Polymerization Catalysts

It is known to homo- and copolymerize ethylene with various types of catalysts. One of the best known catalysts has been obtained by mixing a titanium or vanadium compound with an organometallic derivative of a metal belonging to Groups I to III of the Mendelyeev Periodic Table.

Our group has also disclosed highly active catalysts for polymerizing olefins obtained by mixing hydrides or organometallic compounds of the Groups I to III metals with products obtained by contacting a titanium trihalide with carriers consisting of preactivated anhydrous Mg halides or with normally inactive anhydrous Mg halides but under conditions such that the anhydrous Mg halides are converted to active form.

One object of this invention is to provide new and improved, highly active catalysts for the homo- and copolymerization of ethylene and higher alpha-olefins.

This and other objects are accomplished by the present invention which provides catalysts prepared as stated in the foregoing abstract.

Electron-donor compounds which may be used in preparing the improved catalysts of the invention are characterized in containing one or more electronegative groups such as, for instance, the nitro-, ethero-, ester, amino, and nitrile group in which the electron-donor atom is, in general, a N,O,P,S,As or Sb atom.

The electron-donor compounds are preferably selected from among amines, such as n-butylamine, trimethylamine and triethylamine, pyridine, etc.; P-compounds such as phosphines, oxyhalides of P, alkylphosphoramides, for example tris-N, N-dimethylphosphoramide, the trialkyl phosphates and phosphites; stibines and arsines; ethers and thioethers such as ethylphenyl ether, dioxane, tetrahydrofurane and thiophene; esters including ethyl acetate, diethyl fumarate, dihexyl phthalate; nitriles such as benzonitrile, acetonitrile etc.; ketones such as acetone, benzophenon; the nitro-compounds such as nitrobenzene, dinitrocyclohexene, trinitrobenzene; aldehydes such as acetaldehyde and benzaldehyde; alcohols including ethanol and butanol, etc; amides such as urea, formamide, etc.

Particularly representative addition products are: TiCl.sub.4.1 C.sub.4 H.sub.8 O.sub.2 ; TiCl.sub.4.2 C.sub.4 H.sub.8 O; TiCl.sub.4.1 C.sub.4 H.sub.4 S; TiCl.sub.4.2 C.sub.5 H.sub.5 N; TiCl.sub.4.2 CH.sub.3 CN; [TiCl.sub.4.1 POCl.sub.3 ].sub.2 ; [TiCl.sub.4.1 [(CH.sub.3).sub.2 N].sub.3 PO]; [TiCl.sub.4.1 CH.sub.3 OOOC.sub.2 H.sub.5 ].sub.2 ; TiCl.sub.4.1 C.sub.4 H.sub.9 NH.sub.2 ; TiCl.sub.4.1 N(CH.sub.3).sub.3 ; TiBr.sub.4.2 POBr.sub.3 ; TiCl.sub.4.1 P(C.sub.6 H.sub.5).sub.3 ; TiCl.sub.4.1 C.sub.6 H.sub.5 NO.sub.2 ; Ti(OC.sub.6 H.sub.5).sub.4.1 N(C.sub.2 H.sub.5).sub.3 ; Ti(OC.sub.6 H.sub.5).sub.4.1 C.sub.5 H.sub.5 N; Ti(H.sub.2 O).sub.6 Cl.sub.3 ; Ti[OC(NH.sub.2).sub.2 ].sub.6 Cl.sub.3 ; TiCl.sub.3.3 C.sub.5 H.sub.5 N; TiCl.sub.3.3(C.sub.2 H.sub.5).sub.2 O; TiBr.sub.3.2 N(CH.sub.3).sub.3 ; TiCl.sub.3.2(CH.sub.3).sub.2 CO; Ti(C.sub.2 H.sub.5 OH).sub.6 Cl.sub.3 ; Ti(i-C.sub.4 H.sub.9 OH).sub.6 Cl.sub.3 ; TiCl.sub.3.1 C.sub.4 H.sub.8 O.sub.2.

The formulae C.sub.4 H.sub.8 O, C.sub.4 H.sub.8 O.sub.2, C.sub.4 H.sub.4 S, C.sub.5 H.sub.5 N comprise, respectively, a tetrahydrofurane, a dioxane, a thiophene and a pyridine molecule.

The ratio of Ti compound to complexing compound in the addition product is in general comprised within a very wide range. Particularly high catalytic activities have been obtained by the use of addition products in which said ratio has the value 1.

The preparation of the addition products is generally carried out by adding solutions of the electron-donor compound to solutions of the Ti compound. Usually it is not necessary to heat up the reaction mixture inasmuch as the reaction resulting in the formation of the complexed substance is generally exothermic.

