Catalyst component for producing crystalline polymers and a process for producing the catalyst

Abstract: A catalyst component for producing crystalline olefin polymers comprises a linear olefin/non-olefin block copolmer having at least one linear olefin block copolymer and at least one non-linear olefin polymer block and (a) a titanium trichloride composition or (b) titanium, magnesium, a halogen and an electron donor as components for a carrier; the content of the linear olefin polymer block being from 0.1 to 49.5 by weight, the content of the non-linear olefin polymer block being from 0.01 to 49.5% by weight, the ratio by weight of the linear olefin polymer block to the non-linear olefin polymer block being 2/98 to 98/2 and in the case of (a), the content of the titanium trichloride composition being 99.89 to 1.0% by weight.

Description: This invention relates to a catalyst component which may be used for producing highly crystalline olefin polymers and to a process for producing the catalyst. More particularly, the invention relates to a catalyst component suitable for producing highly crystalline olefin polymers from which a film having improved transparency and very few voids is afforded. It is well known that crystalline olefin polymers, such as crystalline polypropylene, may be obtained by polymerizing olefins by means of so-called Ziegler-Natta catalysts comprising a compound of a transition metal of Groups IV to VI of the Periodic Table and an organometal compound of a metal of Groups I to III of the Table. As the transition metal compound, various titanium trichloride compositions have been particularly widely used. Among these titanium trichloride compositions, those of the type obtained by reducing TiCℓ 4 with an organoaluminum compound, followed by heat treatment, afford a polymer having a good form; and thus many processes for producing the above type compositions have been suggested. For example, a process of reducing TiCℓ 4 with an organoaluminium compound, followed by treating the resulting titanium trichloride with an electron donor and TiCℓ 4 to thereby enhance the catalyst activity and reduce the quantity of amorphous polymers formed (see Japanese Patent Publication No. Sho 53-3,356/1978) is proposed. We have already proposed a number of processes in this field. Of these, the following processes have led to improvements in the storage stability of titanium trichloride compositions, the polymerization activity and the crystallinity of the resulting olefin polymers, a process of producing olefin polymers using a titanium trichloride composition obtained by reacting TiCℓ 4 with a reaction product of an organoaluminum compound with an electron donor, followed by reacting the resulting solid with an electron donor and an electron acceptor (Japanese Patent Publication No. Sho 59-28,573/1984), and a process of producing olefin polymers using a titanium trichloride composition obtained by reacting TiCℓ 4 with a reaction product of an organoaluminum compound with an electron donor, followed by subjecting the resulting solids to polymerization treatment with an olefin and reacting the resulting material with an electron donor and an electron accept or (JP-A-58-17,104/1983). Further, in recent years, there has been widely investigated a process for producing olefin polymers which comprises using a titanium-containing solid catalyst component containing Ti, Mg, a halogen an electron donor, which component exhibits a very high polymerization activity while retaining a high stereoregularity, and polymerizing olefins in the presence of a catalyst obtained by combining the above solid catalyst component, an organoaluminum compound and an electron donor together (See, for example, JP-A-58-83,006/1983). We have also already proposed a number of processes in this field. For example, we have disclosed processes for producing olefin polymers having a high stereoregularity and a good particle form with a high polymerization activity (see, for example JP-A-61-209,207/1986, JP-A-62-104,810/1987, JP-A-62-104,811/1987, JP-A-62-104,812/1987, and JP-A-62-104,813/1987). However, while these improved processes have the above-mentioned advantages, films prepared the resulting polyolefins are translucent so that the commodity value is often damaged depending on the intended fields of use. Thus, an improvement in the transparency would be desirable. Various proposals have been made for improving the transparency of films prepared from olefin polymers. For example, processes of adding a nucleating agent, such as an aluminum salt of an aromatic carboxylic acid (Japanese patent publication No. SHo. 40-1,652/1965), benzylidene sorbitol derivatives (JP-A-51-22,740/1976) to polypropylene have been proposed. However, when aluminium salts of aromatic carboxylic acids are used, their dispersibility in the resulting polymer is not only inferior, but also the effectiveness of improvement in the transparency of the resulting film is insufficient, while when benzylidene sorbitorl derivatives are used, a definite improvement in the transparency is observed, but there are the problems that their smell at the time of processing is strong and a bleeding phenomenon (exudation) occurs. For solving the above-mentioned problem at the time of addition of nucleating agents, there have been proposed processes of polymerizing propylene using a catalyst obtained by polymerizing a small quantity of vinylcyclohexane, p-t-butylstyrene, allyltrimethylsilane or 4,4-dimethylpentene-1, followed by preactivation treatment (see JP-A-60-139,710/1985, JP-A-63-15,803/1988, JP-A-63-15,804/1988, JP-A-63-218,709/1988, EP-A-0 151 883). We have produced polypropylene according to the proposed processes, and as a result found that in any of the processes, not only is the polymerization activity to propylene lowered, but also there occurred operational problems such as formation of bulk polymer, scale adhesion onto the wall of polymerization vessels and inferior controllability of polymerization reaction. Thus these processes could not be employed for commercial, long term, continuous polymerization, particularly in the case of gas phase polymerization process wherein olefin polymerization was carried out. Further, when the resulting polypropylene was processed into film, a definite improvement in the transparency was observed, but a large number of voids occurred in the film to thereby damage its value. Further, as a similar technique, there has been proposed a process of polymerizing propylene using a transition metal catalyst component having vinylcyclohexane polymer or allyltrimethylsilane polymer added midway during the preparation of the component (see JP-A-63-69,809/1988). However, since the proposed process requires a separate step for preparing the vinylcyclohexane polymer or allyltrimethylsilane polymer, not only are there commercial disadvantages but also there has been raised the above-mentioned problem that voids occur in the resulting film, as observed in the prior art. We have now found, in accordance with the present invention, that a titanium trichloride composition or a supported type titanium catalyst component, each having a linear olefin/non-linear olefin block copolymer as hereinafter described may be used to provide improved crystalline polyolefins. The invention provides a process for producing a titanium trichloride composition for producing olefine polymers, which process comprises reacting TiCℓ 4 with an organoaluminum compound or a reaction product (I) of an organoaluminum compound with an electron donor (B 1 ) to form a solid product (II); subjecting said solid product (II) to a multi-stage polymerization treatment once or more with each of (1) a linear olefin and (2) a non-linear olefin to form a linear olefin/non-linear olefin block copolymer; and further reacting said block copolymr with an electron donor (B 2 ) and an electron acceptor to form a solid product (III); the content of the linear olefin polymer block product (III) being from 0.1 to 49.5% by