KR820001052B1 - Chemical composition based on titanium trihalides - Google Patents

Abstract

The compds. nTiCl3MCln (Me = Al, Cr, Mn, V, Ti, Zr, Mo, Zn and Ca; n = the valence of M) are prepd. and used as olefin polymn. catalyst. Thus, TiCl4 was treated with Mn to give a suspension of TiMn3Cl9 which was used with (iso-Bu)3Al in the polymn. of ethylene. The polyethylene product had melt index 0.31 g/10 min (2.16 kg load) and d. 0.972 g/cm2.

Description

Catalyst Composition Based on Titanium Trihalides

The present invention relates to a titanium trihalide obtained by treating a titanium compound (1) having a trivalent or higher valence (1) with a second metal vapor (2) in the presence of a compound capable of supplying a halogen atom (halogen class) (3). The present invention relates to a novel catalyst composition based on halides of dimetals (which may be titanium itself).

Second metal chloride selected from the group of Mg, Al, Ti, V, Cr, Mn and Fe characterized in that the ratio of titanium to the second metal in Korean Patent Application No. 172 No. 172 is represented by the following general formula. A method for producing a special titanium trichloride modified by the presence of is described.

nTiCl ₃ MCl _n (1)

Wherein M is the metal as described above and n is the valence.

According to the application method described above, the titanium trichloride composition and such vanadium composition are obtained by reacting the trichloride with the vapor of metal M. According to the above technical method, it is possible to prepare a composition based on titanium trichloride and magnesium dichloride. Here the ratio of Mg to Ti is higher in the composition (1) and in fact magnesium has an excess of molar ratio Mg to Ti, usually in excess of 1: 2.

The present inventors are made of titanium trihalide and metal halides of 1 or 2 or more, and the molar ratio (the latter is metal to titanium) is 1: n or more (where n is a metal valence present, and several metals of different valences exist at the same time). In the case of figures corresponding to larger valences).

In such a case, a composition having a relatively large amount of halides other than titanium trihalide was obtained as compared with the composition obtained by the method according to the aforementioned patent application. In practice, the M to Ti ratio is on the order of 200 or more.

The composition is prepared by the process of vaporizing the metal shown in (2) above in a vacuum and reacting the titanium compound with the vapor of the metal thus obtained in the presence of a halogen feed compound. The vaporization of the metal can be carried out at a temperature of 300 ° C to 2500 ° C (depending on the metal) under an absolute pressure of 1 to 10 ^-6 Torr. The reaction in the presence of the halogen feed material of the vapor and the titanium compound thus obtained can be carried out at a temperature of -150 ° C to + 100 ° C depending on the special reagent to be used in the gas phase or liquid phase or according to the operating method.

According to a preferred method of the present invention, this reaction is carried out in the presence of an organic diluent (titanium compound and halogen atom are dissolved or sliced in double before contact with the metal vapor), each of which is a liquid phase under the pressure conditions employed in the liquid phase. It may be carried out at a temperature below the boiling point temperature (eg -70 ° C to + 20 ° C).

Halogen feeds are organohalides, in particular compounds having the general formula C _m H _{2m + 2-x} X _x where X is Cl or Br and m is a number from 1 to 18, x is a number from 1 to 4. In this case, these are the diluents described above.

Inorganic halides of other high valence elements may also be used, but may necessarily exist in the oxidation state of the kind, for example, SnCl ₄ , SbCl ₅ , POCl ₃ , VCl _4, and the like. Titanium compounds can be selected from a wide range of compounds, for example titanium trihalides and tetrahalides, titanium tetraalcoholates and halogen alcoholates, titanium tetrabenzyl and halogen benzyl derivatives, titanium tetraaryl and halogen aryls, titanium amides and amidohalides The metal to be vaporized is selected from Titanium chirate and other compounds and is selected from Al, Cr, Mn, Fe, V, Ti, Zr, Mo, Zn and Ca.

As described above, the reaction is suitably carried out in the presence of an organic diluent selected from aliphatic and aromatic hydrocarbons or mixtures thereof, and in the case of organic halogen-providers the halogen donor itself may be a diluent.

By practical implementation of the process described above, byproducts of the reactions carried out with inorganic halides remain in the composition, but they do not cause any bad changes, and the shape and properties of these compositions are formed from halides of low valence metals and provide halogens. It does not change more than things.

Compositions based on titanium trichloride, which is the object of the present invention, have many advantages in use, the use of which has proved particularly effective as a component of the catalyst system in the polymerization of unsaturated compounds, which is also a second form of the present invention.

