CA1310985C - PROCESS FOR PREPARING LINEAR .alpha.-OLEFINS - Google Patents
PROCESS FOR PREPARING LINEAR .alpha.-OLEFINSInfo
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- CA1310985C CA1310985C CA000587056A CA587056A CA1310985C CA 1310985 C CA1310985 C CA 1310985C CA 000587056 A CA000587056 A CA 000587056A CA 587056 A CA587056 A CA 587056A CA 1310985 C CA1310985 C CA 1310985C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for preparing a linear .alpha.-olefin having from 6 to 20 carbon atoms comprising polymerizing ethylene or an ethylene containing .alpha.-olefin in the presence of a catalyst consisting of a zirconium halide, an organoaluminum compound and a Lewis base in an inert solvent and terminating the polymerization by adding a catalyst deactivating agent to the resulting reaction mixture, wherein said catalyst contains a zirconium component comprising a zirconium halide represented by formula (I):
ZrXaA4-a (I) wherein X and A may be the same or different and each represents chloride, bromide atom or iodide and a is 0 or an integer of 1-4;
an aluminum component comprising an alkylaluminum compound represented by formula (II):
AlR11.5 Q11.5 (II) wherein R1 represents an alkyl group of 1-20 carbon atoms, Q
represents chloride, bromide or iodide atom and said formula (II) may also be represented by AL2R13Q13 and an alkylaluminum compound represented by formula (III):
AlR2b Q23-b (III) wherein R2 and Q2 have the same meanings as R1 and Q1 above and b is an integer of 1-3; said catalyst being mixed at a molar ratio (Al/Zr) of said zirconium component and aluminum component of 3-and at a molar ratio (AlR11.5Q11.5/AlR2bQ23-b) of the components represented by formulae (II) and (III) of 2-10: and said catalyst further contains at least one Lewis base selected from the group consisting of thiophene, methyl disulfide, tiourea triphenylphosphine and trioctylphosphine.
Use of the catalyst enables preparation of linear .alpha. -olefins of a high purity and reduction in the amount of by-produced wax.
A process for preparing a linear .alpha.-olefin having from 6 to 20 carbon atoms comprising polymerizing ethylene or an ethylene containing .alpha.-olefin in the presence of a catalyst consisting of a zirconium halide, an organoaluminum compound and a Lewis base in an inert solvent and terminating the polymerization by adding a catalyst deactivating agent to the resulting reaction mixture, wherein said catalyst contains a zirconium component comprising a zirconium halide represented by formula (I):
ZrXaA4-a (I) wherein X and A may be the same or different and each represents chloride, bromide atom or iodide and a is 0 or an integer of 1-4;
an aluminum component comprising an alkylaluminum compound represented by formula (II):
AlR11.5 Q11.5 (II) wherein R1 represents an alkyl group of 1-20 carbon atoms, Q
represents chloride, bromide or iodide atom and said formula (II) may also be represented by AL2R13Q13 and an alkylaluminum compound represented by formula (III):
AlR2b Q23-b (III) wherein R2 and Q2 have the same meanings as R1 and Q1 above and b is an integer of 1-3; said catalyst being mixed at a molar ratio (Al/Zr) of said zirconium component and aluminum component of 3-and at a molar ratio (AlR11.5Q11.5/AlR2bQ23-b) of the components represented by formulae (II) and (III) of 2-10: and said catalyst further contains at least one Lewis base selected from the group consisting of thiophene, methyl disulfide, tiourea triphenylphosphine and trioctylphosphine.
Use of the catalyst enables preparation of linear .alpha. -olefins of a high purity and reduction in the amount of by-produced wax.
Description
1~10985 A PROC~SS ~OR P~EPARING LINE~R a -OL~FINS
FIELD O~ TllE INVENTION
'rhe present invention relates to a process for preparing linear ~ -olefins. More particularly, -the present invention relates to a process for preparing a -olefins by oligomerizing ethylene according to which not only linear ~ -o]efins can be prepared in high puri-ties with by-producing wax in small amounts but also long production run is possible.
BACKGROUND OF THE INVENTION
a -Olefins are useful as a comonomer for modification in the Eleld of preparing polyolefins or as a plasticizer or a surface active agent after they are alcoholized.
Generally, such linear a -olefins are prepared by oligomerizing ethylene in -the presence of a catalyst. ~s for the catalyst there is known, for example, a binary catalyst which consists of titanium tetrachloride and ethylaluminium dichloride. Also, a process for increasing the yield and selectivity of a -olefins using a catalyst which consists of a third component in addition to the above-described binary catalyst composition is known.
On the o-ther hand, binary catalys-ts with increased activities have recently been proposed which comprises zirconium (Zr) instead of the above-described titanium compound. For example, Japanese Patent Application Laid-Open Nos. 109428/83, 201729/~3 and 113138/~3 and Japanese Patent Publica~ion No. 30042/75 disclose binary catalysts whcih consist of a Zr compound and an Al compound.
However, processes for the oligomerization of 131098~
ethylene using the above-descrlbed binary catalysts comprising Zr have caused various problems. For example, final products contain wax fraction in large amoun-ts or the yield of oligomers having a small number of carbon atoms, e.g., those having about ~ carbon atoms, is increased and the purity of the a -olefins obtained is very low. Further, long continuous operation of production unit is difficult since wax Eraction is formed in a large amount or for other reasons.
U. S. Patent 4,486,615 discloses a catalyst composition consisting of a binary catalyst composed of a Zr compound and an Al compound and a Lewis base such as a tertiary amine, a secondary amine, an ether, a phosphine oxide, an alkyl phosphate, an aryl phosphate, a sulfoxide, etc. which is added as a third component in order to increase the activity of the binary catalyst.
However, although it is described in U. S. Patent 4,486,615 that a linear a -olefin having high purity as high as 99.5% can be prepared using the catalyst composition containing triethylamine as the most preferred example of the Lewis base it has been confirmed by the present inventors that use of the catalyst compositions containing Lewis bases referred to in U. S. Patent 4,486,615 other than triethylamine results in the preparation of linear a-olefins having low purity and that a large amount o~ the above-described ternary catalyst containing triethylamine is used in U. S. Patent 4,486,615.
SU~ARY OE THE INVENTION
An object of the present invention is to obviate the defects of the conventional processes and to provide a 131~98~
process for preparing a linear ~ -o:Lefin by oligomerizing ethylene according to which the medium frac-tion containing from abou-t 6 to 20 carbon atoms can be obtained in a high yield and the purity oE the ~ -olefin obtained is high with forming a small amount of wax fraction, thus enabling long production runs.
~ nother object of the present invention is to provide a process ~or preparing a linear a -olefin by oligomerizing ethylene according to which linear a -olefins containing low conten-t of halogen derived from -the catalyst used can be prepared in high purity.
In order to achieve the above objects extensive investigations have been carried out by the present invenlcors and as a result it has now been found that excellent effects are obtained by the use of a novel ternary catalyst which consists of a Zr c~mpound, an Al compound and a specified third component. The present invention is based on this discovery.
That is, the present invention provides a process for preparing a linear ~-olefin having from 6 to 20 carbon atoms comprising polymerizing ethylene or an ethylene containing ~-olefin in the presence of a catalyst consisting of a zirconium halide, an organoaluminum compound and a ~ewis base in an iner~ solvent and terminating the polymeri-zation by adding a catalyst deactivating agent to the 131Q98~
resulting reaction mixture, whereln said catalyst contains a zirconlum component comprising a zirconlum halide represented by formula (I):
ZrxaA4-a ( I) wherein X and A may be the ~ame or dlfferent and each represent~
chloride, bromide atom or lodide and a i~ O or an integer of 1-4;
an alumlnum component comprl~ing an alkylalumlnum compound represented by formula (II):
AlRll 5 Qll~5 tII) whereln Rl represent~ an alkyl group of 1-20 carbon atoms, Q
repre~ent~ chloride, bromide or iodide atom and said formula (II) may also be represented by A12R13Q13 and an alkylaluminum compound repre~ented by formula (III):
AlR2b Q23-b (III) whereln R2 and Q2 have the same meanings a~ Rl and Ql above and b is an integer of 1-3; ~aid cat~lyst being mixed at a molar ratio ~Al/Zr) of said zirconium component and aluminum component of 3-and at a molar ratio (AlRll 5Q~1.5/AlR2bQ23_b) of the component~ represented by formulae (II) and (III) of 2-10: and ~aid cataly~t further contains at least one Lewls base selected from the group con~istlng of thlophene, methyl dlsulfide, thiourea trlphenylphosphine and trloctylphosphine.
DETAILED DESCRIPTION OF THE INVENTION
In the process of the present invention, a novel ~31~985 ternary catalyst is used which consi.sts of a zirconium halide (hereinafter, some-times referred to as "Component A"), the above-described organoaluminium compound (hereinafter, sometimes referred to as "Component B") and a Lewis base specified hereinbelow (hereinafter, sometimes referred to as "Component C").
The zirconium halide used as Component A is a compound represented by formula (I) below Zr~aA4 a (I) wherein X and A, which may be the same or different, each represents Cl, Br or I, and a is 0 or an integer of up to 4.
Specific examples of the zirconium halide represented by the formula (I) include ZrCl~, ZrBr~, ZrI~., ZrBrCl,, ZrBr2Cl,-etc. Among these, ZrCl~ is particularly preferred. They can be used singly or two or more of them can be used in combination.
The organoaluminium compound which can be used in the present invention is an alkylaluminium sesquihalide represented by formula (II) below AlR1 5Q1.5 (II) wherein R represents an alkyl group having from 1 to 20 carbon atoms, and Q represents Cl, Br or I (formula (II) may also be expressed as Al 2 R3Q3) or an alkylaluminium compound represented by formula (III) below AlR bQ 3-b (III) wherein R' and Q', which may be the same or different, have the same meanings as R and Q in formula (II), and b i.s an integer of 1 to 3.
~ 31~8~
The alkylaluminium sesquihali.de represented by formula (II~ above which can be used as Componen-t B
(herelnafter, sometimes referred to as "Component B-1") is n~t limited particularly as far as R and Q in formula (II) satisfy the above-described conditions. Specific examples thereof include Al 2 (CH~J ) 3 C13, Al 2 (clls)3Br3~ Al 2 (C2 Hs)3Cl3~
Al2 (C2Hs)3Brs, Al2 (C2H5)3I3, Al2 (C2H5)3BrCl2, Al2 (C3H7)3Cl3, Al2 (iso-C3H7) 3Cl3, Al2 (C~HD) 3Cl3, A12 (iso-C~H") ~,Cl3, A12 (C5 H")3Cl3, Al2(C~ H, 7 ) 3Cl3, Al2(c2H5 ) 2 (CH3 ) Cl3, etc.
Among these, compounds in which R represents a methyl group, an ethyl group, a propyl group or a butyl group are preferred and those in which R represents an ethyl group are particularly preferred.
It is preferred that Q represents Cl.
Specifically, e-thylaluminium sesquichloride (Al(C2H5)1 5Cl1 5, i.e., Al2(C2H5) 3C13) is preferred.
These alkylaluminium sesquihalides can be used singly or two or more of them can be used in combination.
The al~ylaluminium compound represented by formula (III) above which can be used as Component B (hereinafter, sometimes referred to as "Component B-2") is not limited particularly as far as R' and Q' in formula (II) satisfy the above-described conditions. Specific examples thereof include Al1(CH3) 3, Al(C2H5)3, Al(C3H7)3, Al(iso-C3H7), Al-(C~HU) 3, Al(iso-C.~H~)3, Al(C5H1l)3, Al(C~H,~)3, Al(cuHl7)sl Al(C2H5)2Cl, Al(C2H5)2Br, Al(C2Hs)2I, Al(C2Hs)Cl2, Al(C2Hs)-Br2, Al(C2Hs)I2, etc.
However, among the compounds represented by formula (III), those in which b is 2 or 3 are preferred.
In formula (III), R' is preferably an ethyl group, 1 3~ ~8~
a propyl group, a butyl group or an isobutyl group and more preferably an ethyl group.
It ls preferred that Q' represents C1.
Specifically, compounds such as triethylaluminium, diethylaluminium chloride and ethylaluminium dichloride are preferred.
These alkylaluminium compounds can be used singly or two or more of them can be used in combina-tion as Component B-2.
The Lewis base which can be used as Componen-t C is at least one member selec-ted from the group consisting of thioethers, alkyldisulfides, thiophenes, thiourea, sulfides, phosphines and primary amines.
As for the thioethers, there can be cited, for example, dimethyl sulfide, dipropyl sulfide, dihexyl sulfide, dicyclohexyl sulfide, diphenyl thioether, etc.
As for the alkyl disulfides, there can be ci-ted, for example, methyl disulfide ((CH~)2S2), ethyl disulfide, propyl disulfide, butyl d1sulfide, hexyl disulfide, cyclohexyl disulfide, e-thyl methyl disulfide, etc.
As for the thiophenes, there can be cited, for example, thiophene, 2-methylthiophene, 3-methylthiophene, 2,3-dimethylthiophene, 2-ethyl-thiophene, benzothiophene, tetrahydrothiophene, etc.
As for the sulfides, there can be cited, for example, methyl sulfide, ethyl sulfide, butyl sulfide, etc.
