United States Patent (19) 11 4,223,118 Tsubaki et al. 45) Sep. 16, 1980 54 PROCESS FOR PRODUCING Primary Examiner-Edward J. Smith POLYETHYLENES Attorney, Agent, or Firm-Oblon, Fisher, Spivak, McClelland & Maier 75 Inventors: Kazumi Tsubaki; Hiroshi Morinaga; Takeshi Iwabuchi; Masao Kawahara, 57 ABSTRACT all of Ichihara, Japan A polyethylene is produced by polymerizing ethylene with or without a comonomer in the presence of a cata 73 Assignee: Nissan Chemical Industries, Limited, lyst consisting of an organometallic compound and a Tokyo, Japan solid catalytic component (B) obtained by reacting a (21) Appl. No.: 941,727 titanium or vanadium halide with a reaction product (A) in the presence of one or more aluminum alkoxide 22 Filed: Sep. 12, 1978 having the formula (30) Foreign Application Priority Data Sep. 22, 1977 JP Japan ...... 52-113279 51 Int. Cl2...... C08F 4/02; C08F 10/02 wherein R2 represents a C1-C12 alkyl group and X rep 52) U.S. Cl...... 526/128; 252/429 B; resents a halogen atom and 0Grignard reagent 56) References Cited with an organosilicon compound selected from the U.S. PATENT DOCUMENTS group consisting of hydropolysiloxanes having the structural units of 3,907,759 9/1975 Okada et al...... 526/128 FOREIGN PATENT DOCUMENTS RaHSiO(4-a-b/2) (I) 2365235 7/1974 Fed. Rep. of Germany ...... 526/125 2621591 11/1976 Fed. Rep. of Germany ...... 526/125 wherein R represents an alkyl, aryl, aralkyl, alkoxy or 1275641 5/1972 United Kingdom...... 526/125 aryloxy group; a is 0, 1 or 2; b is 1, 2 or 3; and a--bs 3, 1286867 8/1972 United Kingdom. ... 526/125 and organosilicon compounds having the formula 1434264 5/1976 United Kingdom ...... 526/124 OTHER PUBLICATIONS RSi(OH)4, (II) Kirk-Othmer, Encyclopedia of Chemical Technology, J. Wiley & Sons, Inc., 2nd Ed., vol. 1, (1963), p. 840 wherein R3 represents a C1-C18 hydrocarbon moiety same reference vol. 2, p. 53. and n is 1, 2 or 3, and polycondensates of the compound Texas Alkyls, Aluminum Alkyls . . . Specification, (II). Properties and Procedures, Technical Brochure of Texas Alkyls, Inc., Feb. 1973, pp. 7 & 10. 7 Claims, No Drawings 4,223,118 1. 2 distribtuion of the polyethylene. The degree of the PROCESS FOR PRODUCING POLYETHYLENES shark skin is decreased depending upon the increase of the molecular weight distribution. BACKGROUND OF THE INVENTION In General, the flow ratio (FR) is used as a degree of The present invention relates to a process for poly 5 molecular weight distribution and it is a ratio of flowing merizing ethylene. More particularly, it relates to a quantities of a molten polymer under different extrud process for producing polyethylene having wide molec ing pressures. ular weight distribution which has excllent fabricatabil For example, melt indexes are measured at 190° C. ity such as hollow molding, extrusion molding, which under the load of 2.16 Kg and 10.0 Kg by ASTM-D comprises polymerizing ethylene with a novel catalyst O 1238-65T to give MI2 and MI10 and FR is given by having high catalytic activity and long life. MI10/MI2. The inventors have studied and found that a catalyst When MI2 is similar, larger FR indicates wider mo for polymerizing ethylene which has remarkably high lecular weight distribution. catalytic activity and has not disadvantages, can be In the hollow molding and the extrusion molding, it is obtained by using a solid catalytic component obtained 15 preferable to have FR of higher than 14 in order to by reacting the reaction product (A) with titanium or obtain a molded product having smooth surface. vanadium halide. (Japanese Patent Publication Nos. In some kind of the previously proposed catalysts, it 19308/1975, 19309/1975, 154/1976 and 13232/1977.) is possible to increase molecular weight distribution in It has been found that remarkably high yield of poly certain degree by selecting kinds and amounts of the ethylene per the transition metal halide and remarkably 20 organometallic compound or varying conditions for high yield of polyethylene per the solid catalytic com preparing the solid catalytic component and conditions ponent can be attained in the