PROCESS FOR PRODUCING BRANCHED ALPHA-OLEFIN POLYMERS

Abstract: A process for homopolymerizing an α-olefin branched at the carbon atom of the third position or copolymerizing said α-olefin with another olefin in the presence of a catalyst system comprising a combination of an organo-aluminum compound and a solid catalyst component containing titani­ um, chlorine and a hydrocarbyloxy group, of which the X-­ ray diffraction spectrum has the diffraction lines at least cor­ responding to the diffraction lines of planes [113] and [300] of titanium trichloride having a layer structure and wherein the content of the hydrocarbyloxy group is 0.01 to 0.3 mole per 1 mole of titanium.

Description: PROCESS FOR PRODUCING BRANCHED a-OLEFIN POLYMERS The present invention relates to a process for producing a branched a-olefin polymer. It is known an a that the melting point of/isotactic polymer of/branched a-olefin generally tends to increase when the degree of branching increases and when the position of the branching approaches the position of carbon-carbon double bond. Accordingly, isotactic polymers of branched a-olefins and particularly those having the branch at the carbon atom of the third position are excellent in heat resistance and useful as industrial material. Like usual o'-olefins, branched a-olefins can also be polymerized with Ziegler catalysts. Unlike aolefins, however, in case of branched a-olefins, the polymerization activity lowers extremely as compared with that of a-olefins, and such low polymerizing activity is particularly remarkable when the branch is located on the carbon atom of the third position. Various processes for polymerizing branched a-olefins were proposed in, for example, Japanese Patent Application Kokai (Laid-Open) Nos. 59,989/76, 195,704/82, 182,305/82 and 8,708/83. However, when branched a-olefins are polymerized by these processes, the polymerization activity is still not sufficiently high. The present inventors conducted elaborated studies with the aim of finding a catalyst system showing a high activity on the polymerization of branched a-olefins. As the result, it was found that a catalyst system comprising a combination of an organo-aluminum compound and a solid catalyst component containing titanium, chlorine and hydrocarbyloxy group shows a polymerization activity several times higher than that exhibited by the catalyst systems used in the above-mentioned known processes. Based on this finding, the present invention has been accomplished. It is an object of this invention to provide a novel solid catalyst component for polymerizing branched a-olefins. It is another object of this invention to provide a process for polymerizing branched -olefins by using the novel solid catalyst component. Other objects and advantages of this invention will become apparent from the descriptions presented below. According to this invention, there is provided a process for homopolymerizing an a-olefin branched at the carbon atom of the third position or copolymerizing said a-olefin withazMier olefin in the presence of a catalyst system comprising a combination of an organoaluminum compound and a solid catalyst component containing a titanium, chlorine and/hydrocarbyloxy group, of which the X-ray diffraction spectrum has the diffraction lines at least corresponding to the diffraction lines of planes [1131 and [3001 of titanium trichloride having a layer the structure and of which/hydrocarbyloxy group content is 0.01 to 0.3 mole per 1 mole of titanium. This invention is characterized in that, when an a-olefin branched at the carbon atom of the third position is polymerized by using the catalyst system of this invention, a polymerization activity of several times niger than that achievable in the known processes can be obtained. The solid catalyst component containing titanium, a chlorine and/hydrocarbyloxy group, provided by this invention gives an X-ray diffraction spectrum having diffraction lines at least corresponding to the diffraction lines of planes [113] and [300] of titanium trichloride having a layer structure,and contains 0.01 to 0.3 mole a of/hydrocarbyloxy group per 1 mole of titanium. The hydrocarbyloxy group is represented by the general formula OR1, wherein R1 represents a hydrocarbon group having 1 to 20 carbon atoms. Concrete examples of R1 include alkyl groups,such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl and the like; aryl groups,such as phenyl, cresyl, xylyl, naphthyl and the like; cycloalkyl groups,such as cyclohexyl, cyclopentyl and the like; allyl groups,such as propenyl and the like; and aralkyl groups,such as benzyl and the like. Among them, straight chain alkyl groups having 2 to 18 carbon atoms and aryl groups having 6 to 18 carbon atoms are particularly preferred Said hydrocarbyloxy group may also be two or more kinds of different hydrocarbyloxy groups. The content of the hydrocarbyloxy group in the solid catalyst component is 0.01 to 0.3 mole and preferably 0.02 to 0.25 mole, per 1 mole of titanium. Further, the X-ray diffraction spectrum of said solid catalyst component must have the diffraction lines at least corresponding to the diffraction lines of planes [113] and [300J of titanium trichloride having a layer structure. As used herein, the term "titaniun trichloride having a layer structure tt means the titanium