weight and that of the non-linear olefin polymer block being from 0.01 to 49.5% by weight, and the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block being from 2/98 to 98/2. In the above process the organoaluminium compound is preferably one of the formula: A1R 8 p R 9 p' X 3 - (p+p') wherein R 8 and R 9 are each a hydrocarbon radical selected from alkyl groups, cycloalkyl groups and aryl groups, or an alkoxy group; X is a halogen atom and p and p' are numbers satisfying the relationship: 0 < p + p' ≤ 3 In the above process the non linear olefin is preferably one of the formula: CH 2 = CH - R 1 , or (in which R 1 is a ring containing hydrocarbon radical of 3 to 18 C atoms which may contain silicon, R 2 is silicon or a linear hydrocarbon radical of 1 to 3 carbon atoms which may contain silicon; and R 3 , R 4 and R 5 hydrocarbon radical of 1 to 6 carbon atoms which may contain silicon and any one of R 3 , R 4 and R 5 may be a hydrogen atom; R 6 is linear hydrocarbon radical of 1 to 6 carbon atoms which may contain silicon; R 7 is a hydrogen atom, a halogen atom or a hydrocarbon radical of 1 to 12 carbon atoms which may contain a silicon atom; n is 0 or 1; m is 1 or 2 and, when m is 2, the R 7 's may be different. BRIEF DESCRIPTION OF THE DRAWINGS The drawings show a chart of production steps (flowsheet) of the catalyst component, for illustrating the process of the present invention. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS As described above, the titanium trichloride composition for producing olefin polymers, produced according to the present invention is a titanium trichloride composition comprising a linear olefin-non-linear olefin block copolymer (hereinafter often abbreviated to a specified block copolymer) having at least one linear olefin polymer block and at least one non-linear olefin polymer block, and the production process of the composition will be described below. The production of the titanium trichloride composition is carried out as follows: An organoaluminum compound is at first reacted with an electron donor (B 1 ) to obtain a reaction product (I), which is then reacted with TiCℓl 4 or with an organoaluminum compound and TiCℓ 4 or with an organoaluminum compound and TiCℓ 4 to obtain a solid product (II), which is then subjected to a multi-stage polymerization treatment once or more with each of (1) an linear olefin and (2) a non-linear olefin to form a linear olefin-non-linear olefin block copolymer, which is further reacted with an electron donor (B 2 ) and an electron acceptor to obtain a final solid product (III) which is the titanium trichloride composition of the present invention. In addition, the terms "polymerization treatment" referred to herein means a process of polymerizing a linear olefin or a non-linear olefin in contact with the solid product (II) under polymerizable conditions thereof. Due to this polymerization treatment, the solid product (II) results in a condition coated with the resulting polymer. The above-mentioned reaction of an organoaluminum compound with an electron donor (B 1 ) is suitably carried out in a solvent (D) at -20°C to +200°C, preferably -10°C to +100°C, for 30 seconds to 5 hours. The addition order of the organoaluminum compound, (B 1 ) and (D) has no particular limitation, and the proportions of these compounds used are 0.1 to 8 mols, preferably 1 to 4 mols, of the electron donor (B) and 0.5 to 5 ℓ, preferably 0.5 to 2 ℓ, of the solvent, each based on one mol of the organoaluminum compound. Thus, the reaction product (I) is obtained. The product (I) may be subjected to the succeeding reaction without separating it, that is, in a solution state, as it is, where the reaction has been completed (hereinafter referred to often as "reaction solution (I)"). The process of reacting the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 , followed by subjecting the resulting solid product (II) to a multi-stage polymerization treatment with a linear olefin and a non-linear olefin, preferably includes 1 ○ a process of adding a linear olefin and a non-linear olefin at a multi-stage during an optional process of the reaction of the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 to subject the solid product (II) to a multi-stage polymerization treatment, 2 ○ a process of adding a linear olefin and a non-linear olefin at a multi-stage after completion of the reaction of the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 to subject the solid product (II) to a multi-stage polymerization treatment, and 3 ○ a process of after completion of the reaction of the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 , separating and removing the resulting liquid portion by filtering-off or decantation, followed by suspending the resulting solid product (II) in a solvent, further adding an organoaluminum compound, adding a linear olefin and a non-linear olefin at a multi-stage to carry out polymerization treatment with these olefins. Further, as to the order of the multi-stage polymerization treatment with a linear olefin and a non-linear olefin, either one of the linear olefin and the non-linear olefin may be used in advance, but it is preferred to carry out polymerization treatment at first with 1 ○ the linear olefin and successively carry out polymerization treatment with 2 ○ the non-linear olefin, in the aspect of polymerization operation properties at the time of using the resulting final titanium trichloride composition and also in the aspect of the quality of the resulting polyolefin. A linear olefin-non-olefin block copolymer is formed by the multi-stage polymerization treatment and the solid product (II) results in a state where it is coated by the solid product (II). Further, as described above, in the multi-stage polymerization treatment, the linear olefin and the non-linear olefin are used each at least once to thereby obtain the titanium trichloride composition achieving the object of the present invention, but it is also possible to carry out the polymerization treatment twice or more, for example, to carry out polymerization treatment with the non-linear olefin, followed by further adding 3 ○ the linear olefin to carry out polymerization treatment. The reaction of the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCl 4 is suitably carried out at -10°C to +200°C, preferably 0°C to 100°C for 5 minutes to 10 hours irrespective of whether a linear olefin and a non-linear olefin are added or not added during an optional process of the reaction. It is preferred to use no solvent, but an aliphatic or aromatic hydrocarbon may be used. Mixing of (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 and with a solvent may be carried out in an optional order, and addition of a linear olefin and a non-linear olefin may also be carried out at any stage. Mixing of the total quantity of (I), TiCℓ 4 , an organoaluminum compound and a solvent is preferred to be completed within 5 hours, and the reaction is also carried out during the mixing. After mixing of the total quantity, it is preferred to further continue the reaction within 5 hours. The respective quantities of the above materials used for the reaction preferably are 0 to 3,000 ml of the solvent and 0.05 to 10, more preferably 0.06 to 0.3 in terms of the ratio of the number of aluminum atoms in the reaction product (I) or an organoaluminum compound tp the number of Ti atoms in TiCℓ 4 (Aℓ/Ti), based on one mol of TiCℓ 4 . As to the polymerization treatment with a linear olefin and a non-linear olefin, either in the case where a linear olefin and a non-linear olefin are added during an optional process of the reaction of the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 , or in the case where a linear olefin and a non-linear olefin are added after completion of the reaction of the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 , the polymerization treatment is carried out at a multi-stage, under conditions of a reaction temperature of 0° to 90°C, a reaction time of one minute to 10 hours and a