polymerization of ethylene in the polymerization. However, it is not satisfactory. with a catalyst consisting of the solid catalytic compo On the other hand, various efforts for increasing nent and the organometal compound whereby an ad molecular weight distribution have been made by con verse effect of the transition metal halide etc. in the 25 sidering the catalyst especially the solid catalytic com polymer is not found even though a complicated and ponent. However, in the previously proposed ones, in uneconomical step of removing the catalyst is not em general, the catalytic activity is low, and the yield of ployed. polyethylene per weight of the transition metal halide This is significant advantages in the practical opera or weight of the solid catalytic component, is not high tion. 30 In the previously proposed catalytic system, the vari enough. Accordingly, even though a carrier is used for ation of the catalytic activity during the polymerization improving the catalytic activity, the advantage for elim is small to maintain high catalytic activity for a long inating the catalyst separating step can not be satisfacto time as the initiation whereby a stable continuous poly rily eliminated. merization is attained. The catalyst is highly sensitive to 35 SUMMARY OF THE INVENTION the molecular weight regulator as hydrogen whereby the molecular weight of the polymer can be highly It is an object of the present invention to provide a varied by using a small amount of the molecular weight process for producing polyethylene having high quality regulator and various grades of the polymers in wide and high commercial value in high catalytic activity to range can be obtained. obtain it without a catalyst separating step. The polyethylene obtained by using the previously It is another object of the present invention to pro proposed catalyst system has high bulk density and the vide a process for producing polyethylene having wide powdery form is substantially uniform and spherical molecular weight distribution to provide excellent ex whereby the slurry of the polymer and the dried pow trusion molding characteristic and hollow molding dery polymer have excellent flowability and the failure 45 characteristic. in the polymerization such as clogging of the transfer It is the other object of the present invention to pro ring devices is advantageously small. vide a process for producing polyethylene without However, in the previously proposed processes, it is much oily or waxy by-products which are usually not satisfactorily applied for the production of polyeth formed by using a catalyst system for wide molecular ylene having wide molecular weight distribution. 50 weight distribution. The narrow molecular weight distribution of poly It is the other object of the present invention to pro ethylene is preferable in the field of the injection mold vide a process for producing polyethylene without ing etc. whereas it is quite disadvantageous in the fields much deposition of scale on a wall of a reactor. of the extrusion molding and the hollow molding etc. The foregoing and other objects of the present inven When polyethylene having narrow molecular weight 55 tion have been attained by polymerizing ethylene with distribution is used in the extrusion molding, high extru or without a comonomer in the presence of a catalyst sion speed can not be obtained to decrease the produc consisting of an organometallic compound and a solid tivity of the processing machines, and on the other catalytic component (B) obtained by reacting a titanium hand, ununiformity of the shape of the molded product or vanadium halide with a reaction product (A) ob and rough surface of shark skin are caused to deterio tained by reacting a Grignard reagent with an organo rate quality of the product. silicon compound selected from the group consisting of In the case of the hollow molding, the extrusion hydropolysiloxanes having structural units of speed is also decreased and the shark skin of the surface of the product is caused and strips and pittings are RaHiSiO(4-a-b/2) (I) formed to decrease commercial value of