GB2101610A - Catalyst composition, production and use - Google Patents

Abstract

A composition containing a transition metal is obtained by reacting a solid particulate material with an organic magnesium compound, treating the supported magnesium composition with oxygen, carbon dioxide or a hydroxyl compound, reacting the treated product with a carbonyl compound and simultaneously or subsequently reacting with a transition metal compound. The solid particulate material is typically alumina or silica. The magnesium hydrocarbon compound is typically a dialkyl magnesium compound. The hydroxyl compound may be water or an alcohol, preferably an alkyl alcohol such as ethanol. The carbonyl compound is a carboxylic acid, a carboxylic acid halide or an ester, for example benzoyl chloride or ethyl benzoate. The transition metal compound is typically titanium tetrachloride. The composition obtained may be used, together with an organic metal compound, to give a polymerisation catalyst typically for the polymerisation of ethylene or propylene.

Description

SPECIFICATION Catalyst composition, production and use The present invention relates to a process for the production of a composition containing a transistion metal compound, a polymerisation catalyst including this composition and a polymerisation process using such catalysts.

Compositions containing transition metal compounds are extensively described as components of polymerisation catalysts for the polymerisation of ethylenically unsaturated monomers particularly the olefine monomers such as ethylene and propylene. Recently there have been many proposals in which the transition metal compound is supported on a suitable support material. Support materials which have been proposed include magnesium halides and whilst catalyst systems based on compositions supported on magnesium chloride have been found to have good polymerisation activity, the catalyst contains a high proportion of chlorine and hence the polymer obtained may contain undesirable levels of chlorine. In European Patent application publication no. 1 4523 there is described a catalyst system which is supported on a metal oxide.However, in the production of this catalyst system there is a treatment with a halogen-containing material and hence, although this catalyst system has a reduced halogen content, it is desirable to reduce the level of halogen still further.

According to the present invention there is provided a process for the production of a transition metal composition which process comprises treating at least one substantially inert solid particulate material with at least one organic compound of the formula A in the attached formulae drawings, treating the supported magnesium composition with at least one reagent selected from carbon dioxide, oxygen and a hydroxyl compound of formula B in the attached formulae drawings, reacting the treated product with at least one carbonyl compound of the formula C in the attached formulae drawings and simultaneously or subsequently reacting with at least one compound of a transition metal of Group VA, VA or VIA of the Periodic Table, wherein R1 is a hydrocarbon radical; R2 is hydrogen or a hydrocarbon radical; R3 is a hydrocarbon radical;; X is a halogen atom or a hydrocarbon radical; Y is a halogen atom, a hydroxyl group or a group OR4; and R4 is a hydrocarbon radical.

The formulae A to E in the attached formulae drawings represent compounds which may be used in accordance with various aspects of the present invention.

All references herein to the Periodic Table are to the Short Periodic Table as set out inside the back cover of "General and Inorganic Chemistry" by J R Partington, Second Edition, published by MacMillan and Company Limited, London, in 1954.

For convenience, the expression "solid particulate material" will be used hereafter to mean a "substantially inert solid particulate material". The term "transition metal' will be used to mean a transition metal of Group IVA, VA or VIA of the Periodic Table.

The process of the present invention is effected by adding the reactants in sequence to the at least one solid particulate material or the product of a previous stage. Whilst it is possible to add the at least one compound of a transition metal at the same time as the at least one carbonyl compound, it is preferred that the at least one carbonyl compound is added first and the at least one compound of a transition metal is added subsequently, preferably in a separate stage.

The at least one solid particulate material is preferably one having reactive sites. By "reactive sites" are meant those sites which are capable of abstracting a magnesium hydrocarbon compound from a solution thereof. The number of such reactive sites can be determined by adding, to a known weight of the at least one solid particulate material, a solution containing an excess quantity of a magnesium dihydrocarbyl compound, stirring the mixture at ambient temperature for an hour and anaiysing the supernatant liquid to determine the quantity of the magnesium dihydrocarbyl compound which remains in the solution.From these determinations it is possible to calculate the number of moles of the magnesium dihydrocarbyl compound which have been abstracted from the solution for each gramme of the substantially inert solid particulate material, this being equivalent to the proportion, in moles, of the reactive sites.

The at least one solid particulate material may be any such material which has been proposed previously for use in a polymerisation catalyst system, particularly an olefine polymerisation catalyst system. Thus, the at least one solid particulate material may be an organic or inorganic compound of a metal, which term is used herein to include silicon, and may be a metal halide but is preferably a metal oxide or a mixture or reaction product of two or more metal oxides.

Preferably the at least one solid particulate material is an oxide of a metal of Groups I to IV of the Periodic Table. Solid oxides which may be used include those with a substantially inert matrix material wherein at least some of the reactive sites are present in a hydroxylic surface which is free from adsorbed water. By "hydroxylic surface" is meant a surface having a plurality of -OH groups attached to the surface, the hydrogen atom of the -OH group being capable of acting as a proton source, that is, having an acidic function. A matrix material having a hydroxylic surface is typically substantially inert in that the bulk of the matrix material is chemically inert.

Preferred metal oxides which may be used as the at least one solid particulate material include silica, alumina, magnesia, and mixtures of two or more of these compounds, for example, magnesium trisilicate which may be regarded as a mixture of hydrated magnesium oxide and silicon oxide.

Alternatively, materials based on the foregoing and containing minor amounts, for example not more than 10% by weight, of other suitable solid particulate materials, for example, zinc oxide, may be used.

Particularly useful solid particulate materials are the metal oxides, silica and alumina.

The at least one solid particulate material preferably has a surface area of at least 30 m2/g, particularly at least 100 m2/g and especially at least 200 m2/g. Useful forms of the at least one solid particulate material may be obtained by heating a metal oxide or hydroxide in an inert atmosphere, and/or at a reduced pressure, to a temperature of at least 2000C and not more than 1 200 C and preferably in the range 300 to 1 0000 C. A suitable inert atmosphere for the heating is nitrogen and a suitable reduced pressure is less than 10 mm of mercury. The temperature used will be dependent on the material being heated.Thus, if silica is being heated, it is especially preferred to use a temperature in the range 320 up to 4000C, for example 3500C. Using hydrated alumina, for example Boehmite (which may be regarded as hydrated gamma-alumina), or aluminium hydroxide, it is especially preferred to use a temperature in the range 400 up to 1 0000C, for example 5000C. Alternatively, the at least one solid particulate material may be heated in a high boiling point inert hydrocarbon, or halohydrocarbon, liquid, for example under azeotropic conditions. Heating in the presence of an inert liquid medium is typically effected at a temperature in the range 1 00 C up to 2000C using a liquid having a boiling point in this range.

In the at least one organic magnesium compound of formula A, the group R1 is typically an alkyl group, conveniently an alkyl group containing from 1 up to 20 carbon atoms and especially from 1 up to 6 carbon atoms. The group X may be a halogen atom such as chlorine or bromine but it is particularly preferred that X is a hydrocarbon radical, typically an alkyl group, as specified for the group R'. It is especially preferred that X is the same as R1. Thus, the at least one organic magnesium compound of formula A may be a hydrocarbon magnesium halide compound such as ethyl magnesium chloride or butyl magnesium bromide or may be a complex of such a compound together with a suitable complexing agent particularly a Lewis Base compound such as an ether.However, the at least one organic magnesium compound is preferably a dihydrocarbon magnesium compound particularly a dialkyl magnesium compound such as diethyl magnesium or dibutyl magnesium.

The at least one organic magnesium compound may be used as a mixture or complex with another metal compound particularly an aluminium compound. The aluminium compound which is mixed or complexed with the at least one organic magnesium compound may be an aluminium halide, for example aluminium chloride, or may be an organic aluminium compound such as a hydrocarbon aluminium halide compound and is preferably a trihydrocarbon aluminium compound such as triethyl aluminium ortributyl aluminium.

