GB1594020A - Process for the preparation of titanium trichloride catalyst components for olefine polumerisation - Google Patents

Description

(54) PROCESS FOR THE PREPARATION OF TITANIUM TRICHLORIDE CATALYST COMPONENTS FOR OLEFINE POLYMERISATION (71) We, TOA NENRYO KOGYO K.K., a Corporation duly organized and existing under the laws of Japan, of 1-1 Hitotsubashi, 1-Chome, Chiyoda-Ku, Tokyo, Japan do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a titanium trichloride catalyst useful as a catalyst component for the steroregular polymerization of a-olefins and a process for the production of the same, and more particularly, to a process for the production of a titanium trichloride catalyst for the stereoregular polymerization of a-olefins, whereby polymer particles of uniform shape and size are obtained with high catalytic activity and a high ratio of yield of stereoregular polymer.

Known catalysts for the stereoregular polymerization of a-olefins, in general, are halides of transition metal elements in the reduced valence state, for example, a-type titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, a eutectic substance of titanium trichloride and aluminum chloride, obtained by reducing titanium tetrachloride with aluminium, b-type titanium trichloride obtained by crushing this eutectic substance and the like. As a method of modifying titanium trichloride, it has been proposed to add metal halides, alkylaluminum compounds, halogenated hydrocarbons, ethers, esters, ketones, etc., optionally followed by grinding. For example a-type titanium trichloride may be modified by crushing a-type titanium trichloride with halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and hexachloroethane. However, this method has the disadvantages that titanium trichlorides other than cy-type titanium trichloride cannot be used, preparation of the catalyst is complicated because of the requisite crushing treatment. etc., and the resulting catalyst is unsatisfactory in catalytic activity and ratio of yield of stereoregular polymer.

Other proposed methods comprise reducing titanium tetrachloride with an organoaluminum compound, treating i.e. contacting the thus obtained reduced solid containing titanium trichloride with a complexing agent to extract and remove the aluminum compounds and then treating with titanium tetrachloride United Kingdom Patents 1391067 and 1391068; treating the same with carbon tetrachloride and reducing titanium tetrachloride with an organoaluminum compound and then treating the thus obtained reduced solid containing titanium trichloride with a mixture of a complexing agent and carbon tetrachloride.

However, the first method wherein the aftertreatment is carried out using titanium tetrachloride involves an expensive highly concentrated solution of titanium tetrachloride.

The second method wherein the aftertreatment is carried out using carbon tetrachloride is advantageous in that expensive titanium tetrachloride can be replaced by cheap carbon tetrachloride, but the method is not always satisfactory since the yield of titanium trichloride is low due to the tendency of carbon tetrachloride to dissolve titanium trichloride. As a consequence. the resulting catalyst exhibits a low catalytic activity, low ratio of yield of stereoregular polymer and unfavorable particle shape of polymer.

The present invention provides a process for the production of a titanium trichloride catalyst component comprising a titanium trichloride-containing reduced solid obtained by reducing titanium tetrachloride with an organo metal compound, a chlorinated hydrocarbon having 2 carbon atoms or more and a coomplexing agent, which catalyst is prepared by reducing titanium tetrachloride with an organo metal compound and then treating the resulting product with a chlorinated hydrocarbon having 2 carbon atoms or more in the presence of a complexing agent and an aluminum trichloride-ether complex.

The titanium trichloride-containing reduced solid (which will hereinafter be referred to as "reduced solid") obtained by reducing titanium tetrachloride with an organo metal compound according to the present invention is a reduced solid substance the color of which is brown to red violet and which contains metal compounds, for example, aluminum compounds and has a complicated composition. As the organo metal compound there are generally used, individually or in combination. organoaluminum compounds, organo magnesium compounds and organo zinc compounds (which will hereinafter be referred to as "organo metal compounds"). The reduction is preferably conducted by the use of organoaluminum compounds. The reduced solids obtained in this way contain a metal compound or a mixture or complex compound thereof, e.g., an aluminum compound or a mixture or complex compound thereof, which possibly interact with a complexing agent or a chlorinated hydrocarbon having 2 or more carbon atoms to some extent, thus improving the catalytic activity.

