Transition metal composition and process

The present invention relates to transition metal compositions, the preparation of such compositions and the use of such compositions as a component of a catalyst system for the polymerisation of olefine monomers.
The polymerisation of olefine monomers using the socalled Ziegler-Natta catalysts has been known for a number of years. These catalysts comprise a compound of a transition metal together with an organic compound of a non-transition metal. There have been many proposals to improve the activity and/or stereospecificity of the catalyst system by the use of additional catalyst components or by modifying either the transition metal compound or the non-transition metal compound.
According to the present invention there is provided, as a new composition of matter, a product of the formula:
TiCl.sub.3 (AlR.sub.x X.sub.3-x).sub.n E.sub.a L.sub.b
where
R is a hydrocarbyl group;
X is a halogen atom other than fluorine;
E is an ether or a thioether;
L is an organic sulphur-containing compound of one of the formulae (1), (2) or (3);
x is such that 0.ltoreq.x.ltoreq.3.0;
n is from 0 up to 0.5;
a and b are each, independently, from 0.001 up to 0.50;
formula (1) is ##STR1## formula (2) is ##STR2## formula (3) is ##STR3## where T, or each T is, independently, a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, or arylthio group, or a group --NR.sup.1 R.sup.2, or two groups T can together form a saturated or unsaturated hydrocarbon ring;
Y, or each Y is, independently, a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, or arylthio group, or a group --NR.sup.1 R.sup.2, or two groups Y can together form a saturated or unsaturated hydrocarbon ring; or a group T and a group Y may be replaced by a link between the two phenyl groups attached to the --SO.sub.2 -- group, the linkage being either direct or through a group --O--, --CH.sub.2 --, --NR.sup.1 --, --S-- or --CO--.
Z, or each Z is, independently, a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, or arylthio group, or a group --NR.sup.1 R.sup.2, or two groups Z can together form a saturated or unsaturated hydrocarbon ring;
D, or each D, is independently, a halogen atom, an alkyl, aryl, alkoxy, aryloxy, alkylthio, or arylthio group, or a group --NR.sup.1 R.sup.2 ;
G is --S--, --O--, --NR.sup.2 -- or --CO--;
R.sup.1 is a hydrogen atom or a hydrocarbyl group;
R.sup.2 is a hydrocarbyl group;
R.sup.3 is a hydrocarbyl group or can be a group ##STR4## m, p, q and r are each, independently, an integer from 0 up to 5; and y is a positive integer.
The group R is conveniently a hydrocarbyl group containing from 1 up to 20 carbon atoms and may be an alkyl, aryl, cycloalkyl, alkaryl or aralkyl group. Typically, the group R is an alkyl group containing from 2 up to 10 carbon atoms, for example an ethyl or butyl group.
Typically, X is chlorine and the value of x is such that 0.ltoreq.x.ltoreq.2.0 and is especially about one.
The value of n is preferably greater than 0 and less than 0.3, especially greater than 0 and less than 0.2.
The ether or thioether which is E is a monoether, polyether, monothioether or polythioether which is capable of forming coordination complexes or compounds with aluminium halides or aluminium alkyls, these complexes or compounds being soluble in at least one of the solvents selected from the monoether, polyether, monothioether and polythioether themselves, aromatic and aliphatic hydrocarbons and the halogen-containing derivatives thereof.
The ether or thioether which is E is a compound containing only ether or only thioether groups. The polyether and the polythioether contain at least two ether groups or at least two thioether groups respectively. The ether or thioether may be a compound of the type R.sup.4 --A--R.sup.5 where R.sup.4 and R.sup.5, which may be the same or different, are hydrocarbyl groups containing 1 up to 12 carbon atoms; and A is an oxygen or a sulphur atom.
The groups R.sup.4 and R.sup.5 are conveniently the same and may be alkyl, aryl, alkaryl, aralkyl or cycloalkyl groups. It is preferred that R.sup.4 and R.sup.5 are phenyl groups or particularly alkyl groups containing from 4 up to 6 carbon atoms. Polyethers which may be used as the compound E include 1-methoxy-2-(beta-methoxyethoxy)ethane and 1,2-diphenoxyethane. It is especially preferred that E is di-n-butyl ether or di-isoamyl ether. The compound L is an aromatic sulphone of formula (1); an aromatic sulphonamide of formula (2) or a fused ring system containing a heterocyclic sulphur atom as defined by formula (3). Suitable organic sulphur-containing compounds are disclosed in published German Patent Application No. 2,600,552. The compound L is conveniently diphenyl sulphone, N,N-diethylbenzenesulphonamide or phenoxathiin.
The values of a and b need not be the same and typically will be different. The value of a is conveniently from 0.01 up to 0.2 and the value of b is conveniently from 0.01 up to 0.20.