trichlorides mentioned in G. Natta et al.: J. Polymer the Sci., 51, 399 (1961),wherein the examples include/a-, y- and 6-form titanium trichlorides. The X-ray diffraction spectrum of the solid catalyst component of this invention shows its diffraction lines at least at the lattice spacing (d) of 2.72 - 2.52 and 1.78 - 1.76 . Preferably, the solid catalyst component of this invention gives an X-ray diffraction spectrum having diffraction lines at least corresponding to the diffraction lines of planes 11131 and [300] of the d-form titanium trichloride (d = 2.71 and 1.77 ). As examples of the synthetic procedure of such a solid catalyst component, the following methods can be illustrated. Synthetic Method (I) This is a method which comprises reducing a titanium compound represented by the following general formula: Ti(ORÚ)nCl4-n wherein RÚ represents hydrocarbon group having 1 - 20 carbon atoms and n represents a numerical figure satisfying o < n 4, with an organo-aluminum compound represented by the following general formula: AlR2mX 3-m a wherein Rê represents/hydrocarbon group having 1 - 20 a carbon atoms, X represents/halogen atom and m represents a numerical figure satisfying 1 < m # 3, to obtain a hydrocarbyloxy group-containing solid product insoluble in hydrocarbon solvents, followed by treating said solid product with an ether compound and titanium tetrachloride in the state of a slurry at a temperature of 450C to 120 C. the In/Synthetic Method (1), R1 in the titanium compound represented by the general formula Ti(ORÚ)nCl4-n is a hydrocarbon group having 1 - 20 carbon atoms, and preferably a straight chain alkyl group having 2 - 18 carbon atoms or an aryl group having 6 - 18 carbon atoms. A good result can be obtained when n satisfies 0 < n' 4 and particularly when n satisfies 1' n' 4. Concrete examples of the organo-aluminum com the pound represented by general formula AlRêmX3-m (Rê a represents/hydrocarbon group having 1 - 20 carbon atoms, a X represents/halogen atom, and m represents a numerical figure satisfying 1 < m < 3), used in the reduction, include ethyl aluminum sesquichloride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, trimethylaluminum, triethylaluminum, tri-isobutylaluminum, ethyldicyclohexylaluminum, triphenylaluminum, diethylaluminum hydride, di-isobutylaluminum hydride, diethylaluminum bromide, diethylaluminum iodide and the like. Among them, diethylaluminum chloride and ethylaluminum sesquichloride give particularly good results. The reduction is carried out preferably after diluting the titanium compound and the organo-aluminum compound to a concentration of 10 - 70% by weight with an inert hydrocarbon solvent, such as pentane, hexane, heptane, octane, decane, toluene or decalin. The reaction temperature of the reduction is thy -10 C to 800C, and preferably OOC to 700C. Although/time of the reduction is not critical, it is preferably 1 to 6 hours. The molar ratio of the titanium compound to the organo-aluminum compound can arbitrarily be varied depending on the purpose. A good result can be obtained by using 0.5 to 1.5 moles of diethylaluminum chloride or 1.5 to 2.5 moles of ethylaluminum sesquichloride per 1 mole of the titanium compound. It is also allowable to carry out after reaction at 300 to 1000C after completion of the reduction. The hydrocarbyloxy group-containing solid product insoluble in hydrocarbon solvents, obtained by the reduction, is separated from the liquid phase, washed several times with an inert hydrocarbon solvent,such as pentane, hexane, heptane, octane, decane, toluene,xylene, decalin or the like, and then reacted with an ether compound and titanium tetrachloride. As said ether compound, dialkyl ethers such as diethyl ether, di-n-propyl ether, di-isopropyl ether, di-n-butyl ether, di-n-amyl ether, di-isoamyl ether, di-neopentyl ether, di-n-hexyl ether, di-n-octyl ether, methyl n-butyl ether, methyl isoamyl ether, ethyl isobutyl ether and the like are preferable, among which di-n-butyl ether and di-isoamyl ether are particularly preferred. Said ether compound is used in an amount of 0.1 to 5 moles and preferably 0.3 to 3 moles per 1 mole of the titanium atom contained in the hydrocarbyloxy group-containing solid product. The titanium tetrachloride is added in an amount of 0.1 to 10 moles and preferably 0.5 to 5 moles per 1 mole of the titanium atom contained in the solid product. The ratio of the titanium tetrachloride to the ether compound is 0.5 mole to 10 moles and preferably 1.5 moles to 5 moles per 1 mole of the ether compound. The reaction among the hydrocarbyloxy groupcontaining solid product insoluble in hydrocarbon solvents and the ether compound and titanium tetrachloride is carried out in the state of a slurry. As the solvent used for making a slurry from the hydrocarbyloxy group-containing solid product, aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, decane and the like, aromatic hydrocarbons ,such as toluene, xylene, decalin and the like and alicyclic hydrocarbons,such as cyclohexane, methylcyclohexane and the like can be referred to The concentration of the slurry is 0.05 to 0.5 g-solid/ml-solvent, and preferably 0.1 to 0.3 g-solid/ml-solvent. The reaction temperature is 45" to 1200C and preferably 600 to 1000 C. Although the time of the reaction is not critical, it is usually 30 minutes