Magnesium chloride complexes, process and uses

Abstract: The present invention provides a process for producing a magnesium chloride complex characterised by: dissolving magnesium chloride in a solvent and reacting with a cyclic ether (E); recovering a MgCl₂·E complex which is insoluble in the solvent. The complex can be used as a support for the preparation of a Ziegler-Natta catalysts for the polymerization of olegins.

Description: The present invention relates to novel magnesium chloride compositions in which magnesium chloride is complexed with an ether. The present invention also relates to the use of these complexes in manufacturing high performance alpha-olefin polymerization catalysts. Further it concerns a process for making alpha-olefins polymers having a controlled morphology by using the magnesium chloride complexes of this invention. Activated magnesium chloride has long been important in the manufacture of high performance catalysts for making polyethylene and polypropylene. It is known in the art that anhydrous magnesium chloride has to be activated by mechanical or chemical methods in order to obtain active polymerisation catalysts. The activation methods include : (i) treatment of MgCl 2 with activating agents such as electron donors (ii) ball milling of MgCl 2 and (iii) reaction of compounds such as Mg organic derivatives with chlorinating agents There exists a large number of patents concerning use of magnesium chloride in the manufacture of Ziegler-Natta olefin polymerization catalysts. The Ziegler-Natta catalysts seem to include every combination of a transition metal compound and an organometallic compound from groups I to III of the periodic table that will promote olefin polymerization. Magnesium precursors such as dialkyl magnesium, magnesium dialkoxides, alkyl magnesium alkoxides, alkoxy magnesium chloride and the like are being tested and some used extensively for preparing supported Z/N catalysts for polyolefin production. Although magnesium diethoxides (alkoxides) and commercial anhydrous magnesium chloride are the most extensively used solid magnesium precursors, many other magnesium precursors in solid and soluble form have been transformed by various treatments into activated magnesium chloride catalyst supports. Belgian Patents 785332 and 785333 disclose high yield polymerization catalysts which are prepared from activated MgCl 2 , TiCl 4 and internal electron donors, and activated by a mixture of trialkylaluminum and an external electron donor. Recently compositions of magnesium chloride complexed with tetrahydrofuran (THF) were used in the manufacture of super high activity catalysts for olefin polymerization. In "Polymer Communications, 1988, vol. 29, number 5", P. Sobota et al have studied the reactions between MgCl 2 (THF) 2 and TiCl 4 (THF) 2 and their use as a component of the Ziegler-Natta catalyst for olefin polymerization. It is also known in the art that a control of the polymer particle morphology is very important for the plant operability and the transformation of the polymer. Therefore it would be useful to have a polymerization catalyst which allows to obtain a polymer with a controlled particle size distribution. Commercial anhydrous magnesium chloride contains impurities which cannot easily be removed. Further commercially available magnesium chloride is usually crystalline and thus exhibiting a low activity. Therefore polymer manufacturers often use synthetic routes to MgCl 2 as they attempt to obtain a 100% active MgCl 2 . However it would be useful to find a process which enables the use of commercial anhydrous magnesium chloride for the preparation of polymerization catalysts. The present invention provides magnesium chloride compositions in which magnesium chloride is complexed with an ether. The present invention also provides high performance alpha-olefin polymerization catalysts. Further the present invention also provides a process for making alpha-olefin polymers having a controlled morphology. According to the present invention, there is provided a process for producing a magnesium chloride complex characterized by : dissolving magnesium chloride (MgCl 2 ) in a suitable solvent and reacting with a cyclic ether (E) which is 1,3-dioxolane and recovering a MgCl 2 .E complex which is insoluble in the solvent. According to a preferred embodiment of the present invention, the solvent is identical to the cyclic ether E. When using the cyclic ether E as a solvent of MgCl 2 , the Applicant has found that the resulting MgCl 2 .xE complex was insoluble in its solvent. This represents a considerable advantage since the recovering of the complex can be made by a simple filtration. The MgCl 2 used according to the present invention can be prepared by any of the methods known in the art. For example, MgCl 2 can be prepared according to the in-situ method disclosed by E.C. Ashby in "J. Organometallic Chemistry, 1968, vol. 14, p. 1". However, according to a preferred embodiment of the present invention commercial anhydrous magnesium chloride is used which represents a big advantage for the preparation of the Ziegler-Natta catalyst. The present invention also provides a process for the polymerization of alpha-olefins having 2 to 20, preferably 2 to 8, carbon atoms characterized by the fact that the polymerization is carried out in the presence of a Ziegler-Natta catalyst which is prepared with a magnesium chloride complex obtained according to the present invention. The Applicant has unexpectedly found that polymerization of alpha-olefins in the presence of a Ziegler-Natta catalyst prepared according to the present invention results in a high polymerization activity per unit quantity of the catalyst component. Further the polymer fluff obtained according to the present invention is under the form of spherical particles. It is another advantage of the present invention because this is synonymous with an improved plant operability and this permits to transform the polymer directly into manufactured items, thus avoiding the expensive process of pelletizing. The Ziegler-Natta catalysts of the present invention utilizes a magnesium chloride complex of this