A particularly preferred composition of matter in accordance with the present invention has the formula:
TiCl.sub.3 (AlR.sup.6.sub.x Cl.sub.3-x).sub.n (R.sup.7.sub.2 O).sub.a L'.sub.b
where
a, b, n and x are all as defined;
R.sup.6 is an alkyl group having from 2 up to 10 carbon atoms;
R.sup.7 is a phenyl group or an alkyl group having from 4 up to 6 carbon atoms; and
L' is diphenyl sulphone or phenoxathiin.
The composition of matter has a relatively low specific surface area. Thus, the specific surface area is typically less than 50 m.sup.2 /g and especially from 1 up to 30 m.sup.2 /g. The term "specific surface area" as used herein is the surface area of one gramme of the product, the surface area having been measured using the technique of BS 4359/1.
The colour of the composition of matter may be from violet to brown and the composition of matter is typically a reddish-brown in colour. The X-ray diffraction spectrum is typically that of the beta-form of titanium trichloride, but lines which are characteristic of the layer lattice forms (for example a line corresponding to a lattice spacing of about 5.9 A) may also be present in the spectrum.
As a further aspect of the present invention there is provided a process for the production of a titanium trichloride-containing composition which process comprises
(1) reducing titanium tetrachloride by reacting the titanium tetrachloride with a reducing agent under conditions to give a titanium trichloride product which includes an associated aluminium compound containing aluminium and chlorine atoms, wherein the titanium trichloride is formed predominantly in the beta-form;
(2) contacting the reduction product with both compound E and compound L, compound L being added after the addition of compound E so that both compound E and compound L are present together, at least part of the contacting being effected at a temperature of at least 60.degree. C. in the presence of at least compound E; and
(3) washing the product obtained with an inert hydrocarbon or inert halohydrocarbon liquid.
The reduction product may be subjected to a thermal treatment at a temperature in the range from 40.degree. C. up to 130.degree. C. for a period of from 5 minutes up to 20 hours, and the thermally treated product may then be subjected to stage (2) of the process.
After step (3), the product may be subjected to an additional treatment in which an aluminium alkyl compound, typically diethyl aluminium chloride, is added, followed by an olefine monomer, typically propylene, conveniently in an amount of 0.1 up to 2.0 grammes for each gramme of the titanium trichloride-containing product.
The various stages of the preparation of the titanium trichloride-containing product are preferably effected in the presence of a suitable inert hydrocarbon liquid which is stirred. This hydrocarbon liquid is conveniently an aliphatic or cycloaliphatic hydrocarbon such as hexane, heptane, decane or dodecane or mixtures thereof.
Suitable reducing agents include organic aluminium compounds of the general formulae
AlR.sub.x' X.sub.3-x' or AlR.sub.x' H.sub.3-x'
wherein
R and X are both as hereinbefore defined and
x' is such that 1.0.ltoreq.x'.ltoreq.3.0; and
using such reducing agents the reduction should be effected in the essential absence of aromatic hydrocarbons. An alternative reducing agent is a compound of the general formula
TiCl.sub.2.2AlCl.sub.3.arene
where "arene" means a compound containing a six-membered hydrocarbon ring which ring contains a completely delocalised double bond system. The term "arene" includes benzene, toluene, xylene, durene and hexamethylbenzene and also compounds such as chlorobenzene. The compound TiCl.sub.2.2AlCl.sub.3.arene is soluble in aromatic liquids and thus reduction using this compound is effected either using a solution of the compound in an aromatic liquid or by grinding the solid compound in the presence of an excess of titanium tetrachloride.
If the reducing agent is an organic aluminium compound, it is conveniently one in which the value of x' is from 1.5 up to 2.0. However, satisfactory products may be obtained when x' has a value of 3.0. The organic aluminium compound may be aluminium triethyl or more preferably diethyl aluminium chloride or ethyl aluminium sesquichloride.
The reduction of the titanium tetrachloride is preferably carried out at a temperature which is below about 80.degree. C. The temperature used depends on the particular reducing agent which is used. Thus, if the reducing agent is an alkyl aluminium sesquihalide, it is preferred to carry out the reduction at a temperature of between -20.degree. C. and +20.degree. C., very conveniently at 0.degree. C. If the reducing agent is a dialkyl aluminium halide, whilst the temperature may be lower, for example as low as -40.degree. C., satisfactory products can be obtained by using temperatures in the same range, that is temperatures in the range from -20.degree. C. up to +20.degree. C., although temperatures of -40.degree. C. up to +10.degree. C. are particularly suitable. If the reducing agent is an aluminium trialkyl, or an organic aluminium hydride, then lower reduction temperatures are preferred, particularly temperatures from -100.degree. C. up to 0.degree. C., especially about -70.degree. C. up to about -40.degree. C. If the reducing agent is an alkyl aluminium dihalide the preferred reduction temperatures are in the range from 0.degree. C. up to 40.degree. C., especially from 10.degree. C. up to 30.degree. C. Using the compound TiCl.sub.2.2AlCl.sub.3.arene as the reducing agent, the reduction may be effected at a temperature of from -80.degree. C. up to +80.degree. C., conveniently in the range from 0.degree. C. up to 40.degree. C.
