GB2051092A - Component of an olefine polymerisation catalyst - Google Patents

Abstract

A component of an olefin polymerisation catalyst comprises the reaction product of a dihalide or hydroxyhalide of a metal from Group IIA or IIB of the Periodic Table, preferably magnesium dichloride, with a transition metal compound comprising a metal from Group IVB or VB of the Periodic Table bonded to an O, N or S atom which in turn is bonded to a carbon atom of a carbon containing radical, preferably a titanium tetrahydrocarbyloxide, which may be subsequently reacted with an organometallic compound of a metal from Groups I to III of the Periodic Table. The component is used in conjunction with a further organometallic compound as cocatalyst. Preferably also the active catalyst component of the invention is treated with a halogen ion exchanging compound, e.g. a titanium tetrahalide, before admixture with the cocatalyst.

Description

SPECIFICATION Catalytic composition and process to make and use it for olefin polymerization Background The invention relates to a composition of matter, a method of preparing same, catalyst, a method of producing the catalyst and a process of using the catalyst. In another aspect the invention relates to a particularly effective ethylene polymerization catalyst and process.

In the production of polyolefins, such as for example polyethylene, polypropylene, ethylene-butene copolymers etc., an important aspect of the various processes and catalysts used to produce such polymers is the productivity. By productivity is meant the amount or yield of solid polymer that is obtained by employing a given quantity of catalyst. If the productivity is high enough then the amount of catalyst residues contained in the polymer is low enough that the presence of the catalyst residues does not significantly affect the properties of the polymer and the polymer does not require additional processing to remove the catalyst residues.As those skilled in the art are aware, removal of catalyst residues from polymer is an expensive process and it is very desirable to employ a catalyst which provides sufficient productivity so that catalyst residue removal is not necessary.

In addition, high productivities are desirable in order to minimize catalyst costs. Therefore it is desirable to develop new and improved catalysts and polymerization processes which provide improved polymer productivities.

Accordingly, an object of the invention is a catalyst.

Another object of the invention is a polymerization process for using the catalyst capable of providing improved polymer productivities as compared to prior art catalysts.

Another object of the invention is a catalyst and a polymerization process in which the polymer produced contains catalyst residues in an amount so that catalyst residue removal is unnecessary.

Summary In accordance with the invention a composition of matter comprises the chemical combination of a metal halide compound and a transition metal compound.

Further in accordance with the invention a method for producing the above composition is provided.

Further in accordance with the invention a catalyst is provided which forms on mixing the above composition of matter as a first catalyst component and an organometallic compound as a second catalyst component.

Further, in accordance with the invention, at least one polymerizable compound selected from aliphatic mono-1 -olefins, conjugated diolefins and vinylaromatic compounds is polymerized under polymerization conditions employing the catalyst described above. In a preferred embodiment, the catalyst is treated with a halide ion exchanging source and the polymerization reaction is carried out employing an organometallic cocatalyst Further in accordance with the invention, the above-described catalyst is prepared by mixing together a metal halide compound and a transition metal compound in a suitable solvent to produce a first catalyst component solution, the first catalyst component solution is heated, cooled and optionally filtered in order to remove any undissolved material; a second catalyst component comprising an organo-metallic compound is added to the above-described first catalyst component solution in a manner so as to avoid a significant temperature rise in the solution to produce a solid catalyst in the form of a slurry with the hydrocarbon solvent; and the solid catalyst is separated from the slurry, washed with a hydrocarbon compound and dried, wherein all the above steps are carried out in the essential absence of air and water.

Detailed Description of the Invention The present invention is based at least in part on the discovery of a novel composition of matter resulting from the chemical combination of a metal halide compound and a transition metal compound wherein the metal halide compound is selected from metal di halides and metal hydroxyhalides and the metal of the metal halide compound is selected from Group IA and Group IIB metals of the Mendeleev Periodic Table and wherein the transition metal of the transition metal compound is selected from Group lVB and Group VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one atom selected from oxygen, nitrogen and sulfur, and said oxygen, nitrogen and sulfur atoms are in turn bonded to a carbon atom of a carbon containing radical. As used herein the term "Mendeleev Periodic Table" is meant the Periodic Table of the Elements as shown in the inside front cover of Perry, Chemical Engineer's Handbook, 4th Edition, McGraw Hill 8 Co. (1963).

As noted above the metal compound is selected from metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from Group IIA and Group IIB metals, such as for example beryllium, magnesium, calcium and zinc. Some suitable metal halide compounds include for example, beryllium dichloride, beryllium dibromide, beryllium hydroxyiodide, magnesium dichloride, magnesium dibromide, magnesium hydroxychloride, magnesium diiodide, magnesium difluoride, calcium dichloride, calcium dibromide, calcium hydroxybromide, zinc dichloride, zinc difluoride, and zinc hydroxychloride. While metal hydroxyhalide compounds are known in the art, they are not as common and as readily available as metal dihalide compounds; therefore, metal dihalides are preferred.Of the metal dihalides, magnesium dihalides, and particularly magnesium dichloride is preferred because it is readily available and relatively inexpensive and has provided excellent results. The metal dihalide component is generally used in the form of an anhydrous, particulate solid to facilitate its reaction with the transition metal compound.It is also noted that various techniques for converting a metal halide compound to a fine particulate form, such as for example roll milling, reprecipitating, etc., can be used to prepare the metal halide compound for use according to the present invention and that such additional preparation of the metal halide compound promotes the reaction of the metal halide compound with the transition metal compound; however, it does not appear to make any difference in a catalyst of the present invention prepared from a composition of matter of the present invention if the metal halide compound is in a fine particulate form, that is, polymer productivity for example is not a function of the size of the particles of the metal halide compound.

Preparation of metal hydroxyhalide compounds are described in K. Soga, S. Katano, Y. Akimoto and T.

Kagiya, "Polymerization of alpha-Olefins with Supported Ziegler-type Catalysts", Polymer Journal, Vol.

2, No. 5, pp. 128-134 (1973).

The transition metal of the transition metal compound noted above is selected from Group IVB and Group VB transition metals and is generally selected from titanium, zirconium, and vanadium although other transition metals can be employed. Excellent results have been obtained with titanium compounds and they are preferred. Some of the titanium compounds suitable for use in the invention include for example titanium tetrahydrocarbyloxides, titanium tetraimides, titanium tetraamides and titanium tetra mercaptides. Other transition metal compounds include for example zirconium tetrahydrocarbyloxides, zirconium tetraimides, zirconium tetraamides, zirconium tetramercaptides, vanadium tetra hydrocarbyloxides, vanadium tetraimides, vanadium tetraamides and vanadium tetramercaptides.

The titanium tetrahydrocarbyloxides are the preferred titanium compounds because they produce excellent results and are readily available. Suitable titanium tetrahydrocarbyloxide compounds include those expressed by the general formula Ti(OR)4 wherein each R is individually selected from an alkyl, cycloalkyl, aryl, alkaryl, and saturated aralkyl hydrocarbon radical containing from about 1 to 20 carbon atoms per radical and each R can be the same or different. Titanium tetrahydrocarbyl oxides in which the hydrocarbyl group contains from about 1 to about 10 carbon atoms per radical are most often employed because they are more readily available.Suitable titanium tetrahydrocarbyloxides include, for example, titanium tetramethoxide, titanium dimethoxydiethoxide, titanium tetraethoxide, titanium tetra-n-butoxide, titanium tetrahexyloxide, titanium tetradecyloxide, titanium tetraeicosyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetra-p-tolyloxide and titanium tetraphenoxide.

Of the titanium tetrahydrocarbyloxides, titanium tetraalkoxides are generally preferred and titanium tetraethoxide is particularly preferred because of the excellent results obtained employing this material. Titanium tetraethoxide is also generally available at a reasonable cost.

The molar ratio of the transition metal compound to the metal halide compound can be selected over a relatively broad range. Generally the molar ratio is within the range of about 10:1 to about 1:10, however, the most common molar ratios are within the range of about 2:1 to about 1:2. When titanium tetrahydrocarbyloxide and magnesium dichloride are employed to form a composition of matter of the invention, a molar ratio of titanium to magnesium of about 2:1 is presently recommended as all the magnesium compound apparently goes into solution easily.

The metal halide compound and the transition metal compound employed in the present invention are normally mixed together by heating, e.g. refluxing, these two components together in a suitable dry (essential absence of water) solvent or diluent, which is essentially inert to the these components and the product produced. By the term "inert" is meant that the solvent does not chemically react with the dissolved components such as to interfere with the formation of the product or the stability of the product once it is formed. Such solvents or diluents include, for example, n-pentane, n-heptane, methyl cyclohexane, toluene, xylenes and the like.It is emphasized that aromatic solvents are preferred, such as for example xylene because the solubility of the metal halide compound and the transition metal compound is higher in aromatic solvents as compared to aliphatic solvents, particularly at low temperatures, which as described hereinafter, are preferred when mixing the metal halide compound and the transition metal compound in the solvent with an organo-metallic compound. Such mixing temperatures are generally within the range of from about OOC to about -1 000C and preferably from about -1 50C to about-4O0C. It is also noted that as compared to aliphatic solvents the use of aromatic solvents, such as for example xylene, appears to improve production of larger polymer particles and/or polymer particles with improved resistance to attrition when the composition resulting from the chemical combination of the metal halide compound and the transition metal compound is used to produce a polymerization catalyst as described herein. Generally the amount of solvent or diluent employed can be selected over a broad range. Usually the amount of solvent or diluent is within the range of about 20 to about 100 cc per gram of metal dihalide.The temperature employed during the heating step can also be selected over a broad range. Normally the heating temperature is within the range of about 1 50C to about 1 500C when the heating step is carried out at atmospheric pressure.

Obviously the heating temperatures employed would be higher if the pressure employed is above atmospheric pressure. The pressure employed during the heating step does not appear to be a significant parameter. In addition to the above noted solvents or diluents, more polar solvents or diluents such as nitrobenzene and halogenated hydrocarbons, e.g. methylene chloride, chlorobenzene and 1,2-dichloroethane can be used, particularly when producing compositions of the invention having a molar ratio of the transition metal compound to the metal dihalide compound of other than 2:1.

Generally, the time required for heating these two components together is within the range of about 5 minutes to about 10 hours, although in most instances a time within the range of about 15 minutes to about 3 hours is sufficient. Following the heating operation, the resulting solution can be filtered to remove any undissolved material or extraneous solid, if desired. The composition of matter of the present invention thus produced and which is in solution can be recovered from the solvent or diluent by crystallation or other suitable means.

It is also emphasized that the compositions of matter of the present invention are prepared in an oxygen free system e.g., absence of air as well as a dry system i.e., absence of water. Generally a dry box is employed as known in the art to prepare the compositions of the present invention usually employing a dry oxygen free nitrogen atmosphere.

With respect to the compositions of matter of the present invention the following example is provided for purposes of illustration.

EXAMPLE 1 (First Catalyst Component Preparation) Preparation of a composition of the invention was carried out by reacting 2 moles of titanium tetraethoxide and 1 mole of magnesium dichloride in hydrocarbon solution. All mixing, filtering and washing operations were conducted in a dry box under a nitrogen atmosphere. Anhydrous, powdered magnesium dichloride amounting to 4.758 g (0.050 mole) was roll milled and mixed with 23.010 g (0.101 mole) of titanium tetraethoxide in 200 ml of dry n-heptane in a flask equipped for stirring and refluxing. Under a nitrogen purge, the mixture was stirred, heated to refluxing temperature, refluxed for 45 minutes and cooled to room temperature to yield a solution containing a very small amount of undissolved residue. The reaction mixture was suction filtered to remove the residue to obtain a clear, colorless solution.The solution contained in a flask was first cooled in an ice bath to a temperature of about 00C and then to a temperature of about -220C using a freezer to yield a relatively small crop of crystals. To increase the yield, the mother liquor was heated to boiling under a nitrogen purge to remove about 1/3 of the volume by evaporation. The resulting solution was cooled to room temperature, then to -220C and finally to about -780C in a dry ice-isopropanol bath for about 1 hour.The mother liquor was pumped off the crystals that had formed and the crystals were rinsed off with three 20 ml portions of dry n-hexane cooled to about -78"C. The liquid remaining after the last rinse was pumped off and the product was dried overnight under a nitrogen purge to obtain 23.6 g of white crystals amounting to 85% of the theoretical yield.