The addition products that are formed are in general colored solid substances which are separated by filtering and drying under vacuum.

Titanium compounds particularly suited for use in the preparation of the addition products according to this invention, are the halides, oxyhalides and alcoholates.

The order in which the reactants for the preparation of the supported catalytic component are added, is not critical. However, it is preferred to contact the carrier with the Ti compound in the presence of the electron-donor compound, or to first contact the electron-donor with the carrier in the active form and then add the titanium compound.

The catalysts of this invention are thus the products formed by mixing a hydride or organometallic compound of a Group I to III metal with the product which results when an addition compound of Ti of the type indicated above, or a di-, tri-, or tetravalent Ti compound and an electron-donor compound, is (or are) brought into contact with a carrier consisting of, or containing, an anhydrous Mg halide, more particularly MgCl.sub.2 or MgBr.sub.2, either in preactivated form or in non-active form but under conditions designed to activate the Mg halide.

By "active anhydrous magnesium halide" we intend such a halide having one or both of the following characteristics

(a) in the powder X-ray spectrum thereof the diffraction line corresponding to the most intense line in the spectrum of the normal inert magnesium halide is less intense; and

(b) the active Mg halide has a surface area higher than 3 m.sup.2 /g and preferably higher than 10 m.sup.2 /g

The most active forms of the magnesium halides are characterized in that the X-ray spectra thereof show a broadening of the diffraction line which is normally most intense and/or have a surface area higher than 15 m.sup.2 /g.

In the case of the anhydrous magnesium chloride, the X-ray spectrum of many active forms is characterized in that the diffraction line appearing at a lattice distance (d) of 2.56 .ANG., and which is the most intense in the spectrum of the normal MgCl.sub.2, is less intense, while in its place a broadened halo appears at a lattice distance within the ranges from 2.56 to 2.95 .ANG..

Similarly, the X-ray spectra of many active forms of magnesium bromide are characterized in that the diffraction line at d=2.93 .ANG., which is the most intense in the spectrum of MgBr.sub.2 of the normal type, is less intense, while in its place a broadened halo appears within the range of d=2.80 to 3.25 .ANG..

According to a preferred method, the supported catalytic component is prepared by co-grinding anhydrous Mg halide and the titanium addition compound, or with a di-, tri-, or tetravalent Ti compound and an electron-donor compound, according to known technologies, for grinding times and under conditions sufficient to convert the anhydrous Mg halide into an active form having the above defined characteristics.

The grinding is preferably carried out in a ball mill or grinder operating according to the dry method, in the absence of liquid inert diluents.

The supported catalytic component may be prepared, also, by simply mixing, in the solid state, the Ti-complex, or a di-, tri-, or tetravalent Ti compound and an electron-donor compound, with anhydrous Mg halide which has been preactivated.

The active anhydrous Mg halides can be obtained by methods other than grinding. One such method consists in starting with a compound of the formula RMgX, in which R is a hydrocarbon radical, and X is a halogen, and effecting a disproportioning thereof by known methods, or by treatment with halogenated compounds such as, for instance, anhydrous gaseous hydrochloric acid.

Another method consists in thermally decomposing, under reduced pressure, coordination complexes of the anhydrous Mg halides with Lewis bases or acids or by decomposing the Mg halides in the form of compounds containing organic crystallization solvents. For instance, MgCl.sub.2 in an active form may be obtained by this method from its solutions in ethanol.

The quantity of the Ti addition compound or complex useful in preparing the supported catalytic component may be comprised within a wide range the lower limit of which may be below 0.01% by weight with respect to the carrier, and the upper limit of which may reach values above 30% by weight and more.

Particularly good results are obtained, as far as concerns the yield of polymer on the amount of catalyst used, with reference to both the Ti compound and the carrier, when the amount of the Ti compound present on the carrier is between 1% and 10% by weight.

Hydrides and organometallic compounds particularly suited for the preparation of the catalysts are:

Al(C.sub.2 H.sub.5).sub.3, Al(C.sub.2 H.sub.5).sub.2 Cl, Al(iC.sub.4 H.sub.9).sub.3, Al(iC.sub.4 H.sub.9).sub.2 Cl, Al.sub.2 (C.sub.2 H.sub.5).sub.3 Cl, Al(C.sub.2 H.sub.5).sub.2 H, Al(iC.sub.4 H.sub.9).sub.2 H, Al(C.sub.2 H.sub.5).sub.2 Br, LiAl(iC.sub.4 H.sub.9).sub.4, LiiC.sub.4 H.sub.9, etc.