The quantity of the reducing agent depends on the particular reducing agent which is used. Using an organic aluminium compound the proportion used is typically from 0.1 up to 2.0 moles of the organic aluminium compound for each mole of titanium tetrachloride. Using a dialkyl aluminium halide, or a material such as an aluminium sesquihalide which may be regarded as containing a proportion of a dialkyl aluminium halide, the preferred proportions of the organic aluminium compound are from 0.5 up to 1.5 moles of dialkyl aluminium halide for each mole of titanium tetrachloride. Using an aluminium trialkyl the preferred proportions are less and are typically in the range from 0.25 up to 0.5 mole for every mole of titanium tetrachloride. Using a compound of the type TiCl.sub.2.2AlCl.sub.3.arene, it is preferred to use equimolar proportions of the two reactants or an excess quantity of titanium tetrachloride.
The solid titanium trichloride-containing product obtained in stage (1) of the process may be separated from the reaction medium and washed several times and finally resuspended in a sample of fresh hydrocarbon liquid. However, it is preferred that stage (2), or the optional thermal treatment stage, is effected in the presence of the reaction medium from stage (1), when the reducing agent is an organic aluminium compound.
In the optional thermal treatment stage, the reduction product is preferably heated to a temperature of at least 60.degree. C. The time of heating is dependent on the temperature used and shorter times are preferably used at higher temperatures. It is preferred that the conditions of temperature and time are such that the heated product contains a small proportion of the layer lattice structure as shown by the X-ray diffraction pattern of this material.
If the optional thermal treatment stage is effected, it is preferred that the heated product is separated from the reaction medium and washed several times before effecting stage (2).
The reduction product is conveniently present as a stirred suspension in an inert liquid medium when it is contacted with compound E and with compound L. It is preferred that both compound E and compound L are contacted with the reduction product at the temperature of at least 60.degree. C. Compound E, and possibly compound L also, may be added to the reduction product at ambient temperature and the mixture heated to the temperature of at least 60.degree. C. However, it is preferred to heat the reduction product, which may have been subjected to the optional thermal treatment, to the temperature of at least 60.degree. C., and, whilst maintaining that temperature, add, in turn, compound E and compound L. If desired, the contacting with either compound E or compound L may be repeated and using such a procedure the reaction product is preferably separated from the reaction mixture and washed before repeating the contacting with compound E or compound L.
Compound L is conveniently added to the reduction product at least 5 minutes after the addition of compound E has been completed. Compound L can be added to the reduction product several hours, for example 20 hours, after the addition of compound E has been completed. However it is preferred that compound L is added to the reduction product from 30 minutes up to two hours after the addition of compound E has been completed.
The amount of the compound E which is used is preferably from 0.5 up to 3.0 moles for every mole of titanium trichloride present in the heated product and is particularly preferred to use between 0.8 and 2.5 moles per mole of titanium trichloride present in the heated product.
The amount of the compound L which is used is conveniently in the range from 0.01 up to 2.0 moles for each mole of titanium trichloride present in the heated product. It is particularly preferred to use from 0.02 up to 0.5 mole of the compound L, especially from 0.05 up to 0.4 mole of the compound L.
It will be appreciated that the optimum proportions of the compounds L and E will be dependent on the particular compounds used, but these optimum proportions can be determined readily by experiment.
The temperature at which the contacting of the reduction product with the compound E, or both compound E and compound L, is effected is at least 60.degree. C. and may be up to 150.degree. C. It is preferred to use temperatures of at least 80.degree. C. and not more than 130.degree. C. Especially preferred temperatures are in the range from 90.degree. C. up to 120.degree. C. The heating time is preferably at least one hour and conveniently does not exceed 20 hours, particularly at least 2 hours and not more than 10 hours.
If compounds E and L are added to the reduction product at the temperature of at least 60.degree. C., it is preferred that the compound E is added as soon as the reduction product attains the desired temperature.
The new composition of matter of the present invention may be used as one component of an olefine polymerisation catalyst.
Thus, according to a further aspect of the present invention there is provided an olefine polymerisation catalyst comprising: (1) a titanium trichloride-containing material of the type hereinbefore described; and (2) at least one organo-metallic compound of aluminium, or of a non-transition metal of Group IIA of the Periodic Table, or a complex of an organo-metallic compound of a non-transition metal of Group IA or Group IIA of the Periodic Table with an organo-aluminium compound.
The organo-metallic component which is component (2) of the catalyst can be a Grignard reagent which is substantially ether-free or a compound such as diphenyl magnesium. Alternatively, this component can be a complex of an organo-metallic compound of a non-transition metal of Groups IA or IIA with an organo-aluminium compound, for example Mg[Al(C.sub.2 H.sub.5).sub.4 ].sub.2 or lithium aluminium tetraalkyl. It is preferred that component (2) is an organoaluminium compound such as a hydrocarbyl aluminium sulphate, a hydrocarbyl oxyhydrocarbyl aluminium, or particularly a trihydrocarbyl aluminium or dihydrocarbyl aluminium halide or hydride, especially triethylaluminium or diethylaluminium chloride since catalysts including triethylaluminium give a high polymerisation rate whilst catalysts including diethylaluminium chloride give a relatively high percentage yield of the desirable insoluble (isotactic) polymer. A mixture of compounds can be used if desired, for example, a mixture of a trialkyl aluminium and a dialkyl aluminium halide. It may be preferred to use catalysts giving a low level of residual halogen in the polymer product in which case the organometallic component is desirably a halogen-free compound, particularly a trihydrocarbyl aluminium.