The at least one organic magnesium compound, or its mixture or complex with another metal compound, is conveniently added to the at least one solid particulate material as a liquid medium. The reaction is conveniently effected by suspending the at least one solid particulate material in a suitable inert liquid such as, for example, an aliphatic hydrocarbon liquid and adding to this suspension a solution of the at least one organic magnesium compound. The liquid medium in which the at least one solid particulate material is suspended, and the liquid in which the at least one organic magnesium compound is dissolved, are conveniently the same and are preferably selected from inert liquids such as hydrocarbon liquids, for example, hexane, heptane, octane, decane, dodecane or mixtures of the isomers thereof, or inert halohydrocarbons such as chlorobenzene.

The quantity of the at least one organic magnesium compound which is reacted with the at least one solid particulate material is dependent on the nature of the at least one solid particulate material, the surface area thereof and, in particular, any heat treatment used in obtaining the at least one solid particulate material. The quantity of the at least one organic magnesium compound which is added to the at least one solid particulate material may be at least equal to that required to saturate the surface of the at least one solid particulate material, that is at least equal to one mole for each mole of the reactive sites present on the at least one solid particulate material.In general, it is desired that there is reaction between the at least one organic magnesium compound and all of the reactive sites present and hence it is preferred to use the at least one organic magnesium compound in at least an excess relative to the number of reactive sites present on the solid particulate material and, in general, it is sufficient to use up to 10 moles of the at least one organic magnesium compound for each mole of reactive sites present on the at least one solid particulate material. However, it should be appreciated that the present invention does not exclude the use of smaller quantities of the at least one organic magnesium compound, for example as little as 0.2 moles for each mole of reactive sites on the at least one solid particulate material. The at least one organic magnesium compound can be added to the at least one solid particulate material at any suitable temperature, for example, from 0 up to 1 000C, and is conveniently added at ambient temperature, that is from about 1 50C up to about 300C.

After adding the at least one organic magnesium compound to the at least one solid particulate material, reaction is conveneintly effected by allowing the materials to remain in contact for at least 5 minutes and not more than 20 hours, for example, 0.25 up to 6 hours.

After the desired period of contacting, the solid material which is the reaction product may be separated from the liquid medium, for example, by filtration, decantation or evaporation, and then may be washed one or more times in order to remove any excess of the at least one organic magnesium compound. If desired, the solid material which is the reaction product may be subjected finally to an optional low pressure (about 1 mm of mercury) treatment at ambient temperature or higher, for a time of up to several hours, for example, for 2 hours, before being used in the next stage of the process.

However, the separation and washing stages are not essential, particularly if the at least one organic magnesium compound is used in an amount of less than one mole for each mole of reactive sites present in the at least one solid particulate material.

The supported magnesium composition which is obtained by the procedure previously described is then treated with at least one of carbon dioxide, oxygen or a hydroxyl compound of the formula B in the attached formulae drawings. If a hydroxyl compound is being used it is preferred to use one in which the group R2 is a hydrocarbon radical, particularly an alkyl group. Thus, it is preferred to treat the supported magnesium composition with oxygen and/or with an alcohol such as ethanol or butanol.

The treatment of the supported magnesium composition may be effected using the supported magnesium compound in the absence of any liquid medium and passing through the solid a gaseous medium which contains at least one of carbon dioxide, oxygen and/or the hydroxyl compound. If this procedure is used, it is preferred that the carbon dioxide, oxygen and/or hydroxyl compound is used as a dilute mixture with a suitable inert gas such as nitrogen. Alternatively, the treatment with the carbon dioxide, oxygen and/or hydroxyl compound may be effected by suspending the supported magnesium composition in a suitable inert liquid medium such as, for example, a hydrocarbon solvent and thereafter introducing into this suspension the carbon dioxide, oxygen and/or hydroxyl compound.Using carbon dioxide and/or oxygen as the material for treating the supported magnesium compositibn, the treatment is conveniently effected by passing a gaseous medium which contains carbon dioxide and/or oxygen either through the solid or a suspension of the solid. Using a hydroxyl compound, this is conveniently used by adding the hydroxyl compound to a suspension of the solid in a suitable liquid medium.

The treatment with carbon dioxide, oxygen and/or the hydroxyl compound may be effected at a temperature in the range from 0 up to 1 000C and is conveniently effected at ambient temperature.

The quantity of carbon dioxide, oxygen and/or the hydroxyl compound which is used is preferably at least equivalent, on a molar basis, to the amount of magnesium which has been taken up to give the supported magnesium composition. It is preferred to avoid the use of a large excess of the hydroxyl compound and, in general, it is sufficient to use the hydroxyl compound in the amount of at least one mole and not more than 5 moles for each mole of magnesium which is present in the supported magnesium composition.

The treatment of the supported magnesium composition with carbon dioxide, oxygen and/or the hydroxyl compound is conveniently effected for a time of from one minute up to 10 hours preferably from 1 5 minutes up to 5 hours.

After the treatment with carbon dioxide, oxygen and/or the hydroxy compound, the treated product is conveniently separated from the reaction medium and washed several times. However, whilst such separation and washing is desirable when using the hydroxyl compound, it may not be necessary when using carbon dioxide and/or oxygen for the treatment.

The treated product is then reacted with at least one carbonyl compound of formula C in the attached formulae drawings. It is preferred that the at least one carbonyl compound is one in which the hydrocarbon radical R3 contains an aromatic group, in particular, a phenyl, or a substituted phenyl, group. The group Y is preferably either a halogen atom such as chlorine or a group OR4. If Y is a group OR4, it is preferred that R4 is an alkyl group, particularly one containing from 1 up to 6 carbon atoms.

Conveniently the at least one carbonyl compound is benzoyl chloride or ethyl benzoate.

The at least one carbonyl compound is conveniently added to a suspension of the treated product.

The addition may be effected by adding at least one undiluted carbonyl compound to the suspension of the treated product in a suitable inert liquid medium. However, if desired, the at least one carbonyl compound may be added as a solution in a suitable solvent.

The reaction with the at least one carbonyl compound can be effected at a temperature in the range from 0 up to 1 000C, conveniently at ambient temperature or above.

The reaction with the at least one carbonyl compound is conveniently effected for a time of from 5 minutes up to 20 hours, preferably from 1 up to 5 hours. It will be appreciated that the reaction time will be dependent on the reaction temperature and generally shorter reaction times will be used at higher tempertures.

The quantity of the at least one carbonyl compound is dependent on the nature of the particular carbonyl compound used. Depending on the particular magnesium compound used and the proportion of the magnesium compound which is present in the treated product from the previous stage, the proportion of the at least one carbonyl compound used may be as little as 0.2 moles of the carbonyl compound for each mole of magnesium which is present in the treated product. If the at least one carbonyl compound is an ester, it is preferred to use up to one mole of the ester for each mole of magnesium which is present in the treated product. If the at least one carbon compound is an acid chloride, the quantity thereof is typically at least one mole, but not more than five moles for each mole of magnesium present in the treated product.

After the reaction with the at least one carbonyl compound, the reaction product may be separated from the reaction medium and washed several times although this separation and washing is not necessary.

The at least one compound of a transition metal which is reacted with the solid material is conveniently a compound of the formula D in the attached formulae drawings wherein M is a transition metal of Group IVA, VA or VIA of the Periodic Table; R5 is a hydrocarbon radical, a substituted hydrocarbon radical or a group OR6; R6 is a hydrocarbon radical or a substituted hydrocarbon radical; Z is a halogen atom; ais0,1 or2; b isO or a number up to the valency of M; n isO or a number up to the valency of M; and 2a+b+n is equal to the valency of M, with the proviso that the value of 2a is less than the valency of M.

