CA1141091A - Ethylene polymerisation process - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Ethylene is polymerised, or copolymerised with another olefin monomer, using a catalyst system comprising an organic metal compound and a titanium-containing material which is obtained by reacting together an inert particulate material, an organic magnesium compound, a halogen-containing compound such as carbon tetrachloride, silicon tetrachloride, trichlorosilane, phosphorus trichloride or boron trichloride, and titanium tetrachloride. The process can be used to effect copolymerisation of ethylene with an alpha-olefin monomer such as butene-1 in a fluidised bed reactor.

Description

`

ETHYLENE POLYMERISATION PROCESS
The present invention relates to a process for the production o a polymer or copolymer of ethylene.
~ ccordin~ to the present invention there i9 provided a process for the production o an ethylene polymer which proaess comprises contacting ethylene, or a mixture of ethylene and a monomer which is copolymerisable with ethylene, under polymerisation conditions with a catalyst system obtained by mixing together 1) an organic compound of a metal of Group IIA of the Periodic Table or of aluminium, or a complex of an organic compound of a metal of Group I~ or Group IIA of the Periodic Table with an organic compound of aluminium; and 2) the reaction product obtained by reacting together reagents consisting of a component I which is at least one substantially inert solid particulate material having reactive sites (as hereinafter defined), a component II which is an organic magnesium compound or a complex or mixture of an organic magnesium compound and an aluminium compound, a component III which is at least one halogen-containing compound selected from hydrogen halides, boron halides, halogens, inter-halogen compounds and halides of elements of Groups IVB, VB and VIB of the Periodic Table, and a component IV
which is titanium tetrachloride.
For convenience, the substantially inert solid particulate material having reactive sites will be referred to hereafter as the solid particulate materialO
The formulae A to G in the attached drawing represent comp~unds which may be used in the present invention~
All references herein to the Periodic Table are to the Short Periodic rable 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.

~4~9~

- 2 - 31124 The process of the present invention is preferably used to effect the copolymerisation o ethylene with another monomer. The other monomer i9 preferably an alpha~olein monomer o the formula A in which, Rl is an alkyl radical.
In the ~ormula A, it is preferred that the group contains not more than 10 carbon atoms and conveniently contains up to 4 carbon atoms. Thus, the monomer of formula A may be propylene, butene-l, pentene-l or hexene-l or 4-methylpentene-1 or any other monomer which satis~iès formula A.
If the process of the present inventîon is used for the copolymerisation of eth~lene, the quantity o the comonomer which is copolymerised with the ethylene is conveniently in an amount such that the polymer formed has a density in the range of 915 up to 940 kg/m3. The molar ratio of ethylene to the comonomer during the polymerisation is typically in the range from 15:1 to 1:1, but it will be appreciated that the optimum ratio will be dependent on the particular comonomer being used.
`~ The polymerisation process can be effected under any conditions of temperature and pressure which have previously been used for the polymerisation and copolymerisation o ethylene. Thus, the temperature may be in the range from 2QC up to 300C and the pressure may be from below 1 kg/c~2 up to 3000 kg/cm2. However, it is pre~erred that the polymerisation is carried out under relatively moderate conditions of temperature and pres~ure. Thus, it is preferred that the temperature is in the range from 50C up to 100~ and that the pressure is from 2 kg/cm2 up to 50 kg/cm2. Especially preferred polymerisation conditions are at a temperature in the range from 70 up to 95C and at a pressure of from 1 5 kg/cm2 up to 30 kg/cm2.
Component 1) of the catalyst may be an organic magnesium compound of the same type as is used as ~4~

- 3 - 31124 component 2) in the production of the titanium~containing material. If the magnesium compound is a Grignard reagent it~is preferred that it is substantially ether-free.
~l~ernatively, component 1) may be a complex o a metal of Group I~ of the Periodic Table with an organic aluminium compound such as a compound of the type lithium aluminium tetraalkyl. Useful materials for use as component 1) o the catalyst are organic aluminium compounds such as aluminium hydrocarbyl halides, aluminium hydrocar~yl sulphates, aluminium hydrocarbyl hydrocarbyloxy compounds and in particular, aluminium trihydrocarbyls or dihydrocarbyl aluminium hydrides. The aluminium trihydrocarbyl is ~referably an aluminium trialkyl in particular one in which the alkyl group contains from 2 up to 10 carbon atoms, for example aluminium triethyl, aluminium tributyl, or aluminium trioctyl.
Component 2) of the~ catalyst system is a transition metal composition. This is obtained by reacting together four different components. The xeaction product may be obtained by mixing these four components together in a single stage but it is preferred to produce the reaction product by reacting the various components in more than one stage~ It is particularly preferred to contact the at least one solid particulate material which is component I
with one of components II, III or IV, and then treat in turn with the other two components. The treatments with components II, III and IV may be effected by adding each component, in turn, to the reaction mixture rom the previous stage, and this procedure may be effected without separating the reaction product from the reaction mixture of one stage before adding a further component to effect the next stage However, a solid reaction product may be ! separated from the reaction mixture at the end of any, or all, of the treatment stages and the separated solid reaction product is then preferably washed. If an excess ~14~

- 4 - 31124 of any of components II, III or IV is used, it is very desirable to separate and wash the solid reaction product at the end of any stage in which such an excess is used.
It i9 pre~erred, but not essent~al, to separate and wash the solid reaction product on completion of the ~irst treatment stage and al 30 on completion of the treatment stage in which the halogen-containing compound is used.
It is generally preferred that the treatment with titanium tetrachloride is effected as the last stage and in this preferred process the at least one solid particulate material is treated first with component II or component III, the reaction product is treated with whichever of component II or component III was not used in the first stage and then finally with the titanium tetrachloride. It may, however, be desired to effect an intermediate treatment with titanium tetrachloride in addition to a final titanium tetrachloride treatment. Any intermediate treatment with titanium tetrachloride is conveniently effected after the irst treatment stage in which component I is reacted with component II or component III and before the su~sequent stage in which the solid reaction product is treated with the other one of component II or component III.
Component I which is used in the production of catalyst componant 2) is at least one substantlally inert solid particulate material having reactive sites (as hereinafter defined). By "reactive sites" are meant those sites which are capable of abstracting a magnesium hydrocarbyl compound from a solution thereof. The number of 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 hydrocarbyl compound, stirring the mixture at ambient temperature for an hour and analysing the supernatant liquid to determine the quantity of the magnesium ~ 5 - 31124 hydrocarbyl compound which remains in the solution, from which can be calculated the number o moles of magnesium hydrocarbyl compound which have been abstracted ~xom the solution for each gramme of the solid particulate S material, this being e~uivalent to the proportion, in moles, of the reactive sltes.
The solid particulate material which is used as component I in producing th~ transition metal composition which is component 2) of the catalyst system, may be any such material which has been proposed previously for use in an olefin polymerisation catalys~ system. Thus, the solid particulate material may be an organic or inorganic compound of a metal, which term is used herein to include silicon, such as a metal halide, or a metal oxide or mixtures or reaction products of two or more such metal compounds.
It is particularly preferred that the solid particulate material which is component I is a metal oxide, and in particular is an oxide of a metal of Groups I to IV of the Periodic Table. Solid oxides which may be used as component I include those with a substantially inert matrix material wherein at least some of the reactive sites are present in a hydroxylic surface (as hereinafter defined) 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 substantially inert in that the bulk of the matrix material is chemically inert.
The at least one solid particulate material may be silica, alumina, magnesia, mixtures of two or more thereof, for example magnesium tri~ilicate which may be represented as (MgO)2(SiO2)3xH~O (x is a positive ~; .

