United States Patent (19) 11 Patent Number: 4,783,573 Shiraki et al. 45) Date of Patent: Nov. 8, 1988

54 PROCESS FOR PREPARING LINEAR (56) References Cited OOLEFNS U.S. PATENT DOCUMENTs (75) Inventors: Yasushi Shiraki; Shinichi Kawano; 4,486,615 12/1984 Langer ...... 585/523 Kunio Takeuchi, all of Tokuyama, Primary Examiner-Curtis R. Davis Japan Attorney, Agent, or Firm-Armstrong, Nikaido, Marmelstein & Kubovcik (73) Assignee: Idemitsu Petrochemical Company 57 ABSTRACT Limited, Tokyo, Japan A process for preparing a linear a-olefin having from 4 to 20 carbon atoms is disclosed which comprises poly 21 Appl. No.: 946,218 merizing or gas containing ethylene in the presence of a catalyst consisting of a zirconium halide, an organoaluminium compound and a Lewis base, and (22 Filed: Dec. 24, 1986 adding a catalyst deactivating agent to the resulting reaction mixture, wherein said Lewis base is at least one (30) Foreign Application Priority Data member selected from the group consisting of thioe thers, alkyl disulfides, thiophenes, thiourea, sulfides, Apr. 17, 1986 JP Japan ...... 6-88863 phosphines and primary amines. Aug. 6, 1986 JP Japan ...... 61-184700 Use of the catalyst enables preparation of linear a-ole fins of a high purity and reduction in the amount of

5ll Int. Cl'...... sees sooooooooes C07C2/02 by-produced wax. 52 U.S. C...... 585/523; 585/511 58) Field of Search ...... mi 585/523, 511 6 Claims, No Drawings 4,783,573 1. 2 in a high yield and the purity of the a-olefin obtained is PROCESS FOR PREPARNG LINEAR o-OLEFNS high with forming a small amount of wax fraction, thus enabling long production runs. FIELD OF THE INVENTION Another object of the present invention is to provide The present invention relates to a process for prepar a process for preparing a linear a-olefin by oligomeriz ing linear a-olefins. More particularly, the present in ing ethylene according to which linear a-olefins con vention relates to a process for preparing a-olefins by taining low content of halogen derived from the cata oligomerizing ethylene according to which not only lyst used can be prepared in high purity. linear a-olefins can be prepared in high purities with In order to achieve the above objects extensive inves by-producing wax in small amounts but also long pro 10 tigations have been carried out by the present inventors. duction run is possible. and as a result it has now been found that excellent effects are obtained by the use of a novel ternary cata BACKGROUND OF THE INVENTION lyst which consists of a Zr compound, an Al compound a-Olefins are useful as a comonomer for modification and a specified third component. The present invention in the field of preparing polyolefins or as a plasticizer or 15 is based on this discovery. a surface active agent after they are alcoholized. That is, the present invention provides a process for Generally, such linear a-olefins are prepared by oli preparing a linear a-olefin having from 4 to 20 carbon gomerizing ethylene in the presence of a catalyst. As for atoms comprising polymerizing ethylene orgas contain the catalyst there is known, for example, a binary cata ing ethylene in the presence of a catalyst consisting of a lyst which consists of titanium tetrachloride and 20 zirconium halide, an organoaluminium compound and a ethylaluminium dichloride. Also, a process for increas Lewis base, and adding a catalyst deactivator to the ing the yield and selectivity of a-olefins using a catalyst resulting reaction mixture wherein said Lewis base is at which consists of a third component in addition to the least one member selected from the group consisting of above-described binary catalyst composition is known. thioethers, alkyl disulfides, thiophenes, thiourea, sul On the other hand, binary catalysts with increased 25 fides, phosphines and primary amines. activities have recently been proposed which comprises zirconium (Zr) instead of the above-described titanium DETALED DESCRIPTION OF THE compound. For example, Japanese Patent Application INVENTION Laid-Open Nos. 109428/83, 201729/83 and 113138/83 In the process of the present invention, a novel ter and Japanese Patent Publication No. 30.042/75 disclose 30 nary catalyst is used which consists of a zirconium hal binary catalysts whoih consist of a Zr compound and an ide (hereinafter, sometimes referred to as "Component Al compound. A"), the above-described organoaluminium compound However, processes for the oligomerization of ethyl (hereinafter, sometimes referred to as "Component B”) ene using the above-described binary catalysts compris and a Lewis base specified hereinbelow (hereinafter, ing Zr have caused various problems. For example, 35 final products contain wax fraction in large amounts or sometimes referred to as "Component C"). the yield of oligomers having a small number of carbon The zirconium halide used as Component A is a com atoms, e.g., those having about 4 carbon atoms, is in pound represented by formula (I) below creased and the purity of the a-olefins obtained is very low. Further, long continuous operation of production ZrxaA4-a (I) unit is difficult since wax fraction is formed in a large wherein X and A, which may be the same or different, amount or for other reasons. each represents Cl, Br or l, and a is 0 or an integer of up