CA1174797A - Process for the polymerisation of unsaturated compounds with a catalytic system based on reduced metal alkoxides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:
The present invention is directed to a process for the polymerisation or copolymerisation of unsaturated compounds containing one or more unsaturated bonds, possibly conjugated, either alone or in mixture, consisting of bring-ing the monomer or monomers into contact with a catalytic system constituted by the combination of: a) an organo-metallic compound of group III of the periodic table, b) a compound based on Ti (2+) or Ti (3+) or V (3+) or Cr (3+) or Zr (3+) or an element of the actinide series or an element of the lanthanide series, wherein component b) is prepared by reducing the alkoxides of the aforesaid metals in a liquid phase by means of vapours of metals chosen from the alkaline earth, group III or group IV metals or magnesium, then halo-genating them using suitable halogenating agents.

Description

1~74797 The present ~pp~ication is a division of Canadi~n patent applicatio~ No. 346.861 filed o~ March 3, 1980. The original application relates to:a process fox xeducing alkoxides of transition metals selected from the group con-sisting of Ti (~+), V (~-~), V (5+), Cr (4~) a~d Zr (~+).
Said process consists of reducing the aforesaid alkoxides with the vapour of metals chosen from the alkaline earth metals, metals pertaining to groups III and IV, or manganese. (The use of a solvent medium for the alkoxides is not indispensable)~ The applicant is familiar with the existence of Canadian Patent ~pplication N 270.122 filed on January 20, 1977 relating to a method for preparing tita-nium and vanadium trichlorides starting from their respective tetrachlorides by reduction by -the vapour of metals chosen from Al, Mg, Cr, Mn, Fe, V and Ti.
The use of reduction by metal vapour in the case of the aforesaid alkoxides cannot be considered to be an expected or foreseeable.result on the basis of the above mentioned patent application, as the stability of the bonds involved in the reduction is quite diEferent in the two cases.
In this respect, in the case of the titanium chlo-ride, the reduction involves the breaking of metal-chlorine bonds, and the driving force of the reaction can be the force of format.ion of insoluble ionic TiC13, whereas in the present case the bond concerned is the metal-oxygen bond, which is more covalent than the Me-Cl bond, and the products are not of saline character.
In the case of alkoxides, it was therefore impos-sible to forecast that certain metals in their vapour state would be able to quantitatively break a large range of transi-tion metal-oxygen bonds such as defined herein, under very mild reaction conditions such as those claimed for the reduc-tion of the chlorides.
As a demonstration of thisr it shoul~ be noted tha-t ., . - 1 - ~

` 1 17479~

accoxding to the p~evious pa~e~t application~, while it is p~actically possible to break t~ansition~ metal~ch~lori~e bonds by all metals in the form of VapQUr, on~y the metals chosen from the alkaline earth ~metals, groups III and I~ or manganese can break metal-alkoxide bonds.
In contrast to the previous patent application, the stability of the metal-oxygen bond excludes the possibil-ity of using, inter alia, zinc, antimony, tellurium and iron, which are used in the reduction of TiC14.
It should also be note~ that the processes for preparing titanium (3+) alkoxides already known from the literature differ substantially from the process discovered by us.
In this respect, we can cite the preparation of Ti (OR)3 start~ng from TiC13 and alcoholates of alkaline metals (A.W. Adams et Al. Austral. J. Chem. 19 (1966) 207), or start-ing from Ti (III) amides by alcoholysis (Lappert and Singer, J. Chem. Soc. (1971) 1314), or by reduction of titanium tetra-alkoxides to titanium trialkoxide polymers using lithium, potassium or other alkaline-metals in alcohols or ethers (A.
N. Nermeyanov et al. Dokl, Akad. Nank. SSSR, 95 (1954) 813).
The main limitation of the stated preparation methods is that they are limited to the use of alkaline metals in solvents containing hydroxyl or polar groups.
In contrast, the reduction of titanium tetraalko-xides to titanium trialkoxides or the reduction of alkoxides of other transition metals by our process can also take place in the absence of solvents or in solvents completely apolar such as petroleum, and leads to solutions or suspensions of titanium (3+) alkoxides mixed wi-th alkoxides of the metal used for the reduction. If stoichiometric quantities of Ti (OR)4 (or of another transition metal alkoxide) and the ~educlng metal are used, then the reaction can be expressed by the equation n Ti (OR)4 + M (vap) >Ti (OR)3n . M (OR)n where , - 2 -1 1~479~ ~

