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Патент USA US3080421

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March 5, 1963
PROCESS
M. 1'. ATWOOD ETAL
3,080,411
FOR THE PREPARATION OF 2-METHYL-l-BUTENE
AND TRIALKYLALUMINUM COMPOUNDS
Filed F919. 2, 1959
N2
VENT4?x
7' 7
N2
8
H20'—’
3
\\
k
V I0
-
9 2
—l><1—sAs SAMPLE
4
\
vI
\
PROPENE
—*-———’
ALUMINUM
VENT
5',
6
TRIETHYL
INVENTORS
MARK T. ATWOOD
GIFFORO 6‘. McCLAFL/IV
ALEXANDER S'HADA/V
8’ 92% M'
ATTORNEY
United States
3,080,411
' atnt
Patented Mar. 5, 1963
2
1
methyl-l-butene, propene,.propene dimer, and an allsyl
aluminum residue;
3,080,411
(0) reaction of said. alkylaluminumresiduewith ethylene
to yield a product mixture containing higher molecular
PROCESS FOR THE-PREPARATION 0F Z-METHYL
l-BUTENE. AND. TRIALKYLALUMINUM COM
weight trialkylaluminum compounds.
POUNDS.
Mark T. Atwood, Gilford G. McCla?in, andAlexander
Shadan, Ponca City, Okla, assignors to Continental Oil
Company, Ponca City, Okla., a corporation of Delaware
Filed Feb. 2', 1959, Ser. No. 790,468
10 Claims. (Cl. 260-448)
(d) recycling the recoveredpropene of step (b);
(e) conversion of the‘ higher molecular weight trialkyl
aluminum compounds of step (c) to useful products.
10
The process of the‘ present invention has these distinct
advantages:
The present invention relates to a combined process for
the preparation of 2-myth-yl-1-butene and trialkylalu
minum compounds.
'
(1) Propeue is reacted‘ with triethylaluminurn under
conditions which produce high selectivity, good yield,
More particularly, it relates to a
and a minimum of undesirable products, as for example,
method of preparing (1) Z-methyl-l-butene of high purity
propene dimer.
'
and- in good yields and (2) trialkylaluminum compound-s 15
(2) The impurities, or undesirable products, may be
which may be converted to high-molecular weightalcohols
readily separated from ‘the desired 2imethyl-l-butene.
and a-ole?ns,
This we consider to be a salient feature of the present in
vention. In addition, it is a feature not present in prior
'
This, application is a continuation-in-part ‘of our co¢
pending application, Serial No. 704,742, ?led December
23, 1957.
'
20
Heretofore, methods for the production of 2-methy1-l
butene have been, in the most part, rather expensive
laboratory methods. Commercially, attempts for the pre
art processesconcerned with aluminum trialkyl chemistry.
(3) The process, eliminates the possibility of contami
nation of the 2-methyl-1-butene with’ Raney nickel.
(4) The higher molecular weight trialkylaluminum
compounds may be converted to high-molecular weight
paration of the compound have employed a rather crude
alcohols and a-ole?ns, which are of substantial commer
mixture of isomeric pen-tenes. As a result, the 2-methyl 25 cial value, thereby lowering the cost of the 2-methyl-1
l-butene so ?ormed has been. contaminated with other
butene and, in turn, the isoprene produced therefrom;
compounds. Since the recovery of Z-methyl-l-butene
Other, advantages will be" apparent ‘as the description
from such a. mixture is di?icult and expensive, this mix
proceeds.
ture has been used in the preparationv of isoprene. This,
Before proceeding with speci?c examples illustrating
in turn, has produced an. isoprene which. is impure and 30 our invention, it might be well to indicate the reactions
subsequent puri?cation is necessary. Such puri?cation
used and to indicate the conditions under which the
methods have increasd- the cost ofpreparing isoprene to
process operates. With regard to the reactions shown, it
such an extent that the method of manufacture is un
is to be understood that these are hypotheses and we‘ do
economical.
not intend to be limited thereby.
It is highly desirable in a chemical process that all of 35
The principal reactions of‘ step (a) may be shown as
the products have substantial value. As is well known,
follows:
‘
many chemical processes produce a secondary product
having little or no value. Such processes are commercial
ly feasible because of the inherent value ‘of the primary
product, or because the yield of secondary products is of 40
an insigni?cant amount. Obviously, if the secondary
pressure
A
A1 (iCsHiO'a + CH2=CH~CH5 —-——->
products are present in any quantity, above that of trace
amounts, it is economically desirable that they have a
pressure
value approximately that of the primary product.
