CA1181733A - Transition metal composition, production and use - Google Patents
Transition metal composition, production and useInfo
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- CA1181733A CA1181733A CA000382188A CA382188A CA1181733A CA 1181733 A CA1181733 A CA 1181733A CA 000382188 A CA000382188 A CA 000382188A CA 382188 A CA382188 A CA 382188A CA 1181733 A CA1181733 A CA 1181733A
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- transition metal
- chloride
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- melt
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Abstract
ABSTRACT OF THE DISCLOSURE:
A transition metal composition has the composition Mo,XpTY'Z where M is a metal of Groups Ib, IIa, IIIb, VIIa or VIII of the Periodic Table, Z is an anion, T is a transition metal of Groups IVA-VIA of the Periodic Table, Y is an anion, Z is a melt-producing compound, m' is greater than zero and less than 100, n' is greater than zero and less than 8(m'+1), and p' is m' x(valency of M) /(valency of X). The compositions of this type may be transformed into a liquid by heating and the hot liquid sprayed and the spray cooled. The spayed material has a useful particle form and may be used as a component of a polymerisation catalyst to polymerise an unsaturated monomer such as ethylene.
A transition metal composition has the composition Mo,XpTY'Z where M is a metal of Groups Ib, IIa, IIIb, VIIa or VIII of the Periodic Table, Z is an anion, T is a transition metal of Groups IVA-VIA of the Periodic Table, Y is an anion, Z is a melt-producing compound, m' is greater than zero and less than 100, n' is greater than zero and less than 8(m'+1), and p' is m' x(valency of M) /(valency of X). The compositions of this type may be transformed into a liquid by heating and the hot liquid sprayed and the spray cooled. The spayed material has a useful particle form and may be used as a component of a polymerisation catalyst to polymerise an unsaturated monomer such as ethylene.
Description
3 ;~173~1 TRANSITION METAL COMPOSITION, PE!~ODUCTION AND l~SE
The present invention relates to transition metal compositions, a process of reating such compositions and the use of such compositions as a component of a polymerisation catalyst to polymerise unsaturated monomers such as ethylene.
The desirability oE obtaining transition metal compositions in the form of spheroidal particles which can be used in a catalyst system to effect the ]0 polymerisation, particularly in the gas phase, oE
unsaturated monomers such as the olefin monomers, to produce spheroidal polymer particles, is well recognised.
British Patent Specification No. 1 434 543 describes the preparation of a catalyst component, in which preparation molten hydrated magnesium chloride is sprayed to form spheroidal particles, which are then partially dehydrated and reacted with a halogen~containing titanium component to form the catalyst component~
We have now found that certain liquid compositions which comprise a transition metal compound and optionally a compound which on heating with the transition metal compound forms a single phase liquid (hereinafter referred to for convenience as "melt producing compound") can be sprayed to form catalyst components in the shape o essentially spheroidal particles, having a diameter which is typically between 1 and 5000 micron. Wh re it is desired to obtain a catalyst componPnt in the form of essentially spheroidal particles which comprises a transition metal compound and a non-transition metal compound, the process of the present invention affords gr~ater control of the ratio of transition metal to non-transition metal than the melt process used hitherto and a~oids the dificulties associated with the reacting of particles with a transition metal compound, such as titanium tetrachloride. The e~sentially spheroidal ~h~
The present invention relates to transition metal compositions, a process of reating such compositions and the use of such compositions as a component of a polymerisation catalyst to polymerise unsaturated monomers such as ethylene.
The desirability oE obtaining transition metal compositions in the form of spheroidal particles which can be used in a catalyst system to effect the ]0 polymerisation, particularly in the gas phase, oE
unsaturated monomers such as the olefin monomers, to produce spheroidal polymer particles, is well recognised.
British Patent Specification No. 1 434 543 describes the preparation of a catalyst component, in which preparation molten hydrated magnesium chloride is sprayed to form spheroidal particles, which are then partially dehydrated and reacted with a halogen~containing titanium component to form the catalyst component~
We have now found that certain liquid compositions which comprise a transition metal compound and optionally a compound which on heating with the transition metal compound forms a single phase liquid (hereinafter referred to for convenience as "melt producing compound") can be sprayed to form catalyst components in the shape o essentially spheroidal particles, having a diameter which is typically between 1 and 5000 micron. Wh re it is desired to obtain a catalyst componPnt in the form of essentially spheroidal particles which comprises a transition metal compound and a non-transition metal compound, the process of the present invention affords gr~ater control of the ratio of transition metal to non-transition metal than the melt process used hitherto and a~oids the dificulties associated with the reacting of particles with a transition metal compound, such as titanium tetrachloride. The e~sentially spheroidal ~h~
- 2 - 31~35 particles prepared by the process of the present in~en-tion when they have certain compositions, e.g. they contain magnesium~ can be converted, by treatment with a suitable Ziegler activator, into olefin polymerisation catalysts hav.ing useful characteristics.
Accordinyly, one aspect of the present invention provides a process for the production of a ~ransition metal compos.ition which process comprises spraying a material which comprises a hot single phase liquid and cooling the spray so formed so as to obtain essentially spheroidal particles characterised in that the said single phase li~uid has a composition represented by the general formula-MmXpTY.nZ (I) where M, where present, represents at least one metal ofGroups Ib, ~Ia, IIIb, VIIa, VIII or ~he lanthanide series of the P~riodic Table, X, where present, represents at least one anion, T represents at least one transition metal of Groups IVA, VA or VIA of the Periodic Table, Y represents at least one of the following atoms or groups: halide, oxyha].ide, amino, alkoxide, thioalkoxide, carboxylate or sulphonate in an amount to satisfy the valency which T has in the composition., Z, where present, represents at least one melt-producing compound which, on heating with the transition metal compound TY, forms a single phase liquid, m i5 0 or a number less than 100, n is 0 or a number less than 8 (m ~ one), and p is (valency of X) t 7 3 3
Accordinyly, one aspect of the present invention provides a process for the production of a ~ransition metal compos.ition which process comprises spraying a material which comprises a hot single phase liquid and cooling the spray so formed so as to obtain essentially spheroidal particles characterised in that the said single phase li~uid has a composition represented by the general formula-MmXpTY.nZ (I) where M, where present, represents at least one metal ofGroups Ib, ~Ia, IIIb, VIIa, VIII or ~he lanthanide series of the P~riodic Table, X, where present, represents at least one anion, T represents at least one transition metal of Groups IVA, VA or VIA of the Periodic Table, Y represents at least one of the following atoms or groups: halide, oxyha].ide, amino, alkoxide, thioalkoxide, carboxylate or sulphonate in an amount to satisfy the valency which T has in the composition., Z, where present, represents at least one melt-producing compound which, on heating with the transition metal compound TY, forms a single phase liquid, m i5 0 or a number less than 100, n is 0 or a number less than 8 (m ~ one), and p is (valency of X) t 7 3 3
- 3 31435 A second aspe~t of -the present invention provides a solid product in the form of essentially ~pheroiclal particles, which solid proc1uct comprises a complex of general formula (II) Mm,Xp,TYn'Z
whPre M, X, T, Y and Z are as hereinbefore defined, m' is a number which is greatar than ~ero and less than 100;
n' is a number which is greater than zero and less than 8(m' + one); and p' is - ::
(valency of X) with the provisos a) where Z is an alkyl ester of an aromatic acid, m' is more than 5 and n' is more than 0.8tm' + one); or b) where an inert particulate support material is present and Z is an alcohol, m' is more than 6.
The essentially spheroidal particles obtained by the process of the first aspect of the present invention, or which form the solid product of the second aspect of the present invention, typically have an average particle si~e between l and 5000~ preferably between lO and lO0, microns.
Whilst the hot single phase liquid which is used in the process of the present invention may be ~ormed, for example, either by heating a pra~formed adduct o the at least one transition metal compound and the at least one melt-producing compound or by dissolving ~he at least one tran6ition metal compound and the at least one me~al M
compound in the at lea~t one melt producing compound, where a metal M compouncl is used and the melt-producing 1 ~8~3
whPre M, X, T, Y and Z are as hereinbefore defined, m' is a number which is greatar than ~ero and less than 100;
n' is a number which is greater than zero and less than 8(m' + one); and p' is - ::
(valency of X) with the provisos a) where Z is an alkyl ester of an aromatic acid, m' is more than 5 and n' is more than 0.8tm' + one); or b) where an inert particulate support material is present and Z is an alcohol, m' is more than 6.
The essentially spheroidal particles obtained by the process of the first aspect of the present invention, or which form the solid product of the second aspect of the present invention, typically have an average particle si~e between l and 5000~ preferably between lO and lO0, microns.
Whilst the hot single phase liquid which is used in the process of the present invention may be ~ormed, for example, either by heating a pra~formed adduct o the at least one transition metal compound and the at least one melt-producing compound or by dissolving ~he at least one tran6ition metal compound and the at least one me~al M
compound in the at lea~t one melt producing compound, where a metal M compouncl is used and the melt-producing 1 ~8~3
- 4 - 31435 compound is a liquid, and removing 0xcess melt-producing compound, preferably, however, the hot liquid is ormed by hea-ting a mixture of the at least one -transi-tion metal compound, the at least one metal M compound (where it is S used) and the at least one melt-producing compound ~where it i5 used) in the ratio to give a desired composition of general formula I. It will be appreciated that in at least many cases the hot liquid can be regarded as being a melt of the at least one transition metal compound, the optional at least one metal M compound and the optional at least one melt-producing compound.
The temperatur~ of the hot single phase liquid which is used in the proces~ of th~ present invention is in the range 30C to 400C and preferably in the range 80C -to 180C. Where the hot liquid is a melt it can be at a temperature in the range from ~he melting point of the melt to the decomposition temperature of the melt, however, typically, :it is at a temperature in the range from the said meltinq point to 100C above the said melting point and preferably in the range from the said melting point to 20C above the ~aid melting point.
The hot single phase liquid which is used in the process of the presen-t invention is conveniently formed in an autoclave.
The material which is used in the process of the present invention, may, if desired, comprise the hot single phase liquid together with~ for example mixed with, an inert diluent which is a liquid, a meltable solid or a ~olid which is not meltable, such as an aliphatic, aromatic or cycloparaffin hydrocarbon, atactic polypropylene, polyethylene or an inorganic oxide.
However, whilst the presence of a liquid or meltable diluent is not preferred, the presence of ~ solid diluent i8 often preferred. By solid diluent we mean a compound, or mixture of compounds, which does not mel-t or dissolve
The temperatur~ of the hot single phase liquid which is used in the proces~ of th~ present invention is in the range 30C to 400C and preferably in the range 80C -to 180C. Where the hot liquid is a melt it can be at a temperature in the range from ~he melting point of the melt to the decomposition temperature of the melt, however, typically, :it is at a temperature in the range from the said meltinq point to 100C above the said melting point and preferably in the range from the said melting point to 20C above the ~aid melting point.
The hot single phase liquid which is used in the process of the presen-t invention is conveniently formed in an autoclave.
The material which is used in the process of the present invention, may, if desired, comprise the hot single phase liquid together with~ for example mixed with, an inert diluent which is a liquid, a meltable solid or a ~olid which is not meltable, such as an aliphatic, aromatic or cycloparaffin hydrocarbon, atactic polypropylene, polyethylene or an inorganic oxide.
