NO850439L - PROCEDURE FOR POLYMERIZATION OF OLEFINES USING A CATALYST - Google Patents

Description

Reference to related application

This is a partial continuation of application 192,960, filed October 1, 1980.

The background of the invention

This invention relates to a new catalyst composition

which is suitable for initiating and accelerating the polymerization of one or more α-olefins, and a polymerization process where such a catalyst composition is used.

It is well known that olefins such as ethylene, propylene and

1-butene in the presence of metal catalysts, especially the reaction products of organometallic compounds and transition metal compounds can be polymerized to form approximately linear polymers with a relatively high molecular weight. Typical polymerizations of this type are carried out at relatively high temperatures and pressures.

Among the methods for preparing such linear olefin polymers, some of the most widely used are those described by Professor Karl Ziegler in US Patents 3,113,115 and 3,257,332.

In these methods, the catalyst used is obtained by

mix a compound of a transition metal from group 4b, 5b,

6b and 8 in Mendeleev's periodic table with an organometallic compound. In general, the halides, oxyhalides and alkoxides or esters of titanium, vanadium and zirconium are the most widely used transition metal compounds. Common examples of the organometallic compounds include the hydrides, alkyl-

and the haloalkyl derivatives of aluminum, alkyl aluminum halides, Grignard reagents, alkali metal aluminum hydrides, alkali metal boron hydrides, alkali metal hydrides, alkaline earth metal hydrides and the like. Usually, the polymerization is carried out in a reaction medium comprising an inert organic liquid, for example an aliphatic hydrocarbon, and the above-mentioned catalyst. One or more olefins may be brought into contact with the reaction medium in any suitable manner, and a molecular weight regulator, so-

such as hydrogen, is often added to the reaction vessel to regulate the molecular weight of the polymers. Such polymerization processes out-

conducted either at slurry polymerization temperatures (i.e. where

the resulting polymer is not dissolved in the hydrocarbon reaction medium). or at solution polymerization tempera-

trips (i.e. where the temperature is sufficiently high to

solubilize the polymer in the reaction medium).

After polymerization, it is common to remove catalyst residues from the polymer by repeated treatment of the polymer with alcohol or another deactivating agent such as an aqueous, basic solution. Such catalyst deactivation and/or removal processes are expensive both in terms of time and material consumed as well as in terms of equipment required to carry out such treatment.

Moreover, most slurry polymerization processes where the above-mentioned known catalyst systems are used are accompanied by problems with deposition in the reactor. As a result of such reactor deposition, it is necessary to stop the process frequently to clean the polymerization reactor.

On the basis of the above-mentioned problems encountered when using conventional Ziegler catalysts, it would be highly desirable to provide a polymerization catalyst which is sufficiently active to eliminate the need for removal of catalyst residues and which causes problems with reactor deposition to be minimal. In slurry polymerization processes, it would be particularly desirable to provide a highly efficient catalyst that leads to a polyolefin powder with an increased bulk density.

Summary of the invention

A feature of the present invention is a catalyst support which is the solid reaction product formed by reaction in an inert hydrocarbon diluent of (1) the reaction product of (a) an organomagnesium compound or a hydrocarbyl or hydrocarbyloxy aluminum, zinc or boron -mixture or complex thereof with (b) an oxygen-containing and/or nitrogen-containing compound; and (2) a halide source that is free of a transition metal.

For the purpose of describing the present invention, the organomagnesium compound and the mixture or complex of the organomagnesium compound and the hydrocarbyl or hydrocarbyloxy aluminum, zinc or boron compounds are represented by the formula MgR2"XMeR,x, as defined below.

The oxygen-containing and/or nitrogen-containing compound

is present in an amount sufficient to lower the amount of hydrocarbyl groups present in component (l-a) such that

that the resulting product does not significantly reduce TiCl4 at a temperature of approx. 25°C. The halide source is present in an amount which is sufficient to convert almost all the groups which are bound to a magnesium atom in component (la) into a halide group.

Another feature of the present invention is the hydrocarbon-insoluble solid reaction product of (A) the hydrocarbon-insoluble solid reaction product of (1) the reaction product of (a) a hydrocarbyl magnesium compound or a hydrocarbyl or hydrocarbyloxy aluminum complex thereof with (b ) an oxygen-containing and/or nitrogen-containing compound, with (2) a halide source; (B) a transition metal compound; and (C) a reducing agent.

The components are used in such amounts that a sufficient amount of component (1-b) is obtained to lower the amount of hydrocarbyl groups present in component (l-a) so that the resulting product will not substantially reduce TiCl^ at 2 5° C. At least a sufficient amount of halogen from component (2) is used to convert almost all the groups bound to the magnesium atom in component (1) into a halide group. The amount of component (B) is that which is sufficient to provide a Mg:Tm atomic ratio of about 0.05:1 to approx. 50:1, preferably from approx. 0.1:1 to approx. 5:1, and most preferably from approx. 0.2:1 to approx. 1:1. Sufficient amounts of component (C) are used to theoretically reduce almost all of the transition metal.

The present invention relates to solid, hydrocarbon-insoluble catalysts which, when used with an activator or co-catalyst, are suitable for the polymerization of α-olefins, which catalysts are the inert, diluent-washed product resulting from mixing of:

(I) the reaction product of

(A) the reaction product of

(1) a magnesium component or a mixture of such components represented by the formula MgR2"xMeR'xl, where each R independently of one another is a hydrocarbyl group with from 1 to about 20, preferably from 1 to about 10 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyl oxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms, Me is Al, Zn or B, x has a value from 0 to 10, x' has a value equal to the valence of Me, and

(2) an oxygen-containing and/or nitrogen-containing compound in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) such that the resulting product does not substantially reduce TiCl₂ at a temperature of about 25°C; and

(B) a suitable halide source or mixture thereof represented by the formulas AlR3_axa'siR4-bXb'

SnR4_bXb, POX3, PX3, PX5, SO2X2, GeX4, R4(CO)X, TmY n X z-n and 3 RX where where R independently of each other is hydrogen, a hydrocarbyl or a hydrocarbyloxy group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms; each R4 is independently hydrogen or a hydrocarbyl group with from 1 to about 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms; each X is a halogen atom such as chlorine or bromine; a has a value from 1 to 3; b has a value from 1 to 4; Tm is a metal selected from groups IV-B, V-B or VI-B of the periodic table; Y is oxygen, OR" or NR"2; each R" being independently hydrogen or a hydrocarbyl group with from 1 to about 20 carbon atoms, z having a value equal to the valence of said transition metal, n having a value from 0 to 5, the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source is present in an amount sufficient to convert substantially all of the groups bonded to a magnesium atom in component (A) into a halide group; (II) a transition metal compound represented by the formula TmY il X Z _ ™~ 2*1 where Tm, Y, X, z and n are as indicated above; n has a value from 0 to 5, z-n being from 0 up to a value equal to the valence of the transition metal, in an amount such that one obtains a Mg:Tm atomic ratio from about 0.05:1 to about 50:1, preferably from about 0.1:1 to about 5:1,

particularly preferred from approx. 0.2:1 to approx. 1:1; and

(III) a suitable reducing agent or a mixture of

reducing agents denoted by the formulas B(R3)-, X ,

J 3 J—m m

Al(R3)o X , ZnR<3>, MgR<3>X or MgR3 where each X

3-m m 2 ^ 3 2

independently of each other is halogen, a hydrocarbyloxy group having from 1 to about 20, preferably from 1 to approx. 10 carbon atoms or an NR<3>2~ group; where each R<3> independently of one another is hydrogen or a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms; m has a value from 0 to 2;

in that said reducing agent is used in an amount such that an R<3>:Tm ratio of approx. 1:1 to approx. 50:1, preferably from 1:1 to approx. 10:1, and particularly preferred from approx. 1:1 to approx. 3:1.

When in the above catalyst the halide source is a

reducing halide source, the reducing agent (III) can be omitted, resulting in a further feature of the invention, which is the hydrocarbon-insoluble catalyst washed with inert diluent, comprising:

(I) the reaction product of

(A) the reaction product of

(1) a magnesium component or a mixture of such components is represented by the formula MgR "xMeR' , where R independently of each other is a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms, Me is Al, Zn or B, x has a value from 0 to 10, x<1> has a value equal to the valence of Me, and (2) an oxygen-containing and/or nitrogen-containing compound in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) such that the resulting product does not significantly reduce TiCl^ at a temperature of about 25°C;

(B) a suitable reducing halide source represented by the formula Al (R3)J -, a. X cl where R<3>independent of

each is hydrogen or has the same definition as R above, X is as defined above, and a has a value from 1 to less than 3; said halide source is used in an amount sufficient to convert virtually all the groups attached to the magnesium atom to a halogen atom and to provide an R<3>:Tm ratio from approx. 1:1 to approx. 50:1, preferably from approx. 1:1 to approx. 10:1, and most preferably from approx. 1:1 to approx. 3:1;

(C) a transition metal compound represented by

the formula TmY X where Tm is a metal selected from

n z—n

groups IV-B, V-B or VI-B in the periodic table

system; Y is oxygen, OR" or NR"2; X is halogen;

each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from 0 to 5 with z-n from one up to a value equal to the valence of the transition metal, in an amount such that one obtains a Mg:Tm atomic ratio from about 0.05:1 to about 50:1, preferably from about 0.1:1 to about 5:1.

A further feature of the present invention is a method for producing a hydrocarbon-insoluble catalyst which comprises:

(I) reaction in an inert diluent of

(A) the reaction product of

(1) a magnesium component or a mixture of such components represented by the formula MgR2"xMeR'xwhere each R is independently hydrogen, a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10

carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20, preferably from 1 to approx. 10 carbon atoms, Me is Al, B or Zn,

x has a value from 0 to 10, x' has a value equal to the valence of Me,

(2) an oxygen-containing and/or nitrogen-containing compound in an amount sufficient to lower the amount of hydrocarbyl group present in component (A-I) so that the resulting product does not substantially reduce TiCl 4 at a temperature of about 25°C; and

(B) a suitable halide source or mixture thereof represented by the formulas AlR^_aXa, SiR4_bXb, SnR4_bXb, POX3, PX3, PX5, SO2X2, GeX4, R4(CO)X, TmYnXz_and R4X wherein each R is independently hydrogen, a hydrocarbyl- group or a hydrocarbyloxy group as defined above, R 4 is hydrogen or a hydrocarbyl group with from 1 to about 20, preferably from 1 to approx. 10 carbon atoms; each X is a halogen atom such as chlorine or bromine; a has a value from 1 to 3; b has a value from 1 to 4; Tm is a metal selected from groups IV-B, V-B or VI-B of the periodic table; Y is oxygen, OR" or NR"2; each R" is independently hydrogen or a hydrocarbyl group with from 1 to about 20 carbon atoms, z has a value equal to the valence of said transition metal, n has a value from 0 to 5 with the value of z-n from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in an amount sufficient to convert substantially all of the groups bonded to a magnesium atom in component (A) to a halide group; (II) recovering the resulting hydrocarbon-insoluble product, washing the product with fresh inert diluent; (III) mixing, in fresh, inert diluent, the product of (II) with (C) a transition metal compound represented by the formula TmY n X z-n where Tm, Y, X, z and n are as above stated; z-n has a value from 0

up to a value equal to the valence of the transition metal, in an amount such that a Mg:Tm atomic ratio of approx. 0.05:1 to approx. 50:1, preferably from approx. 0.1:1 to approx. 5:1, particularly preferred from approx. 0.2:1 to approx. 1:1;

(IV) reacting the mixture from (III) with (D) a suitable reducing agent or a mixture of reducing agents selected from compounds represented by the formulas

B(R3K X , A1(R3)^ X , ZnR<3>~, ZnR<3>X, MgR<3>X or

i -m m J -m m2. 3

MgR32 where each X is independently halogen, a hydrocarbyloxy group with from 1 to about 20, preferably from 1 to approx. 10 carbon atoms or an NR<3>2_group; each R<3> is independently hydrogen or a hydrocarbyl group with from 1 to about 20, preferably from 1 to approx. 10 carbon atoms; m has a value from 0 to 2, as said reducing agent is used in an amount such that a R<3>:Tm ratio of approx. 1:1 to approx. 50:1, preferably from 1:1 to approx. 10:1, and most preferably from approx. 1:1 to approx. 3:1; and (V) recovering and washing with fresh inert diluent the resulting solid hydrocarbon-insoluble catalyst prepared in step (IV).

When in the above method the halide source is a reducing halide source, the extraction step II and the reducing agent (IV) can be omitted, resulting in another feature of the present invention, which is a method for producing a hydrocarbon-insoluble catalyst comprising:

(I) reaction in an inert diluent of

(A) the reaction product of

(1) a magnesium compound or a mixture of such components represented by the formula MgR2"<x>MeR',; where each R is independently a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10, carbon atoms , each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20, preferably from 1 to about 10 carbon atoms; Me is Al, Zn or

B; x has a value from 0 to 10, and x' has a value equal to the valence of Me; with

(2) an oxygen-containing and/or nitrogen-containing compound in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) so that the resulting product does not substantially reduce TiCl 4 at a temperature of about 25°C; and

(B) . a suitable reducing halide source represented by the formula AIR3, X where each X is a halogen

atom, preferably chlorine, R<3> is hydrogen or a hydrocarbyl group as defined above, and a has a value from 1 to less than 3; in an amount so that you get an R<3>:Ti ratio from 1:1 to approx. 50:1, preferably from approx. 1:1 to approx. 10:1 and to provide sufficient halogen atoms to convert substantially all of the groups attached to a magnesium atom in component (A) to a halide group; and

(C) a transition metal compound represented by the formula TmY X where Tm is a metal selected from

n z—n

groups IV-B, V-B or VI-B in the periodic table; Y is oxygen, OR" or NR"2; X is halogen;

each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to about 10 carbon atoms; n has a value

from 0 to 5, z-n being from one up to a value equal to the valence of the transition metal, in an amount such that a Mg:Tm atomic ratio of approx. 0.05:1 to approx. 50:1, preferably from approx. 0.1:1 to approx. 5:1;

and

(II) recovering and washing with fresh, inert diluent the resulting solid, hydrocarbon-insoluble catalyst.