number), thereon and containing minor amounts, for example less than lO~ by weight, o other suitable solid particulate materials ~uch as zinc oxide. Particularly u3eul solid particulate materials include alumina and silica.
The at least one solid particulate material preerably has a surace area of at least 30 m2/g, particularly a~ least 100 m2/g, and especially at least 200 m2/g~ Useul forms of the at least one solid particulate material may be obtained by heating an inorganic oxide or hydroxide in an inert atmosphere, and/or at a reduced pressure, to a temperature of at least 200C and not more than l200C and preerably in the range 300C to 1000C. A suitable inert atmosphere for 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 i~ especially pr~ferred to use a temperature in the range 320C up to 400C, for example 350C. Using hydrated alumina, for example Boehmite (which may be regarded a~ hydrated gamma-alumina), or aluminium hydroxide~ it is especially preferred to use a temperature in the range 400C up to 1000C, for example 500C.
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 o an inert liquid medium is typically effected at a temperature in the range 100C up to 200C using a liquid having a boiling point in this range.
Component II of the reaction mixture which i~ used to produce the transition metal component of the catalyst is an organic magnesium compound or complex or mixture thereof with an aluminium compound. The organic magnPsium compound is a compound of formula B in the attached 7 ~ 31124 formula drawings, the complex thereof with an aluminium compound is repre~ented by ~ormula C in the attached formula drawings and the mixture thereof with an aluminium compound is represented by the ormula D in the attached ~ormula drawings.
In the formulae B, C and D, each R , which may be the same or different, is a hydrocarbon radical;
each X, which may be the same or different, i5 an oxyhydrocarbon radical or a halogen atom other than fluorine:
a has a value of greater than 0 up to 2;
b has a value of greater than 0 up to 2; and c has a value of from 0 up to 3.
The groups R are all typically alkyl groups and conveniently are alkyl groups containing from 1 up to 20 carbon atom~ and especially 1 up to 6 carbon atoms. The groups X are all preferably halogen atoms, other than fluorine, for example chlorine or bromine atoms. The value of a is preferably at least 0.5 and it is particularly preferred -that the value of a is 2~ The value of b is typically in the range O.OS up to 1Ø The value of c is typically at least 1 and is preferahly 3.
The organîc magnesium compound of formula B, which is also present in the materials of formulae C and D, may be a Grignard reagent such as ethyl magnesium chloride or butyl magnesium bromide or may be a compound such as ethyl magnesium ethoxide, but is preferably a magnesium dihydrocarbyl compound such as diethyl magnesium or dibutyl magnesium. Whilst the aluminium compound, which is present in the materials of formulae C and D, may be aluminium chloride or aluminium bromide, it is preferably an organic aluminium compound such as ethyl aluminium dichloride, diethyl aluminium monochloride or diethyl aluminium ethoxide, and is particularly a compound such as aluminium triethyl or aluminium tributyl.

It will be appreciated that the materials of formulae C and D ma~ be present together as an equilibrium mixture and indeed such a mixture may be obtained merely by mixing together the organ.ic magnesium compound with the aluminium compound when the resultant product may be a m~xture of the organic ma~nesium compound, the aluminium compound and the complex of formula D. It will be appreciated that it is preferred that the compound of formula B, C or D is a material which i3 soluble in inext liquid hydrocarbons.
m e organic magnesium compound, or the complex or mixture thereof with the aluminium compound, is conveniently added aq a liquid medium to a solid material which is either the at least one solid particulate material or the product of reacting the at least one solid particulate material with one or both of components III
and IV. The solid material to which component II is added, may be suspended in an inert liquid such as an aliphatic hydrocarbon. The liquid medium containing component II is conveniently a solution of the organic magnesium compound, or the mixture or complex thereof with the aluminium compound, in an inert liquid such as a hydrocarbon liquid, for example hexane, heptane, octane, decane, dodecane or mixtures of the isomers thereof, or inert halohydrocarbons such as chlorobenzene.
The quantity of the compound B, C or D which is added ; to the at least one solid particulate material, or the product of reacting the at least one ~olid particulate material with one or both of components III or IV, 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 solid ; particulate material. The quantity of the compound B, C
or D which is added may be in excess of that required to saturate the surface of the at least one solid particulate material, ~hat is in excess of one mole for each mole of .

the reactive sites present on the at least one solid particulate material. When the solld particulate material is a metal oxide, typically at least some of the reactive sites are sur~ace hydroxyl groups.
The quantity of the compound B, C or D which is used is also dependent on the quantity of the halogen-containing compound which is component III and, in particular, it is preferred that the molar quantity of the compound B, C or D which is used is less than the amount of the halogen-containing compound which is component III
and in particular is from 0.25 up to 0.8 mole of compound B, C or D for each mole of the halogen-containing compound which i~ component III.
The compound B, C or D can be added to the at least one solid particulate material, or the prodùct of the at least one solid particulate material and one or both o components III and IV at any suitable temperature, for example from O~C up to 100C, conveniently at ambient temperature, that is from about 15C up to about 25C.
After adding the compound B, C or D to the at least one solid particulate material, or the product of the at least one solid particulate material and at least one of components III and IV, reaction is conveniently 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 may then be washed one or more times. If desired, the solid material whic~ is the reaction product may be ~ubjected finally to an optional low pressure (about 1 mm of mercury) treatment at ambient tempsrature, or higher, for a time of up to several hours, for example 2 hours before being used in the next stage of the preparation.

~ 10 - 31124 However, these separation and wa~hing operations are not essential, particularly if component II is used in an amount of less than one mole for each mole o reactive sites present in the at leaqt one solid particulate material.
The at least one halogen-containing compound which is component III i9 preerably a chlorine-containing compound. If the halogen~containing compound is a halide of an element of Groups IVB, VB or VIB of the Periodic Table, it is preerred that this is an element of the second or third series. The at least one halogen-containing compound may be a hydrogen halide, a silicon halide o~ the formula E, a carhoxylic acid halide of the formula F, a hydrocarbyl halide of the formula G, a phosphorus halide, a phosphorus oxyhalide, a boron halide, sulphuryl chloride, phosgene, nitro~yl chloride, chlori~e, bromine, a chlorinated polysiloxane or an ammonium hexafluorosilicate, wherein R3 is a hydrogen atom or a hydrocarbon radical;
R4 is a hydrocarbon radical;
R5 is the residue obtained obtained by removing one or more hydrogen atoms from a hydrocarbon compound;
Z i9 a halogen atom other than fluorine;
d is 0 or an integer from 1 up to 3; and e is an integer from 1 up to 10.
In the silicon halides of formula E, it is preferred that R3 i~ an alkyl group containing one up to six carbon atoms or an aryl, alkaryl or aralkyl group containing 6 up to 15 carbon atoms. In the carboxylic acids of formula F, it is preferred that R4 is an alkyl group containing 1 up to 4 carbon atoms or an aryl, alXaryl or aralkyl group containing 6 up to 12 carbon atoms. In the hydrocarbyl halides of formula G, the group R may be a carbon residue or may include hydrogen atoms and Z, or each Z, is preferably attached to an aliphatic carbon a~om.

~ 31124 The silicon halides of formula E include silicon tetrachloride, silicon tetrabromide and halosilanes such as trichlorosilane, diethyl silicon dichloride, monobutyl silicon trichloride and monoethyl silicon trichloride.
The carboxylic acid halides o~ ormula F include acetyl chloride, benzoyl chloride and p-methylbenzoyl chloride.
The hydrocarbyl halides of formula G include carbon tetrachloride, chloroorm and l,1,1-trichloroethane.
~uitable materials for use as the halogen-containing compound are halogenating agents by which is meant a halogen-containing compound which, when reacted with the at least one solid particulate material, or the product o~
reacting the at least one solid paxticulate material with a~ least one of the other components, gives a solid reaction product having an increased halogen content.
The at least one halogen-containing compound is conveniently added in a liquid form to a solid material which is the at least one solid par~iculate material, or the solid reaction product from a previous treatment stage. This addition may be effected by using a solution of the halogen-containing compound in an inert solvent such as an aliphatic hydrocarbon solvent. Thus, the reaction with the solid material is conveniently carried out by suspending the solid material in a liquid medium which is, or which contains, the halogen-containing compound. However, the halogen-containing compound may be used in the gas phase. Using a halogen-containing compound which is gaseous at ambient temperature, for example hydrogen chloride or boron trichloride, the gas is conveniently passed into a stirred suRpension containing the solid material. Alternatively, a gaseous halogen-containing compound may be passed, optionally as a mixture with an inert gaseous diluent such as nitrogen, through a bed of the solid material, conveniently a - 1~ - 311~4 1uidised bed. This latter technique can be used both with halogen-aontaining compounds which are gaseous at ambient temperature and also with halogen-co~taining compounds having boiling temperature~ above ambient temperature.
The reaction with the at least one halogen-containing compound can be effected at ambient temperature, or at an elevated temperature which may be as high as 600C but typically does not exceed 100C. The preferred temperature will be dependent on the particular halogen-containing compound, for example, using silicon tetrachloride the temperature is preferably at least 60C.
The quantity of the at least one halogen-containing compound is preerably ~ufficient to provide at least one halogen atom at every reactive site on the solid particulate material. It is convenient to add the halogen-containing compound in the amount of 1 mole for every mole of reactive sites on the solid particulate material. However, it should be appreciated that smaller quantities of the halogen-containing compound may be used, for example as little as 0.2 mole of the halog0n-containing compound for each reactive site.
Alternatively, an excess of the halogen-containing compound may be used, and this is conveniently achieved by suspending the solid material in an excess quantity of a liquid halogen-containing compound. The reaction with the at least one halogen-containing compound is conveniently effected for a time o from 0.25 up to 10 hours, preferably from 1 up to 5 hours.
After the reaction with the at least one halogen-containing compound, the reaction product is conveniently, but not necessarily, separa~ed from the reaction medium and washed several times.