- n is the Yalency assumed by the metal used as the reducing agent. ~oweve~, if tke ~etal used as the reduci~g a~gent is evaporated in an excess of Ti IOR)4, it is sometimes pos-sible to isolate the Ti (OR)3 ~t a good level of purity.
This is because the excess of Ti (OR)4, as is the case o Ti (O n-butyl)4 with respect to the stoichiometric quantity required by the quantity of me-tal evaporated, has no damaging efect on the nature of the product, in this case ~Ti (O-n-butyl)37x which forms in the reaction, whereas it can compete with the Ti (3~) and complex the magnesium alkoxide to give mixed soluble alkoxides, which can be easily separated from the ~Ti (O-n-butyl)37x polymer, which is insoluble and can therefore be separated in a good state of purity by filtration (Ex. 1, test 2 of table 1).
A different case is represented by the reduction of Ti (O-i-C3H7)4 by Mg vapourO In this case the LTi (O-i-C3H7)37y has good solubility, while the Mg (O-i-C3H7)2 tends to precipitate, and can be separated by filtration.
In this case, if it is the L~Ti (o-i-C3H7)37y which ~20 is of interest, then it is advisable to operate with the . stoichiometric quantities required by the reaction (Ti4+/Mg = 2).
If Mg is replaced by Al as the reducing metal, then in all cases mixed Ti3+ - Al alkoxides are obtained, even when operating with a large excess of Ti (OR)4 (ex. 3). The problem of obtaining pure Ti3+ alkoxides obviously does not exist when titanium itself is used as the reducing metal (ex.
4). The reductlon of Ti~+ (or of other transition metals) to a valency lower than 3, or to the maximum valency compatible with the transition metal alkoxide, can be easily carried out using the reduction method described herein, as demonstrated by test 6 of Ex. 1, table 1I where magnesium is used for reducing Ti4 to Ti2 . In this case only the mixed alkoxide is isolated. On -the basis of these consider~tions, even 1 17479~. ~

though in the process according to the invention it is preferable to carry out the ~eduction~ with the s~oichiome-tric quantity of the transition metal alcoholate required by the me-tal to be evaporated, an excess of transition metal alcoholate over this quantity (10-30 times) can sometimes be necessary especially if this can enable the transition metal alcoholate in a reduced form to be isolated at a good level of purity. According to the present invention, the tetraalkoxide is reduced by the following method in the reactor described in the above mentioned patent appln. The metal is evaporated slowly (l 5 g/hr) and made to react with -the titanium (4+) alkoxide ( or another transition metal alkoxide) either in its pure state or dissolved, to give a 0.2-2 mol solution, in hydrocarbon, including a halogenated hydrocarbon provided the halogen reacts only slightly or not at all with the metal vapour, or in an ether or thioether.
The solvents can also be cyclic. Particularly suitable for this purpose are all linear and cyclic aliphatic and aromatic hydrocarbons, including heterocyclic hydrocarbons, such as vaseline*, oil,kerosene, heptane, xylene, cyclohe~ane, deca-hydronaphthalene, cumene, mesitylene, ethylbenzene, toluene, - pyridine and quinoline. Suitable halogenated solvents include fluorobenzene, hexachlorobutadiene. Suitable ethers include diethyl ether, isoamyl ether, butylether, anisole, dioxane, 2S tetrahydrofuran etc. Suitable thioethers include diphenyl-sulphide and thioanisole. Suitable inorganic solvents include polycyclosiloxanes or silicone oils with a limited number of hydro~yls, etc.
All the alkoxides of the transition metals are suit-able for reduction, provided they satisfy the condition ofbeing in a high valency state, and have a certain solubility in at least one of the said solvents.
In the Ti (OR)4 compounds, R can be an alkyl, cyclo-alkyl or aromatic radical (e.g. R = C~3, CH2CH3, n-C3H7, * Trademark.

