CS195282B2 - Catalyst for polymerisation of alpha-olefins - Google Patents

Description

The present invention relates to a catalyst for the polymerization of α-olefins, in particular ethylene, composed of an alkylthiolium compound and the reaction product of a transient lead chloride and thionine trichloride dispersed on a support having a large specific surface area.

It is known to use titanium halides effective from catalytic catalysts. in the polymerization of α-olefins under low pressure. These halides are prepared by the reduction of titanium tetrahalides by alkyl aluminum alcohols. alkyl halide compounds. The reaction is generally carried out under an inert atmosphere and in the presence of an inert solvent. The catalyst thus obtained is subsequently used together with the alkyl metal compounds to polymerize α-olefins in suspension in an organic solvent at an appropriate monomer pressure.

These titanium halides, however, show impurities due to the presence of aluminum compounds and do not show very good catalytic activity, so that the resulting polymer requires costly purification operations to remove catalytic residues.

Furthermore, a catalyst for the polymerization of α-olefins containing mixed crystals of T 1 Cl 3 or TiCl 2 with metal halides in combination with alkyl-aluminum compounds is known.

At the present time they are proposed to proceed.

in which the titanium halides are deposited on inorganic substances, thereby obtaining polymerization catalysts of increased efficiency. Carriers used include, for example, oxide or magnesium hydroxide; it is to be understood, however, that the catalytic activity of the titanium compound carried on these materials varies considerably depending on the chemical nature of the surface of the compounds. Therefore, in many cases, these compounds must be subjected to treatment with Grignard reagents, alkyl aluminum compounds or hydrogen to improve their activity.

SUMMARY OF THE INVENTION The present invention provides a catalyst for the polymerization of α-olefins, consisting of an aluminum compound of the formula AIR3 or Α1 _χ Υ ₃ _ _χ

R is alkyl, aryl or cycloalkyl,

Y is halogen or hydrogen and x is 1 to 2 and

b) a reaction product of a transition metal chloride and a titanium tetrachloride of the formula

198282

MCl _n . >'where

M is vanadium, manganese, cobalt or iron; and n is a number equal to the valency of M, finely dispersed on a carrier having a large specific surface area, wherein the transition metal is present in an amount of 0.1 to 10, preferably 1 to 3 percent by weight carrier weight,

The reaction products described are very stable from a chemical point of view, since titanium tetrachloride and transition metal chloride are isostructural: in addition they contain titanium in the optimum valence state for the best catalytic efficiency.

These reaction products are prepared according to the procedure of U.S. Pat. No. 195,283, which comprises depositing a transition metal compound at the lowest valence stage on a support, heating to reflux temperature in titanium tetrachloride, and removing excess titanium tetrachloride.

The material used as the carrier is selected from the group of materials having a large specific surface area, such as the oxides of the elements belonging to ^: II to IV. groups of the periodic system elements. Preferably, the material used as the support is selected from silica, silica-alumina, ZnO2, MnO, TiO2, CaO.

As previously mentioned, the catalytic systems of the invention do not need to be pretreated, since the efficiency of the catalyst systems of the invention is high and homogeneous, although the chemical nature of the support is subject to variations; however, said carriers can also be pretreated with Grignard reagents or aluminum alkyl halides to further improve the properties thereof.

In any case, the efficiency of the catalyst systems of the present invention in polymerization reactions is higher compared to TiCl4-treated carrier processes, with the other conditions remaining the same. The catalysts of the present invention exhibit good properties in the presence of hydrogen and cause a narrow molecular weight distribution in the case of ethylene polymerization.

The polymerization reaction is carried out in a manner known per se at temperatures ranging from 0 to 200 ° C and at a pressure of 0.01 to 5 MPa.

In the following examples of the process of the invention, the solvent, the organometallic compound [Alf-C4H9J3 at a concentration of 0.2 vol%] and the transition metal reaction products prepared as described are fed to an autoclave thermostatized at 85 ° C. The ethylene pressure was kept constant throughout the six-hour experiment. These standard conditions apply to all procedures given in the following examples (standard polymerization). Acquired: The polymers were vacuum dried to constant weight before evaluation in yield. '

The following examples are provided for convenience only and do not limit the scope of the invention in any way.

Example 1 ..