The at least one compound of a transition metal of formula D can be a metal halide, a metal oxyhalide, a metal hydrocarbon compound or a metal hydrocarboxyl compound and may include a mixture of substituents attached to the metal atom. The metal M may be selected from a wide range of transition metals particularly those which have been used in polymerisation catalysts. Thus, the metal M may be vanadium, zirconium, hafnium, chromium and is preferably titanium. If the at least one compound of a transition metal is a metal halide or oxyhalide, suitable compounds include vanadium tetrachloride, zirconium tetrachloride, vanadium oxytrichloride, and particularly the titanium halides such as titanium trichloride and especially titanium tetrachloride.Metal hydrocarboxyl compounds include metal alkoxy compounds and metal alkoxy halide compounds such as tetrakis(ethoxy)titanium, tetrakis(n-butoxy)titanium, bis(isopropoxy)titanium dichloride and bis(n-butoxy) titanium dichloride.

Transition metal hydrocarbon compounds include a wide range of compounds and suitable compounds of this type are disclosed, in association with a support material, in British Patent specifications 1 314 828 and 1 51 3 673 and include materials such as zirconium tetrabenzyl, titanium tetrabenzyl, and zirconium tetraneonhvl.

The at least one compound of a transition metal may be added with the at least one carbonyl compound or may be added subsequently to the at least one carbonyl compound, preferably in a stage which is distinct from the stage in which treatment is effected with the at least one carbonyl compound. Treatment with the at least one compound of a transition metal may be effected by adding a solution of the at least one compound of a transition metal to a solid material which is the product obtained from the previous stages.However, since some of the compounds of a transition metal which can be used in accordance with the present invention are liquids under normal conditions, for example titanium tetrachloride, the treatment with the at least one compound of a transition metal may be effected by suspending the solid material in an undiluted liquid compound of a transition metal. It will be appreciated that if the solid is suspended in an undiluted liquid compound of a transition metal, the amount of such a compound of a transition metal will be substantially greater than one mole for each mole of the magnesium compound which is present in the solid material.As an alternative to using an undiluted liquid compound of a transition metal, it is possible to use a solution of the at least one compound of a transition metal in an appropriate liquid medium such as, for example, an aliphatic hydrocarbon solvent. If a solution of at least one compound of a transition metal is used, it is then possible to use an amount of the at least one compound of a transition metal which is less than one mole for each gramme atom of the magnesium compound present in the solid. Thus, using a solution of a transition metal compound, the amount thereof may be as little as 0.1 moles for each gramme atom of magnesium which is present in the solid material.However, it is preferred to use the at least one compound of a transition metal in an amount which is equivalent to at least one mole of the at least one compound of a transition metal for each gramme atom of magnesium which is in the solid.

The reaction of the at least one compound of a transition metal with the solid material may be carried out at a temperature which is conveniently in the range of from OOC up to the boiling temperature of the liquid reaction medium. Thus, if the reaction is carried out in an undiluted liquid compound of a transition metal, the temperature may be up to the boiling temperature of the liquid compound of a transition metal for example up to 1 C when titanium tetrachloride is used. It is generally preferred to effect the reaction with an undiluted liquid compound of a transition metal at an elevated temperature which is at least 6O0C and may be as high as 1 500C. However, since some of the compounds of a transition metal which may be used in the process of the present invention have a reduced stability at an elevated temperature, it is preferred that these compounds are used at temperatures at which they do not show an appreciably reduced stability, and this may require the use of a temperature of 00C or even lower. If the reaction is effected at an elevated temperature the at least one compound of a transition metal may be added to the solid material at ambient temperature and the mixture then heated up to the desired elevated temperature.

The reaction between the at least one compound of a transition metal and the solid material is effected by allowing the materials to remain in contact for a period of time which is from 5 minutes up to 10 hours, preferably from 1 up to 5 hours. However, it will be appreciated that the time of contacting will be dependent on the temperature used and if a low reaction temperature is used a longer reaction time may be desirable.

After the requisite period of contacting, the product obtained may be separated from the liquid reaction medium and washed several times with a suitable inert liquid medium. This separation and washing is particularly desirable if the reaction is effected using an undiluted liquid transition compound. However, if a small proportion of the at least one compound of a transition metal has been used, then the separation and washing may not be necessary.

If the reaction with the at least one compound of a transition metal is effected simultaneously with the reaction with the at least one carbonyl compound, the reaction conditions for such a simultaneous reaction are those which are described herein for the treatment with the at least one compound of a transition metal.

In a preferred process according to the present invention the solid material is alumina or more preferably silica, the magnesium hydrocarbon compound is a dialkyl magnesium compound, the supported magnesium composition is treated with oxygen and/or an alkyl alcohol and the product is then treated in sequence with an ester or chloride of an aromatic carboxylic acid and then with titanium tetrahloride.

At the end of each stage, including the last stage, of the process of the present invention, the solid material obtained may be separated and washed but it should be appreciated that it may not be necessary to effect separation and washing at all stages of the process depending on the nature and quantities of the materials which are used in any particular stage.

The product obtained by the process of the present invention contains at least one magnesium material and one or more transition metal compounds, preferably at least a titanium halide compound, supported on at least one solid particulate material, preferably at least one solid inorganic oxide. This product may be used as one component of a polymerisation catalyst system.

Thus, as a further aspect of the present invention, there is provided a polymerisation catalyst system which comprises I a reaction product obtained by the process of the present invention; and II an organic compound of the metal of Group IIA of the Periodic Table or of aluminjum, or a complex of an organic compound of a metal of Group IA or Group IIA of the Periodic Table with an organic compound of aluminium.

Component II of the catalyst system can be an organic magnesium compound of the formula A in the attached formulae drawings and, if the compound is a Grignard reagent, it is preferably one which is substantially ether-free. Alternatively, component II may be a complex of an organic magnesium compound of the formula A in the attached formulae drawings, together with an aluminium compound, particularly an organic aluminium compound. If component II is a complex of a metal of Group IA with an organic aluminium compound, this compound may be of the type lithium aluminium tetralkyl.

Preferred compounds for use as component II of the catalyst system are organic aluminium compounds such as an aluminium hydrocarbyl sulphate or an aluminium hydrocarbyl hydrocarboxyl and is preferably an aluminium hydrocarbyl halide or a especially an aluminium trihydrocarbyl or a dihydrocarbyl aluminium hydride. The aluminium trihydrocarbyl is preferably an aluminium trialkyl, especially one in which the alkyl group contains from 1 to 10 carbon atoms, for example, aluminium triethyl, aluminium tributyl or aluminium trioctyl.

Using an aluminium trihydrocarbyl as component II in a catalyst system which is to be used for the polymerisation of propylene or other higher a-olefine monomer, it is preferred that the catalyst system also includes a Lewis Base compound. The Lewis Base compound, which is especially an organic Lewis Base compound, can be any such compound which has previously been proposed for use in an olefine polymerisation catalyst system.Thus, the Lewis Base compound may be an ether, an ester, a ketone, an alcohol, an orthoester, a sulphide (a thioether), an ester of a thiocarboxylic acid (a thioester), a thioketone, a thiol, a sulphone, a sulphonamide, a fused ring compound containing a heterocyclic sulphur atom, an organic silicon compound such as silane or a siloxane, an amide such as formamide, urea and substituted derivatives thereof such as tetramethyl urea, thiourea, an alkanolamine, an amine (which term includes a cyclic amine, a diamine, or a polyamine, for example, pyridine, quinoline, or tetramethylethylenediamine), or an organic phosphorus compound such as an organic phosphine, an organic phosphine oxide, an organic phosphite or an organic phosphate.The use of organic Lewis Base compounds as components of polymerisation catalyst systems is disclosed, inter alia, in British Patent Specifications 803 198,809 717, 998,896 509,920 118,921 954933 236,940 125, 966 025,969 074,971 248,1 013 363,1 017 977,1 049 723,1 122 010,1 150 850,1 208 815 1 234 657,1 1 324 173 1,359 328, 1 383 207, 1 387 890, 1 423 658, 1 423 659, 1 423 660, 1 495 031,1 527 736,1 554 574 and 1 559194.