U.S. Pat. No. 4,486,615 discloses a catalyst composi to 4. tion consisting of a binary catalyst composed of a Zr Specific examples of the zirconium halide repre compound and an Al compound and a Lewis base such 45 sented by the formula (I) include ZrCl4, Zirbra, Zr, as a tertiary amine, a secondary amine, an ether, a phos ZrBrCl3, Zrbr?Cl, etc. Among these, ZrC14 is particu phine oxide, an alkyl phosphate, an aryl phosphate, a larly preferred. They can be used singly or two or more sulfoxide, etc. which is added as a third component in of them can be used in combination. order to increase the activity of the binary catalyst. The organoaluminium compound which can be used However, although it is described in U.S. Pat. No. 50 4,486,615 that a linear a-olefin having high purity as in the present invention is an alkylaluminium sesquiha high as 99.5% can be prepared using the catalyst com lide represented by formula (II) below position containing triethylamine as the most preferred example of the Lewis base it has been confirmed by the AlRl5O15 (II) present inventors that use of the catalyst compositions 55 wherein R represents an alkyl group having from 1 to containing Lewis bases referred to in U.S. Pat. No. 20 carbon atoms, and Q represents Cl, Br or I (formula 4,486,615 other than triethylamine results in the prepa (II) may also be expressed as Al2R3Q3) or an al ration of linear a-olefins having low purity and that a kylaluminium compound represented by formula (III) large amount of the above-described ternary catalyst below containing triethylamine is used in U.S. Pat. No. 4,486,615. AllR'Q'3-b (III) SUMMARY OF THE INVENTION wherein R and Q', which may be the same or different, An object of the present invention is to obviate the have the same meanings as R and Q in formula (II), and defects of the conventional processes and to provide a 65 b is an integer of 1 to 3. process for preparing a linear a-olefin by oligomerizing The alkylaluminium sesquihalide represented by for ethylene according to which the medium fraction con mula (II) above which can be used as Component B taining from about 6 to 20 carbon atoms can be obtained (hereinafter, sometimes referred to as "Component 4,783,573 3 4. B-1') is not limited particularly as far as R and Q in These compounds can be used singly or two or more formula (II) satisfy the above-described conditions. of them can be used in combination. Specific examples thereof include Al2(CH3)3Cl3, Among the various Lewis bases defined in the present Al2(CH3)3Br3, Al2(C2H5)3Cl3, Al2(C2H6)3Br3, invention, at least one member selected from the group Al2(C2H5)33, Al2(C2H6)3BrCl2, Al2(C3H7)3Cl3, Al2 consisting of methyl disulfide, thiophene, thiourea, tri (iso-C3H7)3Cl3, Al2(C4H3)3Cl3, Al2(iso-C4H9)3Cl3, phenylphosphine, trioctylphosphine and aniline can be Al2(C5H11)3Cl3, Al2(C8H17)3Cl3, Al2(C2H5)2(CHs)Cl8, used particularly advantageously. etc. In the process of the present invention, compounds Among these, compounds in which R represents a belonging to Components A, B and C, respectively, can methyl group, an ethyl group, a propyl group or a butyl 10 be selected appropriately and the selected compounds group are preferred and those in which R represents an are combined to prepare a catalyst which can be used to ethyl group are particularly preferred. achieve the objects of the present invention. It is preferred that Q represents Cl. However, a catalyst which is obtained by selecting a Specifically, ethylaluminium sesquichloride mixture of Component B-1 and Component B-2 as (Al(C2H5)15Cl 15, i.e., Al2(C2H6)3Cl3) is preferred. 5 Component B and combining the mixture with Compo These alkylaluminium sesquihalides can be used sin nent A and Component C, and a catalyst obtained by gly or two or more of them can be used in combination. combining Component A, Component B-1 and Compo The alkylaluminium compound represented by for nent C are preferred. More particularly, a catalyst con mula (III) above which can be used as Component B sisting of a mixture of an alkylaluminium sesquihalide 20 and a trialkylaluminium, zirconium tetrachloride and (hereinafter, sometimes referred to as "Component thiophene, and a catalyst consisting of an al B-2') is not limited particularly as far as R' and Q' in kylaluminium sesquihalide, zirconium tetrachloride and formula (II) satisfy the above-described conditions. thiophene are preferred. This is because when these Specific examples thereof include Al3(CH3)3, catalysts are used not only the content of wax in the Al(C2H5)3, Al(C3H7)0, Al(iso-C3H7), Al-(C4HO)3, Al 25 product of oligomerization reaction can be further re (iso-C4H9)3, Al(C6H11)3, Al(C6H13)3, Al(C8H17)3, duced but also the yield of linear a-olefins per weight of Al(C2H5)2Cl, Al(C2H5)2Br, Al(C2H5)2I, Al(C2H5)Cl2, zirconium halide can be increased and the purity of the Al(C2H5)-Br2, Al(C2H5)2, etc. linear a-olefin obtained can be increased. However, among the compounds represented by When a mixture of Component B-1 and Component formula (III), those in which b is 2 or 3 are preferred. 