to 6 hours. Addition of the solid product, the ether compound and the titanium tetrachloride may be carried out by any of the methodsof adding the ether compound and titanium tetrachloride to the solid product and the inverse method of adding the solid product into a solution of the ether compound and titanium tetrachloride. In the method of adding the ether compound and titanium tetrachloride to the solid product, the procedure of addition may be any of the successive addition (addition of ether compound followed by addition of titanium tetrachloride) and the simultaneous addition of them. The solid catalyst component obtained by the above-mentioned reaction is separated from the liquid phase, washed several times with an inert hydrocarbon solvent, such as hexane, heptane or the like, and then used for polymerization. Synthetic Method (II) This is a method which comprises reducing titanium tetrachloride with an organo-aluminum compound represented by the general formula AlR2mX3 m (R2, X and m are each as defined previously), heat-treating the reduced product at a temperature not higher than l500C to obtain a heattreated solid product, reacting the heat-treated solid product in a hydrocarbon solvent with a mixture comprising a halogen compound represented by the following general formula: X2 (X represents a halogen atom) and an ether compound, and treating the reaction product with a titanium compound represented by the following general formula: Ti (OR1) nCl4n 1 and n are each as defined previously). The organo-aluminum compound represented by the general formula AlR2mX3 m (R2, X and m are each as defined previously) used in the reduction of this synthetic method thy is the same as that used in/Synthetic Method (I). Particularly, ethylaluminum sesquichloride and diethylaluminum chloride give good results. The reduction is preferably carried out in an inert hydrocarbon solvent, particularly aliphatic hydrocarbon solvents such as hexane, heptane and the like, at a temperature of -500C to 500 C, particularly -300C to 300C. Concretely saying, it is preferable to add a solution of the organoaluminum compound in an inert hydrocarbon to a solution of titanium tetrachloride in an inert hydrocarbon so slowly as to maintain the system at the predetermined temperature. The concentrations of titanium tetrachloride and the organo-aluminum compound in the inert hydrocarbon solution are both in the range of fran from 20 to 80% by weight and preferably in the range of/30 to the 60% by weight. The ratio of/organo-aluminum compound represented by the general formula AlR2mX3 m to titanium tetrachloride used in the reaction is m 1 to 2 x (m-l) -I mole organo-aluminum compound and preferably 1 x (m-l) to 1.5 x (m-l) mole organo-aluminum compound, per 1 mole of titanium tetrachloride. (Here, the molar number of organoaluminum compound is counted as a monomer.) Preferably, the reduction is carried out with an appropriate stirring. After mixing titanium tetrachloride with the organo-aluminum compound, the system is preferably stirred at a temperature falling in the above-mentioned reaction temperature range for 15 minutes to 6 hours to complete the reduction. Thus, a suspension of the reduced solid product is obtained. The heat-treatment may be performed after separating the reduced solid product from the suspension formed by the reduction and then washing it with an inert hydrocarbon solvent. More preferably, however, the heattreatment is carried out by directly using the suspension of reduced solid product as it is. The heat-treatment can be performed by heating the suspension of reduced solid product at a temperature not higher than 1500 C, preferably at a temperature of 500 to 1200C. The optimum temperature of the heat treatment varies depending on the kind of organo-aluminum compound used in the reduction. For example, the optimum temperature of heat treatment is 500 to 1000C when the organo-aluminum compound is ethylaluminum sesquichloride, and it is 75" to 1100C when the organoaluminum compound is diethylaluminum chloride. The time of of the heat treatment is usually /15 minutes to 6 hours, and of preferably/30 minutes to 4 hours. After the heat treatment, the solid product is separated from the liquid phase and washed with an inert.hydrocarbon solvent to obtain a heattreated solid product. The halogen compound is represented by the general formula X2, wherein X represents C1, Br or I. Preferably, X is I. The halogen compound is used in an amount of 10 5 mole to 5 x 10 2 mole and preferably 10 4 mole to 10-2 mole, per 1 g of the heat-treated solid product. Preferably, the halogen compound is used in the form of a solution in a hydrocarbon solvent and/or an ether compound. As said ether compound, the same one as in the Synthetic Method (I) is used. Particularly preferred ether compounds are di-n-butyl ether and di-isoamyl ether. The ether compound is used in an amount of 10 4 mole to 0.03 mole, preferably 10 3 mole to 0.02 mole, and par- ticularly preferably 0.002 mole to 0.01 mole, per 1 g of the heat-treated solid product. The reaction between the heat-treated solid product and a mixture composed of the halogen compound and the ether compound is carried out in a hydrocarbon solvent. Concrete examples of said hydrocarbon solvent include aliphatic hydrocarbons, such as