Elemental analysis of a portion of the composition was performed with the following results, in terms of wt.%.

C H Cl Mg Ti O Calculated 34.84 7.32 12.85 4.41 17.37 23.21 Found 32.02 7.21 13.3 3.88 17.3 The results indicate that a composition having a formula consistent with 2Ti(OC2H5)4.MgCI2 was formed and recovered. Thus the composition apparently had a molar ratio of two moles of titanium to one mole of magnesium.

A sample of the white crystals was analyzed by powder X-ray diffraction under conditions to exclude the presence of air and water. The sample revealed the following characteristics: interplanar spacing relative intensity of (meter x 10-' ) spectrum 10.77 weak 10.47 very strong 9.28 very weak 8.73 weak 8.23 very strong 8.10 moderate 7.91 very strong 7.43 strong 7.27 strong 6.52 weak 6.41 weak 6.10 weak 4.90 very weak 4.42 very weak 4.40 very weak 4.09 very weak 3.86 very weak The interplanar spacing lines were sharp and in view of the above number of interplanar spacings it is apparent that the composition formed has essentially a crystalline structure.

The catalysts of the present invention are made up of two components. The first catalyst component comprises a composition of matter as described above and the second catalyst component comprises an organometallic compound. Particularly effective catalysts have been obtained by treating the above-described catalyst with a halide ion exchanging source, such as for example titanium tetrahalide. For convenience, the designation "catalyst A" refers to those catalysts which have not been treated with a halide ion exchanging source and the term "catalyst B" refers to those catalysts which have been so treated. In other words, catalyst B is catalyst A which is treated with a halide ion exchanging source. It has also been found desirable to employ either catalyst A or catalyst B with a cocatalyst comprising an organometallic compound.

The metal halide compounds and the transition metal compounds suitable for producing the composition of matter of the present invention which is used as the first catalyst component of the present invention were described above as was the general and specific nature of the composition of matter. It is noted that the composition of matter of the present invention need not be recovered from the diluent or solvent, such as by crystallation, prior to using such material to produce the catalysts of the present invention. Good results have been obtained by employing the first catalyst component solution which was produced when the composition of matter was prepared as well as by employing composition of matter of the present invention recovered from the diluent or solvent.

The second catalyst component is an organometallic compound in which the metal is selected from metals of Groups I to Ill of the Mendeleev Periodic Table. Some suitable organometallic compounds include, for example, lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, organoaluminium compounds, etc. The second catalyst component is generally an organo-aluminum halide compound which includes for example, dihydrocarbylaluminum monohalides of the formula R'2AIX, monohydrocarbylaluminum dihalides of the formula R'AIX2 and hydrocarbylaluminum sesquihalides of the formula R'3AI2X3 wherein each R' in the above formulas is individually selected from linear and branched chain hydrocarbyl radicals containing from 1 to about 20 carbon atoms per radical and can be the same or different and each X is a halogen atom and can be the same or different.Some suitable organoaluminum halide compounds include, for example methylaluminum dibromide, ethylaluminum dichloride, ethylaiuminum diiodide, isobutylaluminum dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum chloride, rnethyl-n-propylaluminurn bromide, di-n-oetylaluminum bromide, diphenylaluminuril chloride, dicyclo-hexylaluminum bromide, dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum sesquichloride, ethylaluminum sesquiiodide, and the like. Ethylaluminum sesquichloride, ethylaluminium dichloride, and diethylaluminum chloride have been employed with good results and are preferred.The most preferred organoaluminum halide compound is ethylaluminum sesquichloride, which produced the best results.

While it may not be necessary in ail instances to employ a cocatalyst with the catalyst of the present invention, the use of cocatalysts is recommended for best results. The organometallic cocatalysts suitable for use in accordance with the invention are the same as the organometallic compounds suitable for use as the second component of the catalyst of the present invention previously described and in addition to organometallic compounds represented by the general formulas R"AIX2, R"2AIX and R"3Ai2X3, suitable cocatalysts also include compounds of the formula R1,3Al in which R" is the same as P' defined above.Of the organometallic cocatalysts, the organoaluminum cocatalysts are preferred and in addition to those described above as suitable for use as the second component of the catalyst the additional organoaluminum compounds of the formula R"3Al include, for example, trimethylaluminum, triethylaluminum, triisopropylaluminu m, tridecylal uminum, trieicosylaluminum, tricyclohexylaluminum, triphenylaluminum,2-methylpentyidiethylaluminum, and triisoprenylaluminum.

Triethylaluminum is preferred since this compound produced excellent results in the runs hereafter described The metal halide compound/transition metal compound solution described above (which is formed by dissolving the recovered composition of matter of the present invention in a suitable solvent or which is formed initially without recovering the composition of matter from the solvent) is then contacted with hydrocarbon solution containing the organometallic compound of the second component of the catalyst. A solid reaction product is formed which precipitates out of the solution.

The molar ratio of the transition metal compound of the first catalyst component to the organometallic component of the second catalyst component can be selected over a relatively broad range. Generally, the molar ratio of the transition metal of the first catalyst component to the organometallic component of the second catalyst component is within a range of from about 10:1 to about 1:10 and more generally within a range of about 2:1 to about 1:3 since a molar ratio within the latter range usually produces a catalyst which can be employed as an especially active ethylene polymerization catalyst.

The temperature employed while mixing the first and second catalyst components as above described can be selected over a broad range. Generally the temperature employed is within a range of about-i 000C to about 500C or higher, while temperatures within the range of 00C to about 30 C were most often employed, additional investigation has surprisingly established that the use of a temperature within the range of about -1 000C to about 00C for mixing the first and second catalyst component together results in the production of larger polymer particles and/or polymer particles with improved resistance to attrition as compared to polymer produced with a catalyst where the first and second catalyst components were mixed together at a temperature above OOC. As the data hereinafter indicates polymer particles of good size were produced employing a mixing temperature for the first and second catalyst components within the range of from about-i 50C to about -400C and mixing temperatures within this range are preferred.Since heat is evolved when the first catalyst component and the second catalyst component are mixed, the mixing rate is adjusted as required and additional cooling is employed in order to maintain a relatively constant mixing temperature. It is noted with respect to mixing the first and second components that the order of addition is not important and either component can be added to the other. After completing the mixing, the resulting slurry is stirred or agitated for a sufficient time, generally within a range of about 1 5 minutes to about 5 hours to insure that mixing of the component is complete.It is recommended that the stirring or agitation be carried out whereby the slurry is maintained at the mixing temperature for the first 10 to about 30 minutes after mixing and then gradually raising the temperature of the slurry to ambient temperature for the remainder of the stirring or agitation period. Thereafter, stirring is discontinued and the solid product recovered by filtration, decantation, and the like. The product is then washed with a suitable material such as a hydrocarbon, e.g., n-pentane, n-heptane, cyclohexane, benzene, xylenes and the like, to remove any soluble material which may be present. The product is then dried and stored under dry nitrogen. The products formed in this manner are designated as catalyst A as previously described.

In another aspect of the invention, the catalyst previously designated as catalyst A, is treated with a halide ion exchanging source such as for example a halide of a transition metal in order to produce a catalyst of enhanced activity, referred to previously as catalyst B. Some examples of suitable halide ion exchanging sources that have been employed are titanium tetrachloride, vanadium oxychloride (LOCI,) and zirconium tetrachloride. Because titanium tetrachloride is readily available and produced excellent results after somewhat extensive experimentation, it is preferred.

Generally, treating the catalyst with the halide ion exchanging source takes place in a suitable diluent such as a hydrocarbon diluent, for example, n-pentane, n-heptane, cyclohexane, benzene, xylenes, and the like, to facilitate the treating process. The treating temperature can be selected over a relatively broad range and is normally within a range of about 00C to about 2000 0;; however, surprisingly it has also been found that employing a temperature within the range of about 800C to about 1 800C for treating catalyst A with a halide ion exchanging source to produce catalyst B, the use of such catalyst B results in the production of iarger polymer particles and/or polymer particles with improved resistance to attrition as compared to polymer produced with a catalyst B prepared at a lower treating temperature. In view of the above discovery the preferred treating temperature for treating catalyst A with a halide ion exchanging source is from about 10000 to about 1 300C when considering the overall catalyst performance.While the use of treating temperatures in excess of 1 300 C, such as for example 1 5000 to about 1 800 C, produces catalysts that provide larger and/or more attrition resistant polymer particles as compared to polymer particles produced with catalysts prepared at treating temperatures of 1 300C and below, catalysts produced with treating temperatures of about 1 5000 to about 1 800C also show a marked reduction in productivity as compared to catalysts prepared at treating temperatures of 1 3000 and below.

It is also noted that particularly good results have been obtained employing the low mixing temperatures for mixing the first and second catalyst components together as described above to produce catalyst A which is subsequently treated with a halide ion exchanging source employing the high treating temperatures also described above. For Example use of a mixing temperature within the range of about OOC to about 10O0C for mixing the first and second catalyst components together to produce catalyst A (preferably in an aromatic solvent) and then using a treating temperature within the range of about 800C to about 1800C for treating catalyst A with a halide ion exchanging source results in a catalyst which produces especially large and/or attrition resistant polymer particles.

The treating time can also be selected over a broad range and generally is within the range of about 1 0 minutes to about 1 0 hours. While the weight ratio of the halide ion exchanging source to catalyst A can be selected over a relatively broad range, the weight ratio of the halide ion exchanging source to catalyst A is generally within a range of about 10:1 to about 1:10 and more generally from about 7:1 to about 1:4. Following the treatment of catalyst A with the halide ion exchanging source the surplus halide ion exchanging source (the halide ion exchanging source which is not bound to catalyst B) is removed by washing catalyst B with a dry (essential absence of water) liquid such as a hydrocarbon of the type previously disclosed, n-hexane, or xylene for example. The resulting product, catalyst B, after drying, is stored under dry nitrogen.

It has been found that catalyst B can be stored for a month or longer without any significant decrease in activity.

If desired, catalyst A or catalyst B can be admixed with a particulate diluent such as, for example, silica, silica-alumina, silica-titania, magnesium dichloride, magnesium oxide, polyethylene, polypropylene, and poly(phenylene sulfide), prior to using the catalyst in a polymerization process. While the weight ratio of the particulate diluent to catalyst can be selected over a relatively wide range, the weight ratio of particulate diluent to catalyst generally is within the range of about 100:1 to about 1:100. More often, the weight ratio of particulate diluent to catalyst is within the range of about 20:1 to about 2:1 and use of a particulate diluent has been found effective to facilitate charging of the catalyst to the reactor.

The molar ratio of the organometallic compound of the cocatalyst to the transition metal compound of the first catalyst component is not particularly critical and can be selected over a relatively broad range. Generally, the molar ratio of the organometallic compound of the cocatalyst to the transition metal compound of the first catalyst component is within a range of about 1:1 to about 1500:1. However, it has been found that generally when relatively high amounts of the cocatalyst is employed in relation to the catalyst larger and/or more attrition resistant polymer particles are produced.For example, larger and/or more attrition resistant particles are produced when the weight ratio of cocatalyst to catalyst employed is at least about 4:1 up to about 400:1 and higher; however, weight ratios of cocatalyst to catalyst within the range of about 6:1 to about 100:1 are generally recommended as the best compromise between particle size and/or attrition resistance and polymer production since it has been found that generally the higher the cocatalyst level the lower the polymer production per unit weight of catalyst.

A variety of polymerizable compounds are suitable for use in the process of the present invention.