Preferred Lewis Base compounds for use in the catalyst systems of the present invention are esters. Suitable esters are of the type which has been disclosed for the production of component I of the catalyst system. Thus, the esters may be ethyl benzoate, butyl benzoate, methyl p-methylbenzoate or ethyl p-methoxybenzoate.

In addition to, or instead of, the Lewis Base compound which may be present as a further component of the catalyst system, there may also be present in the catalyst system a substituted or unsubstituted polyene. Examples of such polyenes are the acyclic polyenes such as 3-methylheptatriene (1,4, 6), or the cyclic polyenes such as cyclooctatriene, cyclooctatetraene, or cycloheptatriene, or the alkyl- or alkoxy-substituted derivatives of such cyclic polyenes, or the tropylium salts or complexes, or tropolone ortropone.

The proportions of Components I and II of the catalyst system can be varied within a wide range as is well known to the skilled worker. The particular preferred proportions will be dependent on the type of materials used and the absolute concentrations of the components but, in general, we prefer that for each gramme atom of the transition metal which is present in Component I of the catalyst system there is present at least one mole of Component II. The number of moles of Component II for each gramme atom of the transition metal in Component I may be as high as 1000 but conveniently does not exceed 500 and, with some transition metal compositions, may be not more than 25, for example, from 5 up to 10.

When the catalyst system includes a Lewis Base compound as a further component of the catalyst system, it is preferred that this Lewis Base compound is present in an amount of not more than one mole for each mole of Component II and particularly is present in an amount of from 0.1 up to 0.5 moles of the Lewis Base compound for each mole of Component II. However, depending on the particular organic metal compound and Lewis Base compound, the proportion of the Lewis Base compound may need to be varied in order to achieve the optimum catalyst system.

If the catalyst system includes a polyene, it is preferred that the polyene is present in an amount of not more than one mole for each mole of Component II, and especially from 0.01 up to 0.20 moles for each mole of Component II. If the catalyst system includes both the Lewis Base component and the polyene, it is preferred that both of these materials are present together in an amount of not more than one mole for each mole of Component II.

Catalyst systems in accordance with the present invention are suitable for the polymerisation and copolymerisation of unsaturated monomers, particularly ethylenically unsaturated hydrocarbon monomers such as olefine monomers.

Thus, as a further aspect of the present invention, there is provided a process for the production of a polymer or copolymer of an unsaturated monomer wherein at least one ethylenically unsaturated hydrocarbon monomer is contacted under polymerisation conditions with a polymerisation catalyst as hereinbefore defined.

The monomer which may be contacted with the catalyst system is conveniently one having the formula E in the accompanying formulae drawings. in the formula E, R7 is a hydrogen atom or 3 hydrocarbon radical.

Thus, the monomer may be ethylene, propylene, butene-1, pentene-1, hexene-1 ,4-methylpentene- 1, styrene, 1 ,3-butadiene or any other monomer which satisfies the foregoing formula. The monomer is preferably an olefine monomer, particularly an aliphatic mono-olefine monomer containing not more than 10 carbon atoms.

The monomers may be homopolymerised or may be copolymerised together. If propylene is copolymerised it is preferred to effect the copolymerisation with ethylene, conveniently using a sequential copolymerisation process as is described in British Patents 970 478; 970 479 and 1 01 4 944. If ethylene is being copolymerised using the process of the present invention, it is preferred to carry out the copolymerisation using a mixture of ethylene and the desired comonomer, for example butene-1, hexene-1, or 4-methy pentene-1, wherein the mixture of monomers has essentially the same composition throughout the polymerisation process.

Component I of the catalyst may be mixed with the other component, or components, of the catalyst in the presence of the olefin monomer. If the catalyst includes a Lewis Base compound, it is preferred to premix the organic metal compound which is component II with the Lewis Base compound and then to mix this pre-mixture with the reaction product which is component I.

As is well known, Ziegler-Natta type catalysts are susceptible to the presence of impurities in the polymerisation system. Accordingly, it is desirable to effect the polymerisation using a monomer, and a diluent if this is being used, which has a high degree of purity, for example a monomer which contains less than 5 ppm by weight of water and less than 1 ppm by weight of oxygen. Materials having a high degree of purity can be obtained by processes such as those described in British Patent Specifications 1 111 493; 1,226 659 and 1 383 611.

Polymerisation can be carried out in the known manner, for example in the presence or absence of an inert diluent such as a suitably purified paraffinic hydrocarbon, in the liquid phase using an excess of the liquid monomer as the polymerisation medium or in gas phase, this latter term being used herein to mean the essential absence of a liquid medium.

If polymerisation is effected in gas phase, it may be effected by introducing the monomer, for example propylene, into the polymerisation vessel as a liquid and operating with conditions of temperature and pressure within the polymerisation vessel which is such that the liquid monomer vaporises, thereby giving an evaporative cooling effect, and essentially all of the polymerisation occurs with a gaseous monomer. Polymerisation in gas phase may be effected using conditions which are such that the monomer is at a temperature and partial pressure which are close to the dew point temperature and pressure for that monomer, for example as described in more detail in British Patent Specification 1 532 445.Polymerisation in gas phase can be effected using any technique suitable for effecting a gassolid reaction such as a fluidised-bed reactor system, a stirred-bed reactor system or a ribbon blender type of reactor.

Using the catalyst systems of the present invention, ethylene may be polymerised or copolymerised, for example with butene-1 as the comonomer, in a fluidised-bed reactor system to give a high yield of polymer. The fluidising gas is the gas mixture to be polymerised together with any hydrogen which is present as a chain transfer agent to control molecular weight. Thus, for the copolymerisation of ethylene and butene-1 to produce an ethylene copolymer having a density of less than about 940 kg/m3, the gas composition is typically from 50 to 60 mole % ethylene, 15 to 25 mole % butene-1 with the remainder, apart from inert materials and impurities, being hydrogen.

Polymerisation may be effected either in a batch manner or on a continuous basis, and the catalyst components may be introduced into the polymerisation vessel separately or all the catalyst components may be mixed together before being introduced into the polymerisation reactor. If all of the catalyst components are pre-mixed and this pre-mixing is effected in the presence of a monomer, such premixing will result in at least some polymerisation of this monomer before the catalyst system is introduced into the polymerisation vessel. If the polymerisation is being carried out in the gas phase, the catalyst components may be added to the polymerisation reactor suspended in a stream of the gaseous monomer or monomer mixture.

The polymerisation can be effected in the presence of a chain transfer agent such as hydrogen or a zinc dialkyl, in order to control the molecular weight of the product formed. If hydrogen is used as the chain transfer agent in the polymerisation of propylene, it is conveniently used in an amount of from 0.01 up to 5.0%, particularly from 0.05 up to 2.0% molar relative to the monomer. When the monomer being polymerised is ethylene, or a mixture in which ethylene is a major polymerisable component (by moles), the amount of hydrogen used may be greater, for example, in the homopolymerisation of ethylene the reaction mixture may contain in excess of 50% molar of hydrogen, whereas if ethylene is being copolymerised, a proportion of hydrogen which is typically up to 35% molar is used.The amount of chain transfer agent will be dependent on the polymerisation conditions, especially the temperature, which, at polymerisation pressure not exceeding 50 kg/cm2, is typically in the range from 200C up to 100 C, preferably from 500C up to 100 C.

