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Патент USA US3028449

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United States Patent Oiiice
Fatented Apr. 3, 1962
Although a conventional emulsifying agent having a
molecular weight in the range of 264 to 4000 can be used
in the instant process, the preferred emulsifying agent
is a Tergitol.
Louis F. Theiiing, J23, Charleston, and Joseph F. Lacount,
South Charleston, W. ‘Va., assignors to Union Carbide
Tergitol is a trademark of Union Car
bide Chemicals Company for its surface active agents.
There are two general types of these agents, anionic and
nonionic. The anionic type are sulfates or phosphates
of the C8 to C17 alcohols. The nonionics are ethylene
‘Corporation, a corporation of New York
No Drawing. Filed Mar. 23, 1960, ?er. No. 16,914
5 Claims. (Cl. 260M454)
oxide adducts of nonyl phenol, 2,6,8-trimethyl-4-nonanol,
This invention relates to a novel method for the pro
10 and a butanol and ethylene oxide-propylene oxide ad
duct. The molecular Weight range of the nonyl phenol
duction of 1,2,3-trichloropropene.
adducts is 396-4100, that of the nonanol adduct is about
More speci?cally, the invention is concerned with the
264 and that of the butanol adduct is from 2820 to 3414.
dehydrochlorination of 1,2,2,3-tetrachloropropane to ob
The term nonyl phenol is intended to mean a mixture
tain 1,2,3-trichloropropene.
The object of this invention is to provide an e?icient 15 of alkylated phenols whose substituents on the aromatic
ring are predominately mixed ortho and para-isomers.
economical process by which 1.2,2,3-tetrachloropropane
The alkyl side chain. of which is a mixture of branched
isomers containing a varying number of carbon atoms
can be converted to 1,2,3-trichloropropene.
The above object is accomplished by conducting the
(C8, C9, C10) with the C9 predominating.
dehydrochlorination in the presence of an emulsifying
A particularly preferred class of the above surface
active agents are those having a molecular weight range
of 525-975.
The amount of emulsifying agent used is about 0.1 to
about 10 percent by weight based on the 1,2,2,3-tetra
chloropropane. The preferred range is 0.5 to 5 weight
1,2,3-trichloropropene is not a new compound. It is
wel known in the art. The method of making the above
compound by dehydrochlorination of 1,2,253-tetrachloro
propane is also known in the art.
The methods previously employed for dehydrochlo
rination of l,2,2,3-tetrachloropropane included the use
of aqueous sodiumhydroxide, the use of aqueous sodium
The dehydrochlorinating agents employed are the
alkali metal and the alkaline earth metal hydroxides.
hydroxide and methanol, the use of sodium hydroxide
Speci?c examples include lithium hydroxide, sodium hy
and dioxane, and the use of methylethylpyridine residues.
However, theseirnethods of effecting the reaction had 30 droxide, potassium hydroxide, calcium hydroxide, barium
hydroxide‘ and strontium hydroxide. The preferred re
at least two serious disadvantages. Poor conversion of
agent. is sodium hydroxide.‘
1,2,2,3-tetrachloropropane and/or low, efficiency to the
The temperature at which the reaction is conducted
trichloropropene were obtained. Also, the crude reac—
is not narrowly critical. The preferred range is from
tion product frequently contained large amounts of im
purities which could not be easily removed by re?ning. 35 about 100 to 140° C. at atmospheric pressure, although
the kettle temperature may vary during the reaction. In
Surprisingly, the above disadvantages have been found
a preferred embodiment of the invention, not only is the
to be obviated when the dehydrochlorination is con
kettle temperature controlled, but the vapor temperature
ducted in the presence of an emulsifying agent. The
is alsoregulated. At atmospheric pressure, the vapor
reaction proceeds at a rapid rate and the conversion of
the 1,2,2,3-tetrachloropropane to 1,2,3-trichloropropene 40 temperature is maintained from about 93 to about 95°
C. during re?ux. It has been found that this range gives
is higher than any of the known prior art methods. Ad
the highest efficiency.
ditionally, the crude reaction product can be re?ned
The reaction can be conducted by mixing all the re
with comparative ease.
agents together and re?uxing, by adding the l,2.2,3-tet1'a
The following table illustrates the comparison of the
prior art methods with the method of the instant in 45 chloropropane to re?uxing aqueous hydroxide containing
the emulsifying agent or by the gradual addition of the
hydroxide to a mixture of the emulsifying agent and the
1,2,2,3-tetrachloropropane. The latter method is the pre
Preparation of 1,2,3—Trichloropropene—Pr0ducti0n
From 1,2,2,3-Tetrachloropropane
Dehydrohalogcnating Conversion,
Temp, “0.
NaOH° ___________ -_
89. 6
29. 4
47. 9
53. 6
The preferred range is 0.05 to 0.1
The concentration of the aqueous hydroxide solution
16. 04
In this method, the hydroxide is added in
mole per hour.
to 3GP,
Basis 1
OH’ ___________ __
ferred one.
50 the range of 001-05 mole per hour per mole of
employed is not narrowly critical. ' The preferred con
55 centration is from about 20 to about 50 percent by
In order to obtain the maximum e?iciency to 1,2,3
trichloropropene it is desirable to remove the crude prod
uct as rapidly as it is formed. This is done to prevent
60 the dehydrochlorination of the 1,2,3-trichloropropene to
form 1,3-dichloropropyne. This removal can be accom
plished by any conventional manner such as distillation.
1401’ is tetrachloropropane and 30? is trichloropropene.