A further feature of the invention is a method for the polymerization of α-olefins or mixtures thereof which comprises that the polymerization is carried out in the presence of the above-mentioned catalysts. ,

Description of preferred embodiments

The organomagnesium compounds suitably used according to the present invention include those represented by the formula R2Mg"xMeR'x, where each R independently of one another is a hydrocarbyl group, and each R' independently of one another is hydrogen, a hydrocarbyl or hydrocarbyloxy -group, Me is Al, Zn or B, x has a value from 0 to 10, and x' has a value equal to the valence of Me.

The term hydrocarbyl as used here denotes a monovalent hydrocarbon radical such as alkyl, cycloalkyl, aryl, aralkyl, alkenyl and similar hydrocarbon radicals with from 1 to approx. 20 carbon atoms, with alkyl having from 1 to 10 carbon atoms being preferred.

The term hydrocarbyloxy as used here denotes monovalent oxyhydrocarbon radicals such as alkoxy, cycloalkyloxy, aryloxy, aralkyloxy, alkenoxy and similar oxyhydrocarbon groups with from 1 to approx. 2 0 carbon atoms, as alkoxy-

groups with from 1 to 10 carbon atoms are the preferred hydrocarbyloxy radicals.

The amount of MeR'x, i.e. the value of x, is preferably

the minimum amount sufficient to render the magnesium compound soluble in the inert solvent or diluent, which is usually a hydrocarbon or mixture of hydrocarbons. The value of x is therefore from 0 to approx. 10, usually from approx. 0.2 to approx. 2.

Particularly suitable organomagnesium compounds include, for example, di-(n-butyl)-magnesium, n-butyl-sec-butyl-magnesium, diisopropyl-magnesium, di-n-hexyl-magnesium, isopropyl-n-butyl-magnesium, ethyl- n-hexyl-magnesium, ethyl-n-butyl1-magnesium, di-(n-octyl)-magnesium, butyl-octyl- and such complexes as di-n-butyl-magnesium"1/3 aluminum-triethyl, di-( n-butyl)-magnesium"1/6 aluminium-triethyl, mixtures thereof and the like.

Suitable oxygen-containing compounds include, for example, water, carbon dioxide, carbon monoxide, sulfur dioxide, hydroxyl-containing organic compounds such as alcohols, glycols, polyoxyalkylene glycols and the like, aldehydes, ketones, acetals, ketals, carboxylic acids, carboxylic acid esters, orthoesters or halides, carboxylic acid anhydrides, organic carbonates, mixtures thereof and the like.

Suitable nitrogen-containing compounds which can be used here include, for example, ammonia, amines, nitriles, amides, oximes, imides, isocyanates, mixtures thereof and the like.

Suitable hydroxyl-containing compounds include those represented by the formulas

where each R is a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms or a halogen, NHR or NH2-substituted hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms, each R' is

independently of each other a divalent hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms, each R" is independently hydrogen, a hydrocarbyl group with from 1 to about 20, preferably from 1 to 10 carbon atoms or a halogen, NHR- or NH 2 -substituted hydrocarbyl group with from 1 to about 20, preferably from 1 to about 10 carbon atoms, at least one of which is hydrogen, Z is a polyvalent organic radical containing from 2 to about 20 carbon atoms, n has a value from 0 to about 10, and n' has a value from 2 to about 10.

Particularly suitable hydroxyl-containing compounds include alcohols such as, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, glycols, 1,2-butylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexane-diol, other hydroxyl-containing compounds such as glycerol, trimethylol-propane, hexane-triol, phenol, 2,6-di-tert-butyl-4-methylphenol, mixtures thereof and such. Also suitable are the adducts of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide or mixtures of such oxides with the aforementioned or other hydroxyl-containing compounds such as pentaerythritol, sucrose, sorbitol and the like, as well as alkyl- and aryl-dominated hydroxyl-containing compounds as long as there remains at least 1 hydroxyl group per molecule.

Suitable aldehydes that can be used here include the aldehydes represented by the formula

where R is hydrogen or a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably an aliphatic hydrocarbyl group with from 1 to approx. 10 carbon atoms. Particularly suitable aldehydes include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, mixtures thereof and the like.

Suitable ketones that can be used here include, for example, those represented by the formula

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms. Particularly suitable ketones include, for example, acetone, methyl ethyl ketone, 2,6-dimethyl-4-heptanone, mixtures thereof and the like.

The oxygen-containing compounds, especially the alcohols, aldehydes and ketones, can contain up to approx. 50% by weight, preferably approx. 1% or less water by weight.

Suitable carboxylic acids that can be used here include

those represented by the formulas

where each R is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, especially from approx. 1 to approx. 10 carbon atoms. Particularly suitable carboxylic acids include, for example, formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, 2-ethylhexanoic acid, acrylic acid, methacrylic acid, mixtures thereof and the like. Suitable acetals that can be used here include, for example, those represented by the formula where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms. Particularly suitable acetals which can be used include, for example, acetal, 1,1-diethoxypropane, mixtures thereof and the like. Suitable ketals that can be used here include, for example, those represented by the formula

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10

carbon atoms. Particularly suitable ketals include, for example, 2,2-dimethoxypropane, 2,2-dimethoxyhexane, 2,2-diethoxypropane, mixtures thereof and the like.

Suitable esters of carboxylic acids that can be used here include, for example, those represented by the formulas

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms. Particularly suitable esters include, for example, ethyl acetate, ethyl formate, ethyl benzoate, methyl acetate, methyl formate, mixtures thereof and the like. Suitable orthoesters that can be used here include for for example those represented by the formula

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms. Particularly suitable orthoesters include, for example, triethyl orthoformate, triethyl orthoacetate, mixtures thereof and the like. Suitable carboxylic acid halides include those which are represented by the formulas

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms, and each X is halogen, preferably chlorine or bromine. Particularly suitable acid halides include, for example, acetyl chloride, oxalyl chloride, propionyl chloride, benzoyl chloride, mixtures thereof and the like. Suitable organic carbonates that can be used here, if includes, for example, those represented by the formulas

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms. Particularly suitable carbonates include, for example, diethyl carbonate, ethylene carbonate, dipropyl carbonate, propylene carbonate, styrene carbonate, mixtures thereof and the like.

Suitable carboxylic anhydrides include, for example

those represented by the formulas

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20 carbon atoms, preferably from 1 to approx. 10 carbon atoms. Particularly suitable anhydrides include, for example, acetic anhydride, propionic anhydride, mixtures thereof and the like. Suitable amines that can be used here include, for example, those represented by the formula

where each R independently of one another is hydrogen, a hydroxyl or a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms. Particularly suitable amines include, for example, ammonia, ethylamine, diethylamine, diisopropylamine,

isopropylamine, hydroxylamine, mixtures thereof and the like.

Suitable amides that can be used here include, for example, those represented by the formula

where each R independently of one another is hydrogen or a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms. Particularly suitable amides include, for example, formamide, N,N-dimethylformamide, mixtures thereof and the like.

Suitable imides that can be used here include for

for example those represented by the formula

where each R independently of one another is hydrogen or a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms. Particularly suitable imides include, for example, succinimide, phthalimide, mixtures thereof and the like. Suitable oximes which can be used here include for for example those represented by the formulas

where each R independently of one another is hydrogen or a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms. Particularly suitable oximes include, for example, dimethylglyoxime, formamidoxime, acetoxime, acetaldoxime, methyl ethyl ketoxime, mixtures thereof and the like. Suitable nitriles that can be used here include, for example, those represented by the formula

where R is hydrogen or a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to about: 10 carbon atoms. Particularly suitable nitriles include, for example, hydrogen cyanide, acetonitrile, propionitrile, acrylonitrile, mixtures thereof and the like. Suitable isocyanates such as. can be used here, includes for for example those represented by the formulas

where each R independently of one another is a hydrocarbyl group with from 1 to approx. 20, preferably from 1 to approx. 10 carbon atoms, and y has an average value from approx. 1.01 to approx. 6. Particularly suitable isocyanates that can be used here include, for example, methyl isocyanate, ethyl isocyanate, methyl diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, polymethylene-polyphenyl isocyanate, mixtures thereof and the like.

Optionally, the oxygen- or nitrogen-containing compound may contain dissolved or finely dispersed one or more transition metal compound(s) represented by the formula Tm'YnXz n where Tm' is a transition metal selected from groups IV-B, V-B, VI-B, VII-B , VIII, I-B in the periodic table;

Y is oxygen, OR" or NR"; R" is hydrogen or a hydrocarbyl group having from 1 to about 20, preferably from 1 to approx. 10 carbon atoms; X is a halogen atom, preferably chlorine or bromine; z has a value corresponding to the valence of the transition metal,

Tm'; n has a value from 0 to 5; and the value of z-n is from 0

up to the valence of the transition metal, Tm'.

Particularly suitable transition metal compounds include, for example, CoCl2, CoCl2"6H20, NiCl2, NiCl2"6H20, FeCl3"6H20, FeCl3, FeCl2, CrCl3, CrCl2, CrCl3"6H20, MoCl5, WCXg, ZrCl4, Zr (0-iC.jH^ ) ^, V0C13, mixtures thereof and the like.

The transition metal compound, when used, is in an amount such that a Tm':Tm atomic ratio of about 0.01:1

to approx. 0.5:1, preferably from approx. 0.02:1 to approx. 0.2:1. The transition metals denoted by Tm and Tm' are also different. In other words, the transition metal part of the compound dissolved or finely dispersed in the oxygen- or nitrogen-containing compound is different from the transition metal part in

the transitional inetal compound which is later used in the production of the catalyst according to the present invention. When using such transition metal compounds with oxygen-containing or nitrogen-containing compounds, the properties of the polymers produced by polymerization of monomer(s) in the presence of catalysts produced from these are usually changed. Such properties include (1) the melt index of the produced polymer at a given hydrogen concentration in the polymerization reactor and/or (2) the polymer-powder bulk density for a polymer produced under slurry polymerization conditions or by gas phase polymerization.

Suitable halide sources that can be used herein include those represented by the formulas AIR^^X^, SiR4_bXb, SnR4_bXb, POX3, PX3, PX5, SO2X2, GeX4, HX, R(CO)X and RX where each R is independent of each other hydrogen, a hydrocarbyl group or a hydrocarbyloxy group as defined above, each X is a halogen atom such as chlorine or bromine, a has a value from 1 to 3, and b has a value from 1 to 4.

When the halide source is a hydrocarbyl halide, it should contain a labile halogen that is at least as active,

i.e. just as easily lost to another compound, as the halogen in sec-butyl chloride, preferably as active as t-butyl chloride.

Particularly suitable halide sources include, for example, silicon tetrachloride, tin tetrachloride, aluminum trichloride, trichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, methyldichlorosilane, ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, phosphorus oxytrichloride, phosphorus trichloride, hydrogen chloride, t-butyl chloride, benzyl chloride, benzoyl chloride, acetyl chloride, mixtures thereof and such.

Suitable halide sources also include hydrocarbon-soluble transition metal halide compounds represented by the formula TmYnXz_wherein Tm is a transition metal selected from groups IV-B, V-B and VI-B of the Periodic Table, Y is oxygen, OR" or NR£; each R" is independently hydrogen or a hydrocarbyl group as defined above;

X is halogen, preferably chlorine or bromine; z has a value corresponding to the valence of the transition metal, Tm; n has a value from 0 to 5, the value of z-n being from at least 1 up to a value equal to the valence step of the transition metal, Tm.

Particularly suitable transition metal halide compounds include such compounds of titanium, zirconium, vanadium and chromium, such as, for example, titanium tetrachloride, titanium tetrabromide, dibutoxy titanium dichloride, monoethoxy titanium trichloride, isopropoxy titanium trichloride, chromyl chloride, vanadium oxytrichloride, zirconium tetrachloride, vanadium tetrachloride, mixtures thereof and the like.

Suitable reducing agents include those represented

by the formulas Al (R3)j-, -m X m , B(R3)j_ -m X m , ZnR3 2., ZnR<3>X, MgR3 X

or MgR3,,, including mixtures thereof, wherein each R<3> is independently hydrogen or a hydrocarbyl group as defined above; X is halogen, preferably chlorine or bromine, a hydrocarbyloxy group as defined above or an NR<3>2 group; R<3> is as above; m has a value from 0

to 2, preferably 0 or 1.

Particularly suitable reducing agents include for for example triethylaluminum, ethylaluminum dichloride, diethylaluminum chloride, triisobutylaluminum, ethylaluminum sesquichloride, diisobutylaluminum hydride, trimethylaluminum, triethylboron, diethylzinc, dibutylmagnesium-butylethylmagnesium, mixtures thereof and the like.

The reducing agents are used in amounts to give an R<3>:Tm ratio of from approx. 1:1 to approx. 50:1, preferably from approx. 1:1 to approx. 10:1, and particularly preferred from approx. 1:1 to approx. 3:1. The ratio is the number of R<3> groups for each transition metal atom.

Suitable transition metal compounds that can be used include those represented by the formula TmY n X z-n , where Tm is a transition metal in its highest stable valence step and is selected from groups IV-B, V-B and VI-B of the periodic table;

Y is oxygen, OR" or NR£; R" is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is halogen, preferably chlorine or bromine; z has a value corresponding to the valence of the transition metal, Tm; n has a value from 0 to 5, the value of z-n being from 0 up to a value equal to the valence level of the transition metal, Tm.

Particularly suitable transition metal compounds include

for example titanium tetrachloride, titanium tetrabromide, dibutoxy titanium dichloride, monoethoxy titanium trichloride, isopropoxytitanium trichloride, tetraisopropoxytitanium, chromyl chloride, vanadium oxytrichloride, zirconium tetrachloride, tetrabutoxyzirconium, vanadium tetrachloride, mixtures thereof and the like.