30 B-2 is used as a catalyst component Component B-1 and In formula (III), R is preferably an ethyl group, a Component B-2 are mixed desirably in a proportion propyl group, a butyl group or an isobutyl group and such that Component B-2 is not higher than 50 mol% more preferably an ethyl group. (Al basis), preferably not higher than 30 mol%. (Al It is preferred that Q' represents Cl. basis). Specifically, compounds such as triethylaluminium, 35 In the present invention, there is no particular limita diethylaluminium chloride and ethylaluminium dichlo tion on the method of preparing catalysts from Compo ride are preferred. nents A, B and C. However, it is preferred to contact These alkylaluminium compounds can be used singly Component A with Component B in a suitable solvent or two or more of them can be used in combination as to form a catalyst preparation liquor which contain a Component B-2. catalyst precursor and then mix this catalyst preparation The Lewis base which can be used as Component C liquor with Component Cupon or prior to the polymer is at least one member selected from the group consist ization (oligomerization) of ethylene to obtain a catalyst ing of thioethers, alkyldisulfides, thiophenes, thiourea, liquor. sulfides, phosphines and primary amines. Upon preparation of the catalyst preparation liquor As for the thioethers, there can be cited, for example, 45 or catalyst liquor, it is desirable that the mixture is dimethyl sulfide, dipropyl sulfide, dihexyl sulfide, dicy heated at a suitable temperature (usually, a temperature clohexyl sulfide, diphenyl thioether, etc. lower than the temperature of polymerization reaction, As for the alkyl disulfides, there can be cited, for for example, and more specifically within the range of example, methyl disulfide ((CH3)2S2), ethyl disulfide, from 60 to 80° C) for from 10 to 120 minutes to acti propyl disulfide, butyl disulfide, hexyl disulfide, cyclo 50 vate the catalyst. hexyl disulfide, ethyl methyl disulfide, etc. As for the solvent which can usually be used in the As for the thiophenes, there can be cited, for example, present invention, there can be cited, for example, aro thiophene, 2-methylthiophene, 3-methylthiophene, 2,3- matic hydrocarbons and halogenated derivatives dimethylthiophene, 2-ethylthiophene, benzothiophene, thereof such as benzene, toluene, xylene, chloroben tetrahydrothiophene, etc. 55 zene, ethylbenzene, dichlorobenzene, chlorotoluene, As for the sulfides, there can be cited, for example, etc., paraffins such as pentane, , heptane, octane, methyl sulfide, ethyl sulfide, butyl sulfide, etc. nonane, decane, etc., naphthenes such as cyclohexane, As for the phosphines, there can be cited, for exam decaline, etc., haloalkanes such as dichloroethane, di ple, triphenylphosphine, triethylphosphine, tributyl chlorobutane, etc., and the like. Among these, benzene, phosphine, tripropylphosphine, trioctylphosphine, 60 toluene, xylene and chlorobenzene are preferred with tricyclohexylphosphine, etc. benzene being particularly preferred. As for the primary amines, there can be cited, for These solvents can be used singly or two or more of example, organic amines such as methylamine, ethyl them can be used in combination. amine, propylamine, butylamine, pentylamine, hexyla In the present invention, the proportion of Compo mine, cyclohexylamine, octylamine, decylamine, ani 65 nents A, B and C mixed per 250 ml of the solvent is line, benzylamine, naphthylamine, trimethylamine, tri usually from 0.005 to 5 mmol and preferably from 0.01 ethylamine, tributylamine, triphenylamine, pyridine, to 1 mmol, of Component A, usually from 0.02 to 15 picoline, etc. mmol and preferably from 0.05 to 3 mmol, of Compo 4,783,573 l 5 6 nent B, and usually from 0.01 to 20 mmol and preferably to 60° C. under the atmosphere of an inert gas, and from 0.02 to 20 mmol, of Component C when sulfur while stirring the catalyst liquor a gas containing ethyl compounds (thioethers, alkyl disulfides, thiophenes, ene such as high purity ethylene is introduced followed thiourea and sulfides) are used or from 0.01 to 5 mmol of by oligomerizing ethylene under the above-described Component C when phosphines or primary amines are 5 reaction conditions. used. As for the proportion of Components A. and B, After a predetermined period of time a conventional more desirable results can be obtained by setting the catalyst deactivating agent such as an aqueous alkali proportion of Al/Zr by within the range of from solution or an aqueous methanol solution containing an 1 to 15. alkali can be added to the reaction mixture to terminate Upon polymerization, the catalyst liquor can be O the reaction. mixed with the solvent to adjust the concentration of As for the catalyst deactivating agent, there can be the catalyst, if desired. cited, for example, water, (monohydric alco The thus prepared catalyst or catalyst liquor and hols, polyhydric alcohols, cyclic alcohols, acyclic alco ethylene or a gas containing ethylene are contacted in hols, aliphatic alcohols, aromatic alcohols), carboxylic the above-described solvent at a predetermined reaction 15 temperature under a predetermined reaction pressure to acids, phenols, etc. carry out polymerization (oligomerization) of ethylene When the catalysts is deactivated it is preferred to efficiently. . add a nitrogen containing compound in addition to the The gas containing ethylene which can be used in the catalyst deactivating agent described above to the reac present invention include an inert gas containing ethyl 