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Патент USA US3091663

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Unite States i‘ atent 0
Patented May 28, 1963
which react only slowly with alkali metals in the presence
of diole?ns. In principle, it is possible to use chlorides,
bromides and iodides, although it is preferred to employ
the chlorine compounds. Halogenated hydrocarbons of
the aforementioned type suitable for employment in the
process according to the present invention are aliphatic
Josef Nograrli, Cologne-Stammheim, Germany, assignor
to Farbenfabriken Bayer Aktiengesellschaft, Leverku
sen, Germany, a corporation of Germany
N0 Drawing. Filed Dec. 22, 1959, Ser. No. 861,222
Claims priority, application Germany Dec. 24, 1958
7 Claims. (Cl. 260-6815)
The present invention relates to a process for purifying
conjugated diole?ns.
primary halogenated hydrocarbons such as, for example,
ethyl iodide, n-butyl chloride, butyl bromide, primary iso
butyl chloride, primary isobutyl bromide, n-hexyl bro
mide, n~hexyl chloride, n-octyl bromide, n-octyl chloride,
dodecyl bromide, dodecyl chloride, n-octadecyl chloride,
cycloaliphatic halogenated hydrocarbons such as cyclo
hexyl chloride, cyclohexyl bromide, l-chloro-tetra'hydro
It is essential to employ extremely pure monomers
naphthalene, l-chloro-decahydronaphthalene, araliphatic
when conjugated diole?ns, such as butadiene, i-ts homo
halogenated hydrocarbons such as benzyl chloride, benzyl
logues and derivatives, are polymerized in the presence of
bromide, ?-chloro-ethyl-benzene or polyhalogen hydro
an alkali metal, alkali-metal organometallic compound or
carbons such, for example, as 1,4-dichlorobutane, 1,1,2
an organometallic complex catalyst. The presence in the
trichloroethane, benzal chloride, and benzal bromide.
monomers of impurities which react with the catalysts and
The choice of the actual halogen compound employed
render them ineffective, is particularly disturbing. Such
20 depends on the reactivity of the diole?n to be puri?ed
impurities are usually present in very small amounts and
towards polymerization and also on the recovery process
include inter alia water, cyclopentadiene, acetylene, acet
which is provided. Since the puri?ed conjugated diole?n
ylene derivatives and compounds containing oxygen,
must be absolutely free from halogen compounds, which
[nitrogen and sulphur such as aldehydes and alcohols.
would have an unfavorable effect on the polymerization
»It is known to purify monomeric conjugated diole?ns
of the diole?n, it is essential that the halide should be
by treating them with alkali metals, such as ?nely divided 25 carefully separated out. To facilitate separation of the
sodium, followed by distillation. An important disad
halide from the puri?ed diole?n, it is therefore preferred
vantage of this method of puri?cation is that unavoid
to employ relatively nonvolatile higher aliphatic chlorine
able and more or less extensive polymerization of the
compounds, such as dodecyl chloride and n-octadecyl
diole?n takes place resulting not only in losses of mono
chloride in the puri?cation thereof. However, by suitable
mer, but the purifying operation is also made imprac 30 careful fractionation it is also possible to use low-boiling
ticable from a commercial point of view due to the
halides, such as butyl chloride, hexyl chloride, cyclohexyl
polymer which collects in the apparatus.
chloride and benzyl chloride.
It is an object of the present invention to provide a
The halogenated hydrocarbons or mixtures thereof can
very effective and adequate puri?cation process for con 35 be combined with any alkyl metal such as, for example,
jugated diole?ns, especially those of the butadiene series.
lithium, sodium, potassium, their alloys, i.e., any desired
It is a further object of this invention to suppress large
alloy of the alkali metal with one another or with alka
ly the polymerization of conjugated diole?ns during the
line earth metals, although sodium and lithium are pre
ferred from ‘an economic point of view. These alkali
puri?cation thereof.
It is a further object of this invention to provide con— 40 metals may be employed in ?nely divided form, i.e., a
jugated diole?ns of such a degree of purity that a sub
particle size of 1 mm. in diameter and less, advanta
stantially shorter latent or induction period is observed
geously from 20 to 100 microns, produced by stirring
in the polymerizaiton of the conjugated diole?n.