A1 (OHKHT) 31+ OHsOH2—-C = C H
CH3
It is, "therefore, a primary object of the present inven
tion to provide a combined process for the preparation
of Z-methyl-l-butene and useful trialkylalurninum com
(2)
pounds, which process obviates the disadvantages of the
prior art. It is another object of the present invention to
provide a process for the preparation of 2-methyl-1 50
butene, which process gives a high selectivity, good yield,
and a minimum of undesirable products. It is also an
ApreSSll e
A
AlGCoHrs); + CHr-‘CH-CH; ——-—-—> A1(C3H7)3 + iCoHu
pressure
The reactionof step (0) may be shown as follows:
(C2114) 103E?
other object to provide a process in which the secondary
A1(C:H7)a + nCzH; -—-—> Al—-(C2H4)yC3H7
products of the reaction have substantial value in them; 55
‘(ozrm .otm
selves. Other objects and advantages will become ap
where n=x+y-|—Z and x, y, and z,_ may or may not be
parent to those skilled in the art as the description
equal, and may or may not be zero.
proceeds.
:
Thealkyl groups of the aluminum'trialkyl‘ formed in
Broadly stated, the process of, the, present; invention
comprises the following steps:
(a) the reaction of propene with triethylalurninum to
form a. product mixture comprising hydrocarbons and
alkylaluminum compounds;
(lb) distillation of the product mixture to recover. 2
our invention may contain up to~1,000 carbon atoms.
60 Theoretically, there is no known‘lim'itation to the number
of carbon atoms in the-alkyl groups: For practical pur
poses, wev prefer to. prepare aluminum trialkyls inwhich
the alkyl groups contain 100 carbon atoms or less.
The reaction conditions of step '(a), the reaction of
spec/.11
3
4
triethylaluminum with propene, may be summarized as
follows:
overnight, the contents were removed, the flask was rinsed
with toluene, and the washings were added to the reaction
product mixture. The toluene layer of the product mix
Reaction variable
Suitable
ture was separated and distilled to yield hydrocarbons boil
ing within the range of 44.5D to 108° C. The remainder
of the product was hydrolyzed to yield a mixture of hydro
Preferred
range
range
Propene, Al(C2H5l3 mole ratio _______ __
Pressure, p.s.i.g ______________ _.
..__
__
Temperature, °O_._.
-__.
70-300 ....... -_
3-8.
carbons.
200—l,000
collected and analyzed in a mass spectrometer.
100-180.
10
Hydrocarbon:
Ethane
Preferred
range
range
Ethylene/alkylaluminum residue, mole ratio-.. 1:1-1000: 1
Pressure, p.s.i.g _________________________ __
Temperature, "C _ _
. . _.
15
(1)
200-4000
1, 000-2. 000
80-100
110-130
1Mole ratio required to keep the solution saturated with
ethylene under the process conditions.
_____________________________ _ _
{so-butane
Iso~pentane
0.45
___________________________ __
3.14
__________________________ __
1.04
The analytical data indicate that there was a 6.3 percent
conversion of triethylaluminum to a product mixture which
contained approximately 19 mole percent (C5H11)3Al and
Z-methyl-l-butene, which may be considered as isoprene
precursors.
Example II
Aluminum alkyls are pyrophoric and should be handled
in a solvent.
4.98
______________________________ __ 88,70‘
Propene
Suitable
Mole percent
Ethylene _____________________________ __
marized as follows:
Reaction variable
The
composition of the mixture is tabulated below:
Reaction time _______________________ __ 5 min-8 hrs___ 30 min-6 hrs.
The reaction conditions of step (c), the reaction of
ethylene with the alkylaluminum residue, may be sum
A sample of the liberated hydrocarbons was
A suitable solvent would be any material
Into a reactor was introduced 22 parts of triethylalu
which in itself does not react with aluminum alkyls. 25 minum. The flask was placed in an autoclave, the reactor
Examples of preferred solvents are saturated aliphatic and
was ?ushed with dry N2 gas, and propene was forced in.
aromatic hydrocarbons.
