GB1580129A - Titanium trichloride catalyst and process for the production thereof - Google Patents

Description

(54) TITANIUM TRICHLORIDE CATALYST AND PROCESS FOR THE PRODUCTION THEREOF (71) We, TOA NENRYO KOGYO K.K., a Corporation duly organised 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 stereoregular polymerization of a-olefins and a process for the production thereof, and more particularly, it is connected with a titanium trichloride catalyst for the stereoregular polymerization of a-olefins, whereby uniform polymer grains can be obtained with a high polymerization activity and a high stereoregular polymer ratio, and a process for producing the same.

As a catalyst used for the stereoregular polymerization of a-olefins, in general, are known halides of transition metal elements of low valency, for example, a-type titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, an eutectic substance of a-titanium trichloride and aluminum chloride, obtained by reducing titanium tetrachloride with aluminum, A-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, Japanese Patent Application (OPI) No. 59185/1973 describes a method of modifying a-type titanium trichloride by crushing a-type titanium trichloride with halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and hexachloroethane. However, this method is disadvantageous in that other type titanium trichlorides than a-type titanium trichloride cannot be used, preparation of the catalyst is complicated because of requiring a crushing treatment, etc., and the resulting catalyst is unsatisfactory in polymerization activity and stereoregular polymer yielding ratio.

Furthermore, the following have been proposed in the art: A method comprising reducing titanium tetrachloride with an organo aluminum compound, treating 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): A method comprising treating the same with carbon tetrachloride (Japanese Patent Application (OPI) No. 112289/1975); and a method comprising reducing titanium tetrachloride with an organo aluminum compound and then treating the thus obtained reduced solid containing titanium trichloride with a mixture of a complexing agent and carbon tetrachloride (Japanese Patent Application (OPI) No. 143790/1975).

However, the first method wherein the aftertreatment is carried out using titanium tetrachloride is poor economically since an expensive high concentration solution of titanium tetrachloride is required and the second method wherein the aftertreatment is carried out using carbon tetrachloride is advantageous in that expensive titanium tetrachloride can be substituted by cheap carbon tetrachloride, but is not always satisfactory since the yield of titanium trichloride is low due to the tendency of carbon tetrachloride to dissolve titanium trichloride and the resulting catalyst exhibits a low polymerization activity, low stereoregular polymer yielding ratio and unfavourable grain shape of polymer.

The present invention therefore provides a process for the production of a titanium trichloride catalyst component comprising: reducing titanium tetrachloride with an organo metallic compound of the formula RAlX3.n and wherein R is an alkyl or aryl group having 1-18 carbon atoms, X is a halogen atom and n is a numeral expressed as 1any3 at a temperature of from -50 C to +300C to produce a reduced solids product: treating said reduced solids product with a chlorinated saturated aliphatic hydrocarbon having at least 2 carbon atoms in the presence of a complexing agent which is a compound containing 1 or more electron donating atoms or groups selected from ethers, thioethers, thiols, organo phosphorus compounds, organo nitrogen compounds, ketones, esters and mixtures thereof at an elevated temperature of 50"C to 1500C for 1-10 hours and recovering the resulting treated reduced solids product as a titanium trichloride catalyst.

The titanium trichloride-containing reduced solid obtained by reducing titanium tetrachloride with an organo metal compound according to the present invention (which will hereinafter be referred to as "reduced solid") is a reduced solid substance which color is brown to red violet and which contains aluminum compounds or a mixture or complex compound thereof. In particular. It is preferable to use alkylaluminum compounds wherein R radicals have 2 to 6 carbon atoms, such as trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides and alkylaluminum sesquihalides, mixtures or complex compounds thereof. Examples of the trialkylaluminum are trimethylaluminum, triethylalu minum and tributylaluminum. Examples of the dialkylaluminum halide are dimethyalumi num chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diethylaluminum iodide. Examples of the monoalkylaluminum dihalide are methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, ethyla luminum dibromide and ethylaluminum diiodide. Ethylaluminum sesquichloride is an example of the alkylaluminum sesquichloride. Triethylaluminum, diethylaluminum chlor ide, ethylaluminum dichloride, ethylaluminum sesquichloride or their mixtures or complex compounds. for example, a mixture of diethylaluminum chloride and ethylaluminum dichloride is particularly preferable because these compounds are readily obtainable commercially and exhibit excellent effects.

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 +30"C. for a period of time of 30 minutes to three hours and the reverse addition method can be employed. The quantity of an 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 diethylaluminum chloride (DEAC) or a mixture of DEAC and ethylaluminum dichloride (EADC), 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.