100 g of "Low Aluanina" S1O2 / Al2O3, SO = 400 m ² / g, were refluxed in boiling xylene to azeotropically remove the defect. To the product, dried, filtered under nitrogen and washed with hexane, 3 g of tetraicarbonyl-vanadium cyclopentadienyl, V (CO 4 Cp, in 200 ml hexane) was added. After cooling to room temperature for 6 hours, it was suspended in 200 ml of TiCl4, during which time it was dark purple, filtered, washed several times with hexane and dried in vacuo.

The analysis showed the following composition:

Ti 7,30%

V 0,40%

Cl 12.54%

In the polymerization of ethylene under partial pressure H 2 = 1.3 MPa; and C2H4 - 0.8 MPa, 240 mg of this catalyst were used.

500 g of polyethylene MF ₂₁ were obtained as described above. ₆ = 1 [TjJdlkáŮn = 4.6 dl / g and containing 36 ppm Ti-N, wherein the Ti content was about 33 ppm.

Example 1 a d 2

The same SiO 2 - Al 2 O 3 used in Example 1 was refluxed under the same conditions, only with titanium tetrachloride. After the same treatment, the air-sensitive white material showed the following analytical results

Ti 4,10¾

Cl 7.98%

224 mg of this catalyst, under the same polymerization conditions of Jakio 'in the previous example, yielded 60 g of a polymer having

MF ₂ i, 6 ⁼ 0 | 2,. [η] deUůn —6.6 dl / g and a Ti content of 150. ppm · β

EXAMPLE 1 3 g SiO ad _second (> 99%), SA = 400 m ^z / g was dehydrated, subjected, azeotroping with xylene procedure -uvedeným in the previous example, treated with 0.65 g V (CO) 4 Cp in hexane (50 mL) followed by va. After removal of the solvent or solvent in liquid TiCl4 (50 ml), for the time and in the manner described in Example 1. The color of the catalyst thus obtained was dark violet. Analysis of the mixture showed the following values:

Ti 4.65% V 0.40%

Cl. 8.24% 105 mg of the talkto catalyst obtained was used in standard polymerization at a relative pressure of H 2 / C 2 H 4 = 1/10 bar. 102 g of polyethylene were obtained by the above process. pem; Mf ₂ and 6 = 0.3 and the Ti-N corresponded to 52 ppm, wherein the Ti content was 46 ppm.

EXAMPLE 4 g of S-IO2 / Al2O3 of the same type as in Examples 1 and 2 were dried in a muffle furnace at 400 ° C for 24 hours and then impregnated with 4.0 g of Mh 2 (CO) 10 in 200 ml of hexane.

The solvent was removed in a rotary evaporator and the orange-yellow solid was refluxed in boiling TiCl 3 for 6 hours.

The filtered violet material, washed with hexane and dried under vacuum, showed the following analysis:

Ti 5,72%

Mn 1,35%

Cl. 12.60%

169 mg of this product, used in standard polymerization tests at 1.3 MPa H2 and 0.8 MPa C2H4, yielded 151 g of polyethylene having a

MF2 _i i6 ⁼⁼ 0.350

MF _{21 6} = 15684.

MF ₂₁ , ₆ / MF ₂ , ₁₆ = 44, [η] = 3.3 dl / g and 79 ppm Mn + Ti, where Ti = 64 ppm.

EXAMPLE 5 g of finely divided MgO, dried in a muffle furnace at 400 DEG C. overnight, was treated with 1.5 g of Co2 (CO) 8 in 100 ml of hexane. The solvent was then removed on a rotary evaporator and the residue was refluxed under a nitrogen atmosphere in 100 ml of TiCl4 for 8 hours.

The violet powder was filtered from the heat and then filtered.

washed several times with hexane and dried in vacuo. The product had the following composition:

TI. . 3.70%

Co '1,55%

Cl 31.15% mg of the product so obtained was used at. standard polymerization under a hydrogen pressure of 1 MPa and a C2H4 pressure of 1 MPa. 250 g of polyethylene were obtained as described above.

MF ₂ , ₁₆ = 0, 869,

MF ₂₁ .6 = 34.97,.

MF _{2! 6/2 MF>! N} = 40.2, [ijjdekařin = 1.92 dl / g Content

Ti + Co - 6.5 ppm, where

Ti = 4.6 ppm.