1 17~7~ ~

i-C3H7, n-C4H9, i-C4Hg, t-C4~9~ 2 ethyl-hexyl etc.) o~ an i~organic radical such a~s Si (C~3)4, oX contai~ mixed lig-ands of the aforesaid type.
Mixed alkoxides can also be used as the m~terials to be reduced, such as MCTi (OR) ~ I~=Mg, Ca), or M~H~Ti (OR) ~ 2 (M'=Li, Na)-The vanadium alko~ides include V(O-t-C4H9)4 and VO(o-i-c3H7)3 The temperature of the reaction flask is preferably kept between. -30 and +20C during the reaction, but the temperature limits can be considerably wider, because the reaction takes place even when the reaction flask is cooled to the temperature of liquid nitrogen.
On completing the reaction by vaporisation, the mixture can be stirred at ambient temperature or can be heated at moderate temperature, generally less than 150C, and normally between 60 and 130C. This treatment is not indispensable on completing the reaction, but it favours precipitation of the mixed titanium polymer alkoxides in reduced form by accelerating it, so allowing their separation by filtration or centrifuging from the solvent and that alkoxide still present due to deficiency of the reducing me-tal.
In the case of reduction of Ti4+ alkoxides, the material from the reaction flask is in the form of a homoge-neous solution from which the Ti3 or mixed alkoxides sepa-rate only very slowly if the heat treatment is not given.
The mixed alkoxides can be obtai.ned by removing the reaction solvent by distillation or under vacuum, especially when stoichiometric quantities of reducing metal, Ti (OR)4 . or other transition metal alkoxides are used.
The Ti3+ alkoxides or mixed alkoxides - even of other transition metals - are in the form of largely amorphous green coloured powders which are weakly param~gnetic.
They are not further soluble after precipitation 1 17~7g~ ,, from their mother so~utions/ a~nd it can therefo~e be co~sidered that their po~ymerisatio~ prQcess is a typic~lly irre~ersible fact. ~11 the matexials are sensitive to atmospheric oxygen and humidity. When reduction is pro~
ceeded as far as Ti2+, the material is pyrophoric, and must be handled with extreme care.
The present division relates to a process for the polymerisation or copolymerisation of unsaturated compounds containing one or more unsaturated bonds, possibly conjugat-ed, either alone or in mixture, consisting of bringing the monomer or monomers into contact with a catalytic system constituted by the combination of:
a) an organometallic compound of group III of the periodic table, b) a compound based on Ti(2+) or Ti(3+) or V(3+) or Cr(3+) or Zr(3+) or an element of the actinide series or an element of the lanthanide series, wherein component b) is prepared by reducing the alkoxides of the aforesaid metals in a liquid phase by means oE vapours of metals chosen from the alkaline earth, group III or group IV metals or - magnesium, then halogenating them using suitable halogen-ating agents.
The molar ratio of the halide of the halogenating agent to the alkoxide group of the mixed alkoxides in reduced form is > 1.
The substrates to be polymerised or copolymerised are chosen from ethylene, ~-olefines and cyclic olefines, either alone or in mixture.
The halogenating agents are selected from the group consisting of BC13, BBr3, SiC14, SiBr4, TiC14, TiBr4, TiI4, Ti(OR)2 C12, GeC14, SnC14/ SbC15, POC13, POC15, SOC12, MoOC14,

2 2' WOC14j MOC14, WC16, VC14 and VOC13.
For example, the Ti + alkoxides or mixed Ti alko-xides prepared by the ~pplicant find useful application in ~ 17~9~

the preparation of catal~tic systems for the polymerisation and copolymerisation of a la~ge series of unsaturated sub-strates if they are subjected to preliminary treatme~t with one of the above listed chlorinating agents. They are then reacted with o~ganometallic compounds of the group III
metals for the polyme~isation and copolymerisation of a large number of organic substrates containing at least one vinyl, norbornenyl or cyclohexyl group.
The halogenation can be carried out either directly on the mother solutions from the reactor where reduction has taken place by metal vapour before the Ti3+ alkoxides or mixed alkoxides precipitate, or on the suspension of these alkoxides by adding a large e~cess of the chlorinating agent (at least one mole of chlorinating agent for each mole of alkoxide group).
When the chlorination reaction is carried out on solutions, the reaction is conducted by adding the chlorin-ating agent at a temperature of between 0 and 30C.
In the case of the Ti3+ alkoxide, the catalytic material precipitates in the form of a brown powder (~ TiC13) or violet powder (y or ~ TiC13).
If the obtained suspensions of these catalytic materials are heated (65 - 150C), the ~ TiC13 is easily con-verted into the y form. After conversion, if necessary the catalytic material obtained is iltered, and washed with a hydrocarbon or other inert solvent, until there is no further chlorine or halogen in the filtrate, and is finally used either after drying or as a suspension in an inert material such as n-heptane or kerosene. Compared to the above men-tioned patent application in which the transition metalchlorides were reduced directly by metal vapour, the system now described has the drawbacks of being able to use a more limited number of metals as the reducing agent, and to arrive possibly at the same materials but using two successi~e 117~79~ ~