Olefins which can be homopolymerized or copolymerized with the invention catalysts include aliphatic mono-1 -olefins. While the invention would appear to be suitable for use with any aliphatic mono-1 - olefin, those olefins having 2 to 18 carbon atoms are most often used. The mono-1 -olefins can be polymerized according to the present invention employing either a particle form process or a solution form process. Aliphatic mono-1-olefins can be copolymerized with other 1 -olefins and/or with other smaller amounts of other ethylenically unsaturated monomers, such as butadiene 1,3, isoprene, pentadiene-1 ,3, styrene, alpha-methylstyrene, and similar ethylenically unsaturated monomers which do not impair the catalyst.

The catalysts of this invention can also be utilized to prepare homopoiymers and copolymers of conjugated diolefins. Generally the conjugated diolefins contain 4 to 8 carbon atoms per molecule.

Examples of suitable conjugated diolefins include 1,3-butadiene, isoprene, 2-methyl-1 ,3-butadiene, 1 ,3-pentadiene, and 1,3-octadiene. Suitable comonomers, besides the conjugated diolefins listed above include mono-1-olefins previously described and vinylaromatic compounds generally. Some suitable vinylaromatic compounds are those having from about 8 to about 14 carbon atoms per molecule, and include for example styrene and various alkylstyrenes, such as 4-ethylstyrene and such as 1 vinylnaphthalene.

The weight percent of the conjugated diolefin in the copolymerization mixture can be selected over a relatively broad range. Generally the weight percent of the conjugated diolefin is from about 10 to about 95 weight percent and the other comonomers are from about 90 to about 5 weight percent.

However, the weight percent of the conjugated diolefin is preferably from about 50 to about 90 weight percent and the other comonomers are from about 50 to about 10 weight percent.

In one aspect of the invention, the catalysts of the present invention have been found to be particularly effective for polymerization of mono-1-olefins such as ethylene as extremely high productivities have been obtained and thus mono-1-olefins such as ethylene are the preferred monomers for use with the catalysts of the present invention.

The polymerization process according to the present invention employing the catalysts and cocatalysts as above described can be performed either batchwise or continuously. In a batch process, for example, a stirred autoclave is prepared by first purging with nitrogen and then with a suitable compound, such as isobutane for example. When the catalyst and cocatalyst are employed either can be charged to the reactor first or they can be charged simultaneously through an entry port under an isobutane purge. After closing the entry port, hydrogen, if used, is added, and then a diluent such as isobutane is added to the reactor.The reactor is heated to the desired reaction temperature, which for polymerizing ethylene, for example, is, for best results, generally within a range of about 50 C to about 1 200C and the ethylene is then admitted and maintained at a partial pressure within a range of about 5/10 MPa to about 5.0 MPa (70--725 psig) for best results. At the end of the designated reaction period, the polymerization reaction is terminated and the unreacted olefin and isobutane are vented. The reactor is opened and the polymer, such as polyethylene, is collected as a free-flowing white solid and is dried to obtain the product.

In a continuous process, for example, a suitable reactor such as a loop reactor is continuously charged with suitable quantities of solvent or diluent, catalyst, cocatalyst, polymerizable compounds and hydrogen if any and in any desirable order. The reactor product is continuously withdrawn and the polymer recovered as appropriate, generally by flashing the diluent (solvent) and unreacted monomers and drying the resulting polymer.

The olefin polymers made with the catalysts of this invention are useful in preparing articles by conventional polyolefin processing techniques such as injection molding, rotational molding, extrusion of film, and the like. For example, polyethylene made with the catalysts of this invention is typically of narrow molecular weight distribution which is especially desirable for injection molding applications.

Furthermore, the polyethylene produced as described generally has a desirable high bulk density of about 0.44 g/cc as recovered from the polymerization zone. In addition, the polyethylene produced as described is characterized by a high degree of stiffness, e.g. high flexural modulus, which is also desirable in many applications.

EXAMPLE 2 Catalyst Preparation CATALYST A All mixing and filtering operations were performed in a dry box (essential absence of air, i.e.

oxygen, and water) under a dry nitrogen atmosphere employing dry n-heptane as the reaction medium.

An hydrous magnesium dichloride and titanium tetraethoxide (unless otherwise noted) were charged to a flask equipped for refluxing and stirring the contents of the flask. The mixture was brought to reflux temperature (about 1000C), refluxed for the time shown in Table 2, cooled and filtered if extraneous or undissolved material was present. The product was cooled in an ice bath and the indicated organoaluminum halide compound was added to the product at a rate sufficient to avoid a significant temperature rise to produce a slurry.-The resulting slurry was stirred about 30 minutes after removal of the flask from the ice bath. The slurry was filtered to produce a filter cake which was washed with portions of dry n-hexane and dried under a nitrogen purge to produce the product.

The quantities of the materials employed, weight and mole ratios of reactants charged and results obtained are given in Table 2.

TABLE 2 PREPARATION OF CATALYSTS (Catalyst A) Catalyst Designation A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 MgCl2 Grams 0.950 9.518 0.955 2.856 2.856 0.952 0.952 9.516 0.952 0.952 mole 0.010 0.100 0.010 0.030 0.030 0.010 0.010 0.100 0.010 0.010 Ti(OR)4 () grams 4.460 45.59 4.554 13.673 13.673 13.673 4.540 4.540 45.60 3.403 4.54 mole 0.0196 0.200 0.020 0.060 0.060 0.020 0.020 0.200 0.010 0.02 2nd Catalyst Component Type EASC() EASC() EASC( ) EASC( ) DEAC(4) DEAC(4) i-BADC(5) EASC() EASC() EASC() ml 17.5 250 13.5 27 52 26.5 16.7 250 12.5 12.0 mole 0.0140 0.200 0.020 0.040 0.0393 0.020 0.020 0.200 0.010 0.01 Reaction Diluent(7) ml 30 550 60 150 150 60 60 530 60 50 Reflux, Min. 20 45 60 60 60 60 60 60 80 45 Wash Liquid(6) ml 50 600 40 50 50 60 50 250 30 30 Mole Ratios Tu/Mg 1.96:1 2:1 2:1 2:1 2:1 2:1 2:1 2:1 1:1 2:1 Ti/2nd catalyst comp. 1.4:1 1:1 1:1 1.5:1 1.53:1 1: :1 1:1 1:1 1:1 2:1 Recovered Product grams 2.948 25.54 2.925 3.136 2.868 2.613 2.868 29.440 1.350 3.250 Color off-white brown white pink-brown lt. brown cream white lt. brown lt. brown lt. yellow Notes: () Ti(OR)4 in catalysts A-1 through A-8 and A-10 was Ti(OC2H5)4. In catalyst A-9, it was Ti(O n-C4H9)4.

() EASC is ethylaluminum sesquichloride, 25 wt.% in n-heptane.

( ) EADC is ethylaluminum dichloride, 25 wt.% in n-hexane.

(4) DEAC is diethylaluminum chloride, 12.96 wt.% in n-hexane.

(5) i-BADC is isobutylaluminum dichloride, 25.4 wt. % in n-hexane.

(6) n-Hexane.

(7) n-Heptane.

EXAMPLE 3 Catalyst Preparations CATALYST B All mixing and filtering operations were conducted in a dry box under a nitrogen atmosphere employing dry n-hexane as the reaction medium. To a flask equipped for stirring was charged the nhexane, catalyst A and titanium tetrachloride. Generally, each mixture was stirred about 1 hour at ambient temperature, e.g., about 250C, and then filtered. The filter cake was washed with portions of dry n-hexane and dried under a nitrogen purge. The dry powdery product was sieve through a 50 mesh screen to remove the larger particles.

The quantities of components employed, weight ratios of catalyst A to TiCI4 and results obtained are given in Table 3.

TABLE 3 PREPARATION OF CATALYSTS (Catalyst B) Hydrocarbon Used ml.

Catalyst A TiCl4 Reaction Recovered Product Catalyst Weight Ratio Reaction Time Designation No. grams grams TiCl4/Catalyst A Diluent Wash Min. grams Color B-1 A-1 1.014 4.992 4.9:1 20 20 60 0.796 grayish B-2(8) A-2 25-140 129-450 5.1:1 460 500 75 24.540 brown B-3 A-3 1.000 5.000 5:1 20 30 60 0.771 grayish B-4 A-4 0.984 5.000 5.1:1 20 30 25 0.790 grayish B-5 A-5 1.000 5.000 5:1 20 30 60 1.025 lt. brown B-6 A-6 1.000 5.000 5:1 20 30 60 0.870 drayish B-7 A-7 1.000 5.000 5:1 20 30 60 0.695 white B-8(9) A-8 25.440 146.710 5:1 20 20 60 1.095 lt. brown B-10 A-10 2.000 10.000 5:1 40 45 60 1.639 yellow-brown Notes: (8) 21.040 grams of recovered product were diluted with 84.054 grams of 50 mesh polyethylene fines dried in a vaccum oven and the mixture was roll milled overnight (approx. 13 hours).Mixed catalyst consists of about 1 part by weight active component and 4 parts by weight diluent. The mixture was kept under N2.

(9) 27.498 grams of recovered product were diluted with 108.502 grams of dry polyethylene fines and processed as described in footnote (8). The mixture was kept under N2. Mixed catalyst consists of about 1 part by weight active component and 3.95 parts by weight diluent.

Elemental analyses of catalyst A-2 and B-2 (not mixed with polyethylene fines) were performed and the results obtained are shown below in terms of wt.% of each element: Element Catalyst A-2 Catalyst B-2 Carbon 17.5 10.1 Hydrogen 5.0 2.6 Chlorine 39.4 54.7 Oxygen10 16.2 10.9 Titanium 11.9 13.0 Magnesium 7.6 7.2 Aluminum 2.4 1.5 'OThe amount of oxygen was determined by subtracting total weight of other components from the total weight of the catalyst sample.

The results indicate that treating catalyst A compositions with TiCI4 has some effect on the amount of the elements making up the compositions. The Ti concentration increased 1.1 wt.% and chlorine concentration increased 1 5.3 wt.% at the expense of carbon, hydrogen and oxygen in particular.

From the above results it is beiieved that the halide ion exchanging source, which in this instance was titanium tetrachloride, caused an exchange of chloride for ethoxide groups in the catalyst.

Catalysts A-2 and B-2 were also examined by powder X-ray diffraction and X-ray photoelectron spectroscopy to measure the surface composition and bulk crystalline phases.

The results indicated no significant differences in the elemental composition of the surface within experimental error. However, Catalyst 8-2 appeared to be amorphous whereas catalyst A-2 appeared to have a highly crystalline component present with a low surface area.

EXAMPLE 4 Ethylene Polymerization A 3.8 liter, stirred, stainless steel reactor was employed for ethylene polymerization. The reactor was conditioned for each run by charging to it 3 liters of dry n-heptane, closing the port, and heating the reactor and contents at 1 750C for 30 minutes. The reactor was drained and residual heptane purged with dry nitrogen. The reactor was then closed and cooled under nitrogen pressure.

The conditioned reactor was purged with dry isobutane vapor and 3 ml of the cocatalyst solution cdntaining 1 5 wt.% triethylaluminum (TEA) in dry n-heptane (2.8 mmoles TEA) was charged followed by addition of the catalyst. The reactor was closed, about 2.1 liters of dry isobutane was charged, the reactor and contents were heated to 800C and the ethylene and hydrogen, if used, was added.

Each run was terminated by flashing the ethylene and isobutane and hydrogen, if present, from the reactor. The polymer was then recovered, dried and weighed to obtain the yield.

Each polymer yield was divided by the weight of catalyst employed to determine the calculated catalyst productivity which is expressed as kilograms (kg) polyethylene per gram (g) catalyst per hour. In some runs of less than 60 minutes duration, a productivity figure is calculated for 60 minutes in which the reasonable assumption is made based on past experience that the activity of the catalyst remains unchanged during at least the first 60 minutes of each run. When the catalyst is diluted, a calculated productivity based on kg polyethylene produced per gram diluted catalyst per hour is given as well as kg polyethylene produced per gram catalyst contained in the mixture per hour.