Indeed the presence of a system consisting of derivatives of aluminum with the general formula AIR _p X _3-p wherein R is a hydrocarbon group, X is a halogen and P is a number from 1 to 3, and a composition based on the titanium trihalides as described above Under the polymerization reaction, polymerization of the polymer or copolymer of olefin, in particular ethylene, was promoted.

The composition of the present invention can be used directly in the polymerization process obtained by the above production method without any pre-filtration or separation step. The polymerization step is carried out in the presence of a hydrocarbon solvent, which is the same diluent used for the preparation of the titanium derivative, in a tonnage range of 20 to 200 ° C. and a pressure range of 1 to 60 atm.

In the case of ethylene, very high yields were obtained, ie 10,000 grams of polymer per gram of titanium and atmospheric pressure of ethylene were found to be extremely valuable.

The polymers produced are of high linearity and they have high density and high crystallinity and do not require any washing step to remove catalyst residues.

Example 1

The manufacture was carried out in a rotating flask and a spiral tangsten filament wired in alumina acting as a crucible in the flask was arranged and this filament was connected to a power source.

Under the flask, the cooling bath is arranged horizontally, and the upper fixed section of the device contains nitrogen and vacuum.

The crucible was filled with 0.7 g (12.5 mM) of pure manganese in granules and in a 500 ml flask was placed 150 ml of pure petroleum (boiling point 165 ° C-235 ° C), 0.4 ml of TiCl ₄ (3.6 mM) and 10 ml of 1 under a nitrogen atmosphere. Add chlorohexane (72 mM). The flask is cooled to 50 ° C. and rotated, vacuumed to 2.10 ⁻³ mmHg and then heated to helical filaments to vaporize the metal to form a reddish brown precipitate. When the vaporization step is completed over about 2 hours, nitrogen is introduced into the apparatus and the product is left to room temperature and then heated at 100 ° C. for 5 hours. Analysis of the suspension shows TiMn ₃ Cl ₉ .

polymerization

A 5 L autoclave equipped with a stirrer is filled with 2 L of heptane, 4 mM Al (isobutyl) ₃ deaerated, and a predetermined amount of catalyst corresponding to 0.04 mg atom and element Titanium prepared according to the above-described process, and the temperature is 85 After raising to 캜, 2 kg / cm 2 of hydrogen and 2.5 kg / cm 2 of ethylene are charged. Ethylene is injected continuously for 1 hour to keep the total pressure constant. 125 g of polymer with a melt flow of 0.31 g / 10 min and a density of 0.972 g / cm 3 are obtained under a load of 2.16 kg (MFI, ASTM D 1266-65T). Of activity per gram per hour, and the reaction of the styrene Ti Pressure ^{_{(g Ti h atm C 2 -}} ...) A polymer of 26,000g.

Example 2

The same apparatus and the same process as in Example 1 were repeated using tin tetrachloride as the halogen donor. The reagent used was 180 ml of petroleum, 600 mg (11.2 mM) of manganese, 0.062 ml (0.56 mM) of TiCl ₄ and 1.33 ml (11.2 mM) of SnCl ₄ . A brown slurry is obtained by heating at 95 ° C-100 ° C for 2 hours. After the color became almost white, it was collected on a filter, washed with n-octane to remove excess tin tetrachloride, and analyzed to indicate TiMn ₂₄ Sn ₂₄ Cl ₁₀₀ . When used in the polymerization of ethylene under the conditions of Example 1, this composition exhibited an activity of 19,000 g of polymer per gram of Ti and of barometric pressure of ethylene, with a polymer of 0.6 g / 10 min MFI and 0.971 g / cm 3. (See Example 1).

Example 3

Use the same equipment and process as in Example 1 and the halogen donor is 1-chlorohexane.

The amount of reagent used is 100 ml of n-octane, 650 mg (11.8 mM) of Mn, 0.1 ml (0.9 mM) of TiCl ₄ and 10 ml (73 mM) of C ₆ H ₁₃ Cl. Heating for 2 hours with stirring at 95 ° C.-100 ° C. afforded a brown suspension, and the analysis result of the suspension shows TiMn ₆ Cl ₁₅ . The use of this composition in the polymerization of ethylene under the conditions of Example 1 gives an activity of 28,000 g of polymer per gram of Ti, hourly, and barometric pressure of ethylene, with a polymer of 1.21 g / 10 min and 0.970 g / cm 3. Has a density of.