The catalyst can also contain, in addition to components (1) and (2), a further component, component (3), which is an organo-Lewis Base compound. This can be any Lewis Base which is effective to alter the activity and/or stereospecificity of a Ziegler catalyst system. A wide range of Lewis Bases have such an effect and these include compounds containing phosphorus and/or nitrogen atoms, oxygen compounds such as ethers, esters, ketones, and alcohols, and their sulphur-containing analogues, and silicon compounds such as silanes and siloxanes. Component (3) may be a sulphone, sulphonamide or a fused-ring heterocyclic sulphur compound of formula (1), (2) or (3). Catalysts containing organo-Lewis Base compounds, or complexes including organo-Lewis Base compounds are disclosed, inter alia, in British Patent Specification Nos. 803,198; 809,717; 880,998; 896,509; 920,118; 921,954; 933,236; 940,125; 966,025; 969,074; 971,248; 1,013,363; 1,017,977; 1,049,723; 1,122,010; 1,150,845; 1,208,815; 1,234,657; 1,324,173; 1,359,328; 1,383,207; 1,423,658; 1,423,659 and 1,423,660; Belgian Patent Specification 693,551; and published German Patent Application No. 2,600,552. It is preferred to use, as the organo-Lewis Base compound, a Lewis Base which contains at least one atom of sulphur, nitrogen and/or phosphorus. Thus preferred organo-Lewis Base compounds, which can be used as the optical component (3) of the catalyst, include sulphur compounds such as diphenylsulphone, secondary or tertiary amines such as dibutylamine or tributylamine, diamines such as N,N,N',N'-tetramethylethylenediamine, and compounds which include both phosphorus and nitrogen atoms, such as hexamethylphosphoric triamide; N,N,N',N'-tetramethylethyl phosphorodiamidate; N,N,N',N',N"-pentamethyl-N"-beta-dimethylaminoethylphosphoric triamide; 2-dimethylamino-1,3-dimethyl-1,3,2-diaza-phospholidine-2-oxide and octamethyl-pyrophosphoramide.
In addition to, or instead of, the organo-Lewis Base compound which is component (3), the catalyst may also include a substituted or unsubstituted polyene (component 4)), which may be an acyclic polyene such as 3-methylheptatriene (1,4,6) or a cyclic polyene such as cyclooctatriene, cyclooctatetraene or cycloheptatriene or derivatives of the cyclic polyenes such as the alkyl- or alkoxy-substituted cyclic polyenes; tropylium salts or complexes, tropolone or tropone.
The proportions of the various catalyst components can be varied widely depending both on the materials used and the absolute concentrations of the components. Typically for each gramme atom of the transition metal which is present in component (1) of the catalyst, there is present at least 0.05, and preferably at least 1.0, and if desired as many as 50 or even more, moles of component (2). In general it is preferred to use not more than 25 moles of the organo-metallic component for each mole of the transition metal catalyst compound present in component (1). If a Lewis Base is included, then for each mole of the transition metal compound there is present from 0.01 up to 10, preferably from 0.1 up to 4, moles of the Lewis Base, provided that the amount of Lewis Base is less than the amount of component (2). Any polyene which is present, plus any Lewis base, should preferably, in total number of moles, be less than the number of moles of component (2). For each mole of component (2), the number of moles of polyene is conveniently in the range 0.01 up to 1.0, especially 0.05 up to 0.5, for example from 0.1 up to 0.2. If both Lewis Base and polyene are included, these can conveniently be used in equimolar proportions but the relative proportions of these components may be varied to give the optimum results.
The catalysts of the present invention are particularly suitable for the polymerisation and copolymerisation of olefine monomers by contacting at least one olefine monomer with a catalyst of the type hereinbefore defined.
More specifically, there is provided a process for the production of a polymer or copolymer of an olefine monomer wherein at least one olefine monomer, or a mixture of at least one olefine monomer and ethylene, is polymerised by contacting the at least one olefine, or mixture thereof with ethylene, under polymerisation conditions with an olefine polymerisation catalyst as hereinbefore defined.
Monomers which can be polymerised by the present process include butene-1, and 4-methylpentene-1 and particularly propylene. These olefines may be copolymerised together or preferably may be copolymerised with ethylene, conveniently using a sequential polymerisation process such as is described in British Patent Nos. 970,478; 970,479 and 1,014,944.