However, whilst the presence of a liquid or meltable diluent is not preferred, the presence of ~ solid diluent i8 often preferred. By solid diluent we mean a compound, or mixture of compounds, which does not mel-t or dissolve
- 5 ~ 31435 in the hot single phase liquid used in the process o the present invention and which has an averaye particle size of less than 1 micron and preferably less th~n 0.1 microns.
Examples of suitable solid diluents include o~ides, such 5 as silica, alumina and magnesia. Where a solid diluent i5 used in the process of the present invention the ratio by weight of the solid diluent to the hot single phase liquid is typically in the range 2:1 to lolO0 and preferably in the range 1:1 to 1:4.
The hot single phase liquid which is u~ed in the process of the present invention may, if desired, be in contact with, e.g. mixed with, an inert particulate support material the particles of which typically have diameters of many tens of microns, for example from 5 up to 100 microns. Suitable inert particulate support materials, which may be organic or inorganic, include inter alia silica, alumina, thoria, zirconia and mixtures thereof. However, the presence of an inert particulate support material is not preferred.
The spray which is generated in the process of the present invention may be generated by passing the material which comprises hot single phase liquid through any device which is suitable ~or producing a spray, for example, a nozzle, to orm a spray of liquid particles. The spray is typically generated as a cone spray, which may be hollow or solid, or a fan spray or by pneumatic atomisa-tion or by other mechanisms such as centrifugal force in spinning discs .
The size of the liquid particles in the spray, and hence of the solidified particles, depends inter alia on the viscosity and surEace tension of the material which comprises the hot single phase liquid, the pressure which is used to generate the spray, the nozzle diameter and ~he angle of the spray. For any particular composition simple experiment will readily reveal suitable pressure-nozzle 1 ~8~733 ~ 6 - 31~35 diameter combinations to provide a desired size of particles. In general, the pressure used to generate the spray is from 5 to 100 kg/cm2, the actual pressure used being dependent on, inter alia, the viscosity of the hot liquid, the nozzle diameter and the spray angle. THus, where the material is a hot liquid which comprises magnesium chloride, titanium trichloride and methanol and it is desired to form particles of mean diameter about 80 microns we have found that a pressure of about 30 kg/cm2 gauge and a nozzle diameter of about 0~5 millimetres are suitable.
The liquid particles in the spray are solidified in an inert gaseous atmosphere, for example nitrogen, or in a cold inert liquid, for example, a hydrocarbon.
Preferably the particles are solidiied in a gaseous atmosphere, since this increases their sphericity. Where the gaseous atmosphere is above an inert liquid in which the solid essentially spheroidal particles are cooled fur-ther, the solid essentially spheroidal particles can be recovered therefrom, for example, by filtration.
In general formula (I), preferably m is in the range 5 to 50. Transition metal compositions of the present invention iIl which m is less than 5 and in which no solid diluent i8 present tend, when used as a catalyst component .
in the gas phase fluidised bed polymerisation of ethylene, to cause control problems associated with localised overheating. Transition metal compositions of the present invention in which m is more t~an 50 tend not to have a~equate activity when used as a catalyst component in the polymerisation of olefin monomers such as ethylene.
The at least onP metal M, where present, in general formula (I) is preferably copper, magnesium, calcium~
aluminium, iron, cobalt, nickel or mangane~e, more preferably magnesium or a mixture o magnesi~lm either with (a) a Group VII metal, preferably manganese, ~b) a Group I ~1733 VIII metal, preferably nickel or iron or (c) ~ Group Ib metal, preferably copper. Where ît is desired to us~ the transition metal composition in a catalys-t system to obtain polyolefins which have a broad molecular weight distribution, the aforesaid mixtures may usefully be used in the production thereof.
The at least one transition metal in general formula (I) is preferably titanium, zirconium, vanadium, moly~denum, or chromium, more preferably titanium.
It is oten preferred that the at least one transition metal used in the process of the present invention is in less than its maximum valency state since we have found that where the at least one tranaition metal is in its maximum valency state, and where the at least one melt-producing compound is an alcohol t there is a tendency for chemical reaction of the alcohol with the at least one transition metal compound to occur in ~he hot liquid to rupture T-Y bonds. ~here such reaction occurs, it may be necessary to treat the particles with a suitable halogen containing compound to form a product which can b~
used as a catalyst component and it is preferred to heat the particles to remove at least partially the alcohol prior to treatment with the halogen-containing compound.
For example, we have found that essentially spheroidal particles prepared by the process of the present invention from a composition which comprises magnesium chloride, titanium tetrachloride and methanol may be heated at 90C, partially to remove methanol, and the resulting particles are treated with a suitable halogen-containing compound, e.g. AlEtl 5C11 5, ancl then activated with an activator for a Ziegler-catalyst system to form a catalyst system having useful propPrties.
The at lea~t one anion X, where present, in general formula (I) is typically a halide, sulpha-te, phospha~e, ~5 alkoxide, or carboxyla~e, e.g~ an acetate, and is pr~Eerably a hali~e, more preferably a chloride.
~ 1~1733 - 8 - 31~35 The at least one transition metal compound which may be used in the process of the present inven-tion includes halides, halo-ox.ides, alkoxides, haloalkoxides, ace-tyl acetonates, long chain carboxylates, e.g. stearates, and polytitanates having the general formula RO ~ Ti(OR)2-0 ~xR
where R is a hydrocarbyl group, e.g. alkyl, aryl, aralkyl or alkaryl and x .is greater than or equal to 2, especially 2 to 10. Preferably the at least one transition metal compound is a halide, more preferably a chloride.
Sultable melt-producing compounds which may be used in the process of the present invention include organic compounds and inorganic compounds. Organic compounds are preferred, or example aliphatic alcohols having, for example, 1 to 12 carbon atoms, such as methanol, ethanol, isopropanol, octanol, 2-butanol and ethylene glycol;
aromatic alcohols, preferably having 7 to 15 carbon atoms such a benzyl alcohol; phenols, preferably having 6 to 18 carbon atoms such as phenol, cresol and chlorophenol;
aliphatic carboxylic acid esters, preerably having 2 to 30 carbon atoms such as methyl formate, ethyl acetate, butyl acetate, vinyl acetate, methyl acrylate and ethyl laurate; aromatic carboxylic acid esters, preferably having 8 to 30 carbon atoms such as methyl benzoate, ethy~
! 1817~3 benzoate, ethyl p-methylbenzoate and propyl p-hydroxyben-zoate; aliphatic ethers,preferably having 2 to 20 carbon atoms such as ethyl ether, butyl ether, allyl butyl e-ther, methyl undecyl ether and ~myl ether; polyethers; cycllc ethers,preferably having 2 to 20 carbon atoms such as tetxahydrofuran and dioxane; aliphatic amines, preferablv having 1 to 18 carbon atoms such as methylamine, diethyl-amine, tributylamine and octylamine; aromatic amines, pre-~erably having 6 to 18 carbon atoms such as aniline and naphthylamina; aliphatic ketones having 3 to lS carbon atoms such as acetone, -methylisobu~yl-ketone, ethyl butyl ketone and dihexyl ketone; aliphatic aldehydes containing 2 to 12 carbon atoms such as acetaldehyde and propionaldehyde; aliphatic carboxylic acids having 2 to 18 carbon atoms such as acetic acid, ?rop~onic acid, valeric acid and acryli~ acid, aliphatic ni~riles having 2 to 18 c:arbon atoms such as acetonitrile and acrylonl-trile; aromatic nitriles having 7 to 20 carbon atoms such as benzonitrile and phthalonitrile; ~mides having 2 to ~o 18 carbon atoms such as acetamide; phosphines such as triethyl phosphine and triphenyl phosphine; phosphor amides such as hexamethyl phosphoramide; esters o phos~
phoric acid or phosphorous acid, e.g. triphenyl phosphate;
esters of carbonic acid, e.g. ethylene car~onate; hetero-cyclic compounds, e~g. pyridine; and urea. Preferablythe organic compound is an electron donor compound, par-ticularly preferably an aliphatic alcohol having l to 6 carbon atoms and more particularly preferably methanoL.
Suitable inorganic melt-prodllcing compounds include for example, phosphorus oxyhalides such as phos-phorus oxychloride; and sulphur halides and oxyhalides such as sulphur dichloride, sulphuryl chloride and thionyl chloride.
Preferred metal M compounc1/melk-producing com pound adducts which may be used in tha process of thQ
~ ~81~33 - 10 - 31~35 present invention include magnesium halide/alkanol adducts, for example, magnesium chloride/me-thanol, magnesium chloride/ethanol and magnesium choride/
2-b~tanol adducts.
Preferred transition metal compound/melt-producing compound adducts which may be used in t`he process of the present invention include titanium halide/alkanol adducts, for example, titanium trichloride/methanol, titanium trichloride/ethanol, and titanium trichloride/2-butanol adducts.
The solid, essentially spheroidal particles obtained by the process oE the present invention may be used as such as a component of a polymerisation catalyst.
However, it is often preferred to subject the particles to further treatment to effect at leas-t partial removal of the at least one melt-producing compound since such a treatment often increases the voidage of such particles and hence the catalytic activity thereo. Furthermore, we have found that to obtain polymers which have narrow molecular weight distribution it is preferred tha~ in catalyst components of general formula (I) n lies in the range 1.0 (m ~ 1) to 1.8 (m ~ 1) and more preferably is about 1.4 (m + 1), where m has the value hereinbefore ascribed to it.
Where at least partial removal of the at least one melt-producing compound is desired it may be effected, for example, by heating, under vacuum if necessary, or by treating with a suitable compound which will remove either physically or by chernical interaction, all or part of the at least one melt-producing compound without adversely affecting the polymerisation activity o~ catalysts prepared therefrom, for example, by deactivation or over-reduction o~ the at least one transition metal compound.
The at lea~t partial removal of the at least one 35 melt-producing compound, especially when the at lea~t one ~ 18;1733 ~ 31435 melt-producing compound is an alcohol, is preferably carried out by heating, more preferably by hea-ting in a fluiclised bed. Where the at least one melt~producing compound is an alcohol we have found that it is often not possible by heating the essentially spheroidal particles in an inert atmosphere to reduce the concentration of melt-producing compound in the essentially spheroidal particles to below about 0.8 moles per mole of total metal ~ompound (i.e. transition metal compound plus metal M
compound) without at least impairing ~heir capacity to generate active ole~in polymerisation catalysts. However, by heating the essentially spheroidal particles in an atmosphere which contains the anion which is present in the transition metal compound and, where it is present, in the metal M compound, substantially all the melt-producing compound can be removed to leave essentially spheroidal particles which are capable of generating active polymerisation catalysts. For example, where the essentially spheroidal particles con~ist oE a magnesium chloride/titanium trichloride/methanol adduct, substantially all the methanol can be remo~ed therefrom by heating them in an atmosphere whi~h contain~ anhydrous hydrogen chloride.
Where the at least one melt-producing compound is an alcohol, there is an upper limit to the tPmperature at which the alcohol can be removed from the spheroidal particles, which limit is dependent on the composition of the spheroidal particles~ At temperatures above this limit at least partial chemical reaction of the alcohol with the at least o~e transition metal compound and/or the at least one metal M compound, where it is present, occurs with rupture of M-X and/or T-Y bonds. Typically~ this temperature limit lies in the range 100C to 180C and is often above 150C.