As the above-described organoaluminum compound there is ordinarily used an organo aluminum compound represented by the general formula RnAlX3 n wherein R represents an alkyl group or aryl group, X represents a halogen atom and n represents a suitable numeral within a range of 1' n ~ 3, or a mixture or complex compound thereof. In particular, it is preferable to use alkylaluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides and alkylaluminum sesquihalides, or mixtures or complex compounds thereof. Examples of the trialkylaluminum are trimethylaluminum, triethylaluminum and tributylaluminum. Examples of the dialkylaluminum halide are dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diethylaluminum iodide. Examples of the monoalkylaluminum dihalide are methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, ethylaluminum dibromide and ethylaluminum diiodide. Ethylaluminum sesquichloride is given as an example of the alkylaluminum sesquichloride. Triethylaluminum, diethylaluminum chloride, ethyl aluminum dichloride, ethylaluminum sesquichloride or their mixtures or complex compounds thereof, are preferred; for example, a mixture of diethylaluminum chloride and ethylaluminum dichloride is particularly preferable because these compounds are readily obtainable commercially and provide excellent results.

The reduction of titanium tetrachloride is ordinarily carried out by adding the above-described organo metal compound or its solution dropwise to a solution of titanium tetrachloride dissolved in an aliphatic hydrocarbon having 5 to 12 carbon atoms at a temperature of from -50"C. to +3() C. over a period of time of 30 minutes to 3 hours or the titanium tetrachloride may be added to the organo metal compound. The quantity of organo metal compound used is ordinarily 1 to 5 gram atoms as metal per 1 gram atom of titanium. When titanium tetrachloride is reduced with diethvlaluminum chloride (DEAC) or a mixture of DEAC and ethylaluminum dichloride (ED AC), these reagents are preferably mixed in a molar ratio of TiCl4:DEAC = 1:1 to 1:5 and TiCl4:DEAC:EADC 1:1:0.1 to 1:4:1.2. The mixture of titanium tetrachloride and organo metal compound may be aged at a temperature of 20 to 5() C. for I to 3 hours, but this treatment is not always necessary. Then the resulting reduced solid is separated by a suitable method, optionally washed with an inert solvent and optionally dried or heated to thus obtain the reduced solid of the invention. The reduced solid obtained in this way contains uniformly distributed throughout, for each gram atom of titanium 0.2 gram atom or more of metal compound, e.g. an aluminum compound or a mixture or complex thereof.

The titanium trichloride catalyst of the present invention is obtained by subjecting the so obtained reduced solid to a treatment with a chlorinated hydrocarbon having 2 carbon atoms or more in the presence of a complexing agent and an aluminum trichloride-ether complex. As the chlorinated hydrocarbon having 2 carbon atoms or more there can be used chlorinated saturated or unsaturated aliphatic hydrocarbons, chlorinated alicyclic hydrocarbons or chlorinated aromatic hydrocarbons or their isomers. for example. hexachloroethane, pentachloroethane. tetrachloroethane, trichloroethane. dichloroethane, monochloroethane, tetrachloroethylenc. trichloroethylene. dichloroethylene, monochloroethylene. octachloropropane. heptachloropropane, hexachloropropane, pentachloropropane. tetrachloropropane, trichloropropane, dichloropropane, monochloropropane. tetrachlorobutane, trichlorobutane. dichlorobutane. trichloropentane, dichloropentane. dich lorohexane, dichloroheptane, dichlorooctane, dichlorocyclohexane, dichlorobenzene, trichlorobenzene, monochlorobenzene, dichloropropane, trichloropropene and dichlorobutene. Of these various chlorinated hydrocarbons, chlorinated products of aliphatic saturated hydrocarbons are the more effective. Those having 2 to 8 carbon atoms and 2 to 6 chlorine atoms yield better results and hexachloroethane, pentachloroethane, tetrachloroethane, trichloroethane, tetrachloroethylene, hexachloropropane, pentachloropropane, tetrachloropropane, tetrachloropropane, trichloropropane and dichloropropane are particularly preferable. These chlorinated hydrocarbons can be used individually or in combination.