As for the phosphines, there can be cited, for example, triphenylphosphine, triethylphosphine, tributyl-phosphine, tripropylphosphine, trioctylphosphine, tricyclo-hexylphosphine, etc.
131098~
As for the primary amines, there can be cited, for example, organic amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexyl-amine, oc-tylamine, decylamine, aniline, benzylamine, naphthylamine, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, picoline, etc.
These compounds can be used singly or two or more of them can be used in combination.
Among the various Lewis bases defined in -the present invention, at least one member selected from the group consisting of methyl disulfide, thiophene, thiourea, triphenylphosphine, trioc-tylphosphine and aniline can be used particularly advantageously.
In the process of the present invention, compounds belonging to Components A, B and C, respectively, can be selected appropriately and the selected compounds are combined to prepare a catalyst which can be used -to achieve the objects of the presen-t invention.
However, a catalyst which is obtained by selecting a mixture of Component B-1 and Component B-2 as Component B
and combining the mixture with Component A and Component C, and a catalyst obtained by combining Component A, Component B-l and Component C are preferred. More particularly, a catalyst consisting of a mixture of an alkylaluminium sesquihalide and a trialkylaluminium, zirconium tetra-chloride and thiophene, and a catalyst consisting of an alkylaluminium sesquihalide, zirconium tetrachloride and thiophene are preferred. This is because when these catalysts are used not only the content of wax in the product of oligomerization reaction can be further reduced 1310~
but also the yield of linear a -olefins per weight of zirconium halide can be increased and -the purity of the linear a -olefin obtained can be increased.
When a mixture of Component B-1 and Component B-2 is used as a catalyst component Component B-1 and Component B-2 are mlxed desirably ln a proportion such tha-t Component B-2 is not hlgher than S0 mol% (Al basls), preferably not higher than 30 mol% (Al basis).
In the present lnvention, there is no particular limitatlon on the method of preparlng catalysts from Components A, B and C. However, lt ls preferred to contact Component A with Component B in a suitable solvent to form a catalyst preparation liquor whIch contain a catalyst precursor and then mix -this catalyst preparation liquor with Component C upon or prior to the polymerization (oligomerization) of ethylene to obtain a catalyst liquor.
Upon preparation of the catalyst preparation liquor or catalyst liquor, it is desirable that -the mixture is heated at a suitable temperature (usually, a temperature lower than the temperature of polymerization reaction, for example, and more specifically within the range of from 60 to 80 C) for from 10 to 120 minutes to activate the catalys-t.
As Eor the solvent which can usually be used in the present invention, there can be cited, for example, aromatic hydrocarbons and halogenated derivatives thereof such as benzene, toluene, xylene, chlorobenzene, ethyl-benzene, dichlorobenzene, chlorotoluene, etc., paraffins such as pentane, hexane, heptane, octane, nonane, decane, etc., naphthenes such as cyclohexane, decaline, etc., 8 ~
haloalkanes such as dichloroethane, dichlorobutane, etc., and the like. Among these, benzene, toluene, xylene and chlorobenzene are preferred with benzene being particularly preferred.
These solvents can be used singly or two or more of them can be used in combination.
In the present invention, the proportion of Components A, B and C mixed per 250 ml of the solvent is usually from 0.005 to 5 mmol and preferably from 0.01 to 1 mmol, of Component A, usually from 0.02 to 15 mmol and preferably from 0.05 to 3 mmol, of Component B, and usually from 0.01 to 20 mmol and preferably from 0.02 to 20 mmol, of Component C when sulfur compounds (thioethers, alkyl disulfides, thiophenes, thiourea and sulfides) are used or from 0.01 to 5 mmol of Component C when phosphines or primary amines are used. As for the proportion of Components A and B, more desirable results can be obtained by setting the proportion of Al/Zr by mole within the range of from 1 to 15.
Upon polymerization, the catalyst liquor can be mixed with the solvent -to adjust the concentration of the catalyst, if desired.
The thus prepared catalyst or catalyst liquor and ethylene or a gas containing ethylene are contacted in the above-described solvent at a predetermined reaction temperature under a predetermined reaction pressure to carry out polymerization (oligomerization) of ethylene efficiently.
~31~
The ~as containing ethyle~e which can be used in the present in~ention include an inert gas containing ethylene, purlfied ethylene gas for polymerization, ethylene gas for polymerization such as high purity ethylene, etc., with high purity ethylene being preferred.
The reaction temperature upon polymerization is usually from 50 to 200 C , preferably from 100 to 150 C -The reaction pressure is usually not lower than ~ Kg/cm2 (gauge pressure), preferably not lower than 25 Kg/cm2 (gauge pressure). The reaction tirne is usually from about 5 minutes to about 2 hours, preferably frorn about 15 minutes to about 1 hour.
All the operations starting from the preparation of the catalyst to the completion of the polymerization reaction are desirably carried out in the absence of air and moisture.
It is preferred that the preparation of the catalyst is carried out under the atmosphere of an inert gas such as nitrogen, argon, etc.
Further, it is desirable that starting materials for preparing the catalyst, solvent and starting materials for polymerization are dried sufficiently. However, copresence of a minute amount of moisture or air sometimes results in increase in the activity and selectivity of the catalyst.
Hereinafter, example of the process for preparing linear a -olefins according to the present invention will be described in detail.
That is, in a vessel equipped with a stirrer there are dissolved Component A, e.g., zirconium tetrachloride, and Component B, e.g., ethylaluminium sesquichloride, in the solvent, e.g., benzene, under the atmosphere of the inert gas, e.g., argon, nitrogen, etc., and heated at a temperature of from 60 to 80 ~C for from 10 to 120 minutes with stirring to prepare a catalyst preparation liquor.
A portlon oE the catalyst preparation liquor thus obtained is transferred to another vessel equipped with a stirrer under the atmosphere of the inert gas and diluted with the solvent, e.g., benzene, and then Component C, e.g., thiophene, is added thereto at a temperature in the vicinity of room temperature followed by stirring to prepare a catalyst liquor. As a result of the preparation of the catalyst in -this manner a complex catalyst derived from a zirconium hallde such as zirconium tetrachloride and an alkylaluminium compound is formed, and use of the complex catalyst results in increase in the yield and purity of the objective product, linear a -olefins.
Then, the above-described catalyst liquor is pressed into a reaction vessel kept at a temperature of from 50 to 60 C under the atmosphere of an inert gas, and while stirring the catalyst liquor a gas containing ethylene such as high purity ethylene is introduced followed by oligomerizing ethylene under the above-described reaction conditions.
After a predetermined period of time a conventional catalyst deactivating agent such as an aqueous alkali solution or an aqueous methanol solution containing an alkali can be added to the reaction mixture to terminate the reaction.
As for the catalyst deactivating agent, there can 8 ~
be cited, for example, water, alcohols (monohydric alcohols, polyhydric alcohols, cyclic alcohols, acyclic alcohols, aliphatic alcohols, aromatic alcohols), carboxylic acids, phenols, etc.
When the catalyst is deactivated it is preferred to add a nitrogen containing compound in addition to the catalyst deactivatlng agent described above to the reaction mix-ture since addition of halogen derived from the catalyst to the resulting linear a -olefin can be prevented by the addition of the nitrogen containing compound, thus further improving the purity of the linear a -olefin.
As for the nitrogen containing compounds, there can be cited, for example, ammonia or amines such as methyl-amine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, aniline, benzylamine, naphthylamine, dime-thylamine, diethyl-amine, dibutylamine, diphenylamine, methylphenylamine, tri-methylamine, triethylamine, tributylamine, triphenylamine, pyridine, picoline, etc.
These nitrogen containing compounds can be used singly or two or more of them can be used in combination.
The order of adding the deactivating agent and the nitrogen con-taining compound to the reaction mixture is not limited particularly. For example, the order of addition may be (1) first to add the nitrogen containing compound and then the deactivating agent, (2) first to add the deactivat-ing agent and then the nitrogen containing compound or (3) to simultaneously add the nitrogen containing compound and the deactivating agent.
Of the above orders of addition, the order (1) is `- 131~8~
preferred.
After deactivation of the catalyst in the above-described manner the resulting product liquor contains high content of linear ~-olefins which have from 6 to 20 carbon atoms in good yield and which do not contain halogen. On the other hand, by-production of wax component is remarkably reduced.
The reaction product liquor aEter deactivation oE
the ca~alyst can be subjected to post-treatments, e.g., washing with water, etc., separation such as extraction, filtration, etc., drying and the like to recover the objective products, i.e., linear a -olefins of high purity in high efficiency.
That is, accordlng to the process oE the present invention, linear a -olefins of such high purity that they contain from about 6 to about 20 carbon atoms can be obtained stably in high yield. ~nd linear a -olefins having from about 6 to about 20 carbon atoms can be obtained at high selectivity. It is possible to control the carbon atom number distribution of the product to a further narrow range by appropriately selecting the reaction conditions, catalyst composition, concentration, etc.
The unused ethylene or a low boiling point fraction containing unused ethylene which is recovered may be used as it is or recycled after purification for use as a starting material for the reaction.
The linear a -olefins prepared according to the process of the present invention can be used advantageously as a comonomer for preparing various copolymers and also 131~98~
employed in various fields of industry such as plasticizers, and starting materials for preparing surface active agents.
~ ccording to -the present invention, the following effects can be obtained.
That is, in the process oE the present invention, use of -the catalyst prepared from a zirconiwn halide, an organoaluminium compound and a specified Lewis base enables preparation of linear a -olefins of high purity and reduction in the amount of by-produced wax.
More particulariy, the catalysts prepared from zirconium tetrachloride (~), alkylaluminium sesquihalide (~-1) or a mixture of alkylaluminium sesquihalide (B-1) and alkylaluminium halide (B-2), particularly trialkylaluminium halide, and at least one Lewis base (C) selected from the group consisting of thioe-thers, alkyl disulfides, thiophenes, thiourea, sulfides, phosphines and primary amines have a high activi-ty, and when these catalysts are used linear a -oleEins of higher puri-ty can be prepared, the amount of wax by-produced can be reduced further, and the yield of linear a -olefins based on the zirconium tetra-chloride can be increased.
Further, in the process of the present invention, addition of a nitrogen containing compound upon deactivation of the catalyst in the resulting polymerization reac-tion product liquor obtained by oligomerization of ethylene the content of halogen in -the linear a -olefins can be reduced and linear a -olefins of higher purity can be prepared.
In addition, when the reaction is carried out at high temperatures by-production of wax component is in a small amount and therefore operational performance of the ~31~98~
process is improved yreatly, thus enabling long production runs.
EXAMPLES
The present invention will be described in greater detail with reference to the following examples and comparative examples.
_XAMPLES 1-15 Preparation Example of Catalys-t (Preparation of Catalyst Liquor) In a 1,000 ml flask equipped with a s-tirrer were introduced 50 mmol of anhydrous zirconium tetrachloride and 472 ml of dry benzene under the atmosphere of argon and the resulting mixture was stirred for 30 minutes. To the mixture was added the alkylaluminium compound shown in Table 1 in such an amount -that it occupies a molar ratio to zirconium tetrachloride calculated from the amount indicated in Table 1 (for example, in Examples 1 to ~ and 6 to 10 the molar ratio of Al2(C2Hs)3Cl3/ZrCl~ is 5.0 and -therefore 250 mmol of ethylaluminium sesquichloride was added), and the mixture was stirred at 60 C for 30 minutes to obtain a catalyst preparation liquor.
Then, in a 500 ml three-neck flask were in-troduced dry benzene and the catalyst preparation liquor in predetermined amoun-ts, respectively, under the atmosphere of argon, followed by adjusting the amounts of zirconium tetrachloride, the ethylaluminium compound indicated and benzene to the values indicated in Table 1. To -the resulting mixture was added a predetermined amount of the third component (thiophene, aniline, thiourea, triphenyl-phosphine or trioctylphosphine) and the mixture was stirred 131098~
at room temperature for 10 minutes to obtain a catalyst liquor.
Preparation Example of a -Olefln (Oligomerization of __ _ ~ _ E-thylene) In a 1 liter autoclave equipped with a stirrer was introduced the catalyst liquor prepared in the above-described preparation example of catalyst by conveying using pressurized argon under the atmosphere of dry argon. The temperature of the autoclave was kept at 50 to 60 C . After the charging of the catalyst liquor was over stirring was started and high purity ethylene gas was introduced rapidly into the autoclave and charging was continued until the inside pressure reached the reaction pressure indicated in Table 1 and then the temperature was elevated to the reaction temperature indicated in Table 1. Introduction of ethylene was continued in an amount necessary to maintain the reaction pressure. Af-ter the reaction was continued for 1 hour with maintaining the reaction conditions an aqueous solution of sodium hydroxide was pressed into the autoclave to deactivate the catalyst and thus terminate the reaction.
Then, the following post-treatments were carried out.
At first, 20 g of undecane for use as an internal standard for chromatography was added to the reaction product and then wax component was filtered out using a filter paper. The wax component on the filter paper was washed sufficiently with benzene to drip down light fraction in the filtrate. The product in the filtrate was washed twice wlth 500 ml of deionized water and dried over anhydrous potassium carbonate.
The thus-obained transparent solution of -the reaction product was analyzed by gas chroma-tography. The yield of the product was ob-tained by internal standard method.