I ;~8 ~7.33 Where the at least one melt-producing compound i5 arl alcohol, sultable compounds which are capable of removlng all or part of the at least one melt-producing compound from the essentially spheroidal particles prepared by the process of the present invention include inter alia mPtal hydrocarbyl compounds and reactive halogen-containing compounds. Examples of suitable metal hydrocarbyl compounds, which are used in amounts which are approximately stoichiometric with respect to the amount of melt-producing compound present in the essentially spheroidal particles, include dialkyl magnesiums; alkyl alumini~un halides, e.g. ethyl aluminium sesqui-chloride and diethyl aluminium chloride; alkoxy al~ninium alkyls, for example, having the general formula RlAlOR2 where Rl and R2 are alkyl groups; and alkyl and alkoxysilanes, for example those having the general formula ~ SiH4~y and (R30~ySiH4_y where R3 is alkyl and y is an integer rom 1 to 4. Examples of suitable reactive halogen~containing compounds, which are preferably reactive chlorine-containing compounds, include int~r alia, hydrogen halides, e.g. hydrogen chloride; silicon halides, e.g. silicon tetrachloride, trimethyl silicon monochloride, diethyl silicon di~hloride and monobutyl silicon trichloride; carboxylic acid halides, e.g. acetyl chloride, benzoyl chloride, p-methoxybenzoyl chloride and p-fluorobenzoylchloride;
phosphorus halides, e.g. phosphorusoxytrichloride and phosphorus pentachlsride; phosgene; sulphur halidas, e.g. sulphuryl chloride and thionyl chloride; halides of mineral acids, e.g. boron trichloride; chlorinated polysiloxane~; ammonium hexa~luorosilicate: and antimony pentachloride.
The ratio of tha at least one transition metal of Group~. IVA, VA or VIA to the at least one metal M in the essentially spheroidal par-ticles prepared by the proces~
- 13 - 31*35 of the present invention may be varied. For example, where the at least one transition metal of Groups IVA, VA
or VIA comprises titanium which is presen-t as tl-tanium tetrachloride a proportion of -the titanium tetrachloride may be removed from the essentially spheroidal particles by sublimation, or by dissolution in a suitable solvent, for example, where the essentially spheroidal particles comprise a magnesium chloride/titanium tetrachloride/ethyl acetate adduct a titanium tetrachloride/ethyl acetate adduct may be removed by dissolution in toluene or titanium tetrachloride may b~ removed by d.issolution in hot ethyl acetate. ~Iowever, these variations are not preerred.
Preferred solid products in accordance with the second aspect of the present invention ~re magnesium chloride/titanium chloride/methanol adducts. It is particular].y preferred that the solid procluct is a complex of general formula:~
m2MgC12 . TiClxn2CH30H
wherein m is a n~nber which is in the range from S up to S0, n2 is a nurnber which is greater than zero and less than 8 (m2 + one); and x is 3 or 4~
The magnesium chloride/titanium chloride/methanol adduct may also incorporate at least one further metal halide selected from zirconium chloride, vanadium chloride, manganous chloride, a chloride of iron, nicXel chloride and copper chloride. Preferred materials of this type are those represented by the general formula:
m2~gC12.aMlCly.cTiClx.bTlClr~.n3CH30H
i where m2 and x are as hereinbefore defined, M~ is at least one metal selected from man~anese, iron, nickel and copper' Tl is at least one metal selected from vanadiu~ and æirco~ium;
a is zero or a number having a value less than the value of m2;
(m2 + a) has a value of from 5 up to 50, b i~ zero or a number having a value of less than 5c c is a number which is greater than zero and does not exceed one;
(b + c) has a value of one;
n3 is a number which is greater than zero and less than 8 (m2 + a ~ one);
y is equal to the valency of Ml; and z is 3 or 4, with the proviso that at least one of a and b has a value greater than zero.
It is particularly preferred that n2 has a value in 20 -the range l.C) (m2 ~ one) up to 1.8 (m2 ~ one) and n3 has a value in the range 1.0 (m2 + a ~ one) up to 1.8 (m2 + a + one).
A third aspect of the present invention provides a polymerisation catalyst in the form of essentially Qpheroidal particles of a transition metal composition and a suitable Zlegler activator. Preferably the essentially spheroidal particles are prepared by the process of t~e first aspect of the present invention or are formed of the solid product which is the second aspect of the present invention. The suitable activator is an organometallic compound of Groups X-IV of the Periodic Table and preferably is an organometallic derivative of a matal of Groups IA, IIA, IIB, IIIB or IVB of the Periodic Table, particularly preferably the metal is aluminium and more particularly preferably the activator is a trialkyl 1 1~1733 aluminium. It will be appreciated that suficient of -the said activator is employed to transorm -the metal atoms of the transition metal compound known to be useful in forming Ziegler-Natta catalysts to an active state.
The essentially spheroidal particles of a transition metal composition may be treated with the aforesaid activator by methods known in the art, for example, they may be reacted totally outside or inside the polymerisa-tion vessel in which the catalyst is to be u~ed or activation may be effected partially outside the polymerisation vessel and completed inside the said polymerisation ve~sel.
A four th aspect of the present invention provides a process ~or the polymerisation or copolymerisation of an olefinically unsaturated monomer which process comprises contacting, under polymerisation conditions, at least one olefin monomer with a catalyst in accordance with the present invention.
The term "olefinically unsaturated monomer" is intended to include mono-olefins such as ethylene, propylene an~ 4-methylpentene-1.
The catalysts of the present invention may al~o be used to initiate the copolymerisation of two or more oleinically un~aturated moncmers. For example, ethylene may be copolymerised with a small amount of propylane, butene-l, hexene-l or decene-l, l,3-butadiene or styrene to give polymers which typically have less than 10% w/w of the comonom2r.
~olymerisation processes according to the present invention may be carried out by techniques generally used for polymerisation processes of the type using ~iegler catalyst ~ he choic~ of conditions of pressure and temperature will vary with factors such as the nature of -the monomer and catalyst and whether liquid, e.g. bulk or diluent, or gas pha~e polymerisation i9 used.
For example, when ethylene is polymerised, pressures from sub-atmospheric to several thousand atmospheres may be used. L~w pressure (say from 0.1 to 30 atmospheres) and intermediate pressure (say from 30 to 300 atmospheres) S polymerisation may be carried out using conventional equipment; but very high prPssure polymerisation must be performed usiny suitable specialised reactors and pumping equipment. However, since, generally speaking, the higher the pressure the higher the activity, the use of such techniques may be justified. If very high prassures ar~
used, it is preferred that condition~ are such that the ethylene feed and polyethylene produced are maintained in a single fluid phase, i.e. the press~re should exceed 500 Kg/cm2 preferably 1000 to 3000 Kg/cm2 and the temperture should be greater than 125C, say 140-300C.
This type o process is usually operated in a continuous manner.
A wide range of temperatures may be used, but in general low and intermediate pressure ethylene polymerisations are carried out at temperatures in the range 50-160C.
When the process of the present invention is usad to polymerise propylene, it is preferred to operate under conditions commonly used for the polymerisation of propylene. However, polymerisation of propylene under other conditions, e.g. high pressure, is not axcludea.
It is also within the scopP of our invention to use our cornposition~ to initiate the copolymerisation of ethylene and propylene together and/or with other olefinically unsaturated monomers.
The polymerisation process of the present invention may be carried out in the liquid or gaseous phase (i.a. in the essential absence of a liquid medium~ and preferably in the gaseous phase. Where polymerisation is effected in the liquid phase, and the monomer i~ not liquid under the ~ ~1733 polymerisation conditions, the monomer may be dissolved in a suitable soLvent. Examples of suitable solvents are aliphatic or aromatic hydrocarbons; for instance, pentane, hexane, heptane, octane, decane, benzene, toluene and mixtures thereof~
Polymerisation may be effected either in a batch manner or on a continuous basis, and the transition metal composition of the present invention and the activator therefore may be introduced i.nto the polymeris~tion vessel separately or the transition metal composition and activator may be mixed together before being introduced into the polymerisation reactor.
Preferably, however, the polymerisation process of the present invention is effected as a continuous gas phase process such as a fluid bed process. A fluid bed J~ 33 reactor for use in ~he process of the present invention typically comprises a reaction zone and a so-ca1led velocity reduction zone~ The reacti.on zone comprises a b~d of growing polymer particles, formed polymer particles and a minor amount of ca~alyst particles fluidised by ths continuous flow of the gaseous monomer, and gaseous diluent to remove heat of polymerisation through the reaction zone. A suitable xate oE gas low may be readily determined by simple experiment. Make up of gaseous monomer to the circulating gas stream is at a rate equal to the rate at which gas and partic~late polymer ~xoduct is with-drawn from the reactor and the composition of the gas passing through the reactor is adjusted to maintain an essentially steady state gasaous composition within the reaction zone. The gas leaving the reaction zone is passed to the velocity reduction zone where entrair.ed particles are removed. Finer entrained particles and dust may be removed in a cyclone and/or fine filter.
The said gas is passed through a heat exchanger wherein it is stripped o the heat of polymerisation, compressed in a compressor and then xeturned to the reaction zone.
Chain transfer agents may be used in a polymer-isation process according to the present invention, and when othylene is polymerised their use is normally desirable as the polyethylene produced is of very high molecular weight. Hydrogen may be conveniently used in accordance with usual practice. However, some solvents may act as chain transfer agents.
The polymerisation process of the present inven-tion is preferably ef~ected under an atmosphere free ofoxyg~n, for example under an atmosphere of an inert gas, e.g. nitrogen, or of ths monomer to be polymerised.
It is also pre~erred to effect the process using apparatus and solvents which have ~een carefully freed ~rom impurities, such a-Y oxygen, water and other substances which would otherwise react with the catalysts.
The invention is illustrated by the following Examples.
In the examples hexane and heptane were purified by passage through reduced R3 ll copper catalyst (ex BASF
Aktiengeselschaft) and 5A molecular sieve and finally by sparging with pure nitrogen immediately before use, Ethylene and butene were purified by passage through R3 ll copper catalyst and 5A molecular sieve.
~ydrogen was puriied by passing through a catalytic de lO ,oxygenation unit and 5A molecular sieve.
Examp~e 1 This example lllustrate~ the preparation of a magnesium chloride/tltanium trichloride/methanol adduct according to the present invention.
288 grams (1 mole) of MgCl2.6CH30H (prepared by reacting 48.8 gram~ of magnesium turnings in 1330 mls o~
dried methanol, filtexing the solution, passing 73 grams of dry hyclrogen chloride into the riltrate, cooling the filtrate 1:o -30C, collecting the crystals and drying under vacuum; and shown by analysis to have the formula MyCl2.6CH30H) and 16.5 grams (00~48 moles) of TiCl3.6CH30~ (prepared by dissolving 20 grams of titanium trichloride in 50 mls of dried methanol and e~aporating to dryness;and shown by ~nalysis to have the form~la '.
TiCl3.6CH30H).were mixed and transferred,under nitroyen to a one litre InconeL pressure ~e~se~ fitted with a -stirrer, thermocou~le and a bottom outlet and dlscharge valve assembly. A 0.46 mm diameter jet o~ the hollow cone variety having a spray cone angle of 80 was ~itted under the discharge valve, the complete valve and jet assembly being heated by thermostatically controlled heating tape. The mixed methanol adducts were melted and the temperature stabilised at l40C. The pressure was then raised to 30.6 kg/cm2g with pure nitrogen and the melt sprayed through the jet, which was at l80C, into a nltrc~gen a~mosphere. The product was collected , .