Suitable organic inert diluents in which the catalyst support and catalyst can be prepared and in which the α-olefin polymerization can be carried out include, for example, liquefied ethane, propane, isobutane, n-butane, isopentane, n-pentane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes with from 8 to 12 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, eicosane, industrial solvents composed of saturated or aromatic hydrocarbons such as kerosene, naphthas, etc., especially when liberated for any olefin compounds and other contaminants, and especially those with boiling points in the range from approx. -50 to approx. 200°C. Also included as suitable inert diluents are benzene, toluene, ethylbenzene, cumene, decalin and the like.

The catalyst and catalyst carriers according to the invention are advantageously produced under an inert atmosphere such as nitrogen, argon or another inert gas, at temperatures in the range from approx. -50 to approx. 200°C, preferably from approx. 0 to approx. 100°C. The mixing time for the different components is not critical, but times from approx. 1 minute to approx. 36 hours is considered to be most desirable. The time is usually that which will allow complete reaction at the reaction temperature. Rapid mixing of the catalyst components or poor stirring results in a catalyst that is relatively non-uniform in particle size distribution and leads to polymers with an undesirably broad particle size distribution.

The magnesium compound, the possible aluminum, zinc or boron compound, and the oxygen-containing and/or nitrogen-containing compound can be mixed in any order. A precipitate is sometimes formed, depending on the oxygen- or nitrogen-containing compound used, when the oxygen-containing and/or nitrogen-containing compound and magnesium compound are mixed, and lumps will form if the reaction components are mixed with poor stirring, too quickly or in too concentrated mixture. These lumps result in a finished catalyst containing lumps which in turn lead to a polymer under slurry polymerization conditions with an undesirably broad particle size distribution with a significant percentage of particles that cannot pass through a 40 mesh sieve. Addition of an aluminum, zinc or boron compound can result in a hydrocarbon solution of the mixture of magnesium compound and oxygen-containing and/or nitrogen-containing compound and eliminates the previously mentioned undesirable effects. It is preferred to add the oxygen-containing and/or nitrogen-containing compound to a solution of the magnesium compound and the aluminium, zinc or boron compound in order to achieve a desired uniform polymer particle size distribution.

When the catalyst according to the invention is used under solution polymerization conditions, the above-mentioned catalyst particle size distribution is not so important. If, however, an aluminum compound is added as a solubilizing agent, the catalyst production is simplified when closed metal vessels are used for the catalyst production, as would be used in the commercial production of polymers and copolymers of ethylene.

Suitable cocatalysts or activators with which the catalysts according to the invention can be reacted with, brought into contact with or used together with in the polymerization of α-olefins include the aluminium, boron, zinc or magnesium compounds represented by the formulas Al (R3 )., X , B(R<3>)3_aXa,MgR<3>2,MgR<3>X, ZnR<3>2or mixtures thereof, where

X and R<3> are as previously indicated, and a has a value from 0 to

2, preferably 0 to 1, and particularly preferably 0.

Particularly suitable cocatalysts or activators include, for example, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, triethyl aluminum, triisobutyl aluminum, diethyl zinc, dibutyl magnesium, butyl ethyl magnesium, butyl magnesium chloride, diisobutyl aluminum hydride, isoprenyl aluminum, triethyl boron, trimethyl aluminum, mixtures thereof and the like.

The cocatalysts or activators are used in such quantities that Al, B, Mg, Zn:Ti or mixtures thereof have an atomic ratio of from approx. 0.1:1 to approx. 1000:1, preferably from approx. 5:1 to approx. 500:1, and particularly preferred from approx. 10:1

to approx. 200:1.

The catalyst and cocatalyst or activator may be added separately to the polymerization reactor, or they may be mixed together prior to addition to the polymerization reactor.

Olefins which are suitably homopolymerised or copolymerised in carrying out the present invention are generally one or more of the aliphatic α-olefins such as ethylene, propylene, butene-1, pentene-1, 3-methyl-butene-1, 4-methylpentene- 1, hexene-1, octene-1, dodecene-1, octadecene-1, 1,7-octadiene and the like. It should be understood that α-olefins can be copolymerized with one or more other α-olefins and/or with small amounts, i.e. up to 25% by weight based on the polymer, of other ethylenically unsaturated monomers such as styrene, α-methylstyrene and similar ethylenically unsaturated monomers which do not destroy ordinary Ziegler catalysts.

Most advantages are achieved by the polymerization of aliphatic α-monoolefins, especially ethylene and mixtures of ethylene and up to 50% by weight, especially from approx. 0.1 to approx. 40% by weight of propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, 1,7-octadiene or similar α-olefin or α-diolefin based on total monomer.

In the polymerization process where the above-mentioned catalytic reaction product is used, the polymerization is carried out by adding a catalytic amount of the above-mentioned catalyst composition to a polymerization zone containing an α-olefin monomer, or vice versa. The polymerization zone is kept at temperatures in the range from approx. 0 to approx. 300°C, preferably at slurry polymerization temperatures, for example from approx. 0 to approx. 95°C, more preferably from approx. 50 to 90°C, with a residence time of approx. 15 minutes to 24 hours, preferably 30 minutes to 8 hours. It is usually desirable to carry out . The ion is polymerized in the absence of moisture and oxygen, and a catalytic amount of the catalytic reaction product is usually in the range from about 0.0001 to approx. 0.1 milligram-atoms of titanium per liter of diluent. However, it should be understood that the most advantageous catalyst concentration will depend on the polymerization conditions such as temperature, pressure, diluent and presence of catalyst poisons, and that the above range is indicated to show maximum catalyst yields. In the polymerization process, a carrier can generally be used which can be an inert organic diluent or an excess of monomer. In order to take full advantage of the high-efficiency catalyst of the present invention, one must aim to avoid supersaturation of the diluent with polymer. If such saturation takes place before the catalyst is used up, the full efficiency of the catalyst is not achieved. For the best results, it is preferred that the amount of polymer in the carrier does not exceed approx. 50% by weight based on the total weight of the reaction mixture.

It should be understood that inert diluents used in the polymerization mixture can be used as indicated above.

The polymerization pressures that are preferably used are relatively low, for example from approx. 0.7 to approx. 35 ato. However, the polymerization according to the invention can take place at pressures from atmospheric pressure up to a pressure determined by the capacity of the polymerization equipment. During the polymerization, it is desirable to stir the polymerization mixture to achieve better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone.

Hydrogen is often used in carrying out the present invention to regulate the molecular weight of the resulting polymer. For the purposes of this invention, it is advantageous to use hydrogen in concentrations varying from approx. 0 to approx. 80% by volume in gas or liquid phase in the polymerization vessel. The higher amounts of hydrogen within this range have been found to lead to generally lower molecular weight polymers. It should be understood that hydrogen can be added with a monomer stream to the polymerization vessel or added separately to the vessel before, during, or after the addition of monomer to the polymerization vessel, but during or before the addition of the catalyst. Using the generally described method, the polymerization reactor can be operated with liquid material or with a gas phase and under solution or slurry polymerization conditions.

The monomer or mixture of monomers is brought into contact with the catalytic reaction product in a conventional manner, preferably by bringing the catalyst composition and monomer together with thorough agitation achieved by suitable stirring

or otherwise. Stirring can be continued during the polymerization. In the case of faster reactions with more active catalysts, means for reflux cooling of monomer and solvent can be used, if one of the latter

is present and thus remove the heat of reaction. In any case, care must be taken to remove the exothermic polymerization heat, for example by cooling the reactor walls, etc. Optionally, the monomer can be brought in vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material. The polymerization can be carried out in a batch manner or in a continuous manner, such as by passing the reaction mixture through an elongated reaction tube which is externally in contact with a suitable cooling medium to maintain the desired reaction temperature, or by passing the reaction mixture through an equilibrium overflow reactor or a series of such.

The polymer is easily recovered from the polymerization mixture

by driving off unreacted monomer and solvent if such is used. No further removal of contaminants is required. A significant advantage of the present invention is thus

that one eliminates the steps of removing catalyst residue.

In some cases, however, it may be desirable to add

a small amount of a catalyst-deactivating reagent.

The resulting polymer is found to contain negligible amounts of catalyst residue.

The following examples are given to illustrate the invention and should not be regarded as limiting its scope. All parts and percentages are by weight unless otherwise stated.

In the following examples, the melt index values were 1^

and I1Q determined by ASTM D 1238 conditions E and N, respectively. The apparent bulk density was determined as a non-compromised bulk density according to the method of ASTM 1895 using a paint volume meter from Sargent-Welch Scientific Company (catalog no. S-64985 ) as the cylinder instead of the one specified according to the ASTM method.

General procedure

In each of the following examples, unless otherwise indicated, the catalyst components were mixed while in a closed box filled with dry oxygen-free nitrogen.

In the examples, dibutylmagnesium was a commercial one

material obtained as a solution in a heptane-hexane mixture from Lithium Corporation of America, dihexylmagnesium

was a commercial material obtained as a hexane solution from Ethyl Corporation, and butylethylmagnesium was a commercial material obtained as a heptane solution from Texas Alkyls, Inc. All ratios are molar ratios unless otherwise noted. 1.4 6 molar diethylaluminum chloride, 0.616 molar triisobutylaluminum and 0.921 molar triethylaluminum were obtained as solutions in hexane from Ethyl Corporation or Texas Alkyls, Inc. Isopar<->E was obtained from Exxon Company USA and is a mixture of saturated paraffins with mainly 8 to 9 carbon atoms.

EXAMPLE 1

A. Catalyst preparation:

532 milliliters of a 0.470 molar dibutylmagnesium solution (250 mmol) was added dropwise to a stirred solution of n-propyl alcohol (38 mL, 505 mmol) in hexane (400 mL). A solution of titanium tetrachloride (55 mL, 500 mmol) in hexane (200 mL) was added dropwise to the resulting slurry with continuous stirring. 342 milliliters of 1.46 molar diethyl aluminum chloride (500 millimoles) was added dropwise over a period of 2 hours with continuous stirring. The hydrocarbon-insoluble products were allowed to settle, and the supernatant solution was removed by decantation. The solids were reslurried in fresh hexane. The decantation procedure was repeated an additional 4 times to remove the hexane-soluble reaction products.

B. Polymerization of ethylene:

A metered portion of catalyst slurry, prepared in A above, containing 0.025 millimoles of titanium was added to a 1.8 liter stirred stainless steel reactor containing 1.0 liters of dry, oxygen-free hexane and 2.0 ml of 0.616 molar triisobutylaluminum. The Al:Ti molar ratio was 49:1. The reactor nitrogen atmosphere was replaced with hydrogen by purging, the reactor contents were heated to 85°C, and the reactor pressure was regulated to 70 psig (5 kg/cm 2 ) with hydrogen. The ethylene was then added to maintain a reactor pressure of 170 psig (12 kg/cm 2 ). After two hours at 85°C, the contents of the reactor were filtered and the polyethylene dried in a vacuum overnight at approx. 60°C, yielding 283 grams of polyethylene with a melt index of 0.7 and a bulk density of 19.3 lbs/ft 3 (0.31 g/ml). The catalyst's efficiency was 236,000 grams of polyethylene per grams of titanium.

EXAMPLE 2

A. Catalyst preparation:

A solution of n-propyl alcohol (37.6 mL, 500 mmol) in hexane (100 mL) was added dropwise over 1/2 hour to a stirred solution of 532 mL of 0.470 molar dibutylmagnesium (250 mmol). Hexane was added to the resulting slurry to a total volume of 800 ml. A solution of TiCl 4 (55.0 mL, 500 mmol) in hexane (200 mL) was added dropwise over a period of one hour. The slurry was diluted with hexane to 1200 ml and the hydrocarbon insoluble products allowed to settle. A portion of the supernatant (600 mL) was removed by decantation. The solids were reslurried in fresh hexane (600 mL). The decantation was repeated twice more to remove hexane-soluble reaction products. The hydrocarbon-insoluble products were allowed to settle, and the supernatant was removed by decantation, yielding a slurry with a volume of 450. A portion (45 ml) of this slurry was withdrawn and found by analysis to have a molar ratio Mg:Ti of 3.2:1. The remaining slurry (405 mL) was mixed with 49 mL of TiCl₂ (446 mmol). A diethyl aluminum chloride solution (370 mL of 1.46 molar, 540 mmol) was added dropwise to the stirred slurry. The hydrocarbon-insoluble products were allowed to settle for approx. 1/2 hour, and the overlying liquid was removed by decantation. The solids were reslurried in fresh hexane. The decantation was repeated an additional 5 times to remove hexane-soluble reaction products.

B. Polymerization of ethylene:

A measured portion of catalyst slurry, prepared in A above, containing 0.027 millimoles of titanium was added to a 1.8 liter stirred stainless steel reactor containing 1.0 liters of dry, oxygen-free hexane and 0.88 ml of 0.616 molar triisobutylaluminum in hexane. The atomic ratio Al:Ti was 20:1. The reactor's nitrogen atmosphere was replaced with hydrogen by purging, the reactor's contents were heated to 85°C, and the reactor's pressure was adjusted to 90 psig (6 kg/cm 2 ) with hydrogen. The ethylene was then added to maintain a reactor pressure of 170 (12 kg/cm 2 ). After two hours at 85°C, the contents of the reactor were filtered and the polyethylene dried in a vacuum overnight at approx. 60°C, yielding 383 grams of polyethylene having a melt index of 2.7 and a bulk density of 15.4 lbs/ft 3 (0.25 g/ml). The catalyst's efficiency was 295,000 grams of polyethylene per grams of titanium.

EXAMPLE 3

A. Catalyst preparation:

A 100 mL hexane solution containing 32.9 mL (438 mmol) n-propyl alcohol was added dropwise to a stirred 350 mL hexane solution containing 210.8 mL (125 mmol) 0.593 molar dibutylmagnesium and 101.5 mL (62.5 mmol) 0.616 triisobutylaluminum. Successively, a 100 mL hexane solution containing 54.9 mL (500 mmol) of TiCl 4 was added dropwise to the stirred magnesium alkyl-aluminum alkyl alcohol mixture. The resulting solid was allowed to settle for 20 minutes and the supernatant was decanted. The solid was again suspended in fresh hexane, and the overlying liquid was again decanted. A further 6 decantations were performed with fresh hexane. To the final stirred slurry was added 27.5 mL (250 mmol) of TiCl 4 , followed by the dropwise addition of a 250 mL hexane solution containing 171.2 mL (250 mmol) of 1.46 molar diethylaluminum chloride. The resulting solid was allowed to settle for 20 minutes and the supernatant was decanted. A further 7 decantations were performed with fresh hexane. Analysis of the catalyst gave an atomic ratio Mg:Ti of 0.5:1.

