CA1075719A - Oligomerization of alpha-olefins - Google Patents

Abstract

Abstract of the Disclosure A novel, soluble catalyst system is disclosed for use in oligomerizing straight chain alpha-olefins having more than 3 carbon atoms. The novel catalyst system comprises an aluminum alkyl halide compound and an organo halide compound which is used to produce oligomers in the C20 to C60 range which are useful as lubricants, hydraulic fluids, and the like.

Description

~0~5719 This invention relates to a novel catalyst system for oligomeri~ing alpha-olefins and the process in which this catalyst system is used to obtain lubricating oils, hydraulic fluids and the like, which are particularly useful at low temperature.
It is known to prepare polymeric lubricating oils by contacting an alpha-olefin with a metal halide catalyst such as AlC13 and limitîng the extent of polymerization to between about 10 and 20 percent conversion of monomer to polymer as disclosed in U.S. Patent 2,559,984. In the process disclosed in this patent, the reaction temperature can vary between about -20 and 40C. However, if conversion of the alpha-olefin is ::
greater than about 20%, the resultant product has a poor viscosity index and pour point. :
It is also known to obtain synthetic lubricating oils by contacting one or more alpha-olefins of C6-C14 range at a temperature of about 0 to 50C. w-ith a catalyst system ~ -formed from three types of components: -- .
(a) aluminum alkyl sesquichloride, aluminum dialkyl monochloride or aluminum monoalkyl dichloride, (b) ~ -titanium tetrachloride, and (c) an oxygen-containing organic compound which is either an oxirane or a methyl allyl ether.
Su~h a process is disclosed in U.S. Patent 3,206,523.
U.S. Patent 3,179,711 discloses a similar but modified method wherein the third component in the catalyst system is tetra-alkyl silicate, in which the alkyl groups each have 1-4 carbon atoms and are unbranched, rather - 1 - ~ .
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than an oxygen-containing hydrocarbon compound.
The preparation of synthetic lubricating oils by polymerizing an alpha-olefin with AlC13 at 57C. has also been revealed to produce~ e.g., a polyoctene having a viscosity index of 104 and a pour point of -20F. (Industrial and Engineering Chemistry, Vol. 23, No. 6, June, 1931, pp. 604-611,~
A method for producing lubricating oils by treating a petroleum distillate containing a h.igh percentage of unsaturat-ed hydrocarbons in the presence of AlC13 at a temperature of between 300 and 400 F. has also been disclosed in U.S, Patent 1,309,432. -Thus, alpha-olefins of C3 to C14 and high.er such as propene, butene, pentene, hexene, h.eptene, octene, nonene, decene, undecene, dodecene, tridecene and tetradecene can be oligomerized to produce oils useful as lubricants, hydraulic fluids, and the like. Hydrocarbon fractions boiling lo~er than about 750 F. are undesirable since such an oligomer has too low a flash point. Normally, hydrocarbons below C20 are too volatile for inclusion in the products of this invention~ In the oligomerization of olefins, therefore, it is desirable to convert monomers to that degree of polymerization wherein the molecular weight of the oligomer is at least equal to the molecular weight of C20. Conversely, if the degree of poly-merization is too high giving a large amount of product greater than C60, the pour point of the resultant oligomeric mixture is generally too high to have utility.
It would be advantageous, therefore, to be able : :

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to convert alpha-olefins to a mixture of oligomers which are mainly in the C20-C60 range. Hydrocarbon fractions boiling below C20 can be removed by distillation and, optionally, the premium material (C20-C60) may be dis-- tilled from the higher boiling moieties. However, this latter step is costly and difficult because of the high boiling points of the desired material. Thus, any pro-cess which gives good conversion of alpha-olefins to a product greater than C20 but minimizes formation of pro-duct greater than C60 is highly desirable. The actual amount of high molecular weight material allowed depends on the pour point desired in the end product after re-moval of the lower boiling hydrocarbons. Regardless of --the alpha-olefin employed, higher molecular weight -oligomers have greater viscosities and higher pour points.
A pour point as low as -65F. is frequently desired for low temperature utilization of the product fluids.
Another important property necessary in such hydrocarbon oils is a high viscosity index (V~I.), since this means that the viscosity of the oil in question will not change significantly with temperature. In general, a viscosity index of more than 100 is very desirable.
In accordance with the present invention, there is provided a soluble catalyst system for oligomerizing straight '~ chain alpha-olefins having at least 3 carbon atoms, said --catalyst system comprising an aluminum alkyl halide compound wherein said alkyl is a lower alkyl having 1 to 4 carbon atoms; and, an organo halide compound, said organo halide ~ -possessing (a) at least one halogen-bearing carbon atom in the molecule and (b) not more than one halogen atom attached ~ 3 -~0757~9 to any single carbon atom in said molecule, said aluminum alkyl halide compound being present in an amount of at least about 0.1% by weight of said catalyst system and the total Hal/Al ratio in said catalyst system being at least about 2.5/1.
In certain aspects of this invention synthetic lubricating oils are prepared by oligomerizing alpha-olefin utilizing a novel, soluble catalyst system. The resulting product is characterized as having a viscosity index greater than 100, a low pour point and good oxidative stability. Some of the advantages that the process of this invention exhibits over prior art '' - 3~a) -:. .
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1 ~)7571~