The quantity of each catalyst employed, run time, pressures employed, and results obtained are presented in Table 4.

TABLE 4 ETHYLENE POLYMERIZATION AT 80 C.

2.8 MMoles TEA (3 ml) as Cocatalyst in Each Run Reaction Pressures Run Polyethylene Catalyst Productivity Avg. Total Ethylene Hydrogen Run Catalyst Time Yield No. Designation grams min. grams kg polymer/g catalyst/hour MPa psig MPa psig MPa psig 1 A-1 0.0146 60 479 32.8 1.79 260 0.69 100 0 0 2 A-2 0.0093 60 330 35.5 1.93 280 0.69 100 0 0 3 A-3 0.0199 60 270 13.6 1.93 280 0.69 100 0 0 4 A-4 0.0210 60 690 32.9 1.93 280 0.69 100 0 0 5 A-5 0.0198 60 504 25.5 1.93 280 0.69 100 0 0 6 A-6 0.0218 60 68 3.1 1.93 280 0.69 100 0 0 7 A-7 0.0134 60 119 8.9 2.00 290 0.29 100 0 0 8 A-8 0.0167 60 480 28.7 1.93 280 0.69 100 0 0 9 A-9 0.0113 60 233 20.6 1.93 280 0.69 100 0 0 10 A-10 0.0054 60 112 20.7 1.93 280 0.69 100 0 0 11 B-1 0.0039 60 577 148 1.79 260 0.69 100 0 0 12 B-2(11) 0.0121 60 355 147 (29.33 kg/g cat) 2.00 290 0.69 100 0 0 13 B-3(12) 0.0116 30 631 109 (54.4 kg/30 min) 1.97 285 0.69 100 0 0 14 B-3(13) 0.0085 30 510 120 (60.0 kg/30 min) 1.93 280 0.69 100 0 0 15 B-4(14) 0.0051 40 424 125 (83.1 kg/40 min) 1.97 285 0.69 100 0 0 16 B-5 0.0053 60 387 73.0 1.97 285 0.69 100 0 0 17 B-6(15) 0.0118 45 787 88.9 (66)7 kg/45 min 2.00 290 0.69 100 0 0 18 B-7 0.0144 60 538 37.4 2.41 350 1.0 150 0.41 60 19 B-8(16) 0.0220 60 162 36.4 (7.34 kg/g cat) 2.41 350 1.0 150 0.41 60 20 B-9(17) 0.0123 40 688 83.8 (55.9 kg/40 min) 1.93 280 0.69 100 0 0 21 B-10 0.0029 60 610 210 1-97 285 0.69 100 0 0 Notes: (11) One part by weight catalyst diluted with 4 parts by weight polyethylene powder; calculated productivity is 5 x 29.3 or 147 kg polymer/g undiluted catalyst.

(12) 30 minute run time, calculated productivity is 54.4 x 60 # 30 kg/g cat 109 kg/g cat/hour.

(13) 30 minute run time, calculated productivity is 60 x 60 # 30 kg/g cat or 120 kg/g cat/hour.

(14) 40 minute run time, calculated productivity is 83.1 x 60 # 40 kg/g cat or 125 kg/g cat/hour.

(15) 45 minute run time, calculated productivity is 66.7 x 60 # 45 kg/g cat or 88.9 kg/g cat/hour.

(16) One weight part catalyst diluted with 3.95 parts by weight polyethylene powder; calculated productivity is 4.95 x 7.36 or 36.4 kg polymer/g undiluted catalyst (17) 40 minute run time, calculated productivity is 55.9 x 60 # 40 kg/g cat or 83.8 Kg/g cat/hour.

The results given in Table 4 indicate that the A catalysts, while relatively active for ethylene polymerization, are not nearly as active as the B catalysts which are formed from the corresponding A catalysts by a TiCI4 treatment. In terms of kg polyethylene produced per g (undiluted) catalyst per hour, the indicated A catalysts generally produce from about 3 to 36 kg polymer whereas their B counterparts generally produce from about 36 to 210 kg polymer. It is also noted in this regard that catalysts B-6 and B-7 (runs 1 8 and 19) showed exceptionally high productivities as compared to their corresponding "A" catalysts, catalysts A-6 and A-7 (runs 6 and 7).

The best results under the conditions employed, were obtained in run 21 employing catalyst B-1 0 produced from catalyst A-i 0 composition prepared from a titanium ethoxide-magnesium dichloride reaction product treated with ethylaluminum sesquichloride. This catalyst was extremely active and produced 210 kg polyethylene per gram of.catalyst per hour.

EXAMPLE 5 Catalyst Preparation CATALYST A All mixing and filtering operations were performed in a dry box under an argon atmosphere employing a dry hydrocarbon as the reaction medium. Anhydrous magnesium dichloride and titanium tetraethoxide were charged to a flask equipped for refluxing and stirring and containing the chosen reaction medium. Each mixture was heated at the temperature and for the time indicated in Table 5 and cooled to the temperature indicated for the dropwise addition of the 0.783 molar solution of ethylaluminum sesquichloride in n-heptane. The resulting slurry was generally stirred an additional 30 minutes after the reaction was completed, stirring was discontinued and the mixture allowed to warm to room temperature, if cooling had been employed.The slurry was suction filtered to produce a filter cake which was washed with portions of dry n-hexane and dried under an argon purge to produce the product.

The quantities of materials employed, weight and mole ratios of reactants charged and results obtained are presented in Table 5.

TABLE 5 Preparation of Catalysts (Catalyst A) Catalyst Designation A-11 A-12 A-13 A-14 A-15 A-16(a) A-17 MgCl2 grams 1.90 1.90 9.52 1.92 1.92 946 11.4 mole 0.020 0.020 0.100 0.020 0.020 9.94 0.120 Ti(OC2H5)4 grams 9.12 9.11 45.40 9.39 9.10 4309 55.5 mole 0.040 0.040 0.200 0.041 0.040 18.9 0.244 Rection Mediumtype n-hexane xylenes xylenes n-hexane n-hexane n-hexane xylenes ml 100 70 250 75 110 60.6 liters 100 temperature, C 108 107 110 110 105 84 110 heating time, minutes 30 30 30 30 40 45 60 Ethylaluminum Sesquichloride ml 25 25 125 42 42 12.51 301 (b) mole 0.020 0.020 0.098 0.033 0.033 12.7 0.24 reaction temperature, C 25 -18 -20 to -25 -25 -27 21 to 30 -23 to -25 reaction time, minutes 90 80 270 135 280 120 240 Wash liquid ml 30 30 150 120 120 4,57 liter(d) 300 (c) Mole Ratios Ti/Mg 2:1 2:1 2:1 2:1 2:1 1.9:1 2:1 Ti/EASC 2:1 2:1 2:1 1.2:1 1.2:1 1.5:1 1::1 Recovered Product grams 5.21 4.51 20.95 6.33 6.25 not recovered 39.53 color white tan white tan tan not determined light purple (a) several batches of catalysts were made under the conditions shown which were combined and are identified as A-16.

(b) Add to 200 ml of xylenes cooled to -26 C and resting in a CCl4/dry ice bath, the solution of Mg/Cl2 Ti(OC2H5) cooled to 25 C followed by the solution of EASC in a dropwise manner.

(c) Washed filter cake with 50 ml xylenes, then 250 ml of n-hexane.

(d) Used 4,57 liter portions, decanting liquid off product after each addition.

EXAMPLE 6 Catalyst Preparation CATALYST B All mixing and filtering operations were conducted in a dry box under an argon atmosphere employing dry n-hexane as the reaction medium. To a flask equipped for stirring and reflux was charged n-hexane, the catalyst A of Example 5 and titanium tetrachloride. Each mixture was stirred at the temperature and for the time indicated in Table 6, cooled to room temperature, if needed, and then suction filtered. The filter cake was washed with portions of dry n-hexane and dried under an argon purge.

The quantities of components employed, weight ratios of catalyst A to TiCI4 and results obtained are given in Table 6.

TABLE 6 Prepration of Catalyst (Catalyst B) Reaction Condition n-Hexane, ml Catalyst A Weight Ratio Recovered Product Catalyst TiCl4 TiCl4/ Time Max. Reaction Designation No. Grams Grams Catalyst A Min. Temp. C Medium Wash Grams Color B-11 A-11 2.22 8.9 4:1 60 112 11 30(a) 1.70 lt. purple B-12 A-12 2.05 8.0 3.9:1 60 116 10 30(a) 1.83 lt. purple B-13-0 A-13 3.00 12.0 4:1 60 182 15 50 3.58 yellow B-13-1 A-13 3.00 12.0 4:1 80 80 15 30 2.55 white B-13-2 A-13 3.00 12.0 4:1 75 132 15 30 2.71 lt. yellow B-13-3 A-13 2.00 7.7 3.85:1 60 25 10 30(a) 1.61 white B-14 A-14 2.19 7.7 3.5:1 60 122 15 30 2.10 brown B-15 A-15 2.03 7.7 3.8:1 60 105 10 30(a) 1.99 lt. purple B-16 A-16 5255(a) 9072 1.7:1 60 25 18.9 1. 4,57 1. portions 2470 (a) brown B-17 A-17 39.53 154.0 3.9:1 55 110 200 200 33.36 lt. purple B-18 A-11 0.79 3.4 4.3:1 60 25 2 30 (a) 0.69 grayish Note: (a) Estimated.

EXAMPLE 7 Ethylene Polymerization A 3.8 liter, stirred, stainless steel reactor as described and conditioned in Example 4 was employed for ethylene polymerization.

The conditioned reactor for each run was purged with dry isobutane vapor and 1 ml of the cocatalyst solution containing 1 5 wt% triethylaluminum (TEA) in dry n-heptane (0.93 mmoles TEA) was charged followed by addition of the catalyst. The reactor was closed, about 2 liters of dry isobutane was charged, the reactor and contents were heated to 800C and the ethylene was added. Hydrogen was not present in any of the runs, thus each of the polymers produced had a melt index of less than 0.5. Unless indicated to the contrary in Table 7, a run time of 60 minutes was observed in each run.

Each run was terminated anc! the polymer recovered as described in Example 4. If a run time of less than 60 minutes was employed, a calculated productivity figure for 60 minutes is employed as described in Example 4.

The particle size distribution of the recovered polymer as made and/or ground in a Waring Blendor was determined by placing about 100 grams of the polymer on a set of mechanically agitated sieves.

The sieve set consisted of sieves having the mesh sizes (U.S. Sieve Series) of 30, 50, 80, 100, 200 and the bottom pan. Agitation was conducted for 30 minutes unless indicated otherwise and the amount of polymer remaining on each sieve and in the pan was determined by weighing. The ground samples were agitated for 2 minutes at high speed at room temperature in a Waring Blendor. The purpose of grinding the as made polymer is to simulate the attrition polymer particles appear to receive in a large scale reactor such as a ioop reactor, for example, since commercially formed polymer particles are generally subjected to substantial agitation which results in the production of finer particles as compared with those made on the bench scale.

Grinding the polymer in a Waring Blendor as referred to above and throughout this application is carried out by grinding 100 grams of the polymer fluff in a dry condition at room temperature (250C) for 2 minutes using the highest speed on a Waring Blendor Model 31 Dl 42 manufactured by Waring Products Division, Dynamics Corporation of America, New Hartford, Connecticut. Although most any grinder or blender suitable for vigorously agitating relatively small quantities of polymer can be used, the Waring Blendor described above worked very well.

The ground fluff is then screened for 1 5 minutes. An electric Ro-Tap Sieve Shaker manufactured by the U.S. Tyler Manufacturing Company, Cleveland, Ohio, was used; however, most any sieve shaker could be used or the polymer could be sieved by hand.

The quantity of each catalyst employed and results obtained are given in Table 7.