1 Tctrachloropropane and sodium hydroxide were re?uxed for six hours.
51A ten percent excess of equal weights of 50 percent sodium hydroxide
and methanol fed to tetrachloropropane over a two-hour period.
4 Tetrachloropropane was fed to 400 methylethylpyridine residues
(catalyst) at the rate of 487 grams per hour per liter of methylethylpyri
dine residue.
lA ten percent excess of equal weights of 50 percent sodium hydroxide
and dioxane added to tetrachloropropane and re?uxed for five hours.
6Aqueous 20 percent sodium hydroxide fed to tetrachlorcpropane
containing one weight percent Tcrgitol, at the rate of 140 g. per hour
per liter of tetrachloropropane and allowed to re?ux for one hour.
It can be seen that the use of an emulsifying agent
gives e?iciencies which are surprisingly better than the
previously known methods.
The following examples are illustrative of the instant
625 grams of 1,2,2,3-tetrachloropropane and 6.3
grams of Tergitol NP-35 (an ethylene oxide adduct of
nonyl phenol with a molecular weight of about 880) was
charged to a 2-liter kettle equipped with a sealed me
chanical stirrer, therm-owell, and sodium hydroxide feed
The kettle was placed on a IS-theoretical plate
column which was equipped with a decanting still head.
and receiver system. The receiver system was vented
through cold traps.
The kettle contents were heated to 120° C. with stir
of water-trichloropropene azcotrope and re?ned as in
Example 1. Conversion of tetrachioropropane was 66
percent and ei?ciency to trichloropropene was 83 per
cent based on tetrachloropropane.
We claim:
ring and aqueous 20 percent sodium hydroxide fed at the
1. In the dehydrochlorinatlon of 1,2,2,3-tetrachloro
rate of 140 grams ‘per hour per liter of tetrachloropro
propane to obtain 1,2,3~trichloropropene in the presence
pane. After re?uxing for an hour, 1,2,3-trichloropropene
of an aqueous solution of hydroxides selected from the
was removed as lower layer of the water-trichloropro
group consisting of alkali metal hydroxides and alkaline
pen-e azeotrope. The vapor temperature ranged from
93-94“ C. during the reaction. The mole ratio of tetra 10 earth metal hydroxides, the improvement which com
prises carrying out said dehydro-chlorination in the pres
chloropropane to total sodium hydroxide fed Was about
ence of an emulsifying agent having a molecular weight
of 264 to 4900 said emulsifying agent being selected
The crude 1,2,3-trichloropropene was re?ned on a 15
from the group consisting of sulfates of alcohols which
theoretical plate column. Cis- and trans- isomers or
produced in the process in almost equal amounts. The 15 have from 8 to 17 carbon atoms, phosphates of alcohols
which have from 8 to 17 carbon atoms, ethylene oxide
trichloropropeue fraction was collected from 775-91“
adducts ‘of nonyl phenol, ethylene oxide adducts of 2,6,8
C. at 120 mm. Hg. Speci?c gravity of the fraction was
trirnethyl-4-nonanol and ethylene oxide-propylene oxide
1.41 at 26/156" C. Conversion of tetrachloropropane
adducts of butanol.
Was 63.2 percent and e?iciency to trichloropropene was
2. The process of claim 1 in which the emulsifying
86.5 percent based on tetrachloropropane.
is an ethylene oxide adduct of nonyl phenol having
a molecular Weight from 396-1100.
418 grams of 1,2,2,3-tetrachlorop-ropane, 195 grains
3. The process of claim 1 in which the emulsifying
of 50 percent aqueous sodium hydroxide, and 19 grams
agent is present in the range of 0.1 to 10 percent by
of Tergitol E-68 (Tergitol Nil-35 which has been etheri 25 We'ght, based on the l,2,2,3-tetrachloropropane.
lied to remove the active hydrogen. The hydrogen has
4. The process of claim 1 in which the emulsifying
been replaced with an ethyl group to make a caustic
agent is present in the range of 0.5 to 5 percent by
stable surface active agent) were charged to the appara
Weight, based on the 1,2,2,3-tetrachloroprop-ane.
tus described in Example I and heated to 130° C. for
5. The process for the production of 1,2,3-trichloro
eight hours. 200 grams of water was added to the still 30 propene which comprises gradually adding an aqueous
kettle and the organic layer removed as lower layer of
solution of sodium hydroxide to a mixture of 1,2,2,3
the azeotrope. Conversion of tetrachloropropane was
tetrachloropropane and a nonyl phenol adduct of ethyl
72 percent and efficiency to 1,2,3-trichl0ropropene was
ene oxide having a molecular weight of 396-1100 main
76 percent based on tetrachloropropane.
tained at a temperature of 100~14~S° C., said adduct being
present in a concentration of 0.1 to 10 percent by Weight
based on the 1,2,2,3-tetrachloropropane maintaining the
1226 grams of 1,2,2,3-tetrachloroproplane and 13 grams
vapor temperature at 93—95° C. and removing the 1,2,3
of Tergitol NP~27 (an ethylene oxide adduct of nonyl
trichloropropene formed.
phenol with a molecular Weight of about 528) was
charged to the apparatus described in Example I and
References Clted in the ?le of this patent
heated to 140° C. Aqueous 20 percent sodium hydrox
ide Was fed at 155 grams per hour per liter of tetra
chloropropane charged.
Mole ratio of tetrachloropro
pane to total sodium hydroxide fed was about 1:1.
Crude 1,2,3-t1ichloropropene was removed as lower layer 45
Stros-acker et al. ______ __ June 22, 1943
Strosacker et a1. ______ __ Feb. 27, 1951
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