hexane, heptane, octane, decane and the like and aromatic hydrocarbons such as benzene, toluene, xylene and the like. The concentration of the heat-treated solid product in the hydrocarbon solvent is 50 to 500 g/liter and preferably 100 to 400 g/ liter. The reaction temperature is 50 to 1200C and preferably 700 to 100 C. Preferably, the reaction is the carried out while stirring a suspension of/heat-treated solid product. The time of the reaction is preferably in the range of/ t inutes to 6 hours, and particularly in frati the range of/15 minutes to 2 hours. After the reaction, the solid product is separated from the liquid phase, washed with an inert hydrocarbon solvent and then treated with a titanium compound represented by the general formula Ti (OR1)nCl4-n Alternatively, without separating the solid product from the liquid phase the titanium compound represented by the general formula Ti(ORl)nCl4 is directly added to the reacted suspension and then a heat treatment is carried out. In the titanium compound represented by the above-mentioned general formula a Ti(ORÚ)nCl4-n wherein RÚ represents/hydrocarbon group having 1 to 20 carbon atoms and n represents a numerical figure satisfying 0 < n < 4, R1 is preferably a straight chain alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. The numerical figure nmust satisfy 0 < n < 4 and preferably 0.2' n' 2. The treatment with the titanium compound represented by the general formula Ti (OR1) nCl 4-n is carried out in a hydrocarbon solvent. The concentration of Ti (OR1) Cl n 4-n is not lower than 5% by volume, and preferably 15 to 60% by volume. The temperature of the treatment is 0 to 1000 C, and preferably 400 to 800C. The time of the treatment is 5 minutes to 4 hours, and preferably 15 minutes to 2 hours. The solid catalyst component obtained by the above-mentioned reaction is separated from the liquid phase, washed several times with an inert hydrocarbon solvent, such as hexane, heptane or the like, and then used for polymerization. Next, as the organo-aluminum compounds usable for the polymerization of olefins in this invention, trialkylaluminums, dialkylaluminum hydrides, dialkylaluminum chlorides, dialkylaluminum alkoxides, dialkylaluminum siloxides and their mixtures can be referred to. Examples of the preferably usable organo-aluminum compound include dimethylaluminum chloride, diethylaluminum chloride, di-isobutylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, trimethylaluminum, triethylaluminum, tri-isobutylaluminum, diethylaluminum hydride, diethylaluminum ethoxide and mixtures thereof. Among them, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum ethoxide and mixtures thereof are particularly preferred The organo-aluminum compound is used in an amount of 0.5 mole to 100 moles and preferably 1 mole to 50 moles, per 1 mole of titanium atom present in the solid catalyst component. The branched a-olefins used in this invention are a-olefins branched at the carbon atom of the third position. Concrete examples of such branched a-olefin include 3-methylbutene-l, 3-methylpentene-l, 3-ethylpentene1, 3-methylhexene-l, 3,5-dimethylhexene-l, vinylcyclopentane, vinylcyclohexane, 4-vinylcyclohexene-1 and the like. Among these branched a-olefins, 3-methylbutene-l and vinylcyclohexane are particularly preferred, The scope of this invention involves not only the homopolymerization of the above-mentioned branched a-olefins, but also the copolymerization of the above-mentioned branched a-olefins and other olefins copolymerizable therewith. The "other olefins" usable for the copolymerization are straight or branched chain a-olefins having 2 to 12 carbon atoms and straight chain internal olefins having 4 to 12 hereof carbon atoms. . Concrete examples/include ethylene, propylene, butene-l, pentene-l, hexene-l, octene-l, 4methylpentene-l, 4-methylhexene-l, 5-methylhexene- 1, butene-2, pentene-2 and hexene-2. The polymerization is carried out in the presence of an inert hydrocarbon such as hexane, heptane or the like as a diluent. Alternatively, the polymerization is carried out in the state of a slurry by using the liquid monomer itself as a medium for the polymerization. The temperature of the polymerization is in the range of fray 25 to 1500 C. The polymerization is usually carried out under a pressure ranging from 1 atmosphere to about 50 atmospheres. a The mode of the polymerization may be any of/continuous system and batch system. Further, various electrondonative compounds may also be added at the time of polymerization for the purpose of improving the activitv the the of/catalyst and/stereospecificity. It is also allowable to add a chain transfer agent, such as hydrogen or the like for the purpose of regulating the molecular weight of the polymer. Next, the process of this invention will be illustrated with reference to the following examples, but the invention is not limited thereto. Example 1 (A) Synthesis of Solid Product After replacing, with argon, the inner atmosphere ¯ beumr - or a roast having a capacity of 500 ml and/equwpped with a stirrer and a dropping funnel, 90 ml of n-heptane and 100.5 ml of tetra-n-butoxytitanium were charged into the flask. While maintaining the inner temperature of the flask at 35 C, a solution composed of 162 ml of n-heptane and 67.2 ml of ethylaluminium sesquiichloride was slowly