j ~ , ~ 13 - 31124 It is preferred to add the titanium tetrachloride which i5 component IV to a product obtained by reacting the at least one solid particulate material, either simultaneously or in succession, with component II and component III. The reaction may be effected by adding a solution of titanium tetrachloride to a solid material which is the reaction product obtained from the preceding stages. Alternatively, this solid material may be suspended in undiluted titanium tetrachloride. When undiluted titanium tetrachloride is used, the amount thereo will be such as to provide more than one mole of titanium tetrachloride for each mole of the reactive sites preRent on the at least one solid particulate material.
If a solution of the titanium tetrachloride is used, the amount of titanium tetrachloride which is added may be less than one mole for each mole of reactive sites, and is typically in the range from 0.1 mole up to 0.8 mole of titanium tetrachloride for each mole of reactive sites.
The amount of titanium tetrachloride is especially in the range 0.15 up to 0.6 mole of titanium tetrachloride for each mole of reactive sites on the solid particulate material .
The reaction of the titanium tetrachloride with the solid material is conveniently carried out at a temperature of from 0C up to the boiling temperature of titanium tetrachloride which i~ about 137C at atmospheric pressure. If the solid material i~ contacted with neat titanium tetrachloride this may be carried out at the boiling temperature of titanium tetrachloride. However, if the solid material is contacted with a solution of titanium tetrachloride this may conveniently be effected by stirring the mixture at ambient temperature. After adding the titanium tetrachloride to the solid material, the materials are conveniently allowed to remain in contact for from 0.25 up to 10 hours, preferably 1 up to 5 hours. After the desired period of contacting, the solid product obtained may be sepaxated rom the li~uid reaction medium and wa#hed several times with an inert liquid medium, but this ~eparation and washing is not essential.
If the treatment with titanium tetrachloride is efected as an intermediate stage in the process, this intermediate stage is conveniently effected using an excess quantity of titanium tetrachloride. EIowever, it is preferred that there is, in addition to an intermediate treatment with titanium tetrachloride, a final treatment as hereinbefore described. Alternatively, there may be two final treatments with titanium tetrachloride, the irst being with a minor proportion ~less than 1 mole of titanium tetrachloride for each mole of reactive sites), and the second being with an excess quantity of titanium tetrachloride, conveniently using undiluted liquid titanium tetrachloride.
It will be appreciated that the reaction product which is component 2) of the catalyst contains a titanium halide and a magnesium halide composition supported on a solid particulate material.
The proportions of components 1) and 2) of the catalyst system may 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 each material, but in general we prefer that for each gramme atom of titanium which is present in component 2) of the catalyst system, there is present at least one mole of component 1), and preferably at least 5 moles of component 1) for each gramme atom of titanium. The number of moles of component 1) for each gramme atom of titanium which is present in component 2) may be as high as 1000 but conveniently does not exceed S00.

~410~

When the process of the present invention is be~ing used to effect the copolymerisation of ethylene, it is preferred to carry out the copolymerisation using a mixture of ethylene and the de~ired comonomer, for example butene-l or hexene-l, wherein the mixture o monomers has essentially the same composition throughout the polymerisation process.
The process of the present invention can be used for the polymerisation or copolymerisation of ethylene to give a high yield of polymer. Since catalysts of the type used in th~ process of the present invention are susceptible to the presence of impurities in the polymerisation system, 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. Thus, it is preferred that the monomer contains less than 5 ppm by weight of water and le~s than 1 ppm by weight of oxyaen.
Materials having the desired high degree of purity can be obtained in the manner known in the art, for example by passing the material to be purified through a bed of a molecular sieve material and also through a bed of material which will remove o~ygen containing impurities.
The ethylene polymerisation process is conveniently effected in the substantial absence of any liquid medium and such a process is particulArly effected using a fluidised bed reactor system. In such a fluidised bed reactor system, the 1uidising gas is conveniently 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-l to produc~ an ethylene copolymer having a density of les~ than abou~ 940 kg/m3, the gas composition is typically from 50 to 60 mole % ethylene, 15 to 25 mole butene-l with the remainder, apart from inert materials and impurities, being hydrogen. However, if the monomer ~4~

being polymerised is ethylene only, the amount o~ hydrogen used may be greater, for example the reaction mixture may contain in excess o~ 50% molar o~ hydrogen If ethylene is being copolymerised the proportion o~ hydrogen may be le~s and typically an amount o~ hydrogen o up to 35~ molar i8 ~u~ficient. However, it will be appreciated that the amount o~ chain trans~er agent will be dependent upon the polymerisation conditions, and especially the temperature.
The molecular weight distribution (MWD) o~ the polymer has been ~ound to be dependent, to some extent, on the nature of component 2) of the catalyst system. In particular, we have found that the MWD of the polymer is influenced by the nature of the halogen-containing compound and the stage at which this is incorporated into component 2~. Thu~, we have found that using silicon tetrachloride as the halogen-~ontaining compound, a polymer having a narrower MWD is obtained than when using boron trichloride as the halogen-containing compound. The u~e of other halogen-containing compounds such as trichlorosilane or phosphorus trichloride also may result `~ in polymers having a broader MWD than is obtained when using silicon tetrachloride as the halogen-containing compound. m ese effects on MWD are most signiicant when component 2) of the catalyst has been prepared by reacting the at least one solid particulate material with the haloyen-containing compound and thereafter reacting the product obtained, in turn, with ~he other components (component II and component IV).
In carrying out the process of the present invention, ~he catalyst components may be pre-mixed before they are introduced into the polymerisation reactor.
Alternatively, the catalyst components may be added to the polymerisation reactor as separate components. Component 1) o~ the catalyst, which is typically an organic aluminium compound, may be added to the reactor as a liquid either as a solution in an inert hydrocarbon diluent or, if component 1) itself i~ a liquid, aq the neat undiLuted material. Alternatively, component 1) o the catalyst may be adsorbed on a suitable support material which may be an inert organic material such as a polymer o the type being produced or a so~id particulate materiaL o the type which is used for the production of component 2) of the catalyst system.
The catalyst, or catalyst components, may be introduced into the polymerisation reactor as a suspension or solution in a suitable inert liquid medium. However, particularly if polymerisation is being carried out in the gas phase, and both of the catalyst components are used in the form o solid materials, the catalyst components may be added to the polymerisation reactor suspended in a stream of the gaseous monomer or monomer mixture.
Since the process of producing component 2) of the catalyst includes a step of treating with an organic magnesium compound, or a complex or mixture of an organic magne~ium compound and an aluminium compound, component 2) of the catalyst may show some polymerising activity, particularly for ethylene, even in the absence of component 1) of the catalyst. If component 2) of the catalyst system possesses polymerisation activity, this may cause blocking of the catalyst metering or feeding devices when using a stream of a polymerisable monomer as the medium for transporting component 2) of the catalyst system. To avoid this, component 2) may be temporarily deactivated, or "pacified", by treatment with a suitable "pacifying agent". Suitable "pacifying agents" include carbon monoxide, carbon dioxide and also reagents which remove metal-carbon or metal-hydrogen bonds from the transition metal composition which is component 2) of the catalyst system. Typically the "pacifying agent" is a protic reagent such as a carboxylic acid, an aliphatic alcohol having rom one up to six carbon atoms or an anhydrous hydrogen halide. Hydrogen halides, especially hydrogen chloride, are preferred "pacifying agents".
Using hydrogen chloride, this may be bubbled through a suspension of component 2) o the catalyst system in an inert diluent and any excess of the hydrogen chloride can be removed by sparging with an inert gas such as nitrogen.
The "pacifying agent" is used in a manner, and in proportion~, such that when the paciied component 2) is mixed with component 1) an active polvmerisation catalyst system i9 obtained.
It will be appreciated that the particle form of the polymer obtained is dependent on, and hence is affected by, the particle form o the at least one solid particulate material which is used as component I in the production of the transition metal composition which is component 2) of the catalyst system. Hence, by the selection of a solid particulate material having an appropriate particle form, such as essentially spherical particles, a polymer of a desir~d particle orm may be obtained.
Various aspects of the present invention will now be described with referance to the following catalyst preparations and polymerisation Examples, all stages of which were effected under an atmosphere of nitrogen unless otherwise indicated.
A) Treatment of alumina . . _ ~
A sample of hydrated gamma alumina ~Ketjen Grade B
obtainable from Akzo Chemie of Amsterdam, Holland) was heated up to 700C under a stream of nitrogen at atmospheric pressure, maintained at 700C for 2 hours and then allowed to cool, in the oven, to ambient temperature.