The trialkylaluminum compounds of step (c) of the
process of the present invention possess average molecular
The temperature was raised to 112° C. over a period of
about 2.25 hours and was maintained at this level for ap
proximately 0.75 hour. Propene was pumped in as neces
weights of about 240 and above. These materials may 30 sary to maintain a pressure of 700 to 1,500 p.rs.i.g. The
be oxidized and hydrolyzed to produce high-molecular
alkylalunu'num product was hydrolyzed, and the liberated
weight primary straight-chain alcohols along with high
hydrocarbons were analyzed in a mass spectrometer. The
purity aluminum hydroxide. Alternatively, they may be
results are tabulated below:
reacted with ethylene in the presence of Raney nickel to
give a-olelins and aluminum triethyl. If desired, these 35 Hydrocarbon:
Mole percent
materials may be reacted with bromine to give straight
chain alkyl bromides and high-purity aluminum bromide.
It should be noted that the Raney nickel, as used in
Ethane ______________________________ __ 67.40
this process, does not have a chance to contaminate the
Butene
Z-methyl-l-butene formed in step (a).
Iso-butane
As mentioned 40
previously, this is a decided advantage. As is well known,
Raney nickel is di?icult to remove by ?ltration or centrif
ugation.
Ethylene _____________________________ __
Propene
Butane
4.618
_____________________________ __
0.28
______________________________ __
0.5 l
___________________________ _ _
1.5 2
______________________________ __
0.60
Pentenes _____________________________ __
2.42
Pentanes
5.97
Our process may be operated on either a cyclic or a
The conversion of triethylaluminum to other aluminum
continuous basis. In the laboratory and small plant opera 45 alkyls was approximately 28 percent, of which product
tion, it may be preferable to use a cyclic operation, since
approximately 74 mole percent was isoprene precursors.
the apparatus required for a continuous operation is more
In the following examples, a continuous process was
expensive. On the other hand, for large-scale plant opera
used. The experimental equipment is shown in the ?g
tion, this increased cost of apparatus is offset by a higher
ure. The reactor proper consisted of a 1/z-inch diameter
production rate and a lower unit cost.
steel tube, 2, which was surrounded by a 6-inch steel pipe,
In order to disclose the nature of the present invention
9, containing two electric immersion heaters. A liquid
still more clearly, the following illustrative examples will
hydrocarbon having the desired normal boiling point (ex
be given. It is to be understood, however, that the inven
amples of which are xylene and t-butyl benzene) was
tion is not to be limited to the speci?c conditions or details
placed in the jacket. Using nitrogen through a regula
set forth in these examples except insofar as such limita 55 tor, 7, the pressure on the jacket could be varied, thereby
tions are speci?ed in the appended claims. Parts given
permitting a wide range of controlled temperatures. The
are parts by weight.
REACTION OF PROPENE WITH
TRIETHYLALUMINUM
condenser, 3, served to condense the hydrocarbon vapors
and return them to the jacket 9.
In conducting the reaction, the triethylaluminum and
The ?rst step of the process of the reaction of propane 60 pro-pene were introduced into the saturat-or, 1, where the
triethylaluminum was saturated with the pro-pone. From
with triethylaluminu-rn to yield a product mixture compris
the saturator, 1, the reactants passed to the reactor, 2.
ing hydrocarbons and aikylaluminum compounds. Some
A back pressure of nitrogen was maintained on the reac
of the variations possible are illustrated in the following
tor by means of the back pressure regulator, 3. When
examples.
65 the pressure in reactor, 2, Was greater than the back pres
Example I
sure of nitrogen in the back pressure regulator, 3, the di~
Into a ?ask was introduced 20.7 parts of triethylalu~
aphragrn permitted the product to flow to the liquid trap,
minum, and the ?ask was placed in a rocking autoclave.
4., The light gases passed from the liquid trap, 4, through
The reactor was swept with dry N2 gas, propene was forced
vthe scrubber, 5, to the wet test meter, 6, where the vol
in, and the temperature was raised slowly to l08—ll0° C. 70 ume was recorded, and then to the vent. A sample of the
over a period of about 3 hours and the temperature main
gas was taken at 10 for analysis. In a commercial proc
tained within this range for an additional period of ap
ess, the gases from the scrubber, 5, would go to a recovery
proximately 2.5 hours. During this time, the propene
tower, with the propene recovered therefrom being re“
pressure was maintained within a range of 1,100 to 1,480
cycled. The time of reaction is regulated by controlling
p.s.i.g. The reactor was allowed to stand and cool oii
the ?ow rates of propene and triethylaluminum. Gauges,
3,9811%; 1.
temperatures give. higher conversions, but at the same t.
valves, and other minqrequipment are not shown in the
TABLE- II
MATERIALS
Er.