reaction pressure of the atmospheric pressure [0.1 MPa] (0 Kgf/cm 2 G) to 1.08 MPa (10 Kgf/cm 2 G), using 0.1 g to 100 Kg of a linear olefin and 0.01 g to 100 Kg of a non-linear olefin based on 100 g of the solid product (II), and so as to give a content of the resulting linear olefin polymer block in the final solid product (III) i.e. the titanium trichloride composition of the present invention, of 0.1 to 49.5% by weight and a content of the resulting non-linear olefin polymer block therein, of 0.01 to 49.5% by weight, and also a ratio by weight of the liner olefin polymer block to the non-linear olefin polymer block of 2/98 to 98/2. If the content of the linear olefin polymer block is less than 0.1% by weight, the improvement effect in the operational properties at the time of using the resulting titanium trichloride composition and the effect of inhibiting the voids of films prepared from the resulting polyolefin are insufficient, while even if the content exceeds 49.5% by weight, improvement in these effects is not notable, resulting in operational and economical disadvantages. Further, if the content of the non-linear olefin polymer block is less than 0.01% by weight, improvement effect in the transparency of the resulting films is insufficient, while if it exceeds 49.5% by weight, improvements in the effects are not notable, resulting in operational and economical disadvantages. Further, the ratio by weight of the linear olefin block polymer to the non-linear olefin polymer block is preferred to be 2/98 to 98/2 in view of the balance among the improvement effect upon the operational properties, the inhibition effect upon the voids and the improvement effect upon the transparency. In the case where the multi-stage polymerization treatment with a linear olefin and a non-linear olefin is suitably carried out using the solid product (II) obtained by reacting the reaction product (I) with TiCℓ 4 or an organoaluminum compound and TiCℓ 4 , followed by separating and removing the resulting liquid portion by filtering off or decantation and suspending the resulting solid product (II) in a solvent, either polymerization treatment with a linear olefin or with a non-linear olefin is carried out at a multi-stage, in the presence of 100 to 5,000 mℓ of a solvent and 0.5 to 5,000 g of an organoaluminum compound based on 100 g of the solid product (II), under reaction conditions of a reaction temperature of 0° to 90°C, a reaction time of one minute to 10 hours and a reaction process of the atmospheric pressure [0.1 MPa (0 kgf/cm 2 G] to 1.08 MPa (10 Kgf/cm 2 G), using 0.1 g to 100 Kg of linear olefin and 0.01 g to 100 Kg of a non-linear olefin based on 100 g of the solid product (II), and so as to give a content of a linear olefin polymer block in the final solid product (III) i.e. the titanium trichloride composition of the present invention, of 0.1 to 49.5% by weight and a content of a non-linear olefin therein of 0.01 to 49.5% by weight, and a ratio by weight of the linear olefin polymer block to the non-linear olefin polymer block of 2/98 to 98/2. In any of the above-mentioned multi-stage polymerization treatment, after completion of the polymerization treatments with the linear olefin or the non-linear olefin at the respective stages, the resulting reaction mixture may be used, as it is, for the polymerization treatment at the succeeding stage. Further, it is also possible to remove the coexisting solvent, unreacted linear olefin or non-linear olefin or organoaluminum compound by filtering-off or decantation, followed by again adding a solvent and an organoaluminum compound and using the resulting material for polymerization treatment with a non-linear olefin or a linear olefin at the succeeding stage. The solvent used at the time of the polymerization treatment is preferred to be an aliphatic hydrocarbon and the organoaluminum compound may be the same as or different from that used when the reaction product (I) is obtained, or that used for direct reaction with TiCℓ 4 without reacting with an electron donor (B 1 ). After completion of the reaction, the resulting liquid portion is suitably separated and removed by filtering-off or decantation, followed by repeating washing with a solvent to obtain a solid product subjected to polymerization treatment (hereinafter referred to often as solid product (II-A)), which product may be used in a suspended state in a solvent, as it is, for the succeeding step or may be further dried and taken out in the form of a solid material and used. The solid product (II-A) is then reacted with an electron donor (B 2 ) and an electron acceptor (F). This reaction may be carried out without any solvent, but use of an aliphatic hydrocarbon affords preferable results. The quantities of these materials are suitably 0.1 to 1,000 g, preferably 0.5 to 200 g of (B 2 ), 0.1 to 1,000 g, preferably 0.2 to 500 g of (F) and 0 to 3,000 mℓ, preferably 100 to 1,000 mℓ of the solvent, each based on 100 g of the solid product (II-A). The reaction process suitably includes 1 ○ a process of simultaneously reacting an electron donor (B 2 ) and an electron acceptor (F) with the solid product (II-A), 2 ○ a process of reacting (F) with (II-A), followed by reacting (B 2 ), 3 ○ a process of reacting (B 2 ) with (II-A), followed by reacting (F) and 4 ○ a process of reacting (B 2 ) with (F), followed by reacting (II-A), but any of the processes may be employed. As to the reaction conditions, 40° to 200°C, preferably 50° to 100°C and 30 seconds to 5 hours are preferred in the processes 1 ○ and 2 ○,while in the process 3 ○, (II-A) is preferably reacted with (B 2 ) at 0° to 50°c for one minute to 3 hours, followed by reacting (F) under the same conditions as in the processes 1 ○ and 2 ○. Further in the process 4 ○, (B 2 ) is suitably reacted with (F) at 10° to 100°C for 30 minutes to 2 hours, followed by cooling down to 40°C or lower, adding (II-A) and thereafter reacting the mixture under the same conditions as in the processes 1 ○ and 2 ○. After completion of the reaction of the solid product (II-A), (B 2 ) and (F), the resulting liquid portion is suitably separated and removed by filtering-off or decantation, followed by repeated washings with a solvent to obtain a solid product (III) as a titanium trichloride composition for producing olefin polymers, comprising a linear olefin-non-linear olefin block copolymer. The thus obtained solid product (III) i.e. the titanium trichloride composition of the present invention contains a linear olefin-non-linear olefin block copolymer in a ratio by weight of a linear olefin polymer block to a non-linear olefin polymer block of 2/98 to 98/2, the content of the linear olefin polymer block being 0.1 to 49.5% by weight and that of the non-linear olefin polymer block being 0.01 to 49.5% by weight, and is used as a transition metal compound catalyst component for producing olefin polymers,for olefin polymerization, in combination with at least an organoaluminum compound. The organoaluminum compound used for producing the titanium trichloride composition of the present invention is expressed by the formula AℓR 8 p R 9 p' X 3-(p+p') wherein R 8 and R 9 each represent a hydrocarbon radical such as an alkyl group, a cycloalkyl group, an aryl group, etc. or an alkoxy group, X represents a halogen atom and p and p' each represent an optional number satisfying an expression of 0 < p + p' ≦ 3. Concrete examples of the organoaluminum compound are trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum and tri-n-decylaluminium; dialkylaluminum monohalides such as diethylaluminum monochloride, di-n-propylaluminum monochloride, di-i-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide and diethylaluminum monoiodide; dialkylaluminum hydrides such as diethylaluminum hydride; dialkylaluminum sesqui halides such as methylaluminum sesquichloride and ethylaluminum sesquichloride; and monoalkylaluminium dihalides such as ethylaluminum dichloride and i-butylaluminium dichloride ; and, besides, alkoxyalkylaluminums, such