operations, the second of Which consumes a c~nside~able quantity of inorganic chlorinating agent.
In compensation, it is possible according to the new method to prepare catalytic materials in which the ratio of transition metal in its reduced state to the reduc-ing metal can be varied at will between for example 0.5 and lO, by suitably p~ocessing the pLoducts.
It is also possible to incorporate in the catalytic materials halogens which are different from that of the metal used in the reduction, e.g. each time mixed alkoxides or solutions of two or more different alkoxides are reduced.
This is true not only for the saline chlorides such as those of Ca or Sr, but also for AlCl3 or ZrCl4, which could be easily introduced into a catalytic system by reduc-ing Ti (ORt4 in the presence of Al(-O-sec.butyl)3 or Zr(O-n-butyl)4 with Mg or Mn, ollowed by chlorination. Pre-paration of such catalytic systems would not be possible by directly reducing the chlorides, as both ZrCl4 and AlC13 are insoluble in hydrocarbons. A further advantage of the new system is that the metal alko~ides are high boiling materials - which do not give of hydrogen halide acids by hydrolysis or thermal decomposition, in contrast to halides.
This means that unprotected heating elements and higher reaction temperatures can be used in the reactors where vaporisation takes place, with considerable plant sim-pliflcation and energy saving. Both methods allow the prepa-ration of TiCl3-based catalytic materials having a high sur-face area, without using metal alkyls as the reducing agent.
Finally, the use of the catalytic materials prepared by product chlorination as described in the present divisional application leads to polymers or copolymers having character-istics which are considerably better than by any other process, in particular the process described in the above mentioned patent application, these being:

~ 17~79~ ~

- a higher yield for equal ~lg/Ti r~tios - a ~aXrower ~.W. distributiQ~ (MF21 6/MF2 16 25-30) - good morphology (lower content of fine powder less than 75 ~), the polymers bein.g ~ree flowing - high apparent density (generally between 0.35 and 0.45 Kg/l)-For comparison purposes and for- demonstrating the aforesaid, we have carried out e~amples 30, 31 of tables 5 and 33.
These examples compare the results of polymerisa-tion tests on ethylene under different conditions using one of the catalytic systems claimed in this divisional patent application, with polymerisation tests under analogous condi-tions using one of the materials obtained by reducing TiC14 with Mg vapour in accordance with the above menticned patent application.
Example 34 relates to polymerisation of propylene.
Examples 1-17 relate to the reduction of transition metal alkoxides with Mg, Al and other vapours.
EXAMPLES 1-6: Reduction of Ti4 butoxide by Mg vapour.
Table 1 shows the conditions under which Ti (O-n-butyl)4 was reduced by Mg metal. The green or grey-green powdery solid products were filtered from the green-coloured kerosene after the various treatments, were washed repeatedly with n-heptane and were dried.under vacuum in order to deter-mine Ti and Mg analytically.
Analytical determinations were also carried out on the filtered solutions, which were generally of green colour.
The Mg evaporation efficiency (molar ratio of the evaporated magnesium (sum of Mg solution and solid Mg) to that located in the source) was between 50 and 70% due to metal losses on the bars.supporting the furnaces or in other dead parts of the reactor. The TilMg ~atio varies according to reaction conditions between 2.3 (Ex.l, almost correspond-1 17479~

ing to the pure mixed alko,xide) ,a,n,d 8.0 (Ex,3, co~xesponding to a relativel,y pUxe Ti (O-~-butyl)3). These facts are justifiable consideri~g that because o~ the good ev~po~ation efficiency, the Ti (O n-butyl)4 which has not undergone ~eaction competes with the Ti (O-n-butyl)3 in sequestering the Mg (O-n-butyl)2 to give the mixed Mg LTi(O-n-butyl)67 alkoxide. This prod,uct is soluble in hydrocarbon, an.d this is the reason why soluble Mg in the mother solution is constantly found. When the reactions are carried out stoi-chiometrically, i.e. avoiding any excess Ti (OR)4, themagnesi.um precipitates together with the titanium alkoxide reduced quantitatively, and neither the titanium nor the Mg can be further found by analysis in the mother solutions (Ex. 6).
All the products are largely amorphous to X-rays, and are weakly paramagnetic.