In each run the initial ethylene pressure was 0.69 MPa (98.5 psig), and the average total pressure was 1.9 MPa (271.4 psig) for all runs except runs 24 and 26 in which it was 2.0 MPa (285.7 psig). TABLE 7 Effect of Catalyst Formation Conditions on Polymer Particle Size and Productivity Polymer Catalyst Formation Catalyst Calculated wt.% Coarser Run Reaction EASC TiCl4 Weight Productivity Yield Than 100 Mesh No.Medium C C Grams No. kg/g/hr (a) Grams As Made Ground 22 n-hexane 25 112 0.0023 B-11 193.5 445 82 59 23 n-hexane -25 122 0.0050 B-14 107.8 539 81 (d) 54 (d) 24 n-hexane -25 105 0.0034 B-15 248.5 (b) 507 -(e) 46 (d) 25 xylenes (f) -24 25 0.0036 B-13-3 181.7 582 95 82 26 xylenes -24 80 0.0068 B-13-1 97.5 663 93 27 xylenees -18 116 0.0053 B-12 162.1 (c) 573 91 85 28 xylenes -24 132 0.0067 B-13-2 82.7 554 96 89 29 xylenes -25 180 0.0099 B-13-0 19.8 198 99.8 95 30 n-hexane 25 25 0.0045 B-18 144 647 - (e) 34 (a) kg polymer per g catalyst per hour.

(b) Run time of 36 minutes gi ving 507 g polymer. Productivity for 60 minutes is calculated to be 149.1 kg/g/36 min x 60 min. # 36 min. or 248.5 kg/g/60 min.

(c) Run time of 40 minutes gi ving 573 g polymer. Productivity for 60 minutes is calculated to be 108.1 kg/g/40 min. x 60 min. # 40 min. or 162.1 kg/g/60 min.

(d) Sieve agitation for 15 minutes was employed.

(e) A dash signifies no determination was made.

(f) Analytical reagent quality, 137 -144 C boiling point range.

Inspection of the results presented in Table 7 shows that the reaction conditions employed in forming the catalyst are of importance from a productivity standpoint of polymer produced per unit catalyst weight per hour as well as from a particle size distribution of the polymer. The most productive catalysts appear to result as shown in runs 22-24 when catalyst A is formed in a paraffin reaction medium at temperatures ranging from about 250 to about 250C and the final catalyst (catalyst B) is formed by contact of catalyst A with TiCI4 at temperatures ranging from about 1000 to about 1 250C.

These catalysts form relatively coarse polymer as made consisting approximately of 80 wt.% coarser than 100 mesh. The polymer is somewhat friable in nature, however, since after grinding it in a Waring Blendor for 2 minutes the amount of coarse polymer remaining consisting of about 45 to 60 wt.% coarser than 100 mesh.

When catalyst A is made in an aromatic reaction medium at about 200 to -250C and catalyst B is formed by contact of catalyst A with TiC14 at temperatures ranging from about 800 to 1 800C the particle size of as made polymer and ground polymer is coarser in nature as the results of runs 25-29 demonstrate.The coarsest, most attrition resistant polymer was made with catalyst B formed by contact with TiC14 at 1 800 C. However, the productivity of this catalyst was substantially lower as compared to the other catalysts of runs 25-29. The data in runs 25-29 indicate that when catalyst A is formed at about -250C and catalyst B is formed from catalyst A at about 800 to about 1 300C said catalyst B is capable of producing coarse, attrition resistant polymer at high rates in a slurry polymerization process.

All of the polymers shown in Table 7 have relatively low melt index values, i.e., less than about 0.5, as determined in accordance with the procedure of ASTM D1238--6ST, condition E.

EXAMPLE 8 Ethylene Polymerization -- Effect of Cocatalyst Level A 3.8 liter, stirred, stainless steel reactor as described and conditioned in Example 4 was employed for ethylene polymerization.

The conditioned reactor for each run was purged with dry isobutane, the indicated quantity of cocatalyst solution containing 1 5 wt.% triethylaluminum (TEA) in dry n-heptane (1 molar) was charged followed by addition of the catalyst. A portion of catalyst B-i 6 was used in each run. The reactor was closed, about 2 liters of dry isobutane was charged, the reactor and contents were heated to 1 000C and the ethylene and hydrocarbon were charged. Run times of 60 minutes were employed.

Each run was terminated and the polymer recovered as described in Example 4. The particle size distribution of the as made and/or ground polymer was determined as described in Example 7.

The quantity of each catalyst and cocatalyst employed, the melt index of each polymer and the results obtained are given in Table 8.

In each run, the initial hydrogen pressure was 0.34 MPa (50 psig), the initial ethylene pressure was 1.4 MPa (200 psig) and the total pressure attained during polymerization was 3.4 MPa (500 psig) except for run 35 which it was 3.3 MPa (485 psig).

TABLE 8 Effect of Cocatalyst Concentration on Polymer Particle Size Polymer Weight Percent Concen.

Wt. ratio Calculated Run Catalyst Cocat./ Productivity Yield HLMI(c) Than 100 Mesh No. Wt. g mmoles g ppm(a) Catalyst kg/g/hr g MI(b) MI As Made Ground 31 0.0059 0.2 0.023 21 3.9 51.4 303 1.1 29 -(e) 66 32 0.0051 0.25 0.029 26 5.7 24.7 126 0.4 31 99 45 33 0.0052 0.3 0.035 31 6.7 63.5 330 0.6 31 - 87 34 0.0057 0.5 0.058 52 10 44.6 254 1.7 25 - 66 35 0.0099 0.5 0.058 52 5.9 39.7 393 1.6 27 99 88 36 0.0068 1.0 0.115 104 17 38.6 249 4.0 28 99 73 37 0.0071 2.0 0.230 208 32 38.7 275 2.1 29 - 84 38 0.0072 5.0 0.576 520 80 34.2 246 1.3 28 99 95 (a) Parts per million based on the weight of 2 liters of isobutane (1100g).

(b) MI is melt index, g/10 minutes, ASTM D1238-65T, condition E.

(c) HLMI is high load melt index, g/10 minutes, ASTM D1238-65T, condition F. The ratio, HLMI/MI, is believed to relate to molecular weight distribution. The higher the value, the broader the distribution.

(d) The levels of TEA cocatalyst employed in the runs can be related to an approximate mole ratio of TEA to Ti in the above catalysts ranging from about 10:1 to about 450:1.

(e) A dash signifies no determination was made.

The data given in Table 8 show that the coarse polymer as made is produced at all of the cocatalyst levels employed. The trends observed in runs 31-38 indicates that more attrition resistant polymer is formed as the cocatalyst level increases based on the ground polymer results. At the same time, however, the productivity of the catalyst appears to diminish somewhat as the cocatalyst level increases. Since aluminum alkyl cocatalysts are relatively expensive materials it is desirable to use the least amount of cocatalyst consistent with high polymer production and low cocatalyst residues as well as the production of attrition resistant polymer.The results indicate that the objective is reached with the materials and conditions employed when the cocatalyst level ranges between about 20 to 200 ppm TEA (wt. ratio of cocatalyst to catalyst of about 4:1 to about 40:1), more preferably between about 30 to 100 ppm (wt. ratio of cocatalyst to catalyst of about 6:1 to about 35:1).

Melt index determinations of the produced polymer clearly show that commercially useful material was produced since many applications exist for polymers in the 0.4 to 4 melt index range including film, sheet, pipe, bottles, containers, and the like. The HLMI/MI ratios shown are indicative of relatively narrow molecular weight distribution polymer. Ethylene polymers with such molecular weight distribution are especially suitable for injection molding.

EXAMPLE 9 A. Catalyst Preparation (Catalyst A) B. Catalyst Preparation (Catalyst B) C. Ethylene Polymerization in Presence of Hydrogen A. A series of Catalyst A was prepared generally in the manner indicated previously as in Example 5. The quantities of reactants employed, reaction conditions used, and results obtained are given in Table 9. B. Catalyst B was prepared generally in the manner described in Example 6 by contacting a weighed portion of the Catalyst A series with TiC14. The quantities of reactants employed, reaction conditions utilized, and results obtained are shown in Table 9B. A series of ethylene polymerization runs were carried out generally as described in Example 7 using each catalyst B shown in Table 9B; however each polymerization run was carried out in the presence of hydrogen in order to produce a higher melt index polymer.The polymers produced and the conditions employed are shown in Table 9C.

TABLE 9A Preparation of Catalysts (Catalyst A) Catalyst Designation A-19 A-20 A-21 A-22 MgCI2 grams 1.90 9.52 11.40 5.80 mole 0.020 0.100 0.120 0.061 Ti(OC2H, ), grams 9.10 45.40 56.19 28.23 mole 0.040 0.200 0.246 0.124 Reaction Medium type n-hexane xylenes xylenes xylenes ml 100 250 300 150 temp., "C 97 110 120 120 heating time, min. 30 30 40 35 Ethylaluminum Sesquichloride ml 25 125 220 77.5 mole 0.020 0.098 0.170 0.060 reaction temp., C +25 -20 to -25 -25 to -35 -21 to -27 reaction time, min. 95 270 8.6 hours 205 Wash Liquid n-hexane n-hexane n-hexane n-hexane ml 100 100 400 1000(4-250 ml portions) Mole Ratios Ti/Mg 2:1 2:1 2:1 2:1 Ti/EASC 2:1 2:1 1.4:1 2::1 Recovered Product grams 2.10 2.55 not not determined determined color brown white brown brown TABLE 9B Preparation of Catalyst (Catalyst B) Reaction Conditions N-Hexane, ml Catalyst A Wt. Ratio Catalyst TiCl4 Time Max. Temp. Reaction Wash Recovered Product Desig. No. Grams Grams TiCl4/Cat.A Min. C Medium Medium Grams Color B-19 A-19 5.05 10.4 2.1:1 60 25 25 30 4.71 brown B-20 A-20 3.00 12 4:1 60 80 15 " 2.55 white B-21 A-21 31.9(a) 128 4:1 est. 60 122 150 400 est. 32.55 lt. purple B-22 A-12 2.11 7.9 3.7:1 60 25 10 45 1.90 gray (a) Estimated yield based on previous experiments.

TABLE 9C Ethylene Polymerization, Hydroxygen Present, 1 Mmole TEA Effct of catalyst Formation on Productivity and Polymer Particle Size Polymer Catalyst Formation Catalyst Pressures, MPa(c) Calculated Productivity Wt.% Coarser Run Reaction EASC TiCl4 Weight Total Yield Melt Than 100 Mesh No. Medium C C no.Grams Ethylene Hydrogen Reactor kg/g/hr Grams Index (Ground) 39 n-hexane 25 25 B-19 0.0212 1.48 0.446 3.41^21.7 461 3.6 57 40 " " " " 0.0183 " 0.892 3.62 8.42(a) 154(a) 4.7 33 41 " " " " 0.0195 " " " 26.6(b) 518(b) 13 58 42 " " " 0.0156 " " 3.55 12.4 194 19 48 43 xylenes -18 25 B-22 0.0061 " " " 48.5 296 12 57 44 " -25 to -35 B-21 0.0077 " 0.446 3.62 45.7 352 0.17 92.5 45 " " " " 0.0117 " 0.892 3.76 36.4 426 3.2 67 46 " " " " 0.0133 1.20 1.14 3.69 34.7 461 11 63 47 " -20 to -25 80 B-20 0.0119 1.48 0.892 3.55 15.1 180 13 65 (a) Run time is 2 1/4 hours, productivity of kg/g/2 1/4 hours.

(b) Run time is 2 hours, productivity of kg/g/2 hours.

(c) Absolute pressures.

The effects of a low mixing temperature and a high treating temperature on the modified catalysts of the invention with respect to polymer particle size and attrition resistance are demonstrated in the results of the runs shown in Table 7 in which a low melt index polymer was produced and in invention runs 44-47 of Table 9C in which a relatively high melt index polymer was produced. It has been observed from past experience that grinding tests made on polymer formed with the catalysts of the present invention result in less coarse polymer (more fines) when the polymer melt index is above about 1. Also, a leveling effect appears to take place when the melt index ranges from about 5 to at least about 40.The amount of coarse polymer after grinding general!y amounts from about 80 to about 95 wt.% for low melt index polymer and from about 60 to about 70 wt.% for high melt index polymer.