According to the present invention a puri?cation of
conjugated diole?ns, especially those of the butadiene
the metal in a suitable high-boiling solvent such as tolu
ene, xylene, p-ara?in, petroleum, etc., above its melt
ing point in usual manner. Preferably these ?nely di
series, without the above mentioned disadvantages can 45 vided alkali metals are employed in the form of a sus
be effected if the puri?cation is carried out with alkali
metals in the presence of organic halogenated hydro
pension in a ‘high-‘boiling hydrocarbon, such as the afore
mentioned, or in the form of a paste with Vaseline. In
this way they can be easily handled and measured in a
This discovery was particularly surprising, because it
simple and relatively safe manner.
is known from German Patent No. 524,668 that diole?ns 50
The process of the present invention may be employed
can be polymerized with the aid of alkali metals in the
in the puri?cation of aliphatic conjugated diole?ns, pref
presence of small quantities of organic halogen com
erably those containing 4 to 8 carbon atoms, such as
pounds, these quantities being below the equivalence value.
The process according to the present invention on the
butadiene, 2 - methyl - butadiene, 2,3 - dimethylbutadiene,
hexadiene-(l,3), hexadienea(2,4) and the like.
other hand makes it possible almost completely to prevent 55 The quantity of alkali metal usually employed in this
the polymerization of the diole?ns by using preferably
approximately equivalent quantities of halogenated hydro
puri?cation process is from 0.1 to 5 parts by weight,
based on one hundred parts by weight of the monomer
to be puri?ed.
The halogenated hydrocarbons or mixtures thereof em
The quantity of the halogenated hydrocarbon employed
ployed in the process according to the present invention 60 depends on the quantity of the alkali metal utilized. In
may be aliphatic, cycloaliphatic or araliphatic halogenated
practice it will generally be found to be satisfactory to
hydrocarbons containing one or more halogen atoms.
These halogenated hydrocarbons contain halogen atoms
in primary or ‘secondary aliphatic bonding. Hydrocar
employ the halogenated hydrocarbon and alkali metal
in at least equivalent amounts, that is to say in amounts
65 according to which at least one halogen atom is present
bons containing aromatic bonded halogen are not effective.
per atom of alkali metal. It is preferred to use such
Further the halogenated hydrocarbons should be sat
amounts of halogenated hydrocarbons that one to two
urated, except that such hydrocarbons may contain sub
halogen atoms are present per atom of alkali metal, al
stituent aromatic radicals. Those halogenated hydro
carbons are preferred in which the halogen atoms are
connected to primary carbon atoms. The latter com
pounds in general are compounds which do not react or
though also higher amounts may be applied in special
cases. The quantity of halogenated hydrocarbon em
ployed also depends on the activity of the halogenated
For example, with halogenated hydro
crons) and 4.5 parts of dodecyl chloride are boiled under
carbons of high activity, such as aliphatic primary halo
re?ux in an argon atmosphere for 8 hours in a distilla
gen-containing hydrocarbons, equivalent quantities are
tion apparatus. Thereafter, substantially all of the iso
prene is distilled off and used for polymerization.
The temperature at which the puri?cation of the con
jugated diole?n is carried out and the time necessary for
part of lithium butyl is suf?cient for the polymerization
of 100 parts of the isoprene thus puri?ed, the polymeriza
puri?cation depend on the reactivity of the conjugated
tion being carried out in known manner. The polyiso
diole?n being puri?ed. For example, with a very re
prene thereby obtained at 25° C. has a limiting intrinsic
active diole?n, a low temperature and a relatively short
viscosity 1;:531 (measured in chlorobenzene).
reaction time is necessary. The puri?cation process may 10
The distillation residue resulting from the puri?cation
be performed at room temperature or at an elevated
of the isoprene is unchanged and still thinly liquid. After
temperature. In order to obviate polymerization of the
conjugated diole?n, it is preferred to carry out the puri
?cation at a temperature above 0° C., not exceeding
adding isopropyl alcohol to the distillation residue, no
polymer precipitates; only a small quantity of ?nely
divided salt remains undissolved in the alcohol.