processes are: more rapid rate of reaction; cooling is not necessary and, in fact, high temperatures are bene-ficial; no solvent other than the alpha-olefin is required;
high conversion of monomer to oligomer; and the final product does not contain an undesirable amount of high molecular weight species. It is significant to note that both components comprising the catalyst system of the invention are soluble in the monomer; i,e~, the - --alpha-olefin. Thus, premium oligomers can be readily and continuously prepared according to the invention process by combining solutions of an aluminum alkyl halide, e.g., ethyl aluminum sesquichloride, and an ` organo halide, e.g., t-butyl chloride, in an alpha-olefin at elevated temperatures, Accordingly, synthetic lubricating oils are - prepared by contacting one or more straight chain alpha-` o-lefins of C3 and higher at a temperature range of up to about 200 C., preferably about 100 to 150C,, with a soluble catalyst system consisting of an aluminum alkyl halide - - -and an organo halide. -The alpha-olefins which can be used in the invention process include those straight chain compounds previously - --mentioned, i.e., propene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene and tetra- -decene.
The aluminum-containing component of the catalyst system can be either alkyl aluminum sesquichloride (R3A12Cl3), a dialkyl monochloride (R2AlCl), or an alkyl dichloride (RAlCl2) with the alkyl group represented by R being a lower alkyl, typically one containing about l to 4 carbon atoms.

~075719 The organo halides operable in the invention are those containing at least one saturated carbon atom with one halogen atom thereon. The halides may be aliphatic or benzylic.
Typical of such halides are butyl bromide, t-butyl chloride, allyl iodide, methallyl chloride, benzyl bromide, 1,2-dichloroethane, propylchloride, pentyl iodide, 2,3-dichlorooctane,

2,3-dibromooctane, crotyl-chloride, cyclohexyl chloride, cyclohexyl bromide, dodecyl iodide, l-chloro eicosane, 3-chloro eicosane, 1,2-dibromohexadecane, dodecyl benzyl chloride, 1,2,7,8-tetra bromooctane, as well as mixtures of such halides. As can be seen from the above typical halides, they may have from 1 to about 30 carbon atoms or more, the halide can be chlorine, bromine or iodine, and at least one saturated carbon atom must have on it only one halogen atom~
A particularly advantageous source of organo halide results from the halogenation of C24 and lower fraction olefins produced as part of the oligomerization process. Such low boiling olefin by-products must be removed from the product oil in order to reduce its volatility. Halogenation of these ` 20 materials produces not only an efficient organo halide -cocatalyst but permits recylcing of part or all of the by- -product low boiling olefins.
A convenient procedure for carrying out the invention is to dissolve the aluminum alkyl halide compound in an alpha-olefin and combine it with a solution of organo halide compound also in the alpha-olefin. The combining can take place, for example, in a heated stirred autoclave or a pipe reactor. Reaction to form the product is essentially instantan-eous when the temperature is maintained at least 100 C. Depend-ing on temperature, catalyst concentration and rate of ` ' ' ' ' ' ` ` ' 107571~