On the other hand, the wax component which was filtered ou-t was weighed after it was air dried and then dried in a vacuum drier at a pressure of 20 mmHg.
The yield of C4 to C8 fractions was calculated from the Schultz-Flory distribution since operational loss could not be avoided.
The results obtained are shown in Table 1.
The same procedures as in Example 1 were repeated except that as shown in Table 1, at least one of zirconium tetrachloride, ethylaluminium sesquichloride and the third component was omitted. And the amount of each component used and the reaction conditions are as indicated in Table 1. The results obtained are shown in Table 1.
~31098~
Table 1 Catalyst Composition Unit Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 ZrCl4 mmol 1.0 0.2 0.2 0.2 0.2 ~ASC' mmol 5.0 1.0 1.0 1.0 0.5 DEAC2 mmol TEA~ mmol - - - - -Thiophene mmol 2.0 0.4 1.2 1.2 0.4 MDS~ mmol - - - - -Aniline mmol Thiourea mmol TPP~ mmol TOP' mmol Al/Zr mol/mol5.0 5.0 5.0 5.0 2.5 Benzene ml 250 250 250 250 250 Reaction Condition Temperature C 100 120 120 120 120 Pressure Kg/Cm2G35 35 35 45 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
FIELD O~ TllE INVENTION
'rhe present invention relates to a process for preparing linear ~ -olefins. More particularly, -the present invention relates to a process for preparing a -olefins by oligomerizing ethylene according to which not only linear ~ -o]efins can be prepared in high puri-ties with by-producing wax in small amounts but also long production run is possible.
BACKGROUND OF THE INVENTION
a -Olefins are useful as a comonomer for modification in the Eleld of preparing polyolefins or as a plasticizer or a surface active agent after they are alcoholized.
Generally, such linear a -olefins are prepared by oligomerizing ethylene in -the presence of a catalyst. ~s for the catalyst there is known, for example, a binary catalyst which consists of titanium tetrachloride and ethylaluminium dichloride. Also, a process for increasing the yield and selectivity of a -olefins using a catalyst which consists of a third component in addition to the above-described binary catalyst composition is known.
On the o-ther hand, binary catalys-ts with increased activities have recently been proposed which comprises zirconium (Zr) instead of the above-described titanium compound. For example, Japanese Patent Application Laid-Open Nos. 109428/83, 201729/~3 and 113138/~3 and Japanese Patent Publica~ion No. 30042/75 disclose binary catalysts whcih consist of a Zr compound and an Al compound.
However, processes for the oligomerization of 131098~
ethylene using the above-descrlbed binary catalysts comprising Zr have caused various problems. For example, final products contain wax fraction in large amoun-ts or the yield of oligomers having a small number of carbon atoms, e.g., those having about ~ carbon atoms, is increased and the purity of the a -olefins obtained is very low. Further, long continuous operation of production unit is difficult since wax Eraction is formed in a large amount or for other reasons.
U. S. Patent 4,486,615 discloses a catalyst composition consisting of a binary catalyst composed of a Zr compound and an Al compound and a Lewis base such as a tertiary amine, a secondary amine, an ether, a phosphine oxide, an alkyl phosphate, an aryl phosphate, a sulfoxide, etc. which is added as a third component in order to increase the activity of the binary catalyst.
However, although it is described in U. S. Patent 4,486,615 that a linear a -olefin having high purity as high as 99.5% can be prepared using the catalyst composition containing triethylamine as the most preferred example of the Lewis base it has been confirmed by the present inventors that use of the catalyst compositions containing Lewis bases referred to in U. S. Patent 4,486,615 other than triethylamine results in the preparation of linear a-olefins having low purity and that a large amount o~ the above-described ternary catalyst containing triethylamine is used in U. S. Patent 4,486,615.
SU~ARY OE THE INVENTION
An object of the present invention is to obviate the defects of the conventional processes and to provide a 131~98~
process for preparing a linear ~ -o:Lefin by oligomerizing ethylene according to which the medium frac-tion containing from abou-t 6 to 20 carbon atoms can be obtained in a high yield and the purity oE the ~ -olefin obtained is high with forming a small amount of wax fraction, thus enabling long production runs.
~ nother object of the present invention is to provide a process ~or preparing a linear a -olefin by oligomerizing ethylene according to which linear a -olefins containing low conten-t of halogen derived from -the catalyst used can be prepared in high purity.
In order to achieve the above objects extensive investigations have been carried out by the present invenlcors and as a result it has now been found that excellent effects are obtained by the use of a novel ternary catalyst which consists of a Zr c~mpound, an Al compound and a specified third component. The present invention is based on this discovery.
That is, the present invention provides a process for preparing a linear ~-olefin having from 6 to 20 carbon atoms comprising polymerizing ethylene or an ethylene containing ~-olefin in the presence of a catalyst consisting of a zirconium halide, an organoaluminum compound and a ~ewis base in an iner~ solvent and terminating the polymeri-zation by adding a catalyst deactivating agent to the 131Q98~
resulting reaction mixture, whereln said catalyst contains a zirconlum component comprising a zirconlum halide represented by formula (I):
ZrxaA4-a ( I) wherein X and A may be the ~ame or dlfferent and each represent~
chloride, bromide atom or lodide and a i~ O or an integer of 1-4;
an alumlnum component comprl~ing an alkylalumlnum compound represented by formula (II):
AlRll 5 Qll~5 tII) whereln Rl represent~ an alkyl group of 1-20 carbon atoms, Q
repre~ent~ chloride, bromide or iodide atom and said formula (II) may also be represented by A12R13Q13 and an alkylaluminum compound repre~ented by formula (III):
AlR2b Q23-b (III) whereln R2 and Q2 have the same meanings a~ Rl and Ql above and b is an integer of 1-3; ~aid cat~lyst being mixed at a molar ratio ~Al/Zr) of said zirconium component and aluminum component of 3-and at a molar ratio (AlRll 5Q~1.5/AlR2bQ23_b) of the component~ represented by formulae (II) and (III) of 2-10: and ~aid cataly~t further contains at least one Lewls base selected from the group con~istlng of thlophene, methyl dlsulfide, thiourea trlphenylphosphine and trloctylphosphine.
DETAILED DESCRIPTION OF THE INVENTION
In the process of the present invention, a novel ~31~985 ternary catalyst is used which consi.sts of a zirconium halide (hereinafter, some-times referred to as "Component A"), the above-described organoaluminium compound (hereinafter, sometimes referred to as "Component B") and a Lewis base specified hereinbelow (hereinafter, sometimes referred to as "Component C").
The zirconium halide used as Component A is a compound represented by formula (I) below Zr~aA4 a (I) wherein X and A, which may be the same or different, each represents Cl, Br or I, and a is 0 or an integer of up to 4.
Specific examples of the zirconium halide represented by the formula (I) include ZrCl~, ZrBr~, ZrI~., ZrBrCl,, ZrBr2Cl,-etc. Among these, ZrCl~ is particularly preferred. They can be used singly or two or more of them can be used in combination.
The organoaluminium compound which can be used in the present invention is an alkylaluminium sesquihalide represented by formula (II) below AlR1 5Q1.5 (II) wherein R represents an alkyl group having from 1 to 20 carbon atoms, and Q represents Cl, Br or I (formula (II) may also be expressed as Al 2 R3Q3) or an alkylaluminium compound represented by formula (III) below AlR bQ 3-b (III) wherein R' and Q', which may be the same or different, have the same meanings as R and Q in formula (II), and b i.s an integer of 1 to 3.
~ 31~8~
The alkylaluminium sesquihali.de represented by formula (II~ above which can be used as Componen-t B
(herelnafter, sometimes referred to as "Component B-1") is n~t limited particularly as far as R and Q in formula (II) satisfy the above-described conditions. Specific examples thereof include Al 2 (CH~J ) 3 C13, Al 2 (clls)3Br3~ Al 2 (C2 Hs)3Cl3~
Al2 (C2Hs)3Brs, Al2 (C2H5)3I3, Al2 (C2H5)3BrCl2, Al2 (C3H7)3Cl3, Al2 (iso-C3H7) 3Cl3, Al2 (C~HD) 3Cl3, A12 (iso-C~H") ~,Cl3, A12 (C5 H")3Cl3, Al2(C~ H, 7 ) 3Cl3, Al2(c2H5 ) 2 (CH3 ) Cl3, etc.
Among these, compounds in which R represents a methyl group, an ethyl group, a propyl group or a butyl group are preferred and those in which R represents an ethyl group are particularly preferred.
It is preferred that Q represents Cl.
Specifically, e-thylaluminium sesquichloride (Al(C2H5)1 5Cl1 5, i.e., Al2(C2H5) 3C13) is preferred.
These alkylaluminium sesquihalides can be used singly or two or more of them can be used in combination.
The al~ylaluminium compound represented by formula (III) above which can be used as Component B (hereinafter, sometimes referred to as "Component B-2") is not limited particularly as far as R' and Q' in formula (II) satisfy the above-described conditions. Specific examples thereof include Al1(CH3) 3, Al(C2H5)3, Al(C3H7)3, Al(iso-C3H7), Al-(C~HU) 3, Al(iso-C.~H~)3, Al(C5H1l)3, Al(C~H,~)3, Al(cuHl7)sl Al(C2H5)2Cl, Al(C2H5)2Br, Al(C2Hs)2I, Al(C2Hs)Cl2, Al(C2Hs)-Br2, Al(C2Hs)I2, etc.
However, among the compounds represented by formula (III), those in which b is 2 or 3 are preferred.
In formula (III), R' is preferably an ethyl group, 1 3~ ~8~
a propyl group, a butyl group or an isobutyl group and more preferably an ethyl group.
It ls preferred that Q' represents C1.
Specifically, compounds such as triethylaluminium, diethylaluminium chloride and ethylaluminium dichloride are preferred.
These alkylaluminium compounds can be used singly or two or more of them can be used in combina-tion as Component B-2.
The Lewis base which can be used as Componen-t C is at least one member selec-ted from the group consisting of thioethers, alkyldisulfides, thiophenes, thiourea, sulfides, phosphines and primary amines.
As for the thioethers, there can be cited, for example, dimethyl sulfide, dipropyl sulfide, dihexyl sulfide, dicyclohexyl sulfide, diphenyl thioether, etc.
As for the alkyl disulfides, there can be ci-ted, for example, methyl disulfide ((CH~)2S2), ethyl disulfide, propyl disulfide, butyl d1sulfide, hexyl disulfide, cyclohexyl disulfide, e-thyl methyl disulfide, etc.
As for the thiophenes, there can be cited, for example, thiophene, 2-methylthiophene, 3-methylthiophene, 2,3-dimethylthiophene, 2-ethyl-thiophene, benzothiophene, tetrahydrothiophene, etc.
As for the sulfides, there can be cited, for example, methyl sulfide, ethyl sulfide, butyl sulfide, etc.
As for the phosphines, there can be cited, for example, triphenylphosphine, triethylphosphine, tributyl-phosphine, tripropylphosphine, trioctylphosphine, tricyclo-hexylphosphine, etc.
131098~
As for the primary amines, there can be cited, for example, organic amines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexyl-amine, oc-tylamine, decylamine, aniline, benzylamine, naphthylamine, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, picoline, etc.
These compounds can be used singly or two or more of them can be used in combination.
Among the various Lewis bases defined in -the present invention, at least one member selected from the group consisting of methyl disulfide, thiophene, thiourea, triphenylphosphine, trioc-tylphosphine and aniline can be used particularly advantageously.
In the process of the present invention, compounds belonging to Components A, B and C, respectively, can be selected appropriately and the selected compounds are combined to prepare a catalyst which can be used -to achieve the objects of the presen-t invention.
However, a catalyst which is obtained by selecting a mixture of Component B-1 and Component B-2 as Component B
and combining the mixture with Component A and Component C, and a catalyst obtained by combining Component A, Component B-l and Component C are preferred. More particularly, a catalyst consisting of a mixture of an alkylaluminium sesquihalide and a trialkylaluminium, zirconium tetra-chloride and thiophene, and a catalyst consisting of an alkylaluminium sesquihalide, zirconium tetrachloride and thiophene are preferred. This is because when these catalysts are used not only the content of wax in the product of oligomerization reaction can be further reduced 1310~
but also the yield of linear a -olefins per weight of zirconium halide can be increased and -the purity of the linear a -olefin obtained can be increased.
When a mixture of Component B-1 and Component B-2 is used as a catalyst component Component B-1 and Component B-2 are mlxed desirably ln a proportion such tha-t Component B-2 is not hlgher than S0 mol% (Al basls), preferably not higher than 30 mol% (Al basis).
In the present lnvention, there is no particular limitatlon on the method of preparlng catalysts from Components A, B and C. However, lt ls preferred to contact Component A with Component B in a suitable solvent to form a catalyst preparation liquor whIch contain a catalyst precursor and then mix -this catalyst preparation liquor with Component C upon or prior to the polymerization (oligomerization) of ethylene to obtain a catalyst liquor.
Upon preparation of the catalyst preparation liquor or catalyst liquor, it is desirable that -the mixture is heated at a suitable temperature (usually, a temperature lower than the temperature of polymerization reaction, for example, and more specifically within the range of from 60 to 80 C) for from 10 to 120 minutes to activate the catalys-t.