Therefore, it is currently believed that a catalyst can be more accurately evaluated for potential commercial use (in absence of a commercial run) by preparing relatively high melt index polymer (about 5 to 40 melt index) as compared to a low melt index polymer on a bench scale.

A comparison of the results of runs 39-42 with runs 44-47 of Table 9C shows in general that catalysts prepared by contacting a solution of Ti(OR)4-MgCI2 contained in a paraffin, e.g. n-hexane, with an organoaluminum compound at about room temperature or lower and treating the isolated particulate product with TiCI4 at room temperature or higher produce relatively less coarse polymer (more fines) as compared to the preferred catalysts of the invention.

Thus, the preferred catalysts of this invention which produce large and attrition resistant polymer particles are formed by employing an aromatic solvent and low temperatures (00C to -1 000C) to produce catalyst A and an elevated temperature (800C to 1 8000) to produce catalyst B. The low temperatures utilized in preparing catalyst A is beneficial in reducing fines (increasing coarser polymer particles) in polymerization runs with the finished catalysts. The conditions favor the production of catalyst particles which are uniform in size and generally spherically shaped. An elevated temperature used to form catalyst B appears to set Or harden catalyst A particles. The over-all effect results in a catalyst that is capable of producing large, attrition resistant polymer spheres at vey high polymer productivities.

Claims (1)

1. A composition of matter formed-by the chemical combination of a transition metal compound and a metal halide compound selected from the group consisting of metal dihalides and metal hydroxyhalides wherein the transition metal of the transition metal compound is selected from the group consisting of Group IVB and VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur, and said oxygen, nitrogen and sulfur atoms are in turn bonded to a carbon atom of a carbon containing radical, and wherein the metal of the metal halide compound is selected from the group consisting of Group IIA metals and Group IIB metals of the Mendeleev Periodic Table and wherein said composition of matter is soluble in a dry, essentially inert solvent.

2. A composition of matter according to claim 1 wherein the transition metal is selected from the group consisting of titanium, zirconium, and vanadium.

3. A composition of matter according to claim 1 wherein the transition metal compound is selected from the group consisting of titanium tetrahydrocarbyloxide, titanium tetraimide, titanium tetraamide, titanium tetramercaptide, zirconium tetrahydrocarbyloxides, zirconium tetraimides, zirconium tetraamides, zirconium tetramercaptides, vanadium tetrahydrocarbyloxides, vanadium tetraimides, vanadium tetraamides and vanadium tetramercaptides.

4. A composition of matter according to claim 3 wherein the metal halide compound is selected from the group consisting of beryllium dichloride, beryllium dibromide, beryllium hydroxyiodide, magnesium dichloride, magnesium hydroxychloride, magnesium dibromide, magnesium diiodide, magnesium difluoride, calcium dichloride, calcium dibromide, calcium hydroxybromide, zinc dichloride, zinc difluoride, and zinc hydroxychloride.

5. A composition of matter according to claim 1 wherein the transition metal compound is a titanium compound represented by the general formula Ti(OR)4 wherein each R is individually selected from an alkyl, cycloalkyl, aryl, alkaryl, aralkyl saturated hydrocarbon radicals containing from 1 to about 20 carbon atoms per radical and each R can be the same or different.

6. A composition of matter according to claim 5 wherein the transition metal compound is a titanium tetrahydrocarbyloxide and the metal halide compound is selected from the group consisting of magnesium dichloride and magnesium hydroxychloride.

7. A composition of matter according to claim 6 wherein the transition metal compound is selected from the group consisting of titanium tetramethoxide, titanium tetraethoxide, titanium tetra-nbutoxide, titanium tetrahexyloxide, titanium tetradecyloxide, titanium tetraeicosyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetra-p-tolyloxide and titanium tetraphenoxide.

8. A composition of matter according to claim 1 wherein the transition metal compound is titanium tetraethoxide and the metal halide compound is magnesium dichloride.

9. A composition of matter according to claim 8 having a substantially crystalline form and a powder X-ray diffraction pattern, taken under conditions to exclude the presence of air and water, with interplanar spacings and relative intensities as follows: interplanar spacing relative intensity of (meter X 10-10) spectrum

10.77 weak

10.47 very strong

9.28 very weak

8.73 weak

8.23 very strong

8.10 moderate

7.91 very strong

7.43 strong

7.27 strong

6.52 weak

6.41 weak

6.10 weak

4.90 very weak

4.42 very weak

4.40 very weak

4.09 very weak

3.86 very weak 10.A composition of matter which forms on mixing in a suitable solvent a transition metal compound in which the transition metal is selected from the group consisting of Group IVB and Group VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one atom selected from the group consisting of oxygen, nitrogen and sulfur and said oxygen, nitrogen and sulfur atoms are in turn bonded to a carbon atom of a carbon containing radical and a metal halide compound is selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds in which the metal of the metal halide compound is selected from the group consisting essentially of Group IIA metals and Group lIB metals of the Mendeleev Periodic Table wherein the solvent essentially dissolves the transition metal compound and the metal halide compound.

1 A composition of matter according to claim 10 wherein the transition metal compound is a titanium tetrahydrocarbyloxide, the metal halide compound is a metal dichloride and the solvent is a hydrocarbon.

12. A composition of matter according to claim 11 wherein the titanium tetrahydrocarbyloxide is titanium tetraethoxide and the metal dichloride is magnesium dichloride.

1 3. A composition of matter according to claim 12 which is in a substantially crystalline form obtained by crystallization of the composition of matter dissolved in the solvent.

1 4. A composition of matter according to claim 1 wherein the molar ratio of the transition metal of the transition metal compound to the metal of the metal halide compound is within the range of about 10:1 to about 1:10.

1 5. A composition of matter according to claim 1 wherein the molar ratio of the transition metal of the transition metal compour.d to tie metal of the metal halide compound is within the range of 2:1 to 1:2.

1 6. A composition of matter according to claim 9 wherein the transition metal is titanium and the metal of the metal halide compound is magnesium and the titanium to magnesium molar ratio is 2:1.

1 7. A method of preparing a composition of matter comprising: mixing in a suitable solvent a transition metal compound and a metal halide compound wherein the transition metal of the transition metal compound is selected from the group consisting of Group IVB and VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur, and said oxygen, nitrogen and sulfur atoms are in turn bonded to a carbon atom of a carbon containing radical, and wherein the metal of the metal halide compound is selected from the group consisting of Group IIA metals and Group liB metals of the Mendeleev Periodic Table.

1 8. A method according to claim 1 7 wherein the transition metal is selected from the group consisting of titanium, zirconium, and vanadium.

1 9. A method according to claim 1 7 wherein the transition metal compound is selected from the group consisting of titanium tetrahydrocarbyl oxide, titanium tetraimide, titanium tetraamide, titanium tetra mercaptide, zirconium tetrahydrocarbyloxides, zirconium tetraimides, zirconium tetraam ides, zirconium tetramercaptides, vanadium tetrahydrocarbyloxides, vanadium tetraimides, vanadium tetraamides and vanadium tetramercaptides.

20. A method according to claim 1 9 wherein the metal halide compound is selected from the group consisting of beryllium dichloride, beryllium dibromide, beryllium hydroxyiodide, magnesium dichloride, magnesium hydroxychloride, magnesium dibromide, magnesium diiodide, magnesium difluoride, calcium dichloride, calcium dibromide, calcium hydroxybromide, zinc dichloride, zinc difluoride, and zinc hydroxychloride.

21. A method according to claim 1 7 wherein the transition metal compound is a titanium compound represented by the general formula Ti(OR)4 wherein each R is individually selected from an alkyl, cycloalkyl, aryl, alkaryl, aralkyl saturated hydrocarbon radicals containing from 1 to about 20 carbon atoms per radical and each R can be the same or different.

22. A method according to claim 21 wherein the transition metal compound is a titanium tetrahyrocarbyloxide and the metal halide compound is selected from the group consisting of magnesium dichloride and magnesium hydroxychloride.

23. A method according to claim 22 wherein the transition metal compound is selected from the group consisting of titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-butoxide, titanium tetrahexyloxide, titanium tetradecyloxide, titanium tetraeicosyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetra-p-tolyloxide and titanium tetraphenoxide.

24. A method according to claim 17 wherein the transition metal compound is titanium tetraethoxide and the metal halide compound is magnesium dichloride.

25. A method according to claim 1 7 wherein the solvent is selected from the group consisting of n-pentane, n-heptane, methylcyclohexane, toluene, xylenes and the like, and nitrobenzene and halogenated hydrocarbons selected from the group consisting of methylene chloride, chlorobenzene and 1 ,2-dichloroethane.

26. A method according to claim 17 wherein the molar ratio of the transition metal of the transition metal compound to the metal of the metal halide compound is within the range of about 10:1 to about 1:10.

27. A method according to claim 1 7 wherein the molar ratio of the transition metal of the transition metal compound to the metal of the metal halide compound is within the range of 2:1 to 1:2.

28. A method according to claim 1 7 wherein the transition metal is titanium and the metal of the metal halide compound is magnesium and the titanium to magnesium molar ratio is 2:1 and the solvent is essentially inert to the transition metal compound, the metal halide compound and the composition of matter produced.

29. A catalyst which forms on mixing a first catalyst component and a second catalyst component, wherein the first catalyst component is formed by the chemical combination of: (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxy-halide compounds and the metal of the metal halide compound is selected from the group consisting of Group IIA metals and Group lIB metals of the Mendeleev Periodic Table (2) a transition metal compound in which the transition metal is selected from the group consisting of Group IVB and Group VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one atom selected from the group consisting of oxygen, nitrogen and sulfur, and said oxygen, nitrogen and sulfur atoms are in turn bonded to a carbon atom of a carbon containing radical, wherein said first catalyst component is soluble in a dry, essentially inert solvent and wherein the second catalyst component comprises an organometallic compound wherein the metal is selected from the group consisting of Group I, Group II and Group Ill metals of the Mendeleev Periodic Table.

30. A catalyst according to claim 29 wherein the metal halide compound of the first catalyst component is selected from the group consisting of beryllium, magnesium, calcium, and zinc dihalides and hydrooxyhalides and mixtures of any two or more compounds thereof; and the transition metal of the transition metal compound of the first catalyst component is selected from the group consisting of titanium, zirconium, and vanadium.

31. A method according to claim 29 wherein the transition metal compound is selected from the group consisting of titanium tetrahydrocarbyloxide, titanium tetraimide, titanium tetraamide, titanium tetramercaptide, zirconium tetrahydrocarbyloxides, zirconium tetraimides, zirconium tetraamides, zirconium tetramercaptides, vanadium tetrahydrocarbyloxides, vanadium tetraimides, vanadium tetraamides and vanadium tetramercaptides and wherein the metal halide compound is selected from the group consisting of beryllium dichloride, beryllium dibromide, beryllium hydroxyiodide, magnesium dichloride, magnesium hydroxychloride, magnesium dibromide, magnesium diiodide, magnesium difluoride, calcium dichloride, calcium dibromide, calcium hydroxybromide, zinc dichloride, zinc difluoride, and zinc hydroxychloride.

32. A catalyst according to claim 29 wherein the metal halide compound of the first catalyst component is selected from the group consisting of magnesium dichloride and magnesium hydroxychloride and the transition metal compound of the second catalyst component is a titanium compound represented by the general formula Ti(OR)4 wherein each R is individually selected from an alkyl, cycloalkyl, aryl, aralkyl and alkaryl saturated hydrocarbon radical containing from 1 to about 20 carbon atoms per radical and each R can be the same or different.

33. A catalyst according to claim 29 wherein the organometallic compound of the second component of the catalyst is selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compound, dialkyl zinc compounds and organoaluminumhalide compounds.