The molar ratio between the Al compound and the Ti compound is not critical. When the catalysts are used in the polymerization of ethylene, such ratio is preferably comprised between 50 and 1000.

The catalysts of this invention are used in the homo- and copolymerization of olefines according to the known techniques, that is, in the liquid phase, in the presence or absence of an inert solvent, or in the gaseous phase.

The temperature of the polymerization may be comprised between-80.degree. and+200.degree. C., but preferably is comprised between 50.degree. and 100.degree. C., operating at atmospheric pressure or at a pressure greater than atmospheric pressure. The regulation of the molecular weight of the polymer during the polymerization is achieved by known expedients, for instance by operating in the presence of alkyl halides, organometallic Zn or Cd compounds, or hydrogen.

As is well known, the activity of the known catalysts obtained from compounds of transition metals and organometallic compounds of the metals of the I, II and III Groups, is considerably reduced when hydrogen or other chain-transfer agents are included in the polymerization zone for regulating the molecular weight of the polymer produced.

In the case of the catalysts according to this invention, however, it has been found, and this constitutes another advantageous aspect of the invention, that it is possible to regulate the molecular weight of the polymer even down to low or very low values without any appreciable reduction in the activity of the catalysts.

For example, when ethylene is polymerized in contact with the present catalysts, it is possible to regulate the molecular weight of the polyethylene within a practical range corresponding to values of the intrinsic viscosity in tetralin (tetrahydronaphthalene) at 135.degree. C., comprised between about 1.5 and 3 dl/g, without the yield in polymer of the particularly active catalysts dropping to values below which it would be necessary, to carry out a purification of the polymer for removing catalytic residues therefrom, at the end of the polymerization.

The polyethylene obtained with the new catalysts is a substantially linear and highly crystalline polymer with density values equal to or greater than 0.96 g/cc, having high processability characteristics which in general are higher than those of the polyethylene obtained with the normal Ziegler-type catalysts. The content in Ti of the nonpurified polymer is in general less than 20 ppm.

The invention will be further illustrated by the following examples which are not intended to be limiting.

Unless otherwise specifically indicated, the percentages reported in the examples are by weight; the intrinsic viscosity of the polymer was measured in tetralin at 135.degree. C.

In a centrifugal ball mill were ground for three (3) hours in an atmosphere of inert gas 10 g of anhydrous MgCl.sub.2 together with 0.55 g of the addition compound TiCl.sub.4.1 dioxane.

The product discharged has a Ti content of 0.79% and a superficial area of.perspectiveto.13 m.sup.2 /g

Into a 1.8 liter autoclave were then introduced 1000 cc of heptane and 2 g of Al triisobutyl. The temperature was brought up to 75.degree. C. and there were introduced 0.046 g of the previously prepared ground product. Thereupon, the pressure was brought up to 3 atm. with hydrogen d then to 13 atm. with ethylene. Thereby the temperature rose to 85.degree. C.; the pressure was kept constant throughout the polymerization by feeding ethylene.

After 4 hours there were discharged 167 g of polymer having an intrinsic viscosity in tetralin at 135.degree. C.(.eta.)=2.3 dl/g and an apparent density of 0.275 g/cc.

The yield in polymer amounted to 699,000 g/g of Ti

10 g of anhydrous MgCl.sub.2 and 0.94 g of TiCl.sub.4.1 P(C.sub.6 H.sub.5).sub.3 compound were ground under the same conditions as those of Example 1. The Ti content of the ground product amounted to 0.44% by weight and its superficial area was.perspectiveto.13 m.sup.2 /g.

By using 0.071 g of the ground product and operating under the same polymerization conditions as in Example 1, there were obtained 396 g of polyethylene having an intrinsic viscosity of 2.0 dl/g and an apparent density equal to 0.403 g/cc. The yield in polymer amounted to 527,000 g/g of Ti.

5 g of anhydrous MgCl.sub.2 and 0.17 g of the compound TiCl.sub.4.1 thiophene were ground together under the same conditions as those of Example 1.

The Ti content of the ground product amounted to 0.47% by weight and its superficial area was.perspectiveto.13 m.sup.2 /g.

By using 0.186 g of the ground product and operating under the same polymerization conditions as those of Example 1, there were obtained 312 g of polyethylene having an intrinsic viscosity of 2.6 dl/g and an apparent density of 0.352 g/cc. The yield in polymer amounted to 331,000 g/g of Ti.

10 g of anhydrous MgCl.sub.2 and 0.5 g of the compound TiCl.sub.3.1 dioxane were ground under the same processing conditions as those of Example 1.