as monoethoxydiethylaluminum and diethoxymonoethylaluminum, may be used. These organoaluminum compounds may be used in admixture of two or more kinds. As the electron donor used in the present invention, various ones mentioned below may be exemplified, but ethers are mainly used as (B 1 ) and (B 2 ), and other electron donors are preferred to be used together with ethers. Examples of compounds used as the electron donors are organic compounds having any atoms of oxygen, nitrogen, sulfur and phosphorus such as ethers, alcohols, esters, aldehydes, aliphatic acids, ketones, nitriles, amines, amides, ureas, thioureas, isocyanates, azo compounds phosphines, phosphites, phosphinites, hydrogen sulfide, thioethers and thioalcohols. Concrete examples thereof are ethers such as diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, di-i-hexyl ether, di-n-octyl ether, di-i-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, alcohols or phenols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol and naphthol; esters such as methyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluylate, ethyl toluylate, 2-ethylhexyl toluylate, methyl anisate, ethyl anisate, propyl anisate. ethvl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate and ethyl phenylacetate; aldehydes such as acetaldehyde and benzaldehyde; aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid and maleic acid; aromatic acids such as benzoic acid; ketones such as methyl ethyl ketone, methyl isobutyl ketone and benzophenone; nitrile acids such as acetonitrile; amines such as methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, N,N,N',N'-tetramethylethylenediamine, aniline and dimethylaniline; amides such as formamide, hexamethylphosphoric acid triamide, N,N,N',N',N"-pentamethyl-N'-β-dimethylaminomethylphosphoric acid triamide, and octamethylpyrophosphoroamide; ureas such as N,N,N',N'-tetramethylurea, isocyanates such as phenyl isocyanate and toluyl isocyanate; azo compounds such as azobenzene; phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine and triphenylphosphine oxide; phosphites such as dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite and triphenyl phosphite; phosphinites such as ethyldiethyl phosphinite, ethylbutyl phosphinite and phenyldiphenyl phosphinite; thioethers such as diethyl thioether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide and propylene sulfide; and thioalcohols such as ethyl thioalcohol, n-propyl thioalcohol and thiophenol. These electron donors may be used in admixture. The electron donor (B 1 ) used for obtaining the reaction product (I) and (B 2 ) reacted with the solid product (II-A) may be either same or different. The electron acceptor (F) used in the present invention is represented by halides of elements of Groups III to VI of the Periodic Table. Concrete examples thereof are anhydrous aluminum chloride,- silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride and vanadium tetrachloride, antimony pentachloride, and these may be used in admixture. Titanium tetrachloride is most preferred. As the solvent, the following may be used: aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, i-octane; halogenated hydrocarbons used in place of or together with aliphatic hydrocarbons, such as carbon tetrachloride, chloroform, dichloroethane, trichloroethylene and tetrachloroethylene; aromatic hydrocarbons such as napthalene; alkyl derivatives thereof such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene and 1-phenylnaphthalene; and halides thereof such as monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene and bromobenzene. Examples of the linear olefin used for the polymerization treatment in the present invention are ethylene, propylene, butene-1, pentene-1 and hexene-1, and ethylene and propylene are preferably used. These linear olefins may be used alone or in admixture. The non-linear olefin used for the polymerization treatment in the present invention is suitably as follows: 1 ○ saturated ring-containing hydrocarbon monomers expressed by the formula CH 2 =CH-R 1 wherein R 1 represents a saturated ring-containing hydrocarbon radical of 3 to 8 carbon atoms which may contain silicon; 2 ○ branched olefins expressed by the formula wherein R 2 represents a linear hydrocarbon radical of 1 to 3 carbon atoms which may contain silicon or silicon, R 3 , R 4 and R 5 each represent a linear hydrocarbon radical of 1 to 6 carbon atoms which may contain silicon, but either one of R 3 , R 4 and R 5 may be hydrogen atom; and 3 ○ aromatic monomers expressed by the formula wherein n represents 0 or 1, m represents 1 or 2, R 6 represents a linear hydrocarbon radical of 1 to 6 carbon atoms which may contain silicon and R 7 represents a hydrocarbon radical of 1 to 12 carbon atoms which may contain silicon, hydrogen atom or a halogen atom and when m represents 2, the respective R 7 s may be the same or different. Concrete examples of the saturated ring-containing hydrocarbon monomers 1 ○ are vinylcycloalkanes such as vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3-methylvinylcyclohexane, 4-methylvinylcyclohexane and vinylcycloheptane; allylcycloalkanes such as allylcyclopentane and allylcyclohexane; and, besides, saturated ring-containing hydrocarbon monomers having silicon atom in the saturated ring-structure such as cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, cyclotetramethylenevinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane; cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane and cyclopentamethyleneethylallylsilane; saturated ring-containing hydrocarbon monomers having silicon atom outside the saturated ring structure such as cyclobutyldimethylvinylsilane, cyclopentyldimethylvinylsilane, cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylmethylallylsilane, cyclohexyldiethylallylsilane, 4-trimethylsilylvinylcyclohexane, 4-trimethylsilylallylcyclohexane. Concrete examples of the branched olefins 2 ○ are 3-position-branched olefins such as 3-methylbutene-1, 3-methylpentene-1, 3-ethylpentene-1, etc., 4-position-branched olefins such as 4-ethylhexene-1, 4,4-dimethylpentene-1, 4,4-dimethylhexene-1; alkenylsilanes such as vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethylsilane, allyltriethylsilane, allyl-n-propylsilane, 3-butenyltrimethylsilane and 3-butenyltriethylsilane, and diallylsilanes such as dimethyldiallylsilane, ethylmethyldiallylsilane and diethyldiallylsilane, Further, concrete examples of the aromatic monomers 3 ○ are styrene, as its derivatives, alkylstyrenes such as o-methylstyrene, p-t-butylstyrene, dialkylstyrenes such as 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene and 3,5-dimethylstyrene; halogensubstituted styrenes such as 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, o-fluorostyrene and p-fluorostyrene; trialkylsilylstyrenes such as p-trimethylsilylstyrene, m-triethylsilylstyrene, and p-ethyldimethylsilylstyrene, allyltoluenes such as o-allyltoluene and p-allyltoluene; allylxylenes such as 2-allyl-p-xylene, 4-allyl-o-xylene, and 5-allyl-m-xylene, alkenylphenylsilanes such as vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane and allylethylmethylphenylsilane ; 4-(o-tolyl)-butene-1 and 1-vinylnaphthalene. These non-linear olefins may be used alone or in admixture. The thus obtained titanium trichloride composition of the present invention is combined with at least an organoaluminum compound and used as a catalyst for olefin polymerization in a conventional manner, or further preferably the composition is reacted with an olefin and the resulting preactivated catalyst is used for olefin polymerization. As the organoaluminum compound used for olefin polymerization, organoaluminum compounds same as those used when the above titanium trichloride composition of the present invention is prepared may be used. The organoaluminum compounds may be the same as or different from those used when the titanium trichloride composition is prepared. Further, examples of olefins used for the above preactivation are linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, or heptene-1, and branched monoolefins such as 4-methyl-pentene-land 2-methyl-pentene-1. These olefins may be same as or different from those as the object of the polymerization, and two kinds or more of olefins may be used in admixture. The polymerization form in which the above catalyst is used has no particular limitation, but not only liquid phase polymerization such as slurry polymerization or bulk polymerization, but also even gas phase polymerization may be preferably carried out. In the case of slurry polymerization or bulk polymerization, even a catalyst having the titanium trichloride composition combined with an organoaluminum compound exhibits a sufficient effect, but in the case of gas phase polymerization, a preactivated catalyst obtained by reacting an olefin is preferred. In the case where slurry polymerization or bulk polymerization is followed by gas phase polymerization, even if the initially used catalyst is the former catalyst, an olefin reaction has already been carried out in the case of gas phase polymerization; hence the catalyst constitutes the same as in the latter one and exhibits a superior effect. In the preactivation, 0.005 to 500 g of an organoaluminum, 0 to 50 ℓ of a solvent, 0 to 1,000 mℓ of hydrogen and 0.05 to 5,000 g, preferably 0.05 to 3,000 g of an olefin, each based on 1 g of the titanium trichloride composition are used. An olefin is reacted at 0° to 100°C for one minute to 20 hours, and it is preferred to react 0.01 to 2,000 g, preferably 0.05 to 200 g of an olefin per g of the titanium trichloride composition. The preactivation may be carried out in a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-heptane, benzene or toluene, and also may be carried out in a liquefied olefin such as liquefied propylene or liquefied butene-1, or in gaseous ethylene or propylene, and further, may be carried out in the coexistence of hydrogen. The preactivation may be carried out in the coexistence of polymer particles obtained in advance by slurry polymerization or bulk polymerization or gas phase polymerization. The polymer may be same as or different from the olefin polymer as the object of the polymerization. The quantity of the polymer particles capable of being made coexistent is in the range of 0 to 5,000 g per g of the titanium trichloride composition. The solvent or olefin used in the preactivation may be removed midway during the preactivation or after completion of the preactivation by distilling-off under reduced pressure or filtering-off, and in order to suspend the solid product in a solvent in a quantity not exceeding 80 ℓ per g of the product, a solvent may be added. The preactivation process includes various embodiments as follows: 1 ○ a process of carrying out slurry reaction, bulk reaction or gas phase reaction in contact of an olefin with a catalyst having the titanium trichloride composition combined with an organoaluminum compound; 2 ○ a process of combining the titanium trichloride composition with an organoaluminum compound in the presence of an olefin; 3 ○ a process of making an olefin polymer coexistent in the process 1 ○ or 2 ○; and 4 ○ a process of making hydrogen coexistent in the process 1 ○, 2 ○ or 3 ○. There is no essential difference between bringing the catalyst into a slurry state and bringing it into powder. The catalyst consisting of the titanium trichloride composition and an organoaluminum compound combined together as described above, or the catalyst further preactivated with an olefin is used for producing olefin polymers, and it is also possible to add an electron donor as a third component of the catalyst in order to improve its stereoregularity and use the resulting catalyst for polymerization, as in conventional olefin polymerization. The quantities of the respective catalyst components used are similar to those in conventional olefin polymerization, and concretely, 0.01 to 500 g of an organoaluminum compound and 0 to 200 g of an electron donor per g of the titanium trichloride composition are used. The polymerization form of polymerizing olefin includes, as described above, 1 ○ slurry polymerization carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene and toluene; 2 ○ bulk polymerization carried out in a liquefied olefin such as liquefied propylene and liquefied butene-1; 3 ○ gas phase polymerization carried out in a gas phase of an olefin such as ethylene or propylene, and 4 ○ a process of stepwise combining two or more of the above processes 1 ○ to 3 ○ . In any cases, polymerization is carried out at a polymerization temperature of room temperature (20°C) to 200°C, under a polymerization pressure of the atmospheric pressure 0.1 MPa (0 Kg/cm 2 G) to 5 MPa (50 Kg/cm 2 G) and usually for 5 minutes to 20 hours. In the polymerization, a suitable quantity of hydrogen is added for controlling the molecular weight, as in conventional polymerization process. Examples of olefins subjected to polymerization are linear monoolefins such as ethylene, propylene, butene-1, hexene-1 or octene-1, branched monoolefins such as 4-methylpentene-1 or 2-methylpentene-1; diolefins such as butadiene, isoprene or chloroprene; and homopolymerization of these olefins is not only carried out, but also copolymerization of these olefins with each other or one another, for example, propylene with ethylene, butene-1 with ethylene or propylene with butene-1; or propylene with ethylene and butene-1, (combination of three components) is carried out, and further it is also possible to carry out block copolymerization by varying kinds of olefins fed in a multi-stage polymerization. The olefin polymer obtained using the titanium trichloride composition or the titanium catalyst component of the present invention contains a highly stereospecific linear olefin-non-linear olefin block copolymer in an extremely dispersed state; hence when the polymer is made into a film, voids are few and since the non-linear olefin polymer block of the specified block copolymer exhibits a nucleating function at the time of melt-molding, crystallization of the resulting olefin polymer is promoted so that the transparency and crystallinity of the total olefin polymer are enhanced. In particular, in the case where the olefin polymer produced using the titanium trichloride composition or the titanium catalyst component of the present invention is a liear olefin polymer such as polypropylene, the linear olefin polymer block of the linear olefin-non-linear olefin block copolymer is compatible with the linear olefin polymer such as polypropylene so that occurrence of voids in the film prepared from the olefin polymer is further reduced. Further, the specified block copolymer introduced into the olefin polymer by using the titanium trichloride composition or the titanium catalyst component of the present invention is a stereoregular high molecular polymer having a high compatibility with the olefin polymer, as described above, so that the copolymer does not bleed onto the surface of the resulting olefin polymer. (Example) The present invention will be described in more detail by way of Examples, but it should not be construed to be limited thereto. The definitions of the terms employed in Examples and Comparative examples and the measurement methods therein are as follows: TY: This indicates polymerization activity and refers to a polymer yield per gram atom of titan (unit: Kg/gram atom). II: This indicates stereoregularity and refers to a residual quantity after extraction with n-hexane at 20°C (unit: % by weight) BD: Bulk desnity (unit: g/mℓ) MFR: Melt flow rate, JIS K 7210, according to the condition 14 in Table 1 (unit: g/10min.) Inside haze: This refers to a haze inside a film excluding the surface influence; an olefin polymer powder is made into a film of 150 µ thick under conditions of a temperature of 200°C and a pressure of 19.7 MPa (200 Kg/cm 2 G) by means of a press, followed by applying liquid paraffin onto both the surfaces of the film and measuring the resulting