combination, an alpha-olefin can be converted to very high yields of premium oligomer, i.e., oligomer yields of at least 50%.
A premium oligomer is considered to be the C20 through C60 moieties as such a product exhibits optimum viscosity indexes and low pour points coupled with a high flash point. The product obtained, after removal of residual moieties lower than 20 carbon atoms, is useful as a low pour point oil without further distillation, since formation of "heavy ends"; i.e., moieties higher than C60, can be substantially minimized by the use of this procedure. The product may optionally be hydrogenated before use for added thermal-oxidative stability.
Typically, the oligomerization can be readily carried out using three reservoirs such as reservoirs A, B
and C. For example, reservoir A can contain about a 1%
solution of an aluminum alkyl halide in dry alpha-olefin, reservoir B can contain about a 1~ solution of an organo halide in dry alpha-olefin and reservoir C is the stirred reactor.
The contents of A and B are fed at a continuous rate into reactor C which is pre-heated to, preferably, at least 100C.
Optionally, reservoirs A and B can also be pre-heated. Depend- ~ ~
ing on the size of reservoirs A, B and C, the rate of addition --may be varied without encountering an uncontrollable temperature rise. Thus, if A and B each contains 50 pounds of alpha-olefin, -a convenient feed rate is 1.5 lbs per minute from each reservoir A and B. Some temperature rise will be evidenced in C and, if undesirably high, it can be controlled by cooling C
or removing the reacting mass in a continuous fashion. Usually, however, reactor C remains at a reasonable temperature and pressure so that all of A and B can be added in 20-30 minutes or less. A few minutes after A and B have been completely added, the reaction is complete and the mixture can be 1075715~

cooled and short-stopped by adding water. Catalyst residues are then removed by a water washing.
It is advantageous at this point in the process to pass the slightly viscous reaction product through a filtering column, such as a column of activated alumina, to remove the last catalyst traces and residual water.
The product is then analyzed by gas liquid chromatography (G.L.C~) to ascertain molecular weight distribution and the amount of residual monomer and dimer. Monomer is conveniently removed at atmospheric pressure or, optionally, by steam distillation.
The residue is then subjected to vacuum distillation to remove everything of lower molecular weight than about 280. Usually, removal of all products boiling at less than 150C, at 0,1 mm Hg.
insures a flash point in the product oil of not lower than about 450F. The product oil is then again analyzed for molecu- -lar weight distribution.
; Under these process conditions, alpha-olefins can be converted to up to about 90% oligomerized product oil having good pour point and viscosity index. The oligomerized product can optionally be treated w-ith antioxidants or hydrogenated (since there is about one double bond per molecule) to improve even more its already excellent thermal-oxidative stability.
The invention is further illustrated by and will become more clear from a consideration of the following examples which are not intended to, and should not be construed as, limiting the scope of the invention. As set forth in the Examples and as used throughout the application and claims, the term ~Hal/Al~' denotes the ratio of the total moles of halogen in both the organo halide compound and the aluminum alkyl compound to the total moles of aluminum.

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In the practice of this invention, the aluminum alkyl halide compound should be present in the catalyst system in an amount of at least about 0.1% by weight of the total catalyst system to provide a minimum Hal~Al ratio of about 2.5/1. Con-sistent with these minimum, operable conditions, there is no upper limit on the amount of either catalyst compound that can be used, but for purposes of economy~ the Hal!Al ratio should not exceed 25/1.
Example I -This example demonstrates the preparation of polyoctane oil; that is, the oligomerized product oil prior to distillation.
A dry, nitrogen filled, 4~necked, 500 ml round bottom - -- flask was fitted ~ith (1) a y-tube holding one 125 ml dropping - funnel and a water cooled condenser, (2) another 125 ml drop- ~ -ping funnel, (3) a thermometer and (4) a stirrer. A T-tube -was inserted in the top of the water cooled condenser and nitro-7 gen was fed through the condenser to maintain an inert atmos-phere in the reaction flask. Excess nitrogen not required to maintain a partial pressure in the reaction flask was ~--fed into a vessel containing mineral oil. The flask was ~-immersed in an oil bath which was heated to 135 - 140C. and allowed to warm up. Then into one of the dropping funnels there was placed 100 ml of octene-l (pre-dried by passing it through an activated alumina filtering column) and 7.5 ml of a 25%
solution of ethyl aluminum sesquichloride in hexane to provide an Hal/Al ratio of 3/1. Into the other dropping funnel there was placed 100 ml of dry octene-l and 3 ml benzyl chloride.
The stirrer was started and the two solutions added simultaneously at identical rates so that both solutions were added in eleven minutes. The temperature in the flask rose about that of the heating bath, which was then acting as a temperature regulator.

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The record of oil bath temperature and reaction mix temperature is tabulated below:

Temperature, C

Time Oil Total Octene-l -(min) Flask Bath in Flask (ml) . _ .