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o~

B) Treatment of silica The procedure o~ A) was repeated using silica (Davison 952 grade obtainable from W R Grace and Company o~ Maryland, USA).
C) Treatment of silica The procedure of B) was repeated with the exception that a temperature of 350C was used.
D) Treatment of alumina The procedure of A) was repeated with the exception that a temperature of 500C was maintained for four hours.
I Preparation of transition metal reaction product a) Reaction with alumina and 8i licon tetrachloride 29.5 g of the alumina dried as described in treatment A) were suspended in 300 cm3 of an isoparaffin raction, essentially all of which had a boiling temperature in the range from 117C up to 135C, in a 600 cm3 jacketted reaction vessel provided with a sintered glas~ frit and a stirrer. 3.4 cm3 of silicon tetrachloride were added to the suspension, whilst stirring, over a period of two minutesO Stirring was continued and the mixture was heated to 80C and maintained at that temperature for 15 minutes. The mixture was filtered whilst still hot, the solid wàs 25 washed four time- at 80C using 300 cm3 of the isoparaffin fraction for each wash and the washed solid was suspended in 300 cm3 of the isoparaffin fraction at ambient temperatureO
b) Treatment with magnesium dibutyl To the mixture from Ia) were added 23.8 cm3 of a 0.62 M solution of magnesium dibutyl (an equimolar mixture of primary and secondary dibutyl magnesium) in the isoparaffin fraction. This mixture was stirred for 20 minutes at ambient tempera~ure, a further 45 minutes at 80C and then allowed to cool to ambient temperature.

c) Treatment with titanium tetrachloride To the reaction mixture from Ib) was added 0.55 cm3 o~ titanium tetrachloride. The mixture was stirred at amblent temperature for 15 minutes, a ~urther 25 minutes at 80C and was then allowed to cool to ambient t:emperature. The solid reaction product present in the reaction mixture will hereafter be identified as TMC-I.
In the foregoing procedure in step Ia), 1 millimole of silicon tetrachloride was used for each gramme of alumina (which contained approximately 1 millimole of reactive sites per gramme), in step Ib), 0.5 millimole of magnesium dibutyl was used or each gramme of alumina, and in step Ic), 0.17 millimole of titanium tetrachloride was used for each gramme of alumina.
II Preparation of transition metal reaction product a) Reaction with alumina and silicon tetrachloride . .
97.4 g of the alumina dried as described in treatment A) were suspended in lOQ0 cm3 of the isoparaffin fraction in a two litre jacketted reaction vessel provided with a stirrer. 16.7 cm3 of silicon tetrachloride were added to the suspension, whilst stirring, over a period of ; three minutes. Stirring was continued and the mixture was heated to 80C and maintained at that temperature for two hours. Stirring was stopped, the mixture allowed to ; 25 se~tle and the supernatant liquid was removed by ; decantation. The ~olid was washed four times at ambient temperature using 1800 cm3 of the isoparaffin fraction for each wash and the washed solid was suspended in 1000 cm3 of isoparaffin fraction at ambient temperature.
b) Treatment with_magnesium dibutyl To the mixture from IIa) were added 78.5 cm3 of the 0.62 M solution of magnesium dibutyl used in step b) of preparation I. The mixture obtained was stirred, heated to 80C, maintained at ~ha~ temperature for one hour and then allowed to cool to ambient temperature.

c) Treatment with titanium tetrachloride To the reaction mixture from IIb) were added

5.9 am3 o~ titanium tetrachloride. The mixture was stirred a~ ambient temperature for 30 minutes. The mixture was allowed to settle and the supernatant liquid was removed by decantation. The solid waa washed six times by decantation using 1500 cm3 of the isoparaffin fraction at ambient temperature for each wash. The solid was finally suspended in 1000 cm3 of the isoparaffin fraction at ambient temperature. The solid reaction product present in the reaction mixture will hereafter be identified as TMC-II.
In the foregoing procedure in step IIa), 1 millimole of silicon tetrachloride was used for each gramme of alwmina (which contained approximately 1 millimole of reactive sites per gramme), in step IIb), O.S millimole of magnesium dibutyl was used for each gramme of al~mina, and in ~tep IIc), 0.55 millimole of titanium tetrachloride was used for each gramme of alumina.
III Preparation of transition metal reaction product The procedure described for preparation II was repeated with the exception that some of the conditions were varied and additional treatment steps were added.
In step a), 132.5 g of alumina were suspended in 1500 cm3 of the isoparaffin fraction and 73 cm3 of silicon tetrachloride were added. The mixture was heated at 80C for three hours and was then allowed to cool to ambient temperature~ The mixture was not separated.
After atep a), and before effecting step b), to the reaction mixture from step a) were added 2.5 cm3 of titanium tetrachloride. The mixture was stirred at ambient temperature for one hour, allowed to settle and the supernatant liquid removed by decantation. The solid was washed ten times by decantation using 1500 cm3 Of the isoparaffin fraction at ambient temperature for each wash. The ~olid was finally resuspended in 1500 cm3 of the isoparaffin fraction.
In step b) 107 cm3 o the magnesium dibutyl solution was used and the mixture wa~ ~tirred for one hour ak ambient temperature.
In step c), 2.S cm3 of titanium tetrachloride were used, the mixture was stirred for one hour at ambient temperature and was not subsequently separated. m e solid reaction product present in the reaction mixture, when used in a polymerisation process as described in Example 11, was found to give an active polymerisation catalyqt system. A portion of the product of step c) was separated and subjected to a further treatment step.
To this separated portion, which contained 40 g of solid was added 1.32 cm3 of titanium tetrachlorids. The mixture was stirred at ambient temperature for one hour and then filtered. The solid was washed four times using S00 cm3 of the isoparaffin fraction at ambient temperature for each wash. The solid was finally resuspended in 600 cm of the isoparaffin fraction.
The solid reaction product obtained will hereafter be identified as TMC-III.
IV P~aration of transition metal reaction product The procedure described for preparation II was repeated with the exception that some of the condi~ions were varied.
In step a), 74.6 g of alumina, 1200 cm3 of the isoparaffin fraction and 4.1 cm3 of silicon tetrachloride were used. The mixture was stirred at ambient temperature for 1.5 hours but was not heated to 80~C. The solid was washed three times using 1900 cm3 of the isoparafin fraction and finally resuspended in 1200 cm3 of the isoparaffin fraction.