Example 6

A sample of commercial MgO was hydrated in the soil at 80 ° C for 4 hours and then dried in a muffle furnace at 400 ° C in air for 24 hours. ·; ·.

mg of the MgO treated in this way was impregnated with V (CO 4) 4 Cp (1.2 g) in hexane (100 ml) and the solvent was removed in a rotary evaporator. The dry residue was then refluxed in boiling TlCl4 (100 mL) for 4 hours. '

The purple product was filtered. washed and dried under vacuum. Its composition was as follows.

Ti i 3,31%

V 0,58%

Cl 35.23% mg of this catalyst was used in standard polymerization under relative hydrogen pressure (C2H4 = 1/10 bar). 235 g of polyethylene of values were obtained

MF ₂ . _l6 = 1.203, '· / ·

MF ₂ i, ₆ = 49.03,

MF and _{2, 6/2} MF ₆ .i = 40.8, [T _t] decalin of 1.90 dl / g, and containing 3.3 ppm of Ti-N, where Ti was 2.8 ppm.

Example 7 g of MgO treated according to Example 6 was refluxed in boiling TClCl (100 mL) for 4 hours. The white solid was then filtered, washed and dried in vacuo. Its composition was as follows:

Ti 1,43%

Cl 31.62% of the catalyst was used for comparison in standard polymerization according to the procedure of Example 6. 81 g of polyethylene having values of

155182

MiF ₂ . _% = 1.81

MF _{21 <6} = 44

MF ₂ i.y / MF ₂ 4y = 36.3, [η], decalin - 2.73 dl / g and Ti content = 7.4 ppin. Example 8 g of SiO2 type used in Example 3 was dehydrated by azeotropic distillation with xylene and reacted with 2 ml of AlEtCl2 in 100 ml of hexane. 1.0 g of V (CO) 4 Cp and solvent were then added to the suspension. subsequently collected in a rotary evaporator. The material so obtained was refluxed for 6 hours with boiling TlCl4. After filtration, wash with hexane. and dried in vacuo to give a violet product having the following composition:

Ti 2,97%

V 0,86%

AI -. 1.90%

Cl - 8.59%

192 mg of the catalyst thus obtained were used in standard polymerization at a relative pressure of H 2 / C 2 H 4 - 1/10 bar. 96 g of polyethylene were obtained

ME ₂ , = = 0,335,

MF _{21 (I} = 14.1,

MF _2M / MF ₂ , ₁₆ = 42.1, / [η] = 2.63 dl / g and Ti + V = 80 ppm, where the Ti content was 60 ppm.

Example 9 g of SiCl 2 - ss; of the type as in Example 1, dried in an oven at 200 ° C, was reacted with an ethereal solution of chlorobutylGrighardi reagent (10 ml; 1/1 solution) in 10 µl of hexane. The mixture was then evaporated in a rotary evaporator and 1.2 g of V (CQ) 4 Cp in 100 ml of hexane were added. Removal of solvent in the evaporator, the dry product was refluxed in boiling TiCl2 for 6 hours, then filtered, washed and dried, the violet solid having the following composition:

Ti 9,20%

V 0,74%

Mg ..... ''^; 1,07%

Cl, 21.850 / 0

212 mg of this product, used in standard polymerization under 0.85 MPa of ethylene and 1.5 MPa of hydrogen, yielded 325 g of polyethylene

MF ₂ .16 = 1.014,. ,

MF _21i6 = 45.4-4

MF _2! . ₆ / MF ₂ .i ₆ = 45.44, [ηί = 2.0 di / g and containing 65 ppm Ti + V, with a Ti content of 61 ppm?

Claims (2)

SUBJECT CLAIMS 1. Catalyst for the polymerization of .alpha.-olefins, characterized in that:. consists. of a] aluminum compounds of the general formula AIR3 or AI _X Y ₃ _ _X where R is alkyl, aryl or cycloalkyl, Y is halogen or hydrogen and x is an integer from 1 to 2 and b) a reaction product of a transition metal chloride and a titanium tetrachloride of the formula MC1 ". n TiCb, INVENTING WHERE M is vanadium, manganese, cobalt or iron and n is a number equal to the valence of M, finely dispersed on a support having a large specific surface area, the transition metal present in an amount of 0.1 to 10, preferably 1 to 3 percent by weight based on weight of carrier. Catalyst according to claim 1, characterized in that the support having a large specific surface area is selected from oxides of elements II. to IV. groups of the periodic system, a. j., * 4vo4 7, Mott