8 lSl 139 130 11 151.5 140.5 200 (addition complete) At this point, a sample was removed from the flask and quenched in water. The sample, on analysis by gas liquid chromatrography (G.L.C.), was found to have the following molecular weignt distribution:
Wt.~o_ C8 C16 C24 C32 C40 C48 C56+
1.36 7.41 12.59 19.88 22.1 18.15 18.52 The reaction mixture was permitted to stir in the ~eated bath for an additional 50 minutes and was then - - -quenched with water. At this time the temperature in the flask was 133C. while the temperature of the bath was 130C.
A sample, when analyzed by G.L.C., had the following molecular weight distribution:
Wt.%

C8 cl6 C24 C32 C40 C48 C56+
0.64 9.49 14.10 19.49 19.36 14.10 22.82 This example illustrates that octene-l can be rapidly converted to oligomeric materials in a very short period of time and at high yields; in this instance, 90% oligomer. The temperature record reveals that no -dangerous "runaway" exotherms are encountered in the g - - ~ ~ . - . .

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process. Since the molecular weight distributions of ` samples taken immediately after mixing was complete and 50 minutes later were nearly identical, it establishes that under these conditions, not only is the rate of reaction extremely rapid, almost instantaneous, but that there is essentially no change in the oligomeric product by permitting additional time in the reactor after addition is completed.
Example II
This example was carried out in the same manner as Example I using the same ingredientæ and amountæ except that the two octene solutions were mixed over a period of 31 minutes. Again, the time-temperature record shown below reveals that the reaction was readily controllable.
~ Temperature C -- Time Total Octene-l (min) Flask Bath in Flask (ml) . 22 150 150 125 31 147 145 200 (addition complete) .~ Samples taken at 31 minutes and 60 minutes were analyzed as before by G.L.C. and had the following molecular weight distribution:

Wt.%
C8 C16 C24 C32 C40 C48 Cs6+
31' 7.70 9.14 13.19 17.49 17.89 13.71 20.89 60' 4.79 9.46 13.99 18.26 18.52 12.05 22.93 As can be seen, additional reaction time after - 1 0 - ;

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~1)757~9 addition was completed caused essentially no change in the molecular weight distribution of the whole oil obtained, Example III
In this example, a series of runs were made to illustrate the effect of reaction temperature on the molecular weight distribution of the oligomerized product oil. All runs were made in equipment identical to that disclosed in Example I. For each run~ 6.0 ml of ethyl - aluminum sesquichloride were dissolved in lOO ml dry octene-1 and 1.4 ml of t-butyl chloride were dissolved in lOO ml octene-l to provide an Hal/Al ratio of about 3/1, These two solutions were combined over a 15 minute period into the reaction flask which was immersed in an oil bath at the recorded temperature, . At the end of the 15 minute period, the reactions were -quenched in the usual manner with w-ater and analyzed by gas liquid chromatography (G.L.C,), The temperature . conditions and G.L.C. results are tabulated below:

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lQ~5719 The above data clearly show.tha~ as the temperature o~ reaction is increased, monomer conversion re~ains essentially unch2nged, but the molecular weight of the oligomerized product oil progressively decreases. ~nis .
~5 is pointed out most dramatically by co~paring reaction - _ ~empera~ure with the percent o~ heavy ends (C50+) ~ -obtained. Thus, high reaction tempera~ures are preferred - in the invention process. . ~
~ Example IV . - - . . - ~_ - 10 . This example is identical to Exa~ple I in- .
cluding ingredien~s and amounts thereof, except that . the bath temperature in this experiment ~as 103C. at !.
.; the start and the solutions were added in 10 minutes.
. , , -, .
e reaction mixture was allowed to stir in the bath ;
i5 ~or an additional 50 minutes at which t~me it was .
.~ quenched with water. The reaction conditions during -- the run areshown below .

~ . Temoerature a. -. Ti~.o Total Octene-l ;:- 20 . (mi.n) Flask Bath Added (ml) : .
. C~ 94 103 0 - : -137 103 80 .. -. 6 13~ 106 120 . - c . ~ .- 10 128 110 200 (addition - ~
25 .................. . co~plete~ ~-99 103 .