Propylene-99mph percent purity-.-purchased. .
Temperature; ‘’ 0.......
m
E
r
n
y
m
a
p
w
r
h
0
p
o
i
w
m
,
e
w
m
w
h
d
a
w
m
a
.
D
v
n
e
.
%
m
u.rn.
UeOISmO
tP.mweu%.mn,v mebrwlsm a er.mcatw muse?rmPaoe
1%2093 24.7 1i547.269~
1w
ee0Ra
mwaema
.,.el
2134. 03578924.
Conversion, percen
By-products 1n niole
214.
.802974.285 .
.XX.2054.
E1..1
07
e.
.27.5105. 75v6028
. 05
5
.
2.1.6753“
.3956 . 2.16.0
.L0..
15“.
Ethrleeerewrew----.<<--
Exdrnples X-XVI
the reactor. A run was then started.
Examples III-V
These examples were run at the following‘ conditions:
2o
Tempenature, ° C. _..--.
These examples were run at thefollowing conditions:
Temperatu
7H7Rw3OJ2.L201
00
.a
r
PWIm0?PRIrlefo. CPhe1eev.6E.d18.W tmaUwaven.
EV
.. I.
VII
Aluminmn Methyl-96 male. resent ruritywsurchased
aueWe
6
produce a higher ratio of by-products.
?gure.
Pressure, p.s.i.g, ..-..-_V'._-.-V
1.0-6.6’
‘
7
Reaction time ._...__,../.__.'._..__....V. 14.9 min-1.86.111‘.
Mole ratio
e --..__--__--.--__-____--__--._ 250-255
Pressure, p.s.i.g. .._____._..._,_...T......... ‘240-810,
5.6-9.7 25
Mole ratio
The ‘data for these examples are shown in Table III.
In general, these data ‘indicate the» following‘:
(1) Temperatures in the rangeof 200-204? Q. donot
Reaction time -_V_I_.__.__-..--._..___.._..---.. 12'min.-2 hrs.
The data for these examples are shown in Table I.
In general, the data for these run-s indicate that these
give good seleot'ivities, and
'
' (2)’ The pressure mus-t be greater than 250 p.s.i.g. and
conditions give poor seleetiv-ity-andhigh propylene-polye 3.0 less than 1,500“p'.s.i.g'. 'in' order
mer formation.
to ob't‘ain
high selectivi
ties.
TABLE III
TABLE I.
vEx.
X .
Example Example Example 35
III
Ex.
_ Ex.
XI
V
IV >
mwati6975 253679 2.3?. 0.59 L347
23476. 44.06 L.2346
. 124.5 .84236
Reaction time, min.
112
40
Yield. percent. . - .-
Selectivity. percent. _ .
Conversion. percent. _ _ .
By-products
Conversion, percent. ..._-.
By-pcroducts in moles per 11555356.?
in moles
0
.
o66
5
..
362
04-....."
4,_..-._____-______..__-__-_--..__....___
Ethylenerecovery.-..-.......-........
Ex.
XV XVI
0.
45
Temperature,’ ° C.
31. 0
' Ex.
XII XIII
99. 5
1 0 4n 8
n .
n
. .
. n
XMinutes.
Examples VI-IX
50
These examples were run at the following conditions:
Examples XVII-XXIV
These examples were run at the following conditions:
180-221
.
525-560
750475
Pressure, p.s 1 g
2.0-3.4 55
1.2-3.5
25.5-28.8
The data for the examples are shown in Table II.
In general, the data for these runs indicate that higher
The data for these examples are ‘shown in Table IV.
In ‘general, the datafor these runs indicate alow con
version.
TABLE IV
Ex.
' 15X.
Ex.
-X_VII~ XVIII XIX’
Temperature ~°G
35
219450 90.4571 .16840202
31254. 314 407
003...
B‘yfprodncts in moles per mole of i05 _
C4
Ethylene 'reeover‘y
l'seconds.
83
.
Ex.
xx
Ex.
Ex.