Furthermore, a mixture of titanium tetrachloride and an organo metal compound may be aged at a temperature of 20 to 100"C. for 1 to 3 hours, but this treatment is not always necessary. Then the resulting reduced solid may be 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 in a uniform state 0.2 gram atom or more of a metal compound or a mixture or complex thereof as the metal, for example, aluminum, per 1 gram atom of titanium.

The titanium trichloride catalyst complex of the present invention can be 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. As the chlorinated hydrocarbon having 2 carbon atoms or more there can be used chlorinated saturated aliphatic hydrocarbons for example, hexachloroethane, pentachloroethane, tetrachlor oethane, trichloroethane, dichloroethane, monochloroethane, octachloropropane, hep tachloropropane, hexachlororpropane, pentachloropropane, tetrachloropropane. trichlor opropane, dichloropropane, monochloropropane, tetrachlorobutane, trichlorobutane, dichlorobutane, trichloropentane, dichloropentane, dichlorohexane, dichloroheptane and dichlorooctane. In the case of chlorinated hydrocarbons having 2 carbon atoms the effect thereof is increased with increase of the number of chlorine atoms. Hexachloroethane, pentachloroethane, tetrachloroethane, trichloroethane are preferably used and, in particu lar, hexachloroethane and pentachloroethane are more preferable. Above all, chlorinated hydrocarbons having 3 to 8 carbon atoms and 2 to 6 chlorine atoms have larger effects and hexachloropropane, pentachloropropane, tetrachloropropane and dichlorobutane are particularly preferable.

The treatment of the above-described reduced solid with a chlorinated hydrocarbon having two carbons or more and complexing agent may be accomplished by any means.

Thus, the order of contacting with the chlorinating agent and the complexing agent is not important. Such a method would still be included in the term "in the presence of". In practice, treatment may be effected by adding a mixture of the chlorinated hydrocarbon and the complexing agent or a mixture of the chlorinated hydrocarbon, a complexing agent and an inert solvent to the reduced solid or an inert solvent containing the reduced solid.

Other methods which can be employed, for example, which comprise firstly treating the reduced solid with a complexing agent and then contacting with the chlorinated hydrocarbon, or firstly contacting the reduced solid with the chlorinated hydrocarbon and then with a complexing agent. As the method for contacting the reduced solid with the chlorinated hydrocarbon and/or a complexing agent, it is also possible to add the reduced solid or a dispersion of the reduced solid in an inert solvent to the chlorinated hydrocarbon and/or a complexing agent or a mixture thereof with an inert solvent. Furthermore, it is possible to add the chlorinated hydrocarbon, a complexing agent 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 composition of the reduced solid, but in general, at a low temperature, this treatment should be carried out over a long time, and at a high temperature, it can be carried out for a relatively short time.

The quantities of a chlorinated hydrocarbon having 2 carbon atoms or more and a complexing agent are not particularly limited, but, in the case of using hexachloroethane or 1,1,2,2,3,3-hexachloropropane, for example, 0.2 to 3.0 mols, preferably 0.4 to 2.0 moles of chlorinated hydrocarbon and 0.1 to 2.5 mols, preferably 0.3 to 0.8 mol of a complexing agent are used per 1 gram atom of titanium.

The complexing agent used in the present invention means a compound containing one or more electron donating atoms or groups. That is to say, ethers, thioethers, thiols, organo phosphorus compounds, organo nitrogen compounds, ketones and esters 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 and dimethoxybenzene. Useful examples of the thioether are diethyl thioether, di-n-propyl thioether, dicyclohexyl thioether, diphenyl thioether, ditolyl thioether, ethyl phenyl thioether, propyl phenyl thioether and diallyl thioether. Useful examples of the organo phosphorus compound are tri-n-butylphosphine, triphenylphosphine, triethyl phosphite and tributyl phosphite. Useful examples of the organo nitrogen compound are diethylamine, triethylamine, n-propylamine, di-n--propylamine, tri-n-propylamine, aniline and 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 and octane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene and toluene, and mixtures thereof.

The so obtained titanium trichloride catalyst of the present invention may be separated from the chlorinated hydrocarbon, complexing agent and inert solvent, optionally washed with an inert solvent and then contacted with an organo aluminum compound as a cocatalyst in conventional manner as it is or after drying, thus obtaining a catalyst for the polymerization of a-olefins.

The titanium trichloride catalyst complex of the present invention can exhibit best catalytic performance when containing aluminum compound, a mixture thereof or 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 a complexing agent in a proportion of 0.005 to 0.2 mol per 1 gram atom of titanium.