I 18173~
in 3 litres of anhydrous heptane at -40C contalned in a 5 litre nitrogen purged vessel.
The solid product was successively filtered from heptane, dried under vacuum at room temperature and screened to yield a fraction having a particle size distribution between 53 and 106 microns. The particlss were found by analysis to have the composition:
Mg21C142TiC13.125 CH30H
~,2.~
This example illustrates the prepara~ion of a magnesium chloride/titanium trichloride/mathanol adduct according to the present invention.
The procedure of Example 1 was repeated except that 207 grams (1.043 moles) of MyC12.3.22CH30H (prepared by dissolving 400 grams anhydrous magnesium chloride in 3 litres of clried methanol at 60C, filtering -the solu~ion, cooling the filtrate to -30C, collecting the crystals, drying them under vacuum, then heating two 167.4 gram portions of the dried crystals (MgC126CEI30H) in a 62.5 mm fluid bed drier at 65C for 3 hours under a flow of nitrogen ~4 litres per minute) and shown by analysis to have the formula MgC12.3.22C~130H) were u~ed instead of 288 grams of MgC12.6Ca30H and 26.0 grams (0.075 moles) were used instead of 14 grams o~
TiC13.6CH30H and the product, in the form of spheroidal particles, was scre~ned to afford a fraction having a diameter between 45 and 125 microns and a theoretical composition (aYsuming no loss of methanvl) Mgl4C128TiC13.50.8CH30H. Analysis gave Mgl3 7C127.4Ticl3-52-oc~3oH
Example 3 This example illustrates the preparation of a magnesium chloride/~itanium trichloride/zirconium chloride/methanol adduct according to the present .invention~
174.3 grams of MgCl2.6CH30H (prepared as in Example l), 8.3 grams of TiCl3.6CH30H (prepared as in E~ample l) and 19.8 grams of ZrCl2.81(C~3)1.l9--85 C~30H (prepared by dissolving 43.55 grams of zirconium tetrachloridP in 200 mls of dried methanol, refluxing for 2 hours and evaporating to dryness to leave 47.63 grams of a solid which was shown by analysis to have the aforementioned composition~ were mixed and transferred under nitrogen to the presure vessel described in Exampl0 l. A 0.62 mm diameter jet of the hollow cone variety with a spray cone angle of 60 was fitted under the discharge valve, the complete valve and jet assembly being heated by thermostatically controlled heating tape. The mixed methanol adducts were melted and the temperture stabilized at 150C. The pressure was then brought to 27.2 kg/cm2 gauge wit~ pure nitrogen and the melt was sprayed through the jet which had been brought to 180C.
The product was collected in 2.5 litres of anhydrous heptane at -60C contained in a 5 litre ~itrogen purged vessel.
The solid product was successively filtered from the heptane, dri.ed under vacuum at room temperature and screened to yield a catalyst component according to the presen~ invention having a particle size distribution in the range 45 to 106 microns.
Exam~le 4 This exarnple illustrates the preparation of a magnesium chloride/titanium trichloride/vanadium trichloride/
methanol adduct accord.ing to the present invention.
222.4 grams of MgC12.6CH30H (prepared as in Exarnple l), 30.5 grams of VC13.5CH30H ~pr~pared by dissolving 20.48 grams of vanadium trichloride in 100 mls of dried methanol and evaporating to drynes~ -to leave an adduct which was shown by analysis to hav0 the ~18~733 aforementioned composition) and 10.6 grams of TiC13.6CH30EI (prepared as in Example 1) were mixed and melt sprayed under the conditions of Example 3.
Example 5 This example illustrates the preparation of a magnesium chloride/titanium trichloride/manganous chloride/methanol adduct according to the present invention.
108.7 g of MgC12.6CH30H (prepared as in Example 1), 4.39 grams of TiC13.6CH30H (prepared as in Example 1) and 61.9 grams MnC12.6CH30H (prepared by dis~olving 21.2 grams o~ manganese dichloride in 300 mlR of dried methanol and evaporating to dryness to leave a residue which was shown by analysis to have the aforementioned composition) were mixed and melt sprayed using the conditions of Example 1.
~ .
This example illustrates the preparation of a magnesium chloride/titaniwm trichloride/ferric chloride/methanol adduct accorcling to ~he present invention.
A mixture of 209.2 grams of MgC12.6CH30H
(prepared as in Example 1), 10.1 grams of TiC13.6CH30H
(prepared as in Example 1) and 44 mls of a methanol solution containing 20.6 grams of FeCl302CH30H, was evaporated to dryness at room temperature and the residue was melt sprayed using the conditions of Example 1.
This example illus~rates the preparation of a magnesium chloride/titanium trichloride/nickel chloride/methanol adduct accvrding to the present invention.
A mixture of 180.2 grams of MgC12.6CH30H
(prepared as in Example 1), 8.5 grams of TiC13.6CH30H
(E,repared as in Example 1) and a solution o~ 19.7 g NiC12.6CH30H in 100 ml methanol was evaporated to dryne~ at room temperture and the reRidue was melt sprayed using the conditions o~ Example 3.
~ ~31733 E _ ple 8 This example illustrates the preparation of a maynes.ium chloride/titanium trichloride/cupric chloride/methanol adduct according to the present invQntion.
A mixture of 190.6 grams of MgC12.6CH30H
(prepared as in Example 1), 9.9 grams of TiC13.6CH30H
(prepared as in Example 1), and 36.3 grams of CuC12.CH30H (prepared by dissolving 43.8 grams of cupric chloride in 200 mls oE dried methanol at reflux, cooling and evaporating to leave a residue which had the aforementioned compo~ition) was melt sprayed using the conditions of Example 3.
Examples 9-16 These examples illustrate the partial removal by heating of methanol from transition metal compositions prepared by the process of the present invention.
Samples of the spheroidal particles of transition metal compositions prepared in Examples 1 to 8 were dried in a 25 mm f]Luid bed drier at a pre-set temperature under a flow of nitrogen (4 litres/minute). Transition metal compositions in the forrn of sph~roidal particles were recovered and analysed. Details of the procedure and products are given in Table 1~
a~
These examples illustrate the removel of methanol from transition metal compositions of the present invention by trea~nent with acetyl chloride.
General_Procedure Acetyl chloride was added to a slurry of the transition me-tal cornposition in 50 mls of heptane. The mixture was stirred at 90C for 2 hours, cooled, filtered and washed 4 times with 20 ml portions of heptane`to yield a transition metal composition which was analysed.
Details of the quantities used in the procedure and of the products are given in Table 2.
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3 ~1733 This example illustrates -the partial removal of me-thanol rom a magnesium chloride/titanium trichloride/methanol adduct by reaction with an aluminium compound.
80 mls of a 1 molar solution of triethyl aluminium in heptane was added to a slurry of 3.8 grams (containing 77 millimoles of methanol) of the spheroidal transition metal composition prepared in Example 1 in heptane and stirred for 1 hour. The transition metal composition was filtered off, washed twice with 20 ml portions of hexane and dried to yield spheroidal particles (1.5 grams). Analysis of the particles revealed the following concentrations:
Mg 14.8%, Al 5.3%, Ti 1.62%, Cl 48% (Residue 23.48~) which concentrations approximate to the composition-Mgl8.1C136.2Als.g(0CH3)17.4TiC13.9.6 CH30H.Example 24 This example illustrates the partial removal o~ methanol by reaction with an aluminium compound from a magnesium chloride/zirconium tetrachloride/titanium trichloride/
methanol adduct.
81 mls of a 0.49 molar solution o AlEtl 5C11 5 in heptane was added to a slurry of 7 grams of a transition metal composition prepared by heating the particlas prepared in Example 3 at 130~C for 3 hours in a fluid bed drier, in 50 mls of heptane. The mixture was heated at 80C for 2 hours, cooled, filtered and dried to leave
Examples of suitable solid diluents include o~ides, such 5 as silica, alumina and magnesia. Where a solid diluent i5 used in the process of the present invention the ratio by weight of the solid diluent to the hot single phase liquid is typically in the range 2:1 to lolO0 and preferably in the range 1:1 to 1:4.
The hot single phase liquid which is u~ed in the process of the present invention may, if desired, be in contact with, e.g. mixed with, an inert particulate support material the particles of which typically have diameters of many tens of microns, for example from 5 up to 100 microns. Suitable inert particulate support materials, which may be organic or inorganic, include inter alia silica, alumina, thoria, zirconia and mixtures thereof. However, the presence of an inert particulate support material is not preferred.
The spray which is generated in the process of the present invention may be generated by passing the material which comprises hot single phase liquid through any device which is suitable ~or producing a spray, for example, a nozzle, to orm a spray of liquid particles. The spray is typically generated as a cone spray, which may be hollow or solid, or a fan spray or by pneumatic atomisa-tion or by other mechanisms such as centrifugal force in spinning discs .
The size of the liquid particles in the spray, and hence of the solidified particles, depends inter alia on the viscosity and surEace tension of the material which comprises the hot single phase liquid, the pressure which is used to generate the spray, the nozzle diameter and ~he angle of the spray. For any particular composition simple experiment will readily reveal suitable pressure-nozzle 1 ~8~733 ~ 6 - 31~35 diameter combinations to provide a desired size of particles. In general, the pressure used to generate the spray is from 5 to 100 kg/cm2, the actual pressure used being dependent on, inter alia, the viscosity of the hot liquid, the nozzle diameter and the spray angle. THus, where the material is a hot liquid which comprises magnesium chloride, titanium trichloride and methanol and it is desired to form particles of mean diameter about 80 microns we have found that a pressure of about 30 kg/cm2 gauge and a nozzle diameter of about 0~5 millimetres are suitable.
The liquid particles in the spray are solidified in an inert gaseous atmosphere, for example nitrogen, or in a cold inert liquid, for example, a hydrocarbon.
Preferably the particles are solidiied in a gaseous atmosphere, since this increases their sphericity. Where the gaseous atmosphere is above an inert liquid in which the solid essentially spheroidal particles are cooled fur-ther, the solid essentially spheroidal particles can be recovered therefrom, for example, by filtration.
In general formula (I), preferably m is in the range 5 to 50. Transition metal compositions of the present invention iIl which m is less than 5 and in which no solid diluent i8 present tend, when used as a catalyst component .
in the gas phase fluidised bed polymerisation of ethylene, to cause control problems associated with localised overheating. Transition metal compositions of the present invention in which m is more t~an 50 tend not to have a~equate activity when used as a catalyst component in the polymerisation of olefin monomers such as ethylene.
The at least onP metal M, where present, in general formula (I) is preferably copper, magnesium, calcium~
aluminium, iron, cobalt, nickel or mangane~e, more preferably magnesium or a mixture o magnesi~lm either with (a) a Group VII metal, preferably manganese, ~b) a Group I ~1733 VIII metal, preferably nickel or iron or (c) ~ Group Ib metal, preferably copper. Where ît is desired to us~ the transition metal composition in a catalys-t system to obtain polyolefins which have a broad molecular weight distribution, the aforesaid mixtures may usefully be used in the production thereof.