the molded 65 product. wherein R represents an alkyl, aryl, aralkyl, alkoxy or The shark skin phenomenon of the surface of the aryloxy group; a is 0, 1 or 2; b is 1, 2 or 3; and a--bs3, molded product closely related to the molecular weight and organosilicon compounds having the formula 4,223,118 4. methyldiphenylhydroxysilane, benzyldiphenylhydrox R, Si(OH)4-, (II) ysilane etc. The silanes (II) (n=2) include diethyldihydroxysi wherein R3 represents a C1-C1s hydrocarbon moiety, lane, dipropyldihydroxysilane, diallyldihydroxysilane, and n is 1, 2 or 3, and polycondensates of the compound dicyclohexyldihydroxysilane, diphenyldihydroxysilane (II) in the presence of one or more aluminum alkoxide etc. having the formula The silanes (II) (n = 1) include butyltrihydroxysilane, phenyltrihydroxysilane etc. Al(OR),X3-n (III) The organosilicon compounds having organic group wherein R2 represents a C1-C12 alkyl group and X rep and hydroxy group bonded to silicon atom include resents a halogen atom and 0ether-free of a liquid having low polymerization degree to grease or ether complexed compounds or mixtures of them or wax having a viscosity of about 100,000 c.s. at 25 C. having the formula and also can be in a form of solid. (MgR2').(R'MgX) (IV) The terminal groups of the hydropolysiloxane have 45 not substantial effect for the catalytic activity and ac wherein R represents a hydrocarbon moiety and X cordingly, the terminal groups can be protected by inert represents a halogen atom and p and q are respectively groups such as trialkylsilyl group. 0 to 1 and p + q = 1. Suitable hydropolysiloxanes (I) include tetramethyl The Grignard reagents include RMgX; R2Mg (di disiloxane, diphenyidisiloxane, trimethylcyclotrisilox 50 hydrocarbyl magnesium); (MgR2').(R“MgX)(organic ane, tetramethylcyclotetrasiloxane, methylhy magnesium halide); ether complexes and mixtures dropolysiloxane, phenylhydropolysiloxane, ethoxyhy thereof. - dropolysiloxane, cyclooctylhydropolysiloxane, chloro The Grignard reagents can be easily produced by the phenylhydropolysiloxane etc. conventional methods in the presence of suitable The organosilicon compounds having an organic 55 amount of a chelating agent such as ether and amines, in group and hydroxy group bonded to silicon atom in suitable solvent such as ether type solvents e.g. diethyl clude silanes having the formula ether, dibutyl ether, tetrahydrofuran, etc. or hydrocar bon type solvents e.g. heptane, octane, benzene, toluene RSi(OH)4, - (II) etc. 60 The organosilicon compound can be reacted with the wherein R3 represents a C1-C18 hydrocarbon moiety Grignard reagent by suitable manners. such as alkyl, cycloalkyl, aralkyl, aryl or alkaryl group In the reaction of the Grignard reagent with hy which can be straight or branched chain and saturated, dropolysiloxane, the hydropolysiloxane is added drop unsaturated or cyclic group and n is 1, 2 or 3. When a wise to the Grignard reagent formed in suitable solvent plurality of R3 are bonded, R3 can be the same or differ 65 and the mixture is heated for suitable time after the ent. addition. The silanes (II) (n=3) include trimethylhydroxysi The reaction of the Grignard reagent with hy lane, triethylhydroxysilane, triphenylhydroxysilane, dropolysiloxane is performed at room temperature as 4,223,118 5 6 severe exothermic reaction. However, in order to com nol. The alcohol used for the dilution or the alcohol plete the reaction, it is preferable to heat the reaction formed by the reaction is preferably removed by a dis mixture at 50 to 100 C. for 1 to 5 hours, tillation or it is preferably reacted with an organoalumi The ratio of Grignard reagent to hydropolysiloxane num compound having the formula is preferably in a range of 0.05 to 1:1 as MgRSi. 