The titanium trichloride catalyst complex of the present invention may ordinarily be used as a catalyst for the polymerization of a-olefins in contact with an organo metallic compound which is used as a cocatalyst 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 organo aluminum compound is very excellent as a catalyst for the homopolymerization or copolymerization of a-olefins such as propylene, butene-1 and 4-methyl-pentene-1, and can give uniform polymer grains with a high polymerization activity and a high stereoregular polymer ratio in the polymerization of a-olefins in a gaseous phase, liquid monomer or inert solvent. Therefore, this catalyst will render great services to the industry.

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.

Example 1 700 ml of purified heptane and 250 ml of titanium tetrachloride were charged in a 2000 ml flask equipped with a stirrer and placed in a thermostat kept at 0 C. and mixed. Then a mixture of 315 ml of DEAC (1.1 mol to 1 mol of titanium tetrachloride), 117 ml of EADC (0.5 mol to 1 mol of titanium tetrachloride) and 400 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 at 650C. 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 650C. 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 0 = 42.4 (P-type crystal) was considerably smaller than the peak at 2 0 = 51.30 type crystal).

25 g of this reduced solid was suspended in 100 ml of purified heptane to prepare a suspension, to which hexachloroethane was then added in a proportion of 1 mol of hexachloroethane to 1 gram atom of titanium in the form of a solution containing 25 g of hexachloroethane in 100 ml and further di-n-butyl ether was added in a proportion of 0.6 mol of di-n-butyl ether to 1 gram atom of titanium, followed by stirring.

The thus mixed liquor was then heated with agitation to 800C. and held for 5 hours, thus obtaining a titanium trichloride catalyst of the present invention. 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 95% as titanium.

The titanium trichloride catalyst obtained in this way contained aluminum compounds corresponding to 0.019 gram atom of aluminum, 0.023 mol of di-n-butyl ether and 0.011 mol of hexachloroethane per 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 was 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 204 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 efficience E) was 2040. The melt flow rate of this polypropylene (Melt Flow Rate-ASTM D 1238, hereafter referred to as MFR) was 4.9. The heptane-insoluble content (hereafter referred to as HI) of this polypropylene was 98% measured by extracting with heptane for 5 hours using a Soxhlet extractor. These results are shown in Table 1. In this table, 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 (F) at 90who of integral particle diameter distribution curve/particle diameter (F) at 10% of integral particle diameter distribu tion curve).

Comparative Example 1 A polymerization test was carried out in the similar manner to Example 1 except using a reduced solid not treated with chlorinated hydrocarbon and di-n-butyl ether in place of the titanium trichloride catalyst used in Example 1, thus obtaining results shown in Table 1. It is apparent from this result that the performance of the titanium trichloride catalyst is remarkably improved by the treatment with hexachloroethane according to the present invention.

Comparative Example 2 A polymerization test was carried out using a reduced solid treated in the similar manner to Example 1 except that no chlorinated hydrocarbon was used, thus obtaining results shown in Table 1. It is apparent from this result that it is important for the present invention to use hexachloroethane.

Comparative Example 3 When a reduced solid was treated in the similar manner to Example 1 except that di-n-butyl ether (complexing agent) was not used, the reduced solid became massive. The reduced solid was subjected to a treatment with hexachloroethane, as in Example 1, at a treatment temperature of 35"C. for 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 the similar manner to Example 1 to obtain a powdered polypropylene with E = 400 and HI = 94%.

It is apparent from the above-described result that it is important for the titanium trichloride catalyst of the present invention to treat a reduced solid with a chlorinated hydrocarbon in the presence of a complexing agent.

Examples 2 to 5 A polymerization test was carried out using a titanium trichloride catalyst obtained by the same procedure as that of Example 1 except varying the temperature and period of time when the reduced solid of Example 1 was treated with hexachloroethane, thus obtaining results as shown in Table 1.

Examples 6 to 11 A titanium trichloride catalyst was prepared and a polymerization test was carried out in the similar manner to Example 1 except varying the quantity and variety of the complexing agent when the reduced solid was treated with hexachloroethane as in Example 1, thus obtaining results as shown in Table 2.

Examples 12 to 15 A titanium trichloride catalyst was prepared and a polymerization test was carried out in the similar manner to Example 1 except varying the quantity of hexachloroethane used when the reduced solid was treated with hexachloroethane as in Example 1, thus obtaining results shown in Table 3.

Example 16 A titanium trichloride catalyst was prepared in the similar manner to Example 1 except that titanium tetrachloride was reduced with DEAC only. This titanium trichloride catalyst contained aluminum compounds corresponding to 0.021 gram atom of aluminum, 0.018 mol of butyl ether and 0.020 mol of hexachloroethane per 1 gram atom of titanium.

Using the so obtained titanium trichloride catalyst, a polymerization test was carried out in the similar manner to Example 1, thus obtaining a powdered polypropylene with E = 1590, HI = 97%, MFR = 6.3 and bulk density = 0.44 g/cc.