The at least one transition metal in general formula (I) is preferably titanium, zirconium, vanadium, moly~denum, or chromium, more preferably titanium.
It is oten preferred that the at least one transition metal used in the process of the present invention is in less than its maximum valency state since we have found that where the at least one tranaition metal is in its maximum valency state, and where the at least one melt-producing compound is an alcohol t there is a tendency for chemical reaction of the alcohol with the at least one transition metal compound to occur in ~he hot liquid to rupture T-Y bonds. ~here such reaction occurs, it may be necessary to treat the particles with a suitable halogen containing compound to form a product which can b~
used as a catalyst component and it is preferred to heat the particles to remove at least partially the alcohol prior to treatment with the halogen-containing compound.
For example, we have found that essentially spheroidal particles prepared by the process of the present invention from a composition which comprises magnesium chloride, titanium tetrachloride and methanol may be heated at 90C, partially to remove methanol, and the resulting particles are treated with a suitable halogen-containing compound, e.g. AlEtl 5C11 5, ancl then activated with an activator for a Ziegler-catalyst system to form a catalyst system having useful propPrties.
The at lea~t one anion X, where present, in general formula (I) is typically a halide, sulpha-te, phospha~e, ~5 alkoxide, or carboxyla~e, e.g~ an acetate, and is pr~Eerably a hali~e, more preferably a chloride.
~ 1~1733 - 8 - 31~35 The at least one transition metal compound which may be used in the process of the present inven-tion includes halides, halo-ox.ides, alkoxides, haloalkoxides, ace-tyl acetonates, long chain carboxylates, e.g. stearates, and polytitanates having the general formula RO ~ Ti(OR)2-0 ~xR
where R is a hydrocarbyl group, e.g. alkyl, aryl, aralkyl or alkaryl and x .is greater than or equal to 2, especially 2 to 10. Preferably the at least one transition metal compound is a halide, more preferably a chloride.
Sultable melt-producing compounds which may be used in the process of the present invention include organic compounds and inorganic compounds. Organic compounds are preferred, or example aliphatic alcohols having, for example, 1 to 12 carbon atoms, such as methanol, ethanol, isopropanol, octanol, 2-butanol and ethylene glycol;
aromatic alcohols, preferably having 7 to 15 carbon atoms such a benzyl alcohol; phenols, preferably having 6 to 18 carbon atoms such as phenol, cresol and chlorophenol;
aliphatic carboxylic acid esters, preerably having 2 to 30 carbon atoms such as methyl formate, ethyl acetate, butyl acetate, vinyl acetate, methyl acrylate and ethyl laurate; aromatic carboxylic acid esters, preferably having 8 to 30 carbon atoms such as methyl benzoate, ethy~
! 1817~3 benzoate, ethyl p-methylbenzoate and propyl p-hydroxyben-zoate; aliphatic ethers,preferably having 2 to 20 carbon atoms such as ethyl ether, butyl ether, allyl butyl e-ther, methyl undecyl ether and ~myl ether; polyethers; cycllc ethers,preferably having 2 to 20 carbon atoms such as tetxahydrofuran and dioxane; aliphatic amines, preferablv having 1 to 18 carbon atoms such as methylamine, diethyl-amine, tributylamine and octylamine; aromatic amines, pre-~erably having 6 to 18 carbon atoms such as aniline and naphthylamina; aliphatic ketones having 3 to lS carbon atoms such as acetone, -methylisobu~yl-ketone, ethyl butyl ketone and dihexyl ketone; aliphatic aldehydes containing 2 to 12 carbon atoms such as acetaldehyde and propionaldehyde; aliphatic carboxylic acids having 2 to 18 carbon atoms such as acetic acid, ?rop~onic acid, valeric acid and acryli~ acid, aliphatic ni~riles having 2 to 18 c:arbon atoms such as acetonitrile and acrylonl-trile; aromatic nitriles having 7 to 20 carbon atoms such as benzonitrile and phthalonitrile; ~mides having 2 to ~o 18 carbon atoms such as acetamide; phosphines such as triethyl phosphine and triphenyl phosphine; phosphor amides such as hexamethyl phosphoramide; esters o phos~
phoric acid or phosphorous acid, e.g. triphenyl phosphate;
esters of carbonic acid, e.g. ethylene car~onate; hetero-cyclic compounds, e~g. pyridine; and urea. Preferablythe organic compound is an electron donor compound, par-ticularly preferably an aliphatic alcohol having l to 6 carbon atoms and more particularly preferably methanoL.
Suitable inorganic melt-prodllcing compounds include for example, phosphorus oxyhalides such as phos-phorus oxychloride; and sulphur halides and oxyhalides such as sulphur dichloride, sulphuryl chloride and thionyl chloride.
Preferred metal M compounc1/melk-producing com pound adducts which may be used in tha process of thQ
~ ~81~33 - 10 - 31~35 present invention include magnesium halide/alkanol adducts, for example, magnesium chloride/me-thanol, magnesium chloride/ethanol and magnesium choride/
2-b~tanol adducts.
Preferred transition metal compound/melt-producing compound adducts which may be used in t`he process of the present invention include titanium halide/alkanol adducts, for example, titanium trichloride/methanol, titanium trichloride/ethanol, and titanium trichloride/2-butanol adducts.
The solid, essentially spheroidal particles obtained by the process oE the present invention may be used as such as a component of a polymerisation catalyst.
However, it is often preferred to subject the particles to further treatment to effect at leas-t partial removal of the at least one melt-producing compound since such a treatment often increases the voidage of such particles and hence the catalytic activity thereo. Furthermore, we have found that to obtain polymers which have narrow molecular weight distribution it is preferred tha~ in catalyst components of general formula (I) n lies in the range 1.0 (m ~ 1) to 1.8 (m ~ 1) and more preferably is about 1.4 (m + 1), where m has the value hereinbefore ascribed to it.
Where at least partial removal of the at least one melt-producing compound is desired it may be effected, for example, by heating, under vacuum if necessary, or by treating with a suitable compound which will remove either physically or by chernical interaction, all or part of the at least one melt-producing compound without adversely affecting the polymerisation activity o~ catalysts prepared therefrom, for example, by deactivation or over-reduction o~ the at least one transition metal compound.
The at lea~t partial removal of the at least one 35 melt-producing compound, especially when the at lea~t one ~ 18;1733 ~ 31435 melt-producing compound is an alcohol, is preferably carried out by heating, more preferably by hea-ting in a fluiclised bed. Where the at least one melt~producing compound is an alcohol we have found that it is often not possible by heating the essentially spheroidal particles in an inert atmosphere to reduce the concentration of melt-producing compound in the essentially spheroidal particles to below about 0.8 moles per mole of total metal ~ompound (i.e. transition metal compound plus metal M
compound) without at least impairing ~heir capacity to generate active ole~in polymerisation catalysts. However, by heating the essentially spheroidal particles in an atmosphere which contains the anion which is present in the transition metal compound and, where it is present, in the metal M compound, substantially all the melt-producing compound can be removed to leave essentially spheroidal particles which are capable of generating active polymerisation catalysts. For example, where the essentially spheroidal particles con~ist oE a magnesium chloride/titanium trichloride/methanol adduct, substantially all the methanol can be remo~ed therefrom by heating them in an atmosphere whi~h contain~ anhydrous hydrogen chloride.
Where the at least one melt-producing compound is an alcohol, there is an upper limit to the tPmperature at which the alcohol can be removed from the spheroidal particles, which limit is dependent on the composition of the spheroidal particles~ At temperatures above this limit at least partial chemical reaction of the alcohol with the at least o~e transition metal compound and/or the at least one metal M compound, where it is present, occurs with rupture of M-X and/or T-Y bonds. Typically~ this temperature limit lies in the range 100C to 180C and is often above 150C.
I ;~8 ~7.33 Where the at least one melt-producing compound i5 arl alcohol, sultable compounds which are capable of removlng all or part of the at least one melt-producing compound from the essentially spheroidal particles prepared by the process of the present invention include inter alia mPtal hydrocarbyl compounds and reactive halogen-containing compounds. Examples of suitable metal hydrocarbyl compounds, which are used in amounts which are approximately stoichiometric with respect to the amount of melt-producing compound present in the essentially spheroidal particles, include dialkyl magnesiums; alkyl alumini~un halides, e.g. ethyl aluminium sesqui-chloride and diethyl aluminium chloride; alkoxy al~ninium alkyls, for example, having the general formula RlAlOR2 where Rl and R2 are alkyl groups; and alkyl and alkoxysilanes, for example those having the general formula ~ SiH4~y and (R30~ySiH4_y where R3 is alkyl and y is an integer rom 1 to 4. Examples of suitable reactive halogen~containing compounds, which are preferably reactive chlorine-containing compounds, include int~r alia, hydrogen halides, e.g. hydrogen chloride; silicon halides, e.g. silicon tetrachloride, trimethyl silicon monochloride, diethyl silicon di~hloride and monobutyl silicon trichloride; carboxylic acid halides, e.g. acetyl chloride, benzoyl chloride, p-methoxybenzoyl chloride and p-fluorobenzoylchloride;
phosphorus halides, e.g. phosphorusoxytrichloride and phosphorus pentachlsride; phosgene; sulphur halidas, e.g. sulphuryl chloride and thionyl chloride; halides of mineral acids, e.g. boron trichloride; chlorinated polysiloxane~; ammonium hexa~luorosilicate: and antimony pentachloride.
The ratio of tha at least one transition metal of Group~. IVA, VA or VIA to the at least one metal M in the essentially spheroidal par-ticles prepared by the proces~
- 13 - 31*35 of the present invention may be varied. For example, where the at least one transition metal of Groups IVA, VA
or VIA comprises titanium which is presen-t as tl-tanium tetrachloride a proportion of -the titanium tetrachloride may be removed from the essentially spheroidal particles by sublimation, or by dissolution in a suitable solvent, for example, where the essentially spheroidal particles comprise a magnesium chloride/titanium tetrachloride/ethyl acetate adduct a titanium tetrachloride/ethyl acetate adduct may be removed by dissolution in toluene or titanium tetrachloride may b~ removed by d.issolution in hot ethyl acetate. ~Iowever, these variations are not preerred.
Preferred solid products in accordance with the second aspect of the present invention ~re magnesium chloride/titanium chloride/methanol adducts. It is particular].y preferred that the solid procluct is a complex of general formula:~
m2MgC12 . TiClxn2CH30H
wherein m is a n~nber which is in the range from S up to S0, n2 is a nurnber which is greater than zero and less than 8 (m2 + one); and x is 3 or 4~
The magnesium chloride/titanium chloride/methanol adduct may also incorporate at least one further metal halide selected from zirconium chloride, vanadium chloride, manganous chloride, a chloride of iron, nicXel chloride and copper chloride. Preferred materials of this type are those represented by the general formula:
m2~gC12.aMlCly.cTiClx.bTlClr~.n3CH30H
i where m2 and x are as hereinbefore defined, M~ is at least one metal selected from man~anese, iron, nickel and copper' Tl is at least one metal selected from vanadiu~ and æirco~ium;
a is zero or a number having a value less than the value of m2;
(m2 + a) has a value of from 5 up to 50, b i~ zero or a number having a value of less than 5c c is a number which is greater than zero and does not exceed one;
(b + c) has a value of one;
n3 is a number which is greater than zero and less than 8 (m2 + a ~ one);
y is equal to the valency of Ml; and z is 3 or 4, with the proviso that at least one of a and b has a value greater than zero.