:`

In step b), 120~3 cm3 of the magnesium dibutyl solution were added. The mixture was stirred at ambient temperature for 1~25 hours, heated to 80C and maintained at that temperature for one hour. The supernatant liquid was deaanted o, the solid was washed three times by decantation using 1900 cm3 of the isoparaffin raction at ambient temperature for each wash and finally suspended in 1200 cm3 of the isoparaffin fraction.
In step c), 4.1 cm3 o titanium tetrachloride were added and stirring at ambient temperature was effected for 1.25 hours. The solid was washed twice using 1900 cm3 of the isoparaffin fraction and finally suspended in 1500 cm3 of the isoparaffin fraction.
The solid reaction product obtained will hereafter be identified as TMC-IV.
V Preparation of transition metal reaction product To a portion of the suspension obtained in preparation IV was added titanium tetrachloride in an amount equivalent to 0.5 millimole of titanium tetrachloride for each gramme of solid. The mixture was stirred at ambient temperature for three hour~, allowed to settle, the supernatant liquid removed by decantation and the solid washed three times by decantation using 1900 cm3 of the isoparaffin fraction for each wash. The solid was finally suspended in the isoparaffin fraction to give a concentration of 1 gramme of solid for each 40 cm3 of li~uid.
The solid reaction product obtained will hereafter be identified as TMC-V.
VI Pxeparation of transition metal reaction product The procedure described for preparation I was repeated with the exception that some of the conditions were varied.
In step a), 21.7 g of the ilica dried as described in treatment B) were suspended in 150 cm3 of the ~.~4~

isoparafin fraction. The mixture was heated to 60C and 0.72 cm3 o silicon tetrachloride were added. The mixture was stirred at 60C for 1 hour 15 minutes. The solid was washed three times using 75 cm3 o the isoparain fraction at between 65C and 85C for each wash. The solid was then suspended in lS0 cm3 of khe isoparain raction and the mixture allowed to cool to 60~C.
In step b), 36.5 cm3 of the magnesium dibutyl solution were added followed by 16 cm3 of a 0.62 M
magnesium dibutyl solution in a mixture o hexane and heptane. This mixture was stirred at 60C for three hours~ cooled to 25C, filtered and the solid washed three times using 75 cm3 o the isoparaffin fraction at ambient temperature for each wash. The solid was finally suspended in 150 cm3 of the isoparaffin raction.
In step c), the mixture was heated to 70C, O.9S cm3 of titanium tetrachloride was added and the mixture was stirred for 65 minutes. The mixture was ~0 filter~d and the solid resuspended in 150 cm3 of the isoparafin fraction at ambient temperature.
The solid reaction product obtained will hereafter be identii~d as TMC-VI.
VII Preparation of transition metal reaction product The procedure described for preparation II was repeated with the exception that some of the condi~ions were varied.
In step a), 82.0 g of alumina, 1000 cm3 of the isoparaffin fraction and 200 cm3 of a 0.62 M magnesium dibutyl solution in hexane was used (no silicon tetrachloride was added in this step). The mixture was stirred or three hours at ambient temperature. The solid was washed three times using 1900 cm3 of the isoparaffin fraction for each wash and was suspended in 1300 cm3 of the isoparain fraction, all at ambient temperature.

~o~

In step b), to the suspension rom step a~ were added 4.5 cm3 of silicon tetrachloride (no magnesium dibutyl solution was used in this step). The mixture wa~ stirred at ambien~ temperature for one hour, heated to 80C and maintalned at that temperature for one hour.
In step c), 4.5 cm3 of titanium tetrachloride were added to the suspension at 80C from step b). The mixture was stirred at 8QC for 30 minutes and allowed to cool to ambient temperature while continuing to stir. The product was not separated or washed.
The solid reaction product present in the reaction mixture will hereafter be identified as TMC VII.
VIII Preparation of transition metal reaction product About 650 cm3 of the suspension obtained in preparation VII were transferred to a different reaction ves~el, the liquid was filtered of and 550 cm3 of titanium tetrachloride were added. The mixture was stirred, heated to 80C and maintained at that temperature for 3.5 hours. The supernatant liquid was removed and the 20 solid was washed three times at 80C using 1900 cm3 of the isoparaffin fraction for ea~h wash, and then three times at ambient temperature using 1900 cm3 of the isoparaffin fraction for each wash. The solid was finally suspended in 800 cm3 of the isoparaffin fraction.
~he solid reaction product obtained will hereafter be identified as TMC-VIII.
IX Preparation of transition metal reaction product a) Reaction with alumina and trichlorosilane 50 q of the alumina dried as described in treatment A) were su~pended in one litre of the isoparaffin fraction in a two-litre jacketted reaction vessel provided with a stixrer. 5.5 cm3 of trichlorosilane were added to the suspension. The mixture was then stirred at ambient temperature (about 20C) for two and a half hours.
Stirring was stopped, the mi~ture was allowed to settle 11~0~

and the supernatant liquid was removed by decantation.
The solid was washed twice by decantation using 1800 cm3 o~ the isoparafin fraction at ambient temperature for each wash. A~ter the second wash, most o the residual liquid was removed by forcing it through a glass tube at the lower end of which was located a sintered glass frit.
The washed solid was suspended in one litre of the isoparafin fraction at ambient temperature.
b) Treatment with magnesium dibutyl To the mixture from step a)~were added 40 cm3 of the magnesium dibutyl solution used in step b) of preparation I. This mixture was stirred for 30 minutes at ambient temperature.
c) Treatment with titanium tetrachloride . . _ . _ . _ _ To the reaction mixture from step b) were added 3.6 cm3 of titanium tetrachloride. The mixture was stirred at ambient temperature for 30 minutes, allowed to stand without stirring for 16 hours and ~hen stirred for a further one hour. The mixture was allowed to settle and the supernatant liquid was removed by decantation. m e solid was washed twice using 15~0 cm3 of the isoparaffin fraction at ambient temperature for each wash. After ~he second wash, most of the residual liquid was removed by forcing it through a glass tube at the lower end of which was located a sintered glass frit. The washed solid was finally suspended in one litre of the isoparaffin fraction at ambient temperature. The product obtained will hereafter be identified as TMC-IX.
In the foregoing procedure in step a), one millimole of trichloro ilane was used for each gramme of alumina (which contained appxoximately one millimole of reactive sites per gramme~, in st~p b), 0.5 millimole of magnesium dibutyl was used for each gramme of alumina, and in step c), 0.17 millimole of titanium tetrachloride was used for each gramme of alumina.