Example 17 A polymerization test was carried out in the similar manner to Example 1, using the titanium trichloride catalyst obtained in Example 1 but adjusting the polymerization temperature at 73"C. and the polymerization time to 3 hours, thus obtaining a powdered polypropylene with E = 12000, HI = 96%, MFR = 5.3 and bulk density = 0.44 g/cc.

Example 18 The reduced solid obtained in Example 1 was suspended in 100 ml of purified heptane, mixed with di-n-butyl ether in a proportion of 0.6 mol to 1 gram atom of titanium and kept at 35"C. for 1 hour. The reduced solid was separated therefrom, mixed with hexachloroethane in a proportion of 1 mol to 1 gram atom of titanium in the form of a solution containing 25 g of hexachloroethane in 100 ml of heptane and heated at 80"C. for 5 hours to obtain a titanium trichloride catalyst, followed by washing and drying in an analogous manner to Example 1. Using this titanium trichloride catalyst, a polymerization test was carried out in the same manner as that of Example 1, thus obtaining a polypropylene powder with E = 1500, HI = 97%, MFR = 3.8 and bulk density of 0.45 g/cc.

Example 19 A titanium trichloride catalyst was prepared and a polymerization test was carried out in an analogous manner to Example 1 except using pentachloroethane in place of the hexachloroethane of Example 1, thus obtaining a powdered polypropylene with E = 1579 and HI = 97%.

Example 20 A titanium trichloride catalyst was prepared and'a polymerization test was carried out in an analogous manner to Example 1 except using 1,1,2,2-tetrachloroethane in place of the hexachloroethane of Example 1, thus obtaining a powdered polypropylene with E = 1310 and HI = 92%.

Example 21 A titanium trichloride catalyst was prepared and a polymerization test was carried out using the titanium trichloride catalyst, in an analogous manner to Example 1 except using tetrachloroethylene in place of the hexachloroethane of Example 1, thus obtaining a powdered polypropylene with E = 1080 and HI = 90%.

Example 22 A titanium trichloride catalyst was prepared and a polymerization test was carried out using the titanium trichloride catalyst, in an analogous manner to Example 1 except using 1,2-dichloroethane in place of the hexachloroethane of Example 1, thus obtaining a polypropylene powder with E = 1250 and HI = 92%.

Example 23 The reduced solid obtained in Example 1 was suspended in heptane to prepare a suspension, to which di-n-butyl ether was added in a proportion of 0.6 mol to 1 gram atom of titanium, and the mixture was stirred at 65"C. for 1 hour. Then hexachloroethane in a proportion of 1 mol per 1 gram atom of titanium was added thereto in the form of the same solution as that of Example 1 and heated at 80 C. for 4 hours. Thereafter, the procedure of Example 1 was repeated to prepare a catalyst and then to effect a polymerization test using the same, thus obtaining a result with E = 1950 and HI = 98.1%.

Example 24 Preparation of a titanium trichloride catalyst and polymerization test using the titanium trichloride catalyst were carried out in the similar manner to Example 1, except that, in place of the hexachloroethane and di-n-butyl ether used for the treatment of the reduced solid in Example 1, 0.6 mol of di-n-butyl ether, 1 mol of hexachloroethane and 0.3 mol of tetrachloroethylene were added and mixed with agitation, thus obtaining results of a titanium trichloride yield of 97% as titanium, E = 2100, HI = 98%, MFR = 5.0 and bulk density = 0.46 g/cc.