It is particularly preferred that n2 has a value in 20 -the range l.C) (m2 ~ one) up to 1.8 (m2 ~ one) and n3 has a value in the range 1.0 (m2 + a ~ one) up to 1.8 (m2 + a + one).
A third aspect of the present invention provides a polymerisation catalyst in the form of essentially Qpheroidal particles of a transition metal composition and a suitable Zlegler activator. Preferably the essentially spheroidal particles are prepared by the process of t~e first aspect of the present invention or are formed of the solid product which is the second aspect of the present invention. The suitable activator is an organometallic compound of Groups X-IV of the Periodic Table and preferably is an organometallic derivative of a matal of Groups IA, IIA, IIB, IIIB or IVB of the Periodic Table, particularly preferably the metal is aluminium and more particularly preferably the activator is a trialkyl 1 1~1733 aluminium. It will be appreciated that suficient of -the said activator is employed to transorm -the metal atoms of the transition metal compound known to be useful in forming Ziegler-Natta catalysts to an active state.
The essentially spheroidal particles of a transition metal composition may be treated with the aforesaid activator by methods known in the art, for example, they may be reacted totally outside or inside the polymerisa-tion vessel in which the catalyst is to be u~ed or activation may be effected partially outside the polymerisation vessel and completed inside the said polymerisation ve~sel.
A four th aspect of the present invention provides a process ~or the polymerisation or copolymerisation of an olefinically unsaturated monomer which process comprises contacting, under polymerisation conditions, at least one olefin monomer with a catalyst in accordance with the present invention.
The term "olefinically unsaturated monomer" is intended to include mono-olefins such as ethylene, propylene an~ 4-methylpentene-1.
The catalysts of the present invention may al~o be used to initiate the copolymerisation of two or more oleinically un~aturated moncmers. For example, ethylene may be copolymerised with a small amount of propylane, butene-l, hexene-l or decene-l, l,3-butadiene or styrene to give polymers which typically have less than 10% w/w of the comonom2r.
~olymerisation processes according to the present invention may be carried out by techniques generally used for polymerisation processes of the type using ~iegler catalyst ~ he choic~ of conditions of pressure and temperature will vary with factors such as the nature of -the monomer and catalyst and whether liquid, e.g. bulk or diluent, or gas pha~e polymerisation i9 used.
For example, when ethylene is polymerised, pressures from sub-atmospheric to several thousand atmospheres may be used. L~w pressure (say from 0.1 to 30 atmospheres) and intermediate pressure (say from 30 to 300 atmospheres) S polymerisation may be carried out using conventional equipment; but very high prPssure polymerisation must be performed usiny suitable specialised reactors and pumping equipment. However, since, generally speaking, the higher the pressure the higher the activity, the use of such techniques may be justified. If very high prassures ar~
used, it is preferred that condition~ are such that the ethylene feed and polyethylene produced are maintained in a single fluid phase, i.e. the press~re should exceed 500 Kg/cm2 preferably 1000 to 3000 Kg/cm2 and the temperture should be greater than 125C, say 140-300C.
This type o process is usually operated in a continuous manner.
A wide range of temperatures may be used, but in general low and intermediate pressure ethylene polymerisations are carried out at temperatures in the range 50-160C.
When the process of the present invention is usad to polymerise propylene, it is preferred to operate under conditions commonly used for the polymerisation of propylene. However, polymerisation of propylene under other conditions, e.g. high pressure, is not axcludea.
It is also within the scopP of our invention to use our cornposition~ to initiate the copolymerisation of ethylene and propylene together and/or with other olefinically unsaturated monomers.
The polymerisation process of the present invention may be carried out in the liquid or gaseous phase (i.a. in the essential absence of a liquid medium~ and preferably in the gaseous phase. Where polymerisation is effected in the liquid phase, and the monomer i~ not liquid under the ~ ~1733 polymerisation conditions, the monomer may be dissolved in a suitable soLvent. Examples of suitable solvents are aliphatic or aromatic hydrocarbons; for instance, pentane, hexane, heptane, octane, decane, benzene, toluene and mixtures thereof~
Polymerisation may be effected either in a batch manner or on a continuous basis, and the transition metal composition of the present invention and the activator therefore may be introduced i.nto the polymeris~tion vessel separately or the transition metal composition and activator may be mixed together before being introduced into the polymerisation reactor.
Preferably, however, the polymerisation process of the present invention is effected as a continuous gas phase process such as a fluid bed process. A fluid bed J~ 33 reactor for use in ~he process of the present invention typically comprises a reaction zone and a so-ca1led velocity reduction zone~ The reacti.on zone comprises a b~d of growing polymer particles, formed polymer particles and a minor amount of ca~alyst particles fluidised by ths continuous flow of the gaseous monomer, and gaseous diluent to remove heat of polymerisation through the reaction zone. A suitable xate oE gas low may be readily determined by simple experiment. Make up of gaseous monomer to the circulating gas stream is at a rate equal to the rate at which gas and partic~late polymer ~xoduct is with-drawn from the reactor and the composition of the gas passing through the reactor is adjusted to maintain an essentially steady state gasaous composition within the reaction zone. The gas leaving the reaction zone is passed to the velocity reduction zone where entrair.ed particles are removed. Finer entrained particles and dust may be removed in a cyclone and/or fine filter.
The said gas is passed through a heat exchanger wherein it is stripped o the heat of polymerisation, compressed in a compressor and then xeturned to the reaction zone.
Chain transfer agents may be used in a polymer-isation process according to the present invention, and when othylene is polymerised their use is normally desirable as the polyethylene produced is of very high molecular weight. Hydrogen may be conveniently used in accordance with usual practice. However, some solvents may act as chain transfer agents.
The polymerisation process of the present inven-tion is preferably ef~ected under an atmosphere free ofoxyg~n, for example under an atmosphere of an inert gas, e.g. nitrogen, or of ths monomer to be polymerised.
It is also pre~erred to effect the process using apparatus and solvents which have ~een carefully freed ~rom impurities, such a-Y oxygen, water and other substances which would otherwise react with the catalysts.
The invention is illustrated by the following Examples.
In the examples hexane and heptane were purified by passage through reduced R3 ll copper catalyst (ex BASF
Aktiengeselschaft) and 5A molecular sieve and finally by sparging with pure nitrogen immediately before use, Ethylene and butene were purified by passage through R3 ll copper catalyst and 5A molecular sieve.
~ydrogen was puriied by passing through a catalytic de lO ,oxygenation unit and 5A molecular sieve.
Examp~e 1 This example lllustrate~ the preparation of a magnesium chloride/tltanium trichloride/methanol adduct according to the present invention.
288 grams (1 mole) of MgCl2.6CH30H (prepared by reacting 48.8 gram~ of magnesium turnings in 1330 mls o~
dried methanol, filtexing the solution, passing 73 grams of dry hyclrogen chloride into the riltrate, cooling the filtrate 1:o -30C, collecting the crystals and drying under vacuum; and shown by analysis to have the formula MyCl2.6CH30H) and 16.5 grams (00~48 moles) of TiCl3.6CH30~ (prepared by dissolving 20 grams of titanium trichloride in 50 mls of dried methanol and e~aporating to dryness;and shown by ~nalysis to have the form~la '.
TiCl3.6CH30H).were mixed and transferred,under nitroyen to a one litre InconeL pressure ~e~se~ fitted with a -stirrer, thermocou~le and a bottom outlet and dlscharge valve assembly. A 0.46 mm diameter jet o~ the hollow cone variety having a spray cone angle of 80 was ~itted under the discharge valve, the complete valve and jet assembly being heated by thermostatically controlled heating tape. The mixed methanol adducts were melted and the temperature stabilised at l40C. The pressure was then raised to 30.6 kg/cm2g with pure nitrogen and the melt sprayed through the jet, which was at l80C, into a nltrc~gen a~mosphere. The product was collected , .
I 18173~
in 3 litres of anhydrous heptane at -40C contalned in a 5 litre nitrogen purged vessel.
The solid product was successively filtered from heptane, dried under vacuum at room temperature and screened to yield a fraction having a particle size distribution between 53 and 106 microns. The particlss were found by analysis to have the composition:
Mg21C142TiC13.125 CH30H
~,2.~
This example illustrates the prepara~ion of a magnesium chloride/titanium trichloride/mathanol adduct according to the present invention.
The procedure of Example 1 was repeated except that 207 grams (1.043 moles) of MyC12.3.22CH30H (prepared by dissolving 400 grams anhydrous magnesium chloride in 3 litres of clried methanol at 60C, filtering -the solu~ion, cooling the filtrate to -30C, collecting the crystals, drying them under vacuum, then heating two 167.4 gram portions of the dried crystals (MgC126CEI30H) in a 62.5 mm fluid bed drier at 65C for 3 hours under a flow of nitrogen ~4 litres per minute) and shown by analysis to have the formula MgC12.3.22C~130H) were u~ed instead of 288 grams of MgC12.6Ca30H and 26.0 grams (0.075 moles) were used instead of 14 grams o~
TiC13.6CH30H and the product, in the form of spheroidal particles, was scre~ned to afford a fraction having a diameter between 45 and 125 microns and a theoretical composition (aYsuming no loss of methanvl) Mgl4C128TiC13.50.8CH30H. Analysis gave Mgl3 7C127.4Ticl3-52-oc~3oH
Example 3 This example illustrates the preparation of a magnesium chloride/~itanium trichloride/zirconium chloride/methanol adduct according to the present .invention~
174.3 grams of MgCl2.6CH30H (prepared as in Example l), 8.3 grams of TiCl3.6CH30H (prepared as in E~ample l) and 19.8 grams of ZrCl2.81(C~3)1.l9--85 C~30H (prepared by dissolving 43.55 grams of zirconium tetrachloridP in 200 mls of dried methanol, refluxing for 2 hours and evaporating to dryness to leave 47.63 grams of a solid which was shown by analysis to have the aforementioned composition~ were mixed and transferred under nitrogen to the presure vessel described in Exampl0 l. A 0.62 mm diameter jet of the hollow cone variety with a spray cone angle of 60 was fitted under the discharge valve, the complete valve and jet assembly being heated by thermostatically controlled heating tape. The mixed methanol adducts were melted and the temperture stabilized at 150C. The pressure was then brought to 27.2 kg/cm2 gauge wit~ pure nitrogen and the melt was sprayed through the jet which had been brought to 180C.
The product was collected in 2.5 litres of anhydrous heptane at -60C contained in a 5 litre ~itrogen purged vessel.
The solid product was successively filtered from the heptane, dri.ed under vacuum at room temperature and screened to yield a catalyst component according to the presen~ invention having a particle size distribution in the range 45 to 106 microns.
Exam~le 4 This exarnple illustrates the preparation of a magnesium chloride/titanium trichloride/vanadium trichloride/
methanol adduct accord.ing to the present invention.
222.4 grams of MgC12.6CH30H (prepared as in Exarnple l), 30.5 grams of VC13.5CH30H ~pr~pared by dissolving 20.48 grams of vanadium trichloride in 100 mls of dried methanol and evaporating to drynes~ -to leave an adduct which was shown by analysis to hav0 the ~18~733 aforementioned composition) and 10.6 grams of TiC13.6CH30EI (prepared as in Example 1) were mixed and melt sprayed under the conditions of Example 3.