Ex.
no
15308 9.5601 25nwarsl.7034921 lg145z.63.417
4.5 .
127
75...
1
Ex.
,XXI XXII- XXIII XxIv
1I58s4mg.
223%
2.
u-.l
25 .
3,080,411
7
TABLE VII
Examples XX V-XXIX
These examples were run at the following conditions:
Example Example Example
Temperature, ° C ______________________ __
Pressure, p.s.i.g ________________________ __
Mole ratio
__
__
XXXIX
185-208
525-540
036-68
Temperature, °C ..................... __
Reaction time, min ______________________ __ 14.9-15.7
The data for these examples ‘are shown in Table V.
XLI
138
140
Pressure, p.s.i.g.._.
.
695
700
690
Mole/ratio ......... -.
.
7. 86
6. S5
6. 62
Reaction time, hours
_
2.13
2. 29
2. 21
Yield, percent _____ __
._
27. 2
39. 3
3'. 7
_
81. 0
88. 3
78. 8
33. 6
44. 6
45. 3
.044
. 12
. 117
. 020
. 100
. 007
. 038
. 230
. 003
. 030
. 195
. 003
98. 7
108. 5
100. 0
Selectivity, percent.“
In general, ‘the data for these runs, together with those 10
for the runs of Examples XVII t-o XXIV, preceding, indi
cate that a lower temperature gives better selectivity with
a decreasing amount of by-product.
140
XL
TABLE V
Ex.
Ex.
Ex.
Ex.
Example XLII
Ex.
XXV XXVI XXVII XXVIII XXIX
Temperature. °C ____________ _ _
Pressure. p.s.i.g_-
.
185
184
190
199
208
This example illustrates the conversion of the alkyl
aluminum residue to a product mixture containing higher
20
molecular weight trialkylaluminum compounds.
540
525
540
535
540
Mole/ratio _______ _-
_
6.8
0. 36
2. 07
2. 89
2. 97
Reaction time, min
_
14. 9
15. 7
14. 9
14. 9
14. 9
Yield. percent .... __
_
10. 3
7. 98
19. 3
35.8
35.0
in 40.9 grams (48 milliliters) of xylene was added to a
Selectivity. percent_ _
_
41. 7
36. 0
43. 9
01. 4
51. 6
Conversion. percent _________ __
46. 3
22. 2
44.0
58. 3
68.0
stirring autoclave which had been ?ushed with nitrogen.
C4 _______________________ .-
. 47
. 27
. 25
. 36
n05"
. 06
. 09
. 06
.07
1C0“
. 30
. 29
.34
.41
101 ....... -_
. 04
. 03
.04
.12
99.0
94.0
109. O
110. 6
Thirteen grams (16 milliliters) of aluminum tripropyl
The autoclave was heated to 108° C. and ethylene was
added to a pressure of 1,500 p.s.i.g. The reaction was al
lowed to continue for three hours while maintaining a
By-rroduets in moles per mole
Of 1052
Ethylene recovery
temperature of 108-138° C. After venting the autoclave,
the aluminum trialkyls and solvent remaining weighed 92
grams, which represents a gain of 38.1 grams. This ma
30
terial was then hydrolyzed at 50° C. using 25 percent HCl
and an ice water condenser. Hydrolysis gave at standard
Examples XXX-XXXVIII
temperature and pressure 2,770 milliliters (0.123 mole)
These examples were run at the following conditions:
of gas, an aqueous layer and an organic layer. The aque
Temperature, ° C. ____________________ ..
138-158
Pressure, p.s.i.g .
700-710
ous layer was discarded. The ‘total yield of organic layer
was 78 grams (102 milliliters). Correcting for the xylene
Mole ratio ___________________________ __ 137-1040
originally present, the net yield of product in the organic
_ _ s -.... ________________ _.
layer was approximately 37 grams.
The gas was analyzed by mass spectrometer and found
The data for these examples are shown in Table VI.
These examples were run at nearly identical pressures 40 to contain both odd and even number hydrocarbons, rang
ing from C-2 to C-6. The organic layer was analyzed
and at similar temperatures; the mole ratios and reaction
Reaction time _________________ __. 24.8 min-2.97 hrs.
times were varied over a wide range. The data indicate
by GLPC. Analysis showed a major portion of hydro
the bene?cial effect of a longer reaction time. In addition,
it is apparent that mole ratios of 3‘ to 7 are preferable.