B. Polymerization of ethylene:

Polymerization of ethylene was carried out in a stirred 1.0 liter stainless steel reactor containing 0.5 liters of dry, oxygen-free hexane. Triisobutylaluminum (0.81 mL 0.616 molar; 0.50 mmol) and then a measured portion of catalyst containing 0.01 mmol Ti, prepared in A above, was added to the reactor. The atomic ratio Al:Ti was 50:1. The reactor was pressurized to approx. 50 psig (4 kg/cm 2 ) with hydrogen at room temperature and then vented to 5 psig (0.4 kg/cm 2 ). The pressure ventilation with hydrogen was repeated 9 times. The reactor was then heated to 85°C and the reactor pressure adjusted to 60 psig (4 kg/cm 2 ) with hydrogen. The ethylene was added and the reactor pressure was maintained at 170 psig (12 kg/cm 2 ) with ethylene. Polymerization was allowed to proceed

for 2 hours at 85°C, after which the reactor was cooled to room temperature. The contents of the reactor were filtered and the polyethylene dried in a vacuum overnight at approx. 60°C. Polyethylene was obtained

weighed 117 grams. The melt index of the polyethylene was 0.64 and the polymer had a bulk density of 18.0 lbs/ft 3 (0.29 g/ml). The catalyst's efficiency was 244,000 grams of polyethylene per grams of titanium and 58,000 grams of polyethylene per grams of total catalyst calculated as shown in footnote 8 in Table I.

EXAMPLE 4

A. Catalyst preparation:

A 100 ml hexane solution containing 37.6 ml n-propyl alcohol (500 millimoles) was added dropwise to a stirred 375 ml hexane solution containing 168.6 ml 0.593 molar dibutylmagnesium (100 millimoles) and 162.3 ml 0.616 molar triisobutylaluminum (100 millimoles). Successively, a 100 mL hexane solution containing 44.0 mL TiCl 4 (400 mmol) was added dropwise to the stirred magnesium alkyl aluminum alkyl alcohol mixture. The resulting solid was allowed to settle for 15 minutes and the supernatant was decanted. The solid was again suspended in fresh hexane, and the overlying liquid was again decanted. A further 6 decantations were made with fresh hexane. To the final stirred slurry was added 11.0 mL of TiCl 4 (100 mmol) diluted to 25 mL with hexane, followed by dropwise addition of a 100 mL hexane solution containing 68.5 mL of 1.46 molar diethylaluminum chloride (100 mmol). The resulting solid was allowed to settle for 20 minutes and the supernatant was decanted. A further 7 decantations were made with fresh hexane. Analysis of the final catalyst gave an atomic ratio Mg:Ti of 1.0:1.

B. Polymerization of ethylene:

In accordance with the procedure of Example 3B, polymerization of ethylene was carried out using 1.60 ml of 0.616 molar triisobutylaluminum (0.986 millimoles) and a measured portion of catalyst prepared in A above, containing 0.0048 millimoles of titanium. The reactor pressure was set to • 50 psig (4 kg/cm 2 ) with hydrogen instead of 60 psig (4 kg/cm 2 ). The resulting polyethylene weighed 134 grams, had a melt index of 0.36 and had a bulk density of 19.8 lbs/ft<3> (0.32 g/ml). The catalyst's efficiency was 582,000 g PE/g Ti and 112,000 grams of polyethylene per grams of total catalyst

calculated as described in footnote 8 in Table I.

EXAMPLE 5

A. Catalyst preparation:

A 100 ml hexane solution containing 39.0 ml n-propyl alcohol (519 mmol) was added dropwise to a stirred 425 ml hexane solution containing 316.2 ml 0.593 molar dibutylmagnesium (187.5 mmol) and 75.0 ml 0.616 molar triisobutylaluminum (46, 2 millimoles). Successively, a 250 mL hexane solution containing 82.4 mL TiCl 4 (750 mmol) was added dropwise to the stirred magnesium alkyl aluminum alkyl alcohol mixture. The resulting hydrocarbon-insoluble solid was allowed to settle for 20 minutes, followed by decantation of the supernatant. A further 7 decantations were made with fresh hexane. Next, 81.4 mL of TiCl 4 (750 mmol) was added to the stirred slurry, followed by the dropwise addition of a 600 mL hexane solution containing 513.7 mL of 1.46 molar diethylaluminum chloride (750 mmol). The solid was allowed to settle for 30 minutes, followed by decantation of the supernatant. A further 7 decantations were made with fresh hexane. Analysis of the final catalyst gave a Mg:Ti atomic ratio of 0.25:1.0.

B. Polymerization of ethylene:

In accordance with the procedure of Example 3 (B), ethylene polymerization was carried out using 3.20 ml of 0.616 molar triisobutylaluminum (1.97 millimoles) and a measured portion of catalyst, prepared in (A) above, containing 0.018 millimoles of titanium. The collected polyethylene weighed 104 grams, had a melt index of 0.10 and had a bulk density of 18.1 lbs/ft 3 (0.29 g/ml). The catalyst's efficiency was 121,000 grams of polyethylene per grams of titanium and 32,000 grams of polyethylene per grams of total catalyst calculated as described in footnote 8 in Table I.

EXAMPLE 6

A. Catalyst preparation:

A 60 ml hexane solution containing 21.3 ml n-propyl alcohol (283 mmol) was added dropwise to a stirred 200 ml hexane solution containing 126.5 ml 0.593 molar dibutylmagnesium (75.0 mmol) and 34.7 ml 1.08 molar solution of diethylzinc (37.5 mmol) in hexane. Successively, a 60 mL hexane solution containing 16.5 mL TiCl 4 (150 mmol) was added dropwise to the stirred magnesium alkyl-zinc alkyl alcohol mixture. The resulting slurry was allowed to settle for 15 minutes and the supernatant was then decanted. A further 6 decantations were made with fresh hexane. The solid was reslurried in hexane and 8.25 mL of TiCl₂ (75 mmol) was added, followed by the dropwise addition of a 150 mL hexane solution containing 51.4 mL of 1.46 molar diethylaluminum chloride (75.0 mmol). The solid was allowed to settle for 15 minutes and the supernatant was decanted. A further 7 decantations were made with fresh hexane. Analysis of the catalyst slurry gave an atomic ratio Mg:Ti of 1.0:1.0.

B. Polymerization of ethylene:

The procedure of Example 3 (B) was followed except that the hydrogen pressure was set at 40 psig and 0.80 mL of 0.616 molar triisobutylaluminum (0.493 mmol), 0.93 mL of 1.08 molar diethylzinc (1.00 mmol) in hexane , and a measured portion of catalyst prepared in (A) above containing 0.015 millimole of titanium was added to the reactor to catalyze the polymerization reaction.

The resulting polyethylene weighed 228 grams, had a melt index of 0.99 and had a bulk density of 18.1 lbs/ft 3 (0.29 g/ml). The catalyst's efficiency was 317,000 grams of polyethylene per grams of titanium and 61,000 grams of polyethylene per grams of total catalyst calculated as described in footnote 8 in Table I.

EXAMPLE 7

A. Catalyst preparation:

A solution of n-propyl alcohol and water (35.0 mL; 375 mmol water and 375 mmol n-propyl alcohol) was added dropwise to a stirred solution of 406 mL 0.616 molar triisobutylaluminum (250 mmol) and 210 mL 0.595 molar dihexylmagnesium (125 mmol ). To the resulting stirred solution was added dropwise a solution of 13.7 ml of titanium tetrachloride

(125 millimoles) dissolved in 200 ml of hexane. The resulting up-

slurry was diluted to 800 mL with hexane. A portion of the slurry (400 ml) was stirred while 64.2 ml of 1.46 molar diethylaluminum chloride (94 millimoles) was added dropwise over a period of approx. 1 hour. The hydrocarbon-insoluble solids were allowed to settle for 20 minutes, and the supernatant was decanted. Fresh hexane was added to a volume of 400 ml and the decantation procedure was repeated 4 more times to remove the hydrocarbon soluble products.

B. Polymerization of ethylene:

The procedure in Example 1(B) was used with 2.4 ml of 0.616 molar triisobutylaluminum and a measured portion of catalyst prepared in (A) above containing 0.030 millimoles of titanium. The atomic ratio Al:Ti was 50:1. The reactor pressure was adjusted to 60 psig (4 kg/cm 2 ) with hydrogen prior to ethylene addition. The resulting polyethylene weighed 183 grams, had a melt index of 0.15 and had a bulk density of 15.5 lbs/ft 3 (0.25 g/ml). The catalyst's efficiency was 127,000 grams of polyethylene per grams of titanium.

EXAMPLES 8-14

A. Catalyst preparation:

Using the amounts indicated in Table I, a mixture of an oxygen or nitrogen containing compound and hexane was added dropwise to a stirred dialkylmagnesium solution. A solution of titanium tetrachloride in hexane was then added dropwise to the resulting slurry. An aluminum alkyl reducing agent was then added dropwise to the stirred slurry. The hydrocarbon-insoluble products were allowed to settle, and the supernatant solution was removed by decantation. The solids were reslurried with fresh hexane. The decantation procedure was repeated an additional 5 times to remove the hydrocarbon soluble reaction products.

B. Polymerization of ethylene:

Using the quantities indicated in Table I, a measured portion of the catalyst prepared in (A) above was added to a 1.8 liter stirred stainless steel reactor containing 1.0 liter of dry, oxygen-free hexane and the amount of triisobutylaluminum as set forth in Table I. The reactor nitrogen was replaced with hydrogen by purging, the reactor contents were heated to 85°C, and the reactor pressure was adjusted to 70 psig (5 kg/cm 2 ) with hydrogen. The ethylene was then added to maintain a reactor pressure of 170 psig (12 kg/cm 2 ). After two hours at 85°C, the contents of the reactor were filtered and the polyethylene dried in a vacuum overnight at approx. 60°C. The results are listed in Table I.

EXAMPLE 15

A. Catalyst preparation:

In an inert atmosphere at room temperature, a 100 ml hexane solution containing 3.55 g (50 millimoles) ethyl isocyanate was added dropwise to a stirred 200 ml hexane solution of 42.2 ml 0.593 molar dibutyl magnesium (25 millimoles). Successively, a 200 mL hexane solution containing 32.7 mL (50 mmol) of 1.53 molar diethylaluminum chloride in hexane was added dropwise to the magnesium alkyl-ethyl isocyanate reaction mixture while stirring. The resulting slurry was allowed to settle, the supernatant was decanted, and the remaining solid was slurried in fresh hexane. A further decantation was carried out with fresh hexane. A 50 ml hexane solution of 5.50 ml (50 millimoles) TiCl 2 was added dropwise with stirring to the hexane slurry of the substance prepared above. The resulting solid was allowed to settle, the supernatant was decanted, and the solid was reslurried in fresh hexane. A further 7 decantations were made with fresh hexane. Analysis of the final catalyst gave an atomic ratio of Mg:Ti of 4.3:1.

B. Polymerization of ethylene:

The polymerization procedure of Example 3(B) was repeated using 1.6 mL of 0.616 molar triisobutylaluminum

(1.0 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.010 millimoles of titanium. The resulting polyethylene weighed 232 grams, had a melt index of 2.57 and had a bulk density of 16.1 lbs/ft 3 (0.26 g/ml). The catalyst's efficiency was 480,000 grams of polyethylene per grams of titanium and 41,000

grams of polyethylene per grams of total catalyst calculated as described in footnote 8 in Table I.

EXAMPLE 16

A. Catalyst preparation:

In an inert atmosphere at room temperature, a 100 ml hexane solution containing 15.0 (200 millimoles) n-propyl alcohol was added dropwise to a stirred 200 ml hexane solution of 169 ml 0.593 molar dibutyl magnesium (100 millimoles). Successively, a 125 mL solution containing 23.3 mL (261 mmol) of phosphorus trichloride was added dropwise, and the reaction mixture was stirred for 30 minutes. The slurry was allowed to stir for 15 minutes, the supernatant was decanted, and the solid was slurried in fresh hexane. A further 5 decantations were made with fresh hexane. A 200 ml hexane solution containing 22.0 ml (200 millimoles) TiCl 2 was added dropwise to the hexane slurry of the above-prepared solid with stirring. Successively, a 200 ml hexane solution containing 137.0 ml (200 millimoles) 1.46 molar diethyl aluminum chloride was added dropwise. The resulting slurry was allowed to stir for 20 minutes, the supernatant was decanted, and the remaining solid was slurried in fresh hexane. A further 7 decantations were made with fresh hexane. The final solid was slurried in fresh hexane and stored in a capped flask. Analysis of the catalyst gave an atomic ratio Mg:Ti of 0.21:1.

B. Polymerization of ethylene:

The polymerization procedure of Example 3(B) was repeated using 2.8 mL of 0.616 molar triisobutylaluminum

(1.75 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.0175 millimoles of titanium. The resulting polyethylene weighed 131 grams, had a melt index of 2.61 and had a bulk density of 15.4 lbs/ft 3 (0.25 g/ml). The catalyst's efficiency was 156,000 grams of polyethylene per grams of titanium and 43,000 grams of polyethylene per grams of total catalyst calculated as described in footnote 8 in Table I.

EXAMPLE 17

A. Catalyst preparation:

An inert atomosphere at room temperature, 23.20 g (200 millimoles) of dimethylglyoxime was slurried in 300 ml of hexane. A hexane solution of 100 millimoles of dibutylmagnesium was added dropwise to

added to the stirred dimethylglyoxin-hexane slurry. A 200

ml of hexane solution containing 230.7 ml (200 millimoles) 1.53 molar

ethyl aluminum dichloride was then added dropwise to the magnesium alkyl-dimethylglyoxime mixture. The resulting slurry was allowed to stand for 30 minutes, the supernatant was decanted, and the remaining solid was slurried in fresh hexane. A further 5 decantations were made with fresh hexane. A 100 mL hexane solution of 22.0 mL (200 mmol) TiCl4 was added dropwise to the solid previously prepared above, and this was followed by the dropwise addition of a 100 mL hexane solution containing 137.0 mL (200 mmol)

1.46 molar diethyl aluminum chloride. Successively, the resulting solid was allowed to settle, the supernatant was decanted, and the solid was reslurried in fresh hexane. A further 7 decantations were made with fresh hexane.