haze according to JIS K 7105 (unit: °C). Crystallization temperature: Measured using a differential scanning calorimeter at a temperature-lowering rate of 10°C/min. (unit: °C). Flexural elastic modulus: Tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane (0.1 part by weight) and calcium stearate (0.1 part by weight) were blended with an olefin polymer powder (100 parts by weight), followed by granulating the resulting blend by means of an extrusion-granulator having a screw bore diameter of 40 mm, molding the resulting granules by means of an injection-molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C to prepare a JIS type test piece, allowing this test piece to stand for 72 hours in a room at a humidity of 50% and at room temperature (23°C) and measuring the flexural elastic modulus according to JIS K 7203. [(unit: MPa (Kgf/cm 2 )] Void: An olefin polymer is granulated in the same manner as in the above item, followed by extruding the resulting granules by means of a T-die type film-making machine at a molten resin temperature of 250°C to prepare a sheet of 1 mm thick by means of a cooling roll at 20°C, heating the sheet by a hot air at 150°C for 70 seconds,and stretching the sheet in both the longitudinal and lateral directions, each to 7 times the respective original lengths to obtain a biaxially stretched film of 20 µm thick. The film is observed by means of an optical microscope, followed by measuring the number of voids having a diameter of 10 µm or larger. A film having 10 voids or less per cm 2 was denoted by o; that having 10 to 30 voids per cm 2 was denoted by Δ; and that having more than 30 voids per cm 2 was denoted by ×. Example 1 (1) Preparation of titanium trichloride composition: n-Hexane (6 ℓ), diethylaluminum monochloride (DEAC) (5.0 mols) and diisoamyl ether (12.0 mols) were mixed at 25°C for 5 minutes, followed by reacting the mixture at the same temperature, for 15 minutes to obtain a reaction solution (I) (the molar ratio of diisoamyl ether/DEAC: 2.4). TiCℓ 4 (40 mols) was placed in a nitrogen-purged reactor, followed by heating it to 35°C, dropwise adding the total quantity of the above reaction solution (I) over 180 minutes, keeping the mixture at the same temperature for 60 minutes, raising the temperature up to 80°C, further reacting the resulting material for one hour, cooling down to room temperature, removing the supernatant, and 4 times repeating a procedure of adding n-hexane (20 ℓ) and removing the supernatant by decantation to obtain a solid product (II). The total quantity of this product (II) was suspended in n-hexane (30 ℓ), followed by adding diethylaluminum monochloride (400 g), adding propylene (1.5 Kg) at 30°C, subjecting the mixture to polymerization treatment at the same temperature for one hour, thereafter removing the supernatant by decantation, twice washing the resulting solids with n-hexane (30 ℓ), successively adding n-hexane (30 ℓ) and diethylaluminum monochloride (400 g), making the temperature 40°C, adding vinylcyclohexane (1.9 Kg), subjecting the mixture to polymerization treatment at 40°C for 2 hours, thereafter removing the supernatant, and 5 times repeating a procedure of adding n-hexane (30 ℓ) and removing the supernatant by decantation to obtain a solid product (II-A) subjected to a multi-stage polymerization treatment with propylene-vinylcyclohexane. The total quantity of this solid product was suspended in n-hexane (9 ℓ), followed by adding TiCℓ 4 (3.5 Kg) to the resulting suspension at room temperature over about 10 minutes, reacting the mixture at 80°C for 30 minutes, further adding diisoamyl ether (1.6 Kg), reacting the mixture at 80°C for one hour, thereafter 5 times repeating a procedure of removing the supernatant, and drying under reduced pressure to obtain a solid product (III) as the titanium trichloride composition of the present invention. The content of the propylene polymer block in this titanium crichloride composition was 25.0% by weight, the content of the vinylcyclohexane polymer block therein was 25.0% by weight and the titanium content therein was 12.6% by weight. (2) Preparation of preactivated catalyst: Into a 80 ℓ capacity stainless reactor provided with slant blades and purged with nitrogen gas were added n-hexane (40 ℓ), diethylaluminum monochloride (28.5 g) and the titanium trichloride composition of the present invention (450 g) obtained above in item (1) at room temperature, followed by feeding ethylene (0.5 Nm 3 ) at 30°C over 2 hours, reacting the mixture (ethylene reacted per g of the titanium trichloride composition: 1.0 g), removing unreacted ethylene, washing with n-hexane and drying to obtain a preactivated catalyst component. (3) Production of olefin polymer: A polypropylene powder having an MFR of 2.0 (30 Kg) was fed into a 150 ℓ capacity stainless polymerization vessel of L/D=4 provided with a stirrer and purged with nitrogen gas, followed by adding n-hexane to the preactivated catalyst component obtained above in item (2) to prepare a n-hexane suspension of the component in a concentration of 4.0% by weight, and continuously feeding the suspension at a rate of 5.1 mg atom/hr as calculated from titanium atom and a 30% by weight solution of diethylaluminum monochloride in hexane at a rate of 4.2 g/hr in terms of diethylaluminum dichloride. Further, feeding hydrogen gas so as to keep its concentration in the gas phase of the polymerization vessel at 1.0% by volume, and feeding propylene so as to keep the total pressure at 2.36 MPa (23 Kg/cm 2 G), the gas phase polymerization of propylene was continuously carried out at 70°C for 160 hours. During the polymerization, the polymer was continuously withdrawn at a rate of 13.5 Kg/ hr so as to give a level of the polymer retained in the polymerization vessel of 45% by volume. The withdrawn polymer was successively subjected to contact treatment with nitrogen gas containing 0.2% by volume of propylene oxide at 95°C for 30 minutes to obtain polypropylene. Comparative example 1 (1) The item (1) of Example 1 was repeated except that the solid product (II) was converted into a substance corresponding to the solid product (II-A) without subjecting the product (II) to the multi-stage polymerization treatment with propylene and vinylcyclohexane, to obtain a titanium trichloride composition. (2) The item (2) of Example 1 was repeated except that the titanium trichloride composition obtained above in the item (1) was used as a titanium trichloride composition, to prepare a preactivated catalyst component. (3) The item (3) of Example 1 was carried out except that the preactivated catalyst component obtained above in the item (2) was used as a preactivated catalyst component, to carry out propylene polymerization. Comparative example 2 (1) A titanium trichloride composition was obtained in the same manner as in the item (1) of Comparative example 1. (2) Into the reactor used in the item (2) of Example 1 were added n-hexane (20 ℓ), diethylaluminum monochloride (30 g) and the titanium trichloride composition (180 g) obtained above in the item (1) at room temperature, followed by adding vinylcyclohexane (150 g), reacting the mixture at 40°C for 2 hours (the quantity of vinylcyclohexane reacted per g of the titanium trichloride composition: 0.5 g), thereafter removing the supernatant by decantation, twice washing the resulting solids with n-hexane (20 ℓ), successively adding n-hexane (20 ℓ) and diethylaluminum monochloride (30 g), making the temperature 30°C, adding propylene (120 g), reacting the mixture at 30°C for one hour, successively removing the supernatant, washing with n-hexane, filtering and drying to obtain a preactivated catalyst component. (3) The item (3) of Example 1 was repeated except that the catalyst component obtained above in the item (2) was used as a preactivated catalyst component, to carry out propylene polymerization. As a result, since the resulting bulk polymer clogged the withdrawing piping, propylene polymerization had to be stopped 6 hours after the polymerization