~.410YI~

X Preparation of transition metal reaction product a) Reaction with alumina and phosphorus tri hloride 49.3 ~ of the alumina dried as described in treatment A) were ~uspended in 300 cm3 o the S i30para~in raction in a two-litre jacketted reaction ves~el provided with a stirrer. 4.5 cm3 o phosphorus trichloride were added to the suspension. The m~xture was then stirred at ambient temperature (about 20C) or four hours. The mixture was allowed to settle, the supernatan liquid was removed by decantation and the solid wa~ washed four times by decantation using 1500 cm3 o the isoparaffin fraction at ambient temperature for each wash.
The washed solid was suspended in 1000 cm3 of the isoparaffin fraction at ambient temperature.
b) Treatment with magnesium dibutyl To the mixture from step a) were added 40 cm3 of the magnesium dibutyl solution used in step b) of preparation I. The mixture obtained was stirred for 30 minutes at ambient temperature.
c) Treatment with titanium tetrachloride ~ ~ . .. . . , . . _ _ _ . _ . _ . _ To the reaction mixture fr~m step b) were added 2.75 cm3 of titanium tetrachloride. m e mixture was stirred at ambient temperature for 30 minutes. The mixture was allowed to settle and the supernatant liquid was removed by decantation. The sol.id was washed four times using 1500 cm3 of the isoparaffin fraction at ambient temperature for each wash. ~he solid was finally suspended in 1000 cm3 of the isoparaffin fraction at ambient temperature. The solid reaction product obtained will hereafter be identified as TMC-X.
In the foregoing procedure in step a), one millimole of phosphorus trichloride was used for each gramme o alumina (which contained approximately one millimole of reactive sites per gramme), in step b) 0.5 millimole of 3$ magnesium dibutyl was used for each gramme of alumina, and - 28 - 311~4 in step c), 0.5 millimole of titanium tetrachloride was used ~or each gramme of alumina.
XI Preparation o~ transition metal reaction product a) Reactlon with silica and magnesium dibuty~
146 g o~ the silica dried as described in treatment C) were suspended in 600cm3 of the isoparaffin fraction in a two~litre jacketted reaction ves~el provided with a stirrer. 471 cm3 of the solution of magnesium dibutyl used in step b) of preparation I were added to the suspension. The mixture was then stirred at ambient temperature (about 20C) for four hours. Stirring was stopped, the mixture allowed to settle and the supexnatant liquid waa removed by decantation. The solid was washed six times by decantation using 1500 cm3 o~ the isoparafin raction at ambient temperature for each wash.
b) Treatment with silicon tetrachloride The washed solid from step a) was suspended in 729 cm3 of silicon te~rachloride and a quantity of the isoparaffin fraction was added to give a total volume of the reaction mixture of 1500 cm3. mis mixture was stirred, heated to 80C and maintained at that temperature - for four hours. The mixture was then allowed to settle, the supernatant liquid was decanted off and the solid was waqhed nine times u~ing 1500 cm3 of the isoparaffin fraction at ambient temperature for each wash. After 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.
c) Treatment with titanium tetrachloride .. . ..
The washed solid from step b) was suspended in 1460 cm3 of titanium tetrachloride . The mixture was stirred, heated to 80C and maintained at that temparature for four hours. ~le mixture was allowed to settle, the supernatant liquid was decanted of~ and the solid was washed by decantation six times using 1500 cm3 of the isopara~fin fraction at 80C for each wash and a further our times using 1500 cm3 o the isoparaffin fraction at ambient temperature or each wash. The solid wa~ finally suspended in the isoparafin fraction at ambient temperature to give a total volume of 1500 cm3~ The solid reaction product obtained will hereafter be identified as TMC~XI.
In the foregoing procedure, an excess quantity of each o the reactants, relative to the silica, was used.
The products of prepara~ions I to XI were used to efect the copolymerisation o~ ethylene with a l-olefine monomer as described in the following Examples.

Into a stirred stainless steel autoclave of 30 litres capacity were introduced, under hydrogen at a pressure of 4.2 kg/cm2 gauge, 13 litres o a mixture of hexane and but~ne-l. The mixture also contained 40 millimoles of aluminium trioctyl and 50 ppm by weight of an antistatic agent of the formula C6F13(CH2CH2)gCnH(2n~1) where n a value of rom 16 to 18~ -The contents of the reactor were stirred and heatedup to 80C. The reactox was vented to reduce the pressure. Ethylene was added to give a total pressure of 80 psi gauge ~5.6 kg/cm~ gauge). A titanium-containing component was then added in a quantity to attain, and Rubsequently to maintain, a monitored ethyLene consumption of between 1.0 and 1.5 kg per hour. Ethylene was added at a rate suficient to maintain the pressure of 80 psi gauge (5.6 kg/cm2 gauge). During the reaction, unless otherwise indicated, a 0.1 M solution o~ aluminium trioctyl in hexane was added continuously at a rate of 40 millimoles per hour.

~4~

~ 30 - 31124 The polymerisation was terminated and the polymer product consequently recovered by trans~erring to a ves.~el of ~00 litre~ capacity containing 50 litres of a 0.01 N
aqueous solution o.~ sodium hydroxide and then passing S ~team through the stirred mixture until all o~ the hexane had been evaporated~ The aqueous polymer suspension was then ~iltered and the polymer was dried in a fluid bed drier using hot nitrogen as the fluidising gas.
Further details of the polymerisations, and the re~ults obtained, are set out in Table I.

~ 31 - 31124 . .. . .
:4-- CO ~7 lO a~ N ~J ~ U~ N
F~ r) u~ u~ ul ~ ~r ~ u U) _ ~ i , ____ - .. ~
tn u~ o o o o o o o o o -~ S ~î ~ O ~ O
t~ ~ i ~i r`i ~i N -i ._ .. _ .... __ . _ ~ ~_ ~ 0 _1 ~ In ~ u~ ~g U~ N ~9 0 ~ _ --I O ~ I N
_ .. .-.
~ j~) !~ .c ~ ~ o co d' I~
1~ _ ~ ~ a~ N N N _I
. .. -.~ -- ~
a) I~ l ~ o ~D CO
~ ~ o co a~
o ~ ~ o o o -~ o ~ ~
` a~l ,.. . _. .
~ o E~ ~ _ ~1 ~ 1~ ~ ~ ~ ~ ~ ~ ~ ~ ~
--I ~ _ N N N N N N N N N N
,~ X
H
' . . _ ..
~_ ~r ~ o ~ o o 0 ~ ~ o ~ O ~) O ~ O O ~ O
., 0~ a~
~ ~
~ ~_ u7 ~
Q o u ~ u~ r-l o N ~ i C~ 11-~ H ~ ~ H H 1-1 X X H
5 IY ~2 H H ~ ~ H l--I X
.._____ .._ ~ _.

~ ~05 0 --I N ~ ~ In ~ 1` 0 Ci~ O
. -- ~_ ~

Notes to Table 1 (a) In the Examples marked *, 200 millimoles of aluminium trioctyl were present in the i~itial reaction mixture and no urther alumini-~ trioctyl was added during the course o the polymerisation.
~b) As defined in Preparations I to XI.
(c) is given as total mM of titanium contained in the product of Preparations I to XI which was added to initiate and maintain the polymerisation.
(d) Expressed as (Wt butene-l) x 100 Wt initial mixture of butene-l plus hexane (e) This is the pressure to which the reactor was vented before adding the ethylene.
(f) MFI is melt flow index measured by ASTM Method D
1238-70 at 190C using a 2.16 kg wei~ht.
(h) Density was measured as described in ASTN 1928/70, Method A, using a density gradient column at 23C.
(i) Figures af~er the decimal point equal minutes, that is l.I0 means 1 hr 10 minutes.
(j) S.Ex. is stress exponent and is given by the relationship.
~10 MFI 5 - Log10 MFI-2.16 Log10 5 - Log10 2.16 2S where MFI 5 is the melt flow index mea~ured as in (f) using a 5kg weight and MFI 2.16 is the melt flow index measured as in (f).

A 20 cm internaL diameter fluidised bed reactor vessel, operated in a continuous manner, was used to produce an ethylene/butene-l copolymer. A reaction mixture comprising ethylene, butene-l and hydrogen was circulated continuously through the bed at a superficial velocity estimated to be about four times the ~09~ :

minimum necessary for fluidisation. In the fluidi3ed bed, the reactlon temperatuxe was controlled at 80C by adjusting the temperature of the ga~ fed to the fluidised bed reactor vessel using a heat exchanger in the S circulating gas loop. Aluminium trioctyl was pumped continuously into the reactor as a 0.25 molar solution in n-hexane. The solid reaction product TMC II 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 by admitting an ethylene/hydrogen mixture through a control valve. Liquid butene-l was pumped into the circulating gas stream so as to maintain a constant composition as determined by 5as Liquid Chromotography.
The polymer formed was removed periodically so as to maintain an essentially constant level in the reactor vessel. m e 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 al~o de-activated the catalyst and alkyl residues~
Further details, together with some characteristics of the polymers obtained, are set out in Table 2.

