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Патент USA US2406674

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2,406,674
Patented Aug; 27, 1946
. UNITED, STATES PATENT OFFICE '
William John Roy Evans, Manchester, England, ’
assignor to Imperial Chemical’ Industries Lim
ited, a corporation of Great Britain
"No Drawing. Application November_9,.1944,>Se
rial No. 562,736. In Great. Britain November
22, 1943
1'5 Claims. (Cl. 2609-614‘)
1
This invention relates to improvements in the
manufacture .of n-butyl vinyl. ether, more par
ticularly to improvements in the manufacture of
this vinyl ether from acetylene and n-butyl alco
hol.
It is known that vinyl ethers may be obtained
by reacting acetylene and alcohols in the presence
of basic substances which act as catalysts during
the reaction, for example, potassium- alkoxides.
However, such processes usually requirefthe use
of high pressures and are accompanied by the
hazards necessarily associated with the use of
acetylene at high pressures.
,
or tertiary amine.
2
The mixture is heated in a
reaction vessel'for example, at 150-180" C‘., under
conditions such that the presence of oxygen is
avoided, as by passing a stream of an inert gas
such as nitrogenthrough the liquid. Acetylene
gas. and the alcohol in vapour form are then
passed thrugh the liquid, for example, at a pres
sure. of 2-5 lbs. per square inch, the liquid prefer
ably being maintained at about 170-190° C‘. The
issuing vapours are fractionated and condensed,_
and the ether, which is in the condensate, is col
lected and, if desired, puri?ed by conventional
means.
7
.
The invention is illustrated but not limited by
acetylene and alcohols at ordinary pressures by 15 the following example, in which parts are ex
pressedby weight.
interacting them in the presence of basic sub
stances, for example, potassium alkoxides, and in
the presence of liquids, for example liquid para?in,
13 parts of potassium are dissolved in 60 parts
which boil at temperatures higher than the re
action temperature. Although working in accord 20 of ,nebutyl'alcohol and 0.5 part of N‘:N'-diphenyl
p-phenylene-diérmine and 75 parts of diethylani
ance with this proposal obviates the hazards in
line are added. This solution is then transferred
volved in using acetylene at highv pressures, ex
to a reaction tower, which is ?tted with a frac
periments show that, under such conditions, the
tionating column with dephlegmator control and
life of the catalyst is short.
‘
It has now been found that, when vinyl n-butyl 25 a _means for condensing vapours which pass
through the‘ column, vthe tower containing 865
ether is made by reacting acetylene and n-butyl
parts of di'ethylaniline at a temperature of 160° C.
alcohol at ordinary pressure with a potassium al
through which a ‘stream of dry nitrogen‘i's pass
koxide as the catalyst, the use of secondary or ter
ing. The temperature. is raised to 180'-190° 0.,
tiary aromatic amines, as high boiling media for
and-‘the nitrogen: ?ow reduced gradually to zero
the reaction, greatly lengthens the life of the cat
whilst‘a mixture of n-butyl alcohol at 200 parts
alyst and also appreciably enhances its activity.
per hour and acetylene at 35 parts per vhour,
Thus, according to the present invention there
preheated to 180° C., is fed at a pressure above
is provided a process for the manufacture of n
atmospheric pressure into the base of the tower
butyl vinyl ether which comprises bringing acetyl
ene and n-butyl alcohol into contact with a po 35 through a gas distributor. A mixture of Vinyl-n
butyl ether, n-butyl alcohol and acetylene passes
tassium alkoxide dissolved or suspended in a me
from the top of the tower to the base of a frac
dium consisting solely or mainly of a secondary
tionating column. The n-butyl alcohol returns
or tertiary aromatic amine at pressure not sub
to the reaction tower, while the azeotropic mix
stantially greater than atmospheric and at a tem
40 ture of Vinyl-n-butyl ether and n-butyl alcohol,
perature of about 150-2005 C.
89% ether-11% alcohol, (or a weaker mixture ac
As secondary or tertiary aromatic amines there
cording to the control exercised in the column)
may be used, for example, methylaniline, di
passes out of head of the column and is condensed
methylaniline, ethylaniline, diethylaniline, ben
and collected. The production of the ether ini
zylaniline and dibenzylaniline.
As catalyst it is preferred to use potassium n 45 tially is 157 parts per hour; it is 94 parts per hour
after 6 hours and 63 parts per hour after 71/2
butyl alkoxide.
‘
hours. The ether may be puri?ed by long re?ux
The reaction is preferably effected in an atmos
ing over sodium followed by fractional distillation.
phere free from oxygen.
The conversion of acetylene is 50-60% per single
Preferably an antioxidant, for example, N:N'
diphenyl-p-phenylenediamine, is included with 50 passage.