Polymerisation can be effected at any pressure which has been previously proposed for effecting the polymerisation of monomers such as olefin monomers. However, although the polymerisation may be effected at pressures up to 3000 kg/cm2, at which pressures the polymerisation temperature may be as high as 3D00C, it is preferred to carry out the polymerisation at relatively low pressures and temperatures. Whilst the polymerisation may be effected at atmospheric pressure, it is preferred to use a slightly elevated pressure and thus it is preferred that the polymerisation is effected at a pressure of from 1 kg/cm2 up to 50 kg/cm2, preferably from 5 up to 30 kg/cm2.

Various aspects of the present invention will now be described with reference to the following Examples which are illustrative of the invention. In the Examples, all operations are effected under an atmosphere of nitrogen unless otherwise indicated. All the glass apparatus was dried in an air oven at 1 200C for at least one hour and purged with nitrogen before use.

(A) Treatment of silica A sample of silica having a high specific surface area (Davison 952 grade obtainable from W R Grace and Company of Maryland USA) was heated up to 3500C under a stream of nitrogen at atmospheric pressure, maintained at 3500C for four hours and then allowed to cool, in the oven, to ambient temperature.

(B) Treatment of silica The procedure of (A) was repeated using a time of five hours.

(C) Preparation of magnesium butyl chloride-butyl ether complex The preparation was carried out in a one litre, three-necked flask fitted with a tap adaptor, a stirring rod (plus air-tight seal) and a two necked adaptor holding a gas-balanced dropping funnel and water cooled condenser. Into this flask were placed magnesium turnings (13.2 g, 0.54 mol) and pure, dry, air-free heptane (375 cm3) in which was dissolved n-butyl chloride (3 cm3, 28 mmol). Into the dropping funnel was placed a solution of n-butyl chloride (52.3 cm3, 0.5 mol) dissolved in di-n-butyl ether (83.3 cm3,0.5 mol). The mixture in the flask was stirred and gently heated to reflux the mixture while a little of the n-butyl chloride solution, plus a few crystals of iodine, were added.The stirring was stopped occasionally and the mixture studied to watch for fading of the deep violet iodine colouration and the formation of bubbles. After 5 to 10 minutes the start of the reaction was signalled by the disappearance of the iodine colouration. Stirring was then resumed and sufficient heat applied to keep the mixture refluxing, while the n-butyl chloride solution was added dropwise over a period of one hour.

The reaction mixture was then stirred for a further four hours.

The solution of the magnesium n-butyl chloride-n-butyl ether complex was left to settle, and kept under nitrogen. Aliquots of the supernatant were titrated against standard acid to indicate the concentration of magnesium n-butyl chloride complex in solution.

EXAMPLE 1 A) Reaction with silica and magnesium dibutyl 12.8 grammes of the silica dried as described in treatment A) were suspended in 1 00 cm3 of a heptane fraction essentially all of which has a boiling temperature in the range 990C up to 1020C (hereafter referred to simply as the "heptane fraction"), in a 300 cm3 reaction vessel provided with a sintered glass frit and a stirrer. Sufficient of a 0.65 M solution of magnesium dibutyl (an equimolar mixture of primary and secondary dibutyl magnesium) in an isoparaffin fraction, essentially all of which had a boiling point in the range from 11 70C to 1 35 OC (hereafter referred to simply as the "isoparaffin fraction"), was added to the suspension to provide 32 millimoles of magnesium dibutyl.The mixture was then stirred at ambient temperature (about 200 C) for 1 6 hours.

B) Treatment with ethanol To the mixture from step A) were added 29 millimoles of ethanol. This mixture was stirred, heated up to 800C and stirred at this temperature for 2 hours. The mixture was then allowed to settle, the supernatant liquid was removed by filtration and the solid was washed five times using 100 cm3 of the heptane fraction 80"C for each wash.

C) Treatment with carbonyl compound The washed solid from step B) was suspended in a solution of 25.5 millimoles of benzoyl chloride in 100 cm3 of the heptane fraction. The mixture was heated up to 800 C, stirred at this temperature for two hours, allowed to cool to ambient temperature and stirred at ambient temperature for 1 6 hours. The mixture was then filtered and the solid was washed five times using 100 cm3 of the heptane fraction at ambient temperature for each wash. Residual quantities of the heptane fraction were removed by heating the vessel to 800C and passing dry nitrogen through the solid.

D) Treatment with titanium tetrachloride The washed and dried solid from step C) was suspended in 100 cm3 of titanium tetrachloride, the mixture was stirred, heated to 800C and maintained at that temperature for four hours. The mixture was filtered without cooling and the solid was then washed six times using 100 cm3 of the heptane fraction at 80 C for each wash. The solid was finally suspended in 1 DO cm3 of the heptane fraction at ambient temperature.

EXAMPLE 2 A) Reaction with silica and magnesium dibutyl 8.9 grammes of the silica dried as described in treatment A) were suspended in 100 cm3 of the heptane fraction in a 300 cm3 reaction vessel provided with a sintered glass frit and a stirrer. Sufficient of a solution of magnesium dibutyl (0.6 M but otherwise similar to that used in Example 1) was added to the suspension to provide 30 millimoles of magnesium dibutyl. The mixture was then stirred at ambient temperature (about 200 Cl for 1 6 hours. The stirring was stopped, the solid allowed to settle and the liquid was filtered off. The solid was washed five times using 1 DO cm3 of the heptane fraction at ambient temperature for each wash. The washed solid was finally suspended in 1 DO cm3 of the heptane fraction.

B) Treatment with ethanol To 85 cm3 of the mixture from step A) were added 1 3.6 millimoles of ethanol. This mixture was stirred, heated up to 800C and stirred at this temperature for one hour. The mixture was then allowed to cool and settle, the liquid was filtered off and the solid was washed once using 1 50 cm3 of the heptane fraction at ambient temperature.

C) Treatment with carbonyl compound The washed solid from step B) was suspended in a solution of 4.9 millimoles of ethyl benzoate in 100 cm3 of the heptane fraction and the mixture was stirred at ambient temperature for 1 6 hours. The mixture was then filtered and the solid was washed three times using 100 cm3 of the heptane fraction at ambient temperature for each wash.

D) Treatment with titanium tetrachloride The washed solid from step C) was suspended in 1 DO cm3 of titanium tetrachloride, the mixture was stirred, heated to 800C and maintained at that temperature for four hours. The mixture was filtered without cooling and the solid was then washed six times using 1 DO cm3 of the heptane fraction at 800C for each wash. The solid was finally suspended in 100 cm3 of the heptane fraction at ambient temperature.

EXAMPLE 3 The procedure of Example 2 was repeated with the changes noted hereafter.

In step A), the amount of silica was 11.3 grammes and the solid was washed six times.

In step B), the amount of ethanol was 87 millimoles and the temperature of 800C was maintained for three hours. The solid was washed six times using 100 cm3 of the heptane fraction for each wash and was then dried at 800C and a pressure of 0.1 mm of mercury.

In step C), the ethyl benzoate was replaced by 34.50 millimoles of benzoyl chloride, the mixture was heated to 800C and maintained at this temperature for 16 hours. The solid was washed five times and dried at 800C and a pressure of 0.1 mm of mercury.

EXAMPLE 4 The procedure of Example 2 was repeated with the changes noted hereafter.

In step A), 13.8 grammes of the silica were suspended in 100 cm3 of an aliphatic hydrocarbon fraction consisting essentially of dodecane isomers, essentially all of which has a boiling temperature in the range of 1 700C to 1 850C (hereafter referred to simply as the "aliphatic hydrocarbon") and 26 millimoles of magnesium dibutyl (as a solution of molarity 0.65 M) were used. The solid was washed three times with 1 50 cm3 of, and finally suspended in 100 cm3 of, the aliphatic hydrocarbon.