TABLE 1 Comparative Example Example 1 2 3 4 5 1 2 Complexing Agent Di-n-butyl ether Mol of Complexing Agent 0.6 0.6 per 1 gram atom of Ti Mol of Hexachloroethane 1 1 1 1 1 -- -per 1 gram atom of Ti Treatment Temp. ( C.) 80 65 65 80 90 -- 80 Treatment Time (hr.) 5 2 5 2 2 -- 5 E 2040 1660 1690 1700 1830 410 760 HI 98 96 97 97 98 77 68 MFR 4.9 6.1 5.1 4.8 7.1 9.0 6.8 Bulk Density (g/cc) 0.45 0.46 0.46 0.45 0.45 0.32 0.29 PSD Index 0.20 0.19 0.19 0.21 0.20 0.93 0.47 Per 1 Mol of Catalyst Solid Mol of Complexing Agent 0.023 0.019 0.010 0.022 0.018 -- 0.09 Mol of Aluminum Compound 0.019 0.018 0.021 0.016 0.015 0.54 0.11 Mol of Hexachloroethane 0.011 0.012 0.030 0.027 0.033 -- -- TABLE 2 Example 6 7 8 9 10 11 Complexing Agent -Di-n-Butyl ether- Di-n-Amyl Diisoamyl Di-n-Heptyl Di-2-Ethyl ether ether ether hexyl ether Mol of Complexing Agent per 1 gram atom of Ti 0.3 0.9 0.6 0.6 0.6 0.6 Mol of Hexachloroethane per 1 gram atom of Ti 1 1 1 1 1 1 Treatment Temp. ( C.) 80 80 80 80 80 80 Treatment Time (hr.) 5 5 5 5 5 5 E 1490 1790 1640 2040 1890 1680 HI 97 98 97 97 96 97 MFR 4.6 4.8 6.3 5.1 5.0 5.9 Bulk Density (g/cc) 0.46 0.46 0.45 0.45 0.43 0.46 Per 1 mol of Catalyst Solid Mol of Complexing Agent 0.020 0.083 0.024 0.026 0.048 0.032 Mol of Aluminum Compound 0.12 0.017 0.023 0.014 0.031 0.024 Mol of Hexachloroethane 0.012 0.018 0.017 0.010 0.020 0.018 TABLE 3 Example 12 13 14 15 Complexing Agent Di-n-Butyl ether Mol of Complexing Agent 0.6 per 1 Gram atom of Ti Mol of Hexachloroethane 0.5 0.8 1.5 2.0 per 1 gram atom of Ti Treatment Temp. ( C.) 80 80 80 80 Treatment Time (hr.) 5 5 5 5 E 1690 1860 2010 1790 HI 97 98 97 98 MFR 5.4 6.3 4.8 4.9 Bulk Density (g/cc) 0.46 0.45 0.46 0.44 Per 1 mol of Catalyst Solid Mol of Complexing Agent 0.020 0.029 0.049 0.013 Mol of Aluminum Compound 0.018 0.017 0.022 0.032 Mol of Hexachloroethane 0.010 0.020 0.012 0.024 Reference Example 1 When 25 g of the reduced solid obtained in Example 1 was suspended in 100 ml of purified heptane, mixed with butyl ether in a proportion of 1 mol to 1 gram atom of titanium and carbon tetrachloride in a proportion of 4 mols to 1 gram atom of titanium and heated at 80"C. for 5 hours in an analogous manner to Example 1, the most part of titanium trichloride in the reduced solid was dissolved and the yield of a titanium trichloride catalyst was 5% as titanium. This catalyst was brown.

Reference Example 2 25 g of the reduced solid obtained in Example 1 was suspended in 100 ml of purified heptane, mixed with 1 mol of butyl ether and 4 mols of carbon tetrachloride per 1 gram atom of titanium and heated at 350C. for 4 hours in an analogous manner to Example 1 to obtain a titanium trichloride catalyst. In this case, the titanium trichloride was also dissolved and the yield of the catalyst was only 40%. This catalyst was black brown, Using the so obtained catalyst, a polymerization test was carried out in an analogous manner to Example 1, thus obtaining a powdered polypropylene with E = 400, HI = 85% and bulk density of 0.3 g/cc.

Reference Example 3 25 g of the reduced solid obtained in Example 1 was suspended in 100 ml of purified heptane, mixed with di-n-butyl ether in a proportion of 1 mol to 1 gram atom of titanium and kept at 350C. for 1 hour. Then the reduced solid was separated therefrom, suspended in 100 ml of purified heptane, mixed with carbon tetrachloride in a proportion of 4 mols to 1 gram of titanium and kept at 35"C. for 16 hours, thus obtaining a titanium trichloride catalyst with a yield of 40%.

Using this titanium trichloride catalyst, a polymerization test was carried out in an analog us manner to Example 1, thus obtaining a powdered polypropylene with E = 670, HI = 84.5% and bulk density = 0.33 g/cc.

Example 25 700 ml of purified heptane and 250 ml of titanium tetrachloride were charged into a 2000 ml flask equipped with a stirrer and placed in a thermostat at 0 C. and mixed. Then a mixture of 315 ml of DEAC (1.1 mol to 1 mol of titanium tetrachloride), 117 ml of EADC (0.5 mol to 1 mol of titanium tetrachloride) and 400 ml of purified heptane was dropwise added to this heptane solution of titanium tetrachloride kept at OOC. for a period of 3 hours.

After the dropwise addition, the reaction mixture was heated for 1 hour to 650C. while hereinafter referred to as "E") was 1810. The melt flow rate of this polypropylene (Melt Flow Rate - ASTM D 1238, hereinafter referred to as "MFR") was 4.5. The heptaneinsoluble content (hereinafter referred to as "HI") of this propylene was 97.5% measured by extracting with heptane for 5 hours using a Soxhlet extractor. These results are shown in Table 4. 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 (Il) at 90% of integral particle diameter distribution curve/particle diameter (y) at 10% of integral particle diameter distribution curve).