In most cases, reaction times of from 4 to 24 15
By comparison therewith, 100 parts of isoprene was
80° C.
hours and temperatures of from 35 to 60° C. are suffi
treated in a similar manner with 0.5 part of ?nely di
cient. However, a high-boiling diole?n, such as phenyl
vided sodium without adding dodecyl chloride and at
the re?ux temperature of the isoprene. The puri?cation
butadiene, may necessitate the employment of higher
temperatures It is true that higher temperatures acceler
was stopped after 4 hours due to commencement of
ate the. puri?cation, but an upper temperature limit is 20 polymerization of the isoprene. The isoprene was dis
nevertheless set by the thermal polymerization which
tilled off from the residue which gradually became a
takes place and the losses of monomer which are caused
more viscous liquid. At least 0.1 part of lithium butyl
thereby, for instance, an upper temperature limit is given
was required to polymerize 100 parts of the isoprene
in purifying butadiene at about 90° C. or isoprene at
thus puri?ed. The polyisoprene thereby obtained at 25°
about 100° C.
25 C. had an intrinsic viscosity 11=2.l5 (measured in chlo—
The puri?cation of conjugated diole?ns when using the
aforementioned combinations may be carried out either
Isopropyl alcohol was added to the viscous liquid dis
continuously or intermittently. For example, the mono
tillation residue resulting from the puri?cation of the
mers‘ may be heated with the previously described com
isoprene to destroy the sodium. As a result, copious
binations of alkali metals and halogenated hydrocarbons 30 quantities of a soft rubber-like polymer precipitated.
in a conventional distillation apparatus equipped with a
The polymer was washed with methanol and dried in
supplementary re?ux condenser until the impurities have
vacuo at 50° C. It weighed 9.8 g.
been rendered harmless. The sequence of adding the
Example 2
alkali metal and halogenated hydrocarbon to the con
jugated diole?n to be puri?ed is unimportant. They
1000 grams of butadiene, containing impurities of
should not, however, be added simultaneously or mixed
oxygen, peroxides and oc-acetylenes, are contacted in a
with one another. The halogenated hydrocarbons may
6000 cc. steel autoclave with 10 grams of ?nely divided
be added to the conjugated diole?ns undiluted or diluted
sodium and 39.6 grams of butyl chloride during 4 hours
with suitable inert solvents such as, for example, satu
at a temperature of 35° C. After this time, butadiene
rated aliphatic, cycloaliphatic or aromatic hydrocarbons 40 is distilled off and fractionated by an elfective column
such as pentane, hexane, heptane, isooctane, paraffin oil,
with external cooling. The butadiene puri?ed in this
hydrogenated diesel oil and the like, cyclohexane, methyl
manner shows a substantially shortened induction period
cyclohexane, benzene, toluene, xylene and the like.
in polymerization when compared with butadiene puri
?ed by known methods.
The course or progress of the puri?cation may be con
trolled advantageously by gas-chromatography methods.
The separation of the monomer from the reaction mix
ture is generally effected by fractional distillation, the
degree of fractionation depending on the volatility of the
particular halide employed.
Example 3
100 parts of commercial isoprene (95%) are heated
for 6 hours under re?ux together with 1 part of ?nely
divided (particle size<l mm.) sodium (33% in Vaseline)
In a preferred embodiment of the present puri?cation 50 and 13 parts of cyclohexyl bromide. The isoprene ob
tained after distillation polymerizes extremely easily at
process, the air (especially oxygen) in the apparatus
low temperatures after adding an organometallic catalyst.
should as far as possible, be displaced by ?ushing with
The distillation residue contains no polymeric material.
an inert gas, such as nitrogen, argon, krypton, xenon or
inert gaseous hydrocarbon such as methane, ethane, eth
Example 4
ylene and the like.
isoprene (95%) are con
The diole?ns puri?ed by the process according to the
tacted during 4 hours at 70° C. under pressure with 0.5
present invention polymerize in some cases with an ex
part of ?nely divided lithium and 8.8 parts of 1,4-di
ceptionally short latent or induction period and require
the use of smaller quantities of polymerization catalyst
The isoprene which is obtained after distillation re
and yield polymers of higher molecular weight than di
quires in polymerization smaller quantities of polymeri
ole?ns which have not been so puri?ed.