added dropwise into the flask from the dropping funnel over a period of 2 hours. After dropping it, the inner temperature was elevated to 600C and the content of the flask was stirred for one hour. The flask was allowed to stand at room temperature and the reaction mixture was separated into solid and liquid phases, after which the solid product was washed four times with 100 ml of n-heptane and dried under reduced pressure to obtain a red-brown colored solid product. One gram of this solid product contained 4.68 millimoles of titanium, 6.29 millimoles of n-butoxy group and 0.23 millimole of aluminum, and the ratio of n-butoxy group/titanium was 1.34 (by mole). In the X-ray diffraction spectrum of this solid product measured with Cu-Kti rays, the characteristic peaks of titanium trichloride crystal were not found at all. the (B) Synthesis of/Solid Catalyst Component After replacing the inner atmosphere of a flask having a capacity of 100 ml with argon, 6.95 g of the solid product prepared in (A) above and 35 ml of n-heptane were charged into the flask. While maintaining the inner temperature of the flask at 750C, 5.2 ml of di-n-butyl ether and 6.8 ml of titanium tetrachloride were added and reacted at this temperature for 1 hour. The flask was allowed to stand at room temperature and the reaction mixture was separated into solid and liquid phases, after which the solid product was washed four times with 50 ml of n-heptane and then dried under reduced pressure to obtain a red-violet colored solid catalyst component. One gram of this solid catalyst component contained 5.91 millimoles of titanium, 0.42 millimole of n-butoxy group and 0.01 millimole of aluminum, and the ratio n-butoxy group/ titanium was 0.071 (by mole). The X-ray diffraction spectrum of this solid catalyst component had diffraction lines corresponding to the diffraction lines of planes [113] the and [300] of/#-form titanium trichloride. (C) Polymerization of Vinylcyclohexane After replacing, with argon, the inner atmosphere being of a flask having a capacity of 100 ml and/equipped with a magnetic stirrer, 9.6 ml of n-heptane, 2.6 millimoles of triethylaluminum, 98.4 mg of the solid catalyst component obtained in (B) above and 5 ml of vinylcyclohexane were added. The inner temperature of the flask was elevated to 500 C, and polymerization was carried out at this temperature for one hour. For the sake of after-treatment, the product was washed several times with 40 ml of a 1 : 9 (by volume) mixture of hydrochloric acid (hydrogen chloride content 36%) and methanol and then it was thoroughly washed with water. Then, it was washed twice with 40 ml of methanol, filtered and dried under reduced pressure to obtain a granular polymer. Yield of the granular polymer was 2.87 g. This means that the yield (g) of polyvinylcyclohexane per 1 g of solid catalyst component (hereinafter, simply referred to as "Polym/Cat") was 29.2. Comparative Example 1 Vinylcyclohexane was polymerized by repeating the procedure of Example 1-(C), except that the solid catalyst component obtained in Example 1- (B) was replaced with 101.5 mg of a commercially available titanium trichloride [this titanium trichloride had been prepared by reducing TiC14 with organo-aluminum to obtain a complex compound of TiC13 and AlCl3 (molar ratio Ca. 3 : 1), treating the complex with di-isoamyl ether to extract off the major part of AlCl3 and then activating the residue by a treatment with TiC14; 1 g of this solid catalyst component contained 6.05 millimoles of titanium and 0.16 millimole The the of aluminum. / yield of/granular polymer was 0.51 g, and Polym/Cat was 5.0. Example 2 Vinylcyclohexane was polymerized by repeating the procedure of Example 1-(C), except that the solid catalyst component obtained in Example 1- (B) was used in an amount of 90.2 mg and the triethylaluminum was replaced - - - - -- - - The The with 2.6 millimoles of trimethylaluminum. / yield of/granular polymer was 1.65 g, and Polym/Cat was 18.3. Example 3 Vinylcyclohexane was polymerized by repeating the procedure of Example l-(C), except that the solid catalyst component obtained in Example 1- (B) was used in an amount of 106.3 mg, the 2.6 millimoles of triethylaluminum was replaced with a mixture consisting of 1.3 millimoles of triethylaluminum and 1.3 millimoles of diethvlaluminum ethoxide and the time of the polymerization The the was 25 minutes. / yield of/granular polymer was 2.97 g, and Polym/Cat was 27.9. Example 4 A violet-colored solid catalyst component was prepared by repeating the procedure of Example 1-(B), except that the reaction was carried out at 950C for 2 hours by using 9.69 g of the solid product obtained in Example l-(A), 48.5 ml of n-heptane, 7.3 ml of di-n-butyl ether and 23.6 ml of titanium tetrachloride. One gram of this solid catalyst component contained 6.05 millimoles of titanium, 0.15 millimole of n-butoxy group and 0.01 millimole of aluminum, and its n-butoxy group/titanium ratio was 0.025 (by mole). The X-ray diffraction spectrum of this solid catalyst component had diffraction lines corresponding to the diffraction lines of planes [113] and the [300] of/3-form titanium trichloride. Then, vinylcyclohexane was polymerized by repeating the procedure of Example 1- (C), except that this solid catalyst component was used in an amount of the - - - - - - 