As Eor the solvent which can usually be used in the present invention, there can be cited, for example, aromatic hydrocarbons and halogenated derivatives thereof such as benzene, toluene, xylene, chlorobenzene, ethyl-benzene, dichlorobenzene, chlorotoluene, etc., paraffins such as pentane, hexane, heptane, octane, nonane, decane, etc., naphthenes such as cyclohexane, decaline, etc., 8 ~
haloalkanes such as dichloroethane, dichlorobutane, etc., and the like. Among these, benzene, toluene, xylene and chlorobenzene are preferred with benzene being particularly preferred.
These solvents can be used singly or two or more of them can be used in combination.
In the present invention, the proportion of Components A, B and C mixed per 250 ml of the solvent is usually from 0.005 to 5 mmol and preferably from 0.01 to 1 mmol, of Component A, usually from 0.02 to 15 mmol and preferably from 0.05 to 3 mmol, of Component B, and usually from 0.01 to 20 mmol and preferably from 0.02 to 20 mmol, of Component C when sulfur compounds (thioethers, alkyl disulfides, thiophenes, thiourea and sulfides) are used or from 0.01 to 5 mmol of Component C when phosphines or primary amines are used. As for the proportion of Components A and B, more desirable results can be obtained by setting the proportion of Al/Zr by mole within the range of from 1 to 15.
Upon polymerization, the catalyst liquor can be mixed with the solvent -to adjust the concentration of the catalyst, if desired.
The thus prepared catalyst or catalyst liquor and ethylene or a gas containing ethylene are contacted in the above-described solvent at a predetermined reaction temperature under a predetermined reaction pressure to carry out polymerization (oligomerization) of ethylene efficiently.
~31~
The ~as containing ethyle~e which can be used in the present in~ention include an inert gas containing ethylene, purlfied ethylene gas for polymerization, ethylene gas for polymerization such as high purity ethylene, etc., with high purity ethylene being preferred.
The reaction temperature upon polymerization is usually from 50 to 200 C , preferably from 100 to 150 C -The reaction pressure is usually not lower than ~ Kg/cm2 (gauge pressure), preferably not lower than 25 Kg/cm2 (gauge pressure). The reaction tirne is usually from about 5 minutes to about 2 hours, preferably frorn about 15 minutes to about 1 hour.
All the operations starting from the preparation of the catalyst to the completion of the polymerization reaction are desirably carried out in the absence of air and moisture.
It is preferred that the preparation of the catalyst is carried out under the atmosphere of an inert gas such as nitrogen, argon, etc.
Further, it is desirable that starting materials for preparing the catalyst, solvent and starting materials for polymerization are dried sufficiently. However, copresence of a minute amount of moisture or air sometimes results in increase in the activity and selectivity of the catalyst.
Hereinafter, example of the process for preparing linear a -olefins according to the present invention will be described in detail.
That is, in a vessel equipped with a stirrer there are dissolved Component A, e.g., zirconium tetrachloride, and Component B, e.g., ethylaluminium sesquichloride, in the solvent, e.g., benzene, under the atmosphere of the inert gas, e.g., argon, nitrogen, etc., and heated at a temperature of from 60 to 80 ~C for from 10 to 120 minutes with stirring to prepare a catalyst preparation liquor.
A portlon oE the catalyst preparation liquor thus obtained is transferred to another vessel equipped with a stirrer under the atmosphere of the inert gas and diluted with the solvent, e.g., benzene, and then Component C, e.g., thiophene, is added thereto at a temperature in the vicinity of room temperature followed by stirring to prepare a catalyst liquor. As a result of the preparation of the catalyst in -this manner a complex catalyst derived from a zirconium hallde such as zirconium tetrachloride and an alkylaluminium compound is formed, and use of the complex catalyst results in increase in the yield and purity of the objective product, linear a -olefins.
Then, the above-described catalyst liquor is pressed into a reaction vessel kept at a temperature of from 50 to 60 C under the atmosphere of an inert gas, and while stirring the catalyst liquor a gas containing ethylene such as high purity ethylene is introduced followed by oligomerizing ethylene under the above-described reaction conditions.
After a predetermined period of time a conventional catalyst deactivating agent such as an aqueous alkali solution or an aqueous methanol solution containing an alkali can be added to the reaction mixture to terminate the reaction.
As for the catalyst deactivating agent, there can 8 ~
be cited, for example, water, alcohols (monohydric alcohols, polyhydric alcohols, cyclic alcohols, acyclic alcohols, aliphatic alcohols, aromatic alcohols), carboxylic acids, phenols, etc.
When the catalyst is deactivated it is preferred to add a nitrogen containing compound in addition to the catalyst deactivatlng agent described above to the reaction mix-ture since addition of halogen derived from the catalyst to the resulting linear a -olefin can be prevented by the addition of the nitrogen containing compound, thus further improving the purity of the linear a -olefin.
As for the nitrogen containing compounds, there can be cited, for example, ammonia or amines such as methyl-amine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, aniline, benzylamine, naphthylamine, dime-thylamine, diethyl-amine, dibutylamine, diphenylamine, methylphenylamine, tri-methylamine, triethylamine, tributylamine, triphenylamine, pyridine, picoline, etc.
These nitrogen containing compounds can be used singly or two or more of them can be used in combination.
The order of adding the deactivating agent and the nitrogen con-taining compound to the reaction mixture is not limited particularly. For example, the order of addition may be (1) first to add the nitrogen containing compound and then the deactivating agent, (2) first to add the deactivat-ing agent and then the nitrogen containing compound or (3) to simultaneously add the nitrogen containing compound and the deactivating agent.
Of the above orders of addition, the order (1) is `- 131~8~
preferred.
After deactivation of the catalyst in the above-described manner the resulting product liquor contains high content of linear ~-olefins which have from 6 to 20 carbon atoms in good yield and which do not contain halogen. On the other hand, by-production of wax component is remarkably reduced.
The reaction product liquor aEter deactivation oE
the ca~alyst can be subjected to post-treatments, e.g., washing with water, etc., separation such as extraction, filtration, etc., drying and the like to recover the objective products, i.e., linear a -olefins of high purity in high efficiency.
That is, accordlng to the process oE the present invention, linear a -olefins of such high purity that they contain from about 6 to about 20 carbon atoms can be obtained stably in high yield. ~nd linear a -olefins having from about 6 to about 20 carbon atoms can be obtained at high selectivity. It is possible to control the carbon atom number distribution of the product to a further narrow range by appropriately selecting the reaction conditions, catalyst composition, concentration, etc.
The unused ethylene or a low boiling point fraction containing unused ethylene which is recovered may be used as it is or recycled after purification for use as a starting material for the reaction.
The linear a -olefins prepared according to the process of the present invention can be used advantageously as a comonomer for preparing various copolymers and also 131~98~
employed in various fields of industry such as plasticizers, and starting materials for preparing surface active agents.
~ ccording to -the present invention, the following effects can be obtained.
That is, in the process oE the present invention, use of -the catalyst prepared from a zirconiwn halide, an organoaluminium compound and a specified Lewis base enables preparation of linear a -olefins of high purity and reduction in the amount of by-produced wax.
More particulariy, the catalysts prepared from zirconium tetrachloride (~), alkylaluminium sesquihalide (~-1) or a mixture of alkylaluminium sesquihalide (B-1) and alkylaluminium halide (B-2), particularly trialkylaluminium halide, and at least one Lewis base (C) selected from the group consisting of thioe-thers, alkyl disulfides, thiophenes, thiourea, sulfides, phosphines and primary amines have a high activi-ty, and when these catalysts are used linear a -oleEins of higher puri-ty can be prepared, the amount of wax by-produced can be reduced further, and the yield of linear a -olefins based on the zirconium tetra-chloride can be increased.
Further, in the process of the present invention, addition of a nitrogen containing compound upon deactivation of the catalyst in the resulting polymerization reac-tion product liquor obtained by oligomerization of ethylene the content of halogen in -the linear a -olefins can be reduced and linear a -olefins of higher purity can be prepared.
In addition, when the reaction is carried out at high temperatures by-production of wax component is in a small amount and therefore operational performance of the ~31~98~
process is improved yreatly, thus enabling long production runs.
EXAMPLES
The present invention will be described in greater detail with reference to the following examples and comparative examples.
_XAMPLES 1-15 Preparation Example of Catalys-t (Preparation of Catalyst Liquor) In a 1,000 ml flask equipped with a s-tirrer were introduced 50 mmol of anhydrous zirconium tetrachloride and 472 ml of dry benzene under the atmosphere of argon and the resulting mixture was stirred for 30 minutes. To the mixture was added the alkylaluminium compound shown in Table 1 in such an amount -that it occupies a molar ratio to zirconium tetrachloride calculated from the amount indicated in Table 1 (for example, in Examples 1 to ~ and 6 to 10 the molar ratio of Al2(C2Hs)3Cl3/ZrCl~ is 5.0 and -therefore 250 mmol of ethylaluminium sesquichloride was added), and the mixture was stirred at 60 C for 30 minutes to obtain a catalyst preparation liquor.
Then, in a 500 ml three-neck flask were in-troduced dry benzene and the catalyst preparation liquor in predetermined amoun-ts, respectively, under the atmosphere of argon, followed by adjusting the amounts of zirconium tetrachloride, the ethylaluminium compound indicated and benzene to the values indicated in Table 1. To -the resulting mixture was added a predetermined amount of the third component (thiophene, aniline, thiourea, triphenyl-phosphine or trioctylphosphine) and the mixture was stirred 131098~
at room temperature for 10 minutes to obtain a catalyst liquor.
Preparation Example of a -Olefln (Oligomerization of __ _ ~ _ E-thylene) In a 1 liter autoclave equipped with a stirrer was introduced the catalyst liquor prepared in the above-described preparation example of catalyst by conveying using pressurized argon under the atmosphere of dry argon. The temperature of the autoclave was kept at 50 to 60 C . After the charging of the catalyst liquor was over stirring was started and high purity ethylene gas was introduced rapidly into the autoclave and charging was continued until the inside pressure reached the reaction pressure indicated in Table 1 and then the temperature was elevated to the reaction temperature indicated in Table 1. Introduction of ethylene was continued in an amount necessary to maintain the reaction pressure. Af-ter the reaction was continued for 1 hour with maintaining the reaction conditions an aqueous solution of sodium hydroxide was pressed into the autoclave to deactivate the catalyst and thus terminate the reaction.
Then, the following post-treatments were carried out.
At first, 20 g of undecane for use as an internal standard for chromatography was added to the reaction product and then wax component was filtered out using a filter paper. The wax component on the filter paper was washed sufficiently with benzene to drip down light fraction in the filtrate. The product in the filtrate was washed twice wlth 500 ml of deionized water and dried over anhydrous potassium carbonate.
The thus-obained transparent solution of -the reaction product was analyzed by gas chroma-tography. The yield of the product was ob-tained by internal standard method.
On the other hand, the wax component which was filtered ou-t was weighed after it was air dried and then dried in a vacuum drier at a pressure of 20 mmHg.
The yield of C4 to C8 fractions was calculated from the Schultz-Flory distribution since operational loss could not be avoided.
The results obtained are shown in Table 1.
The same procedures as in Example 1 were repeated except that as shown in Table 1, at least one of zirconium tetrachloride, ethylaluminium sesquichloride and the third component was omitted. And the amount of each component used and the reaction conditions are as indicated in Table 1. The results obtained are shown in Table 1.
~31098~
Table 1 Catalyst Composition Unit Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 ZrCl4 mmol 1.0 0.2 0.2 0.2 0.2 ~ASC' mmol 5.0 1.0 1.0 1.0 0.5 DEAC2 mmol TEA~ mmol - - - - -Thiophene mmol 2.0 0.4 1.2 1.2 0.4 MDS~ mmol - - - - -Aniline mmol Thiourea mmol TPP~ mmol TOP' mmol Al/Zr mol/mol5.0 5.0 5.0 5.0 2.5 Benzene ml 250 250 250 250 250 Reaction Condition Temperature C 100 120 120 120 120 Pressure Kg/Cm2G35 35 35 45 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
3) TEA stands for Triethylaluminium.
4) MDS stands for methyl disulfide.
5) TPP stands for triphenylphosphine.
6) TOP stands for trioctylphosphine.
13~ ~8~
Table 1 (Continued) Catalyst Composition Unit Ex.6 Ex.7 Ex.8 Ex.9 Ex.1 ZrCl, mmol 0.2 0.2 0.2 0.2 0.2 EASC' mmol 1.0 1.0 1.0 1.0 1.0 DEAC2 mmol TEA3 mmol Thiophene mmol - - - - -MDS~ mmol 0.0~ - - - -Aniline mmol - 0.3 Thiourea mmol - - 0.6 TPP5 mmol - - - 0.4 TOP mmol - - - - 0.25 Al/Zr mol/mol5.0 5.0 5.0 5.0 5.0 ~enzene ml 250 250 250 250 250 Reaction Condition Temperature C 120 120 120 120 120 Pressure Kg/Cm2G35 35 35 35 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
3) TEA stands for Triethylaluminium.
4) MDS stands for methyl disulfide.
5) TPP stands for triphenylphosphine.
o) TOP stands for trioctylphosphine.