In step B), all of mixture from step A) was used, 20.4 millimoles of ethanol were added and the solid was washed with the aliphatic hydrocarbon.

In step C), a solution of 11.2 millimoles of ethyl benzoate in the aliphatic hydrocarbon was used.

The solid was washed using 1 50 cm3 of the aliphatic hydrocarbon for each wash.

In step D), the solid was washed five times using 100 cm3 of the aliphatic hydrocarbon at 800C for each wash.

EXAMPLE 5 The procedure of Example 4 was repeated with the changes noted hereafter.

in step A), 9.87 grammes of silica were suspended in the aliphatic hydrocarbon.

In step B), 1 5.3 millimoles bf ethanol were used.

In step C), 8.02 millimoles of ethyl benzoate were used.

In step D), the solid was washed with heptane but was not finally suspended in heptane.

In a further step, the damp solid from step D) was suspended in a 100 cm3 of titanium tetrachloride and the procedure of step D) of Example 2 was repeated with the exception that the solid was washed five times.

EXAMPLE 6 The procedure of Example 2 was repeated with the changes noted hereafter.

In step A), the amount of silica was 12.1 grammes and the solid was washed six times.

In step B), 90 cm3 of the mixture from step A) was used, the amount of ethanol was 172 millimoles and the temperature of 800C was maintained for 1.5 hours. The solid was washed six times with the heptane fraction at 800 C.

In step C), the ethyl benzoate was replaced by 36.2 millimoles of benzoyl chloride, the mixture was heated to 800C and maintained at this temperature for 1 6 hours. The solid was washed four times with the heptane fraction at 800 C.

EXAMPLE 7 The procedure of Example 2 was repeated with the changes noted hereafter.

Instep A), the amount of silica was 14.1 grammes and the solid was washed three times.

In step B), 95 cm3 of the mixture from step A) was used, the amount of ethanol was 102 millimoles, the mixture was initially stirred at ambient temperature for 1 6 hours, heated up to 800C and stirred at that temperature for a further one hour. The solid was washed three times using 100 cm3 of the heptane fraction for each wash.

In step C), 11.2 millimoles of ethyl benzoate were used.

EXAMPLE 8 The procedure of Example 2 was repeated with the changes noted hereafter.

In step A), the amount of silica was 12.7 grammes.

In step B), 95 cm3 of the mixture from step A) was used, the amount of ethanol was 102 millimoles, and the solid was washed five times with the heptane fraction at 800C.

In step C), the ethyl benzoate was replaced by 9.48 millimoles of benzoyl chloride, the mixture was heated to 800C and maintained at this temperature for four hours. The solid was washed twice with the heptane fraction at 80 C.

In step D), the temperature of 8O0C was maintained for three hours.

EXAMPLE 9 The procedure of Example 2 was repeated with the changes noted hereafter.

In step A). 10.3 grammes of silica were used.

In step B), all of the mixture from step A) was used, the ethanol was replaced by 53 millimoles oft butanol, the mixture was stirred, heated up to 800 C, maintained at this temperature for one hour, cooled and stirred at ambient temperature for one hour. The solid was washed five times with the heptane fraction at 800 C.

In step C), 8.36 millimoles of ethyl benzoate were used.

EXAMPLE 10 The procedure of Example 2 was repeated with the changes noted hereafter.

In step A), 10.8 grammes of silica were used and the solid was washed three times.

In step B), the ethanol was replaced by oxygen gas. The treatment was effected by passing 1 dm3 (measured at NTP) of oxygen (from a cylinder) through the suspension at ambient temperature over a period of 1.5 hours. The solid was washed three times using 100 ml of the heptane fraction at ambient temperature for each wash.

In step C), 8.7 millimoles of ethyl benzoate were used. After washing the solid, the flask was evacuated to 0.1 mm of mercury and nitrogen was introduced, this procedure being effected a total of three times.

In step D;, the temperature of 80"C was maintained for three hours.

EXAMPLE 11 A) Reaction with silica and magnesium dibutyl 125.3 9 of the silica dried as described in treatment B) were suspended in 1200 cm3 of an isoparaffin fraction in a two dm3 reaction vessel provided with a vapour jacket and a stirrer. 387.9 cm3 of a 0.646 M solution of the magnesium dibutyl in the isoparaffin fraction were added to the suspension. The mixture was then stirred at ambient temperature for four hours. The stirring was stopped and the solid was allowed to settle. The supernatant liquid was then siphoned off, the solid was washed four times using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash and the washed solid was suspended in 1 200 cm3 of the isoparaffin fraction at ambient temperature.

B) Treatment with ethanol To the mixture from step A) were added 13.2 cm3 (225.5 millimoles) of ethanol. This mixture was stirred at ambient temperature for one hour then heated up to 800C and stirred at this temperature for a further hour. The mixture was then allowed to settle, the supernatant liquid was removed and the solid was washed three times using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash. The solid was finally suspended in 1 200 cm3 of the isoparaffin fraction at ambient temperature.

C) Treatment with ethyl benzoate To the mixture from step B) was added 1 4.4 cm3 of ethyl benzoate and the mixture was allowed to stand overnight (about 1 6 hours). The mixture was stirred at ambient temperature for two hours, the supernatant liquid was then removed and the solid was washed three times using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash. After the second and the final wash, most of the liquid was removed by forcing it through a glass tube at the lower end of which was located a sintered glass frit.

D) Treatment with titanium tetrachloride The washed solid from step C) was suspended in 1 253 cm3 of titanium tetrachloride, the mixture was heated to 800C and maintained at that temperature for four hours. The supernatant liquid was removed without cooling and the solid was then washed three times using 1 500 cm3 of the isoparaffin fraction at 800C for each wash, then four times using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash. After the penultimate wash, most of the liquid was removed by forcing it through a glass tube at the lower end of which was located a sintered glass frit. The solid was finally suspended in 1300 cm3 of the isoparaffin fraction at ambient temperature.

About 1 50 cm3 of the suspension obtained was transferred to a nitrogen purged flask and this material will hereafter be identified as 11 S. The remainder of the suspension was filtered and dried by healing at 60oC and a pressure of 0.1 mm of mercury for four hours and this material will hereafter be identified as 11 D.

EXAMPLE 12 A) Reaction with silica and butyl magnesium chloride complex 27.3 g of the silica dried as described in treatment B) were suspended in 500 cm3 of the isoparaffin fraction in a two dm3 reaction vessel provided with a vapour jacket and a stirrer. 88.1 cm3 of a 0.62 M solution of the n-butyl magnesium chloride/di-n-butyl ethyl complex obtained by the procedure of preparation C) were added to the suspension. The mixture was then stirred at ambient temperature for two hours. The stirring was stopped and the solid was allowed to settle. The supernatant liquid was then removed, the solid was washed twice using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash and the washed solid was suspended in 500 cm3 of the isoparaffin fraction at ambient temperature.

B) Treatment with ethanol To the mixture from step A) were added 3.2 cm3 of ethanol. This mixture was stirred, heated up to 800C and stirred at this temperature for a further 1.5 hours. The mixture was then allowed to settle, the supernatant liquid was removed and the solid was washed twice using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash. The solid was then suspended in 500 cm3 of the isoparaffin fraction at ambient temperature.

C) Treatment with benzoyl chloride To the mixture from step B) were added 6.4 cm3 of benzoyl chloride. The mixture was stirred, heated to 800C and maintained at this temperature for two hours. The mixture was allowed to cool and settle and the supernatant liquid was then removed. The solid was washed three times using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash.