B. Polymerization of ethylene:

The polymerization procedure of Example 3(B) was repeated using 2.4 ml of 0.616 molar triisobutylaluminum (1.50 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.030 millimoles of titanium. The resulting polyethylene weighed 115 grams, had a melt index of 0.19 and had a bulk density of 12.8 lbs/ft 3 (0.21 g/ml). The catalyst's efficiency was 80,000 grams of polyethylene per grams of titanium.

EXAMPLE 18

A. Catalyst preparation:

To a solution of 101 ml of 0.593 molar dibutylmagnesium (60 millimoles) and 200 ml of hexane was added with stirring isobutyronitrile (120 millimoles) in hexane solution (50 ml of hexane). The addition was done dropwise over 30 minutes and gave a cream-colored solid. The solid was slurried in the hexane,

and TiCl₂ (120 mmol) in 70 mL of hexane was added dropwise over 20 minutes. The resulting solid was washed and decanted several times and then again slurried in 300 ml of hexane. To this mixture was added diethylaluminum chloride (130 millimoles) in hexane solution. This addition was regulated to maintain a temperature below 40°C. The resulting brown solid was decanted as in Example 1(A) to remove the hexane-soluble materials.

B. Polymerization of ethylene:

A measured portion of catalyst slurry prepared in (A) above containing 0.050 millimoles of titanium was added to a 1.8 liter stirred stainless steel reactor containing 1.0 liters of dry oxygen-free hexane and 3.9 ml of 0.616 molar triisobutylaluminum (2.40 millimoles) . The reactor's nitrogen atmosphere was replaced with hydrogen by purging, the reactor contents were heated to 85°C, and the reactor pressure was adjusted to 50 psig (3.52 kg/cm 2 ) with hydrogen. The ethylene was then added to maintain a reactor pressure of 170 psig. After two hours at 85°C, the contents of the reactor were filtered and the polyethylene dried in a vacuum overnight at approx. 6 0°C, which gave 74 grams of polyethylene with a melt index of 0.01. The catalyst's efficiency was 31,000 grams of polyethylene per grams of titanium.

EXAMPLE 19

A. Catalyst preparation:

To a 1 L round bottom flask equipped with a nitrogen inlet, magnetic stir bar, and a fritted glass dipper was added 143 mL of 0.593 molar dibutylmagnesium (85 millimoles) and 500 mL of hexane. While the solution was stirred, ammonia gas was bubbled through the liquid, and an exotherm reaction began which caused the formation of a white precipitate. When no further exotherm could be detected, the mixture was stirred for an additional 30 minutes, allowing the contents to cool to ambient temperature. The white solid was suspended with stirring, and TiCl 4 (290 mmol) dissolved in 50 mL hexane was added dropwise over 20 minutes.

An immediate reaction took place in which the white solid was converted to a yellow solid. This material was washed and decanted several times to remove all hexane soluble compounds. The solid was slurried in 300 mL of hexane, and TiCl₂ (60 mmol) was added in a single portion. To this mixture was added, over a 30 minute period, diethylaluminum chloride (120 millimoles) dissolved in 100 ml of hexane. The resulting brown solid was washed and decanted several times to remove the hydrocarbon soluble products.

B. Polymerization of ethylene:

The polymerization procedure of Example 18 (B) was repeated using 1.46 mL of 0.616 molar triisobutylaluminum

(0.90 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.030 millimoles of titanium. The polyethylene obtained weighed 150 grams and had a melt index of 0.4. The catalyst's efficiency was 104,000 grams of polyethylene per grams of titanium.

EXAMPLE 20

A. Catalyst preparation:

To a 1 liter round bottom flask equipped with a nitrogen inlet, magnetic stir bar and a fritted glass dipper was added 50.6 ml of 0.593 molar dibutylmagnesium (30 millimoles) and 350 ml of dry hexane. The flask was equipped to maintain a nitrogen atmosphere over the liquid. While the solution was stirred, ammonia gas was bubbled through the liquid and an exothermic reaction began which caused the formation of a white precipitate. When no further exotherm was detected, the mixture was stirred for an additional 30 minutes while passing dry nitrogen through the dip tube. The resulting white solid was suspended with stirring while SiCl₂ (30 mmol) dissolved in 50 mL of hexane was added dropwise. After the addition was complete, the solution was stirred for an additional 15 minutes. The white solid was washed and decanted several times to remove all hexane soluble material. The solid was slurried in 300 mL of dry hexane, and a single portion of TiCl 4 (30 mmol) was added. To this mixture was added, with stirring, diethylaluminum chloride (35 millimoles) in 100 ml of hexane, dropwise, over a 20 minute period while maintaining a temperature below 40°C. The resulting solid was washed and decanted several times to remove the hexane soluble products.

B. Polymerization of ethylene:

The polymerization procedure of Example 18(B) was repeated using 1.22 ml of 0.616 molar triisobutylaluminum (0.75 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.015 millimoles of titanium. The polyethylene obtained weighed 115 grams and had a melt index of 0.15. The catalyst's efficiency was 160,000 grams of polyethylene per grams of titanium.

hexane. The hydrocarbon-insoluble products were allowed to settle, and the supernatant solution was removed by decantation. The solids were reslurried in fresh hexane. The decantation procedure was then repeated 2 more times to remove the hydrocarbon soluble reaction products. Hexane was added to a volume of approx. 300 ml, and the slurry was mixed with 200 ml of 1.0 molar titanium tetrachloride (200 millimoles)

in hexane. To the stirred mixture was added dropwise

137.0 mL of 1.47 molar diethylaluminum chloride (200 millimoles). The hydrocarbon-insoluble products were allowed to settle,

and the supernatant was removed by decantation. The solids were reslurried in fresh hexane. The decantation procedure was repeated an additional 5 times to remove the hexane-soluble reaction products.

B. Polymerization of ethylene:

The polymerization procedure of Example 8(B) was repeated using 3.2 mL of 0.616 molar triisobutylaluminum

(2.0 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.020 millimoles of titanium. The polyethylene obtained weighed 183 grams and had a melt index of 0.20. The catalyst's efficiency was 191,000 grams of polyethylene per grams of titanium.

EXAMPLE 23

A. Catalyst preparation:

A solution of 7.9 ml of methyl acetate (100 millimoles) i

100 ml of hexane was added dropwise to a stirred solution

of 84.3 ml (50 millimoles) of 0.593 molar dibutylmagnesium. Silicon tetrachloride (23.0 mL, 200 mmol) in hexane (100 mL) was added dropwise and the hydrocarbon-insoluble solids were allowed to settle. The supernatant solution was removed by decantation and fresh hexane added. The decantation procedure was then repeated an additional 3 times to remove the hydrocarbon soluble reaction products. Titanium tetrachloride (100 mL 1.0 molar in hexane, 100 mmol) was added. A 1.46 molar diethylaluminum chloride solution (68 mL, 100 mmol) was added dropwise to the stirred slurry. The solids

was allowed to settle, and the supernatant was removed by decantation. Fresh hexane was added and the decantation procedure was repeated 5 more times to remove the hexane solubles.

B. Polymerization of ethylene:

The polymerization procedure of Example 8(B) was repeated using 5.7 mL of 0.616 molar triisobutylaluminum

(3.5 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.035 millimoles of titanium. The resulting polyethylene weighed 219 grams, had a melt index of 1.37 and had a bulk density of 15.5 lbs/ft 3 (0.248 g/ml). The catalyst's efficiency was 131,000 grams of polyethylene per grams of titanium.

EXAMPLE 24

A. Catalyst preparation:

A solution of 12.0 ml of diethyl carbonate (100 millimoles)

in 100 ml of hexane was added dropwise to a stirred solution of 84.3 ml of 0.593 molar dibutylmagnesium (50 millimoles). A hexane solution of ethyl aluminum dichloride (49.0 mL 1.53 molar, 75 mmol) was added dropwise to the stirred mixture of dibutyl magnesium and diethyl carbonate. The solids were allowed to settle, and the overlying liquid was decanted. Fresh hexane was added and the decantation repeated until a total of 3 decantations had been made. A titanium tetrachloride solution (25.0 mL 1.0 molar, 25 mmol) in hexane was added with hexane to a total volume of approx. 250 ml. The mixture was stirred while 17.1 mL of 1.46 molar diethylaluminum chloride solution (25 mL,

100 millimol) was added dropwise. The solids were allowed to settle, and the overlying liquid was removed by decantation. Fresh hexane was added and the decantation repeated a total of 6 times to remove the hexane-soluble substances.

B. Polymerization of ethylene:

The polymerization procedure of Example 8(B) was repeated using 5.2 mL of 0.616 molar triisobutylaluminum (3.2 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.035 millimoles of titanium. The obtained poly ethylene weighed 264 grams, had a melt index of 2.44, and had a bulk density of 10.3 lbs/ft 3 (0.17 g/ml). The catalyst's efficiency was 172,000 grams of polyethylene per grams of titanium.

EXAMPLE 25

A. Catalyst preparation;

Succinimide (4.95 grams, 50 mmol) was slowly added to a stirred solution of 42.2 mL (25 mmol) of 0.593 molar dibutylmagnesium. After 2 hours of continuous stirring, 32.7 ml of 1.53 molar ethyl aluminum dichloride (50 millimoles) in hexane was added dropwise. The solids were allowed to settle, and the overlying liquid was removed by decantation. Fresh hexane was added to the slurry and the decantation repeated until a total of 3 decantations had been made. Fresh hexane was added to a total volume of approx. 7 5 ml. Then, 100 ml of 1.0 molar titanium tetrachloride (100 millimoles) was added to the stirred mixture, followed by the dropwise addition of 68.5 ml of 1.46 molar diethylaluminum chloride (200 millimoles). The previous decanting procedure was repeated 6 times to remove the hydrocarbon solubles.

B. Polymerization of ethylene:

The polymerization procedure of Example 3(B) was repeated using 70 psig (4.92 kg/cm 2 ) of hydrogen, 3.2 ml of 0.616 molar triisobutylaluminum (2.0 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.020 millimoles of titanium. The resulting polyethylene weighed 181 grams, had a melt index of 1.78 and had a bulk density of 10.6 lbs/ft<3>

(0.17 g/ml). The catalyst's efficiency was 147,000 grams of polyethylene per grams of titanium.

EXAMPLE 26

A. Catalyst preparation:

A solution of 8.6 ml of isopropylamine (100 millimoles)

in 100 ml of hexane was added dropwise to a stirred solution of 84.3 ml of 0.593 molar dibutylmagnesium (50 millimoles). A hexane solution of ethyl aluminum dichloride (49.0 mL 1.53 molar, 75 mmol) was added dropwise to the stirred mixture of dibutyl magnesium and isopropylamine. The solids were allowed to

settle, and the overlying liquid was decanted. Fresh hexane was added and the decantation procedure repeated until a total of 4 decantations had been made. A titanium tetrachloride (100 mL, 1.0 molar, 100 mmol) in hexane was added with hexane to a total volume of approx. 300 ml. The mixture was stirred while 68.5 mL of 1.46 molar diethylaluminum chloride (100 mmol) was added dropwise. The solids were allowed to settle and the overlying liquid was removed by decantation. Fresh hexane was added and the decantation repeated a total of 6 times to remove the hexane-soluble substances.

B. Polymerization of ethylene:

The polymerization procedure in example. 8(B) was repeated using 4.2 mL of 0.616 molar triisobutylaluminum (2.6 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.026 millimoles of titanium. The polyethylene obtained weighed 181 grams, had a melt index of 0.12. The catalyst's effectiveness was 145,000 grams of polyethylene per grams of titanium.

EXAMPLE 27

A. Catalyst preparation:

A mixture of 169 ml of 0.59 3 molar dibutylmagnesium

(100 millimoles) and 325 mL of 0.616 molar triisobutylaluminum (200 millimoles) were added to a 1 liter stainless steel stirred reactor. Carbon dioxide was added to the reactor to a pressure of 30 psig. The reaction's heat generation heated the reactor to 50 - 60°C. After 2 hours, the reactor had cooled to ambient temperature. The carbon dioxide atmosphere in the reactor was replaced with nitrogen

by blow-through, and the reactor was placed in a glove box. The contents of the reactor were filled up to 500 ml with hexane, which gave a mixture which was 0.20 molar in magnesium. 250 ml of the above mixture with 0.20 molar magnesium (50 millimoles magnesium) was placed in a stirred glass container. Ethyl aluminum dichloride (49.0 mL 1.53 molar, 75 mmol) was added dropwise. The solids were allowed to settle and the overlying liquid was removed by decantation. Fresh hexane was added and the decantation procedure repeated until a total of 3 decantations had been made. A titanium tetrachloride (100 ml 1.0 molar,

100 millimoles) in hexane was added together with hexane to a total volume of approx. 400 ml. The mixture was stirred while 68.5 ml

1.46 molar diethylaluminum chloride (100 millimoles) was added dropwise. The solids were allowed to settle and the overlying liquid was removed by decantation. Fresh hexane was added and the decantation repeated a total of 6 times to remove the hexane-soluble substances.

B. Polymerization of ethylene:

The polymerization procedure of Example 8(B) was repeated using 4.1 mL of 0.616 molar triisobutylaluminum (2.5 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.025 millimoles of titanium. The resulting polyethylene weighed 126 grams, had a melt index of 0.40 and had a bulk density of 15.1 lbs/ft 3 (0.24 g/ml). The catalyst's efficiency was 105,000 grams of polyethylene per grams of titanium.