When production falls to an uneconomic rate,
the reagents.
spent catalyst, which comes out of solution,
In a convenient way of operating the process
may be settled and withdrawn from the tower,
of the invention the alkoxide dissolved in some of
while fresh catalyst solution may be added to the
the alcohol which is to be converted into the ether
is added to a large proportion of the secondary 55 tower, thus making. the process continuous.
It has been proposed to make vinyl ethers from
'
'
'
Ear-ample
2,406,674
3
4
Using kerosene, which has been distilled over
potassium, in place of the diethylaniline the pro
duction of ether initially is about 60 parts per
hour and the catalyst is expended after 3 hours’
7. Process for the manufacture of vinyl n-butyl
ether, which comprises interacting acetylene and
n-butyl alcohol in the presence of a potassium
alkoxide in diethylaniline.
8. Process for the manufacture of vinyl n-butyl
working“
I claim:
'
l
ether, which comprises interacting acetylene and
"
n-butyl alcohol in the presence of potassium
n-butoxide in diethylaniline.
1. Process for the manufacture of vinyl n-butyl
ether, which comprises bringing acetylene and.
n-butyl alcohol into contact with a potassium
‘ 9. Process for the manufacture of vinyl n-butyl
alkoxide in a medium composed at least mainly 10' ethenwhich comprises interacting acetylene and
n-butylyalcohol in the presence of a potassium
of an amine selected from the group consisting
‘ alkoxide and N : N’-diphenyl-p-phenylenediamine.
of secondary and tertiary aromatic amines, at a
10. Process for the manufacture of vinyl n
temperature of ISO-200° C.
'
butyl ether, which comprises interacting acet
2. Process for the manufacture of vinyl n-butyl
ylene and n.-butyl alcohol in the presence of a
ether, which comprises bringing acetylene and
n-butyl alcohol into contact with potassium
potassium alkoxide and N:N'-diphenyl-p-phen
n-butoxide in a medium composed at least main
ly of an amine selected from the group consist
ylenediamine at a pressure of ‘700-900 mm. and
at a temperature of 150—200° C.
11.' Process for the manufacture of vinyl n
ing of secondary and tertiary aromatic amines,
at a temperature of 150-200" C.
20
butyl ether, which comprises interacting acetyl
ene and n-butyl alcohol in the presence of a po
tassium alkoxide in diethylaniline under an at
3. Process for the manufacture of vinyl n-butyl
ether, which comprises bringing acetylene and
n-butyl alcohol into contact with a potassium
mosphere free from oxygen.
12. Process for the manufacture of vinyl n
alkoxide and an antioxidant in a medium com
posed at least mainly of an amine selected from 25 butyl ether, which comprises interacting acetyl
ene and n-butyl alcohol in the presence of po
the group consisting of secondary and tertiary
tassium n-butoxide in diethylaniline under an
aromatic amines, at a temperature of 150-200° C.
atmosphere free from oxygen. ‘
4. Process for the manufacture of vinyl n-butyl
13. Process for the manufacture'of vinyl n~
ether which comprises bringing acetylene and n
butyl alcohol into contact with potassium n-bu 30 butyl ether, which comprises interacting acetyl~
ene and n-butyl alcohol in the presence of a
toxide and an antioxidant in a medium composed
potassium alkoxide and NINf-diphenyl-p-phen
at least mainly of an amine selected from the
ylenediamine in an atmosphere from from oxy
group consisting of secondary and tertiary aro
gen.
'
matic amines, at a pressure of 700-900 mm. and
at a temperature of ISO-200° C.
35
5. Process for the manufacture of vinyl n-butyl
ether, which comprises bringing acetylene and
n-butyl alcohol into contact with a potassium
14‘. Process for the manufacture of vinyl n
butyl ether, which comprises interacting acetyl
ene and n-butyl alcohol in the presence of potas
sium n-butoxide and N :N’-‘dipheny1-p—pheny1
alkoxide and N:N’-diphenyl-p-phenylenediamine
enediamine at a pressure of 700-900 mm. at the
in a medium composed at least mainly of an 40 temperature of vli’50--200° C. under an atmosphere
free from oxygen.
amine selected from the group consisting of sec—
ondary and tertiary aromatic amines, at a tem
15. Process for the manufacture of vinyl n
'
butyl ether, which ‘comprises interacting acetyl
' 6. Process for the manufacture of vinyl n-butyl
ene and n-butyl alcohol in the presence of potas
perature of 150-200° C.
ether which comprises bringing acetylene and 45 sium n-butoxide and N:N'-diphenyl-p-phenyl
enediamine in diethylaniline at a pressure of
n-butyl alcohol into contact with potassium n
butoxide and N:N'-diphenyl-p-phenylenedi
150-200° C. imder an atmosphere free from oxy
amine in a medium composed at least mainly of
an amine selected from the group consisting of
secondary and tertiary aromatic amines, at a
temperature of 150-200“ C.
‘
gen.
WILLIAM JOHN ROY EVANS.
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