The Ti content of the ground product amounted to 1.15% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.137 g of the ground product and operating under the same conditions as those of Example 1, there were obtained 435 g of polyethylene having an intrinsic viscosity of 3.0 dl/g and an apparent density of 0.344 g/cc. The yield in polymer amounted to 272,000 g/g of Ti.

10 g of anhydrous MgBr.sub.2 and 0.5 g of the compound TiCl.sub.4.1 dioxane were ground under the same conditions as those of Example 1.

Using 0.046 g of the ground product and operating under the same polymerization conditions as those used in Example 1, there was obtained a very high yield in polyethylene having an intrinsic viscosity of 2.6 dl/g and an apparent density of 0.34 g/cc.

10 g of anhydrous MgCl.sub.2 and 0.65 g of the compound TiCl.sub.4.1 C.sub.6 H.sub.5 NO.sub.2 were ground under the same conditions as described in Example 1.

Using 0.074 g of the ground product and operating under the same conditions as those of Example 1, there were obtained 204 g of polyethylene having an intrinsic viscosity of 2.1 dl/g. The yield in polymer was 265,000 g/g of Ti.

10 g of anhydrous MgCl.sub.2 and 0.54 of the compound TiCl.sub.4.1 C.sub.4 H.sub.9 NH.sub.2 were ground under the same conditions as those of Example 1. The Ti content of the ground product amounted to 0.7% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.097 g of the ground product and under the polymerization conditions indicated in Example 1 there were obtained 232 g of polyethylene having an intrinsic viscosity of 2.6 dl/g and an apparent density of 0.328 g/cc. The yield in polymer amounted to 331,000 g/g of Ti.

7.1 g of MgCl.sub.2 and 1.2 g of the compound TiCl.sub.3.4 pyridine were ground under the same conditions as those of Example 1.

Using 0.085 g of the ground product and operating under the conditions of Example 1 there were obtained 325 g of polyethylene having an intrinsic viscosity 2.6 dl/g. The yield in polymer amounted to 340,000 g/g of Ti.

In a centrifugal ball mill were ground for 3 hours in an atmosphere if inert gas 20 g of anhydrous MgCl.sub.2 together with 0.8 g of TiCl.sub.4 and 0.55 g of p-chlorophenol. The product coming out of the mill had a Ti content of 0.79% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Into an autoclave of 1.8 liter capacity, were introduced 1000 cc of n-heptane and 2 g of Al triisobutyl. Thereupon the temperature was brought up to 75.degree. C. and there were introduced 0.061 g of the catalytic component herein described. The pressure in the autoclave was then brought up to 3 atm. with hydrogen and then to 13 atm. with ethylene. Thereby the temperature rose to 85.degree. C. and the pressure was maintained constant by feeding in ethylene.

After 4 hours, 388 g of a polymer having an intrinsic viscosity of 1.8 dl/g and an apparent density of 0.472 g/cc were discharged from the autoclave. The yield in polymer amounted to 800,000 g/g of Ti.

20 g of anhydrous MgCl.sub.2 were ground together with 2.17 g of p-chlorophenol and 0.8 g of TiCl.sub.4, under the same conditions as those of Example 1. The Ti content of the ground product amounted to 0.82% b.w. and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.073 g of the ground product and operating under the same polymerization conditions as those of Example 9, there were obtained 473 g of polyethylene having an intrinsic viscosity of 1.9 dl/g and an apparent density of 0.477 g/cc. The yield in polymer amounted to 790,000 g/g of Ti.

Example 10 was repeated except that 13.02 g of-chlorophenol were used.

The Ti content of the ground product amounted to 0.36% b.w. and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.136 g of the ground product there were obtained 368 g of polyethylene with an intrinsic viscosity of 2.1 dl/g. The yield in polymer amounted to 441,000 g/g of Ti.

20 g of anhydrous MgCl.sub.2 were ground under the same conditions as those of Example 9, in the presence of 1.01 g of isopropanol and 0.8 g of TiCl.sub.4. The Ti content of the ground product was 1.10% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.071 g of the ground product there were obtained 310 g of a polyethylene having an intrinsic viscosity of 2.2 dl/g and an apparent density of 0.351 g/cc. The yield in polymer amounted to 400,000 g/g of Ti.

20 g of anhydrous MgCl.sub.2 were ground under the same conditions as those of Example 9, together with 0.64 g of TiCl.sub.3 of the composition 3 TiCl.sub.3.AlCl.sub.3 and with 0.53 g of p-chlorophenol.