34. A catalyst according to claim 29 wherein the second component of the catalyst comprises a hydrocarbylaluminum halide reprsented by the general formulas R'AIX2, R'2AiX, and R'3AI2X3 wherein R' is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to about 20 carbon atoms per radical and each R' can be the same or different, and X is a halogen atom.

35. A catalyst according to claim 29 wherein the first and second catalyst components are contacted together at a temperature within the range of from about OOC. to about -1 000C.

36. A catalyst according to claim 29 wherein the first and second catalyst components are contacted together at a temperature within the range of from about -1 5 OC. to about -400C.

37. A catalyst according to claim 29 further comprising a cocatalyst comprising an organometallic compound wherein the metal is selected from the group consisting of Group I, Group II and Group Ill metals of the Mendeleev Periodic Table.

38. A catalyst according to claim 29 wherein the cocatalyst comprises at least one organoaluminum compound represented by the general formulas R"3AI R"AIX2 R"2AIX R"3AI2X3 wherein each R" is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to about 20 carbon atoms and each R" can be the same of different and X is a halogen atom.

39. A catalyst according to claim 29 wherein the catalyst comprising the first and second components is treated with a halide ion exchanging source.

40. A catalyst according to claim 37 wherein the catalyst comprising the first and second components is treated with the halide ion exchanging source.

41. A catalyst according to claim 40 wherein the catalyst comprising the first and second catalyst components is treated with the halide ion exchanging source at a temperature within the range of from about 800 C. to about 1 800C.

42. A catalyst according to claim 40 wherein the catalyst comprising the first and second catalyst components is treated with the halide ion exchanging source at a temperature within the range of from about 1 000C. to about 1 300C.

43. A catalyst according to claim 41 wherein the first and second catalyst components are contacted together at a temperature within the range of from about 0 C. to about -1 000C.

44. A catalyst according to claim 42 wherein the first and second catalyst components are contacted together at a temperature within the range of from about -1 50C. to -400C.

45. A catalyst according to claim 29 wherein the metal halide compound of the first catalyst component is selected from the group consisting of magnesium dichloride and magnesium hydroxychloride, the transition metal compound of the first catalyst component is selected from the group consisting of titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-butoxide, titanium tetrahexyloxide, titanium tetradecyloxide, titanium tetraeicosyloxide, titanium tetracyclohexyloxide, titanium tetraphenoxide, titanium tetrabenzyloxide and titanium tetra-p-tolyloxide, and the organometallic compound of the second component is selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds and organoaluminum compounds.

46. A catalyst according to claim 45 wherein the organoaluminum compounds of the organometallic compound of the second component are selected from the group consisting of methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, dodecylaluminum dibromide, dimethylalu minum bromide, diethylaluminum chloride, d iisopropylaluminum chloride, methyl-n-propylaluminum bromide, di-n-octylaluminum bromide, diphenylaluminum chloride, dicyclohexylaluminu m bromide, dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminu m sesquichloride, and ethylaluminum sesquiiodide.

47. A catalyst according to claim 37 wherein the cocatalyst is an organoaluminum compound selected from the group consisting of trimethylaluminum, triethylaluminum, triisopropylaluminum, tridecylaluminum, trieicosylaluminum, tricyclohexylaluminum, triphenylaluminum, 2-methylpentyldiethylaluminum, and triisoprenylaluminum.

48. A catalyst according to claim 29 wherein the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the metal of the metal halide compound of the first catalyst component is from about 10:1 to about 1:10 and the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the second catalyst component is from about 10:1 to 1:10.

49. A catalyst according to claim 29 wherein the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the metal of the metal halide compound of the first catalyst component is from about 2:1 to 1:2 and the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the second catalyst component is from about 2:1 to 1 :3.

50. A catalyst according to claim 40 wherein the weight ratio of the halide ion exchanging source to the total weight of the catalyst is from about 10:1 to about 1:10 and the molar ratio of the cocatalyst to the transition metal of the transition metal compound of the first catalyst component is from about 1:1 to about 1500:1.

51. A catalyst according to claim 50 wherein the weight ratio of the cocatalyst to the catalyst is within the range of from about 4:1 to about 400:1.

52. A catalyst according to claim 50 wherein the weight ratio of the cocatalyst to the catalyst is within the range of from about 6:1 to about 100:1.

53. A catalyst according to claim 50 wherein the weight ratio of the halide ion exchanging source to the total weight of the catalyst is from about 7:1 to about 1:4.

54. A catalyst according to claim 37 further comprising a particulate diluent.

55. A catalyst according to claim 54 wherein the particulate diluent is selected from the group consisting of silica, silica-alumina, silica-titania, magnesium dichloride, magnesium oxide, polyethylene, polypropylene and polyphenylene sulfide and the weight ratio of the particulate diluent to the total weight of the catalyst and cocatalyst is within a range of from about 100:1 to about 1:100.

56. A catalyst according to claim 55 wherein the weight ratio of particulate diluent to the total weight of the catalyst and cocatalyst is from about 20:1 to about 2:1.

57. A catalyst according to claim 53 wherein the halide ion exchanging source is titanium tetrachloride.

58. A catalyst according to claim 39 wherein the metal halide compound of the first catalyst component is magnesium dichloride; the transition metal compound of the first catalyst component is titanium tetraethoxide; the organometallic compound of the second catalyst component is ethylaluminum sesquichloride; and the halide ion exchanging source is titanium tetrachloride.

59. A catalyst according to claim 58 further comprising a triethylaluminum cocatalyst.

60. A catalyst according to claim 59 wherein the first catalyst component isolated in a substantially crystalline form has a powder X-ray diffraction pattern, taken under conditions to exclude the presence of air and water, with interplanar spacings and relative intensities as follows: interplanar spacing relative intensity of (meter x 10-1 ) spectrum

10.77 weak

10.47 very strong

9.28 very weak

8.73 weak

8.23 very strong

8.10 moderate

7.91 very strong

7.43 strong

7.27 strong

6.52 weak

6.41 weak

6.10 weak

4.90 very weak

4.42 very weak

4.40 very weak

4.09 very weak

3.86 very weak 61.A catalyst which forms on mixing a first catalyst component and a second catalyst component wherein said first catalyst component is formed by mixing magnesium dichloride and a compound selected from the group consisting of titanium tetraethoxide and titanium tetra-n-butoxide, and wherein said second catalyst component is selected from the group consisting of ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride and isobutylaluminum dichloride.

62. A catalyst according to claim 61 which is treated with titanium tetrachloride.

63. A catalyst of claim 62 further comprising a triethylaluminum cocatalyst.

64. A catalyst according to claim 63 wherein the first and second catalyst components are mixed at a temperature within the range of from about -1 50C. to about -400C. and the resulting catalyst is treated with titanium tetrachloride at a temperature within the range of from about 1 000C. to about 1 30 C.

65. A process comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1 -olefins, conjugated diolefins, vinylaromatic compounds and mixtures of any two or more thereof under polymerization conditions with a catalyst which forms on mixing a first catalyst component and a second catalyst component, wherein the first catalyst component comprises:: (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds wherein the metal of the metal halide compound is selected from the group consisting of Group II A metals and Group II B metals of the Mendeleev Periodic Table (2) a transition metal compound in which the transition metal of the transition metal compound is selected from the group consisting of Group IV B and V B transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur, and said oxygen, nitrogen and sulfur atoms are in turn bonded to a carbon atom of a carbon containing radical, and wherein the second catalyst component comprises an organometallic compound wherein the metal is selected from the group consisting of Group 1, Group II and Group Ill metals of the Mendeleev Periodic Table.

66. A process according to claim 65 wherein the polymerizable compound comprises at least 90 weight percent aliphatic mono-1-olefin having from 2 to about 18 carbon atoms per molecule with the remainder of the polymerizable compound selected from the group consisting of acyclic conjugated dienes and vinyl aromatic hydrocarbons.

67. A process according to claim 65 wherein the polymerizable compound comprises at least about 90 weight percent ethylene with the remainder of the polymerizable compound selected from the group consisting of propylene, butene-1, butene-2, hexene-1, butadiene-1 ,3, isoprene, pentadiene-1,3, styrene and a-methylstyrene.

68. A process according to claim 65 wherein the polymerizable compound is essentially ethylene.

69. A process according to claim 65 wherein the polymerizable compound comprises a conjugated diolefin having from about 4 to about 8 carbon atoms per molecule.

70. A process according to claim 65 wherein the first and second catalyst components are contacted together at a temperature within the range of from about OOC. to about -1000C.

71. A process according to claim 65 wherein the first and second catalyst components are contacted together at a temperature within the range of from about -1 50C. to about -400C.

72. A process according to claim 65 wherein the polymerizable compound comprises a conjugated diolefin and a vinylaromatic compound; wherein the conjugated diolefin is selected from the group consisting of 1,3-butadiene, isoprene, 2-methyl 1,3-butadiene, 1,3-pentadiene, and 1,3-octadiene, and wherein the vinylaromatic compound has from 8 to about 14 carbon atoms per molecule.

73. A process according to claim 65 wherein the polymerization temperature is within a range of about 500C to about 1 200C and the partial pressure of the polymerizable compound is within the range of about 0.5 MPa to about 5.0 MPa (70--725 psig).

74. A process according to claim 65 wherein the organometallic compound of the second component of the catalyst is selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compound, dialkyl zinc compounds and organoaluminum compounds.

75. A process according to claim 65 wherein the metal halide compound of the first catalyst component is selected from the group consisting of beryllium, magnesium, calcium, and zinc dihalides and hydroxyhalides and mixtures of any two or more compounds thereof; and the transition metal of the transition metal compound of the first catalyst component is selected from the group consisting of titanium, zirconium, and vanadium.

76. A process according to claim 65 wherein the transition metal compound is selected from the group consisting of titanium tetrahydrocarbyloxide, titanium tetraimide, titanium tetraamide, titanium tetramercaptide, zirconium tetrahydrocarbyloxides, zirconium tetraimides, zirconium tetraamides, zirconium tetramercaptides, vanadium tetrahydrocarbyloxides, vanadium tetraimides, vanadium tetraamides and vanadium tetramercaptides, and wherein the metal halide compound is selected from the group consisting of beryliium dichloride, beryllium dibromide, beryllium hydroxyiodide, magnesium dichloride, magnesium hydroxychloride, magnesium dibromide, magnesium diiodide, magnesium difluoride, calcium dichloride, calcium dibromide, calcium hydroxybromide, zinc dichloride, zinc difluoride, and zinc hydroxychloride.

77. A process according to claim 65 wherein the metal halide compound of the first catalyst component is selected from the group consisting of magnesium dichloride and magnesium hydroxychloride and the transition metal compound of the second catalyst component is a titanium compound represented by the general formula Ti(OR)4 wherein each R is individually selected from an alkyl, cycloalkyl, aryl, aralkyl and alkaryl saturated hydrocarbon radical containing from 1 to about 20 carbon atoms per radical and each R can be the same or different.

78. A process according to claim 65 wherein the second component of the catalyst comprises a hydrocarbylaluminum halide represented by the general formulas R'AlX2, R'2AIX, and R'3AI2X3 wherein R' is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to about 20 carbon atoms per radical and each R' can be the same or different and X is a halogen atom.

79. A process according to claim 65 wherein the polymerizable compound is contacted with a mixture of the catalyst and a cocatalyst comprising an organometallic compound wherein the metal is selected from the group consisting of Group I, Group II and Group Ill metals of the Mendeleev Periodic Table.

80. A process according to claim 79 wherein the cocatalyst comprises at least one organoaluminum compound represented by the general formulas R"3Al R"AIX2 R"2AIX R"3Al2X3 wherein each R" is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to about 20 carbon atoms and R" can be the same or different and X is a halogen atom.

81. A process according to claim 65 wherein the catalyst comprising the first and second components is treated with a halide ion exchanging source.

82. A process according to claim 81 wherein the catalyst comprising the first and second catalyst components is treated with the halide ion exchanging source at a temperature within the range of from about 800C. to about 1 800 C.