, _ . U~
~ ~ .~ .
. ~_ ,i ~O ,1 _ _ o~ tn ~ ~ ~ ~q ~
~ ~ ~ ~ ~ ~ ~
n ,~ ~ . s~
u ~n ~ o . ~ s~ o ~ q CD O ~
,~ h--,~3 ~ ~ U
. ,1 ....... _. _ ~ ~ ~ _~ ' ,1 ~ ~ ~ ~ ,~
O a~,Y O~
C~
__ __ ~
Ll o O
_1 ,0 ~ _~
!~ ~n `
O .,~
111 :~
- .. _ _ _ ~ O ~
~ ~ ~ O
O Q)-rl ).1 .,1 ~ ~
~ ~ CO ~ ~q _l a) ~ ~ I ~`I Q~
~ ~ ~1 ~ Cll-- . ~ ,1 0 E1 ,~ ~ o _l tq P~ n~
_ r~ r~
~ ,~
~ ~ ~ 0 O _ ,~ a~ ~
~rl X -- ~ ~U
.,, I . rl ~q ` ~ O w :n ~ _ ~: ~ _ ~
: ` ~ ~ ~ ~ :
` ~ ~ ~ U~ ~ ~ ~
_ ~ r~
r~ s~
~ ~ ~ u~ ~
, ~5 ~`I ~ O ~ 0 la K 13 a~
.- - . .__ . _ ,~ _ ~ ~ ~ ~
H ~ U ,8 -- Sl U~ $
H Q~ 0 ~ Ul Ul ~rl ~ ~ O ~ ~rl ~rl Ul L
C~ . O ~
æ P; ~ ~ o ~ u s E~ ~, ~
_ rn ~ O
X o _l ~ ~ ~ ~
~ ,~z _, Zo ~ X ~' ~L~4~;D9i ~ 35 ~ 31124 XII Preparation of transition metal reaction product a) Reaction with silica and magnesium dibutyl 10.6 g of the silica dried as described in treatment C) were suspended in 100 cm o~ a heptane fraction, essentially all of which had a boiling point in the range 99C up to 102aC ~hereater re~erred to simply as the "heptane fraction") in a 200 cm3 three ne~ked glass flask provided with a glasq frit and a stirrer. 45.1 cm3 of a 0.705 M solution, in the isoparaffin fraction, of the magnesium dibutyl used in step b) of preparation I were added to the suspension. The mixture was stirred, heated to 70C and maintained at that temperature for one hour.
Stirriny was stopped, the mixture was allowed to settle and the suparnatant liquid wa~ removed by filtration. The solid was washed 5 times by filtration using 100 cm3 of the heptane frac~ion at ambient temperature for each wash.
The damp solid was dried at ambient temperature at a pressure of 5 mm of mercury until it became a free flowing powder.
b) Reaction with titanium tetrachloride/carbon .
tetrachloride The dried solid obtained in stage a) was transferred, in portions, through a flexible PVC tube into a similar 200 cm3 three necked glass flask containing a stirred mixture o 72 cm3 of titanium tetrachloride and 28 cm3 of carbon tetrachloride at ambient tempera~ure. The contents of the reaction vessel were then stirred for one hour at ambient temperature. The supernatant liquid was removed by fil ration and the solid was washed 8 times by filtration using 100 cm3 of the heptane fraction at ambient t~mperature for each wash. ~he solid was finally suspended in a total of 500 cm3 o the heptane fraction.
The solid reaction product obtained will hereafter be identified as TMC-XII.

~41~1 XIII Preparation of transition metal reaction ~roduct a) Reaction with silica and magnesium dibutyl The procedure o qtage a) of preparation XII was repeated using 9.81 g of silica and 41.7 cm3 of the magnesium dibutyl solution.
b) Reaction with titanium tetrachloride/carbon tetra-~ ... = .... .. ... . .... _ ... .
chloride mixture The procedure of staye b) of preparation XII wasrepeated u9ing a mixture of 65 cm3 of titanium tetrachloride and 35 cm3 of carbon tetrachloride.
The solid reaction product obtained will hereafter be identiied as TMC-XlII.
XIV Preparation of transition metal reaction product a) Xeaction wlth ~ilica and ma~nesium dibutyl The procedure of stage a) of preparation XII was repeated using 10 g of silica and 42.5 cm3 of the magnesium dibutyl solution.
b) Reaction with titanium tetrachloride/carbon tetra-_ .
chloride _ixture The procedure of stage b) of preparation XII was repeated with the exception tha~, after adding the solid to the liquid mixture, the contents of the reaction vessel were heated up to 80C and maintained at that temperature for four hours. Subsequently, the solid was washed 8 times with the heptane fraction at 80C.
m e solid reaction product obtained will hereafter be identified as TMC-XIV.
XV and XVI Preparation of transition metal reaction products a) Reaction with silica and boron trichloride __ _ Into a 250 cm3, three necked, round-bottom flask provided with a magnetic stirrer were placed 18.64 g of the silica dried as described in treatment C). To one neck of the flask were connected a cold finger containing an acetone/solid carbon dioxid~ mixture. The cold finger ~L:41~9~L

was also connected to a container of boron trichloride~
The whole sy~tem was evacuated to a residual pressure o about 0.1 mm o mercury. The boron trichloride vaporised, aondensed on tha cold finger and dripped into the flask containing the silica.
The contents of the round-bottom flask were agitated for three hours, using the magnetic stirrer and manual haking. During this time the contents of the cold finger were removed and the cold finger was allowed to warm up to ambient temperature. m e boron txichloride container was replaced by a bubbler containing BDH liquid paraffin. At the end of three hours, nitrogen was passed into the round bottomed flask to raise the pressure to atmospheric and the nitrogen was passed through the bubbler for five minutes in order to remove any unreacted boron trichloride ~rom the Rilica.
XVb) Treatment wlth magnesium dib~yl

6.23 g o the solid reaction product rom step a) were placed in a 200 cm3 three necked glass flask provided with a glass frit and a stirrer. 50 cm3 of the heptane fraction were added to the flask followed by 17.2 cm3 of a 0.618 M solution of the magnesium dibutyl in the isoparaffin fraction. m e mixture was stirrer for one hour at ambient temperature. The mixture was filtered, and washed five times using 100 cm3 of the heptane fraction at ambient temperature for each wa~h.
XVc) Treatment with titanium tetrachloride To the solid from step XVb) were added 100 cm3 of tithnium tetrachloride. The mixture was stirred, heated up to 80C and maintained at that temperature for four hours~ me mixture was filtered, washed 8 times using 100 cm3 of the heptane fraction at 80C for each wash and finally suspended in 100 cm3 of the heptane fraction at ambient temperature. The mixture was transferred to a storage vessel and a fur~her 150 cm3 of the heptane fraction were added.

~L

The solid reaction product obtained will hereafter be identified as TMC XV.
XVIb) Treatment with ma~nesium dibutyl The pxocedure described in step XVb) was repeated using 6.81 g o the solid reaction product ~rom step a) and 18.8 cm3 o the magnesium dibutyl solution.
XVIc) Treatment with titanium tetrachloride To the solid from step XVIb) were added 50 cm3 of the heptane fraction and 0.64 cm3 of titanium tetrachloride. m e mixture was stirred for two hours at ambient temperature, filtered, the solid was washed once with 100 cm3 o~ the heptane fraction at ambient temperature and suspended in 100 cm3 of the heptane fraction at ambient temperature. The mixture was transfarred to a storage vessel and a urther 150 cm3 of the heptane fraction were added.
The olid reaction product obtained will hereafter be identified as TMC XVI.
XVII Preparation o transition metal reaction Rroduct a) Reaction with alumina and ma~nesium dibutyl 11.5 g of the alumina dried as described in treatment D) were placed in a 200 cm3 three necked glass flask provided with a glass frit and stirrer. 50 cm3 of the heptane fraction were added and the mixture was stirred.
55.8 cm3 of an 0.618 M solution of the magnesium dibutyl were added and the mixture was stirred for one hour at ambient temperature. m e mixture was filtered~and the solid was washed five times using 100 cm3 of the heptane fraction at ambient temperature for each wash.
b) Treatment of boron trichloride ,~ ~

7.5 cmJ of liquid boron trichloride were evaporated on to the damp solid obtained in step a) using the procedure described in step a) of preparations XV and XVI.
The mixture was allowed to stand for three hours. The solid wa~ washed five times using 100 cm3 of the heptane fraction at ambient temperature or each wash.