The chlorinated hydrocarbon treatment is carried out by contacting the above-described reduced solid with a chlorinated hydrocarbon having 2 carbon atoms or more in the presence of a complexing agent and an aluminum trichloride-ether complex, but, in practice, it is simplest to effect this treatment by adding a mixture of the chlorinated hydrocarbon, the complexing agent and an aluminum trichloride-ether complex or a mixture of the chlorinated hydrocarbon, a complexing agent, an aluminum trichloride-ether complex and an inert solvent to the reduced solid or an inert solvent containing the reduced solid. Of course, other methods can be employed; for example, first treating the reduced solid with complexing agent and then contacting with the chlorinated hydrocarbon and an aluminum trichloride-ether complex; or first contacting the reduced solid with the chlorinated hydrocarbon and then with the complexing agent and an aluminum trichlorideether complex. As the method for contacting the reduced solid with the chlorinated hydrocarbon, complexing agent and an aluminum trichloride-ether complex, it is also possible to add the reduced solid or a dispersion of the reduced solid in an inert solvent to the chlorinated hydrocarbon, complexing agent and an aluminum trichloride-ether complex or a mixture thereof with an inert solvent. Furthermore, it is possible to add the chlorinated hydrocarbon, complexing agent, an aluminum trichloride-ether complex and optionally an inert solvent to the reduced solid. followed by crushing.

For the above-described treatment with a chlorinated hydrocarbon having 2 carbon atoms or more, there are optimum conditions depending on the property, composition and the like of the reduced solid. However, in general, at low temperature, this treatment should be carried out over a long time, while at high temperature, it can be carried out in relatively short time. For example, the treatment time is generally 5 minutes to 20 hours at 0 to 1700C., preferably 30 minutes to 20 hours at 20 to 1500C. and more preferably 1 to 10 hours at 50 to 100do., but this is not always necessary.

The quantities of chlorinated hydrocarbon having 2 carbon atoms or more, complexing agent and aluminum trichloride-ether complex are not particularly limited, but, 0.2 to 3.0 mols, preferably 0.4 to 2.0 mols of the chlorinated hydrocarbon, 0.1 to 2.5 mole, preferably 0.3 to 0.8 mol of complexing agent and 0.05 to 3.0 mols, preferably 0.1 to 0.6 mol of aluminum trichloride-ether complex are preferably used per 1 gram atom of titanium in the reduced solids.

When the reduced solid is treated with complexing agent and then with the chlorinated hydrocarbon and an aluminum trichloride-ether complex. the contact with the complexing agent is carried out at 0 to 120 C. for 5 minutes to 8 hours, preferably at 20 to 90"C. for 30 minutes to 3 hours and then the contact with the chlorinated hydrocarbon and an aluminum trichloride-ether complex is carried out at 20 to 150 C. for 1 to 10 hours. In this case also, the quantities of complexing agent. the chlorinated hydrocarbon and aluminum trichlorideether complex are not particularly limited, but, in general, 0.1 to 2.5 mols, preferably 0.3 to 0.8 mol of complexing agent and 0.2 to 3.0 mols. preferably 0.4 to 2.0 mols of hexachloroethane and 0.05 to 3.0 mols, preferably 0.1 to 0.6 mol of aluminum trichloride-ether complex are preferably used per 1 gram atom of titanium in the reduced solid.

The complexing agent used in the present invention means a compound containing one or more electron donating atoms or groups i.e. an organic electron donor compound. That is to say, ethers, thioethers, thiols, organo phosphorus compounds. organo nitrogen compounds, ketones, esters and the like are used as such a compound. Useful examples of the ether are diethyl ether, diisopropyl ether. di-n-butyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether. di-2-ethylheptyl ether, allyl ethyl ether. allyl butyl ether, diphenyl ether, anisole, phenetole. chloroanisole. bromoanisole, dimethoxybenzene.

Useful examples of the thioether are diethvl thioether. di-n-propyl thioether. dicyclohexyl thioether. diphenyl thioether, ditolyl thiether. ethyl phenyl thioether. propyl phenyl thioether, diallyl thioether. Useful examples of the organo phosphorus compound are tri-n-butylphosphine, triphenylphosphine. triethyl phosphite. tributyl phosphite. Useful examples of the organo nitrogen compound are diethylamine. triethylamine, n propylamine, di-n-propylamine, tri-n-propylamine, aniline. dimethylaniline. In particular, ethers are preferably used and, above all, those having 4 to 16 carbon atoms are more desirable. As the inert solvent there are suitably used hydrocarbons, for example, aliphatic hydrocarbons such as pentane. hexane, heptane, octane alicyclic hydrocarbons such as cyclohexane, cyclopentane. aromatic hydrocarbons such as benzene, toluene and mixtures thereof.