Surprisingly, although component 1) of the catalyst system contains some titanium trichloride in the betaform, it has been found that the process of the present invention can be used for the polymerisation of propylene to give a relatively low proportion of the undesirable soluble polymer. Furthermore, many of the catalyst systems give a high rate of polymerisation.
It is preferred to effect polymerisation using monomers (and diluents when used) which have a high degree of purity, for example a monomer containing less than 5 ppm by weight of water and less than 1 ppm by weight of oxygen. Materials having a high degree of purity can be obtained by processes such as those described in British Patent Specifications Nos. 1,111,493, 1,226,659 and 1,383,611.
Polymerisation can be carried out in the known manner, for example in the presence or absence of an inert diluent such as a suitably purified paraffinic hydrocarbon, in the liquid phase using excess liquid monomer or in the gaseous phase.
If polymerisation is effected in the gaseous phase, it may be effected by introducing the monomer, for example propylene, into the polymerisation vessel as a liquid and operating with conditions of temperature and pressure within the polymerisation vessel which are such that the liquid monomer vaporises, thereby giving an evaporative cooling effect, and essentially all of the polymerisation occurs with the monomer in the gaseous phase. Polymerisation in the gaseous phase is preferably effected using conditions which are such that the monomer is at a temperature and partial pressure which are close to the dew point temperature and pressure for that monomer. Such a procedure is described in more detail in published German Patent Application No. 2,616,356. Polymerisation in the gaseous phase can be effected using any technique suitable for effecting a gas solid reaction such as a fluidised bed reactor system, a stirred bed reactor system or a ribbon blender type of reactor.
Polymerisation may be effected either in a batch manner or on a continuous basis and the catalyst components may be introduced into the polymerisation vessel separately or all the catalyst components may be mixed together before being introduced into the polymerisation reactor.
The polymerisation can be effected in the presence of a chain transfer agent such as hydrogen or a zinc dialkyl, in order to control the molecular weight of the product formed. If hydrogen is used as the chain transfer agent, it is conveniently used in an amount of from 0.01 up to 5.0%, particularly from 0.05 up to 2.0% molar relative to the monomer. The amount of chain transfer agent will be dependent on the polymerisation conditions, especially the temperature, which is typically in the range from 20.degree. C. up to 100.degree. C., preferably from 50.degree. C. up to 85.degree. C.
Using catalysts in accordance with the present invention propylene may be polymerised to give a polymer having a high flexural modulus, for example at least 1.00 GN/m.sup.2, particularly at least 1.30 GN/m.sup.2 and especially up to 1.60 GN/m.sup.2.
Polymers produced by the process of the present invention have a high molecular weight as indicated by the melt flow index measured according to ASTM Test Method D 1238-70, using Condition N (that is a temperature of 190.degree. C. and a weight of 10 kgm). Polymers obtained in accordance with the present invention have a melt flow index of less than 200 and preferred polymers have a melt flow index of less than 100, particularly less than 50, for example between 5 and 50.

Various aspects of the present invention will now be described with reference to the following Examples which are illustrative of the invention. In the Examples, all operations were effected under an atmosphere of nitrogen unless otherwise indicated.
EXAMPLE 1
(A) Reduction of titanium tetrachloride
A solution of 4.21 moles of titanium tetrachloride in 2.2 liters of pure n-heptane was placed in a five-liter nitrogen-purged dry jacketed glass reaction vessel. The solution was cooled to a temperature in the range 8.degree. C. to 10.degree. C. and stirred at 250 rpm. A solution of ethyl aluminium sesquichloride in n-heptane (containing 500 grammes of the sesquichloride for each liter of n-heptane) was added to the contents of the reaction vessel over a period of 90 minutes. The quantity added was sufficient to provide 2.868 moles of the ethyl aluminium sesquichloride (this contained 2.868 moles of diethyl aluminium chloride). The temperature was maintained at 8.degree. C. to 10.degree. C. throughout the addition and the mixture was stirred. At the end of the addition of the sesquichloride solution, the mixture was stirred for a further 4 hours whilst maintaining the temperature of 8.degree. C. to 10.degree. C.
The whole mixture was then heated up to a temperature of 90.degree. C. whilst still stirring. The temperature was maintained at 90.degree. C. for 90 minutes, the mixture was allowed to cool and settle, the supernatant liquid was decanted off and the residual solid was then washed 5 times using 2 liters of purified n-heptane for each wash. The washed product was then suspended in 2.5 liters of heptane and the suspension obtained was then split up into several portions.
(B) Treatment with di-n-butyl ether
A portion equivalent to one fifth of the suspension obtained by the foregoing procedure was then treated with neat di-n-butyl ether in the following manner. A sufficient quantity of the di-n-butyl ether was added to provide 1.1 mole of the ether for each mole of titanium trichloride present in the suspension, which was being stirred. The addition was effected at room temperature and the product was then heated up to 90.degree. C. which temperature was maintained for one hour.