Comparative Example 4 When the reduced solid was treated in an analogous manner to Example 25 except that di-n-butyl ether (complexing agent) was not used and then subjected to a treatment with 1,1,2,2,3,3-hexachloropropane, as in Example 25, 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 result that it is important for the titanium trichloride catalyst of the present invention to treat the reduced solid with 1,1,2,2,3,3hexachloropropane in the presence of a complexing agent.

Examples 26 to 29 A polymerization test was carried out using a titanium trichloride catalyst obtained by the same procedure as that of Example 1 except varying the temperature and period of time when the reduced solid of Example 1 was treated with 1,1,2,2,3,3-hexachloropropane, thus obtaining results as shown in Table 4.

TABLE 4 Example 25 26 27 28 29 Complexing Agent Di-n-tubyl ether Mol of Complexing Agent 0.6 per 1 gram atom of Ti Mol of 1,1,2,2,3,3-Hexachloropropane per 1 gram 1 atom of Ti Treatment Temp. ( C.) 80 70 70 80 90 Treatment Time (hr.) 5 2 5 2 2 E 1810 1580 1650 1670 1700 HI 97.5 95.5 96 96 97.0 MFR 4.5 5.1 5.3 4.8 6.1 Bulk density (g/cc) 0.45 0.46 0.46 0.45 0.45 PSD Index 0.22 0.19 0.20 0.21 0.20 Per 1 mol of Catalyst Solid Mol of Complexing Agent 0.10 0.011 0.010 0.009 0.008 Mol of Aluminum Compound 0.031 0.033 0.032 0.030 0.029 Mol of 1,1,2,2,3,3-hexa- 0.033 0.034 0.031 0.032 0.031 chloropropane Examples 30 to 36 A titanium trichloride catalyst was prepared and a polymerization test was carried out in an analogous manner to Example 1 except varying the quantity and variety of the complexing agent when the reduced solid was treated with 1,1,2,2,3,3-hexachloropropane as in Example 25, thus obtaining results as shown in Table 5.

TABLE 5 Example 30 31 32 33 34 35 36 Complexing Agent Di-n-butyl Di-n-butyl Di-n-amyl Diisoamyl Di-n-heptyl Di-2-ethyl Anosole ether ether ether ether ether hexyl ether Mol of Complexing Agent per 1 gram atom of Ti 0.3 0.9 0.6 0.6 0.6 0.6 0.6 Mol of 1,1,2,2,3,3-hexachloropropane per 1 gram 1 1 1 1 1 1 1 atom of Ti Treatment Temp. ( C.) 80 80 80 80 80 80 80 Treatment time (hr.) 5 5 5 5 5 5 5 E 1010 1700 1650 1800 1700 1590 1550 HI 94 98 97 97.5 97 96.5 97.0 MFR 4.3 4.7 6.0 5.0 4.9 4.5 4.3 Bulk Density (g/cc) 0.43 0.45 0.45 0.45 0.45 0.44 0.45 Per 1 mol of catalyst solid Mol of Complexing Agent 0.005 0.015 0.013 0.014 0.016 0.017 0.020 Mol of Aluminum Compounds 0.100 0.029 0.030 0.031 0.032 0.030 0.035 Mol of 1,1,2,2,3,3,-hexachloropropane 0.031 0.035 0.029 0.028 0.031 0.029 0.025 Examples 37 to 40 A titanium trichloride catalyst was prepared and a polymerization test was carried out in an analogous manner to Example 25 except varying the quantity of 1,1,2,2,3,3hexachloropropane used when the reduced solid was treated with 1,1,2,2,3,3hexachloropropane as in Example 25 thus obtaining results as shown in Table 6.

TABLE 6 Example 37 38 39 40 Complexing Agent Di-n-butyl ether Mol of Complexing Agent 0.6 per 1 gram atom of Ti Mol of 1,1,2,2,3,3-hexa- 0.5 0.8 1.5 2.0 chloropropane per 1 gram atom of Ti Treatment Temp. C. 80 80 80 80 Treatment Time (hr.) 5 5 5 5 E 1450 1700 1780 1650 HI 95 97 97 96.5 MFR 5.3 6.2 4.5 4.9 Bulk Density (g/cc) 0.44 0.45 0.45 0.44 Per 1 mol of Catalyst Solid Mol of Complexing Agent 0.015 0.011 0.012 0.011 Mol of Aluminum Compounds 0.035 0.029 0.030 0.031 Mol of 1,1,2,2,3,3-hexa- 0.027 0.031 0.033 0.034 chloropropane Example 41 The reduced solid obtained in Example 25 was suspended in heptane to prepare a suspension, to which 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 the mixture was stirred at 650C. for 1 hour. Then 1,1,2,2,3,3-hexachloropropane in a proportion of 1 mol per 1 gram atom of titanium in the reduced solid was added thereto in the form of the same solution as that of Example 1 and heated at 800C. for 4 hours.