Preferably the aluminum trichloride-ether complex used in the present invention is a complex made of 1 mol of aluminum trichloride and 1 mol of an ether. This complex can generally be obtained by dispersing aluminum trichloride in a hydrocarbon solvent, adding thereto ether in at least equimolar quantity to the aluminum trichloride at a temperature of at least room temperature and stirring the mixture until the aluminum trichloride is completely dissolved. Aluminum trichloride and ether can also be contacted in a system wherein the reduced solid is treated with a complexing agent and chlorinated hydrocarbon according to the process of the present invention. However, it is preferable to use the previously prepared complex by the above described method.

The ether used herein is not particularly limited, but an ether having 4 to 16 carbon atoms is preferably used because it is readilv obtained commercially.

The titanium trichloride catalyst product of the present invention is separated from the chlorinated hydrocarbon. complexing agent, aluminum trichloride-ether complex and inert solvent, optionally washed with an inert solvent and then contacted with an organoaluminum compound as co-catalyst in conventional manner as it is or after drying, thus obtaining a catalyst for the polymerization of a-olefins.

The titanium trichloride catalyst obtained by the process of the present invention can exhibit the best catalytic performance when containing a metal compound, in particular, an aluminum compound, a mixture thereof of a complex compound thereof corresponding to the metal in a proportion of 0.0001 to 0.2 gram atom per 1 gram atom of titanium, the chlorinated hydrocarbon in a proportion of 0.005 to 0.2 mol per 1 gram atom of titanium and complexing agent in a proportion of 0.005 to 0.2 mol per 1 gram atom of titanium.

The titanium trichloride catalyst of the present invention is ordinarily used as a catalyst for the polymerization of a-olefins in contact with an organo metal compound which is used as a co-catalyst for the Ziegler type catalyst, for example, monoalkylaluminum dichloride, dialkylaluminum monochloride or trialkylaluminum. If necessary, various compounds, for example complexing agents such as used in the present invention can further be added as a third component.

The catalyst for the polymerization of a-olefins consisting of the titanium trichloride catalyst of the present invention and an organoaluminum compound is an excellent catalyst for the homopolymerization or copolymerization of a-olefins such as propylene, butene-1, 4-methylpentene-t, etc., and can give uniform polymer particles at high catalytic activity and a high ratio of yield of stereoregular polymer in the polymerization of a-olefins in gaseous phase, liquid monomer or inert solvent. Therefore, this catalyst will render great service to industry.

When using the titanium trichloride catalyst prepared by the process of the present invention as a catalyst for the production of an ethylene-propylene block copolymer, as described below desirable effects are obtainable as compared with those obtainable by means of catalvsts well known in the art.

That is to say, in a process for producing an ethylene-propylene block copolymer by preparing a propylene homopolvmer in the first stage and reacting the propylene homopolymer with ethylene or ethylene and propylene, the titanium trichloride catalyst obtained by the process of the present invention is used and the reaction conditions are respectively adjusted so that the melt index of the homopolypropylene obtained in the reaction of the first stage may range from 3 to 20 and the ethylene-propylene block copolymer obtained in the copolymerization reaction of the second stage may have (1) a content of ethylene-propylene block portion of 5 to 3()% by weight and (2) an ethylene content in the ethylene-propylene block portion of 20 to 90coo by weight. Thus an ethylene-propylene block copolymer excellent in rigidity as well as shock resistance and having excellent particle characteristics, for example, a high bulk density. large mean particle size and narrow particle size distribution can be produced with a high yield and with a markedlv decreased quantity of atactic polymers as a by-product.

The present invention will now be illustrated in detail by the following Examples in which a reduced solid obtained by reducing titanium tetrachloride with DEAC or a mixture of DEAC and EADC is used for the sake of convenience. but is not intended that the invention be limited thereby.

EXAMPLE I 700 ml of purified heptane and 250 ml of titanium tetrachloride were charged in a 20()() ml flask equipped with a stirrer and placed in a thermostated bath at 0". and mixed. Then a mixture of 315 ml of DEAC (1.1 mol to I mol of titanium tetrachloride), 117 ml of EADC (0.5 mol to 1 mol of titanium tetrachloride) and 40() ml of purified heptane was dropwise added to this heptane solution of titanium tetrachloride kept at 0 C for a period of 3 hours.