Table 1 (Continued) Catalyst Composition Unit Ex.11 Ex.12 Ex.13 Ex.14 Ex 15 ZrCl~ mmol 0.1 0.2 0.1 0.05 0.05 EASC' mmol 0.47 0.93 0.33 0.38 0.33 DEAC2 mmol 0.02 0.05 - - -TEA~ mmol - - 0.08 0.08 0.11 Thiophene mmol 0.2 0.4 0.2 0.3 0.3 MDS~ mmol Aniline mmol Thiourea mmol TPP'~ mmol TOP~ mmol A1/Zr mol/mol 4.9 4.9 4.6 9.2 8.8 Benzene ml 250 250 250 250 250 Reaction Condition Temperature ~C 120 100 120 120 120 Pressure Kg/Cm2G 35 35 35 35 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
3) TEA stands for Triethylaluminium.
4) MDS stands for methyl disulfide.
5) TPP stands for triphenylphosphine.
6) TOP stands Eor trioctylphosphine.
Table 1 (Continued) Catalyst Composition Unit C.Ex.1 C.Ex.2 C.Ex.3 C.Ex.4 C.Ex.5 ____ _ ZrCl, mmol 0.2 0.1 - 0.1 EASC' mmol 1.0 - 1.0 - -DEAC2 mmol - - - 0.125 0.5 TEA3 mmol - 0.5 - 0.125 Thiophene mmol - 0.2 - 0.2 MDS~ mmol Aniline mmol Thiourea mmol TPPr~ mmol TOP~ mmol Al/Zr mol/mol 5.0 5.0 ~ 2.5 ~
Benzene ml 250 250 250 - 250 Reaction Conditio Temperature C 100 120 120 120 120 Pressure Kg/Cm2G 35 35 35 35 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
3) TEA stands for Triethylaluminium.
4) MDS stands for methyl disulfide.
5) TPP stands for triphenylphosphine.
6) TOP stands for trioctylphosphine.
~3~ ~98~
Table 1 (contin~ed) ____Produ_t _ _Example 1 _Example 2 Example 3 a -Olefin (wt.%) (wt.%) (wt-%) C, 23.9 100 9.4 100 15.2 100 Cfi 21.1 99 10.6 100 15.3 100 Cn 16.9 98 10.7 99 14.3 100 C, D 12.2 97 10.4 98 12.0 100 C, 2 8.6 95 9.1 97 9.2 99 C,~ 5.6 94 7.6 97 6.8 98 C. G 3.8 93 7.0 96 5.4 97 C,l, 2.8 92 6.2 96 4.9 96 C20-t 4.8 - 20.2 - 13.7 Wax (w-t.%) 0.3 8.8 3. 2 Yield (g/g- ZrCl~) 1530 2320 1900 Notes: "C" and "P" stand Eor composition and purity, respectively.
Purity is expressed in -terms o-E wt.% of linear a -olefins in each fraction.
~i 3~9~i5 Table 1 (continued) Product Example 4 Example 5Example 6 ___ _ _ __ _ a -Olefin C P C P C P
(wt.~) (wt.%) (wt.%) C~ 14.5 100 9.4100 10.7 100 C,j 14.8 100 10.4100 12.6 100 C,l 13.4 100 10.0100 13.4 100 Cln 11.9 100 9.4 99 12.1 100 C, 2 9.3 100 8.2 98 9.9 99 C,~ 7.0 100 6.6 98 7.4 98 C,u 5.8 99 5.7 96 6.7 97 C~u 4.7 98 5.0 94 6.0 96 C20~ 14.4 - 17.3 - 15.7 Wax (wt.%) 4.2 18.0 5.5 Yield (g/g- ZrCl~) 2760 2600 1720 Notes: "C" and "P" stand for composition and purity, respec~ively.
Purity is expressed in terms of wt.% of linear a-olefins in each fraction.
~A,3~a~
Table 1 (cont nued) Product__ Ex_ple 7 Example 8_ Example 9_ a _O efln (wt.o) (wt.%) (wt.%) C, 1~.0 100 15.0 10012.2 100 C~, 13.4 100 14.5 10012.9 100 Cu 11.7 100 12.6 9912.3 98 Cln 9.5 99 10.2 9811.1 98 Clz 7.1 98 7.6 97 8.9 97 C,~ 5.1 96 5.5 96 6.8 97 C~ 6 3.7 95 4.0 96 5.9 96 C,~ 3.1 94 3.4 95 5.1 96 C20~ 11.4 - 12.1 - 15.3 Wax (wt.%) 21.0 15.0 9.5 Yield (g/g ZrCl~) 2000 1500 730 Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms of wt.% oE linear a -olefins in each frac-tion.
~ 31~
able 1 (continued) _ Product __ Example 1_ _Example 11 Example 12 a -Olefin C P C P C P
twt . "~0~ '(w~' . %) ~ . %) Cl 9.0 100 9.8 100 18.2 100 CG 9.5 99 10.8 100 17.5 100 Cn 10.9 98 10.4 100 15.2 100 CI O 9.7 97 10.0 99 12.4 99 Cl 2 8.9 96 8.7 99 9.2 99 C,~ 7.9 95 7.1 98 6.6 99 C~ G 8.3 94 5.9 98 4.8 99 Cl ~ 7.3 93 5.3 98 4.1 98 C21,~ 18.2 - 20.4 - 11.3 Wax (wt.%) 10.3 11.6 0.7 Yield (g/g ZrCl~) 1850 3790 2730 Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms of wt.% of linear a -olefins in each fraction.
~ 310~
Table 1 (continued) _ _roduct Example 13 Example 14 Example 15 a -Olefin C P C P C P
(wt.%) (wt.%) (wt.%) C~ 12.3 100 17.9 100 17.3 100 CO 13.0 100 17.5 100 16.7 100 C~ 12.0 98 15.2 99 14.3 98 C 11 3 97 12.4 98 11.8 97 ~ o Cl 2 9.2 96 9.0 98 8.7 96 C,4 7.2 96 6.4 97 6.1 95 C,O 6.1 96 5.0 96 4.8 98 C 5 1 97 4.0 96 3.8 92 ~ 11 .
C20+ 18.1 - 11.6 - 14.6 Wax (wt.%) 5.7 1.0 1.9 Yield (g/g- ZrCl4)4270 11980 15620 Notes: "C" and "P" stand for composition and purity, - respectively.
Purity is expressed in terms of wt.% of linear a -olefins in each fraction.
~ 3 ~
Table 1 (continued) * **
Product C. Ex. 1 C. Ex. 2 C. Ex. 3 a -Olefin C _ P C _ _ P C P
(wt.%) (wt.%) (wt.%) C~ 10.9 100 Cc 11.7 99 Cu 11.4 97 C,O 9.7 95 Cl2 8.6 92 C,~ 6.8 89 C,c 5.3 86 C~u 5.0 85 C20+ 15.5 Wax (wt.%)15.1 Yield (g/g- ZrCl4) 2600 Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms oE wt.% of linear a -olefins in each Eraction.
* Only high polymer was synthesized.
** No reaction.
~ , ~ 3 ~ 5 Table 1 _ontinued) ProductC. Ex. 4 C. Ex. 5 _ _ _ __ _ _ _ _ ~ _ _ _ _ _ a ~OlefinC __P _ _ C _ _P _ (wt.%) (wt.%) Cl C"
C, o Cc' 2 C
I ~
C, 11 C? O ~
Wax (wt.%) Yield (g/g- ZrCl~) Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms of wt.% of linear a-olefins in each frac-tion.
* Only high polymer was synthesized.
** No reaction.
_~9_ EXAMPLES 16-27 ~3~98~
Preparation Example of Catalyst (Preparation of Catalyst Liquor) The same procedures as in Example 1 were repeated except -that the catalyst compositions indicated in Table 2 were used to prepare catalyst preparation liquors.
Then, catalyst liquors were prepared from the catalyst preparation liquors in the same manner as in Example 1.
Preparation Example of a -Olefins (Oligomerization of Ethylene) Polymerization of ethylene was carried out in the same manner as in Example 1 except that the deactivating agents shown in Table 3 were used and the nitrogen containing compounds shown in Table 3 were added in amoun-ts shown in Table 3 prior to the addition of the deactivating agents, and then the catalyst was deactivated.
Thereafter, the resulting polymerization reaction product liquor after deactivation of the catalyst was washed with water, and the concentration of chloride ion in the oily layer thus obtained (a mixture of benzene as a solvent and linear a -olefin produced) was determined and the chlorine content of the resulting linear a -olefin was obtained. The same pos-t-treatments as in Example 1 were carried out. The results obtained are shown in Table 3.
As shown in Table 3, the same procedures as in Examples 16-27 were repeated except that the nitrogen containing compound was not used. The amount of each component and reaction conditions are as shown in Table 3.
` 13~098~
The results obtained are shown in Table 3.
Table 2 Catalyst Composition Unit Zirconium tetrachloride mmol 0.05 Ethylaluminium sesquichloride mmol 0.21 Triethylaluminium mmol 0.04 Thiophene mmol 0.30 Al/Zr mol/mol 5 Benzene ml 250 Reaction Condltion Temperature C 120 Pressure Kg/cm2G 35 Time min. 60 Table 2 (Continued) Product Composition Purity a -Olefin C~ 14.9 100 Cc 15.1 100 Cu 14.0 99 C,0 12.3 98 Cl 2 9.7 98 C,~ 7.2 97 C~u 5.a 96 C,O 5.2 96 c2o~ 14.2 Wax (wt.%) 1.6 Yield (g/g~ ZrCl4 ) 10300 Amount of a -Olefin (g) 120 1~0985 Table 3 Zirconium te-trachloride: 0.05 mM
Triethylaluminium: 0.04 mM
Ethylaluminium sesquichloride: 0.21 mM
Ex.16 Ex.17 Ex 18 Ex~19Ex.20 N-Containing TEA TEA TMA NH3NH3 aq.
Compound (28%) Amount (mM) 14 4 90 10 165 Temperature (C) 20 20 20 20 20 Deactivating Agent Water Water Water WaterWater Amount (g) 10 10 10 10 7 Cl Con-tent in Product (ppm) 5 2 5 2 5 2 ~ 2 5 2 Table 3 (Continued) Zirconium tetrachloride: 0.05 mM
Triethylaluminium: 0.04 mM
Ethylalùminium sesquichloride: 0.21 mM
Ex.21 Ex.22 Ex.23 Ex.24Ex.25 -N-Containing NH3 aq. NH3 aq. NH3 aq. NH3 aq. NH~ aq.
Compound (10%) (10~) (10%) (10%)(28%) Amount (mM) 58 29 29 18 165 Temperature (~C) 20 20 40 40 120 Deactivating Agent Water Water Water WaterWater Amount (g) 9 9 4 4 7 Cl Content in Product (ppm) 5 2 5 2 ~ 2 4 22 131098~
Table 3 (Continued) Zirconium tetrachloride: 0.05 mM
Trie-thylaluminium: 0.04 mM
Ethylaluminiu~ sesquichloride: 0.21 mM
Ex.26 Ex.27 C.Ex.6 C.Ex.7 C.Ex.8 N-ContainingN-MP TEA
Compound - - - - -Amount (mM) 17 14 - _ _ Temperature (C) 20 20 100 20 20 Deactivating *1 AgentMethanol Methanol Water Wa-ter Water Amount (g) 10 10 50 50 50 Cl Content in Product (ppm)7 ~ 2 200 80 80 Table 3 (Continued) C.Ex.9 C.Ex.10 C.Ex.11 C.Ex.12 _.Ex.13 N-Containing Compound Amount (mM) Temperature (DC ) 40 40 40 20 20 Deactivating *1 AgentMethanol Methanol Butanol Octanol Methanol Amount ~g) 5 5 5 5 5 Cl Content in Product (ppm)50 45 50 50 20 Notes: TEA: Triethylamine, TMA: Trime-thylamine, N-MP: N-Methylpiperidine, *1: containing 1% NaOH, NH3 aq.: aqueous ammonia, NH~: ammonia gas 131~8~
~ XAMPLES 28-36 AND COMPARATIVE EXAMPLES 14-16 Preparation Example of Catalyst (Preparation of Catalyst Liquor) In a 2 liter autoclave equipped with a stirrer was introduced a slurry solu-tion composed oE 100 ml of dry chlorobenzene and a predetermined amount (mmol) of zirconium compounds shown in Table 4 under the atmosphere of dry argon.
On the other hand, aluminium compounds and sulfur compounds or nitrogen compounds shown in Table 4 were added to 150 ml of dry chlorobenzene and the mixture was stirred for 10 minutes and then introduced into the above-described autoclave to obtain a catalyst llquor.
Preparation Example of a -Olefins (Oligomerization of EthyleneL
At first, the catalyst liquor was heated for 1 hour until the temperature reached 100 C while stirring in the autoclave to effect activation, and at this timing high purity ethylene gas was introduced rapidly into the autoclave and the charging was continued until the pressure reached 35 Kg/cm2-G. Thereafter, introduction of ethylene was continued in amounts necessary for maintaining the pressure. The reaction was continued under these conditions for about 30 minutes and then the catalyst was deactivated by pressing a methanol solution containing sodium hydroxide into the autoclave to termina-te the reaction.