Example 4

The catalyst described in Example 1 was used to carry out the copolymerization of ethylene and propylene as the same process as described in Example 1, with the same polymerization conditions and with the same concentration of catalyst and cocatalyst.

Injection of propylene is carried out simultaneously with ethylene in an amount equal to 3% of ethylene and the gas is measured with a calibrated drifter. After 2 hours of polymerization, 200 g of a polymer having a MFI of 0.33 g / 10 min and a density of 0.9539 and corresponding to an activity of 21,000 g of polymer per gram of Ti, per hour and at atmospheric pressure of ethylene are obtained.

Example 5

The same equipment and process as in Example 1 was applied and the reagents used TiCl ₄ , nC ₆ H ₁₃ Cl, metal Zn and n-octane as diluent in the following amounts.

1.5 g (23 mM) of Zn, 0.1 ml (0.91 mM) of TiCl ₄ , 7.1 ml (51.6 mM) of nC ₆ H ₁₃ Cl and 230 ml of n-octane, Zn all vaporize and the suspension is allowed to come to room temperature After extraction, it is heated at 100 ° C. for 3 hours. Analysis of the suspension shows TiZn ₉ · ₅ Cl ₂₁ .

Example 6

The amount of reagent adapted and used with the same process as in Example 1 is 0.77 g (14.8 mM) of Cr, 0.20 ml (1.81 mM) of TiCl ₄ , 1.8 ml (15.4 mM) of SnCl ₄ and 90 ml of petroleum. .

The resulting suspension is heated at 100 ° C. for 2 hours and then filtered to recover the collected solid with n-heptane, degassed three times and then zestilled in n-heptane. The analysis of the slurry indicates that the general formula TiCr ₁ .5 Cl ₇ .5.

Example 7

The same apparatus and the same process as in Example 1 were used and the following reagents were used.

Ie 1.05 g (19.15 mM) Mn, 1.71 ml (15.5 mM) TiCl ₄ , 1.65 ml (15.5 mM) VCl ₄ and 100 ml n-heptane.

The metal is increased to 80% and then the suspension is left to room temperature and heated at 85 ° C. for 2 hours. The suspension is filtered and the recovered solid is washed with n-heptane and reslurried in 100 ml of hexane.

The suspension has an analysis of TiMnV ₇ Cl ₂₆ . The activity in the polymerization of ethylene is 40,000 g of polymer per gram of Ti, per hour and the pressure of ethylene and the density of the polymer is 0.970 g / cm 3.

Example 8

Follow the process of Example 1 and use the following reagents.

0.24 g (6 mM) Ca, 0.66 ml (6 mM) TiCl ₄ , 6 ml VCl ₄ and 100 ml n-heptane.

The vaporization of the metal is complete and a brown suspension is obtained which, when heated at 65 ° C. for 3 hours, turns the suspension purple.

The suspension is recovered on a filter and the solid residue is washed with n-heptane and reslurried in 100 ml of n-heptane. Analysis of the product shows the composition of TiCaV ₈ Cl ₂₉ .

Example 9

The same equipment, process and conditions of temperature and pressure as described in Example 1 were applied and the following reagents were used.

0.6 g (11.2 mM) of Mn, 0.74 g (3.7 mM) of TiCl ₃ form ( ₃ TiCl ₃ AlCl ₃ ), 5 ml (36 mM) of nC ₆ H ₁₃ Cl and 100 ml of n-octane.

The suspension obtained after the vaporization of the metal is completed is left to room temperature and then heated at 100 ° C. for 10 hours.

Each operation is carried out under a nitrogen atmosphere and the analysis of the suspension shows the composition as TiMn ₃ Al _{0 · 3} Cl _{9 · 3} . The activity of this composition in the polymerization of ethylene is 23,000 g of polymer per gram of Ti, per hour and per atmosphere of ethylene.

Claims (1)

As described above, the titanium compound having a trivalent or higher valence is reacted with a metal vapor selected from the group Al, Cl, Mn, Fe, V, Ti, Zr, Mo, Zn and Ca in the presence of a halogen compound. Gram-atomic to Titanium gram-atomic ratio of the metals and metals reacting in the phase is greater than 1: n, where n is a metal atom and is equivalent to a greater valency when several metals are present simultaneously). A catalyst composition having a catalytic action in a polymer of a halogenated titanium trioxide and an unsaturated compound based on a halide of the metal.