Example 5 This example illustrates the preparation of a magnesium chloride/titanium trichloride/manganous chloride/methanol adduct according to the present invention.
108.7 g of MgC12.6CH30H (prepared as in Example 1), 4.39 grams of TiC13.6CH30H (prepared as in Example 1) and 61.9 grams MnC12.6CH30H (prepared by dis~olving 21.2 grams o~ manganese dichloride in 300 mlR of dried methanol and evaporating to dryness to leave a residue which was shown by analysis to have the aforementioned composition) were mixed and melt sprayed using the conditions of Example 1.
~ .
This example illustrates the preparation of a magnesium chloride/titaniwm trichloride/ferric chloride/methanol adduct accorcling to ~he present invention.
A mixture of 209.2 grams of MgC12.6CH30H
(prepared as in Example 1), 10.1 grams of TiC13.6CH30H
(prepared as in Example 1) and 44 mls of a methanol solution containing 20.6 grams of FeCl302CH30H, was evaporated to dryness at room temperature and the residue was melt sprayed using the conditions of Example 1.
This example illus~rates the preparation of a magnesium chloride/titanium trichloride/nickel chloride/methanol adduct accvrding to the present invention.
A mixture of 180.2 grams of MgC12.6CH30H
(prepared as in Example 1), 8.5 grams of TiC13.6CH30H
(E,repared as in Example 1) and a solution o~ 19.7 g NiC12.6CH30H in 100 ml methanol was evaporated to dryne~ at room temperture and the reRidue was melt sprayed using the conditions o~ Example 3.
~ ~31733 E _ ple 8 This example illustrates the preparation of a maynes.ium chloride/titanium trichloride/cupric chloride/methanol adduct according to the present invQntion.
A mixture of 190.6 grams of MgC12.6CH30H
(prepared as in Example 1), 9.9 grams of TiC13.6CH30H
(prepared as in Example 1), and 36.3 grams of CuC12.CH30H (prepared by dissolving 43.8 grams of cupric chloride in 200 mls oE dried methanol at reflux, cooling and evaporating to leave a residue which had the aforementioned compo~ition) was melt sprayed using the conditions of Example 3.
Examples 9-16 These examples illustrate the partial removal by heating of methanol from transition metal compositions prepared by the process of the present invention.
Samples of the spheroidal particles of transition metal compositions prepared in Examples 1 to 8 were dried in a 25 mm f]Luid bed drier at a pre-set temperature under a flow of nitrogen (4 litres/minute). Transition metal compositions in the forrn of sph~roidal particles were recovered and analysed. Details of the procedure and products are given in Table 1~
a~
These examples illustrate the removel of methanol from transition metal compositions of the present invention by trea~nent with acetyl chloride.
General_Procedure Acetyl chloride was added to a slurry of the transition me-tal cornposition in 50 mls of heptane. The mixture was stirred at 90C for 2 hours, cooled, filtered and washed 4 times with 20 ml portions of heptane`to yield a transition metal composition which was analysed.
Details of the quantities used in the procedure and of the products are given in Table 2.
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3 ~1733 This example illustrates -the partial removal of me-thanol rom a magnesium chloride/titanium trichloride/methanol adduct by reaction with an aluminium compound.
80 mls of a 1 molar solution of triethyl aluminium in heptane was added to a slurry of 3.8 grams (containing 77 millimoles of methanol) of the spheroidal transition metal composition prepared in Example 1 in heptane and stirred for 1 hour. The transition metal composition was filtered off, washed twice with 20 ml portions of hexane and dried to yield spheroidal particles (1.5 grams). Analysis of the particles revealed the following concentrations:
Mg 14.8%, Al 5.3%, Ti 1.62%, Cl 48% (Residue 23.48~) which concentrations approximate to the composition-Mgl8.1C136.2Als.g(0CH3)17.4TiC13.9.6 CH30H.Example 24 This example illustrates the partial removal o~ methanol by reaction with an aluminium compound from a magnesium chloride/zirconium tetrachloride/titanium trichloride/
methanol adduct.
81 mls of a 0.49 molar solution o AlEtl 5C11 5 in heptane was added to a slurry of 7 grams of a transition metal composition prepared by heating the particlas prepared in Example 3 at 130~C for 3 hours in a fluid bed drier, in 50 mls of heptane. The mixture was heated at 80C for 2 hours, cooled, filtered and dried to leave
6.3 grams of a transition metal composition. Analysis of the transition metal composit~on revealed the following concentrations:
Mg 15.69%, Al 1.53%, Ti 1.52%~ Zr 7.1%, Cl 60.9~
(Residue 13.27%) which concentrations approxim~te to tha composition Mg5 gClll 8ZrO.71C12,0~0CH3)0.60T10.29 Clo 87Alo 51cl0.765(ocH3)o 765 2 4 C 3 - 27 3~43 Ex~nple 25 This example illustrates the use of a transi-tion metal oE
maximum valency in the process of the present invention and the preparation of a transition metal composition therefrom.
8.79 mls (0.0~ moles) of titanium tetrachloride and then 76.17 grams (0.8 moles) of anhydrous magnesium chloride were added to 600 mls of methanol and the mixture was heated to give a clear solution. The solution was Pvaporated to dryness to leave 248 grams of a solid residue of theoretical composition Mglocl2oTicl2(OcE~3)2-61 CH30H-The solid residue was transferred to the apparatu~described in Example 1 and was melted and the temperature stabilised at 155~C. The pres~ure was raised to 34 kgm/cm2 gauge with pure nitrogen and the melt was sprayed through the jet, which was at 175C, into a nitrogen atmosphere~ The sprayed particles were collected under anhydrous heptane (3 litres).
The particles were successively filtered from the heptane, dried under vacuum at room temperature and screened to yield a fraction having a particle size between 45 and 120 microns. The particles were found by analysis to have the composition 25 MglO.lC120.1TiC12(0CH3)2-60.5 CH30H.
22 gms of the aforesaid fraction were dried in a 25 mm fluid bed drier at 90C for 3 hours with a 4 litre/minute flow of nitrogen.
42 mls of a 0.49 molar solution of 30 AlEtl 5C11 5 were added to a slurry of 3.2 grams of the dried fraction in 100 mls of heptanP and the mixture wa~ stirred at room temperature for 30 minutes and then at 85C ~or 1 hour. The reaction mixture was ~iltered, washed twice wikh 50 mls of hep-tanP, and dried under vacuum to yield 2.5 grams of a -transition metal
Mg 15.69%, Al 1.53%, Ti 1.52%~ Zr 7.1%, Cl 60.9~
(Residue 13.27%) which concentrations approxim~te to tha composition Mg5 gClll 8ZrO.71C12,0~0CH3)0.60T10.29 Clo 87Alo 51cl0.765(ocH3)o 765 2 4 C 3 - 27 3~43 Ex~nple 25 This example illustrates the use of a transi-tion metal oE
maximum valency in the process of the present invention and the preparation of a transition metal composition therefrom.
8.79 mls (0.0~ moles) of titanium tetrachloride and then 76.17 grams (0.8 moles) of anhydrous magnesium chloride were added to 600 mls of methanol and the mixture was heated to give a clear solution. The solution was Pvaporated to dryness to leave 248 grams of a solid residue of theoretical composition Mglocl2oTicl2(OcE~3)2-61 CH30H-The solid residue was transferred to the apparatu~described in Example 1 and was melted and the temperature stabilised at 155~C. The pres~ure was raised to 34 kgm/cm2 gauge with pure nitrogen and the melt was sprayed through the jet, which was at 175C, into a nitrogen atmosphere~ The sprayed particles were collected under anhydrous heptane (3 litres).
The particles were successively filtered from the heptane, dried under vacuum at room temperature and screened to yield a fraction having a particle size between 45 and 120 microns. The particles were found by analysis to have the composition 25 MglO.lC120.1TiC12(0CH3)2-60.5 CH30H.
22 gms of the aforesaid fraction were dried in a 25 mm fluid bed drier at 90C for 3 hours with a 4 litre/minute flow of nitrogen.
42 mls of a 0.49 molar solution of 30 AlEtl 5C11 5 were added to a slurry of 3.2 grams of the dried fraction in 100 mls of heptanP and the mixture wa~ stirred at room temperature for 30 minutes and then at 85C ~or 1 hour. The reaction mixture was ~iltered, washed twice wikh 50 mls of hep-tanP, and dried under vacuum to yield 2.5 grams of a -transition metal
7 3 3 composition of the present invention. Analysis of -the transition metal composition gave the following concentrations:
Mg, 19.85~, Al, 1.8%; Ti, 3.94~: Cl, 69.4~; residue, 5.00%. These concentrations approximate to the composition:
MglO.lC120.2A10~32Cll.23(0CH3)1.23TiC12 (OCH3)2.
E ~
These e~amples illustrate the use of spheroidal transition metal compositions prepared by a process of the present invention in the preparation of polyolefins.
A stainless steel pressure vessal having a capacity of 3.8 litres was pr~pared by heating it to 100C and evacuating with an efficient vacuum pump. The vessel was cooled to 60C and 2 litres of purified hexane added. The vessel was then sparged at reaction pr~ssure with about 200 litres o~E pure ethylene over a period of 30 minutes to remove any re~sidual moisture and oxygen, after which it was vented, 6 ml of a molar solution of aluminium triethyl in heptane as activator and then the transition metal composition ilS a slurry was injected against a stream of thylene. The vPssel was then sealed and pressurised with hydrogen to 2.0 kg/cm2gauge and then to 10.2 kg/cm2 gauge with ethylene. During pressurisation, 200 mls of butene~l was added from a Klinger gauge. When full reaction pressure (10.2 kg/cm2 gauge3 was reached the vessel was stirred at 1000 rpm and polymerisation commenced. Reaction was allowed to continue for 2 hours at 80C, during which tima ethylene was added as required to maintain reaction pre sure at 10.2 Xg/cm2gauge. After 2 hours, the reactor was vented and cooled.
The copolymer slurry was removed from the autoclave and to thi~ was added 1 litre of de~ionised water and 0.2 wt/vol ~ of sodium di(ethylhexyl) sulphosuccinate (Aerosol Or) calculated on polymer ~lurry, i.e. diluent, 1 ~8~733 -- 29 - 31~35 as a wetting agent. Steam at 100C was then passed into the stirred vessel at about 25 g per minute and the mixture distilled at a temperature of about 60C, distillation being continued until no more organic material s~parated from the distillate. The copolymer product, which was granular in form, was then filtered from the aqueous slurry remaining in the distillation vessel, washed with water and dried under vacuum at approximately 60iC.
Details of the preparation and product are given in Table 3.
In Table 3 _ ._ Fully annealed density was measured as described in ASTM
1928-70, Procedure A, using a density gradient column at 23C and includes a correction for the presence of catalyst residues.
Melt flow index ~MFI~ was measured by the method of ASTM D-1238-70, Procedure A, Condition E using a 2.16 Kg weight at 190C and reported as grams per 10 ~inutes.
Flow raLtio was measured by the method of ASTM
D-1238-70, E'rocedure A, Condition F using a 21.60 Kg weight at 190C and dividing by the MFI measured as deined above.