83. A process according to claim 81 wherein the catalyst comprising the first and second catalyst components is treated with the halide ion exchanging source at a temperature within the range of from about 1000C. to about 1 300C.

84. A process according to claim 82 wherein the first and second catalyst components are contacted together at a temperature within the range of from about OOC. to about -1 000C.

85. A process according to claim 83 wherein the first and second catalyst components are contacted together at a temperature within the range of from about --1 5"C. to about -400C.

86. A process according to claim 79 wherein the catalyst comprising the first and second components is treated with a halide ion exchanging source.

87. A process according to claim 65 wherein the metal halide compound of the first catalyst component is selected from the group consisting of magnesium dichioride and magnesium hydroxychloride, the transition metal compound of the first catalyst component is selected from the group consisting of titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-butoxide, titanium tetrahexyloxide, titanium tetradecyloxide, titanium tetraeicosyloxide, titanium tetracyclohexyloxide, titanium tetraphenoxide, titanium tetrabenzyloxide, and titanium tetra-p-tolyloxide, and the organometallic compound of the second component is selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds and organoaluminum compounds.

88. A process according to claim 87 wherein the organoaluminium compounds of the organometallic compound of the second component are selected from the group consisting of methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum chloride, methyl-r propylaluminum bromide, di-n-octylaluminum bromide, diphenylaluminum chloride, dicyclohexylaluminum bromide, dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum sesquichloride and ethylaluminum sesquiiodide.

89. A process according to claim 79 wherein the cocatalyst is an organoaluminum compound selected from the group consisting of trimethylaluminum, triethylaluminum, triisopropylaluminum, tridecylal uminum, trieicosylaluminum, tricyclohexylaluminum, triphenylaluminum, 2-methylpentyldiethylaluminum, and triisoprenylaluminum.

90. A process according to claim 65 wherein the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the metal of the metal halide compound of the first catalyst component is from about 10:1 to about 1:10 and the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the second catalyst component is from about 10:1 to 1:10.

91. A process according to claim 90 wherein the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the metal of the metal halide compound of the first catalyst component is from about 2:1 to 1:2 and the molar ratio of the transition metal of the transition metal compound of the first catalyst component to the second catalyst component is from about 2:1 to 1 :3.

92. A process according to claim 86 wherein the weight ratio of the halide ion exchanging source to the total weight of the catalyst is from about 10:1 to about 1:10 and the molar ratio of the cocatalyst to the transition metal of the transition metal compound of the first catalyst component is from about 1:1 to about 1 500:1.

93. A process according to claim 92 wherein the weight ratio of the cocatalyst to the catalyst is within the range of from about 4:1 to about 400:1.

94. A process according to claim 92 wherein the weight ratio of the cocatalyst to the catalyst is within the range of from about 6:1 to about 100:1.

95. A process according to claim 92 wherein the weight ratio of the halide ion exchanging source to the total weight of the catalyst is from about 7:1 to about 1:4.

96. A process according to claim 79 further comprising a particulate diluent.

97. A process according to claim 96 wherein the particulate diluent is selected from the group consisting of silica, silica-alumina, silica-titania, magnesium dichioride, magnesium oxide, polyethylene, polypropylene and polyphenylene sulfide and the weight ratio of the particulate diluent to the total weight of the catalyst and cocatalyst is within a range of from about 100:1 to about 1:100.

98. A process according to claim 97 wherein the weight ratio of particulate diluent to the total weight of the catalyst and cocatalyst is from about 20:1 to about 2:1.

99. A process according to claim 95 wherein the halide ion exchanging source is titanium tetrachloride.

100. A process according to claim 81 wherein the metal halide compound of the first catalyst component is magnesium dichloride; the transition metal compound of the first catalyst component is titanium tetraethoxide; the organometallic compound of the second catalyst component is ethylaluminum sesquichloride; the halide ion exchanging source is titanium tetrachloride.

101. A process comprising contacting ethylene under polymerization conditions with a catalyst which forms on mixing a first catalyst component and a second catalyst component wherein the first catalyst component is formed by mixing magnesium dichloride and a transition metal compound selected from the group consisting of titanium tetraethoxide and titanium tetra-n-butoxide, and wherein the second catalyst component is selected from the group consisting of ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride and isobutylaluminum dichloride.

102. A process according to claim 101 wherein the catalyst is treated with titanium tetrachloride.

103. A process according to claim 102 wherein said contacting is carried out employing a triethylaluminum cocatalyst.

104. A process according to claim 1 03 wherein the first and second catalyst components are mixed at a temperature within the range of from about -1 50C. to about -400C. and the resulting catalyst is treated with titanium tetrachloride at a temperature within the range of from about 1 000C. to about 1 300C.

105. A method for preparing a catalyst comprising: mixing together a first catalyst component comprising a metal halide compound and a transition metal compound in a suitable solvent to produce a first catalyst component solution wherein the metal halide compound is selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from the group consisting of Group II A metals and Group II B metals of the Mendeleev Periodic Table, and the transition metal of the transition metal compound is selected from the group consisting of Group IVB and VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur, and said oxygen, nitrogen and sulfur atoms are in turn bonded to a carbon atorn of a carbon containing radical; heating the first catalyst component solution; cooling the first catalyst component solution after heating and optionally filtering the first catalyst component solution to remove any undissolved material from the cooled first catalyst component solution; adding a second catalyst component to the cooled first catalyst component solution so as to avoid a significant temperature rise in the solution to produce a solid catalyst in the form of a slurry with the hydrocarbon solvent wherein the second catalyst component comprises an organometallic compound wherein the metal is selected from the group consisting of Group I, Group II and Group III metals of the Mendeleev Periodic Table; separating the solid catalyst from the slurry;; washing the solid catalyst with a hydrocarbon compound; and drying the washed solid catalyst wherein all of the above steps are carried out in the essential absence of air and water.

106. A method according to claim 105 wherein the first catalyst component solution is cooled to a temperature within the range of from about OOC. to about -l 000C. prior to adding the second catalyst component thereto and maintained at said temperature during the addition of said second catalyst component to said first catalyst component solution.

107. A method according to claim 1 05 wherein the first and second catalyst components are mixed at a temperature within the range of from about -1 5"C to about -400C and the resulting catalyst is treated with titanium tetrachloride at a temperature within the range of from about 1 000C to about 1300 C.

108. A method according to claim 105 wherein the metal halide compound of the first catalyst component is selected from the group consisting of beryllium, magnesium, calcium, and zinc dihalides and hydroxyhalides and mixtures of any two or more compounds thereof; and the transition metal of the transition metal compound of the first catalyst component is selected from the group consisting of titanium, zirconium, and vanadium.

109. A method according to claim 1 05 wherein the transition metal compound is selected from the group consisting of titanium tetrahydrocarbyloxide, titanium tetraimide, titanium tetraamide, titanium tetramercaptide, zirconium tetrahydrocarbyloxides, zirconium tetraim ides, zirconium tetraamides, zirconium tetramercaptides, vanadium tetrahydrocarbyloxides, vanadium tetraimides, vanadium tetraamides and vanadium tetramercaptides, and wherein the metal halide compound is selected from the group consisting of beryllium dichloride, beryllium dibromide, beryllium hydroxyiodide, magnesium dichloride, magnesium hydroxychloride, magnesium dibromide, magnesium diiodide, magnesium difluoride, calcium dichloride, calcium dibromide, calcium hydroxybromide, zinc dichloride, zinc difluoride, and zinc hydroxychloride.

110. A method according to claim 105 wherein the metal halide compound of the first catalyst component is selected from the group consisting of magnesium dichloride and magnesium hydroxychloride and the transition metal compound of the second catalyst component is a titanium compound represented by the general formula Ti(OR)4 wherein each R is individually selected from an alkyl, cycloalkyl, aryl, aralkyl and alkaryl saturated hydrocarbon radical containing from 1 to about 20 carbon atoms per radical and each R can be the same or different.

111. A method for preparing a catalyst according to claim 105 wherein the organometallic compound of the second catalyst component is selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds and organoaluminum compounds.

112. A method for preparing a catalyst according to claim 105 wherein the second catalyst component comprises a hydrocarbylaluminum halide represented by the general formulas R'AIX2 R'2AIX, and R'3AI2X3 wherein each R' is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to about 20 carbon atoms per radical and each R' can be the same or different and X is a halogen atom.

1 3. A method for preparing a catalyst according to claim 1 05 wherein the washed and dried solid catalyst is treated with a halide ion exchanging source by mixing together the washed and dried solid catalyst, the halide ion exchanging source and a liquid hydrocarbon to produce a slurry; and separating the solid catalyst from the liquid hydrocarbon followed by washing and drying the solid catalyst.

1 4. A method according to claim 113 wherein the halide ion exchanging source and the catalyst are contacted at a temperature within the range of from about 800 C. to about 1800 C.

1 5. A method according to claim 11 3 wherein the halide ion exchanging source and the catalyst are contacted at a temperature within the range of from about 1 000C. to about 1 300 C.

1 6. A method according to claim 114 wherein the first catalyst component solution is cooled to a temperature within the range of from about OOC. to about 000C. prior to adding the second catalyst component thereto and maintained at said temperature during the addition of said second catalyst component to said first catalyst component solution.

1 7. A method according to claim 11 5 wherein the first and second catalyst components are mixed at a temperature within the range of from about -1 50C to about -400C and the resulting catalyst is treated with titanium tetrachloride at a temperature within the range of from about 1 00 C to about 1300C.

1 8. A method for preparing a catalyst according to claim 105 wherein the metal halide compound of the first catalyst component is selected from the group consisting of magnesium dichloride and magnesium hydroxychloride the transition metal compound of the first catalyst component is selected from the group consisting of titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-butoxide, titanium tetrahexyloxide, titanium tetradecyloxide, titanium tetraeicosyloxide, titanium tetracyclohexyloxide, titanium tetraphenoxide, titanium tetrabenzyloxide and titanium tetra-p-tolyloxide, and the organometallic compound of the second catalyst component is selected form the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds and organoaluminum compounds.

119. A method for preparing a catalyst according to claim 118 wherein the organoaluminum compound of the organometallic compound of the second catalyst component is selected from the group consisting of methylaluminum dibromide, ethylaluminum dichloride, ethylaluminum diiodide, isobutylaluminum dichloride, dodecylaluminum dibromide, dimethylaluminum bromide, diethylaluminum chloride, diisopropylaluminum chloride, methyl-n-propylaluminum bromide, di-n-octylaluminum bromide, diphenylaluminum chloride, dicyclohexylaluminum bromide, dieicosylaluminum chloride, methylaluminum sesquibromide, ethylaluminum sesquichloride and ethylaluminum sesquiiodide.

1 20. A method for preparing a catalyst according to claim 1 3 wherein the metal halide compound of the first catalyst component is magnesium dichloride; the transition metal compound of the first catalyst component is titanium tetraethoxide; the organometallic compound of the second catalyst component is ethylaluminum sesquichloride; and the halide ion exchanging source is titanium tetrachloride.

121. A method according to claim 120 wherein the first and second catalyst components are contacted together at a temperature within the range of from about -1 50C. to about 400 C. and the catalyst resulting therefrom is contacted with titanium tetrachloride at a temperature within the range of from about 1000C.to about 1300C.

122. A method according to claim 1 05 wherein the suitable solvent is selected from the group consisting of n-pentane, n-heptane, methylcyclohexane, toluene, xylenes and the like, and nitrobenzene and halogenated hydrocarbons selected from the group consisting of methylene chloride, chlorobenzene and 1,2-dichloroethane.

123. A method according to claim 1 05 wherein the solvent is essentially inert to the catalyst components and the catalyst produced.

124. A method according to claim 1 20 wherein the solvent is n-hexane.

125. A method according to claim 120 wherein the solvent is an aromatic compound.

126. A method according to claim 121 wherein the suitable solvent is xylene.