20 tion mixture since addition of halogen derived from the ene, purified ethylene gas for polymerization, ethylene catalyst to the resulting linear a-olefin can be prevented gas for polymerization such as high purity ethylene, by the addition of the nitrogen containing compound, etc., with high purity ethylene being preferred. thus further improving the purity of the linear a-olefin. The reaction temperature upon polymerization is As for the nitrogen containing compounds, there can usually from 50 to 200 C, preferably from 100 to 150 25 be cited, for example, ammonia or amines such as me C. The reaction pressure is usually not lower than 5 thylamine, ethylamine, propylamine, butylamine, pen Kg/cm2 (gauge pressure), preferably not lower than 25 tylamine, hexylamine, cyclohexylamine, octylamine, Kg/cm2 (gauge pressure). The reaction time is usually decylamine, aniline, benzylamine, naphthylamine, di from about 5 minutes to about 2 hours, preferably from methylamine, diethylamine, dibutylamine, diphonyla about 15 minutes to about 1 hour. 30 mine, methylphenylamine, trimethylamine, triethylam All the operations starting from the preparation of the ine, tributylamine, triphenylamine, pyridine, picoline, catalyst to the completion of the polymerization reac etc. tion are desirably carried out in the absence of air and These nitrogen containing compounds can be used moisture. singly or two or more of them can be used in combina It is preferred that the preparation of the catalyst is 35 tion. carried out under the atmosphere of an inert gas such as The order of adding the deactivating agent and the nitrogen, argon, etc. nitrogen containing compound to the reaction mixture Further, it is desirable that starting materials for pre is not limited particularly. For example, the order of paring the catalyst, solvent and starting materials for addition may be (1) first to add the nitrogen containing polymerization are dried sufficiently. However, copres compound and then the deactivating agent, (2) first to ence of a minute amount of moisture or air sometimes add the deactivating agent and then the nitrogen con results in increase in the activity and selectivity of the taining compound or (3) to simultaneously add the ni catalyst. trogen containing compound and the deactivating Hereinafter, example of the process for preparing agent. linear o-olefins according to the present invention will 45 Of the above orders of addition, the order (1) is pre be described in detail. ferred. That is, in a vessel equipped with a stirrer there are After deactivation of the catalyst in the abovede dissolved Component A, e.g., zirconium tetrachloride, scribed manner the resulting product liquor contains and Component B, e.g., ethylaluminium sesquichloride, high content of linear a-olefins which have from about in the solvent, e.g., benzene, under the atmosphere of 50 6 to about 44 carbon atoms, particularly from 6 to 20 the inert gas, e.g., argon, nitrogen, etc., and heated at a carbon atoms in good yield and which do not contain temperature of from 60' to 80 C. for from 10 to 120 halogen. On the other hand, by-production of wax com minutes with stirring to prepare a catalyst preparation ponent is remarkably reduced. liquor. The reaction product liquor after deactivation of the A portion of the catalyst preparation liquor thus ob 55 catalyst can be subjected to post-treatments, e.g., wash tained is transferred to another vessel equipped with a ing with water, etc., separation such as extraction, filtra stirrer under the atmosphere of the inert gas and diluted tion, etc., drying and the like to recover the objective with the solvent, e.g., benzene, and then Component C, products, e.g., linear a-olefins of high purity in high e.g., thiophene, is added thereto at a temperature in the efficiency. vicinity of room temperature followed by stirring to That is, according to the process of the present inven prepare a catalyst liquor. As a result of the preparation tion, linear a-olefins of such high purity that they con of the catalyst in this manner a complex catalyst derived tain from about 6 to about 22 carbon atoms can be ob from a zirconium halide such as zirconium tetrachloride tained stably in high yield. And linear o-olefins having and an alkylaluminium compound is formed, and use of from about 6 to about 20 carbon atoms can be obtained the complex catalyst results in increase in the yield and 65 at high selectivity. It is possible to control the carbon purity of the objective product, linear a-olefins. atom number distribution of the product to a further Then, the above-described catalyst liquor is pressed narrow range by appropriately selecting the reaction into a reaction vessel kept at a temperature of from 50 conditions, catalyst composition, concentration, etc. 4,783,573 7 8 The unused ethylene or a low boiling point fraction mixture was stirred at 60° C. for 30 minutes to obtain a containing unused ethylene which is recovered may be catalyst preparation liquor. used as it is or recycled after purification for use as a Then, in a 500 ml three-neck flask were introduced starting material for the reaction. dry benzene and the catalyst preparation liquor in pre The linear a-olefins prepared according to the pro- 5 determined amounts, respectively, under the atmo cess of the present invention can be used advanta sphere of argon, followed by adjusting the amounts of geously as a comonomer for preparing various copoly zirconium tetrachloride, the ethylaluminium compound mers and also employed in various fields of industry indicated and benzene to the values indicated in Table 1. such as plasticizers, and starting materials for preparing To the resulting mixture was added a predetermined surface acitve agents. 