Thereafter the procedure of Example 25 was repeated to prepare a catalyst and then to effect a polymerization test using the same, thus obtaining a result of E = 1760 and HI = 97.4%.

Example 42 A titanium trichloride catalyst was prepared in an analogous manner to Example 25 except that titanium tetrachloride was reduced with DEAC only. This titanium trichloride catalyst contained aluminum compounds corresponding to 0.031 gram atom of aluminum, 0.010 mol of butyl ether and 0.033 mol of 1,1,2,2,3,3-hexachloropropane per 1 gram atom of titanium.

Using the so obtained titanium trichloride catalyst, a polymerization test was carried out in an analogous manner to Example 1, thus obtaining a powdered polypropylene with E = 1800, HI = 97%, MFR = 4.9 and bulk density = 0.44 g/cc.

Example 43 A polymerization test was carried out in an analogous manner to Example 25, using the titanium trichloride catalyst obtained in Example 25 but adjusting the polymerization temperature to 730C. and the polymerization time to 3 hours, thus obtaining a powdered polypropylene with E = 10,000, HI = 96%, MFR = 5.3 and bulk density = 0.44 g/cc.

Examples 44 to 61 A titanium trichloride catalyst was prepared and a polymerization test was carried out by the same method as that of Example 1 except using other chlorinated hydrocarbons of C3 or higher than 1,1,2,2,3,3-hexachloropropane in Example 1, thus obtaining results shown in Tables 7 to 9.

TABLE 7 Example 44 45 46 47 48 49 50 Chlorinated Compound *1) *2) *3) *4) *5) *6) *7) Mol of Chlorinated Compound 1.0 per 1 gram atom of Ti Mol of n-butyl ether per 1 0.6 gram atom of Ti Treatment Temp. C. 80 Treatment Time (hr.) 5 E 1650 1580 1700 1510 1450 1450 1400 HI 97.5 96.8 97.3 96.7 96.5 96.0 95.8 MFR 4.9 4.3 4.1 3.8 3.8 3.1 4.5 Bulk Density (g/cc) 0.45 0.45 0.46 0.45 0.44 0.44 0.44 Per 1 mol of Catalyst Solid Mol of Chlorinated Cpd 0.035 0.036 0.031 0.033 0.032 0.033 0.035 Mol of Aluminum Cpds 0.027 0.030 0.029 0.035 0.033 0.034 0.031 Mol of n-butyl ether 0.009 0.010 0.008 0.010 0.011 0.012 0.013 Note: *1) 1,1,2,3,3,-pentachloropropane *2) 1,1,2,3-tetrachloropropane *3) 1,1,1,2-tetrachloropropane *4) 1,1,1,2,2,3,3-heptachloropropane *5) octachloropropane *6) 1,1,2-trichloropropane *7) 1,1-dichloropropane TABLE 8 Example 51 52 53 54 55 56 Chlorinated Compound *1) *2) *3) *4) *5) *6) Mol of Chlorinated Compound per 1 gram atom of Ti 1.0 Mol of n-butyl ether per 1 gram atom of Ti 0.6 Treatment Temp. C. 80 Treatment Time (hr) 5 E 1700 1730 1470 1390 1430 1400 HI 96.0 97.0 94.8 93.7 94.9 94.5 MFR 5.1 5.3 4.3 4.1 3.5 3.3 Bulk Density (g/cc) 0.44 0.44 0.44 0.44 0.45 0.44 Per 1 mol of Catalyst Solid Mol of Chlorinated Cpd 0.029 0.030 0.027 0.031 0.026 0.030 Mol of Aluminum Cpds 0.036 0.035 0.033 0.037 0.034 0.033 Mol of n-butyl ether 0.015 0.013 0.014 0.011 0.009 0.009 Note: *1) 1,2-dichlorobutane *2) 1,4-dichlorobutane *3) 1,5-dichloropentane *4) 2,2-dimethyl-1,3-dichloropropane, *5) 1,6-dichlorohexane *6) 1,8-dichlorooctane TABLE 9 Example 57 58 59 60 61 Chlorinsted Compound 1,1-Dichloro 1,2,3-Tri- 1,3-dichloro- 1,2-dichloro- o-Dichloro -1-propene chloro-1- 2-butene cyclohexane benzene propene Mol of Chlorinated Compound 1.0 per 1 gram atom of Ti Mol fo n-butyl ether per 0.6 1 gram atom of Ti Treatment Temp. C. 80 Treatment Time (hr.) 5 E 1350 1410 1370 1300 1310 HI 93.5 93.7 93.3 93.1 93.5 MFR 3.8 3.5 3.3 3.3 3.1 Bulk Density (g/cc) 0.43 0.43 0.43 0.43 0.43 Per 1 mol of Catalyst Solid Mol of Chlorinated Cpd 0.037 0.035 0.033 0.037 0.038 Mol of Aluminum Cpds 0.033 0.034 0.031 0.030 0.023 Mol of n-Butyl 0.017 0.015 0.013 0.014 0.010 Example 62 A titanium trichloride catalyst was prepared and a polymerization test was carried out using the titanium trichloride catalyst, in an analogous manner to Example 25 except that 0.6 mol of di-n-butyl ether, 1 mol of 1,1,2,2,3,3-hexachloropropane and 0.3 mol of 1,2,3-trichloropropene per 1 gram atom of titanium in the reduced solid were added in place of the 1,1,2,2,3,3-hexachloropropane and di-n-butyl ether used for the treatment of the reduced solid in Example 25, followed by stirring and mixing, thus obtaining the following results.