initiation. Comparative example 3 (1) The item (1) of Comparative example 1 was repeated except that when the reaction solution (I) was reacted with TiCℓ 4 , vinylcyclohexane (1.3 Kg) added into n-hexane (100 ℓ) was polymerized at 60°C for 2 hours, separately using a titanium trichloride composition (500 g) obtained in the same manner as in the item (1) of Comparative example 1 and diethylaluminum monochloride (120 g) as catalyst, followed by washing with methanol and drying to obtain a vinylcyclohexane polymer (950 g), grinding this polymer in a 10 ℓ capacity vibration mill at room temperature for 5 hours and suspending the ground polymer in the above-mentioned TiCℓ 4 , to obtain a titanium trichloride composition containing 33.3% by weight of the vinylcyclohexane polymer. (2) The item (2) of Example 1 was repeated except that the titanium trichloride composition obtained above in the item (1) was used in place of the titanium trichloride composition of Example 1, item (2). (3) The item (3) of Example 1 was repeated except that propylene polymerization was carried out using the preactivated catalyst component obtained above in the item (2) in place of the preactivated catalyst component in Example (1), to obtain a polypropylene. Comparative example 4 and Examples 2 and 3 The quantities of propylene and vinylcyclohexane used for the polymerization treatment in Example 1, item (1) were varied to obtain titanium trichloride compositions having the respective contents of the above materials shown in Table listed later. Thereafter, polypropylenes were obtained in the same manner as in the items (2) and (3) of Example 1 Example 4 n-Heptane (4 ℓ), diethylaluminum monochloride (5.0 mols), diisoamyl ether (9.0 mols) and di-n-butyl ether (5.0 mols) were reacted at 18°C for 30 minutes, followed by dropwise adding the resulting reaction solution into TiCℓ 4 (27.5 mols) at 40°C over 300 minutes, reacting the mixture at the same temperature for 1.5 hour, raising the temperature up to 65°C, further reacting for one hour, removing the supernatant, 6 times repeating a procedure of adding n-hexane (20 ℓ) and removing the supernatant by decantation, suspending the resulting solid product (II) (1.8 Kg) in n-hexane (40 ℓ), adding diethylaluminum monochloride (500 g), and adding and reacting propylene (0.6 Kg) at 30°C for one hour, to carry out the first step polymerization treatment. After lapse of the reaction time, the supernatnat was removed, followed by twice repeating a procedure of adding n-hexane (20 ℓ) and removing the supernatant by decantation, successively adding n-hexane (40 ℓ) and diethylaluminum monochloride (500 g), adding allyltrimethylsilane (3.0 Kg), and reacting the mixture at 50°C for one hour to carry out the second step polymerization treatment and thereby obtain a solid product (II-A) subjected to a multi-stage polymerization treatment with propylene-allyltrimethylsilane. After the reaction, the supernatant was removed, followed by twice repeating a procedure of adding n-hexane (20 ℓ) and removing the supernatant by decantation, suspending the solid product (II-A) subjected to the above polymerization treatment in n-hexane (7 ℓ), adding TiCℓ 4 (1.8 Kg) and n-butyl ether (1.8 Kg), reacting the mixture at 60°C for 3 hours, thereafter removing the supernatant by decantation, three times repeating a procedure of adding n-hexane (20 ℓ), agitating the mixture for 5 minutes, allowing it to stand still and removing the supernatant, drying under reduced pressure to obtain a solid product (III), and polymerizing propylene in the same manner as in the items (2) and (3) of Example 1 except that the above solid product (III) was used as a final titanium trichloride composition. Comparative example 5 Example 4 was repeated except that the solid product (II) was converted into a substance corresponding to the solid product (II-A), without the polymerization treatment with propylene and allyltrimethylsilane, to obtain a titanium trichloride composition, and propylene was polymerized using the composition. Example 5 The item (1) of Example 1 was repeated except that diethylaluminum monochloride (5.0 mols) was replaced by di-n-butylaluminum monochloride (4.0 mols) to obtain a reaction solution (I), this solution was dropwise added to TiCℓ 4 at 45°C and vinylcyclohexane was replaced by 4,4-dimethylpentene-1 (3.0 Kg), to obtain a titanium trichloride composition. Thereafter, propylene was polymerized in the same manner as in the items (2) and (3) of Example 1, to obtain a polypropylene. Comparative example 6 Example 5 was repeated except that a multi-stage polymerization treatment with propylene and 4,4-dimethylpentene-1 was not carried out, to obtain a titanium trichloride composition. A polypropylene was then obtained. Example 6 The item (1) of Example 1 was repeated except that a multi-stage polymerization treatment was carried out using 0.9 Kg of propylene and using 3-methylbutene-1 (1.1 Kg) in place of vinylcyclohexane, and further, a mixed solution of SiCℓ 4 (1.8 Kg) with TiCℓ 4 (2.0 Kg) in place of TiCℓ 4 and 2.2 Kg of diisoamyl ether were reacted with the solid product (II-A), to obtain a solid product (III), and this solid product (III) was used as a final titanium trichloride composition. Thereafter, the items (2) and (3) of Example 1 were repeated to obtain a polypropylene. Comparative example 7 Example 6 was repeated except that a titanium trichloride composition was obtained without carrying out the multi-stage polymerization treatment with propylene and 3-methylbutene-1, to obtain a polypropylene. Example 7 TiCℓ 4 (27.0 mols) was added to n-hexane (12 ℓ), followed by cooling the mixture down to 1°C, further dropwise adding n-hexane (12.5 ℓ) containing diethylaluminum monochloride (27.0 mols) at 1°C over 4 hours, thereafter reacting the resulting material at the same temperature for 15 minutes, successively raising the temperature up to 65°C over one hour, and reacting at the same temperature for one hour. The supernatant was removed, followed by 5 times repeating a procedure of adding n-hexane (10 ℓ) and removing the supernatant by decantation, suspending a portion (1.8 Kg) of the resulting solid product (II) (5.7 Kg) in n-hexane (50 ℓ), adding diethylaluminum monochloride (350 g), further adding propylene (0.6 Kg) at 30°C, thereafter subjecting it to polymerization treatment at the same temperature for one hour, successively removing the supernatant by decantation, washing the resulting solids with n-hexane (50 ℓ), adding n-hexane (50 ℓ) and diethylaluminum monochloride (350 g), further adding p-trimethylsilylstyrene (6.9 Kg) and subjecting the mixture to polymerization treatment at 40°C for 2 hours. After the polymerization treatment, the supernatant was removed, followed by twice repeating a procedure of adding n-hexane (30 ℓ) and removing the supernatant by decantation, suspending the total quantity of the resulting solid product (II-A) subjected to the multi-stage polymerization treatment in n-hexane (11 ℓ), adding diisoamyl ether (1.6 ℓ), agitating the resulting suspension at 35°C for one hour, 5 times washing with n-hexane (3 ℓ) to obtain treated solids and suspending the solids in a n-hexane solution (6 ℓ) containing 40% by volume of TiCℓ 4 . This suspension was raised to 65°C, followed by reacting it at the same temperature for 2 hours, thereafter three times washing the resulting solids with n-hexane (each time 20 ℓ) and drying under reduced pressure to obtain a solid product (III) as a final titanium trichloride composition. Successively, in a 200 ℓ capacity polymerization vessel provided with a stirrer having a two-stage turbine element, n-hexane was added to the above titanium trichloride composition to prepare a 4.0% by weight n-hexane suspension, and continuously feeding the suspension at a rate of 12.8 mg atom/hr as calculated from titanium atom and diethylaluminum monochloride at a rate of 6.2 g/hr, each through the same piping and n-hexane at a rate of 21 Kg/hr through a separate piping. Further, feeding hydrogen so as to