87.9 mg. / yield or/granular polymer was i g, anct Polym/Cat was 13.1. Example 5 A solid catalyst component was prepared by repeating the procedure of Example l-(B), except that the reaction was carried out at 700C for one hour by using 11.41 g of the solid product obtained in Example l-(A), 57.1 mg of n-heptane, 8.5 ml of di-n-butyl ether and 8.3 ml of titanium tetrachloride. One gram of this solid catalyst component contained 5.41 millimoles of titanium, 1.18 millimoles of n-butoxy group and 0.02 millimole of aluminum, and its n-butoxy group/titanium ratio was 0.218 (by mole). The X-ray diffraction spectrum of this solid catalyst component had diffraction lines corresponding to the diffraction lines of planes [113] and [300J of 6-form titanium trichloride. Then, vinylcyclohexane was polymerized by repeating the procedure of Example 1-(C), except that 94.7 mg of this solid catalyst component was The the used. / yield of' granular polymer was 1.16 g, and Polym/Cat was 12.2. Comparative Example 2 A solid catalyst component was prepared by repeating the procedure of Example 1-(B), except that the reaction was carried out at 1000C for one hour by using 4.42 g of the solid product obtained in Example 1- (A) and 20 ml of titanium tetrachloride and using neither n-heptane nor di-n-butyl ether. One gram of this solid catalyst component contained 5.85 millimoles of titanium, 0.22 millimole of n-butoxy group and 0.18 millimole of aluminum, and its n-butoxy group/titanium ratio was 0.038 (by mole). The X-ray diffraction spectrum of this solid catalyst component had the same diffraction lines as those of ss-form titanium trichloride having a fibriform structure. Then, vinylcyclohexane was polymerized by repeating the procedure of Example 1-(C), except that The 107.4 mg of this solid catalyst component was used./ yield of the granular polymer was 0.44 g, and Polym/Cat was 4.1. Comparative Example 3 A solid catalyst component was prepared by repeating the procedure of Example 1- (B), except that the reaction was carried out at 900C for one hour by using 6.62 g of the solid product obtained in Example l-(A), 33.1 ml of n-heptane and 9.7 ml of titanium tetrachloride and using no di-n-butyl ether. One gram of this solid catalyst component contained 5.36 millimoles of titanium, 2.11 millimoles of n-butoxy group and 0.17 millimole of aluminum, and its n-butoxy group/titanium ratio was 0.394 (by mole). In the X-ray diffraction spectrum of this solid catalyst component, the characteristic peaks of titanium trichloride crystal were not found at all. Then, vinylcyclohexane was polymerized by repeating the procedure of Example l-(C), except that 98.0 mg of this solid catalyst component was used. As the result, no granular polymer was formed at all. Comparative Example 4 Vinylcyclohexane was polymerized by repeating the procedure of Example 1- (C), except that the solid product obtained in Example l-(A) was used in an amount of 81.2 mg. As the result, no granular polymer was formed at all. Example 6 the (A) Synthesis of/Solid Product After replacing, with argon, the inner atmosphere being of a flask having a capacity of 500 ml and/equipped with a stirrer and a dropping funnel, 100 g of tetra-o-cresoxytitanium and 250 ml of toluene were charged into the flask and the tetra-o-cresoxytitanium was dissolved. Then, while maintaining the inner temperature of the flask at 600C, a solution composed of 100 ml of toluene and 47.8 ml of ethylaluminum sesquichloride was slowly added dropwise thereinto from the dropping funnel over a period of 2 hours. After dropping it, the content of the flask was stirred at 600C for one hour. Then, the flask was allowed to stand at room temperature and the reaction mixture was separated into solid and liquid phases, after which the solid product was washed four times with 200 ml of nheptane and dried under reduced pressure to obtain a browncolored solid product. One gram of this solid product contained 3.8 millimoles of titanium and 4.7 millimoles of o-cresoxy group. In the X-ray diffraction spectrum of this solid product measured with Cu-Ka rays, no characteristic peaks of titanium trichloride crystal were found at all. (B) Synthesis of/ t id Catalyst Component After replacing the inner atmosphere of a flask having a capacity of 100 ml with argon, 6.3 g of the solid product synthesized in (A) above and 32 ml of nheptane were charged into the flask and the inner temperature of the flask was maintained at 300 C. Then, 5.7 ml of di-isoamyl ether was added and treated at 350C for one hour. Subsequently, 6.2 ml of titanium tetrachloride was added, the temperature was elevated to 650 C, and the content of the flask was reacted at 650C for one hour. The flask was allowed to stand at room temperature and the reaction mixture was separated into solid and liquid phases, after which the solid product was washed five times with 50 ml of n-heptane and dried under reduced pressure to obtain a solid catalyst component. One gram of this solid catalyst component contained 5.3 millimoles of titanium, 0.19 millimole of o-cresoxy group and 0.02 millimole of aluminum, and its o-cresoxy group/titanium ratio was 0.036 (by mole). The X-ray diffraction spectrum of this solid catalyst component had diffraction lines corresponding to the diffraction lines the of planes [113] and [300] of/6-form