5 The reaction of the Grignard reagent with the hy AlRY3. droxy group containing organosilicon compound (II) can be attained by the conventional methods as follows. to form the aluminum alkoxide having the formula (III), The Grignard reagent formed in suitable solvent is before adding the titanium or vanadium halide, gradually, dissolved into an organosilicon compound O The compound (III) or the reaction product obtained (II) under stirring in an inert gas atmosphere. After the by reacting the compound (III) with water is preferably addition, the reaction mixture is further stirred to com used in a range of 0.1 to 10 mole per 1 mole of magne plete the reaction. sium in the reaction product (A). The organosilicon compound (II) is preferably used When it is less than 0.1 mole, the effect for increasing under diluting it with a hydrocarbon solvent, etc. 15 molecular weight distribution of polyethylene is not though it is possible to use it without diluting it. enough whereas when it is more than 10 mole, the cata The reaction is usually performed at a reaction tem lytic activity is remarkably low, disadvantageously. perature of -50° C. to 100° C. and preferably at room The compound (III) or the reaction product obtained temperature or higher. by reacting the compound (III) with water can be re The reaction time is enough to be 30 minutes to 5 20 acted with the reaction product (A) obtained by react hours. ing the organosilicon compound with the Grignard A ratio of the organosilicon compound (II) to the reagent, in an inert hydrocarbon solvent at -10 to 150 Grignard reagent can be selected from a range of 1:0.05 C. for 5 minutes to 10 hours. And then, the product can to 1 of OH:MgRas hydroxy group of the organosilicon be reacted with the titanium or vanadium halide. compound (II) to the magnesium component. 25 When the resulting reaction product (A) is used with The compound (III) or the reaction product obtained large amount of an ether used as solvents for the or by reacting the compound (III) with water, can be ganomagnesium compound, disadvantageous effect is reacted with the titanium or vanadium halide in an inert given for the quality of the solid catalytic component hydrocarbon solvent at -10° to 150° C. for 5 minutes to (B). Accordingly, it is preferable to remove the volatile 10 hours. And then, the product can be reacted with the component such as ether solvent and then, to dissolve 30 reaction product (A). the residue in an inert hydrocarbon solvent or it is also The titanium halides used in the process of the pres preferable to add an inert hydrocarbon solvent and then ent invention can be the compounds having the formula to remove only the ether solvent by a distillation. TiXOR)4- The aluminum alkoxide having the formula 35 Al(OR)2X3-n (III) wherein X represents a halogen atom; R represents a C1-C3 hydrocarbon moiety and 1 is an integer of 1 to 4. wherein R2 represents a C1-C12 alkyl group and X rep Suitable titanium halides include titanium tetrachlo resents a halogen atom and 0alkoxides can be produced by reacting especially 1.5 to 10 times based on the total of the mag an organoaluminum compound having the formula nesium component in the reaction product (A), the aluminum component in the compound (III) or the AIRY3 50 reaction product obtained by reacting the compound wherein R2 represents a C1-C12 alkyl group and (III) with water. 0diethylzinc nitrogen gas, 75 ml of solution of n-butylmagnesium and dibutylzinc etc. 45 chloride in tetrahydrofuran (0.167 mole of n-butylmag When the organometallic compound is combined nesium chloride) was charged and then 10.5 ml of with the solid catalytic component (B), the catalyst for methyl hydropolysiloxane having terminal trimethyl polymerizing ethylene can be obtained. silyl group (viscosity about 30 c.s. at 25 C.) (0.175 mole In a reactor, the organometallic compound and the as Si) was added dropwise under stirring it. solid catalytic component (B) are separately charged to 50 The reactor was cooled with a coolant because of the form the catalyst and then ethylene is fed to polymerize exothermic reaction. After the addition, the reaction it. It is also possible to react the organometallic com mixture was kept at 70° C. for 1 hour and it was cooled pound with the solid catalytic component (B) in an inert to the room temperature to obtain a dark brown trans solvent to form a dispersion of the catalyst and then, to parent solution. charge the dispersion in a reactor for