- A sam~le o~ the product taken a~ ~he end o~ . .
.60 minu~es revealed the ~ollor.~ing excellent molecular -~ ~ weight distribution by G.L.C.:
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C8 C16 C24 C32 Cl~0 C~ c55 0.5 9.7 18.23 2J~.~5 21.05 13.99 11.81 ~ne product C24 and higher, t~ough removal by distillation ~ C8 and C~6 moieties, ~r~s o~ su~ficien~
low molecular weight; tnat is, less than 550, and ,~n~ . -pour point was -75F. The 90% yield o~taine~ in- ~he . .
. example, in.addition to obtaining a good pour point, - . is considerably higher than has been disclosed in pr~or . 10 art prac~ices.
., . . Exam~le V ' '-.'! . ''' ' ' This example demonstrates that the level o~ .
catalyst employed is not critical. In fact, under the conditions at which the experiments A, 3 and C belo~ . - .
were ru,n, experiment A~ which contained the lowest .i: . - . - . -ca~alyst level, produced the best product~ Each -experiment was carried out as descr~bed below. - --~. , , .............. . - .
~sing the same apparatus as in 3xample I, 200 -; ml of octene-l were placed in: a 500 ml round.boi~om -20.~ ~ flask and the specified amount of e-hyl aluminum - -~ ~
se3quichloride f~ASC) was then adled to the octene. - ~-.
` The solut~on was heate~ to appro~:imately 100C. b~ ~ - ~.
immersion in an oil.bath. The speci~ied amount o~
tertiary butyl chIoride (t-BuCl) was then added dr,~p-wise over a period of 20-25 minutes. ~ne samples were -quenched and the molecular weig~lt dis~r:butions de~er~
. mined. The amounts of ingredien~s used, the temperature .
conditions and G.L.C. molecular weign~ distributi~n analys~s are tabulated below wherein tne Hal/Al ratio . .. , - . .
~ 3 ~- in e~ch run was 3/1: -: ~ .. . .
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The yield of oligomer in the C24 to C56 range for the runs were as follows: A, 88.1%; B, 91.3%; C, 89.9%. From the results shown above, it can be seen that while the yield of run A
was lowest, this run had a lower average molecular weight and, as is known to those skilled in the art, thus had lower pour point than either runs B or C.
Example VI
This example demonstrates the preparation of polyoctene on a much larger scale.
10A dry twenty gallon jacketed steel autoclave reactor was steam heated to 256F. under nitrogen~ Two eight gallon solvent storage bombs, with top and bottom access vents, were `~ loaded as follows to provide an Hal/Al ratio of 3/1:
Bomb A - 50 pounds of octene-l and 0.5 pound ~, of ethyl aluminum sesquichIoride Bomb B - S0 pounds of octene-l and 0.5 pound of tertiary butyl chloride.
The contents from bombs A and B were each fed at the rate of about 1.2 pounds/min. into the stirred reactor on which the heat had been turned of f. Time, temperature and l, reactor p-ressure were recorded during the addition, which required 40 minutes.~ The reaction conditions are tabulated below: -- ' ~ 30 :~`

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~075719 Reaction PSIG in In~ernal Jacket Tem~.
Time (min) Reactor Te~.~. (~ (Heat 0~ C) - 5 1~ 109 26 132 137 _ . 15 25 141 137 `
26 1i40 - - 137 .

. 30 31 133.7 137 `
33 32 .133.7 137 ` :
. 37 133.7- 137 . ..
~: ' . At the end o~ 40', cooling water was circulate~ .
`I through the jacke~ ~or 10 minutes after which the re- .-ac~i~n was shortstopped by the addition o~ 5 pounds .o~
i5 water. The react~on-mixture was washed wi~h 5% caust~c .
. . solution (5~ sodium hydroxide solution) and then again with water. The organic phase was separated and passed............. .
- . through a ~ilterinO column o~ activated alumina. ~-` me w~ole oil obtained in this proces~: had the following molecular weight distribution,.as d~ermine~ -- . by G.L.C. - -~'-' ' ' ~ ' -' ~

-~: - C8 C12 + C16 + C20 C24 C32 Cj~0 C48 C~6+
358-7 1i~.3 13.1 11.~ 7.6 ~.2 . :-. 25 The whole oil-was then subjected to distilla~ion . : whereby all hydrocarbons boiling below 150C at 0.1 m~
: .
. . Hg. were removed resulting in a product yield of C24 .
to C56 ~ 56~ having the following ~om~os~tion:
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3 <C24 C24 C32 C40 C~8 C56~ .
<1.0 21.8 23.2 21.8 13.1 . 19.2 1 ~