(C) Treatment with phenoxathiin
To the stirred suspension from (B), which was being maintained at 90.degree. C., phenoxathiin was added as a solid in a quantity sufficient to provide 0.3 mole of phenoxathiin for each mole of titanium trichloride present. The temperature of 90.degree. C. was maintained for one hour with stirring. The mixture was then allowed to cool to room temperature and the solid was allowed to settle. The supernatant liquid was decanted off and the solid was then washed 5 times with n-heptane using 500 ml of n-heptane for each wash. A sample of the product was dried and subjected to surface area measurements and to analysis. The remainder of the product was suspended in 500 ml of n-heptane.
EXAMPLE 2
The procedure described in Example 1 was repeated with the exception that, at the end of stage (B), the liquid phase was removed and the solid product was washed 3 times with cold (that is at ambient temperature of about 20.degree. C.) n-heptane using 500 ml of n-heptane for each wash. The solid product was then suspended in 100 ml of n-heptane, the solid phenoxathiin was added at ambient temperature and the mixture was heated up to 90.degree. C., whilst stirring and the temperature of 90.degree. C. maintained for one hour with stirring.
COMPARATIVE EXAMPLE A
Treatment with di-n-butyl ether only
The heat treatment in the presence of di-n-butyl ether described in Example 1 was repeated except that the reaction mixture was maintained at 90.degree. C. for a time of 2 hours. This heated product was then allowed to cool and was washed 5 times with n-heptane and finally resuspended in n-heptane. The washing procedure was also as described in Example 1.
EXAMPLE 3
A quantity of n-heptane supplied by British Drug Houses and conforming to the Institute of Petroleum specification was passed, at room temperature, through a column containing BTS catalyst and a molecular sieve. After this treatment, the only impurity which could be detected was toluene at a level of about 0.01% by volume. This will be referred to as "purified n-heptane".
A further quantity of n-heptane was purged with nitrogen at ambient temperature for one hour. This will be referred to as "purged n-heptane".
The reduction stage was as described in Example (1A) and used the purified n-heptane.
The treatment with di-n-butyl ether was effected on a one-sixth portion of the product from stage (A), the ether being added in an amount of 1.1 moles of ether for each mole of titanium trichloride present and the addition being made when the suspension had attained a temperature of 90.degree. C. After one hour at 90.degree. C., 0.20 mole of diphenyl sulphone was added for each mole of titanium trichloride present in the product from stage (A), and heating at 90.degree. C. was continued for a further hour.
The product obtained was allowed to cool and was washed as in Example 1. All stages of the preparation, other than the last three washes, were effected using purified n-heptane. The last three washes were effected using purged n-heptane and the product was suspended in purged n-heptane.
During this preparation the suspension could be handled easily and there were no problems of agglomeration of the solid particles. In the process of Examples 1 and 2 there were agglomeration problems and these problems were reduced when the temperature of 90.degree. C. was attained.
The product of this Example had a superior particle form compared to the product of Examples 1 and 2, and could be handled more readily than the product of Examples 1 and 2.
EXAMPLE 4
The procedure of Example 3 was repeated except that, in stage (B), di-isoamyl ether was used rather than di-n-butyl ether.
The products of Examples 1 to 4 were subjected to chemical analysis and the surface areas of the products of Examples 1 to 3 were determined.
The results are set out in Table 1.
Table 1______________________________________Analysis E:TiCl.sub.3 S:TiCl.sub.3Product Al:Ti Cl:Ti (molar (molar Surfaceof (atomic (atomic ratio) ratio) AreaExample ratio) ratio) (a) (b) (m.sup.2 /g)______________________________________1 0.247 3.59 1.92 0.143 3.39 9.43 0.081 3.34 0.106 0.11 20.24 0.117 3.33 0.075 0.087______________________________________ Notes to Table 1? (a) Molar ratio of ether (E) to TiCl.sub.3 deduced from ether analysis on solutions of catalyst decomposed in methanol. (b) Molar ratio of diphenyl sulphone (S) to TiCl.sub.3 deduced from sulphone analysis on solutions of catalyst decomposed in methanol.
EXAMPLES 5 to 8
Polymerisations were carried out in a 20 gallon (91 liter) stainless steel autoclave.
64 liters of an aliphatic hydrocarbon diluent (a C.sub.12 fraction having a boiling temperature in the range 170.degree. C. to 180.degree. C.) were charged into the vessel, and degassed at 60.degree. C. for 30 minutes at a pressure of 50 millimeters of mercury. Propylene containing 0.15% by volume of hydrogen, was then admitted to the vessel in an amount to give a pressure of 1 psi (7 kN/m.sup.2) gauge. The diluent was stirred and stirring was continued throughout the following procedures. 0.536 mole of diethyl aluminium chloride, as a 25% by weight solution in the hydrocarbon diluent, was then added to the autoclave followed by 1 liter of the hydrocarbon diluent. 0.134 mole of titanium trichloride (prepared as described in Examples 1 to 4 or Comparative Example A) was added as a suspension of titanium trichloride in the hydrocarbon diluent. 2 liters of the hydrocarbon diluent were then added.