invention together with a compound of a metal selected from Croups IV-B and V-B of the Periodic Table of the Elements. Preferred metal compounds are those of titanium, vanadium and zirconium. Examples of the titanium compound used in the present invention include halides, alkoxyhalides, alkoxides and halogenated oxides, of titanium. As preferred examples of the titanium compound, there may be mentioned tetravalent and trivalent titanium compounds. As tetravalent titanium compounds, those represented by the general formula Ti(OR) y X 4-y are preferred wherein R is a hydrocarbon radical such as an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, X is a halogen atom and 0 ≤ y ≤ 4, such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium and tetraphenoxytitanium. As trivalent titanium compounds, there may be used, for example, titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium or an organometallic compound of a Group I-III metal in the Periodic Table, as well as trivalent titanium compounds obtained by reducing tetravalent alkoxytitanium halides represented by the general formula Ti(OR) s X 4-s with an organometallic compound of a Group I-III metal in the Periodic Table, in which formula R is a hydrocarbon radical such as an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, X is a halogen atom and 0 < s < 4. More preferably the catalyst used according to the present invention is a TiCl 4 /MgCl 2 .xE compound. The Ziegler-Natta catalysts of the present invention usually utilizes as cocatalyst an organometallic compound from groups I to III of the periodic table that will promote olefin polymerization. Preferably, those cocatalysts are selected from aluminum alkyls, more preferably triethylaluminum. According to an embodiment of the present invention an electron donor compound can be added to the cocatalyst in order to improve the catalyst performance. Among the various electron donor compounds which can be used, one can cite those disclosed in Belgian Patents 785332 and 785333 which are enclosed herewith by reference. The following examples further illustrate the invention. Examples All manipulations were performed under nitrogen atmosphere. Anhydrous magnesium chloride was obtained either from Aldrich Chemicals or from Toho Titanium and used without further purification. Anhydrous cyclic ethers and titanium (IV) were obtained from Aldrich Chemicals. Example 1 Preparation of MgCl 2 .DXL complex A 500 ml round bottom flask equipped with a magnetic stirring bar, a reflux condenser and a nitrogen inlet was charged with 2 g of anhydrous MgCl 2 in 200 ml of 1,3-dioxolane. The temperature of the reaction mixture was subsequently increased by means of heating bath to the boiling point of dioxolane while vigorous stirring. While reflux proceeded the solution became turbid. After 3 hours at this temperature, the mixture was allowed to reach the room temperature and the solid formed was separated by filtration from the supernatant solution and dried under vacuum. 4.24 g of a white solid was obtained. After evaporation of the dioxolane solution, hardly any solids remained. Comparative example C 1 Preparation of MgCl 2 .2THF complex A 1 l round bottom flask equipped with a magnetic stirring bar, a reflux condenser and a nitrogen inlet was charged with 5 g of anhydrous MgCl 2 in 500 ml of tetrahydrofuran. The temperature of the reaction mixture was subsequently increased by means of heating bath to 80°C. While reflux proceeded all the magnesium chloride solubilized. After one night at this temperature, a clear solution was obtained. After evaporation of the THF and drying, 12.3 g of white solid was obtained. Example Mg compound Ether compound Reaction temperature Reaction time 1 MgCl 2 , 2 g 1,3-dioxolane, 200 ml (DXL) 90°C 3 hr C 1 MgCl 2 , 5 g tetrahydrofuran, 500 ml (THF) 80°C 18 hr Example 5 Catalyst preparation In a glove box with nitrogen atmosphere, a 100 ml round bottom flask equipped with a magnetic stirring bar and a reflux condenser was charged with 2 g of MgCl 2 .DXL (prepared according to example 1) suspended in 20 ml of TiCl 4 . The content of flask was refluxed for 1 hour while stirring. At this point, the solid was separated by filtration without previous cooling and contacted with another 20 ml of TiCl 4 (1 hour, reflux temperature). After filtration, the solid so obtained was washed once with n-heptane, then suspended in 50 ml n-heptane and refluxed overnight. After cooling to room temperature the solid was filtered, washed once with n-heptane and dried under vacuum (1.11 g solid). Ethylene polymerization A Büchi reactor (2 l) was filled with hydrogen (10 Nl), isobutane (0.51) and ethylene until a final reactor pressure of 30 bars was reached. Then a mixture of 10 mg catalyst (suspended in 4 ml mineral oil) and triethylaluminum (TEA) (2.1 ml) (1.9 M in toluene), precontacted for 30 seconds, was introduced into the reactor by means of a second amount of isobutane (0.5 l). Then polymerization was carried out at 90°C under a constant ethylene pressure of 39 bars for 1 hour. After the polymerization was stopped, polyethylene fluff was collected in the amount and with properties as specified in table 2. The polymer melt index (MI 2 ) and high load melt index (HLMI) were determinated following ASTM D 1238-89. The polymer density was determinated following ASTM D 1505-85.

Claims: Process for producing a magnesium chloride complex characterized by : dissolving magnesium chloride (MgCl 2 ) in a suitable solvent and reacting with a cyclic ether (E) which is 1,3-dioxolane ; recovering a MgCl 2 .E complex which is insoluble in the solvent. Process according to claim 1 wherein the solvent is identical to the cyclic ether (E). Process for the polymerization of alpha-olefins in the presence of a Ziegler-Natta catalyst which is prepared with a magnesium chloride complex obtained according to any of the preceding claims. Process according to claim 3 wherein the polymer obtained is in the form of spherical particles.

Inventors: BREMS PATRICK, DEBRAS GUY, BREMS, PATRICK, DEBRAS, GUY
Applicants: FINA RESEARCH, FINA RESEARCH S.A.
Application year: 1992
Main classification: C08F4
IPC codes: C08F4, C08F10