D) Treatment with titanium tetrachloride The washed solid from step C) was suspended in 500 cm3 of titanium tetrachloride, the mixture was heated to 800C and maintained at that temperature for three hours. The supernatant liquid was removed without cooling and the solid was then washed five times using 1 500 cm3 of the isoparaffin fraction at 8D0C for each wash, then twice using 1 500 cm3 of the isoparaffin fraction at ambient temperature. The solid was finally suspended in 500 cm3 of the isoparaffin fraction at ambient temperature.

EXAMPLE 13 The procedure of Example 12 was repeated with the changes noted hereafter.

In step A), 38.1 g of silica and 112.1 cm3 of a 0.68 M solution of the n-butyl magnesium chloride complex were used.

In step B), 10.7 cm3 of a solution of ethanol in the heptane fraction (8.23 g of ethanol in 25 cm3 of the heptane fraction) were used.

In step C), 8.8 cm3 of benzoyl chloride were used and the temperature of 8O0C was maintained for three hours. The solid was washed twice and finally suspended in 500 cm3 of the isoparaffin fraction.

In step D), 4.2 cm of titanium tetrachloride were added to the suspension from step C), to give a solution of titanium tetrachloride. The mixture was heated to 80 C and maintained at 800C for two hours. After removing the supernatant liquid, one dm3 of the isoparaffin fraction was added and 500 cm3 of the suspension formed was removed. The retained mixture was allowed to settle, the supernatant liquid was removed and the solid was washed three times using 1 500 cm3 of the isoparaffin fraction at ambient temperature for each wash. The solid was finally suspended in 500 cm3 of the isoparaffin fraction at ambient temperature.

EXAMPLE 14 The procedure of Example 11 was repeated with the changes noted hereafter.

In step A), 86.9 grammes of silica, 800 cm3 of the isoparaffin fraction and 360 cm3 of a 0.59 M solution of magnesium dibutyl were used. The solid was washed twice and the washed solid was suspended in 800 cm3 of the isoparaffin fraction.

In step B), 80 cm3 of ethanol were used and the mixture was heated at 800C for 1.5 hours. The solid was washed twice and the washed solid was suspended in 800 cm3 of the isoparaffin fraction.

In step C), 33.6 cm3 of benzoyl chloride were used instead of the ethyl benzoate. The mixture was heated directly up to 800C and maintained at this temperature for three hours. The solid was washed four times. The step of removing the liquid by forcing through the tube having the sintered glass frit was omitted.

In step D), 800 cm3 of titanium tetrachloride were used. The solid was washed five times using 1800 cm3 of the isoparaffin fraction at 800C for each wash and then five times using 1 800 cm3 of the isoparaffin fraction at ambient temperature for each wash. After the last washing step the whole of the mixture was filtered and dried at a pressure of 0.1 mm of mercury and 58 to 600C for four hours.

EXAMPLES 15 TO 33 1.5 dm3 of the aliphatic hydrocarbon were added to a five dm3 stainless steel autoclave and were purged with nitrogen and evacuated at 60 C, this procedure being repeated three times and the autoclave was then evacuated to a pressure of 0.1 mm of mercury whilst stirring vigorously. Stirring was continued and propylene was introduced to raise the pressure to one atmosphere.

A solution, in the aliphatic hydrocarbon, containing 1 6 millimoles of triethyl aluminium was added followed by a solution, in the aliphatic hydrocarbon, containing ethyl p-methoxybenzoate. Then a quantity of a suspension of the product of one of Examples 1 to 9 was added and propylene was added to the autoclave until a pressure of 7 kg/cm2 gauge was achieved. Polymerisation was continued at 600C for two hours at 7 kg/cm2 and was then terminated by venting off the excess propylene and exposing the contents of the autoclave to air. An aliquot portion of the diluent was taken and the proportion of polymer dissolved in this aliquot was determined by evaporation to dryness. Further details of the polymerisation conditions, and the results obtained, are given in Table One.

TABLE I

Ti Compn Diluent Amount Ester Soluble Ex. Type (cm3) Amount H2 Yield Polymer (a) (b) (c) (mM) (d) (e) i (f) 15 1 2.5 4 A 301.2 4.0 16 2 5.0 3 A 550.5 16.1 17 3 5.0 3 A 205.1 5.0 18 3 5.0 4 A 133.5 2.0 19 3 5.0 4 P 110.1 4.3 20 4 5.0 3 A 483.7 13.1 21 4 2.5 4 A 223.0 8.3 22 4 2.5 4 P 258.0 6.6 23 5 5.0 3 A 463.3 18.9 24 5 5.0 4 A 317.1 14.7 25 1 5 2.5 3 A 270.0 N.D.

26 7 5.0 4 P 382.2 9.6 27 7 5.0 5 P 239.3 7.0 28 8 5.0 3 A 371.6 17.9 29 8 5.0 4 A 226.9 11.9 30 8 5.0 4 P 314.5 13.3 31 9 5.0 3 A 150.0 14.6 32 9 5.0 4 A 137.6 11.9 33 9 5.0 4 P 133.6 15.2 Notes to Table One (a) * in this example, 1 5 millimoles of triethyl aluminium were used.

(b) The number indicates the Example in which the preparation of the titanium composition is described.

(c) This column gives the number of cm3 of the suspension of the titanium composition which were added.

(d) In some Examples, hydrogen was added to the polymerisation system. The hydrogen was introduced into a gas burette of 1 50 cm3 capacity to give a pressure of 24.6 kg/cm2 gauge. The hydrogen was added to the autoclave containing propylene at atmospheric pressure, the quantity of hydrogen added being sufficient to produce a pressure drop of 1.8 kg/cm2 in the gas burette.

P means hydrogen was present.

A means hydrogen was absent.

(e) Yield is given in grammes of total polymer (solid + soluble) formed.

(f) Given by the relationship (Wt of diluent soluble polymer) x 100 (Wt of total polymer) N.D. means not determined.

EXAMPLES 34 TO 42 Into a stirred stainless steel autoclave of 30 dm3 capacity were introduced, under hydrogen at a pressure of 4.2 kg/cm2gauge, 13 cm3ofa mixture of hexane and butene-1.The mixture also contained 50 millimoles of an aluminium trialkyl compound and 50 ppm by weight of an antistatic agent of the formula C6F13O(CH3CH3O)8CflH(3fl+1) where n has a value of from 1 6 to 18.

The contents of the reactor were stirred and heated up to 8D0C and then the reactor was vented to reduce the total pressure to 2.54 kg/cm2 gauge. Ethylene was added to give a total pressure of 5.6 kg/cm2 gauge. A titanium-containing composition obtained as described in one of Examples 3, 4, 6 and 8 to 13 was then added in a quantity to attain, and subsequently to maintain, a monitored ethylene consumption of between 1.0 and 1.5 kg per hour. Ethylene was added at a rate sufficient to maintain the pressure of 5.6 kg/cm2 gauge. During the reaction, unless otherwise indicated, a 0.5 M solution of the aluminium trialkyl compound in the polymerisation diluent was added continuously at a rate of 50 millimoles per hour.

The polymerisation was terminated, and the polymer product consequently recovered, by transferring to a vessel of 200 dm3 capacity containing 50 dm3 of a 0.01 M aqueous solution of sodium hydroxide and then passing steam through the stirred mixture until all of the hexane had been evaporated. The aqueous polymer suspension was then filtered and the polymer was dried in a fluid bed drier using hot nitrogen as the fluidising gas.

Further details of the polymerisations, including the nature of the titanium-containing component and the results obtained, are set out in Table Two.

TABLE 2

Ti Compn.