The autoclave was maintained at 60.degree. C. while propylene was passed into the autoclave at a constant rate of 22 pounds per hour (about 10 kilograms per hour). The propylene charge contained 0.15% by volume of hydrogen. A total of 33.5 kilograms of propylene were passed into the autoclave, after which the propylene feed was terminated and the autoclave pressure was allowed to run down to 5 psi (35 kN/m.sup.2) gauge. The residual propylene was then vented off and the polymer suspension passed into a glass-lined vessel. The autoclave was washed with 20 liters of the diluent which was also added to the glass-lined vessel. The contents of the glass-lined vessel were mixed with isopropanol in an amount of 2% by volume relative to the diluent. The mixture was stirred for one hour at 70.degree. C., a mixture of isopropanol and water (containing 10% by volume of water) was added in an amount of 0.6% by volume relative to the diluent and stirring at 70.degree. C. was continued for a further 2 hours.
The polymer suspension was then run into a further vessel containing 40 liters of demineralised water at ambient temperature, and the mixture was stirred for 30 minutes. The aqueous phase was then decanted off and a further 40 liters of demineralised water at ambient temperature were added and the process was repeated. The diluent was then filtered off and the polymer was dried at 100.degree. C. in the fluidised bed using nitrogen as fluidising gas.
The results obtained, which include information on the properties of the polymer formed, are set out in Table 2.
Table 2______________________________________ Yield of solubleEx Form polymeror of (% by wt) P.D. F.M.Comp TiCl.sub.3 Dil Res (g/l) MFI (GN/m.sup.2) ActEx (c) (d) (e) (f) (g) (h) (i)______________________________________5 1 1.5* 5.5* 500* 24* 1.37* 22.1*6 2 1.6* 4.1 500 26 1.40 20.6 2.0B A 5.3* 6.4 294 27 1.33 23.5 6.17 3 2.2* 5.2 513 14.5 1.41 15.9 3.18 4 3.6* 3.9 519 10.5 1.52 10.8 4.4______________________________________ Notes to Table 2? (c) Product of Examples 1 to 4 or Comparative Example A respectively. (d) Polymer dissolved in the diluent determined at the end of the polymerisation after adding the isopropanol, *determined at the end of the polymerisation before adding the isorpropanol. (e) Residual soluble polymer determined by dissolving 1 gramme of solid polymer in 50 ml of the same hydrocarbon diluent as is used for the polymerisation, by heating at 185.degree. C. The solution is cooled to 60.degree. C. and stirred at this temperature for 18 hours. The precipitated polymer is separated by filtration at 60.degree. C., and the proportion of polymer which remains dissolved in the diluent at 60.degree C. is determined by heating the solution to dryness. (f) P.D. is packing density determined by introducing 10 grammes of the polymer powder into a 50 ml flatbottomed graduated tube of 2 cm internal diameter. The powder was compacted by striking the base of the tube against a horizontal surface a total of 30 times. The volume occupied by the polymer powder was then determined. Duplicate measurements were made. (g) The melt flow index (MFI) was measured by ASTM Test Method D 123870, Condition N (190.degree. C. and 10 kg). (h) The flexural modulus (F.M.) was measured using a cantilever beam apparatus as described in Polymer Age, March 1970, pages 57 and 58. The deformation of a test strip at 1% skin strain after 60 seconds at 23.degree. C. and 50% relative humidity was measured. The test strip, which had dimensions of approximately 150 .times. 19 .times. 1.6 mm, was prepared by mixing 23 g of the polymer with 0.1% by weight of antioxidant (`Topanol`CA), and adding the mixture to a Brabender Plasticiser, at 190.degree. C., 30 rpm and under a load of 10 kg to convert it to a crepe The crepe was placed within a template, between aluminum foil and pressed by means of an electric Tangye press at a temperature of 250.degree. C. The pressing was preheated for a period of 6 minutes, under just enough pressure to make the polymer flow across the template, that is an applied force of about 1 ton. After the preheat period, the applied force was raised to 15 tons in 5 ton increments, degassing (that is releasing pressure) every 5 tons. After 5 minutes at 15 tons, the press was cooled by means of air and water for 10 minutes or until room temperature was reached. The placque obtained was then cut into strips of dimensions 150 .times. 19 .times. 1.6 mm. Duplicate strips of each polymer were placed into an annealing oven at 130.degree. C. and after 2 hours at this temperature the heat was switched off and the oven cooled to ambient temperature at 15.degree. C. per hour. (i) Activity (Act) is calculated from the weight of monomer fed per millimole of TiCl.sub.3 in the catalyst during the final hour of the polymerisation for each atmosphere pressure of propylene. The propylene pressure is determined by correcting the total pressure for the presence of inert materials such as nitrogen and propane which are determined by titrating the gas space at the end of the polymerisation with bromine water.
EXAMPLE 9
The product of Example 3 was used to prepare a copolymer of propylene with ethylene.