After the dropwise addition, the reaction mixture was heated for 1 hour to 65"C. while stirring and the stirring was further continued at the same temperature for another hour to obtain a reduced solid. The resulting reduced solid was separated, washed with purified heptane and dried at 65"C. for 30 minutes under reduced pressure. The resulting reduced solid was red violet and the X-ray diffraction spectrum thereof showed that the peak at 2 8 = 42.4 ( -type crystal) was considerably smaller than the peak at 2 6 = 51.3 (5-type crystal).

25 g of this reduced solid was suspended in 100 ml of purified heptane to prepare a suspension. To this suspension, di-n-butyl ether was then added in a proportion of 0.6 mol to 1 gram atom of titanium in the reduced solid and stirred at 65"C. for 1 hour.

Furthermore, hexachlorethane in a proportion of 1 mol to 1 gram atom of titanium in the reduced solid and a previously prepared aluminum trichloride di-n-butyl ether complex in a proportion of 0.3 mol to 1 gram atom of titanium in a reduced solid were added thereto and stirred at 80"C. for 5 hours, thus obtained a titanium trichloride catalyst. The resulting titanium trichloride catalyst was further washed five times with 100 ml of purified heptane and then dried at 65"C. for 30 minutes to obtain a powdered titanium trichloride catalyst with a yield of 99%.

The titanium trichloride catalyst obtained in this way contained aluminum compounds corresponding to 0.019 gram atom of aluminum, 0.025 mol of di-n-butyl ether and 0.011 mol of hexachloroethane per 1 gram atom of titanium.

A polymerization test was carried out as to a polymerization catalyst using the titanium trichloride catalyst of the present invention. 100 mg of the titanium trichloride catalyst and DEAC in a proportion of 4 mols to 1 gram atom of titanium were charged in a 1000 ml autoclave, into which 600 ml (Normal State) of hydrogen and then 800 ml of liquid propylene were introduced. The contents in the autoclave were heated at 68"C. and polymerization was carried out for 30 minutes. Thereafter, the unreacted propylene was removed and then removal of the catalyst was carried out in conventional manner to obtain 213 g of polypropylene powder having a bulk density of 0.45 g/cc. Therefore, the polymerization activity (g of formed polymer per 1 g of catalyst, i.e., catalytic efficiency hereinafter referred to as "E") was 2130. The melt flow rate of this polypropylene (Melt Flow Rate- ASTM D 1238, hereinafter referred to as "MFR") was 4.8. The heptaneinsoluble content (hereinafter referred to as "HI") of this propylene was 98% measured by extracting with heptane for 5 hours using a Soxhlet extractor. These results are shown in Table I, in which P.S.D. index is an index to show the particle size distribution of a polymer powder calculated by the following formula: P.S.D. index = log (particle diameter (l) at 90% of integral particle diameter distribution curve/particle diameter ( > ) at 10% of integral particle diameter distribution curve) Comparative Example 1 A polymerization test was carried out in a manner similar to that of Example 1 except using a reduced solid not treated with the hexachloroethane, di-n-butyl ether and aluminum trichloride-di-n-butyl ether complex in place of the titanium trichloride catalyst used in Example 1; results obtained are shown in Table 1. It is apparent from these results that the performance of the titanium trichloride catalyst is remarkably improved by the treatment with hexachloroethane etc. according to the present invention.

Comparative Example 2 A polymerization test was carried out using a reduced solid treated in an analogous manner to Example 1 except that the hexachloroethane and aluminum trichloride-di-nbutyl ether complex were not used; results obtained are shown in Table I. It is apparent from these results that it is important for the present invention to use the hexachloroethane and aluminum trichloride-di-n-butyl ether complex.

Comparative Example 3 A polymerization test was carried out using a reduced solid treated in an analogous manner to Example 1 except that the hexachloroethane was not used, thus obtaining results shown in Table I.

Comparative Example 4 When the reduced solid was treated in an analogous manner to Example I except that the di-n-butyl ether (complexing agent) and aluminum trichloride - di-n-butyl ether complex were not used, the reduced solid became massive. The reduced solid was then subjected to a treatment with hexachloroethane, as in Example 1, at a treatment temperature of 35"C. over a treatment time of 16 hours without using the complexing agent, thus obtaining a titanium trichloride catalyst. Using this catalyst, a polymerization test was carried out in an analogous manner to Example 1 to obtain a powdered polypropylene with E = 400 and HI = 94%.