the polymeriza 55 . A part of the solution was sampled and the unreacted tion. n-butyl magnesium chloride was measured by the It is also possible to react the solid catalytic compo Gilman's method (J. Am Chem. Soc. 47 2002 (1925). As nent (B) with a small amount of an organoaluminum the result, no unreacted n-butylmagnesium chloride was compound preferably triethylaluminum; or an organo found. The solution was kept at 50° C. and the solvent aluminum chloride e.g. diethylaluminum monochloride, 60 was distilled off under a reduced pressure and the resi ethylaluminum sesquichloride, ethylaluminum dichlo due was dissolved in toluene to give 83.5 ml of the ride, or an organoaluminum alkoxide e.g. diethylalu solution. minum isopropoxide, and then, to feed the reaction (b) Preparation of Solid catalytic component (B) product with suitable amount of an organometallic In a glass flask dried and purged with nitrogen gas, compound into the polymerization system for polymer 65 16.3 g of aluminum triisopropoxide was charged and it izing ethylene. was dissolved in 133 ml of toluene and 40 ml of a solu The conditions for polymerizing ethylene with the tion of the reaction product (A) in toluene (0.08 mole as catalyst of the present invention is substantially the magnesium) was added dropwise to the solution at O C. 4,223,118 9 10 After stirring the solution for 30 minues, 35.2 ml of EXAMPLE 2 titanium tetrachloride was added dropwise to it at 0°C. After the addition, the mixture was heated at 100 C. to (b) Reaction of Solid catalytic component (B) and or react them for 3 hours. ganoaluminum compound After the reaction, the solid component was sepa A mixture of 1 g of the solid catalytic component (B) rated and washed with 1 liter of n-hexane by decanta obtained by Example 1-(b) and 100 ml of n-hexane was tions for 4 times and then, it was dried at 50 C. under mixed to form a slurry and 5 mmole of diethylaluminum a reduced pressure to obtain 35.7g of the grayish green monochloride was added and the mixture was stirred at solid catalytic component (B). room temperature for 1 hour. The solid catalytic component (B) corresponded to 10 (c) Polymerization 446 g per 1 mole of magnesium based on the magnesium In accordance with the process of Example 1-(c) component in the reaction product (A). except using the catalyst for 8 mg of the solid catalytic The titanium content in 1 g of the solid catalytic component (B) and feeding 3.5 Kg/cm2 of hydrogen component (B) was 162 mg. gas, the polymerization was performed to obtain 74.5g (c) Polymerization 15 of white powdery polyethylene having a bulk density of In a 1.2 liter autoclave equipped with a jacket for 0.333 g/cc. heating and cooling and a stirrer which was dried and The resulting polyethylene had MI2 of 0.31 g/10 min purged with nitrogen gas, 600 ml of purified n-hexane and FR of 15.4. The catalytic activity was 57.4 Kg PE/g Tihr and 9.3 Kg PE/g cat.hr. was charged and heated at 60° C. and then, 0.5 mmole 20 of triisobutyl aluminum and 10 mg of the solid catalytic EXAMPLE 3 component (B) obtained in the step (b) were sequen tially added. Then, 3 Kg/cm2 of hydrogen gas was fed (b) Preparation of Solid catalytic component (B) and the autoclave was heated to 80 C. and then, ethyl In a glass flask which was dried and purged with ene was continuously fed to maintain the total pressure nitrogen gas, 10.9 g of aluminum diisopropoxy mono of 9 Kg/cm2 to perform the polymerization for 1 hour. 25 chloride was charged and was dissolved in 100 ml of After cooling the autoclave, the polymer was separated toluene and then, 25 ml of the toluene solution of the by a glass filter and it was dried at 60° C. for 5 hours reaction product (A) obtained in Example 1-(a) (0.05 under a reduced pressure to obtain 101 g of a white mole as magnesium component) was added and the powdery polyethylene having a bulk density of 0.297 30 mixture was stirred at room temperature for 30 minutes. g/cc. Then, 25 ml of titanium tetrachloride was added to the The resulting polyethylene had MI2 of 0.33 g/10 min mixture and the reaction was performed at 100° C. for 2 and