keep its concentration in the gas phase of the polymerization vessel at 1.5% by volume, and feeding propylene so as to keep the total pressure at 1.08 MPa (10 Kg/cm 2 G), slurry polymerization of propylene was continuously carried out at 70°C for 120 hours. During the polymerization, the resulting slurry was continuously withdrawn from the polymerization vessel into a 50 ℓ capacity flash tank so as to give a level of the slurry retained in the polymerization vessel of 75% by volume. The pressure of the slurry was dropped in the flash tank and unreacted propylene was removed, while methanol was fed at a rate of 1 Kg/hr and the slurry was subjected to contact treatment at 70°C. Successively, the solvent was separated from the slurry by means of a centrifugal separator and the resulting material was dried to obtain a product powder at a rate of 10 Kg/hr. Comparative example 8 Example 7 was repeated except that the solid product (II) was converted into a substance corresponding to the solid product (II-A) without carrying out the multi-stage polymerization treatment with propylene and p-trimethylsilylstyrene to obtain a titanium trichloride composition. Slurry polymerization of propylene was carried out using the composition in the same manner as in Example 7. Example 8 In the item (1) of Example 1, using propylene in a quantity of 0.9 Kg, and using 2-methyl-4-fluorostyrene (7.6 Kg) in place of vinylcyclohexane, a multi-stage polymerization was carried out to obtain a solid product (II-A) subjected to polymerization treatment, followed by adding TiCℓ 4 (3.0 Kg) into n-heptane (10 ℓ), adding the total quantity of the above solid product (II-A) and reacting the mixture at 80°C for 30 minutes. After completion of the reaction, di-n-pentyl ether (2.8 Kg) was further added, followed by reacting the mixture at 80°C for one hour to obtain a solid product (III). Gas phase polymerization of propylene was carried out in the same manner as in the items (2) and (3) of Example 1 except that the above solid product (III) was used as a final titanium trichloride composition. Comparative example 9 Propylene was polymerized in the same manner as in Example 8 except that a titanium trichloride composition was obtained without carrying out the multi-stage polymerization treatment with propylene and 2-methyl-4-fluorostyrene. Example 9 (1) The item (1) of Example 1 was repeated except that the total quantity of the solid product (II) was suspended in n-hexane (30 ℓ), followed by adding diethylaluminum monochloride (400 g), feeding ethylene (950 Nℓ) at 30°C over one hour to carry out a first step polymerization, removing unreacted ethylene, adding vinylcyclohexane (1.9 Kg) without washing the reaction mixture and carrying out a second polymerization treatment at 40°C for 2 hours, to obtain a solid product (III) as the titanium trichloride composition of the present invention. (2) The item (2) of Example 1 was repeated except that the titanium trichloride composition obtained above in the item (1) was used as a titanium trichloride composition, to obtain a preactivated catalyst component. (3) Propylene-ethylene copolymerization was carried out in the same manner as in the item (3) of Example 1 except that the preactivated catalyst component obtained above in the item (2) was used as a preactivated catalyst component and ethylene was further fed at the time of the gas phase polymerization of propylene, so as to keep its concentration in the gas phase in the polymerization vessel at 0.2% by volume, to obtain a propylene-ethylene copolymer. Comparative example 10 A propylene-ethylene copolymerization was carried out in the same manner as in the item (1) of Example 9 except that a titanium trichloride composition was obtained without carrying out the multi-stage polymerization treatment with ethylene and vinylcyclohexane and the resulting titanium trichloride composition was used, to obtain a propylene-ethylene copolymer. The titanium trichloride compositions obtained in the above Examples and Comparative examples, polymerization results therewith and evaluation results thereof are shown in the following Table: The main effectiveness of the present invention consists in that when the titanium trichloride composition of the present invention is used in olefin polymerization as a transition metal compound catalyst component for producing olefin polymers, it is possible to produce a highly crystalline olefin polymer without causing any operational problems and with a very high productivity and when made into a film, to afford a film having few occurrence of voids and also having a superior clearance. As apparent from the above-mentioned Examples, when olefin polymers are produced using the titanium trichloride composition of the present invention, a long term stabilized production is possible without any problem in production. Further, films produced using the resulting olefin polymer have an inside haze of 1.1 to 3.0%, that is, have a very high transparency, as compared with the inside hazes about 9 to 13% of films produced from conventional olefin polymers using titanium trichloride compositions containing no specified block copolymer. The crystallization temperature also rose by about 8°C to about 12°C, resulting in a notably improved crystallinity. As a result, the flexural elastic modulus was also improved (see Examples 1 to 9 and Comparative examples 1, 5 to 10). Whereas, according to conventional process of introducing the non-linear olefin polymer in a manner other than that of the present invention, an operational problem occurs, and further there are problems that when the resulting olefin polymer is made into film, voids very often occur in the film and improvements in the transparency of film and the crystallinity of the polymer are insufficient due to inferior- dispersibility of the polymer (see Comparative examples 2 and 3).

Claims: A process for producing a titanium trichloride composition for producing olefin polymers, which process comprises reacting TiCℓ 4 with an organoaluminum compound or a reaction product (I) of an organoaluminum compound with an electron donor (B 1 ) to form a solid product (II); subjecting the solid product (II) to a multi-stage polymerization treatment once or more with each of (1) a linear olefin and (2) a non-linear olefin to form a linear olefin/non-linear olefin block copolymer; and further reacting said block copolymer with an electron donor (B 2 ) and an electron acceptor to form a solid product (III); the content of the linear olefin polymer block in product (III) being 0.1 to 49.5% by weight and that of the non-linear olefin polymer block being 0.01 to 49.5% by weight, and the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block being 2/98 to 98/2. A process according to claim 1 in which the organoaluminum compound is one of the formula AℓR 8 / pR 1 / p'X 3-(p+p') (in which R 8 and R 9 each represent a hydrocarbon radical selected from alkyl groups, cycloalkyl groups or aryl groups, or an alkoxy group; X is a halogen atom and p and p' are each a number satisfying the relationship. 0 < p + p' ≤ 3. A process according to claim 1 or claim 2 in which the non-linear olefin has the formula: CH 2 =CH-R 1 , or in which R 1 is a ring containing hydrocarbon radical of 3 to 18 C atoms which may contain silicon, R 2 is silicon, a linear hydrocarbon radical of 1 to 3 carbon atoms which may contain silicon and R 3 , R 4 and R 5 are each a linear hydrocarbon radical of 1 to 6 carbon atoms which may contain silicon, and one of R 3 , R 4 and R 5 may be a hydrogen atom; n is 0 or 1, m is 1; or 2; R 6 is a linear hydrocarbon radical of 1 to 6 carbon atoms which may contain silicon; R 7 is a hydrogen or halogen atom or a hydrocarbon radical of 1 to 12 carbon atoms which may contain silicon, and, when m is 2, the R 7 s may be the same or different.

Inventors: SAITO JUN, SANPEI AKIHIKO, SAITO, JUN, SANPEI, AKIHIKO
Applicants: CHISSO CORP, CHISSO CORPORATION
Application year: 1990
Main classification: C08F4
IPC codes: C08F4, C08F10