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EX~MPLES~ eduction, of Ti4~ a,lkoxides with M~ vapou~.
Table 2 shows the xeductio~ co~,dition,s ~or certa,in titanium ~lkoxides and the yields and charactexistics of the products obtained.
The suspensions o~iginating rom the reduction reactions are of green or grey-green colour, with the excep-tion of the Ti(O-i-propyl)4, which is blue. When this par-ticular type of suspension is heated, the Ti/Mg ratio in the precipitate changes profoundly (compare examples 9 and 10) in the opposite direction to that observed in the reduction :of Ti(O-n-butyl)4. This effect is due to the greater solu-bility of Ti(O-i-propyl)3 than Ti(O-n-butyl)3.

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EXAMPLE 12-14:
Examples are given of the xeductio~ of TilO-~-butyl)4 with Ca or Al vapour~
The products are greent poorly soluble, and were isolated after treatments ~alogous to those given for the preceding examples.
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~ 17479 ~ ~ -EXA~PLE lS: Reductio~ of VO(0-i-p~opyl)3 with Mg.
U~der the expexime~tal conditio~s of ex~mples 1-14, Mg (47 ma) is vaporised into a kerosene solution of VO(O-i-propyl)3 (100 mm). ~fter the evaporation, the sus~
pension is stirred for 2 hours at ambient temperature, the product is iltered of~ and washed with heptane and dried under vacuum (12 g, violet colour).
The product shows the foliowing percentage analy-sis: V 17.9%, Mg 7.6%. CVO(O-i-propyl)37Mg comprises V
16.9%, Mg 8.0%. The V/Mg ratio is 1.1, and the vaporisation efficiency 75%.
EXAMPLE 16: Reduction of Zr(O-n-propyl)4 with ~g.
Under the experimental conditions of examples 1-14, Mg (40 ma) is vaporised into a kerosene solution of Zr(O~n-propyl)4 (S0 mm). Gas is given off during vaporisa-tion, and care must be taken to control the reaction so that it does not become too vigorous. It is then allowed to cool to ambient temperature while stirring vigorously, and after 4 hours the solid product is filtered off, washed repeatedly with heptane, and finally dried under vacuum (yield 1.2 g of a grey pyrophoric powdery product).
Analysis shows the following values: Zr 26.3%, Mg 1.8%.
EXAMPLE 17: Reduction of Ti(O-n-butyl)4 with Mg in the pre-sence of Al (O-sec.-butyl)3.
Mg (35 mm) is evaporated under the same conditions as e~amples 1-14 into a kerosene solution of Ti(O~n-butyl)4 (80 mm) and Al (O-sec.-butyl)3 (18 mm)~
After evaporation, it is allowed to cool to ambien-t temperature while stirring vigorously for 1 1/2 hours, and is finally heated for 2 hours at 105C.
A green powder (9.6 g) is filtered off, and is washed with heptane and dried under vacuum, to show the follow-ing composition: Ti 14.7%; Mg 1.94%; Al 0.66%.
The filtrate contains 38 mm oE Ti, 15 mm of Mg and - - 16 ~

1 17479~ ~

13 mm of Al- The vaporisation~ efEicien.cy is 65%.
EXAMPLES 18-25: Reductio~ of ,a~lkoxi~es with ~g, Ca ,an~d, Al vapour, and chlorination, With an inorganic chlo~i~a,ting agent. Chlorination of mixed tita~ium and magnesium alko-xides with SiC14.
In these examples, the ~on-isolated mixed alko-xides are chlorinated by means of a~ excess of SiC14 (~ 1 mole SiC14lmole of OR gXoup)- The chlorination is carried out by dripping pure SiC14 into the solution-suspen.sion from the vaporisation reactor, while vigorously stirring so , as to maintain the temperature around 20-30C. After the - addition, the reaction temperature is raised to 65C under stirring, and is maintained for 1 hour.
Finally, the solid product is filtered off, washed with heptane un*il the inorganic chlorine is eliminated, and finally resuspended in n-heptane. The reuslts of these tests and the analytical data for the products obtained are given in table 4.
All the products are of brown or red-brown colour, , and are in the form of mainly weakly paramagnetic amorphous powder.