FR of 14.6. The catalyticativity was 62.3 Kg PE/g hours. After the reaction, the solid component was Tihr or 10.1 Kg PE/g cat.hr. separated and washed with 1 liter of n-hexane by decan tations for 4 times, and then, it was dried at 50 C. under Reference 1 35 a reduced pressure to obtain 23.8 g of gray solid cata (b) Preparation of Solid catalytic component lytic component (B). In accordance with the process of Example 1-(b) The titanium content in 1 g of the solid catalytic except excluding aluminum triisopropoxide, the solid component (B) was 97.3 mg. catalytic component was prepared to obtain 17.2 g of 40 (c) Polymerization grayish solid catalytic component. In accordance with the process of Example 1-(c) The solid catalytic component corresponded to 215g except using 8 mg of the solid catalytic component (B) per 1 mole of magnesium component in the reaction and feeding 2.5 Kg/cm2 of hydrogen gas, the polymeri product (A). zation was performed to obtain 114.4 g of powdery The titanium content in 1 g of the solid catalytic 45 polyethylene having a bulk density of 0.275 g/cc. component was 95 mg. The resulting polyethylene had MI2 of 0.35 g/10 min (c) Polymerization and FR of 14.2. In accordance with the process of Example 1-(c) The catalytic activity was 147 Kg PE/g Tihr and except using 4 mg of the solid catalytic component and 14.3 Kg PE/g cat.hr. feeding 2 Kg/cm2 of hydrogen, the polymerization was 50 performed to obtain 150 g of white powdery polyethyl EXAMPLE 4 ene. The resulting polyethylene had MI2 of 0.37 g/10 (b) Preparation of Solid catalytic component (B) nin and FR of 9.5 wherein the molecular weight distri In a glass flask dried and purged with nitrogen gas, tution was remarkably narrow. 7.5 g of aluminum triisopropoxide was sampled and 55 dissolved in 100 ml of toluene. Then, a mixture of 10 ml Reference 2 of isopropyl alcohol and 1.3 ml of water was added at (b) Preparation of Solid catalytic component 60 to 65 C. and then, the mixture was refluxed for 2 In accordance with the process of Example 1-(b) hours and 35 ml of a mixture of isopropyl alcohol and except excluding the reaction product (A), the solid toluene was distilled off by a distillation under the atmo catalytic component was prepared to obtain 21 g of pale 60 spheric pressure to obtain a viscous solution having yellow solid component. slight turbidity. To the solution, 19 ml of the toluene The titanium content in 1 g of the solid catalytic solution of the reaction product (A) obtained in the component was 199 mg. process of Example 1-(a) (0.038 mole as magnesium) (c) Polymerization - was added and the mixture was stirred at room tempera In accordance with the process of Example 1-(c) 65 ture for 30 minutes and then 25 ml of titanium tetrachlo except using 20 mg of the solid catalytic component ride was added and the reaction was performed at 100 obtained in the step (b), the polymerization was per C. for 2 hours. After the reaction, the solid component formed to obtain quite small amount of polyethylene. was washed with 400 ml of n-hexane by decantations 4,223,118 12 for 4 times to obtain a slurry of the solid catalytic com ponent (B) in n-hexane. EXAMPLE 7 The titanium content in 1 g of the solid catalytic (b) Preparation of Solid catalytic component (B) component (B) was 147 mg. In a glass flask dried and purged with nitrogen gas, (c) Polymerization 110 ml of toluene and 40 ml of the toluene solution of In accordance with the process of Example 1-(c) the reaction product (A) obtained by the process of except using 20 mg of the solid catalytic component (B), Example 1-(a) were charged and cooled to 0 C. Then, the polymerization was performed to obtain 100 g of in the other glass flask, 40 ml of toluene was charged powdery polyethylene. The polyethylene had MI2 of and 32.6 g of aluminum triisopropoxide and 17.6 ml of 0.45 g/10 min and FR of 14.5. 