titanium trichloride. (C) Polymerization of Vinylcyclohexane Vinylcyclohexane was polymerized by repeating the procedure of Example l-(C), except that 75.4 mg of the solid catalyst component obtained in (B) above was used. the the As the result,/yield of/granular polymer was 1.83 g, and Polym/Cat was 24.3. Example 7 the (A) Synthesis of/Solid Product After replacing, with argon, the inner atmosphere being of a flask having a capacity of 300 ml and/equipped with a stirrer and a dropping funnel, 15 ml of n-heptane and 15 ml of titanium tetrachloride were charged into the flask, and the inner temperature of the flask was maintained at 800 C. Then, while maintaining the inner temperature of the flask at 800C, a solution composed of 40 ml of n-heptane and 52 ml of n-decyl alcohol was slowly added dropwise thereinto from the dropping funnel over a period of one hour. After dropping it, the content of the flask was stirred at 800C for 1.5 hours. After lowering the inner temperature of the flask to 500C, a solution composed of 40 ml of n-heptane and 17 ml of diethylaluminum chloride was slowly added dropwise thereinto from the dropping funnel over a period of 2 hours, while maintaining the inner temperature of the flask at 500 C. After dropping it, the temperature was elevated to 600C, and the content of the flask was stirred for one hour. The flask was allowed to stand at room temperature and the reaction mixture was separated into solid and liquid phases, after which the solid product was washed six times with 100 ml of n-heptane and dried under reduced pressure to obtain a brown-colored solid product. (B) Synthesis of/Solid Catalyst Component A solid catalyst component was prepared by repeating the procedure of Example l-(B), except that 6.75 g of the solid product obtained in (A) above, 24 ml of n-heptane, 10 ml of monochlorobenzene, 4.1 ml of di-n-butyl ether and 5.4 ml of titanium tetrachloride were used. One gram of this solid catalyst component contained 5.1 millimoles of titanium, 0.17 millimole of n-decylalkoxy group and 0.02 millimole of aluminum, and the n-decylalkoxy group/titanium ratio was 0.033 (by mole). The X-ray diffraction spectrum of this solid catalyst component had diffraction lines corresponding to the diffraction lines the of planes [113] and [300] of/6-form titanium trichloride. (C) Polymerization of Vinylcyclohexane Vinylcyclohexane was polymerized by repeating the procedure of Example l-(C), except that 131.1 mg of the solid catalyst component obtained in (B) above was used and the time of the polymerization was 25 minutes. The the yield of/granular polymer was 1.94 g, and Polym/Cat was 14.8. Example 8 the (A) Synthesis of/Heat-treated Solid Product After replacing, with argon, the inner atmosphere of a four-necked flask having a capacity of 500 ml and equipped with a stirrer and a dropping funnel, 114 ml of n-heptane and 30 ml of titanium tetrachloride were thR charged into the flask and/temperature of the resulting solution was maintained at -100C. Then, while maintaining the inner temperature of the flask at -50C to 100 C, a solution composed of 150 ml of n-heptane and 68.3 ml of ethylaluminum sesquichloride was added dropwise thereinto from the dropping funnel over a period of 2 hours. After dropping it, the content of the flask was stirred at room temperature for 30 minutes. Then, the temperature was elevated to 650 C, and a heat-treatment was carried at this temperature for 2 hours. Then, the flask was allowed to stand at room temperature and the reaction mixture was separated into solid and liquid phases, after which the solid product was washed four times with 200 ml of n-heptane and dried under reduced pressure to obtain a heat-treated solid product. (B) Synthesis of/ibfid id Catalyst Component After replacing, with argon, the inner atmosphere being of a flask having a capacity of 200 ml and/equipped with a stirrer, 91.5 ml of n-heptane, 24.0 ml of di-isoamyl ether and 3.0 g of iodine were charged into the flask, and the iodine was dissolved at 500C for 30 minutes. Then, 18.3 g of the heat-treated solid product obtained in (A) above was charged into the flask and reacted at 950C for one hour. After the reaction, the reaction mixture was cooled to 650C, 30 ml of a titanium compound represented by Ti(OBu)o 5C13 5 was added, and the reaction mixture was treated at 650C for 30 minutes. Then, the flask was allowed to stand at room temperature and the reaction mixture was separated into solid and liquid phases, after which the solid product was washed five times with 50 ml of n-heptane and dried under reduced pressure to obtain a violet-colored solid catalyst component. One gram of this solid catalyst component contained 5.8 millimoles of titanium, 0.21 millimole of n-butoxy group and 0.41 millimole of aluminum, and its n-butoxy group/titanium ratio was 0.036 (by mole). The X-ray diffraction spectrum of this solid catalyst component had diffraction lines corresponding to the diffraction lines of planes [0031, [113] the and [300] of/6-form titanium trichloride. (C) Polymerization of Vinylcyclohexane Vinylcyclohexane was polymerized by repeating the procedure of Example l-(C), except that 95.8 mg of the solid catalyst component obtained in (B) above was used. the the As the result,yield of/granular poiymer was 2.53 g, and Polym/Cat was 26.4.