TABLE VI
carbons containing 8 carbon atoms or more, with both
odd and even number hydrocarbons being present. The
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
Ex.
XXX XXXI YXXIT XYXTTT XXXIV XXXV XXXVI XXXVII XXXVIII
'l‘em erature. “O ‘
158
158
700
700
710
700
700
700
700
700
710
10. 40
27. 9
7. 5
49. 4
138
1.72
l2.97
33. 0
46. 3
5.35
27. 9
8.3
35. 7
1. 37
1 1. 98
20.1
51. 0
1. 91
24. 8
5.9
45. o
5.45
l 1. 84
43. e
61. 5
5. 7
32.7
15. 7
52. 3
2.8
1 2.21
33. 0
74. 2
2.8
40.
13. 9
52. 6
15.2
72. 5
23.3
39. 4
12.9
70. 8
30.1
44.5
26.5
.05
.182
.112
.139
.122
.110
.002
.092
.082
.013
.010
.421
.005
75. 7
.019
.075
.019
90. 5
.030
.183
.005
s7. 5
.011
.100
0. 000
94. 6
.034
.338
.004
85. 9
.020
.082
.030
.238
.022
.000
0.000
90. 7
0.000
90.
0.000
e0. 4
Pressure. 1') si
Mole/ratio"- _Reaction tirn ,ml
Yield. percent -_
Selectivity, perce
Conversion. percent _____________ __O_ ________ ._
B - o uctsin moles er mole ofi :
y
____________
___________ "5________ __
.
139
140
141
141
158
157
1 Hours.
over-all ratio, both gas and organic layer, of odd to even
number hydrocarbons was 0.4 to 1. In calculating the
composition of the organic layer, correction was made
Examples XXXlX-XLI
These examples were run at the following conditions:
Temperature, ° C. _____________________ __
138-140
Pressure, p.s.i.g ________________________ __
690-700
Mole ratio
6.62-7.86
Reaction time, hrs. ____________________ __ 2.13-2.29
65
for the xylene present. Table VIII gives the composition
of this organic layer, as corrected.
TABLE VIII
Composition of Hydrolysis Products-Organic Layer
[Corrected for xylene present]
The data for these examples are shown in Table VII. 70
These examples were run at very similar conditions and
Hydrocarbon
group _________ _indicate, in general, the repeatability of the process. It
is evident that the selectivity is high on all of these exam
pies. In addition, itis evident that ‘the by-prcducts, in I Moles ........... ...
75
general, are very low.
C4
C5
C0
C1
Ca
C1
C10
. 007
. 008
. 025
. 006
. 025
. 008
. 024
C11
. 023
3,080,411
0
l0
Ethylene/alkylaluminum residue, mole ratio..-
The GLPC analysis refers to gas liquid partition chro
1-1,000
Pressure, p.s.i.g ________________________ .... ZOO-4,000
matography. This analytical technique is adequately de
scribed in either of the following publications: Analyst,
Temperature, “ C ______________________ _._.
77, 1952, pages 915-932, or Petroleum Re?ner, Novem
ber 1955, pages 165-169.
5. The process of claim 1 wherein step (a) is conducted
under the following conditions:
In the laboratory example we have hydrolyzed the
80-150
Propene to triethylaluminum mole ratio---"
aluminum trialkyl in order to convert the alkyl groups to
3-8
Pressure, p.s.i.g ________________________ __ ZOO-1,000
hydrocarbons for analysis. Commercially, these alumi
Temperature, ° C ______________________ __
100-180
num trialkyls would be converted to useful products, e.g.
10 and wherein step (c) is conducted under the following
alcohols, as hereinbefore described.
In summary, we have shown a combined process for
conditions:
the preparation of Z-methyl-I-butene and trialkylalumi
Ethylene/alkylaluminum residue, mole ratio__ 1-1,000
num compounds. The 2-methyl-l-butene may be pre
Pressure, p.s.i.g ________________________ __ 200—4,000
pared under a wide range of conditions, but we have shown
Temperature, ° C ______________________ __
'80-150
a narrower range of conditions under which the selectivity 15
6. The process of claim 1 wherein said process is oper—
of the desired product is increased and the formation of
ated on a cyclic basis.
undersirable products is kept at a minimum. We have
7. The process of claim 1 wherein said process is oper
shown further that the trialkylaluminum compound,
ated on a continuous basis.
formed as a by-product of the ?rst step of our process,
8. The reaction of propene with triethylaluminum
20
may be converted to useful products.
essentially in the absence of ethylene under the following
While particular embodiments of the invention have
conditions:
been described, it will be understood, of course, that the
invention is not limited thereto, since many modi?cations
Propene to triethylaluminum mole ratio_____.