It is apparent from the above-described results that it is important for the titanium trichloride catalyst of the present invention to treat the reduced solid with hexachlor oethane in the presence of the complexing agent and aluminum trichloride -di-n-butyl ether complex.

TABLE I Example Comparative Example 1 1 2 3 Complexing Agent Di-n-Butyl Ether - Di-n-Butyl Ether Mol of Complexing Agent per 1 Gram Atom of Ti in Reduced 0.6 - 0.6 0.6 Solids Mol of Hexachloroethane per 1 Gram Atom of Ti in Reduced 1.0 - - Solids Mol of AlCl3-Di-n-butvl Ether per 1 Gram Atom of Ti in Re- 0.3 - - 0.3 duced Solids E 2130 410 760 780 HI 98 77 68 54 MFR 4.8 9.0 6.8 6.3 Bulk Density (g/cc) 0.44 0.32 0.29 0.28 P.S.D. Index 0.21 1.04 0.60 0.47 EXAMPLE 2 A titanium trichloride catalyst was prepared in an analogous manner to Example 1 except that titanium tetrachloride was reduced with DEAC only. The yield was 99%. Using this titanium trichloride catalyst, a polymerization test of propylene was then carried out in an analogous manner to obtain a powdered polypropylene with E = 2010. HI = 98%, MFR 5.0 Bulk Density = 0.46 g/cc.

EXAMPLES 3 TO 13 A titanium trichloride catalyst was prepared in an analogous manner to Example 1 except using the chlorinated hydrocarbon shown in Table II in place of the hexachloroethane used for the treatment of the reduced solid in Example 1 and using the same, a polymerization test was carried out with results as shown in Table II obtained.

TABLE 11 Example Chlorinated Hydrocarbon E HI 3 Pentachloroethane 1590 97 4 1.1.2,2- Tetrachloroethane 1350 92 5 1,1,2- Trichloroethane 1300 92 6 Tetrachlorocthylene 1200 90 7 l,1,2,2,3,3- Hexachloropropane 1900 98 8 1,1,2,3,3- Pentachloropropane 1700 97 9 1,1,2,3- Tetrachloropropane 1650 97 1 1,1,1,2- Tetrachloropropane 1780 97 11 1,1,2- Trichloropropane 1530 96 12 1,1- Dichloropropane 1500 96 13 1,2- Dichloropropane . 1530 95 EXAMPLES 14 and 15 A titanium trichloride catalyst was prepared in analogous manner to Example 1 except using aluminum trichloridediethyl ether complex (AlCl-Et2O) or aluminum trichloridediphenyl ether complex (AlCl-Ph2O) in place of the aluminum trichloride-di-n-butyl ether complex used in Example 1 and using the same, a polymerization test was carried out with results as shown in Table Ill obtained.

TABLE 111 Example Aluminum Chloride-Ether Complex E HI 14 AlCl3-Et2O 1850 96 15 AlCl3-Ph2O 1760 94 EXAMPLE 16 A polymerization test was carried out in an analogous manner to Example 1 except that, in addition to 800 ml of liquid propylene, 5.3 g of ethylene was intermittently added little by little under pressure during the polymerization for 30 minutes in the polymerization test using the titanium trichloride catalyst of Example 1, thus obtaining 255 g of an ethylene-propylene copolymer containing 2.0% of ethylene portion. The polymerization activity was 2550 and HI in the resulting copolymer was 94%.

EXAMPLES 17 to 20 50 mg of the titanium trichloride catalyst obtained in Example 1 and DEAC in a proportion of 5 mols to 1 gram atom of titanium were added to an autoclave in a nitrogen atmosphere, into which 900 ml of hydrogen and then 800 ml of liquid propylene were introduced. Then the contents in the autoclave were heated at 68"C. and the polymerization was carried out for 40 minutes. Thereafter, the excessive unreacted propylene was released and the pressure in the autoclave was lowered to 0 Kg/cm2 gauge, after which a previously prepared gaseous mixture of ethylene and propylene was fed in to effect polymer