The content of the ground product amounted to 0.43% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.027 g of the ground product and operating under the same conditions as those of Example 9, there were obtained 163 g of polyethylene having an intrinsic viscosity of 2.0 dl/g and an apparent density of 0.348 g/cc. The yield in polymer amounted to 1,420,000 g/g of Ti.

Example 13 was repeated except that anhydrous MgBr.sub.2 (20 g) was used as the carrier.

By using 0.020 g of the ground product there were obtained 120 g of a polyethylene having an intrinsic viscosity of 1.8 dl/g and an apparent density of 0.380 g/cc. The yield in polymer amounted to 1,510,000 g/g of Ti.

20 g of anhydrous MgCl.sub.2 were ground under the same conditions as those applied in Example 9, together with 0.37 g of dioxane and 0.8 g of TiCl.sub.4. The Ti content of the ground product amounted to 1.00% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.026 g of the ground product and operating under the same conditions as those of Example 9, there were obtained 239 g of a polyethylene having an intrinsic viscosity of 1.7 dl/g and an apparent density of 0.319 g/cc. The yield in polymer amounted to 990,000 g/g of Ti.

Example 15 was repeated except that 8.80 g of dioxane were used. The Ti content of the ground product amounted to 0.76% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.089 g of the ground product, there were obtained 124 g of polyethylene with an intrinsic viscosity of 2.4 dl/g and an apparent density=0.364 g/cc. The yield in polymer amounted to 188,000 g/g of Ti.

20 g of anhydrous MgCl.sub.2 together with 0.61 g of thiophene and 0.8 g of TiCl.sub.4 were ground under the same conditions as in Example 9. The Ti content of the ground product amounted to 0.82% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.045 g of the ground product and operating under the same conditions as those of Example 9, there were obtained 280 g of polyethylene having an intrinsic viscosity of 2.0 dl/g while the yield in polymer amounted to 767,000 g/g of Ti.

Example 17 was repeated except that 0.55 g of benzenealdehyde was used as the complexing agent. The Ti content of the ground product amounted to 0.85% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.073 g of the ground product there were obtained 298 g of polyethylene having an intrinsic viscosity of 2.6 dl/g and an apparent density of 0.364 g/cc. The yield in polymer amounted to 534,000 g/g of Ti.

Example 18 was repeated except that 0.24 g of acetone was used as the complexing agent.

The Ti content of the ground product amounted to 0.85% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.116 g of the ground product there were obtained 379 g of polyethylene with an intrinsic viscosity of 2.4 dl/g and an apparent density of 0.380 g/cc. The yield in polymer amounted to 379,000 g/g of Ti.

10 g of anhydrous MgCl.sub.2 were ground under the same conditions as those of Example 1 together with 0.41 g of TiCl.sub.3 of the composition 3 TiCl.sub.3.AlCl.sub.3 and 0.18 g of naphthadioxane. The Ti content of the ground product amounted to 0.32% and its superficial area was.perspectiveto.13 m.sup.2 /g.

Using 0.216 g of the ground product and by operating under the same conditions as those of Example 9, there were obtained 306 g of polyethylene having an intrinsic viscosity of 2.7 dl/g and an apparent density amounting to 0.330 g/g. The yield in polymer amounted to 537,000 g/g of Ti.

Example 9 was repeated except that the magnesium chloride and p-chlorophenol were first ground for 2 hours, in the absence of TiCl.sub.4, and that the product thus obtained was then re-ground for another 2 hours in the presence of TiCl.sub.4. The Ti content of the ground product amounted to 0.79% and its superficial area was.perspectiveto.13 m.sup.2 /g.

By using 0.0616 g of the ground product thus prepared there were obtained 388 g of a polyethylene having an intrinsic viscosity of 1.8 dl/g and an apparent density of 0.412 g/cc. The yield in polymer amounted to 800,000 g/g of Ti.

Example 9 was repeated but with the difference that first the magnesium chloride was ground for 2 hours in the presence of TiCl.sub.4 and that, thereafter, the product thus obtained, was reground for another 2 hours in the presence of p-chlorophenol.

Using 0.0754 g of the ground product thus obtained, there were obtained 375 g of polyethylene having an intrinsic viscosity of 1.9 dl/g and an apparent density of 0.357 g/cc. The yield in polymer amounted to 478,000 g/g of Ti.

Although the Group I to III metal derivative used in the examples, as one catalyst-forming component, was aluminum triisobutyl, equivalent results are obtained when other derivatives of said metals are used, such as the hydrides and organometallic compounds specified herein.

Some changes can be made in practicing the invention, without departing from its spirit. Therefore, we intend to include in the scope of the appended claims all modifications and variations which will be obvious to those skilled in the art from the description and working examples given herein.