10 amount of the third component (thiophene, aniline, According to the present invention, the following thiourea, triphenylphosphine or trioctylphosphine) and effects can be obtained. the mixture was stirred at room temperature for 10 That is, in the process of the present invention, use of minutes to obtain a catalyst liquor. the catalyst prepared from a zirconium halide, an or Preparation Example of a-Olefin (Oligomerization of ganoaluminium compound and a specified Lewis base 15 Ethylene) enables preparation of linear a-olefins of high purity In a 1 liter autoclave equipped with a stirrer was and reduction in the amount of by-produced wax. introduced the catalyst liquor prepared in the abovede More particularly, the catalysts prepared from zirco scribed preparation example of catalyst by conveying nium tetrachloride (A), alkylaluminium sesquihalide 20 using pressurized argon under the atmosphere of dry (B-1) or a mixture of alkylaluminium sesquihalide (B-1) argon. The temperature of the autoclave was kept at 50 and alkylaluminium halide (B-2), particularly trialk to 60° C. After the charging of the catalyst liquor was ylaluminium halide, and at least one Lewis base (C) over stirring was started and high purity ethylene gas selected from the group consisting of thioethers, alkyl was introduced rapidly into the autoclave and charging disulfides, thiophenes, thiourea, sulfides, phosphines 25 was continued until the inside pressure reached the and primary amines have a high activity, and when reaction pressure indicated in Table 1 and then the these catalysts are used linear a-olefins of higher purity temperature was elevated to the reaction temperature can be prepared, the amount of wax by-produced can be indicated in Table 1. Introduction of ethylene was con reduced further, and the yield of linear a-olefins based tinued in an amount necessary to maintain the reaction on the zirconium tetrachloride can be increased. 30 pressure. After the reaction was continued for 1 hour Further, in the process of the present invention, addi with maintaining the reaction conditions an aqueous tion of a nitrogen containing compound upon deactiva solution of sodium hydroxide was pressed into the auto tion of the catalyst in the resulting polymerization reac clave to deactivate the catalyst and thus terminate the tion product liquor obtained by oligomerization of eth reaction. Then, the following post-treatments were ylene the content of halogen in the linear a-olefins can 35 carried out. be reduced and linear a-olefins of higher purity can be At first, 20g of undecane for use as an internal stan prepared. dard for chromatography was added to the reaction In addition, when the reaction is carried out at high product and then wax component was filtered out using temperatures by-production of wax component is in a a filter paper. The wax component on the filter paper small amount and therefore operational performance of 40 was washed sufficiently with benzene to drip down the process is improved greatly, thus enabling long light fraction in the filtrate. The product in the filtrate production runs. was washed twice with 500 ml of deionized water and dried over anhydrous potassium carbonate. EXAMPLES The thus-obained transparent solution of the reaction The present invention will be described in greater product was analyzed by gas chromatography. The detail with reference to the following examples and yield of the product was obtained by internal standard comparative examples. method. On the other hand, the wax component which was EXAMPLES 1-15 filtered out was weighed after it was air dried and then Preparation Example of Catalyst (Preparation of 50 dried in a vacuum drier at a pressure of 20 mmHg. Catalyst Liquor) The yield of C4 to C8 fractions was calculated from the Schultz-Flory distribution since operational loss In a 1,000 ml flask equipped with a stirrer were intro could not be avoided. duced 50 mmol of anhydrous zirconium tetrachloride The results obtained are shown in Table 1. and 472 ml of dry benzene under the atmosphere of 55 argon and the resulting mixture was stirred for 30 min COMPARATIVE EXAMPLES 1-5 utes. To the mixture was added the alkylaluminium The same procedures as in Example 1 were repeated compound shown in Table 1 in such an amount that it except that as shown in Table 1, at least one of zirco occupies a molar ratio to zirconium tetrachloride calcu nium tetrachloride, ethylaluminium sesquichloride and lated from the amount indicated in Table 1 (for exam- 60 the third component was omitted. And the amount of ple, in Examples 1 to 4 and 6 to 10 the molar ratio of each component used and the reaction conditions are as Al2(C2H6)3Cl3/ZrCl4 is 5.0 and therefore 250 mmol of indicated in Table 1. The results contained are shown in ethylaluminium sesquichloride was added), and the Table 1.