2-10
may be made; and it is, therefore, contemplated to cover
Pressure (p.s.i.g.) ______________________ __ 100-2,000
by the appended claims any such modi?cations as fall 25 Temperature (° C.) ____________________ __ 100-180
within the true spirit and scope of the invention.
to yield a product mixture comprising hydrocarbons and
alkylaluminum compounds, said mixture being substan
tially free from n-pentenes, and recovery of 2-methyl-1
1. A process for the production of 2-methyl-1-butene
and trialkylaluminum compounds of the general formula: 30 butene from said product mixture.
The invention having thus been described, what is
claimed and desired to be secured by Letters Patent is:
9. In a continuous process for manufacture of Z-meth
yl-l-butene, the steps of reacting propene with triethyl
aluminum essentially in the absence of ethylene under the
following conditions:
where R, R’, and R" represent alkyl radicals containing
35
from 5 to 100 carbon atoms, said process comprising the
Propene to triethylaluminum
mole ratio _____________ _. 0.36-10.4
following steps:
Pressure (p.s.i.g.)______.._-_ Above about 525
(a) reaction of propene with triethylaluminum essen
Temperature (° C.) _______ ... About 135-about 185
tially in the absence of ethylene at a temperature
Reaction time ____________ _. About 20 sec-about 3 hr.
below 200° C. where decomposition of triethylalumi 40 to yield a product mixture comprising hydrocarbons and
num does not occur, at a pressure of IOU-2,000
alkylaluminum compounds, said mixture being substan
tially free from n-pentenes, and recovering 2-methyl~1
p.s.i.g. and in the ratio of about 0.3 to about 10 moles
of propene per mole of triethylaluminum to form a
butene from said product mixture.
10. 1In a continuous process for manufacture of 2-meth
product mixture comprising hydrocarbons and alkyl
aluminum compounds, said mixture being substan~
tially free from n-pentenes,
yl-l-butene, the steps of reacting propene with triethyl~
aluminum essentially in the absence of ethylene under the
(b) distillation of the product mixture to recover there
following conditions:
from 2-methyl-1-butene, propene, propene dimer, and
Propene to triethylaluminum mole
an alkylaluminum residue,
ratio ____________________ _- Approx. 2-8
(c) reaction of said alkylaluminum residue with ethyl 50
Pressure (p.s.i.g.) ___________ _. Above about 700
ene to yield a product mixture containing higher
molecular weight trialkylaluminum compounds.
Temperature (° C.) _________ _. From about 135 to
about 160
2. The process of claim 1 wherein step (a) is conducted
under the following conditions:
Propene to triethylaluminum mole ratio_..__..
55
Reaction time ______________ _. From about 30 min. to
about 2.3 hr.
2-10
to yield a product mixture comprising hydrocarbons and
100-2,000
Pressure, p s i g
alkylaluminum compounds, said mixture being substan
Temperature, ° C ______________________ __
100-180
tially free from n-pentenes, and recovering 2-methyl-1~
3. The process of claim 1 wherein step (a) is conducted
60 butene from said product mixture.
under the following conditions:
Propene to triethylaluminum mole ratio_____
Pressure, p s i g
3-8
__ ZOO-1,000
Temperature, ° C ______________________ __
100-180
4. The process of claim 1 wherein step (a) is conducted
under the following conditions:
2-10
Propene to triethylaluminum mole ratio_____
Pressure, p s i g
Temperature, ° C ______________________ __
100-2,000
100-180
and wherein step (c) is conducted under the following
conditions:
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,695,327
2,699,457
Ziegler et a1 ___________ .... Nov. 23, 1954
Ziegler et al. __________ .. Jan. 11, 1955
2,863,896
2,889,385
Johnson ______________ __ Dec. 9, 1958
Cotterall et al __________ __ June 2, 1959
OTHER REFERENCES
'Coates: Organo-Metallic Compounds, Methuen’s Mono
graphs on Chemical Subjects, London 1956, pp. 77-78.
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