The extent of these improvements, however, depends
largely on the duration and the temperature of the pre
treatment with alkali metals. in the case of the known
process, a limit is soon set because of the polymeriza~
tion which occurs. It is only the addition of the halo
zation catalyst, for example, lithium butyl, and shows
a substantially shorter induction period.
What is claimed is:
1. A process for the puri?cation of a conjugated di
ole?n without the formation of substantial amounts of
diole?n polymers which comprises contacting the con
genated hydrocarbons which permits the time and the
jugated diole?n at a temperature between about 0° and
temperature of the pre-treatment to be so increased that
about 80° C., in the absence of oxygen, with an alkali
advantages such as hitherto were not possible are ob
70 metal in an amount between 0.1 and 5 parts by weight
tained as regards the aforementioned properties.
In the following examples all parts are by Weight.
Example I
per hundred parts by weight of the conjugated diole?n,
together with a halogen-substituted hydrocarbon of the
group consisting of chlorine-substituted and bromine
substituted araliphatic hydrocarbons free from nonben
100 parts of normal commercial isoprene (95%), 0.5 75 zenoid halogen substituents, and chlorine-substituted and
part of ?nely divided sodium (particle size 20—100 mi
bromine-substituted saturated aliphatic and cycloaliphatic
6. A process for the puri?cation of isoprene which
hydrocarbons, in such an amount that the ratio of atoms
comprises heating approximately 100 parts by weight of
of the halogen in the halogen-substituted hydrocarbon to
isoprene at a temperature between 35 and 80° C. in con~
atoms of the alkali metal is between 1:1 and 2:1, and
tact with between 0.1 and 5 parts by weight of ?nely
divided sodium and an amount of cyclohexyl bromide
subsequently recovering the puri?ed conjugated diole?n.
2. A process as de?ned in claim 1 in which the alkali
such that at least one atom of halogen of the cyclohexyl
bromide is present for each atom of sodium, and there
metal and halogenated hydrocarbon are contacted with
the conjugated diole?n at a temperature between 35 and
after distilling off the puri?ed isoprene.
7. A process for the puri?cation of isoprcne which
60° C.
3. A process as de?ned in claim 1 in which the halo
comprises heating approximately 100 parts by Weight of
genated hydrocarbon is a saturated aliphatic chlorinated 10 isoprene at a temperature between 35 and 80° C. in con
hydrocarbon in which the chlorine atom is connected to
tact with between 0.1 and 5 parts by weight of ?nely
a primary carbon atom.
4. A process for the puri?cation of isoprene which
comprises heating approximately 100 parts by weight of
isoprene at a temperature between 35 and 80° C. in con
tact with between 0.1 and 5 parts by weight of ?nely
divided sodium and an amount of dodecyl chloride such
that at least one atom of halogen of the dodecyl chloride
is present for each atom of sodium, and thereafter dis
tilling oif the puri?ed isoprene.
5. A process for the puri?cation of butadiene which
comprises heating approximately 100 parts by Weight of
butadiene at a temperature between 35 and 80° C. in
contact with between 0.1 and 5 parts by weight of ?nely
divided sodium and an amount of butyl chloride such 25
that at least one atom of halogen of the butyl chloride is
present for each atom of sodium, and thereafter distill
ing off the puri?ed butadiene.
divided lithium and an amount of 1,4-dichlorobutane
such that at least one atom of halogen of the 1,4-dichlo
robutane is present for each atom of lithium, and there—
after distilling off the puri?ed isoprene.
References Cited in the ?le of this patent
Ebert et al. ___________ __ Aug. 8,
Soday _______________ __ Apr. 23,
Ziegler et al. _________ __ Jan. 11,
Burke _______________ __ June 25,
Pines et a1 ____________ __ Aug. 27,
Germany _____________ __ May 11, 1931
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