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13 4,783,573 14 EXAMPLES 16-27 TABLE 2 Preparation Example of Catalyst (Preparation of Unit Catalyst Liquor) Catalyst Composition The same procedures as ino Example 1 were repeated 5 ZirconiumEthylaluminium tetrachloride sesquichloride minol 0.210.05 except that the catalyst compositions indicated in Table Triethylaluminium mmol 0.04 2 were used to prepare catalyst preparation liquors. Thiophene nmol 0.30 Then,y catalyst liquorsli were preparedd ffrom theh cata A/ZrBenzene mlmol/mol 2505 lyst preparation liquors in the same manner as in Exam- 10 Reaction Condition ple 1. Temperature °C. 2 120 Preparation Example of a-Olefins (Oligomerization of TimePressure Kg/em G 6035 Ethylene) Product Composition Purity Polymerization of ethylene was carried out in the 15 ot-Olefin same manner as in Example 1 except that the deactivat- C4 14.9 100 ing agents shown in Table 3 were used and the nitrogen C8 15.1 100 containing compounds shown in Table 3 were added in C8 14.0 99 amounts shown in Table 3 prior to the addition of the Sg 3. deactivating agents, and then the catalyst was deacti- 20 C14 72 97 vated. C16 5.8 96 Thereafter, the resulting polymerization reaction C18 5.2 96 product liquor after deactivation of the catalyst was S. 4.2 washed withO water, and the concentration of chloride Yieldax (wt.%) (g/g.ZrCl4) 03001.6 ion in the oily layer thus obtained (a mixture of benzene 25 Amount of a-Olefin (g) 120 as a solvent and linear a-olefin produced) was deter TABLE 3 Zirconium tetrachloride: 0.05 mM Triethylaluminium: 0.04 mM Ethylaluminium sesquichloride: 0.21 mM Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 N-Containing TEA TEA TMA NH3 NH3 aq. NH3 aq. NH3 aq. NH3 aq. NH3 aq. NH3 aq. Compound (28%) (10%) (10%) (10%) (10%) (28%) Amount (mM) 14 4. 90 10 165 58 29 29 18 65 Temperature (C.) 20 20 20 20 20 20 20 40 40 120 Deactivating Water Water Water Water Water Water Water Water Water Water Agent . Amount (g) 10 10 10 10 7 9 9 4. 4 7 Cl Content in s2 S2 S2 S2 s2 S2 S2 s2 4 22 Product (ppm) Ex. 26 Ex. 27 C. Ex. 6 C. Ex. 7 C. Ex. 8 C. Ex. 9 C. Ex. 10 C. Ex. 11 C. Ex. 12 C. Ex. 13 N-Containing N-MP TEA - - Compound - - -- Amount (mM) 7 14 - - un Temperature (C) 20 20 100 20 20 40 40 40 20 20 Deactivating Methanol Methanol Water Water Water Methanol Methanol" Butanol Octanol Methanol Agent Amoint (g) O 10 50 50 50 5 5 5 5 5 Cl Content in 7 S2 200 80 80 50 45 50 50 20 Product (ppm) Notes: TEA: Triethylamine, TMA: Trimethylamine, N-MP: N-Methylpiperidine, '': containing 1% NaOH, NH3 aq: aqueous ammonia, NH3: ammonia gas

EXAMPLES 28-36 AND COMPARATIVE mined and the chlorine content of the resulting linear EXAMPLES 14-16 a-olefin was obtained. The same post-treatments as in P ion E le of Catalyst (P f Example 1 were carried out. The results obtained are reparation XE O E. yst (Preparation o shown in Table 3. 60 atalyst Liquor) In a 2 liter autoclave equipped with a stirrer was COMPARATIVE EXAMPLES 6-13 introduced a slurry solution composed of 100 ml of dry As shown in Table 3, the same procedures as in Ex chlorobenzene and a predetermined amount (mmol) of amples 16-27 were repeated except that the nitrogen zirconium compounds shown in Table 4 under the at containing compound was not used. The amount of 65 mosphere of dry argon. each component and reaction conditions are as shown On the other hand, compounds and sulfur in Table 3. compounds or nitrogen compounds shown in Table 4 The results obtained are shown in Table 3. were added to 150 ml of dry chlorobenzene and the 4,783,573 15 16 mixture was stirred for 10 minutes and then introduced In the post-treatment, reaction products having 4 to 6 into the above-described autoclave to obtain a catalyst carbon atoms (C4-C6) were trapped in a dry ice liquor. re methanol bath upon depressurizing the autoclave in order to reduce loss of light fractions comprising Preparation Example of hvila-Olefins (Oligomerization of 5 C4-C6. Other reaction products were treated as fol Ethylene) lows. That is, at first wax component was filtered out At first, the catalyst liquor was heated for 1 hour until using a filter paper, and then the filtrate was washed the temperature reached 100° C. while stirring in the twice with 500 ml of deionized water followed by dry autoclave to effect activation, and at this timing high ing over anhydrous potassium carbonate. The transpar purity ethylene gas was introduced rapidly into the 10 ent solution thus obtained was analyzed by gas chroma autoclave and the charging was continued until the tography. On the other hand, the wax component fil pressure reached 35 Kg/cm2-G. Thereafter, introduc- tered was weighed after air drying and drying in a vac tion of ethylene was continued in amounts necessary for uum drier at a pressure of 20 mmHg. maintaining the pressure. The reaction was continued The composition (wt.