EXAMPLE 28

A. Catalyst preparation:

In an inert atmosphere at room temperature, a 100 ml hexane solution containing 350 millimoles of an n-propyl alcohol was added dropwise to a stirred 500 ml hexane solution containing 168.6 ml 0.593 molar dibutylmagnesium (100 millimoles) and 81.2 ml 0.616 molar triisobutylaluminum (50 millimoles ) successively, a 100 ml hexane solution containing 22.0 ml 9.1 molar TiCl 2 (200 millimoles) was added dropwise. The resulting solid was allowed to settle for 15 minutes and the supernatant was decanted. The solid was reslurried in fresh hexane, and the supernatant was again decanted. A further 6 decantations were made with fresh hexane. The slurry was divided into two parts of equal volume, and one part was discarded. To the second portion was added 11.0 mL of 9.1 molar TiCl₂ (100 mmol), followed by the dropwise addition of a 200 mL hexane solution containing 74.8 mL of 1.47 molar diethylaluminum dichloride (110 mmol). The final solid was allowed to settle for 10 minutes, then the supernatant was decanted. The solid was again slurried in fresh hexane and the overlying liquid was again decanted. A further 6 decantations were made with fresh hexane. The washed solid was then used as a polymerization catalyst i

examples B and C below.

B. Copolymerization of ethylene and 1-octene:

To a stirred 1.0 liter reactor containing 375 ml of dry oxygen-free hexane was added 1.6 ml of 0.616 molar triisobutylaluminum (0.986 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.0195 millimoles of titanium. After the pressure venting procedure of Example 3(B) was used, the reactor was pressurized to 15 psig with hydrogen, and the reactor temperature was set at 75°C. Then the 1-octene was fed into the reactor by blowing ethylene at 170 psig through a side-flow cylinder containing 125 ml of 1-octene. The reactor pressure was then maintained at 170 psig with ethylene. The polymer obtained weighed 136 grams. The melt index of the polymer was 0.27, and the density, measured according to ASTM-D792-66, was 0.9444 grams per cubic meter. cm 3. The catalyst's efficiency was 145,000 grams of polymer per grams of titanium and 35,000 grams of polymer per grams of total catalyst calculated from the ratio Mg:Ti assuming a mixture of MgCl2 and TiCl3.

C. Copolymerization of ethylene and 1-butene:

The procedure in (B) above was followed except that the reactor was pressurized to 10 psig with hydrogen and 1.6 mL of 0.616 molar triisobutylaluminum (0.986 millimoles) and a measured portion of catalyst prepared in (A) above containing 0.200 millimoles titanium was added to the reactor to catalyze the polymerization reaction. The 1-butene was fed into the reactor by blowing ethylene gas at 170 psig through a side-flow cylinder containing 16.0 grams of 1-butene. The reactor pressure was maintained at 170 psig with ethylene. The resulting polymer weighed 158 grams, had a melt index of 0.15 and had a density, measured according to ASTM-D792-66, of 0.9304 grams per cubic meter. cm 3. The catalyst's efficiency was 165,000 grams of polymer per grams of titanium and 39,000 grams of polymer per grams of total catalyst calculated from the ratio Mg:Ti assuming a mixture of MgCl^ and TiCl^.

EXAMPLE 2 9

A. Catalyst preparation:

A solution of 30.1 ml of n-propyl alcohol (400 millimoles) and 100 ml of hexane was added dropwise to a stirred solution of 157 ml of 0.637 molar butylethylmagnesium (100 millimoles) in heptane and 81 ml of 0.616 molar triisobutylaluminum (50 millimoles) in hexane. The resulting solution was cooled to 30°C, and a solution of 44.0 mL of titanium tetrachloride (400 mmol) in 200 mL of hexane was added dropwise with continuous stirring. The slurry was stirred for 1/2 hour, the hydrocarbon insoluble products were allowed to settle, and the supernatant was removed by decantation. The solids were reslurried in fresh hexane. The decantation procedure was repeated 2 more times to remove most of the hexane-soluble reaction products. The hydrocarbon insoluble products were slurried in hexane to a total volume of 800 ml. Half of this slurry (400 ml) was mixed with 44.0 ml of titanium tetrachloride (400 millimoles) and 274 ml of 1.46 molar diethylaluminum chloride in hexane was added dropwise to the stirred mixture over a period of approx. 1 hour. The resulting mixture was stirred for an additional 1 hour, the hydrocarbon insoluble products were allowed to settle, and the supernatant was removed by decantation. The solids were reslurried in fresh hexane. The decantation procedure was repeated an additional 5 times to remove the hydrocarbon soluble products. A measured portion of catalyst slurry was diluted with Isopar E to a slurry that was 0.001 molar with respect to titanium.

B. Polymerization of ethylene:

A 1.8 L stirred stainless steel reactor containing 1.0 L of dry, oxygen-free Isopar E and 0.54 mL of 0.921 molar triethylaluminum (0.50 mmol) in hexane was vented to 0 psig. The reactor was heated to 150°C and hydrogen added to a reactor pressure of 25 psig. Ethylene was then added to the reactor to a pressure of 120 psig. The catalyst (25 mL of 0.001 molar slurry in Isopar E) prepared in Example 29(A) was pressurized in the reactor using nitrogen. The reactor temperature was maintained at 150°C by heating or cooling, and the reactor pressure was maintained at 145 psig by addition of ethylene. After 15 minutes, 0.27 ml of 0.921 molar triethyl aluminum (0.25 millimoles) in hexane was diluted to approx. 10 ml of Isopar E pressurized in the reactor with nitrogen. After 15 minutes, the contents of the reactor were cooled to room temperature, the contents of the reactor were filtered and the polyethylene was dried in a vacuum overnight at approx. 60°C, which gave 35.0 grams of polyethylene with a melt index of 0.48. The catalyst's efficiency was 29,200 grams of polyethylene per grams of titanium.

EXAMPLE 30

A. Catalyst preparation:

A solution (4.14 parts by weight, dpv) of butylethylmagnesium containing 2.40 wt% magnesium in heptane and a solution (2.19 dpv) of 20.3 wt% triisobutylaluminum in hexane were mixed in a jacketed stirred reactor . The temperature of the solution was maintained at below 40°C while 1.00 dpv n-propyl alcohol and 6.33 dpv hexane were added. The resulting solution temperature was maintained at 35°C while 3.08 dpv of titanium tetrachloride was slowly added. The resulting slurry was cooled to approx. 25°C, the solids allowed to settle and the overlying liquid removed by decantation. The solids were reslurried in fresh hexane and the decantation procedure repeated until less than 10 mol% of the total titanium content is in solution.

The resulting slurry after the decantations was 140 millimolar with respect to magnesium and had a total weight of 6.84 dpv. Titanium tetrachloride (0.59 dpv) was added to the stirred slurry. A 25% by weight diethylaluminum chloride solution (1.64 dpv) in hexane was slowly added to the stirred mixture. The solids were allowed to settle and the overlying liquid was removed by decantation. The solids were reslurried in fresh hexane and the decantation procedure repeated several times to remove the hydrocarbon solubles.

B. Polymerization:

The catalyst prepared in Example 30(A) was diluted with hexane to 0.3 millimolar with respect to titanium. This diluted catalyst was then added, at a rate of approx. 12 dpv per hour, to a partially full agitated reactor. At the same time, 100 dpv ethylene per hour, 1 dpv buten-1 per hour and 22 3 dpv hexane per hour added to the reactor while the reactor temperature and pressure were regulated at 85°C and 170 psig respectively. A 2% by weight solution of triisobutylaluminum in hexane was added at such a rate that it gave an Al/Ti atomic ratio of approx. 50:1 in the reactor. Hydrogen was added to the gaseous phase of the reactor so that the desired polymer melt index was achieved. The contents of the reactor were withdrawn continuously, the polymer and hexane were separated and the dried polymer collected. The polymer had a melt index of 11. The catalyst's efficiency was approx. 400,000 pounds of polymer per pound of titanium.

EXAMPLE 31

A. Catalyst preparation:

A solution of 50 ml of 0.5 molar anhydrous cobalt dichloride (25 millimoles) in n-propyl alcohol was added dropwise to 526 ml

of a stirred solution of 0.475 molar dibutylmagnesium (250 millimoles). A solution of 55 ml titanium tetrachloride (500 millimoles)

in 100 ml of hexane was added dropwise to the resulting slurry. The solids were allowed to settle and the overlying liquid was removed by decantation. Fresh hexane was added^ and the decantation procedure was repeated an additional 5 times to remove the hexane solubles. Titanium tetrachloride (55 mL, 500 mmol) was added to the stirred hexane slurry, and then 342 mL of a 1.46 molar diethylaluminum chloride solution was added dropwise. The solids were allowed to settle and the overlying liquid was removed by decantation. Fresh hexane was added and the decantation procedure was repeated an additional 5 times to remove the hexane solubles.

B. Polymerization of ethylene:

Triisobutylaluminum (0.49 mL 0.616 molar; 0.30 mmol) and then a measured portion of catalyst containing 0.015 mmol Ti, prepared in (A) above, was added to a stirred 1.0 liter stainless steel reactor containing 0.5 liter of dry, oxygen-free hexane. The reactor was put under a pressure of approx. 50 psig (4 kg/cm 2 ) with hydrogen at room temperature and then vented to 5 psig (0.4 kg/cm 2 ). The pressure ventilation with hydrogen was repeated 9 times. The reactor was then heated to 85°C and the reactor pressure set to 60 psig (4 kg/cm 2 ) by addition of hydrogen. The ethylene was added and the reactor pressure maintained at 170 psig

(12 kg/cm 2 ) with ethylene. The polymerization was allowed to proceed

for two hours at 85°C, after which the reactor was cooled to room temperature. The contents of the reactor were filtered and the polyethylene dried in a vacuum overnight at approx. 60°C. The polyethylene obtained weighed 219 grams, had a melt index of 0.35 and a bulk density of

24.0 lbs/ft 3 (0.39 g/cc). The catalyst's efficiency was 305,000 grams of polyethylene per grams of titanium.

EXAMPLE 32

A. Catalyst preparation:

A solution of 5.9 grams of nickel dichloride hexahydrate

(25 millimoles) dissolved in 39.1 ml of n-propyl alcohol (520 millimoles)

was added dropwise to 526 mL of a stirred solution of 0.475 molar dibutylmagnesium (250 millimoles). A solution of 55 ml of titanium tetrachloride in 100 ml of hexane was added dropwise to the resulting slurry. The solids were allowed to settle and the overlying liquid was removed by decantation. Fresh hexane was added and the decantation procedure was repeated

a further 5 times to remove the hexane-soluble substances. Titanium tetrachloride (55 mL, 500 mmol) was added to the stirred hexane slurry, and then 342 mL of a 1.46 molar diethylaluminum chloride solution was added dropwise. The solids were allowed to settle and the overlying liquid was removed by decantation. Fresh hexane was added and the decantation procedure was repeated an additional 5 times to remove the hexane solubles.

B. Polymerization of ethylene:

The procedure of Example 31(B) was repeated using 1.0 ml of 0.616 molar triisobutylaluminum (0.62 millimole) and a measured portion of catalyst prepared in (A) above. Containing 0.0312 millimoles of titanium. The resulting polyethylene weighed 227 grams, had a melt index of 0.08 and a bulk density of 19.0 lbs/ft 3 (0.32 g/ml). The catalyst's efficiency was 152,000 grams of polyethylene per grams of titanium.

Claims (68)

1. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions, where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R3)__ X , B(R3)_ X , MgR <3>0 , jaa j—a aM gR<3>X ,ZnR<3>2 , where each R3 independently of one another is hydrogen or a hydrocarbyl group having from 1 to approx. 20 carbon atoms, and X is halogen; characterized by using as the transition metal-containing catalyst the hydrocarbon-insoluble product which has been washed with an inert solvent, and which results from the mixture of: (I) the reaction product of (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof, where such components are represented by the formula MgR2*xMeR1,, where each R independently is a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10, and x <1> has a value equal to the valence of Me; and (2) a transition-metal-free oxygen-containing compound, a transition-metal-free nitrogen-containing compound, or mixture of such compounds in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) such that the resulting product does not substantially reduce TiCl , at a temperature of approx. 25°C; and (B) a suitable halide source or mixture thereof represented by the formulas AlR^ _a Xa , SiR^^ Xtø , 2. Method as stated in claim 1, characterized in that in component (A-I) each R and R' group is independently an aliphatic hydrocarbon group having from 1 to approx. 10 carbon atoms; Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates, glycols, alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; the halide source is represented by the formulas A1R_ X or j —a a TmY n X z-n ; in comp c onent (II) Y is equal to OR"; the reduct ion agent is represented by the formula AIR3 3-m X m ; the Mg^:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing agent is present in such an amount as to provide an R<3>;T m ratio of from about 1:1 to about 10:1, and wherein said cocatalyst contains aluminum. 3. Method as stated in claim 2, characterized in that R and R <1> and the value of x is such that the organo-magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; the halide source is TiCl^ ; component (II) is omitted; in the formula for the reducing agent, each R3 is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, each X is chlorine, m has a value of zero or 1; the atomic ratio M g:Ti is from approx. 0.2:1 to approx. 1:1 and the reducing agent is used in such an amount that an R<3>:Ti ratio of from approx. 1:1 to approx. 3:1. 4. Method as stated in claim 3, characterized in that the value of x and each R and R <1> is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to approx. 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination. 5. Method as stated in claim 4, characterized in that the alcohol is methyl alcohol, ethyl alcohol, SnR4 _b Xb , POX3 , PX3 , PX5 , SO2 X2 , GeX^ , R <1*> (CO)X, TmYn xz- n°9 rI*x nwhere each R independently is hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to approx. 20 carbon atoms; each R<1*> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4, Tm is a metal selected from groups IV-B, V-B and VI-B in the periodic table; Y is oxygen, OR" or NR"2; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, z has a value equal to the valence of said transition metal, n has a value from zero to 5, where the value of z-n is from at least 1 and up to a value equal to the valence of the transition metal, said halide source being present in an amount sufficient to convert substantially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) a transition metal compound represented by formula TmY n X z-n where Tm, Y, X, z and - D n are as defined above; z-n has a value from zero up to the valence of Tm in an amount so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to approx. 50:1; and (III) a suitable reducing agent or a mixture of re dux ionic agents represented by the formulas B(R3)_ X , J e 3-m irr Al(R3) «3 in X Til ,ZnR3 X, ZnR3 4^ , MgR <3> X or MgR3 £ where each X independently is halogen, a hydrocarbyloxy group having from 1 to about. 20 carbon atoms or a NR <3> ,, group; each R<3> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms each; m has a value from zero to 2; the said reducing agent being used in such an amount that a R<3> :Tm ratio of from approx. 1:1 to approx. 50:1; provided that when component (I-B), the halide source, contains a sufficient amount of transition metal to satisfy the Mg:Tm ratio, then component (II) may be omitted. n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixture thereof in any combination. 6. Method as stated in claim 5, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol. 7. Process as stated in claim 1, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 8. Method as stated in claim 7, characterized in that component (A-2) is ammonia or an amine. 9. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R3) j — a X a , B(R3)j _ — a X a , MgR3 2.,M gR<3>X , ZnR3^ where each R<3> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; characterized by using as transition metal-containing catalyst the hydrocarbon-insoluble reaction product washed with an inert diluent of: (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR Å -xMeR' Xt where each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10, x' has a value equal to the valence of Me, and (2) a transition-metal-free oxygen-containing and/or a transition-metal-free nitrogen-containing compound in an amount sufficient to lower the amount of hydrocarbyl groups that are present in component (A-I) so that the resulting product does not significantly reduce TiCl^ at a temperature of approx. 25°C; (B) an appropriate reducing halide source represented by the formulas Al (R 3 ).- .X ; where R <3> is independently 3 —a a hydrogen or has the same definition as R above, X is as defined above and a has a value of from 1 to less than 3; said halide is used in a sufficient amount to convert essentially all the groups linked to a magnesium atom in component (A) to a halide atom and so that the R<3> :Tm ratio is from approx. 1:1 to approx. 50:1; and (C) a transition metal compound represented by formula TmYn Xz _n where Tm is a metal selected from groups IV-B, V-B or VI-B of the periodic table; Y is oxygen, OR" or NR"2; X is a halogen, each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5, z-n being from 1 up to a value equal to the valence of the transition metal in such quantity that a Mg:Tm atomic ratio of from approx. 0.05:1 to approx. 50:1. 10. Method as stated in claim 9, characterized in that in component (A-I) each R and R' group is independently an aliphatic hydrocarbon having from 1 to approx. 10 carbon atoms, Me is Al and x <1> has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates and glycols, alcohols, aldehydes, ketones, carboxylic acids , or mixture thereof in any combination; in component (C), Y is equal to OR"; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1, and the reducing halide is present in such an amount as to provide an R <3 > :Tm ratio of from about 1:1 to about 10:1; and wherein the cocatalyst contains aluminum. 11. Method as stated in claim 10, characterized in that R and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, carboxylic acids or mixtures thereof in any combination; the halide source is diethylaluminum chloride or ethylaluminum dichloride; in the formula for component (C), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms and n has a value of from zero to 2; the atomic ratio Mg:Ti is from about .0.2:1 to about 1:1, and the reducing halide is used in such an amount as to provide an R<3> :Ti ratio of from about 1:1 to about 3:1. 12. Method as stated in claim 11, characterized in that the value of x and each R and R <1> is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to approx. 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination. 13. Method as stated in claim 12, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl- 4-methylphenol, or mixtures thereof. 14. Method as stated in claim 13, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol. 15. Method as stated in claim 9, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 16. Method as stated in claim 15, characterized in that component (A-2) is ammonia, an amine, an isocyanate or mixture thereof in any combination. 17. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas A1(R3)j_ —a X a , B(R <3> )j, —a X a , MgR 3 z. , MgR <3> X, ZnR <3>2 where each R <3> independently is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; characterized in that the hydrocarbon-insoluble catalyst produced by a method comprising: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR0«xMeR', where each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to approx. 10; and x' has a value equal to the valence of Me; and (2) a transition-metal-free oxygen-containing compound, a transition-metal-free nitrogen-containing compound, or mixture of such compounds in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) such that the resulting product does not substantially reduce TiCli" at a temperature of approx. 25°C; and (B ) a suitable halide source or mixture thereof represented by the formulas AIR-, X , SiR. , X, r 3-a a 4-b b ' SnR4 _b Xb , P0X3 , PX3 , PX5 , SO2 X2 , GeX4, RMC0)X, TmY n X and R <4> X where each R independently is hydrogen, a hydrocarbyl or a hydrocarbyloxy group which has from 1 to approx. 20 carbon atoms, R1* is independently hydrogen or an i hydrocarbyl group having from 1 to approx. 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4; Tm is a metal selected from groups IV-B, V-B and VI-B of the periodic table; Y is oxygen, OR" or NR"2; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; z has a value equal to the valence of said transition metal, n has a value of from zero to 5, the value of z-n being from at least 1 and up to a value equal to the valence of the transition metal, said halide source being present in an amount sufficient to convert substantially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) recovering the resulting hydrocarbon-insoluble product, washing the product with fresh, inert diluent; and (III) mixing, in fresh, inert diluent, the product of (II) with (C) a transition metal compound represented by formula TmY X wherein Tm, Y, X, z and n are as defined above; z-n has a value from zero up to the valence of Tm; in such an amount that a Mg:Tm atomic ratio of from approx. 0.05:1 to approx. 50:1; (IV) reacting the product of (III) with (D) a suitable reducing agent or a mixture of reducing agents selected from compounds represented by the formulas B (R 3 ) 0 X , AMR 3 )- X , ZnR < 3> X , ZnR 3 , MgR<3>X or j-m m j— m m 2 MgR32 where each X is halogen or a hydrocarbyloxy group having from 1 to approx. 20 carbon atoms or an NR<3>2 group; each R<3> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; m has a value from zero to 2; with the reducing agent being used in such an amount that a R<3>:T m ratio of from approx. 1:1 to approx. 50:1; and (V) recovering and washing, with fresh, inert diluent, the resulting solid hydrocarbon-insoluble catalyst produced in step IV. 18. Method as stated in claim 17, characterized in that in component (A-I) each group R and R<1> is independently an aliphatic hydrocarbon group having from 1 to approx. 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixtures thereof in any combination; the halide source is represented by the formulas AlR 3 -a X a or TmY n X z-n; in component (C), Y is equal to OR "; the reducing agent is represented by the formula AIR33- -m X m ; the Mg3:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing agent is present in a such amount as to provide an R<3> :Tm ratio of from about 1:1 to about 10:1; and wherein said cocatalyst contains aluminium. 19. Method as stated in claim 18, characterized in that R, R' and the value of x are such that the organo-magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; the halide source is represented by the formula T iCl4 ; component (C) is TiCl4 , in the formula of the reducing agent each R<3> is independently an aliphatic hydrocarbon group having from 1 to approx. 10 carbon atoms, each X being chlorine; m has a value of zero or 1; the atomic ratio Mg:Ti is from approx. 0.2:1 to approx. 1:1, and the reducing agent is used in such an amount that a R<3>:Ti ratio of from approx. 1:1 to approx. 3:1. 20. Method as stated in claim 19, characterized in that the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to approx. 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenyl aluminum or a mixture thereof in any combination. 21. Method as stated in claim 20, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl- 4-methylphenol, or mixture thereof in any combination. 22. Method as stated in claim 21, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or a mixture thereof in any combination. 23. Method as stated in claim 17, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 24. Method as stated in claim 23, characterized in that component (A-2) is ammonia or an amine. 25. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R <3> )3 _a Xa ,B (R<3> )3 _aXa , MgR3 2 iM gR<3>X , ZnR32 where each R3 is independently hydrogen or a hydrocarbyl group having from 1 to approx. 20 carbon atoms, and x is halogen; characterized in that the hydrocarbon-insoluble catalyst produced by a method comprising: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR_-xMeR' , where each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to approx. 10, and x <1> has a value equal to the valence of Me; with (2) a transition-metal-free oxygen-containing compound, a transition-metal-free nitrogen-containing compound or mixture of such compounds in an amount sufficient to reduce the amount of hydrocarbyl groups present in component (A-I) so that the resulting product does not in significantly reduces TiCli» at a temperature of 2 5°C; (B) a suitable reducing halide source represen tert by the formula Al(R3)- X where each X un- j —a a hangig is a halogen atom; R<3> independently is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and a has a value of from 1 to less than 3; the halide being used in such an amount that the R<3> :Tm ratio is from approx. 1:1 to approx. 50:1, and to provide a sufficient amount of halogen atoms to convert substantially all the groups attached to a magnesium atom in component (A) to a halide group; and (C) a transition metal compound represented by formula TmY n X z-n where Tm is a metal selected from groups IV-B, V-B and VI-B of the periodic table; Y is oxygen, OR" or NR"2; X is halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5, z-n being from 1 up to a value equal to the valence of the transition metal in such an amount as to provide a Mg:Tm atomic ratio of from approx. 0.05:1 to approx. 50:1; and (II) recovering and washing, with fresh, inert diluent, the resulting solid, hydrocarbon-insoluble catalyst. 26. Method as stated in claim 25, characterized in that in component (A-I) each group R and R' is independently an aliphatic hydrocarbon having from 1 to approx. 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixture thereof in any combination; in component (C), Y equals OR"; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing halide is present in such an amount as to provide an R <3 >:Tm ratio of from about 1:1 to about 10:1. 27. Method as stated in claim 26, characterized in that R and R <1> and the value of x is such that the organo-magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; in the formula for component (C ), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms and n has a value from zero to 2; the atomic ratio Mg:Ti is from about . 0.2:1 to approx. 1:1, and the reducing halide is used in an amount which provides an R<3> :Ti ratio of from approx. 1:1 to approx. 3:1. 28. Method as stated in claim 27, characterized in that the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to approx. 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination. 29. Method as stated in claim 28, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl- 4-methylphenol, or mixture thereof in any combination. Cm 30. Method as stated in claim 29, characterized in that the alcohol is selected from methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or a mixture thereof in any combination. 31. Method as stated in claim 25, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 32. Method as stated in claim 31, characterized in that component (A-2) is ammonia or an amine. 33. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R3)j_ —a X a , B(R3)j_ —a x a , MgR3 z, MgR <3> X,Z nR <3>2 where each R <3> independently is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; characterized by using as the transition metal-containing catalyst the hydrocarbon-insoluble product washed with an inert diluent resulting from a mixture of: (I) the reaction product of (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof, such components being represented by the formula MgR2'X MeR'x , , where each R independently is a hydrocarbyl group having from 1 to about 20 carbon atoms, each R<1> independently is hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10 and x' a value equal to the valence of Me; and (2) a transition-metal-free oxygen-containing compound, a transition-metal-free nitrogen-containing compound or mixture of such compounds in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) such that the resulting product does not substantially degree reduces Tidi" at a temperature of approx. 25°C; one or more transition metal compounds represented by formula Tm'Y X where Tm' is a transition metal selected from groups I-B, IV-B , V-B, VI-B ) VII-B or VIII of the periodic table, and is not the same element such as that represented by Tm in component (II); Y is oxygen, OR" or NR"; each R" is unsubstituted hydrogen or a hydrocarbyl group having 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein the transition metal compound is present in such an amount that the atomic ratio Tm':Tm, from component II, is from 0.01:1 to about 0.5:1; and (B) a suitable halide source or mixture thereof represented by the formulas AlR3 _a X& , SiR^^ ^, SnR4 _b Xb , P0X3 , PX3 ,P X5 ,S 02 X2 , GeX4 , R <4> (C O)X, TmYn xz _n and R<4> X wherein each R is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R<1*> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of 1 to 3; b has a value of 1 to 4, Tm is a metal selected from groups IV-B, V-B and VI-B of the periodic table; Y is oxygen, OR" or NR"2; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, z has a value equal to the valence of transition the metal, n has a value of zero to 5 where the value of z-n is from at least 1 and up to a value equal to the valence of the transition metal; said halide source being present in a sufficient amount to convert substantially all of the groups attached to a magnesium atom in component (A) into a halide group; (II) a transition metal compound represented by formula TmY X where Tm, Y, X, z and n are as defined above n z-n iii ^ for; z-n has a value from zero up to the valence of Tm in such an amount that a Mg:Tm atomic ratio of from approx. 