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Mg, 19.85~, Al, 1.8%; Ti, 3.94~: Cl, 69.4~; residue, 5.00%. These concentrations approximate to the composition:
MglO.lC120.2A10~32Cll.23(0CH3)1.23TiC12 (OCH3)2.
E ~
These e~amples illustrate the use of spheroidal transition metal compositions prepared by a process of the present invention in the preparation of polyolefins.
A stainless steel pressure vessal having a capacity of 3.8 litres was pr~pared by heating it to 100C and evacuating with an efficient vacuum pump. The vessel was cooled to 60C and 2 litres of purified hexane added. The vessel was then sparged at reaction pr~ssure with about 200 litres o~E pure ethylene over a period of 30 minutes to remove any re~sidual moisture and oxygen, after which it was vented, 6 ml of a molar solution of aluminium triethyl in heptane as activator and then the transition metal composition ilS a slurry was injected against a stream of thylene. The vPssel was then sealed and pressurised with hydrogen to 2.0 kg/cm2gauge and then to 10.2 kg/cm2 gauge with ethylene. During pressurisation, 200 mls of butene~l was added from a Klinger gauge. When full reaction pressure (10.2 kg/cm2 gauge3 was reached the vessel was stirred at 1000 rpm and polymerisation commenced. Reaction was allowed to continue for 2 hours at 80C, during which tima ethylene was added as required to maintain reaction pre sure at 10.2 Xg/cm2gauge. After 2 hours, the reactor was vented and cooled.
The copolymer slurry was removed from the autoclave and to thi~ was added 1 litre of de~ionised water and 0.2 wt/vol ~ of sodium di(ethylhexyl) sulphosuccinate (Aerosol Or) calculated on polymer ~lurry, i.e. diluent, 1 ~8~733 -- 29 - 31~35 as a wetting agent. Steam at 100C was then passed into the stirred vessel at about 25 g per minute and the mixture distilled at a temperature of about 60C, distillation being continued until no more organic material s~parated from the distillate. The copolymer product, which was granular in form, was then filtered from the aqueous slurry remaining in the distillation vessel, washed with water and dried under vacuum at approximately 60iC.
Details of the preparation and product are given in Table 3.
In Table 3 _ ._ Fully annealed density was measured as described in ASTM
1928-70, Procedure A, using a density gradient column at 23C and includes a correction for the presence of catalyst residues.
Melt flow index ~MFI~ was measured by the method of ASTM D-1238-70, Procedure A, Condition E using a 2.16 Kg weight at 190C and reported as grams per 10 ~inutes.
Flow raLtio was measured by the method of ASTM
D-1238-70, E'rocedure A, Condition F using a 21.60 Kg weight at 190C and dividing by the MFI measured as deined above.
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Claims (19)
1. A process for the production of a transition metal composition which process comprises spraying a material which comprises a hot single phase liquid and cooling the spray so formed so as to obtain essentially spheroidal particles characterised in that the said single phase liquid has a composition represented by the general formula:
MmXpTY?nZ (I) where M, where present, represents at least one metal of Groups Ib, IIa, IIIb, VIIa, VIII or the lanthanide series of the Periodic Table, X, where present, represents at least one anion, T represents at least one transition metal of Groups IVA, VA or VIA of the Periodic Table, Y represents at least one of the following atoms or groups: halide, oxyhalide, amino, alkoxide, thioalkoxide, carboxylate or sulphonate in an amount to satisfy the valency which T has in the composition, Z, where present, represents at least one melt-producing compound which, on heating with the transition metal compound TY, forms a single phase liquid, m is zero or a number less than 100;
n is zero or a number less than 8 (m + one); and p is
MmXpTY?nZ (I) where M, where present, represents at least one metal of Groups Ib, IIa, IIIb, VIIa, VIII or the lanthanide series of the Periodic Table, X, where present, represents at least one anion, T represents at least one transition metal of Groups IVA, VA or VIA of the Periodic Table, Y represents at least one of the following atoms or groups: halide, oxyhalide, amino, alkoxide, thioalkoxide, carboxylate or sulphonate in an amount to satisfy the valency which T has in the composition, Z, where present, represents at least one melt-producing compound which, on heating with the transition metal compound TY, forms a single phase liquid, m is zero or a number less than 100;
n is zero or a number less than 8 (m + one); and p is
2. A process as claimed in claim 1 wherein the hot single phase liquid is formed by heating a mixture of at least one transition metal compound, at least one metal M
compound and at least one melt-producing compound in the radio to give a composition of formula (I).
compound and at least one melt-producing compound in the radio to give a composition of formula (I).
3. A process as claimed in claim 1 wherein the hot single phase liquid is at a temperature in the range 30°C up to 400°C.
4. A process as claimed in claim 1 or claim 2 where the hot single phase liquid is a melt and is at a temperature in the range from the melting point of the melt to 100°C above the said melting point.
5. A process as claimed in any one of claims 1 to wherein the material which is sprayed comprises the hot single phase liquid together with an inert diluent which is a liquid, a solid which is meltable at the temperature of the hot single phase liquid or a solid which remains unmolten and undissolved at the temperature of the hot single phase liquid.
6. A process as claimed in any one of claims 1 to 3 wherein spraying is effected using a spray nozzle, pneumatic atomization or a spinning disc.
7. A process as claimed in any one of claims 1 to 3 wherein spraying is effected using an elevated pressure of from 5 to 100 kg/cm2 to generate the spray.
8. A process as claimed in any one of claims 1 to 3 wherein the melt-producing compound is in alcohol and the essentially spheroidal particles are treated with a halogen-containing compound; or the essentially spheroidal particles are heated to at least partially remove the alcohol therefrom; or the essentially spheroidal particles are heated to at least partially remove the alcohol therefrom and simultaneously or subsequently are treated with a halogen containing compound.
9. A solid product in the form of essentially spheroidal particles, which solid product comprises complex of general formula Mm,Xp,TYn'Z
where M, represents at least one metal of Groups Ib, IIa, IIIb, VIIa, VIII or the lanthanide series of the Periodic Table, X, represents at least one anion, T represents at least one transition metal of Groups IVA, VA or VIA of the Periodic Table, Y represents at least one of the following atoms or groups: halide, oxyhalide, amino, alkoxide, thioalkoxide, carboxylate or sulphonate in an amount to satisfy the valency which T has in the composition, Z, represents at least one melt-producing compound which, on heating with the transition metal compound TY, forms a single phase liquid, m' is a number which is greater than zero and less than 100, n' is a number which is greater than zero and less than 8(m' + one); and p' is with the provisos a) where Z is an alkyl ester of an aromatic acid, m' is more than 5 and n' is more than 0.8 (m' + one); or b) where an inert particulate support material is present in the solid product and Z is an alcohol, m' is more than 6.
where M, represents at least one metal of Groups Ib, IIa, IIIb, VIIa, VIII or the lanthanide series of the Periodic Table, X, represents at least one anion, T represents at least one transition metal of Groups IVA, VA or VIA of the Periodic Table, Y represents at least one of the following atoms or groups: halide, oxyhalide, amino, alkoxide, thioalkoxide, carboxylate or sulphonate in an amount to satisfy the valency which T has in the composition, Z, represents at least one melt-producing compound which, on heating with the transition metal compound TY, forms a single phase liquid, m' is a number which is greater than zero and less than 100, n' is a number which is greater than zero and less than 8(m' + one); and p' is with the provisos a) where Z is an alkyl ester of an aromatic acid, m' is more than 5 and n' is more than 0.8 (m' + one); or b) where an inert particulate support material is present in the solid product and Z is an alcohol, m' is more than 6.
10. A solid product as claimed in claim 9 wherein M
is at least one of copper, magnesium, calcium, aluminium, iron, cobalt, nickel and manganese.
is at least one of copper, magnesium, calcium, aluminium, iron, cobalt, nickel and manganese.
11. A solid product as claimed in claim 9 wherein T is at least one of titanium, zirconium, vanadium, molybdenum and chromium.
12. A solid product as claimed in any one of claims 9 to 11 where Z is an aliphatic alcohol having 1 to 6 carbon atoms.
13. A magnesium chloride/titanium chloride/
methanol adduct of the general formula:
m2MgCl2?TiClxn2CH3OH
wherein:
m2 is a number which is in the range from 5 up to 50;
n2 is a number which is greater than zero and less than 8 (m2 + one); and is 3 or 4.
methanol adduct of the general formula:
m2MgCl2?TiClxn2CH3OH
wherein:
m2 is a number which is in the range from 5 up to 50;
n2 is a number which is greater than zero and less than 8 (m2 + one); and is 3 or 4.
14. A magnesium chloride/titanium chloride/methanol adduct which incorporates at least one further metal halide selected from zirconium chloride, vanadium chloride, manganous chloride, a chloride o iron, nickel, chloride and copper chloride.
15. A metal halide adduct of the general formula:
m2MgC12.aM1ClycTiC1xbT1Clz.n3CH3OH
wherein M1 is at least one metal selected from manganese, iron, nickel and copper;
T1 is at least one metal selected from vanadium and zirconium;
a is zero or a number having a value less than the value of m2;
b is zero or a number having a value of less than 5c;
c is a number which is greater than zero and does not exceed one;
m2 is a number which is in the range from 5 up to 50;
n3 is a number which is greater than zero and less than 8 (m2 + a + one);
x i8 3 or 4;
y is equal to the valency of M1;
z is 3 or 4;
(m2 + a) has a value of from 5 up to 50; and (b + c) has a value of one;
with the proviso that at least one of a and b has a value of greater than zero.
m2MgC12.aM1ClycTiC1xbT1Clz.n3CH3OH
wherein M1 is at least one metal selected from manganese, iron, nickel and copper;
T1 is at least one metal selected from vanadium and zirconium;
a is zero or a number having a value less than the value of m2;
b is zero or a number having a value of less than 5c;
c is a number which is greater than zero and does not exceed one;
m2 is a number which is in the range from 5 up to 50;
n3 is a number which is greater than zero and less than 8 (m2 + a + one);
x i8 3 or 4;
y is equal to the valency of M1;
z is 3 or 4;
(m2 + a) has a value of from 5 up to 50; and (b + c) has a value of one;
with the proviso that at least one of a and b has a value of greater than zero.
16. A polymerisation catalyst which comprises a) a transition metal composition obtained by the process of Claim 1; and b) a Ziegler activator.
17. A polymerisation catalyst which comprises a) a solid product as claimed in Claim 9; and b) a Ziegler activator.
18. A process for the production of a polymer of an olefinically unsaturated monomer which comprises contacting at least one olefin monomer, under polymerisation conditions, with a polymerisation catalyst as claimed in Claim 16 or Claim 17.
19. A process for the production of a polymer of ethylene which comprises contacting ethylene, or a mixture of ethylene with a minor proportion of a monomer copoly-merisable therewith, under polymerisation conditions, with a polymerisation catalyst as claimed in Claim 16 or Claim 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000382188A CA1181733A (en) | 1981-07-21 | 1981-07-21 | Transition metal composition, production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000382188A CA1181733A (en) | 1981-07-21 | 1981-07-21 | Transition metal composition, production and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1181733A true CA1181733A (en) | 1985-01-29 |
Family
ID=4120491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000382188A Expired CA1181733A (en) | 1981-07-21 | 1981-07-21 | Transition metal composition, production and use |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1181733A (en) |
-
1981
- 1981-07-21 CA CA000382188A patent/CA1181733A/en not_active Expired
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