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EXAMPLE 22: Chlo~i~ation of a mi~ed isolated Ti a,nd Mg alkoxide With SiC14, 40 ml of SiC14 i~ 50 cc of n,-heptane wexe added to the product of example 2 of table 1 (2.8 g) and the mixture was stirred vigorously at ambien,t temperature and then Eor 1 hour at 65C~ The material changed from green to violet. It was filtered off, washed with heptane and finally dried under vacuum. Analysis gave the following values for the solid material obtained ~1.5 g):
Ti 20.4%, Mg 2.4%, Cl 34.8%, this satisfying a crude formula of Mgl Ti4,3 Cllo ( 5.9 EXAMPLE 23: Reduction of Ti(OR)4 with Mn vapour, and chlo-rination of the resultant solution-suspension with SiC14.
Ti(O-n-butyl)4 ~50 mm) are reduced with Mn vapour (11.8 mm) in kerosene in the manner described for examples 1-14. Without isolating the products, the suspension is directly chlorinated with SiC14 (430 mm), which is added at ambient temperature under stirring.
This suspension is heated to 70C for 1 hour, and finally the violet product is filtered off, washed with heptane and resuspended 'n 70 ml of n-heptane. The suspen-sion shows the following analysis (mm/l): Ti 69.8, Mn 80.1, Cl 320.
The evaporation efficiency is 68%.
EXAMPLE 24: Reduction of Ti(O-n-butyl)4 with Al vapour, and chlorination of the obtained mixtures with TiC14.
Metal Al (7 mm) was vaporised into 200 ml of kero-sene containing Ti(O-n-hutyl)4 (20 mm). TiC14 (220 mm) was ' added to the green suspension-solution, which was stirred for 2 hours at ambient temperature and then for 1 hour at 80C.
The brown product obtained was then fi~tered off, washed repeatedly with n-heptane and xesuspended in 20 ml of n-heptane, to give a suspension of the following composi-tion (mm/l): Ti 360, Al 138, C1 1400, Ti/Al ratio = 2.6.

117479~ ~

The vapo~isation ef~icie~cy (Al analysed/Al evapoxated) was 40%.
EXAMPLE 25: Reduction of Ti(O-n-propyl)4 with ~1 vapour, and direct c~lorination o~ the obtained mixtures as in exam-ple 24.
~1 (4.0 mm) was evaporated into a ke~osene solution (150 ml) of Ti(O-n-propyl)4 (25 mm).
The suspension-solution obtained was brought to ambient temperature stirred at this temperature for 2 hours, after which TiC14 (220 mm) was added to it. I-t was heated to 120C for 1 hour while continuing stirring, the TiC13 was then filtered off, washed with heptane and dried under vacuum to give 1.1 g of product with the following analysis:
Ti 24.5~, Al 6.7%, Cl 66.2 Evaporation efficiency 70~
EXAMPLE 26: Reduction of solutions of titanium 4 and zir-conium 4+ alkoxide solutions in the presence of Al(O-sec-butyl)3 with Mg vapour.
; - Mg (80 mm) was evaporated into a kerosene solution ; 20 (150 ml) of Zr(O-n-butyl)4 (n-but. OH) (40 mm), Ti(O-n-- butyl)4 (40 mm) and Al(O-sec-butyl)3 (12 rnm).
Gas is evolved during the tests, and the vaporisa-tion is therefore carried out with some care.
The mixture was allowed to reach ambient tempera-ture, and was then heated to 80C for 1 hour.
After cooling, 140 ml of SiC1~ were dripped in, and the mixture was stirred at ambient ternperature for 1 hour and finally at 60C for 2 hours. The brown solid was filtered off, washed repeatedly w-ith n-heptane and resuspended in hep-tane (70 ml). The suspension gave the following values (rnm/l) on analysis:
Ti 179.6, Zr 38.4, Al 27.80, Cl 1340, Mg 156.2.
- The evaporation efficiency was 27%.
EXAMPLES 27-33: Polymerisation of ethylene with some of the .
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117~797 products of,examples 18-25 (ta,ble 5).
The polymerisations were carried out in a 2 litre autoclave temperature controlled at 85C, by introducing' successively a heptane solution of TiBAL (1 litre, 8 mmjl of TiBAL) containing the desired quantity of catalytic com-ponent (0.024-0.05 ma/l in Ti) as a hydrocarbon suspension (that o examples 19~21), then hYdrogen (5 atm) and finally ethylene up to a total pressu~e of 15 atm. This total pressure was maintained by continuously feeding ethylene during the course of the tests (5 hours).
The tests were blocked with isopropanol (5 ml), and the polyethylene obtained was dried to constant weight.
The results of the ethylene polymerisations are shown in table 5, which also gives at the end an example (31) as a test of comparison with ethylene obtained using one of the catalytic systems prepared by the procedure de-scribed in the above mentioned patent appln. and having the same Mg/Ti ratio.
The average particle size was measured by sieving the polymer powders through a series of sieves with a mesh - aperture lying between 710 and 75 ~.

