last wash is performed at 65 ° C. The solid was decanted and an additional 50 ml of hexane was added. 1.0 ml of the final suspension contains 0.141 g of brown solid.

X-ray powder diffraction pattern,

19B2B9 measured for dry brown solid, showing peaks corresponding to 5,8 w, 5,4 s,

2.75 bs, 2.14 m, 2.0 ms, 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 slurrying into 4 equal portions, one portion is decanted and 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; decantation at the last wash is performed 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 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 bs, 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% isopentylether.

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 20 are added to the solid _; 3% (v / v) titanium tetrachloride solution in hexane. Suspension 105. The mixture was stirred slowly at 65 ° C for 1 min. room temperature. The solid was washed with five 25 ml portions of dry hexane, decanting at the last wash at 65 ° C. Fixed; decant and add 50 ml of hexane. 1.0 ml final suspension contains 0.158 g of brown solid. ¹ ·

Example 1 and d 5

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

Example

Propylene polymerization is carried out in a cylinder at 0.28 MPa 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 (g)

0,0 · ’0.0875

-,. 0.0875 '0.0754 · 0.0843

0,099 ’

0.0948 ** 0.2

** 0.2 * 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.

Example 7

The polymerizations are carried out at 71 ° C about 1 ° C

Speed g / g / h Soluble fraction%

253 10.9 219 2.5 * ^** 213 5.4 165 6.0 106 19.6 195 5.7 65 6.0 35 ‘2,2 *

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 of 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.

198289

Table II

Example Weight (gj Speed (g / g / h) 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 i Ύ * * # # # * 0.4 628 2.6 * ⁴ 401 4.6 *** AAT1C13, Stauffer Chemical Company Example 8 ** Molar ratio diethylaluminiumchlo- titanium trichloride, BTS. and Coll 2,8 / 1 / Liquid phase polymerization of propylene / 0.028 / 0.054. (block) are carried out in a 1 liter reactor. *** Four-hour cycles. for 2 hours at 71 ° C under pressure pyrene 3.22 MPa and s small amount of water thanks. 0.3 ml is used for each cycle 24.4% (w / w) diethylallyl solution of minium chloride in hexane. Table 111 Example Weight (g) Speed (g / g / h) Soluble Extractable share (%) share (%) 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 * AATlCh, Stauffer Chemical Company Example 10 0.0025: ml BTS and 0.00125 Coll *** 0.32 ml 24.4% % by weight of the solution Stock solution of brown catalyst component diethylaluminum chloride in hexane. was prepared as in Example 9 with the following wells: Example 9 1. 24.6 ml hexane and 12.5 ml of tl- Stock solution of brown catalyst component The reaction mixture was cooled to 0 ° C and added

is prepared by adding 80 ml of hexane and 40 ml of titanium tetrachloride to a 500 ml flask and cooling to 0 ° C. To this solution was added 247 ml of 24.4% (by weight) dlethylaluminum 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 2 hours, the resulting brown solid was washed with hexane and aliquots of the slurry were used in the polymerization.

74.8 ml diethylaluminum chloride.

2. To the washed solid from 1. was added 144 mL hexane and 20.1 mL benzylisopentyl ether.

3. To the solid of 2. add 60.4 mL of 11.9 why. (v / v) solution of titanium tetrachloride in hexane.

They did

Example 10 is repeated, except that 79.5 ml of 9.04 o / o (v / v titanium tetrachloride solution in hexane) is used in step 3. Example 10 is repeated.

Example 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 TiCl4 are cooled to 0 DEG C. and 594.8 ml of a 25% EtaAlCl solution are added. To the washed and decanted solid was added 400 mL hexane.

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

3. To the washed solid from 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.

... · '.T ··.'. '

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. .

Ia

Example

Table IV

Speed (g / g / hj Soluble fraction ('%)

9 * Comparisons were made with a brown catalytic component containing ^{isopentyletheru,:} Prepared as in Example 1-4, which has a speed of 178 and a soluble portion of 1.3%.

.61. . . 3.2

Example16

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 Coll was used.

Example

68.5 - 51.7 161

10 *. . · 11 *

12 ***

13**

14 **

The comparison is always carried out with a brown isopentylether-containing catalyst component, prepared similarly to Examples 1-4.

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

Table V Speed (g / g / hj)

Soluble fraction (%)

20.3

21.5 - 4.2

17.2

15.5

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) Solubility (%) * Comparison for 12, 13 and 14 is made with a brown catalyst component containing Isopentylether, prepared similarly to Examples 1-4 having a rate. and a soluble fraction of 178 and 1%, respectively. 164 and 1.2%, respectively. 164 and 1.2%.

159

1,2

11.6

7,2,

Example 18

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

Ϊ9Έ'2 ^: Ο

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 of isopentylether

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 / jg. Analysis yielded 26.0% 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 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. Analysis provided 26.8% Ti, 60.0% Cl, 0.36% Al and 6.26% isopentyl ether.

Example 20

A brown catalyst component was prepared as in Example 10 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 propylene polymerizations were carried out as in Example 6.

Table VII

Example Weight (g) Speed (g / g / h) Soluble fraction (%) 18 0.08 259 5.0 0.08 263 3.9 19 Dec 0.08 264 5.7 0.08 240 5.2 20 May 0.08 173 6.4 0,08 * 168 1.4

* 0.008 ml BTS and 0.004 ml Coll were used. Example 22

The polymerizations of propylene are carried out as

in Example 8. Table VUI Example Weight (g) *** Speed (g / g / h) Extractable share (%) 18 0.05 * 3065 3.6 0.05 ** 2276 3.8 19 Dec 0.05 * 1766 2.9 0.05 ** 1393 2.8

* 2-hour cycle ** 4-hour cycle *** Use a brown solid EtzAlCl / BTS / Coll ratio of 1.0 / 3.0 / 0.03 / 0.06.

Claims (11)

• 1. Brown solid mixture suitable as a catalyst component for the polymerization of olefins, in particular propylene, characterized in that it contains (S-titanium chloride) and up to 10 mole% 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 and has a surface area greater than 50 m ² / g and a pore volume greater than 0.10 c, m ³ / g. 2. The brown solid mixture of claim 1, wherein the organic ethertrononor is selected from the group consisting of ethers. . 3. The brown solid mixture of claim 1 wherein the organic electron donor is a single compound, namely an ether. 4. The brown solid mixture of claim 2 wherein the ethers are lower alkyl ethers. VYNALEZU 5. The brown solid mixture of claim 3 wherein the ether is a lower alkyl ether. 6. The brown solid mixture of claim 4 wherein the lower alkyl ethers are isopentylether. and n-butyl ether. 7. The brown solid composition of claim 5, wherein the lower alkyl ether is isopentyl ether. -. ? 8. The brown solid composition of claim 4 having a surface area greater than 80 m &^lt; ^{2 >} / g and a pore volume greater than 0.15 cm < ³ > / g. :. , 9. Brown solid mixture according to clause. 5, characterized in that it has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 µm ³ / g. 10. Brown solid mixture. according to point. 6 characterized in that it has a surface area greater than 80 m ² / g and a pore volume greater than 0.15 cm ³ / g. 11. The brown solid composition of claim 7 having a surface area greater than 80 m &^lt; ² &^gt; / g and a pore volume greater than 0.15 cm / g. Severography, n. p., iSvod 7, Most