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The molecular weight of the product was calculated to be 538 and, when measured by osometry, it was found to be 502.
This product oil had the following property characteris-tics, wherein all kinematic viscosity values were obtained ac-cording to ASTM D445-64: -Pour Point (ASTM D97-57) -75F.
(Method B) Flash Point (ASTM D92-57) 450F.
Kinematic Viscosity at 100 F. 32.7 cs.
Kinematic Viscosity at 210 F. 5.6 cs.
Kinematic Viscosity at -40 F. 8534 cs.
Kinematic Viscosity at -65 F.62500 cs.
. Viscosity Index (ASTM D567-53) 117 The above data clearly demonætrate that poly-~` octene oil having excellent properties can be attained ' in good conversion, using relatively small amounts of the novel soluble catalyst system and in very short reaction time.
j~ The following examples were performed in equip-i ment identical to that used in Example I above. Variations ~ were made in the type of aluminum alkyl compound used, the wt.%
`1 of the aluminum alkyl compound, the Hal/Al ratio, and the temperature of reaction.
Example VII
~ All of the following runs utilized 212 ml. of ~ `-octene-l (106 ml. in each addition funnel) and all were ~- shortstopped after addition was completed in 30 minutes time.
The resultant whole oils were analyzed by G.L.C. The yields were calculated as % - C24. The ?

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,'' ` -~. ' ` ' ` ` ' ' molecular wel3h~ ~igures correspond ~o product oil ~ro~ which everything belo~r C24 has been separated by distillation. As ~entioned earlier, id2ally the yield of oligomer is to be maximized lJi~hout the production o~ co~oonents h~gher than C60.
The follo~.ring table lists :;he reactio~ .
components and conditions for each run and illustrates ~ .
the ef~ect o~ changes in catalyst concen~ration~ Hal/Al ratioj and reac~ion ~e~perature on a series of oligo.~er-izations in which oc~ene solu~ions o~ Et3A12C13 (EASC) _ - iand benzyl chloride were mixed over a thirty minute - .
period. ` . ~
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~ ~oles ` Reaction `
`~ Run MMoles Benzyl Wt. % Ratio Tempera-. 15 ~- EASC Chloride EASC Hal/Al ~ure(C) 'i ' .: 1. 3 9 o. 5 3/1 120 - `
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i :` 2. 3 9 o. 53/1 140 :
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i,-`; - : ~. - 3 27 0.5 6/1 120 `
6. 3 ` 27 o.5 6/1 - 140` . - `
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The data tabulated above reveal that:
Runs performed at 140C. produce lower molecular weight products than identical runs at 120C. Thus, MW 1> 2, 3 >4, and 5> 6.
Higher catalyst levels increase the molecular weight of the product oil in otherwise identical experiments.
Thus, MW 3> 1, and 4~ 2.
Higher Hal/Al ratios lower the molecular weight of the product oil. Thus, MW 1 > 5, and 2~ 6.
Example VIII
The following runs illustrate the utility of ethyl aluminum dichloride (EADC) as the aluminum alkyl compound in the catalyst system of the invention. The reaction conditions and components used are tabulated below: -o ~00 ~1 . '' v I N N ¦r ~ N ~ N

N ~ 0~

- , ' ~rl . v~ t - .

O ~ ~

. ~
~D V . . V I U~ -O ~ . . V
~ ¦ ~I ~

~ ~ ~ . .
~z'l In o .. . : . . . . . ~ . . t 10~7~

~xarple IX
This example, carried out in th~ same way as E~ample VIII above, illu~trates the use of diethyl aluminum chloride (D~AC) as the al~minum al1~yl compound in the catalyst system of the invention, th~ _ - details being tabulated below:
~ .
: ' ' ' ' ~

-, . .
' ' ' ' ' . ~ .

. . . .

'' . '- ' : , ."'- . ~ ' -'' '~
- - . .. -'' , - ' ' - ' ' . , ' .' ~' ' . . -~ ~ -, . . F--.,. .,~ . . ~1 ', " ' '- .

~ 23- . .
!
. - - . '.

. . .... . .