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1174~9~ -EX~PLE 33 ~ test Was ca,~ried out With the cat~lytic material of Ex. 23. The polymerisatio~ conditio~s wexe those of Ex.
26-31, except for the parti~l pressure of the kyarogen which in th~is test was 10 atm. and the polymerisation~ duration which was 2 hours. The tita~ium concentration was 0.069 mm/l.
The polythene produced was 160 g with a MF2 16 ~g/10 min) of 3.9. The production, yield was'~9 Kg oE PE/g Ti.

An autoclave of 5 litres capacity temperature con-trolled at 85C was charged with 2 litres of n-heptane containing TiBAL at a concentration of 4 mm/l, and the pro-duct of Ex. 19 of table 4 at a Ti concentration of 0.063 mm/l.
The autoclave was pressurised with 2 atm. of H2 and then with 3.3 atm. o C2H4, maintain~ng the pressure - constant at 5.3 atm. for 2 hours.
The polymerisation was blocked to give 403 g of . polythene with a MFI at 2.16 Kg of 1.27 (g/10 min) and MF21 6/
MF2 16 of 26, with a specific activity of 10,000 g PE/g Ti x hr. x atm.
The polymer was free fl~wing with an apparent density of 0.367 Kg/l.
' A polymerisation test under identical conditions '~ to those stated heretofore with the material prepared in Ex.
2 of applican~'s Canadian patent application No. 270.122 filed on January 20, 1977 gave 278 g of polythene, with a MFI of 0.06 (g/10 min3, MF21 6/MF2 16 of 45 and a specific activity of 7000 PE g/g Ti x hr. x atm.
The polymer,was not free flowing, and had an apparent density o~ 0~21 Kg/l.

117~79~

Polymerisation,of pr:apylene.
The cata,lytic materi,al p~epared in, E~. 19 Qf table 4 WaS used in, polymerising propylene under t~e follow-ing conditions~ 0.5 1 of n-heptane containing component 19 (rri) 2 mm/l, Al Et2 Cl 8 mm/l, Al Et3 0.8 mm!l was fed into a 1 litre autoclave temperature controlled at 70C, and pressurised with 7 atm. of propylene immediately after intro-ducing the catalytic components. rrhe pressure was maintained constant for 90 minutes. After venting the autoclave, 75 g of p~lypropylene w re reco,ered.

Claims (4)

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

1. A process for the polymerisation or copoly-merisation of unsaturated compounds containing one or more unsaturated bonds, possibly conjugated, either alone or in mixture, consisting of bringing the monomer or monomers into contact with a catalytic system constituted by the combination of:
a) an organometallic compound of group III of the periodic table, b) a compound based on Ti(2+) or Ti(3+) or V(3+) or Cr(3+) or Zr(3+) or an element of the actinide series or an element of the lanthanide series, wherein component b) is prepared by reducing the alkoxides of the aforesaid metals in a liquid phase by means of vapours of metals chosen from the alkaline earth, group III or group IV
metals or magnesium, then halogenating them using suit-able halogenating agents.

2. A process as claimed in claim 1, wherein the molar ratio of the halide of the halogenating agent to the alkoxide group of the mixed alkoxides in reduced form is > 1.

3. A process as claimed in claim 1, wherein the substrates to be polymerised or copolymerised are chosen from ethylene, .alpha.-olefines and cyclic olefines, either alone or in mixture.

4. A process as claimed in claim 1 or 3, wherein the halogenating agents are chosen from BC13, BBr3, SiC14, SiBr4, TiC14, TiBr4, TiI4, Ti(OR)2 C12, GeC14, SnCl4, SbC15, POC13, POC15, SOC12, MoOC14, CrO2 C12, WOC14, MOC14, WC16, VC14 and VOC13.