~41~91 c) Treatment with titanium tetrachloride _ ", . . .
The solid from step b) was suspended in 100 cm3 of titanium tetrachloride, the mixture was stirred, heated to 80C and maintained at that temperature for four hours.
The mixture was iltered and the solid was washed 8 times using 100 cm3 of the heptane fraction at ambient temperature or each wash. The solid was suspended in 100 cm3 of the heptane fraction, transferred to a storage vessel and a further 150 cm3 of the heptane fraction were added~
The solid reaction product obtained will hereafter be identified as TMC-XVII.
XVIII Pre~?aration of ~ e ~ct a) Reaction with alumina and magnesium dibutyl .
The procedure of step a) of preparation XVII was repeated using 12.91 g of the alumina dried as described in treatment A), 50 cm3 of the heptane fraction and 62.7 cm3 of the magnesium dibutyl solution.
b) Treatment with boro_ichloride The damp solid from step a) was treated with 8~4 cm3 of boron trichlorid~, the procedure otherwise being as described for step b) of preparation XVII.
c) Treatnlent with titanium tetrachloride .
The solid from step b) was treated with titanium tetrachloride and washed using the procedure of step c~ of preparation XVII.
The solid reaction product obtained will hereafter be identified as IMC-XVIII.
XIX Preparation of transition metal reaction product .
a) Reaction with alun:ina and ma~nesium dibutyl The procedure was as described for step a) of preparation XVIII with the exception that 10.72 g of alumina, 50 cm3 of the heptane fraction and 52 cm of the magnesium dibutyl solution were used.

~4~09~ i b) Treatment with boron trichloride The damp solid from step a) was treated with 7.0 cm3 o boron trichloride, the procedure otherwiqe being as described or step b) of preparation XVII.
c) Treatment with titanium tetrachloride .
The solid from step b) wa~ suspended in a solution of 0.6 cm3 of titanium tetrachloride in 100 cm3 of the heptane fraction. ~he mixture wa~ stirred for two hours at ambient temperature, filtered and the solid was washed twice u~ing 100 cm3 of the heptane fràction at ambient temperature for each wash. The solid was suspended in 100 cm3 o the heptane fraction, transferred to a ~torage vessel and a further 150 cm3 of the heptane fraction were added.
The solid reaction product obtained will hereafter be identified as TMC-XIX.
XX Preparation of transition metal reaction product a) Reaction with alumina and magnesium dibutyl 85.3 g of the alumina dried as described in treatment A) were suspended in 870 cm3 of the isoparaffin ~raction in a ~wo litre jacketted reaction vessel provided with a stirrer. 132 cm3 of a 0.646 M ~olution, in the isoparaffin fraction, of the magnesium dibutyl used in step b) of preparation I wexe added to the ~uspension.
The mixture was stirred at ambient temperature for 30 minutes.
b) Treatment with titanium tetrachloride To the stirred suspension from step a) were added 4~7 ~m3 of titanium tetrachloride over a period of four minutes. The mixture was stirred for one hour at ambient temperature. The mixture was allowed to settle and th~
supernatant liquid was removed by decan~ation to give a final total volume of 780 cm3.

c3 Treatment with silicon tatrachloride To the stirred suspension from step b) were added 180 cm3 of silicon tetrachloride. The mixture was ~tirred, heated to 80C and maintained at that temperature for 3 hours. The mixture was allowed to settle and the supernatant liquid Wa5 removed by decantation. The solid was wa~hed 9 times using one litre of the isoparaffin fraction at ambient temperature for each wash. The solid was finally suspended in 850 cm3 o the isoparaffin ~raction at ambient temperature.
The solid reaction product obtained will hereafter be identified as TMC-XX.
In the foregoing procedure in step XXa), one millimole of magnesium dibutyl was used for each gramme of alumina, in step XXb), 0.5 millimole of titanium tetrachloride was used for each gramme of alumina and in step XXc), an excess quantity o silicon tetrachloride, relative to the reactive sites on the alumina, wa~ used.

The products of preparations XII to XX were used to effect the copolymerisation of ethylene and butene-l using the procedure described for E~ample~ 1 to 10.
Further details of the polymerisations, and the results obtained, are set out in Table 3.

~ ~ l o o o a) -- O OOD ~ O ~~9 _1 _1 ~ ~~ ~ '.
~_ ~:~
_ ~
_ _ ~ _ . ~ ,~
~~ ~ a n . . .. ~z;
._, ~ l : U~ . ~ ~
__ _ . .
$ a) ~
~' o co ~ D Q~
. ~ S~ u~ O O ~ ~ ~ ~ X
a ~ ~ , ~ o ~1 ~o~ a~ .~
~1 . .. .. . _ I ~

_ o~ D CD CO ~ ~ rl S~ ~
H U~ 9 ~ O U td _l - _~_____A _ _,, ___ _ , . _.__ _ _ __ __ a) E~ O ~U
H
~i ~ H H ~ H H H X ,a 1~ _ H X H ~ j H ~ ^ cq .

_ ~ . .. _ _~ . .. E-~
~1 , IJ _~
E O N ~ d' ~ 1` ~ ~ O a~
~ X _ ~ ~ ~ o ~_ __ _ .
.:
,~:
:

Claims (9)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the production of an ethylene polymer which process comprises contacting ethylene, or a mixture of ethylene and a monomer which is copolymerisable with ethylene, under polymerisation conditions with a catalyst system obtained by mixing together 1) an organic compound of a metal of Group IIA of the Periodic Table or of aluminium, 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; and 2) a reaction product obtained by reacting together reagents consisting of a component I, a component II, a component III, and a component IV, wherein component I is at least one substantially inert solid particulate material having reactive sites, component II is an organic magnesium compound or a complex or mixture of an organic magnesium compound and an aluminium compound, component III is at least one halogen-containing compound selected from hydrogen halides, boron halides, halogens, inter-halogen compounds and halides of elements of Groups IVB, VB and VIB of the Periodic Table, and component IV is titanium tetrachloride.

2. The process of claim 1 in which ethylene is copolymerised with propylene, butene-1, pentene-1, hexene-1 or 4-methylpentene-1.

3. The process of claim 1 in which a mixture of ethylene and another monomer is contacted with the catalyst system, wherein, in the mixture, the molar ratio of ethylene to the other monomer is in the range from 15:1 to 1:1.

4. The process of claim 1 in which polymerisation is effected in the gas phase.

5. The process of claim 1 wherein component 1) of the catalyst system is an aluminium trialkyl.

6. The process of claim 1 wherein component 2) of the catalyst system is the reaction product obtained by reacting together a component I which is an oxide of a metal, including silicon, of Groups I to IV of the Periodic Table; a component II which is a dihydrocarbyl magnesium compound; a component III which is a hydrogen halide, a silicon halide of the formula , a hydrocarbyl halide of the formula , a phosphorus halide, a phosphorus oxyhalide, a boron halide, chlorine or bromine; and a component IV which is titanium tetrachloride, wherein R3 is a hydrogen atom or a hydrocarbon radical;
R5 is the residue obtained by removing one or more hydrogen atoms from a hydrocarbon compound;
Z is a halogen atom other than fluorine;
d is 0 or an integer from 1 up to 3, and e is an integer from 1 up to 10.

7. A process for the production of an ethylene polymer which process comprises contacting ethylene, or a mixture of ethylene and a monomer which is copolymerisable with ethylene, under polymerisation conditions with a catalyst system obtained by mixing together 1) an organic compound of a metal of Group IIA of the Periodic Table or of aluminium, 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; and 2) the reaction product obtained by reacting together reagents consisting of a component I, a component II, a component III, and a component IV, wherein component I is at least one substantially inert solid particulate material having reactive sites, component II is an organic magnesium compound or a complex or mixture of an organic magnesium compound and an aluminium compound, component III is at least one halogen-containing compound selected from hydrogen halides, boron halides, halogens, inter-halogen compounds and halides of elements of Groups IVB, VB and VIB of the Periodic Table, and component IV is titanium tetrachloride and the reaction product which is component 2) of the catalyst system has been obtained either a) by mixing together all of components I, II, III
and IV in a single stage or b) by reacting components II, III and IV with component I in more than one stage subject to the proviso either i) that at least one further component which is component II and/or component IV is added after the addition of component III or ii) the last stage is effected by reaction with component IV.

8. The process of claim 7 wherein component 2) of the catalyst system is the reaction product obtained by reacting components II, III and IV with component I in more than one stage, using an excess of at least one of components II, III or IV, and separating and washing the reaction product at the end of any stage in which an excess is used.

9. The process of claim 7 wherein component 2) of the catalyst system is the reaction product obtained by adding components II, III and IV in turn to component I to give more than one stage and the process is effected without separating the reaction product from the reaction mixture of one stage before adding a further component to effect the next stage.