In the post-treatment, reaction products having 4 to 6 carbon atoms (C4 - C6) were trapped in a dry ice-methanol bath upon depressurizing the autoclave in order to reduce loss of light fractions comprising C4 - C6. Other 131098~
reaction products were treated as follows. That is, at first wax component was filtered out using a filter paper, and then the filtrate was washed twice with 500 ml of deionlzed water followed by drying over anhydrous potassium carbonate. The transparent solution thus obtained was analyzed by gas chromatography. On the other hand, the wax component filtered was weighed after air drying and drying in a vacuum drier at a pressure of 20 mmHg.
The composition (wt.%) and purity (wt.% of linear a -olefin in each fraction) of each fraction of a -olefin obtained by the above-described process and the composition of wax (wt.%) are shown in Table 4.
-- 131098~
Table 4 Catalyst Composition Example 28 Example 29 Example 30 ZrCl~ (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC:' (mmol) MDS~ (mmol) 0.15 0.4 0.6 TP5 (mmol) - - -AN~ (mmol) - - -TU' (mmol) - - -Al/Zr (mol/mol)2.5 2.5 2.5 CBD (ml) 250 250 250 Yield (g) 530 162 90 Product C P C P _ C P
(wt.%) (%) (wt.%) (%) (wt.
a -Olefin C~ 1.7 100 3.3 100 5.6. 100 Cn 7.6 98 10.2 100 15.7 100 C0 10.3 96 16.8 99 19.9 99 C,0 10.0 93 15.1 98 16.3 97 C, 2 9.8 90 13.2 98 12.6 96 C,~ 8.4 87 10.3 97 9.0 95 C, G 7.6 85 8.2 96 7.4 95 C, D 7.0 83 6.1 95 5.0 94 C20+ 11.3 ~0 6.8 95 5.8 94 Wax 26.3 - 10.0 - 2.7 -- 13~0~5 I
Table_4 _Continued) Ca-talyst Compositlon Example 31_ Example 32 _ Example 33 ZrCl, (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC~ (mmol) - - -MDS~ (mmol) TP5 (mrnol) 0.6 1.2 ANG (mmol) - - 0.6 TU7 (mmol) Al/Zr (mol/mol) 2.5 2.5 2.5 CBD (ml) 250 250 250 Yield (g) 535 263 540 Product C P C P C _ P
(wt.~) (%) (wt.%) (%) (wt.%) (%) a -Olefin C, 1.7 100 2.4 100 2.0 100 C6 4.9 97 6.3 99 3.8 96 C" 9.4 93 13.2 97 7.0 95 CIO 9.7 88 16.1 95 7.8 91 C, 2 10.3 85 15.9 93 9.0 88 Cl~ 8.2 84 8.3 92 10.2 87 C I G 7.6 83 7.6 90 8.0 86 Cl D 7.4 81 6.7 89 7.3 84 C2~+ 11.3 80 8.3 87 9.9 82 Wax 29.8 - 15.2 - 35.0 131 ~98~
Table 4 (Contlnued) Catalyst Composi-tion Example 34 _xample 35 Example 36 ZrCl, (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 5.0 EADC3 (mmol) MDS~ (mmol) - - 0.5 TP5 (mmol) ANG (mmol) 1.2 TU7 (mmol) - 0.6 Al/Zr (mol/mol) 2.5 2.5 5.0 C~" (ml) 250 250 250 Yield (g) 252 62 316 Product C PC _ _ P _ _ _ _C_ P
(wt.%) (%) (wt.%) (%) (wt.%) (%) a -Olefin C~ 4.5 100 4.3 100 6.1 100 CG 6.3 99 12.1 100 13.9 99 CO 10.3 98 12.4 100 15.4 96 C~u 12.0 96 9.9 100 10.8 92 Cl 2 15.1 94 7.5 99 9.2 90 C,, 14.3 93 6.0 99 6.8 89 C,~ 8.2 91 4.6 98 5.1 87 C,~ 5.2 89 3.5 97 3.8 85 C20~ 6.7 89 4.4 97 3.5 83 Wax 17.4 - 35.3 - 25.4 ~ 3 1 ~
Table 4 (Contlnued) Catalyst Composition C.Ex. 14 C.Ex. 15 C.Ex. 16 ZrCl4 (mmol) 1.0 1.0 ZTP' (mmol) - - 1.0 DEAC2 (mmol) 2.5 _ 2.5 EADC3 (mmol) - 2.5 MDS~ (mmol) - - -TP~ (mmol) AN" (mmol) TU7 (mmol) Al/Zr (mol/mol)2.5 2.5 2.5 CB" (ml) 250 250 250 Yield (g) 610 60 Product C P C P C P
___ _ _ (wt.%) (%) (wt.%) (%) (wt.%) (%) a -Olefin C4 2.8 8555.6 75No Reaction C~ 6.8 7822.1 55 Cn 8.4 7714.8 27 Cl n 9.0 75 4.5 12 C, 2 8.2 73 2.6 3 Cl~ 6.2 71 -C~ n 5.0 68 0.4 -Cla 4.5 64 - ~
C20+ 6.8 64 - "
Wax 42.3 - - -Notes: 1) ZTP: Zirconium tetra(n-propoxide), 2) DEAC: Diethylaluminum chloride, 131098~
3) EADC: Ethylalumi,num dichloride, ~) MDS: Methyl disulfide, 5) TP: Thiophene, 6) AN: Aniline, 7~ TU:, Thiourea, a) CB: Chlorobenzene E_AMPL,ES 37-44_AND COMPARATIVE EXAMPLES 17-19 Preparation Example of Catalyst (Preparation of Catalyst Liquor) Catalyst liquors were prepared in the same manner as in Examples 28 to 36 except that the zirconium compounds shown in Table 5 were used in amounts indicated in Table 5.
Pre aration Example of a -Olefins (Oligomerization of Ethylene) a -Olefins were prepared in the same manner as in Examples 28 to 36 except that the above-described catalyst liquors were used.
The same post-treatments as in Examples 28 to 36 were carried out.
The composition (wt.%) and purity (wt.% oE linear a -olefin in each fraction) of each fraction of a -olefin obtained by the above-described process and the composition of wax (wt.%) are shown in Table 5.
. -40-13~0~85 Table 5 Catalyst Compos1tionExample 37__Example 38__Example 39 ZrCl, (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC3 (mmol) TBP~ (mmol) 0.4 0.3 0.25 TOP5 (mmol) - - -TPP (mmol) Al/Zr (mol/mol)2.5 2.5 2.5 Benzene (ml) 250 250 250 Yield (g) 50 137 432 Product C P C P C P
(wt.%) (%) (wt.%) (%) (wt. D) (%) a -Olefin C~ 30.0 100 13.7 100 5.3100 CG 30.6 100 19.8 9912.7 99 Cfl 16.8 99 18.5 9717.6 97 ClO 8.5 98 12.8 9614.6 95 Cl 2 3.5 98 9.3 9413.1 92 Cl~ 2.8 97 7.9 939.7 89 C,O 2.7 96 6.2 919.3 86 C, fl 1.8 96 4.8 907.8 84 C20+ 1.6 95 5.0 908.0 82 Wax 1.7 - 2.0 - 1.9 131098~
Table 5 (Contlnued) Ca-talyst CompositionExample 40Example 41Example 42 ZrCl., (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC~ (mmol) - - -TBP~ (mmol) 0.4 0.3 0.25 TOP5 (mmol) TPPG (mmol3 Al/Zr (mol/mol) 2.5 2.5 2.5 Benzene (ml) 250 250 250 Yield (g) 32 112 441 Product C _ P C P C Y
(wt.%) (%) (wt.%) (%) (wt.%) (%) a -Olefin C4 38.6 100 17.6 100 5.0 100 CG 24.2 100 19.3 99 11.2 99 Ca 15.2 99 16.7 98 12.8 97 C,O 7.8 99 13.2 97 11.3 96 C,z 3.1 99 8.2 97 10.4 95 C,~ 2.5 98 5.7 96 9.7 94 Cl G 1.8 98 4.5 94 9.3 93 C,u 1.8 97 3.8 93 8.5 92 C20+ 1.6 97 4.3 93 9.6 90 Wax 3.4 - 6.7 - 12.2 131~985 _ble 5 (Con-tinued) Catalyst CompositionExample 43Example 44 C.Ex. 17 _ _ _ _ _ ZrCl.~ (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -D~AC2 (mmol) 2.5 2.5 2.5 EADC3 (mmol) - - -TBP~ (mmol) TOP5 (mmol) TPPG (mmol) 0.4 0.25 Al/Zr (mol/mol) 2.5 2.5 2.5 Benzene (ml) 250 250 250 Yield (g) 120 153 485 Product _ C P C P C P_ _ _ (wt.%) (%) (wt.%) (%) (wt.%) a -Olefin C~ 15.2 100 20.6 100 5.896 Cn 22.2 100 18.3 99 8.294 CO 17.8 99 17.5 98 10.1 89 C,O 10.9 96 14.3 97 14.2 87 C, 2 9.6 98 10.4 97 9.8 85 C,~ 8.5 97 6.7 96 6.7 83 Cl n 7.8 96 5.3 95 5.2 80 C,~ 4.7 95 3.7 94 3.8 78 C20.~ 2.6 94 2.0 94 4.3 78 Wax 0.7 - 1.2 - 31.9 - l3ln~
Table 5 (Continued) Catalyst Composition C~Ex. 18 C.Ex. 19 ZrCl4 (mmol) 1.0 ZTP' ~mmol) - 1.0 DEAC2 (mmol) - 2.5 EADC' (mmol) 2.5 TBP~ (mmol) TOP5 (mmol) TPPG (mmol) Al/Zr (mol/mol)2.5 2.5 Benzene (ml) 250 250 Yield (g) 53 0 Product C P C P
_ (wt.%) (%)(wt.%) (%) a -Olefin , _ .
C4 58.2 82No Reaction CG 23.1 68 ~
CD 1 3.2 45 "
Cl0 3.8 32 C,2 1.4 23 Cl ~. _ "
Cl G 0.3 - "
,. _ "
,. _ "
~- 2 n +
Wax - _ "
Notes: 1) ZTP: Zirconium tetra(n-propoxide), 2) DEAC: Diethylaluminium chloride, 3) EADC: Ethylaluminium dichloride, 131098~
4) TBP: Tributylphosphine, 5) TOP: Trloctylphosphine, 6) TPP: Triphenylphosphine, While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art tha-t various changes and modifications can be made therein without departing from the spirit and scope thereof.
13~ ~8~
Table 1 (Continued) Catalyst Composition Unit Ex.6 Ex.7 Ex.8 Ex.9 Ex.1 ZrCl, mmol 0.2 0.2 0.2 0.2 0.2 EASC' mmol 1.0 1.0 1.0 1.0 1.0 DEAC2 mmol TEA3 mmol Thiophene mmol - - - - -MDS~ mmol 0.0~ - - - -Aniline mmol - 0.3 Thiourea mmol - - 0.6 TPP5 mmol - - - 0.4 TOP mmol - - - - 0.25 Al/Zr mol/mol5.0 5.0 5.0 5.0 5.0 ~enzene ml 250 250 250 250 250 Reaction Condition Temperature C 120 120 120 120 120 Pressure Kg/Cm2G35 35 35 35 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
3) TEA stands for Triethylaluminium.
4) MDS stands for methyl disulfide.
5) TPP stands for triphenylphosphine.
o) TOP stands for trioctylphosphine.
Table 1 (Continued) Catalyst Composition Unit Ex.11 Ex.12 Ex.13 Ex.14 Ex 15 ZrCl~ mmol 0.1 0.2 0.1 0.05 0.05 EASC' mmol 0.47 0.93 0.33 0.38 0.33 DEAC2 mmol 0.02 0.05 - - -TEA~ mmol - - 0.08 0.08 0.11 Thiophene mmol 0.2 0.4 0.2 0.3 0.3 MDS~ mmol Aniline mmol Thiourea mmol TPP'~ mmol TOP~ mmol A1/Zr mol/mol 4.9 4.9 4.6 9.2 8.8 Benzene ml 250 250 250 250 250 Reaction Condition Temperature ~C 120 100 120 120 120 Pressure Kg/Cm2G 35 35 35 35 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
3) TEA stands for Triethylaluminium.
4) MDS stands for methyl disulfide.
5) TPP stands for triphenylphosphine.
6) TOP stands Eor trioctylphosphine.
Table 1 (Continued) Catalyst Composition Unit C.Ex.1 C.Ex.2 C.Ex.3 C.Ex.4 C.Ex.5 ____ _ ZrCl, mmol 0.2 0.1 - 0.1 EASC' mmol 1.0 - 1.0 - -DEAC2 mmol - - - 0.125 0.5 TEA3 mmol - 0.5 - 0.125 Thiophene mmol - 0.2 - 0.2 MDS~ mmol Aniline mmol Thiourea mmol TPPr~ mmol TOP~ mmol Al/Zr mol/mol 5.0 5.0 ~ 2.5 ~
Benzene ml 250 250 250 - 250 Reaction Conditio Temperature C 100 120 120 120 120 Pressure Kg/Cm2G 35 35 35 35 35 Time min. 60 60 60 60 60 1) EASC stands for ethylaluminium sesquichloride.