Polymerisation was effected in a 20 gallon (91 liter) stainless steel autoclave. 64 liters of the hydrocarbon diluent (as used in Examples 5 to 8) were charged into the vessel and degassed at 60.degree. C. for 30 minutes at a pressure of 50 mm Hg. Propylene containing 0.145% by volume of hydrogen was then admitted to the vessel at a rate of 22 lbs/hour in an amount to give a pressure of 1 psi (7 kN/m.sup.2) gauge. A vent on the vessel was opened and the propylene/hydrogen addition was continued for a further 5 minutes, the pressure in the autoclave being maintained at 1 psi gauge throughout. The vent was then closed and the addition of the propylene/hydrogen mixture stopped. The contents of the vessel were stirred throughout the following procedures. 0.536 mole of diethyl aluminium chloride, as a 25% by weight solution in the hydrocarbon diluent, was added to the autoclave, followed by 1 liter of the hydrocarbon diluent. 0.134 mole of the product of Example 3 was added as a suspension of the titanium trichloride in the hydrocarbon diluent. This was washed in with a further 1 liter of hydrocarbon diluent.
The autoclave temperature was maintained at 60.degree. C. whilst a total of 55.3 lbs (25.1 kg) of propylene containing 0.145% by volume of hydrogen was passed into the autoclave at a constant rate of 22 lbs/hour (about 10 kg/hour), after which the propylene/hydrogen feed was terminated and the autoclave pressure was allowed to run down to 18 psi gauge, (equivalent to 30 psi absolute of propylene), the excess pressure being due to the presence of inert materials. A total of 4.4 kg of ethylene was then metered into the autoclave at a feed rate of 2.3 kg/hour for 20 minutes, then 4.0 kgm/hour for 56 minutes. The ethylene feed was then terminated and the autoclave pressure allowed to run down to a total pressure of 2 psi gauge.
The polymer suspension was passed into a 20 gallon (91 liter) glass-lined vessel. The autoclave was washed with 20 liters of the hydrocarbon diluent which was also added to the glass-lined vessel. The contents of the glass-lined vessel were mixed with isopropanol in an amount of 3% by volume relative to the diluent. The mixture was stirred for 1/2 hour at 70.degree. C., and a mixture of isopropanol and distilled water (containing 10% by volume of water) was added in an amount of 0.6% by volume relative to the diluent and stirring at 70.degree. C. continued for a further 11/2 hours.
The polymer suspension was run into a further 20 gallon vessel containing 40 liters of demineralised water at ambient temperature and the mixture was stirred for 30 minutes. The stirrer was then stopped and the aqueous phase decanted off. A further 40 liters of demineralised water were added, stirring restarted and the process repeated. The diluent was then filtered off and the polymer was dried at 100.degree. C. in a fluidised bed using nitrogen as the fluidising gas.
The polymer obtained had the properties set out in Table 3.
Table 3______________________________________ Yield of soluble polymerEthylene (% by wt) P.D. F.M. LTBPContent Dil Res (g/l) MFI (GN/m.sup.2) (.degree. C.)(% by wt) (d) (j) (e) (f) (g) (h) (k)______________________________________13.3 1.3** 3.7*** 5.8 9.8 485 9.5 1.03 -45______________________________________ Notes to Table 3? (d) to (h) are as defined in Notes to Table 2. (j) **Determined by taking an aliquot portion of the polymerisation diluent at the end of the propylene rundown, before adding the ethylene. ***Determined by taking an aliquot portion of the polymerisation diluent at the end of the ethylene rundown, before adding the isopropanol. (k) The low temperature brittle point (LTBP) was determined using the technique of ASTM Test Method D 746 modified by using specimens and specimen holder as in ASTM Bulletin No. 231, July 1958. The specimens wer cut from a plaque prepared in the same manner as that from which were cut the test strips used in the flexural modulus test (Note (h) to Table 2).

Number	Name	Date
3758621	Morikawa et al.	Sep 1973
3960765	Shiga et al.	Jun 1976
3984350	Karayannis et al.	Oct 1976
4007133	Rust et al.	Feb 1977
4110248	Sandis et al.	Aug 1978
4111834	Caunt et al.	Sep 1978
4115532	Yamaguchi et al.	Sep 1978
4115533	Yamaguchi et al.	Sep 1978

Number	Date	Country
842337	May 1975	BEX
2099150	Feb 1972	FRX
2314924	Jan 1977	FRX
2320308	Mar 1977	FRX
52-91794	Aug 1977	JPX
1359328	Jul 1974	GBX
1388308	Mar 1975	GBX
1391068	Apr 1975	GBX
1482669	Aug 1977	GBX
1487393	Sep 1977	GBX
1495031	Dec 1977	GBX

Transition metal composition and process

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Entry
Dutch OPI Specification No. 76, 08629 (2/10/77).
Research Disclosure, Apr. 1977, Disclosure No. 15662, pp. 78-80.
Published U.S. Application T 965,004, 12/6/77, filed 4/18/77, as S.N. 788,642.