TABLE IV Example Comparative Example 17 18 19 20 5 6 7 8 Copolymerization Time (hr.) 5 4 3 2.5 5 4 3 2.5 Ethylene/Propylene Ratio (mol/mol) 0.71 1.20 2.23 4.75 0.64 1.03 2.16 4.50 E (g/g-cat) 3500 3520 3430 3560 642 640 637 637 Ec (g/g-cat) 553 493 443 581 92 90 87 87 Ec/Time (g/g-cat.hr) 111 123 148 232 18 22 29 35 HI (% by weight) 97.5 97.5 98.0 97.8 93.6 93.7 93.6 93.5 MI (g/10 min) 2.8 2.5 3.0 2.8 2.5 2.7 2.3 3.0 Atactic Polymer Byproduct (% by weight) 3.1 2.5 2.8 3.0 10.3 11.5 11.0 9.0 Bulk Density (g/cm ) 0.49 0.47 0.48 0.47 0.40 0.39 0.38 0.38 Mean Grain Size ( ) 490 495 480 475 300 290 285 280 P.S.D. Index 0.25 0.27 0.26 0.27 0.93 0.95 1.01 1.13 Ethylene Content (% by Weight) 5.0 6.3 8.2 12.0 4.3 5.7 8.1 10.3 C-Value (% by weight) 15.8 14.0 12.9 16.3 14.3 14.0 13.7 13.7 G-Value (% by weight) 31.6 45.0 63.6 73.7 30.0 40.7 59.0 75.0 Stiffness 20 C (Kg/cm) 11800 11000 11050 10800 7950 8010 9550 10900 Izod Impact Strength 20 C with notch (Kg.cm/cm) 11 26 47 35 20 40 18 7.5 -40 C no notch (Kg.cm/cm) 19 28 39 29 20 28 23 15

Claims (14)

WHAT WE CLAIM IS:

1. A process for the production of a titanium trichloride catalyst component which comprises (a) reducing titanium tetrachloride with an organo metal compound and then (b) contacting the resulting product with a chlorinated hydrocarbon having at least 2 carbon atoms in the presence of an organic electron donor compound and an aluminum trichloride ether complex.

2. A process according to claim 1. wherein the chlorinated hydrocarbon having at least 2 carbon atoms is selected from hexachloroethane, pentachloroethane, tetrachloroethane, trichloroethane, tetrachloroethylene, hexachloropropane, pentachloropropane, tetrachloropropane, trichloropropane and dichloropropane.

3. A process according to claim 1 or 2 wherein the reduction of titanium tetrachloride is carried out in a solution thereof at a temperature of from -50 C. to +30"C. over a period of time from 30 minutes to 3 hours.

4. A process according to claim 3 wherein the organo metal compound or a solution thereof is added dropwise to a solution of titanium tetrachloride in an aliphatic hydrocarbon having 5 to 12 carbon atoms.

5. A process according to claims 1 to 4 wherein the treating step (b) is carried out at a temperature of 0 to 17ü C. for 5 minutes to 20 hours.

6. A process according to claim 5 wherein step (b) is carried out at a temperature of 20 to 15ü C. for a period of 30 minutes to 20 hours.

7. A process according to claim 5 wherein step (b) is carried out at a temperature of 50 to 100"C. for a period of 1 to 10 hours.

8. A process according to any of the preceding claims wherein the step (b) 0.2 to 3.0 mols of the chlorinated hydrocarbon, 0.1 to 2.5 mols of the complexing agent and 0.05 to 3.0 mols of aluminum trichloride ether complex are used per gram atom of titanium in the reduced solids.

9. A process according to claim 8 wherein in step (b) 0.4 to 2.0 mols of the chlorinated hydrocarbons, 0.3 to 0.8 mol of the complexing agent and 0.1 to 0.6 mol of aluminum trichloride ether complex are used per gram atom of titanium in the reduced solids.

10. A process according to any of the preceding claims wherein the ether-aluminum chloride complex is prepared by adding the ether to aluminum chloride which had been dispersed in a hydrocarbon solvent.

11. A process according to any of the preceding claims wherein the aluminum trichloride-ether complex is a complex of 1 mol of aluminum chloride and 1 mol of ether.

12. A process according to claim 11 wherein the ether used in the complex is an ether having 4 to 16 carbon atoms.

13. A process for producing a catalyst component according to claim 1 substantially as described with reference to the examples.

14. A catalyst whenever prepared by the process of any of claims 1 to 13.