2) DEAC stands for diethylaluminium chloride.
3) TEA stands for Triethylaluminium.
4) MDS stands for methyl disulfide.
5) TPP stands for triphenylphosphine.
6) TOP stands for trioctylphosphine.
~3~ ~98~
Table 1 (contin~ed) ____Produ_t _ _Example 1 _Example 2 Example 3 a -Olefin (wt.%) (wt.%) (wt-%) C, 23.9 100 9.4 100 15.2 100 Cfi 21.1 99 10.6 100 15.3 100 Cn 16.9 98 10.7 99 14.3 100 C, D 12.2 97 10.4 98 12.0 100 C, 2 8.6 95 9.1 97 9.2 99 C,~ 5.6 94 7.6 97 6.8 98 C. G 3.8 93 7.0 96 5.4 97 C,l, 2.8 92 6.2 96 4.9 96 C20-t 4.8 - 20.2 - 13.7 Wax (w-t.%) 0.3 8.8 3. 2 Yield (g/g- ZrCl~) 1530 2320 1900 Notes: "C" and "P" stand Eor composition and purity, respectively.
Purity is expressed in -terms o-E wt.% of linear a -olefins in each fraction.
~i 3~9~i5 Table 1 (continued) Product Example 4 Example 5Example 6 ___ _ _ __ _ a -Olefin C P C P C P
(wt.~) (wt.%) (wt.%) C~ 14.5 100 9.4100 10.7 100 C,j 14.8 100 10.4100 12.6 100 C,l 13.4 100 10.0100 13.4 100 Cln 11.9 100 9.4 99 12.1 100 C, 2 9.3 100 8.2 98 9.9 99 C,~ 7.0 100 6.6 98 7.4 98 C,u 5.8 99 5.7 96 6.7 97 C~u 4.7 98 5.0 94 6.0 96 C20~ 14.4 - 17.3 - 15.7 Wax (wt.%) 4.2 18.0 5.5 Yield (g/g- ZrCl~) 2760 2600 1720 Notes: "C" and "P" stand for composition and purity, respec~ively.
Purity is expressed in terms of wt.% of linear a-olefins in each fraction.
~A,3~a~
Table 1 (cont nued) Product__ Ex_ple 7 Example 8_ Example 9_ a _O efln (wt.o) (wt.%) (wt.%) C, 1~.0 100 15.0 10012.2 100 C~, 13.4 100 14.5 10012.9 100 Cu 11.7 100 12.6 9912.3 98 Cln 9.5 99 10.2 9811.1 98 Clz 7.1 98 7.6 97 8.9 97 C,~ 5.1 96 5.5 96 6.8 97 C~ 6 3.7 95 4.0 96 5.9 96 C,~ 3.1 94 3.4 95 5.1 96 C20~ 11.4 - 12.1 - 15.3 Wax (wt.%) 21.0 15.0 9.5 Yield (g/g ZrCl~) 2000 1500 730 Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms of wt.% oE linear a -olefins in each frac-tion.
~ 31~
able 1 (continued) _ Product __ Example 1_ _Example 11 Example 12 a -Olefin C P C P C P
twt . "~0~ '(w~' . %) ~ . %) Cl 9.0 100 9.8 100 18.2 100 CG 9.5 99 10.8 100 17.5 100 Cn 10.9 98 10.4 100 15.2 100 CI O 9.7 97 10.0 99 12.4 99 Cl 2 8.9 96 8.7 99 9.2 99 C,~ 7.9 95 7.1 98 6.6 99 C~ G 8.3 94 5.9 98 4.8 99 Cl ~ 7.3 93 5.3 98 4.1 98 C21,~ 18.2 - 20.4 - 11.3 Wax (wt.%) 10.3 11.6 0.7 Yield (g/g ZrCl~) 1850 3790 2730 Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms of wt.% of linear a -olefins in each fraction.
~ 310~
Table 1 (continued) _ _roduct Example 13 Example 14 Example 15 a -Olefin C P C P C P
(wt.%) (wt.%) (wt.%) C~ 12.3 100 17.9 100 17.3 100 CO 13.0 100 17.5 100 16.7 100 C~ 12.0 98 15.2 99 14.3 98 C 11 3 97 12.4 98 11.8 97 ~ o Cl 2 9.2 96 9.0 98 8.7 96 C,4 7.2 96 6.4 97 6.1 95 C,O 6.1 96 5.0 96 4.8 98 C 5 1 97 4.0 96 3.8 92 ~ 11 .
C20+ 18.1 - 11.6 - 14.6 Wax (wt.%) 5.7 1.0 1.9 Yield (g/g- ZrCl4)4270 11980 15620 Notes: "C" and "P" stand for composition and purity, - respectively.
Purity is expressed in terms of wt.% of linear a -olefins in each fraction.
~ 3 ~
Table 1 (continued) * **
Product C. Ex. 1 C. Ex. 2 C. Ex. 3 a -Olefin C _ P C _ _ P C P
(wt.%) (wt.%) (wt.%) C~ 10.9 100 Cc 11.7 99 Cu 11.4 97 C,O 9.7 95 Cl2 8.6 92 C,~ 6.8 89 C,c 5.3 86 C~u 5.0 85 C20+ 15.5 Wax (wt.%)15.1 Yield (g/g- ZrCl4) 2600 Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms oE wt.% of linear a -olefins in each Eraction.
* Only high polymer was synthesized.
** No reaction.
~ , ~ 3 ~ 5 Table 1 _ontinued) ProductC. Ex. 4 C. Ex. 5 _ _ _ __ _ _ _ _ ~ _ _ _ _ _ a ~OlefinC __P _ _ C _ _P _ (wt.%) (wt.%) Cl C"
C, o Cc' 2 C
I ~
C, 11 C? O ~
Wax (wt.%) Yield (g/g- ZrCl~) Notes: "C" and "P" stand for composition and purity, respectively.
Purity is expressed in terms of wt.% of linear a-olefins in each frac-tion.
* Only high polymer was synthesized.
** No reaction.
_~9_ EXAMPLES 16-27 ~3~98~
Preparation Example of Catalyst (Preparation of Catalyst Liquor) The same procedures as in Example 1 were repeated except -that the catalyst compositions indicated in Table 2 were used to prepare catalyst preparation liquors.
Then, catalyst liquors were prepared from the catalyst preparation liquors in the same manner as in Example 1.
Preparation Example of a -Olefins (Oligomerization of Ethylene) Polymerization of ethylene was carried out in the same manner as in Example 1 except that the deactivating agents shown in Table 3 were used and the nitrogen containing compounds shown in Table 3 were added in amoun-ts shown in Table 3 prior to the addition of the deactivating agents, and then the catalyst was deactivated.
Thereafter, the resulting polymerization reaction product liquor after deactivation of the catalyst was washed with water, and the concentration of chloride ion in the oily layer thus obtained (a mixture of benzene as a solvent and linear a -olefin produced) was determined and the chlorine content of the resulting linear a -olefin was obtained. The same pos-t-treatments as in Example 1 were carried out. The results obtained are shown in Table 3.
As shown in Table 3, the same procedures as in Examples 16-27 were repeated except that the nitrogen containing compound was not used. The amount of each component and reaction conditions are as shown in Table 3.
` 13~098~
The results obtained are shown in Table 3.
Table 2 Catalyst Composition Unit Zirconium tetrachloride mmol 0.05 Ethylaluminium sesquichloride mmol 0.21 Triethylaluminium mmol 0.04 Thiophene mmol 0.30 Al/Zr mol/mol 5 Benzene ml 250 Reaction Condltion Temperature C 120 Pressure Kg/cm2G 35 Time min. 60 Table 2 (Continued) Product Composition Purity a -Olefin C~ 14.9 100 Cc 15.1 100 Cu 14.0 99 C,0 12.3 98 Cl 2 9.7 98 C,~ 7.2 97 C~u 5.a 96 C,O 5.2 96 c2o~ 14.2 Wax (wt.%) 1.6 Yield (g/g~ ZrCl4 ) 10300 Amount of a -Olefin (g) 120 1~0985 Table 3 Zirconium te-trachloride: 0.05 mM
Triethylaluminium: 0.04 mM
Ethylaluminium sesquichloride: 0.21 mM
Ex.16 Ex.17 Ex 18 Ex~19Ex.20 N-Containing TEA TEA TMA NH3NH3 aq.
Compound (28%) Amount (mM) 14 4 90 10 165 Temperature (C) 20 20 20 20 20 Deactivating Agent Water Water Water WaterWater Amount (g) 10 10 10 10 7 Cl Con-tent in Product (ppm) 5 2 5 2 5 2 ~ 2 5 2 Table 3 (Continued) Zirconium tetrachloride: 0.05 mM
Triethylaluminium: 0.04 mM
Ethylalùminium sesquichloride: 0.21 mM
Ex.21 Ex.22 Ex.23 Ex.24Ex.25 -N-Containing NH3 aq. NH3 aq. NH3 aq. NH3 aq. NH~ aq.
Compound (10%) (10~) (10%) (10%)(28%) Amount (mM) 58 29 29 18 165 Temperature (~C) 20 20 40 40 120 Deactivating Agent Water Water Water WaterWater Amount (g) 9 9 4 4 7 Cl Content in Product (ppm) 5 2 5 2 ~ 2 4 22 131098~
Table 3 (Continued) Zirconium tetrachloride: 0.05 mM
Trie-thylaluminium: 0.04 mM
Ethylaluminiu~ sesquichloride: 0.21 mM
Ex.26 Ex.27 C.Ex.6 C.Ex.7 C.Ex.8 N-ContainingN-MP TEA
Compound - - - - -Amount (mM) 17 14 - _ _ Temperature (C) 20 20 100 20 20 Deactivating *1 AgentMethanol Methanol Water Wa-ter Water Amount (g) 10 10 50 50 50 Cl Content in Product (ppm)7 ~ 2 200 80 80 Table 3 (Continued) C.Ex.9 C.Ex.10 C.Ex.11 C.Ex.12 _.Ex.13 N-Containing Compound Amount (mM) Temperature (DC ) 40 40 40 20 20 Deactivating *1 AgentMethanol Methanol Butanol Octanol Methanol Amount ~g) 5 5 5 5 5 Cl Content in Product (ppm)50 45 50 50 20 Notes: TEA: Triethylamine, TMA: Trime-thylamine, N-MP: N-Methylpiperidine, *1: containing 1% NaOH, NH3 aq.: aqueous ammonia, NH~: ammonia gas 131~8~
~ XAMPLES 28-36 AND COMPARATIVE EXAMPLES 14-16 Preparation Example of Catalyst (Preparation of Catalyst Liquor) In a 2 liter autoclave equipped with a stirrer was introduced a slurry solu-tion composed oE 100 ml of dry chlorobenzene and a predetermined amount (mmol) of zirconium compounds shown in Table 4 under the atmosphere of dry argon.
On the other hand, aluminium compounds and sulfur compounds or nitrogen compounds shown in Table 4 were added to 150 ml of dry chlorobenzene and the mixture was stirred for 10 minutes and then introduced into the above-described autoclave to obtain a catalyst llquor.
Preparation Example of a -Olefins (Oligomerization of EthyleneL
At first, the catalyst liquor was heated for 1 hour until the temperature reached 100 C while stirring in the autoclave to effect activation, and at this timing high purity ethylene gas was introduced rapidly into the autoclave and the charging was continued until the pressure reached 35 Kg/cm2-G. Thereafter, introduction of ethylene was continued in amounts necessary for maintaining the pressure. The reaction was continued under these conditions for about 30 minutes and then the catalyst was deactivated by pressing a methanol solution containing sodium hydroxide into the autoclave to termina-te the reaction.
In the post-treatment, reaction products having 4 to 6 carbon atoms (C4 - C6) were trapped in a dry ice-methanol bath upon depressurizing the autoclave in order to reduce loss of light fractions comprising C4 - C6. Other 131098~
reaction products were treated as follows. That is, at first wax component was filtered out using a filter paper, and then the filtrate was washed twice with 500 ml of deionlzed water followed by drying over anhydrous potassium carbonate. The transparent solution thus obtained was analyzed by gas chromatography. On the other hand, the wax component filtered was weighed after air drying and drying in a vacuum drier at a pressure of 20 mmHg.
The composition (wt.%) and purity (wt.% of linear a -olefin in each fraction) of each fraction of a -olefin obtained by the above-described process and the composition of wax (wt.%) are shown in Table 4.