Polymer Polyn Ex. Amount B-1 Polymer Density Ethylene Time S No. Type (mM) (cm ) Al alkyl MFI (Kg/m ) added (hrs) Ex (h) (b) (i) (j) (k) (l) (m) (Kg) (n) (o) 34 4 5.91 1000 TEA 2.94 917.2 0.74 1.55 1.31 35 4 0.574 1100 TOA 1.24 920.4 1.89 1.55 1.35 36 6 1.13 1000 TEA 1.59 923.0 1.46 1.52 1.22 37 8 2.27 1000 TEA 3.97 926.4 2.57 2.28 1.31 38 9 11.0 1000 TEA 3.78 921.0 1.94 1.73 1.33 39 10 1.71 1300 TEA 2.00 921.0 2.00 1.77 1.29 40 11S 1.47 1100 TOA 4.69 924.9 1.96 1.78 1.33 41* 12 7.02 1000 TEA 5.98 916.7 2.11 1.82 1.35 42* 13 3.31 1000 TEA 4.93 925.5 1.97 2.17 1.28 Notes to Table Two (b) Is as defined in notes to Table One.

(h) In the Examples marked *, the polymerisation diluent was heptane, the initial hydrogen pressure was 3.5 kg/cm2 gauge, the reactor was vented to reduce the pressure to 1.3 kg/cm2 gauge and ethylene was added to give a total pressure of 4.4 kg/cm2 gauge and this pressure was maintained throughout the polymerisation by the addition of more ethylene, the procedure otherwise being as described.

(i) The amount is given as millimoles of titanium contained in the product of the Examples and added to the autoclave.

(j) B-1 is butene-1 which was present in the specified amount in the initial mixture of polymerisation diluent and butene-1.

(k) TEA is triethyl aluminium.

TOA is trioctyl aluminium.

(I) MFI measured by ASTM Method D 1238-70 at 190C using a 2.16Kg weight.

(m) Density was measured as described in ASTM 1928/70, Method A, using a density gradient column at 230C.

(n) 1.25 means 1 hour 1 5 minutes etc.

(o) S.Ex. is stress exponent and is given by the relationship Log1O MFI S - Log10 MFI 2.16 Log10S-Log102.16 where MFI 5 is the melt flow index measured as in (1) using a 5 kg weight and MFI 2.1 6 is the melt flow index measured as in (1).

EXAMPLES 43 AND 44 A 20 cm internal diameter fluidised bed reactor vessel, operated in a continuous manner, was used to produce a series of ethylene/butene-1 copolymers. A reaction mixture comprising ethylene, butene-1 and hydrogen was circulated continuously through the bed at a superficial velocity estimated to be about four times the minimum necessary for fluidisation. In the fluidised bed, the reaction temperature was controlled at 80 & by adjusting the temperature of the gas fed to the fluidised bed reactor vessel using a heet exchanger in the circulating gas loop. Aluminium triethyl was pumped continuously into the reactor as a 0.25 molar solution in the heptane fraction.The product of Example 11 (material 11 D) or 14 was blown into the reactor as a dry powder in a stream of process gas at frequent intervals so as to maintain a rate of polymer production of about 1.5 Kg/hr, which corresponds to a mean residence time of four hours. The reaction pressure was maintained automatically at IS Kg/cm2 absolute by admitting ethylene/hydrogen mixture through a control valve. Liquid butene-1 was pumped into the circulating gas stream so as to maintain a constant composition as determined by Gas Liquid Chromotography.

The polymer formed was removed periodically so as to maintain an essentially constant level in the reactor vessel. The polymer collected was degassed in a stream of nitrogen which had been passed over a bath of water at ambient temperature, and then through a steam jacket. The use of this warm, moist nitrogen removed monomers and also de-activated the catalyst and alkyl residues.

Further details, together with some characteristics of the polymers obtained, are set out in Table Three.

TABLE 3

Ti Compn. Rate of Gas Composition Polymer Polymer Polymer Rate Alkyl Mole % (q) Production MFI Density Ex. Type (cm /hr) Rate Kg/hr dl/g Kg/cm No. (b) (i) (p) mM/hr Eth B-1 Hy (r) (l) (m) 43 11D 0.48 6 62.5 21.9 15.5 1.5 1.0 921.9 44 14 1.09 12 61.6 22.8 15.6 1.2 0.94 918.4 Notes to Table 3 (b) Is as defined in Notes to Table 1.

(i) and (m) are as defined in Notes to table 2.

(p) The titanium composition is added as a solid using a solid metering device of known volume capacity.

(q) Eth is ethylene B-1 is butene-1 Hy is hydrogen Mole % is calculated from the relationship (Mole of gas) x 100 (Mole of eth) + (Mole of B-1) + (Mole of Hy) (r) This is the rate which polymer is removed from the reactor vessel in order to maintain an essentially constant level in the reactor vessel.

Claims (14)

1. A process for the production of a transition metal composition in which at least one substantially inert solid particulate material is treated with at least one organic magnesium of the formula

treating the supported magnesium composition with at least one reagent selected from carbon dioxide, oxygen and a hydroxyl compound of the formula

reacting the treated product with at least one carbonyl compound of the formula

and simultaneously or subsequently reacting with at least one compound of a transition metal of Group IVA, VA or VIA of the Periodic Table, wherein R' is a hydrocarbon radical; R2 is hydrogen or a hydrocarbon radical; R3 is a hydrocarbon radical; X is a halogen atom or a hydrocarbon radical; Y is a halogen atom, a hydroxyl group or a group OR4; and R4 is a hydrocarbon radical.

2. A process as claimed in claim 1 wherein the at least one substantially inert solid particulate material has reactive sites which are capable of abstracting a magnesium hydrocarbon compound from a solution thereof.

3. A process as claimed in claim 1 or claim 2 wherein the at least one substantially inert solid particulate material is an oxide of a metal, including silicon, of Groups I to IV of the Periodic Table.

4. A process as claimed in claim 3 wherein the oxide is silica, alumina, magnesia or mixtures of two or more thereof.

5. A process as claimed in any one of claims 1 to 4 wherein the at least one organic magnesium compound is a magnesium dihydrocarbyl compound.

6. A process as claimed in any one of claims 1 to 5 wherein the supported magnesium composition is treated with oxygen and/or an alcohol.

7. A process as claimed in any one of claims 1 to 6 wherein the supported magnesium composition is treated with a hydroxyl compound in an amount of at least one mole, and not more than five moles, of the hydroxyl compound for each mole of magnesium which is present in the supported magnesium compound.

8. A process as claimed in any one of claims 1 to 7 wherein the treated product is reacted with the carbonyl compound and subsequently, in a separate stage, with the at least one compound of a transition metal.

9. A process as claimed in any one of claims 1 to 7 wherein the carbonyl compound is one in which R3 contains an aromatic group and Y is either a halogen atom or a group OR4 in which R4 is an alkyl group.

10. A process as claimed in any one of claims 1 to 9 wherein the at least one compound of a transition metal is titanium tetrachloride, and a solid material, which is the product obtained from the previous stages, is suspended in undiluted titanium tetrachloride and reaction is effected at a temperature of at least 6D0C.

11. A process as claimed in any one of claims 1 to 10 which is effected in several stages and between at least two of the stages, the solid material obtained as the product of one stage is separated from the reaction medium and washed before being subjected to the next stage.

1 2. A polymerisation catalyst system which comprises I a transition metal component which is the product obtained by the process of any one of claims 1 to 11; and II an organic compound of a metal of Group IIA of the Period Table or of aluminium, or a complex of an organic compound of a metal of Group IA or IIA of the Periodic Table with an organic compound of aluminium.

1 3. A polymerisation catalyst system as claimed in claim 12 wherein component II is an aluminium trihydrocarbyl compound and the system also includes a Lewis Base compound.

14. A process for the production of a polymer or a copolymer of an unsaturated hydrocarbon monomer which comprises contacting at least one ethylenically unsaturated hydrocarbon monomer under polymerisation conditions with a polymerisation catalyst system as claimed in claim 12 or claim 13.