%) and purity (wt.% of linear under these conditions for about 30 minutes and then 15 a-olefin in each fraction) of each fraction of a-olefin the catalyst was deactivated by pressing a methanol obtained by the above-described process and the com solution containing sodium hydroxide into the auto- position of wax (wt.%) are shown in Table 4. clave to terminate the reaction. TABLE 4 Catalyst Composition Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 ZrCl4 (mmol) 10 1.0 1.0 1.0 1.0 1.0 ZTPl (mmol) ------DEAC2 (mmol) 2.5 2.5 2.5 2.5 2.5 2.5 EADC (mmol) ------MDS (mmol) 0.15 0.4 0.6 - - TPs (mmol) ------0.6 1.2 - AN (mmol) -- - - - 0.6 TU (mmol) ------Al/Zr (mol/mol) 2.5 2.5 2.5 2.5 2.5 2.5 CB (ml) 250 250 250 250 250 250 Yield (g) S30 162 90 535 263 540 C P C P C P C P C P C P Product (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) a-Olefin C4 1.7 00 3.3 100 5.6 00 1.7 100 2.4 100 2.0 100 C6 7.6 98 10.2 100 15.7 100 4.9 97 6.3 99 3.8 96 C8 10.3 96 16.8 99 19.9 99 9.4 93 13.2 97 7.0 95 C10 10.0 93 15.1 98 16.3 97 9.7 88 16. 95 7.8 9. C12 9.8 90 13.2 98 12.6 96 10.3 85 15.9 93 9.0 88 Cl4 8.4 87 10.3 97 9.0 95 8.2 84 8.3 92 0.2 87 C16 7.6 85 8.2 96 7.4 95 7.6 83 7.6 90 8.0 86 C18 7.0 83 6.1 95 5.0 94 7.4 8 6.7 89 7.3 84 C20+ 11.3 80 6.8 95 5.8 94 11.3 80 8.3 87 9.9 82 Wax 26.3 - 10.0 -- 2.7 - 29.8 --- 15.2 - 35.0 --- Catalyst Composition Example 34 Example 35 Example 36 C. Ex. 14 C. Ex. 15 C. Ex. 16 ZrCl4 (mmol) 1.0 1.0 .0 1.0 1.0 - ZTPl (mmol) - - - - - 1.0 DEAC2 (mmol) 2.5 2.5 5.0 2.5 - 2.5 EADC (mmol) ------2.5 --- MDS (mmol) - --- 0.5 ---- - TP3 (mmol) -- - r -- - -- AN (mmol) 1.2 - - - - TU (mmol) --- 0.6 - - - - Al/Zr (mol/mol) 2.5 2.5 5.0 2.5 2.5 2.5 CB8 (ml) 250 250 250 250 250 250 Yield (g) 252 62 316 60 60 - C P C P C P C P C P C P Product (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) ot-Olefin C4 4.5 100 4.3 100 6.1 100 2.8 85 55.6 75 No Reaction C6 6.3 99 12,1 100 13.9 99 6.8 78 22.1 55 r C8 10.3 98 12.4 100 15.4 96 8.4 77 4.8 27 f C10 12.0 96 9.9 100 10.8 92 9.0 75 4.5 12 C12 5. 94. 7.5 99 9.2 90 8.2 73 2.6 3 C14 14.3 93 6.0 99 6.8 89 6.2 71 - f C16 8.2 91 4.6 98 5.1 87 5.0 68 0.4 --- C18 5.2 89 3.5 97 3.8 85 4.5 64 -- C20+ 6.7 89 4.4 97 3.5 83 6.8 64 - 4,783,573

TABLE 4-continued Wax 17.4 D 35.3 - 25.4 va 42.3 O AF Notes: ZTP: Zirconium tatra(n-propoxide), DEAC: Diethylaluminum chloride, EADC: Ethylaluminum dichloride, MDS: Methyl disulfide, 5p, Thiophene, AN: Aniline, 'TU: Thiourea, cB: Chlorobenzene cated in Table 5. Preparation Example of a-Olefins EXAMPLES 37-44. AND COMPARATIVE (Oligomerization of Ethylene) EXAMPLES 17-19 ol-Olefins were prepared in the same manner as in Preparation Example of Catalyst (Preparation of 15 Example 28 to 36 except that the above-described cata Catalyst Liquor) lyst liquors were used. The same post-treatments as in Examples 28 to 36 Catalyst liquors were prepared in the same manner as were carried out, in Examples 28 to 36 except that the zirconium com The composition (wt.%) and purity (wt.% of linear pounds shown in Table 5 were used in amounts indi 20 a-olefin in each fraction) of each fraction of a-olefin obtained by the above-described process and the com position of wax (wt.%) are shown in Table 5. TABLE 5 Catalyst Composition Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 ZrCl4 (mmol) 1.0 10 10 1.0 1.0 O ZTP1 (mmol) ra va OO DEAC2 (mmol) 2S 2S 2.5 2.5 2.5 2.5 EADC (mmol) O D are- - TBP (mmol) 0.4 0.3 0.25 0.4 0.3 0.25 TOP5 (mmol) ada O TPP6 (mmol) are ra O ma Al/Zr (mol/mol) 2.5 2.5 2S 2.5 2.5 2.5 Benzene (ml) 250 250 250 250 250 250 Yield (g) 50 137 432 32 2 441 C P C P C P C P C P C P Product (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) o-Oefin C4 300 : 00 13.7 100 5.3 100 38.6 100 17.6 00 50 00 C6 30.6 100 19.8 99 2.7 99 24.2 100 19.3 99 11.2 99. C8 16.8 99 18.5 97 7.6 97 15.2 99 16.7 98 2.8 97 C10 8.5 98 12.8 96 46 95 7.8 99 3.2 97 113 96 C12 3.5 98 9.3 94 3.1 92 3. 