Claims: WHAT IS CLAIMED IS: 1. A process for homopolymerizing an a-olefin branched at the carbon atom of the third position or copolymerizing said a-olefin with another olefin in the presence of a catalyst system comprising a combination of an organo-aluminum compound and a solid catalyst component a containing titanium, chlorine and/hydrocarbyloxy group, of which/ t-ray diffraction spectrum has diffraction lines at least corresponding to the diffraction lines of planes ±1131 and [3001 of titanium trichloride having a layer structure and wherein the content of the hydrocarbyxoly group is 0.01 mole to 0.3 mole per 1 mole of titanium. 2. A process according to Claim 1, wherein said hydrocarbyloxy group is represented by the following general formula: ORÚ a wherein RÚ represents/hydrocarbon group having 1 to 20 carbon atoms. 3. A process according to Claim 2, wherein RÚ in the general formula OR1 is a straight chain alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. 4. A process according to Claim 1, wherein the content of the hydrocarbyloxy group is 0.02 mole to 0.25 mole per 1 mole of titanium. 5. A process according to Claim 1, wherein the X-ray diffraction spectrum of said solid catalyst component has diffraction lines at least corresponding to the the diffraction lines of planes [113] and [300] of/6-form titanium trichloride. 6. A process according to Claim 1, wherein said solid catalyst component is a solid catalyst component synthesized by reducing a titanium compound represented by the following general formula: Ti (OR1) nC 14-n a wherein RÚ represents/hydrocarbon group having 1 to 20 carbon atoms and n represents a numerical figure satisfying o < n 4, with an organo-aluminum compound represented by the following general formula: : AlRêmX3-m a wherein Rê represents/hydrocarbon group having 1 to 20 carbon atoms, X represents/halogen atom and m represents a numerical figure satisfying 1 < m m 3, to obtain a hydrocarbyloxy group-containing solid product insoluble in hydrocarbon solvents, followed by treating said solid product at a temperature of 450C to 1200C in the presence of an ether compound and titanium tetrachloride in the state of a slurry. 7. A process according to Claim 1, wherein said solid catalyst component is a solid catalyst component synthesized by reducing titanium tetrachloride with an organo-aluminum compound represented by the following general formula: AlRêmX3-m wherein R2, X and m are each as defined above, followed by heat-treating the reduced product at a temperature not higher than 1500 C, reacting the heat-treated product with a mixture consisting of a halogen compound represented by the following general formula: X2 a wherein X represents/halogen atom, and an ether compound in a hydrocarbon solvent, and then treating the reaction product with a titanium compound represented by the following general formula: Ti (OR1) )nC14-n wherein RÚ and n are each as defined above. 8. A process according to Claim 1, wherein the organo-aluminum compound used for the polymerization is trialkylaluminum, dialkylaluminum hydride, dialkylaluminum chloride, dialkylaluminum alkoxide, dialkylaluminum siloxide or a mixture thereof. 9. A process according to Claim 8, wherein the organo-aluminum compound is trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum ethoxide or a mixture thereof. 10. A process according to Claim 1, wherein the organoaluminum compound used for the polymerization is used in an amount ranging from 0.5 mole to 100 moles per 1 mole of titanium atom present in the solid catalyst component. 11. A process according to Claim 1, wherein said a-olefin branched at the carbon atom of the third position is 3-methylbutene-1 or vinylcyclohexane. 12. A process according to Claim 1, wherein the temperature of the polymerization is in the range of frown 2'5 to 1500C. 13. A solid catalyst component synthesized by reducing a titanium compound represented by the following general formula: Ti (OR1) ,C14-n a wherein RÚ represents/hydrocarbon group having 1 to 20 carbon atoms and n represents a numerical figure satisfying 0 < n < 4, with an organo-aluminum compound represented by the following general formula: : m 3-m wherein R2 represents/hydrocarbon group having 1 to 20 a carbon atoms, X represents/halogen atom and m represents a numerical figure satisfying 1 < m 3, to obtain a hydro- carbyloxy group-containing solid product insoluble in hydrocarbon solvents, followed by treating said solid product at a temperature of 450C to 1200C in the presence of an ether compound and titanium tetrachloride in the state of a slurry. 14. A solid catalyst component synthesized by reducing titanium tetrachloride with an organo-aluminum compound represented by the following general formula: AlR2mX3-m wherein R2, X and m are each as defined above, followed by heat-treating the reduced product at a temperature not higher than 1500C, reacting the heat-treated product with a mixture comprising a halogen compound represented by the general formula: X2 wherein X represents a halogen atom, and an ether compound in a hydrocarbon solvent, and then treating the reaction product with a titanium compound represented by the following general formula: Ti (OR1) nCl 4-n wherein R1 and n are each as defined above.

Inventors: KOJIMA, JUNPEI, SASAKI, TOSHIO, SHIGA, AKINOBU
Applicants: SUMITOMO CHEMICAL COMPANY, LIMITED
Application year: 1984
Main classification: C08F10
IPC codes: C08F4, C08F10