107S71S~ ~

~ ~ , ~

~q S I 1 ~ l o i~¦ ¦ o ~075'715~

Example X
This example illustrates the preparation of polydecene by the process of the invention on a large scale.
The apparatus used was the same as described in Example VI above.
A dry 20 gallonjacketed steel autoclave reactor was steam heated to 140C. Two 8 gallon solvent bombs, A and B, with top and bottom access vents were loaded as follows:
Bomb A: 50 pounds of decene -1 and 0.5 pound of Et3A12C13(EASC) (as 2 pounds of a 25%
hexane solution).
Bomb B: 50 pounds of decene-l and 3 pounds of allyl chloride, Hal/Al ratio: 1611 The contents from bombs A and B were each fed at the rate of one pound/minute into the stirred reactor.
After 25 minutes, the internal temperature had reached 152 C and the external heating was turned off. Fifty minutes were required for addition of both A and B contents. At the end of this time, the internal pressure was 27.5 PSIG and the internal temperature was 156C.
At this point, cooling water was circulated through the reactor jacket for ten minutes after which the reaction was shortstopped by the addition of 5 pounds of water. The reaction mixture was washed with 5% caustic solution (5% sodium hydroxide solution) and then again with water.
The whole oil obtained in this process had the following molecular weight distribution as determined by 1075'71~
G.L.C. analysis:
Wt.%__ Clo C13 c20 C23 C30 C40 C50 c60+

10.6 4.4 20 0 24.6 20.4 10.7 8.9 The yield of product - C20 was 85%.
The whole oil was then distilled under reduced pressure to remove all hydrocarbons below C20. G.L.C.
analysis of the resulting product oil showed the following:

Wt.%
C C C o C50 C60+

21.7 28.2 23.9 12.9 12.8 This product oil had-the following property characteristics:
Pour Point (ASTM D97-57) -80 F

Kinematic Viscosity at 100 F
(ASTM D445-64) 26.4 cs Kinematic Viscosity at 210 F.
(ASTM D445-64) 4.9 cs Viscosity Index (ASTM D567-53) 123 Average M.W. by osmometry 472 Example_XI
This example was carried out in the same manner as Example X above to illustrate how good yields and higher molecular weights are attainable by increasing the amount of aluminum alkyl compound and lowering the Hal/Al ratio to 4/1.
In this example, bomb A contained 50 pounds of decene-l and one pound of Et3A12C13 (EASC)- (As 4 pounds of a 25% hexane solution).
Bomb B contained 1.5 pounds of allyl chloride dissolved in 50 pounds of decene -l.

~07571~

The reactants were mixed over a 30 minute period in the 20 gallon autoclave which had been pre-heated to 140C.
The maximum temperature attained was 167C. and the internal pressure reached 30 PSIG.
Cooling water was then circulated for ten minutes, following which the solution was shortstopped and washed. The whole oil obtained had the following molecular weight distribution as determined by G.L.C. analysis:
Wt. %
C10 C13 c20 C23 C30 C40 cSo C60+

6.6 2.2 17.1 0 22.8 23.1 12.7 15.6 The product yield of - C20 was 91.2%.
The oil was distilled under reduced pressure to remove all hydrocarbons below C20. G.L.C. analysis of the resulting product oil showed the following composition:
Wt. %

C20 C30 C-- C50 C60+
19 24 24.3 14.3 17.6 The product oil had the following property characteristics: :
Pour point (ASTM D97-57) 70F

Kinematic Viscosity at 100 F. 31.2 cs (ASTM D445-64) Kinematic Viscosity at 210 F. 5.5 cs (ASTM D445-64) Viscosity Index (ASTM D567-53) 124 Average M.W. by osmometry 490 1075715~

Example XII
A mixture (ca 2/1) of C16 and C24 olefins (lOOg), which was distilled off from a previously prepared oil derived from octene-l, was treated with 50 grams of bromine at room temperature over the course of an hour. After the addition was complete, the red oily product was washed with aqueous base, the layers separated and the organic layer dried. The resultant halogenated product w-eighed 135 grams and contained 26% bromine. This alkyl bromide is used below as the cocatalyst with ethyl aluminum ses-quichloride for the oligomerization of octene-l.
A 3-necked round bottom flask, fitted with 2 Y
tubes into which were mounted a stirrer, thermometer, an N2 inlet and 2 dropping funnels (125 ml), was placed in an oil bath heated to 120C. ~n one of the dropping funnels was placed 106 ml (76.5 g) octene-l and 4 ml of 25% ethyl aluminum sesquichloride. In the other dropping funnel was placed 10 grams of the above-prepared alkyl bromide so that the hal/al ratio was 811 and 96 ml (69.2g) octene-l. A head of nitrogen was kept over the contents of each funnel during the entire reaction:
The contents of both dropping funnels were added simultaneously to the stirred heated flask at such a rate as to require 30 minutes for the complete addition of both, During this time, the temperature in the flask reached 125 C, only slightly warmer than the surrounding bath temperature. After addition was complete, the reaction was stirred for an additional 5 minutes and was then quenched by the addition of 100 ml of 5% NaOH (aqueous).
The organic layer was then separated, dried and analyzed ~07571~

for its molecular weight distribution:
The molecular weight distribution of the product was, in weight percent:

C8+ C16 C16+ C24 C32 C40 C48 C56+--6.2 2.0 7.1 1.4 15.0 21 20.2 16.6 10.4 This corresponds to an 83% yield of oil having m w -> C
In a similar experiment, 20 grams of the alkyl bromide of above was utilized as cocatalyst such that the hal/al ratio was 14/1. The above procedure w-as repeated and the resultant product had the following molecular weight ; distribution in weight percent: -8 C8+ C16 C16+ C24 C32 C40 C48 C56 5.9 4.1 9.9 1.8 20.2 22.4 18.2 13.1 4.7 This corresponds to a yield of 78.7% of oil having molecular weight = C2 Example XIII
The following example illustrates the variety of : organo halides which are operable as cocatalysts with the alkyl aluminum halides in the present invention.
The examples are run as previous examples, employing 2 dropping funnels, one containing 106 ml (76.5g) octene-l and 4 ml of 25% EASC and the other containing 106 ml octene-l and the specified amount of alkyl halide. The reaction temperature is 120 C and the time of addition is 30 minutes.

, 30 ; - 29 -~075719 Organo Halide, g Hal/al Ratio Halide formula (a) Cyclohexyl bromide, 1.45 3/1 6 11 r (b) Dodecyl iodide, 3.17 3/1 C12H25I
(c) l-chloro eicosane 2.85 3/1 C20H41Cl (d) 2-chloro eicosane 2.85 3/1 "
(e) 1,2-dibromo hexade- 1.65 3/1 16 32 2 (f) dodecyl benzyl chlo- 3.55 3/1 19 31 In all cases above, the resultant oil is obtained having at least 70~ of the olegomer as an oil - C24, This example illustrates that the structure, molecular weight and choice of halogen of the organo halide has little effect on its efficiency as a cocatalyst in the method.
While the invention has been described with particularity and in some detail, it will be recognized by those skilled in the art that various changes and modifications can be made therein ~ithout departing from the scope and spirit of the invention.

Claims (8)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method of oligomerizing straight chain alpha-olefins comprising mixing, in an inert atmosphere and at a temperature up to about 200°C., a feed consisting essentially of a straight chain alpha-olefin having at least 3 carbon atoms with a soluble catalyst system to obtain an oligomer having from about 20 to 60 carbon atoms, said catalyst system being prepared in the presence of the alpha-olefin reactants and consisting essentially of an aluminum alkyl halide compound wherein the alkyl is a lower alkyl having 1 to 4 carbon atoms and an organo halide compound having at least one saturated carbon atom which has only one halogen atom thereon wherein the halogen is selected from chlorine, bromine, and iodine, said aluminum alkyl halide being present in said catalyst system in an amount of at least about 0.1% by weight of the total monomer content and in sufficient amount to provide a total Hal/Al ratio in said catalyst system of at least about 2.5/1.

2. The method of claim 1 wherein said straight chain alpha-olefin is a member selected from the group consisting of propene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, and tetradecene; said aluminum alkyl halide compound is a member selected from the group consisting of ethyl aluminum sesquichloride, ethyl aluminum dichloride and diethyl aluminum chloride; said organo halide is a member selected from the group consisting of t-butyl chloride, allyl chloride, benzyl chloride and a mixture of halogenated C24 and below oligomers and alpha-olefin; and, said temperature is at least about 100°C.

3. The method of claim 1 wherein products having a molecular weight of less than about 280 are removed by vacuum distillation.

4. The method of claim 1 wherein the products removed are halogenated and then recycled as the organo halide compound.

5. The method of claim 1 wherein the yield of oligomer obtained is at least about 56% based upon the weight of said straight chain alpha-olefins, and the average molecular weight of said oligomer is at least about 280 and no greater than about 650.

6. The method of claim 5 wherein said straight chain alpha-olefin is octene-1.

7. The method of claim 5 wherein said straight chain alpha-olefin is decene-1.

8. A method according to claim 1, wherein the organo halide is a mixture of halogenated oligomers and alpha-olefin having 24 or fewer carbon atoms.