99 8.2 97 10.4 95 C14 2.8 97 7.9 93 9.7 89 . . . 2.5 98 5.7 96 9.7 94 C18 2.7 96 6.2 91 9.3 86 1.8 98 4.5 94 9.3 93 C18 .8 96 4.8 90 7.8 84 18 97 3.8 93 8.5 92 C20+ 1.6 95 5.0 90 8.0 82 1.6 97 4.3 93 9.6 90 Wax 1.7 - 20 aara 1.9 3.4 6.7 - 2.2 Catalyst Composition Example 43 Example 44 C. Ex. 17 C. Ex. 18 C. Ex. 19 ZrCl4 (mmol) 10 0 1.0 O var ZTP (mmol) a- 1.0 DEAC2 (mmol) 2.5 2.5 2S D 2.5 EADC (mmol) area 2.5 TBP (mmol) ada ar O TOPs (mmol) - m re TPP6 (mmol) 0.4 0.25 ar O Al/Zr (mol/mol) 2.5 2.5 2.5 2S 2.5 Benzene (ml) 250 250 250 250 250 Yield (g) 120 153 485 53 O C P C P C P C P C P Product (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) (wt.%) (%) ol-Olefin C4 S.2 OO 20.6 100 5.8 96 58.2 82 No Reaction C6 22.2 100 18.3 99 8.2 94. 23. 68 f C3 7.8 99 7.5 98 0.1 89 13.2 45 f C10 0.9 96 4.3 97 14.2 87 3.8 32 8A C12 9.6 98 0.4 97 9.8 85 1.4 23 C14 8.5 97 6.7 96 6.7 83 X A. C16 7.8 96 5.3 95 5.2 80 0.3 ap C8 4.7 95 3.7 94 3.8 78 a- f C20 + 2.6 94 2.0 94 4.3 78 aua 4,783,573 19 20 TABLE 5-continued Wax 0.7 2 3.9 O Notes: ZTP: Zirconium tetra(n-propoxide), DEAC: Diethylaluminium chloride, EADC: Ethylaluminium dichloride, TBP: Tributylphosphine, TOP; Trioctylphosphine, TPP: Triphenylphosphine,

10 wherein R2 and Q2 have the same meanings as R1 and Ql above and b is an integer of 1-3; said catalyst being While the invention has been described in detail and mixed at a molar ratio (Al/Zr) of said zirconium com with reference to specific embodiments thereof, it will ponent and aluminum component of 3-15 and at a molar be apparent to one skilled in the art that various changes ratio (AlR 15O15/AlR2O23-) of the components and modifications can be made therein without depart 15 represented by formulae (II) and (III) of 2-10; and said ing from the spirit and scope thereof. catalyst further contains at least one Lewis base selected What is claimed is: from the group consisting of thiophene, methyl disul 1. A process for preparing a linear o-olefin having fide, thiourea triphenylphosphine and trioctylphos from 6 to 18 carbon atoms comprising polymerizing phine. ethylene or an ethylene containing a-olefin in the pres 2. A process according to claim 1 wherein 0.005-5 ence of a catalyst consisting of a zirconium halide, an mmols of the zirconium component, 0.02-15 mmols of organoaluminum compound and a Lewis base in an the alkylaluminum compound and 0.02-20 nmols of the inert solvent and terminating the polymerization by Lewis base are used per 250 ml of the inert solvent adding a catalyst deactivating agent to the resulting when the Lewis base is selected from group consisting reaction mixture, wherein said catalyst contains a zirco 25 of thiophene, methyl disulfide and thiourea. nium component comprising a zirconium halide repre 3. A process according to claim 1, are used per 250 ml sented by formula (): of the inert solvent when the is selected from the group consisting of triphenylphosphine and trioctylphosphine ZrxaA4-a (I) 0.01-5 mmols of the Lewis base. wherein X and A may be the same or different and each 30 4. A process according to claim 1 where the zirco represents chloride, bromide atom or iodide and a is 0 or nium halide is zirconium tetrachloride and R1 and R2 an integer of 1-4; an aluminium component comprising are ethyl and Q and Q2 are chlorine. an alkylaluminum compound represented by formula 5. A process according to claim 1 wherein the zirco (II): nium halide represented by the formula () is zirconium 35 tetrachloride, the alkylaluminum represented by the AlR 15q11.5 (II) formula (II) is ethylaluminum sesquichloride and the alkylaluminum represented by the formula (III) is tri wherein R represents an alkyl group of 1-20 carbon ethylaluminum. atoms, Q represents chloride, bromide or iodide atom 6. A process according to claim 1 further comprising and said formula (II) may also be represented by the addition of at least one nitrogen compound selected Al2R3Q3 and an alkylaluminum compound repre from the group consisting of trimethylamine, triethyl sented by formula (III): amine, ammonia gas, ammonia water and n-methyl piperidine prior to the addition of the catalyst deactivat AlRQ3-b (III) ing agent. 45

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