-- 131098~
Table 4 Catalyst Composition Example 28 Example 29 Example 30 ZrCl~ (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC:' (mmol) MDS~ (mmol) 0.15 0.4 0.6 TP5 (mmol) - - -AN~ (mmol) - - -TU' (mmol) - - -Al/Zr (mol/mol)2.5 2.5 2.5 CBD (ml) 250 250 250 Yield (g) 530 162 90 Product C P C P _ C P
(wt.%) (%) (wt.%) (%) (wt.
a -Olefin C~ 1.7 100 3.3 100 5.6. 100 Cn 7.6 98 10.2 100 15.7 100 C0 10.3 96 16.8 99 19.9 99 C,0 10.0 93 15.1 98 16.3 97 C, 2 9.8 90 13.2 98 12.6 96 C,~ 8.4 87 10.3 97 9.0 95 C, G 7.6 85 8.2 96 7.4 95 C, D 7.0 83 6.1 95 5.0 94 C20+ 11.3 ~0 6.8 95 5.8 94 Wax 26.3 - 10.0 - 2.7 -- 13~0~5 I
Table_4 _Continued) Ca-talyst Compositlon Example 31_ Example 32 _ Example 33 ZrCl, (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC~ (mmol) - - -MDS~ (mmol) TP5 (mrnol) 0.6 1.2 ANG (mmol) - - 0.6 TU7 (mmol) Al/Zr (mol/mol) 2.5 2.5 2.5 CBD (ml) 250 250 250 Yield (g) 535 263 540 Product C P C P C _ P
(wt.~) (%) (wt.%) (%) (wt.%) (%) a -Olefin C, 1.7 100 2.4 100 2.0 100 C6 4.9 97 6.3 99 3.8 96 C" 9.4 93 13.2 97 7.0 95 CIO 9.7 88 16.1 95 7.8 91 C, 2 10.3 85 15.9 93 9.0 88 Cl~ 8.2 84 8.3 92 10.2 87 C I G 7.6 83 7.6 90 8.0 86 Cl D 7.4 81 6.7 89 7.3 84 C2~+ 11.3 80 8.3 87 9.9 82 Wax 29.8 - 15.2 - 35.0 131 ~98~
Table 4 (Contlnued) Catalyst Composi-tion Example 34 _xample 35 Example 36 ZrCl, (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 5.0 EADC3 (mmol) MDS~ (mmol) - - 0.5 TP5 (mmol) ANG (mmol) 1.2 TU7 (mmol) - 0.6 Al/Zr (mol/mol) 2.5 2.5 5.0 C~" (ml) 250 250 250 Yield (g) 252 62 316 Product C PC _ _ P _ _ _ _C_ P
(wt.%) (%) (wt.%) (%) (wt.%) (%) a -Olefin C~ 4.5 100 4.3 100 6.1 100 CG 6.3 99 12.1 100 13.9 99 CO 10.3 98 12.4 100 15.4 96 C~u 12.0 96 9.9 100 10.8 92 Cl 2 15.1 94 7.5 99 9.2 90 C,, 14.3 93 6.0 99 6.8 89 C,~ 8.2 91 4.6 98 5.1 87 C,~ 5.2 89 3.5 97 3.8 85 C20~ 6.7 89 4.4 97 3.5 83 Wax 17.4 - 35.3 - 25.4 ~ 3 1 ~
Table 4 (Contlnued) Catalyst Composition C.Ex. 14 C.Ex. 15 C.Ex. 16 ZrCl4 (mmol) 1.0 1.0 ZTP' (mmol) - - 1.0 DEAC2 (mmol) 2.5 _ 2.5 EADC3 (mmol) - 2.5 MDS~ (mmol) - - -TP~ (mmol) AN" (mmol) TU7 (mmol) Al/Zr (mol/mol)2.5 2.5 2.5 CB" (ml) 250 250 250 Yield (g) 610 60 Product C P C P C P
___ _ _ (wt.%) (%) (wt.%) (%) (wt.%) (%) a -Olefin C4 2.8 8555.6 75No Reaction C~ 6.8 7822.1 55 Cn 8.4 7714.8 27 Cl n 9.0 75 4.5 12 C, 2 8.2 73 2.6 3 Cl~ 6.2 71 -C~ n 5.0 68 0.4 -Cla 4.5 64 - ~
C20+ 6.8 64 - "
Wax 42.3 - - -Notes: 1) ZTP: Zirconium tetra(n-propoxide), 2) DEAC: Diethylaluminum chloride, 131098~
3) EADC: Ethylalumi,num dichloride, ~) MDS: Methyl disulfide, 5) TP: Thiophene, 6) AN: Aniline, 7~ TU:, Thiourea, a) CB: Chlorobenzene E_AMPL,ES 37-44_AND COMPARATIVE EXAMPLES 17-19 Preparation Example of Catalyst (Preparation of Catalyst Liquor) Catalyst liquors were prepared in the same manner as in Examples 28 to 36 except that the zirconium compounds shown in Table 5 were used in amounts indicated in Table 5.
Pre aration Example of a -Olefins (Oligomerization of Ethylene) a -Olefins were prepared in the same manner as in Examples 28 to 36 except that the above-described catalyst liquors were used.
The same post-treatments as in Examples 28 to 36 were carried out.
The composition (wt.%) and purity (wt.% oE linear a -olefin in each fraction) of each fraction of a -olefin obtained by the above-described process and the composition of wax (wt.%) are shown in Table 5.
. -40-13~0~85 Table 5 Catalyst Compos1tionExample 37__Example 38__Example 39 ZrCl, (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC3 (mmol) TBP~ (mmol) 0.4 0.3 0.25 TOP5 (mmol) - - -TPP (mmol) Al/Zr (mol/mol)2.5 2.5 2.5 Benzene (ml) 250 250 250 Yield (g) 50 137 432 Product C P C P C P
(wt.%) (%) (wt.%) (%) (wt. D) (%) a -Olefin C~ 30.0 100 13.7 100 5.3100 CG 30.6 100 19.8 9912.7 99 Cfl 16.8 99 18.5 9717.6 97 ClO 8.5 98 12.8 9614.6 95 Cl 2 3.5 98 9.3 9413.1 92 Cl~ 2.8 97 7.9 939.7 89 C,O 2.7 96 6.2 919.3 86 C, fl 1.8 96 4.8 907.8 84 C20+ 1.6 95 5.0 908.0 82 Wax 1.7 - 2.0 - 1.9 131098~
Table 5 (Contlnued) Ca-talyst CompositionExample 40Example 41Example 42 ZrCl., (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -DEAC2 (mmol) 2.5 2.5 2.5 EADC~ (mmol) - - -TBP~ (mmol) 0.4 0.3 0.25 TOP5 (mmol) TPPG (mmol3 Al/Zr (mol/mol) 2.5 2.5 2.5 Benzene (ml) 250 250 250 Yield (g) 32 112 441 Product C _ P C P C Y
(wt.%) (%) (wt.%) (%) (wt.%) (%) a -Olefin C4 38.6 100 17.6 100 5.0 100 CG 24.2 100 19.3 99 11.2 99 Ca 15.2 99 16.7 98 12.8 97 C,O 7.8 99 13.2 97 11.3 96 C,z 3.1 99 8.2 97 10.4 95 C,~ 2.5 98 5.7 96 9.7 94 Cl G 1.8 98 4.5 94 9.3 93 C,u 1.8 97 3.8 93 8.5 92 C20+ 1.6 97 4.3 93 9.6 90 Wax 3.4 - 6.7 - 12.2 131~985 _ble 5 (Con-tinued) Catalyst CompositionExample 43Example 44 C.Ex. 17 _ _ _ _ _ ZrCl.~ (mmol) 1.0 1.0 1.0 ZTP' (mmol) - - -D~AC2 (mmol) 2.5 2.5 2.5 EADC3 (mmol) - - -TBP~ (mmol) TOP5 (mmol) TPPG (mmol) 0.4 0.25 Al/Zr (mol/mol) 2.5 2.5 2.5 Benzene (ml) 250 250 250 Yield (g) 120 153 485 Product _ C P C P C P_ _ _ (wt.%) (%) (wt.%) (%) (wt.%) a -Olefin C~ 15.2 100 20.6 100 5.896 Cn 22.2 100 18.3 99 8.294 CO 17.8 99 17.5 98 10.1 89 C,O 10.9 96 14.3 97 14.2 87 C, 2 9.6 98 10.4 97 9.8 85 C,~ 8.5 97 6.7 96 6.7 83 Cl n 7.8 96 5.3 95 5.2 80 C,~ 4.7 95 3.7 94 3.8 78 C20.~ 2.6 94 2.0 94 4.3 78 Wax 0.7 - 1.2 - 31.9 - l3ln~
Table 5 (Continued) Catalyst Composition C~Ex. 18 C.Ex. 19 ZrCl4 (mmol) 1.0 ZTP' ~mmol) - 1.0 DEAC2 (mmol) - 2.5 EADC' (mmol) 2.5 TBP~ (mmol) TOP5 (mmol) TPPG (mmol) Al/Zr (mol/mol)2.5 2.5 Benzene (ml) 250 250 Yield (g) 53 0 Product C P C P
_ (wt.%) (%)(wt.%) (%) a -Olefin , _ .
C4 58.2 82No Reaction CG 23.1 68 ~
CD 1 3.2 45 "
Cl0 3.8 32 C,2 1.4 23 Cl ~. _ "
Cl G 0.3 - "
,. _ "
,. _ "
~- 2 n +
Wax - _ "
Notes: 1) ZTP: Zirconium tetra(n-propoxide), 2) DEAC: Diethylaluminium chloride, 3) EADC: Ethylaluminium dichloride, 131098~
4) TBP: Tributylphosphine, 5) TOP: Trloctylphosphine, 6) TPP: Triphenylphosphine, While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art tha-t various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (6)
1. A process for preparing a linear .alpha.-olefin having from 6 to 20 carbon atoms comprising polymerizing ethylene or an ethylene containing .alpha.-olefin in the presence of a catalyst consisting of a zirconium halide, an organoaluminum compound and a Lewis base in an inert solvent and terminating the polymerization by adding a catalyst deactivating agent to the resulting reaction mixture, wherein said catalyst contains a zirconium component comprising a zirconium halide represented by formula (I):
ZrXaA4-a (I) wherein X and A may be the same or different and each represents chloride, bromide atom or iodide and a is 0 or an integer of 1-4;
an aluminum component comprising an alkylaluminum compound represented by formula (II):
AlR11.5 Q11.5 (II) wherein R1 represents an alkyl group of 1-20 carbon atoms, Q
represents chloride, bromide or iodide atom and said formula (II) may also be represented by A12R13Q13 and an alkylaluminum compound represented by formula (III):
AlR2b Q23-b (III) wherein R2 and Q2 have the same meanings as R1 and Q1 above and b is an integer of 1-3; said catalyst being mixed at a molar ratio (Al/Zr) of said zirconium component and aluminum component of 3-and at a molar ratio (AlR11 5Q11,5/AlR2bQ23-b) of the components represented by formulae (II) and (III) of 2-10; and said catalyst further contains at least one Lewis base selected from the group consisting of thiophene, methyl disulfide, thiourea triphenylphosphine and trioctylphosphine.
ZrXaA4-a (I) wherein X and A may be the same or different and each represents chloride, bromide atom or iodide and a is 0 or an integer of 1-4;
an aluminum component comprising an alkylaluminum compound represented by formula (II):
AlR11.5 Q11.5 (II) wherein R1 represents an alkyl group of 1-20 carbon atoms, Q
represents chloride, bromide or iodide atom and said formula (II) may also be represented by A12R13Q13 and an alkylaluminum compound represented by formula (III):
AlR2b Q23-b (III) wherein R2 and Q2 have the same meanings as R1 and Q1 above and b is an integer of 1-3; said catalyst being mixed at a molar ratio (Al/Zr) of said zirconium component and aluminum component of 3-and at a molar ratio (AlR11 5Q11,5/AlR2bQ23-b) of the components represented by formulae (II) and (III) of 2-10; and said catalyst further contains at least one Lewis base selected from the group consisting of thiophene, methyl disulfide, thiourea triphenylphosphine and trioctylphosphine.
2. A process according to claim 1 wherein 0.005-5 mmols of the zirconium component, 0.02-15 mmols of the alkylaluminum compound and 0.02-20 mmols of the Lewis base are used per 250 ml of the inert solvent when the Lewis base is selected from group consisting of thiophene, methyl disulfide and
3. Aprocess according to claim 1, are used per 250 ml of the inert solvent when the is selected from the group consisting of triphenylphosphine and trioctylphosphine 0.01-5 mmols of the Lewis base.
4. A process according to claim 1 where the zirconium halide is zirconium tetrachloride and R1 and R2 are ethyl and Q1 and Q2 are chlorine.
5. A process according to claim 1 wherein the zirconium halide represented by the formula (I) is zirconium tetrachloride, the alkylaluminum represented by the formula (II) is ethylaluminum sesquichloride and the alkylaluminum represented by the formula (III) is triethylaluminum.
6. A process according to claim 1 further comprising the addition of at least one nitrogen compound selected from the group consisting of trimethylamine, triethylamine, ammonia gas, ammonia water and n-methylpiperidine prior to the addition of the catalyst deactivating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000587056A CA1310985C (en) | 1986-08-06 | 1988-12-23 | PROCESS FOR PREPARING LINEAR .alpha.-OLEFINS |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61184700A JPS6341430A (en) | 1986-08-06 | 1986-08-06 | Production of linear alpha-olefin |
| CA000587056A CA1310985C (en) | 1986-08-06 | 1988-12-23 | PROCESS FOR PREPARING LINEAR .alpha.-OLEFINS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1310985C true CA1310985C (en) | 1992-12-01 |
Family
ID=25672334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000587056A Expired - Lifetime CA1310985C (en) | 1986-08-06 | 1988-12-23 | PROCESS FOR PREPARING LINEAR .alpha.-OLEFINS |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1310985C (en) |
-
1988
- 1988-12-23 CA CA000587056A patent/CA1310985C/en not_active Expired - Lifetime
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