10 titanium tetrachloride were added and the reaction was performed at 100° C. for 1 hour. The reaction mixture EXAMPLE 5 was added dropwise to the toluene solution of the reac (b) Preparation of Solid catalytic component (B) tion product (A) at 0°C. Then, 35 ml of titanium tetra In a glass flask dried and purged with nitrogen gas, chloride was added dropwise to the mixture. After the 8.2 g of aluminum triisopropoxide was charged and it 15 addition, the reaction was further performed at 110° C. was dissolved in 50 ml of toluene and then a mixture of for 2 hours. After the reaction, the solid component was 5 ml of isopropyl alcohol and 1.1 ml of water was added separated and washed with 1 liter of n-hexane by decan dropwise at room temperature and then, the reaction tations for 4 times and then, it was dried at 50 C. under was performed at 80° C. for 1.5 hours to obtain a vis a reduced pressure to obtain 48.2 g of dark green solid cous solution having turbidity. To the solution, 20 ml of 20 catalytic component (B). the toluene solution of the reaction product (A) ob The titanium content in 1 g of the solid catalytic tained by the process of Example 1-(a) was added and component (B) was 174 mg. A slurry of 1 g of the solid the reaction was performed at 90° C. for 1 hour to ob catalytic component (B) and 100 ml of n-hexane was tain a white slurry. Toluene was added to give 200 ml of prepared and 3.6 mmole of diethyl aluminum mono 25 chloride was added and the mixture was stirred at room the solution and then, 0.1 mole of diethyl aluminum temperature for 1 hour. monochloride was added dropwise at room tempera (c) Polymerization ture and the reaction was performed at 90° C. for 30 In accordance with the process of Example 1-(c) minutes. Then, 35 ml of titanium tetrachloride was except using 8 mg of the solid catalytic component (B) added dropwise at room temperature and the reaction 30 treated with the organoaluminum compound, heating to was performed at 95 C. for 1 hour. After the reaction, 85 C. in the polymerization, the polymerization was a part of the solid component was sampled and washed performed to obtain 56 g of powdery polyethylene. with n-hexane by decantations for 4 times to obtain a The resulting polyethylene had MI2 of 0.11 g/10 min n-hexane slurry of the solid catalytic component (B). and FR of 16.8. The titanium content in 1 g of the solid catalytic 35 component (B) was 163 mg. EXAMPLE 8. (c) Polymerization (b) Preparation of Solid catalytic component (B) In accordance with the process of Example 1-(c) In accordance with the process of Example 1-(b) except using 20 mg of the solid catalytic component (B), except using 32.7 g of aluminum triisopropoxide and the polymerization was performed to obtain 81.7 g of 40 adding dropwise 50 ml of titanium tetrachloride at room powdery polyethylene. temperature, the solid catalytic component was pre The resulting polyethylene had MI2 of 0.33 g/10 min pared to obtain 52.8g of gray solid catalytic component and FR of 16.0. (B). EXAMPLE 6 The solid catalytic component (B) corresponded to 45 660 g per 1 mole of magnesium component in the reac (b) Preparation of Solid catalytic component (B) tion product (A). In accordance with the process of Example 1-(b) The titanium content in 1 g of the solid catalytic except using 19.7 g of aluminum triisobutoxide instead component (B) was 176 mg. of aluminum triisopropoxide, the solid catalytic compo A slurry of 1 g of the solid catalytic component (B) in nent was prepared to obtain 39.3 g of brown solid cata 50 n-hexane was prepared and 3.6 mmole of triethyl alumi lytic component (B). The solid catalytic component (B) num was added and the mixture was stirred at room corresponded to 491 g per 1 mole of magnesium in the temperature for 1 hour. reaction product (A). (c) Polymerization The titanium content in 1 g of the solid catalytic In accordance with the process of Example 1-(c) component (B) was 163 mg. 55 except using 20 mg of the solid catalytic component (B) A slurry of 1 g of the solid catalytic component (B) in and feeding 4.0 Kg/cm2 of hydrogen gas, the polymeri 100 ml of n-hexane was prepared and 3.4 mmole of zation was performed to obtain 75.0 g of white powdery diethyl aluminum monochloride was added to the polyethylene. slurry and the mixture was stirred at room temperature The resulting