Yield of titanium trichloride catalyst = 97% as titanium, E = 1900, HI = 98%, MFR = 5.0, Bulk Density = 0.47 g/cc.

Claims (19)

WHAT WE CLAIM IS:

1. A process for the production of titanium trichloride catalyst component comprising: reducing titanium tetrachloride with an organo metallic compound of the formula RnAlX3 n and wherein R is an alkyl or aryl group having 1-18 carbon atoms, X is a halogen atom and n is a numeral expressed as 1suns3 at a temperature of from -50"C to +30"C to produce a reduced solids product: treating said reduced solids product with a chlorinated saturated aliphatic hydrocarbon having at least 2 carbon atoms in the presence of a complexing agent which is a compound containing 1 or more electron donating atoms or groups selected from ethers, thioethers, thiols, organo phosphorus compounds, organo nitrogen compounds, ketones, esters and mixtures thereof at an elevated temperature of 50"C to 1500C for 1-10 hours and recovering the resulting treated reduced solids produce as a titanium trichloride catalyst.

2. A process according to claim 1 wherein the chlorinated hydrocarbon has 2 carbon atoms.

3. A process according to claim 1 wherein the chlorinated hydrocarbon has 3-8 carbon atoms.

4. A process according to claims 1-3 wherein the chlorinated hydrocarbon is selected from hexachloroethane, pentachloroethane, hexachloropropane, pentachloropropane tetrachloropropane, dichlorobutane and mixtures thereof.

5. A process according to claim 1, 2 or 4 wherein the chlorinated hydrocarbon is hexachloroethane.

6. A process according to claims 1, 3 or 4 wherein the chlorinated hydrocarbon is hexachloropropane.

7. A process according to claims 1, 3 or 4 wherein the chlorinated hydrocarbon is pentachloropropane.

8. A process according to claims 1, 3 or 4 wherein the chlorinated hydrocarbon is dichlorobutane.

9. A process according to claims 1-8 wherein said complexing agent is an ether having 4-16 carbon atoms.

10. A process according to claim 9 wherein the complexing agent is selected from di-n-butyl ether, di-n-amyl ether, diisoamylether and mixtures thereof.

11. A process according to claims 1-10 wherein said organo metal compound is an alkyl aluminum chloride compound.

12. A process according to claim 11 wherein said alkyl aluminum chloride compound contains diethyl aluminum chloride.

13. A process according to claims 1-12 wherein said reduced solids product is contacted with the chlorinated hydrocarbon in a ratio of 0.2-3.0 moles chlorinated hydrocarbon per one gram atom of titanium and with said complexing agent at a ratio of 0.1-2.5 moles complexing agent per one gram atom of titanium.

14. A process according to claims 1 to 13 wherein the reduced solids product is contacted with a mixture of the chlorinated hydrocarbon and complexing agent.

15. A process according to claims 1 to 13 wherein the reduced solids product is first mixed with the chlorinated hydrocarbon.

16. A process according to claims 1 to 13 wherein the reduced solids product is first mixed with the complexing agent.

17. A process according to claim 16 wherein the reduced solids product is mixed with the complexing agent at an elevated temperature of 20"-90"C for 30 minutes to 3 hours prior to the addition of said chlorinated hydrocarbon.

18. A process according to claim 1 substantially as hereinbefore described with reference to the accompanying Examples.

19. A titanium trichloride catalyst component wherever prepared by a process according to any one of the preceding claims.