0.05:1 to approx. 50:1; and (III) a suitable reducing agent or mixture of reducing agents represented by the formulas B(R3)_X , J c 3-m m Al(R3)-, X , ZnR <3> X, ZnR3 , MgR<3>X or MgR <3>- where each X independently is halogen, a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR<3>2 group; each R<3> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms each; m has a value from zero to 2; with the reducing agent being used in such an amount that a R<3>:T m ratio of from approx. 1:1 to approx. 50:1; provided that when component (I-B), the halide source, contains a sufficient amount of transition metal to satisfy the Mg:Tm ratio, then component (II) may be omitted. 34. Method as stated in claim 33, characterized in that in component (A-I) each group R and R<1> is independently an aliphatic hydrocarbon group having from 1 to approx. 10 carbon atoms; Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates, glycols, alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination, in component (A-2) is Tm <1> equal to Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to about 10 carbon atoms; X is chlorine or bromine, and the atomic ratio Tm':Tm is from about 0.02:1 to about 0.2:1; the halide source is represented by the formulas A1R30 -a X a or TmY n X z-n; in component (II), Y is equal to OR"; the reducing agent is represented by the formula AIR3 3-m X m; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing agent is present in such an amount as to provide an R<3> :Tm ratio of from about 1:1 to about 10:1; and wherein the cocatalyst contains aluminum. 35. Method as stated in claim 34, characterized in that R and R' and the value of x are such that the organo-magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, ketones and carboxylic acids or mixtures thereof in any combination; said transition metal compound represented by formula Tm <1> Y X is NiCl- , NiCl«6Ho 0, FeCl_, n z-n 2' 2 3 FeCl3 -6H2 0, CrCl3 , CrCl2 , CrCl3 -6H2 0, MoCl5 , WClg, ZrCl4, Zr(0-iC3 H7 )4 , V0C13 or mixture thereof in any combination; the halide source is TiCl4; component (II) is omitted; in the formula for the reducing agent, each R<3> is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, each X is chlorine, m has a value of zero or 1; the atomic ratio Mg:Ti is from approx. 0.2:1 to approx. 1:1, and the reducing agent is used in such an amount that an R<3>:Ti ratio of from approx. 1:1 to approx. 3:1. 36. Method as stated in claim 35, characterized in that the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to approx. 20 carbon atoms; and the cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination. 37. Method as stated in claim 36, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl- 4-methylphenol, or mixture thereof in any combination. 38. Method as stated in claim 37, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol. 39. Method as stated in claim 33, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 40. Method as stated in claim 39, characterized in that component (A-2) is ammonia or an amine. 41. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al (R3)-. X , B ( <R> 3)^ X , MgR3 0 , a aM gR<3>X ,Z nR <3>2 eHere mixtures thereof where each R <3> independently is hydrogen or a hydrocarbyl group having from 1 to approx. 20 carbon atoms and X is halogen; characterized by using, as the transition metal-containing catalyst, the inert diluent-washed hydrocarbon-insoluble reaction product of: (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula M gR2 -xMeR'x , where each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10, x' has a value equal to the valence of Me; and (2) a transition-metal-free oxygen-containing and/or a transition-metal-free nitrogen-containing compound in sufficient amount to lower the amount of hydrocarbyl groups present in component (A-I) so that the resulting product does not substantially reduce TiCl , at a temperature of about 25°C; one or more transition metal compounds represented by the formula Tm'Y Xz-n n z-n where Tm <1> is a transition metal selected from groups I-B, IV-B,V-B, VI-B^II-B or VIII in the periodic table and is not the same element as that represented by Tm in component (C ); Y is oxygen, OR" or NR"; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value from 0 to 5; the value of z-n is from zero and up to the valence of the transition metal Tm'; and wherein the transition metal compound is present in such an amount that the atomic ratio Tm':Tm, from component (C), is from 0.01:1 to about 0.5: 1; (B) a suitable reducing halide source represented by the formulas Al (R 3 )-j , —a X a ; wherein R<3> is independently hydrogen or has the same definition as R above, X is as defined above and a has a value from 1 to less than 3; said halide is used in a sufficient amount to convert essentially all the groups associated with a magnesium atom in component (A) into a halide atom and so that the ratio R<3> :Tm is from approx. 1:1 to approx. 50:1; and (C) a transition metal compound represented by formula TmY n X z-n where Tm is a metal selected from groups IV-B, V-B or VI-B of the periodic table; Y is oxygen, OR" or NR"2; X is halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value of from zero to 5, z-n being from 1 up to a value equal to the valence of the transition metal in such an amount that a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1 is provided. 42. Method as stated in claim 41, characterized in that in component (A-I) each group R and R' is independently an aliphatic hydrocarbon having from 1 to approx. 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates and glycols, alcohols, aldehydes, ketones, carboxylic acids , or mixture thereof in any combination; in component (A-2), Tm <1> is equal to Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to approx. 10 carbon atoms; X is chlorine or bromine, and the atomic ratio Tm':Tm is from approx. 0.02:1 to approx. 0.2:1; in component (C), Y equals OR"; the atomic ratio M g:Tm is from about 0.1:1 to about 5:1; and the reducing halide is present in such an amount as to provide a ratio R <3 > :Tm of from about 1:1 to about 10:1; and wherein the cocatalyst contains aluminum. 43. Method as stated in claim 42, characterized in that R and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, carboxylic acids or mixtures thereof in any combination; whereas the transition metal compound represented by the formula Tm'Y X is NiCl^ , NiCl *6H„0, r n z-n 2 2 2 FeCl3 , FeCl3' 6H2 0, CrCl3 , CrCl2 , CrCl3' 6H2 0, MoCl5 , WClg, ZrCl4 , Zr(0-iC3 H7 )4 , VOCl3 or mixture thereof in any combination; the halide source is diethylaluminum chloride or ethylaluminum dichloride; in the formula for component (C), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, and n has a value from 0 to 2; the atomic ratio Mg:Ti is from about .0.2:1 to about 1:1, and the reducing halide is used in such an amount as to provide a ratio R<3>:Ti of from about 1:1 to about 3:1. 44. Method as stated in claim 43, characterized in that the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols with from 1 to approx. 20 carbon atoms; and the cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination. 45. Method as stated in claim 44, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl- 4-methylphenol, or mixtures thereof. 46. Method as stated in claim 45, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol. 47. Method as stated in claim 41, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 48. Method as stated in claim 47, characterized in that component (A-2) is ammonia, an amine, an isocyanate or mixture thereof in any combination. 49. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al (R3)j-, —a X a , B(R3)j_ —a X a , MgR3 A,M gR<3>X ,Z nR <3>2 where each R <3> independently is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; characterized in that the hydrocarbon-insoluble catalyst produced by a method comprising: (i) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR2' xMeR'x , where each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R<1> is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to approx. 10; and x <1> has a value equal to the valence of Me; and (2) a transition-metal-free oxygen-containing compound, a transition-metal-free nitrogen-containing compound or mixture of such compounds in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) such that the resulting product does not substantially reduces TiCli+ at a temperature of approx. 25°C; one or more transition metal compounds represented by formula Tm'Y X where Tm1 is a transition metal n z-n 3 13 selected from groups I-B, IV-By V-B, VI-B/ VII-B or VIII of the periodic table and is not the same element as that represented by Tm in component (C); Y is oxygen, OR" or NR"2; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein the transition metal compound is present in such an amount that the atomic ratio Tm':Tm, from component (C), is from 0.01:1 to about 0.5:1; and (B) a suitable halide source or mixture thereof represented by the formulas AIR^^ X^ , SiR^^ ^, SnR4 _b Xb , P0X3 , PX3 , PX5 , S02 X2 , GeX4 , R <4> (C0)X, TmYn Xz _n and R <**> X where each R is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; R<1*> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom, a has a value from 1 to 3; b has a value from 1 to 4; Tm is. a metal selected from groups IV-B, V-B and VI-B of the periodic table; Y is oxygen, OR" or NR"2; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; z has a value equal to the valence of said transition metal, n has a value from zero to 5, the value of z-n being from at least 1 and up to a value equal to the valence of the transition metal, said halide source being present in an amount sufficient to convert substantially all of the groups attached to a magnesium atom in component (A) into a halide group; (II) converting the resulting hydrocarbon-insoluble product, washing the product with fresh, inert diluent; and (III) mixing, in fresh, inert diluent, the product of (II) with (C) a transition metal compound represented by formula TmY n X where Tm, Y, X, z and ^ n z-n rir i n is as defined above; z-n has a value from zero up to the valence of Tm; in such an amount that an atomic ratio Mg:Tm of from approx. 0.05:1 to approx. 50:1; (IV) reacting the product of (III) with (D) a suitable reducing agent or mixture of reducing agents selected from compounds represented by the formulas B(R <3> )3 _m Xm , Al(R <3> )3 _m Xm , ZnR <3> X, ZnR <3>2 , MgR3 X or MgR <3>2 where each X is halogen or a hydrocarbyloxy group having from 1 to about 20 carbon atoms or a N R <3>2~ group; each R<3> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; m has a value from zero to 2; with the reducing agent being used in such an amount that a R<3> :Tm ratio of from approx. 1:1 to approx. 50:1; (V) recovering and washing, with fresh, inert diluent, the resulting solid hydrocarbon-insoluble catalyst produced in step IV. 50. Method as stated in claim 49, characterized in that in component (A-I) each group R and R' is independently an aliphatic hydrocarbon having from 1 to approx. 10 carbon atoms, Me is Al and x <1> has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixtures thereof in any combination; in component (A-2), Tm' is equal to Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to about 10 carbon atoms; X is chlorine or bromine and the atomic ratio Tm':Tm is from about 0.02:1 to about 0.2:1; the halide source is represented by the formulas AlR3-, -a X a or TmY n X z-n; in component (C) Y equals OR"; the reducing agent is represented by the formula AIR3 3-m X m; the atomic ratio Mg:Tm is from approx. 0.1:1 to approx. 5:1; and the reducing agent is present in such an amount as to provide an R<3> :Tm ratio of from about 1:1 to approx. 10:1; and wherein said cocatalyst contains aluminium. 51. Method as stated in claim 50, characterized in that R, R' and the value of x are such that the organo-magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; the transition metal compound represented by formula Tm'Y X is NiCl~ , NiCl -6H„0, c n z-n 2 2 2F eCl3 , FeCl3' 6H2 0, CrCl3 , CrCl2 , CrCl3' 6H2 0, MoCl5 , WClg, ZrCl^ , Zr(0-iC3 H7 )^ , V0C13 or mixture thereof in any combination; the halide source is represented by the formula TiCl^ ; component (C) is TiCl4 ; in the formula for the reducing agent, each R<3> is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, each X is chlorine, m has a value of zero or 1; the atomic ratio Mg:Ti is from approx. 0.2:1 to approx. 1:1, and the reducing agent is used in such an amount that a R<3>:Ti ratio of from approx. 1:1 to approx. 3:1. 52. Method as stated in claim 51, characterized in that the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to approx. 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination. 53. Method as stated in claim 52, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl- 4-methylphenol or mixture thereof in any combination. 54. Method as stated in claim 53, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or a mixture thereof in any combination. 55. Method as stated in claim 49, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 56. Method as stated in claim 55, characterized in that component (A-2) is ammonia or an amine. 57. Process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions where the polymerization is carried out in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas A1(R3)j_ —a X a , B(R3)3_ —a X a,M gR<3>2/M gR<3> X, ZnR <3>2 where each R <3> is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, and X is halogen; characterized by using, as the transition metal-containing catalyst, the hydrocarbon-insoluble catalyst prepared by a method comprising: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR„-xMeR', where each R independently is a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to approx. 10 and x * have a value equal to the valence of Me; with (2) a transition-metal-free oxygen-containing compound, a transition-metal-free nitrogen-containing compound or mixture of such compounds in an amount sufficient to lower the amount of hydrocarbyl groups present in component (A-I) such that the resulting product does not substantially reduce TiCl^ at a temperature of 25°C; one or more transition metal compounds represented by formula Tm'Yn Xz _n where Tm' is a transition metal selected from groups I-B, IV-B, V-B, VI-B, VII-B or VIII of the periodic table and is not the same element such as that represented by Tm in component (C); Y is oxygen, OR" or NR'^; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein the transition metal compound is present in such an amount that the atomic ratio Tm':Tm, from component (C), is from 0.01:1 to about. 0.5:1; (B) a suitable reducing halogen source represented by the formulas Al (R 3 )' X where each X is unsubstituted j -' Sl a pendant a halogen atom; R<3> independently is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and a has a value of from 1 to less than 3; the halide being used in such an amount that the ratio R<3>:Tm is from approx. 1:1 to approx. 50:1, and to provide a sufficient amount of halogen atoms to convert substantially all of the groups attached to a magnesium atom in component (A) to a halide group; and (C) a transition metal compound represented by formula TmY n X z-n where Tm is a metal selected from groups IV-B, V-B and VI-B of the periodic table; Y is oxygen, OR" or NR'^ ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 where z-n is from 1 and up to a value equal to the valence of the transition metal in such an amount that an atomic ratio Mg:Tm of from approx. 0.05:1 to approx. 50:1; and (II) recovering and washing, with fresh, inert diluent, the resulting solid, hydrocarbon-insoluble catalyst. 58. Method as stated in claim 57, characterized in that in component (A-I) each group R and R<1> is independently an aliphatic hydrocarbon having from 1 to approx. 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixtures thereof in any combination; in component (A-2), Tm <1> is equal to Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to about 10 carbon atoms; X is chlorine or bromine, and the atomic ratio Tm <1> :Tm is from about 0.02:1 to about 0.2:1; in component (C) Y is equal to OR", the atomic ratio Mg:Tm is from approx. 0.1:1 to approx. 5:1; and the reducing halide is present in an amount such that a ratio ,R <3> .:Tm of from approx. 1:1 to approx. 10:1. 59. Method as stated in claim 58, characterized in that R and R' and the value of x are such that the organo-magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, and carboxylic acids or mixture thereof in any combination; said transition metal compound represented by the formula Tm'Y X _ is NiCl„, NiCl„•6H-0, c n z-n 2' 2 2' FeCl3 , FeCl3» 6H20 , CrCl3 , CrCl2 , CrCl3' 6H2 0, MoCl5 , WClg, ZrCl4 , Zr(0-iC3 H7 )4 , VOCl3 or mixture thereof in any combination; in the formula for component (C), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms and n has a value of from zero to 2; the atomic ratio Mg:Ti is from about .0.2:1 to about 1:1, and the reducing halide is used in such an amount as to provide an R<3> :Ti ratio of from about 1:1 to about 3:1. 60. Method as stated in claim 59, characterized in that the value of x and each R and R <1> is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to approx. 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination. 61. Method as stated in claim 60, characterized in that the alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl- 4-methylphenol, or mixture thereof in any combination. 62. Method as stated in claim 61, characterized in that the alcohol is selected from methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or a mixture thereof in any combination. 63. Method as stated in claim 57, characterized in that component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination. 64. Method as stated in claim 63, characterized in that component (A-2) is ammonia or an amine. 65. Method as specified in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 , 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 , 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63 or 64, characterized in that ethylene or a mixture of ethylene and one or more a- olefins having from 3 to approx. 10 carbon atoms are polymerized under slurry polymerization conditions. 66. Method as set forth in claim 65, characterized in that a Jolanding of ethylene and one or more of butene-1, hexene-1 or octene-1 is polymerized. 67. Method as specified in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 , 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 , 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63. or 64, characterized in that ethylene or a mixture of ethylene and one or more a -olefins having from 3 to about 10 carbon atoms are polymerized under solution polymerization conditions. 68. Method as stated in claim 67, characterized in that a mixture of ethylene and one or more of butene-1, hexene-1 or octene-1 is polymerised.