polyethylene had MI2 of 0.20 g/10 min for 1 hour. 60 and FR of 16.5. (c) Polymerization In accordance with the process of Example 1-(c) EXAMPLE 9 except using 8 mg of the solid catalytic component (B) (a) Preparation of Reaction Product (A) obtained from treated with the organoaluminum compound and feed dihydroxydimethyl polysiloxane and Grignard rea ing 2.0 Kg/cm2 of hydrogen gas, the polymerization 65 gent was performed to obtain 61 g of powdery polyethylene. In a glass flask dried and purged with nitrogen gas, 54 The resulting polyethylene had MI2 of 0.10 g/10 min ml of a,c)-dihydroxydimethyl polysiloxane having an and FR of 14.7. average degree of polymerization of 9 (SiOH content: 4,223,118 13 14 0.146 mol) and 100 ml of toluene were charged and 50 ture. After the addition, the reaction was performed at ml of a diethyl ether solution of n-butyl magnesium 70° C. for 2 hours and the solid component was sepa chloride (0.146 mole as n-butyl magnesium chloride) rated and washed with n-hexane for 4 times by a decan was added dropwise under stirring it. The reactor was tation...... cooled with a coolant because of the exothermic reac 5 The vanadium content in 1 g of the solid component tion. After the addition, the reactor was kept at 70 C. (B) was 188 mg...... for 1 hour to obtain a solution having slight turbidity. (c) Polymerization . . . A part of the solution was sampled and the unreacted In accordance with the process of Example 1-(c) n-butylmagnesium chloride was measured by the except using 40 mg of the solid catalytic component (B) Gilman's method. As the result, the unreacted n-butyl O and feeding 2.0 Kg/cm2 of hydrogen, the polymeriza magnesium chloride was not found. tion was performed to obtain 46 g of powdery polyeth Then, 50 ml of the solution (36 mmole as magnesium) ylene having a bulk density of 0.335 g/cc. The polyeth was sampled and diluted with 100 ml of toluene, and ylene had MI2 of 0.30 g/10 min and FR of 18.9. then, it was heated at 80 C. to remove excess diethyl What is claimed is: ether by distilling off to be about . The resulting vis 15 1. A process for producing polyethylene which com cous solution was diluted with 100 ml of toluene. prises polymerizing ethylene with or without a como (b) Preparation of Solid catalytic component (B) nomer in the presence of a catalyst consisting of an After dissolving 7.3 g of aluminum triisopropoxide organometallic compound and a solid catalytic compo into the toluenescution of the resulting reaction prod nent (B) obtained by reacting a titanium or vanadium uct (A), 30 ml of titanium tetrachloride was added drop 20 halide with a reaction product (A) obtained by reacting wise at room temperature. a Grignard reagent with an organosilicon compound After the addition, the reaction was performed at selected from the group consisting of hydropolysilox 110° C. for 3 hours and the solid component was sepa anes having structural units of rated and washed with 500 ml of n-hexane by decanta tions for four times and dried at 50 C. under a reduced 25 RaHiSiO(4-a-b/2) (I) pressure to obtain 16.6 g of pale yellow solid catalytic component (B). wherein R represents an alkyl, aryl, aralkyl, alkoxy or The titanium content in 1 g of the solid catalytic aryloxy group; a is 0, 1 or 2; b is 1, 2 or 3; and a--bs3 component (B) was 135 mg. and organosilicon compounds having the formula (c) Polymerization 30 In accordance with the process of Example 1-(c) RSi(OH)4, (II) except using 20 mg of the solid catalytic component (B) and charging 2 g ofbutene-1 at the beginning, the poly wherein R3 represents a C1-C18 hydrocarbon moiety merization was performed to obtain 92 g of powdery and n is 1, 2 or 3, and polycondensates of the compound polyethylene having a bulk density of 0.296 g/cc. The 35 (II) in the presence of one or more aluminum alkoxide resulting polyethylene had MI2 of 0.27 g/10 min and FR having the formula of 16.3. Al(OR)K3. (III) EXAMPLE 10 wherein R2 represents a C1-C12 alkyl group and X rep Preparation of Solid catalytic component (B) resents a halogen atom and O

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