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United States Patent (19) 11 Patent Number: 4,783,573 Shiraki Et Al

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United States Patent (19) 11 Patent Number: 4,783,573 Shiraki Et Al 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 ethylene 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.
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