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Патент USA US3023234

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United- ‘States Patent '0 " "ice
Patented Feb. 27, 1962
As initial materials there are suitable polyhalogen
Ferdinand Meyer, Mannheim, and Kurt Demmler, Lud
wlgshaven (Rhine), Germany, assignors to Badische
Anilln- 8: Soda-Fabrik Aktiengesellschaft, Ludwigs
hafen (Rhine), Germany
vNo Drawing. Filed Apr; 23, 1956, Ser. No. 579,760v
1 Claim.
(Cl. 260-348.6)
This invention relates to an improved process for the
production of epoxy ethers from polyhalogenhydrin
ethers of saturated aliphatic polyhydric alcohols.‘
hydrin ethers of polyhydric aliphatic saturated alcohols,
such asv glycerine, butane-triol, pentaerythritol, tri
methylol propane, trimethylol ethers, hexamethylol ‘ethers
of melamine, sorbitol, dipentaerythritol and hexanetriol.
The polyhalogenhydrin ethers for example polybrom
hydrin_ or 'polychlorhydrin ethers of these polyhydric
alcohols are known and may be prepared in the usual
way, as for example by etheri?cation‘ by the action of
10 corresponding amounts of epoxychlorhydrin or dichlor
hydrin or the corresponding brom-compounds on all or
only part of the hydroxyl groups of the polyhydric alco
hol in the presence of.a catalyst, as for example boron
tri?uoride. Suitable polyhalogenhydrin ethers are espe
Epoxy ethers have heretofore been obtained by treat
ing monohalogenhydrin ethers of monohydric or poly 15 cially those which contain more than 2, as for example
2.1 to 3, halogenhydrin ether groups.
hydric alcohols with ‘aqueous solutions of compounds
having a strong basic action, as for example caustic
alkali or alkaline earth solutions, at reduced or normal,
Monohydric alcohols which. are suitable as solvents
and dissolve both the initial polyhalogenhydrin ether and
the epoxy compound formed are chie?y the saturated
temperature, and extracting the reaction mixture with
selective solvents, such as ether, hydrocarbons or carbon 20 primary, secondary or tertiary aliphatic alcohols, in par
ticular those of a medium number of carbon atoms, espe
This method cannot beused however in the ‘case of
. halogenhydrin ethers of polyhydric alcohols which con
tain more‘ than ‘one halogenhydrin ether group because
-- cially with 4 to 8 carbon atoms.
Suitable alcohols ‘are for example normal butanol,
normal amyl alcohol, secondary n-amyl alcohol, tertiary
in this case the quality of the end product is consider 25 amyl alcohol and ethylhexanol. The alcohols ‘should
only take up small amounts'of water, preferably 2 to
ably reduced by reason of hydrolysis and/or polymeriza
10% of weight, at the working temperatures. They may
tion of the epoxy compounds. ‘For the dehydrohalo
be separated well from the aqueous mother
genation of such halogenhydrin ethers there have there
liquor. The alcohols may also be used in admixture
fore been developed processes in which the splittingoil
is carried out with solid caustic soda 30 with each other or with an addition of other vwater-in
soluble organic solvents, as for example aromatic hy
alkali salts of amphoteric oxides, as
drocarbons, such as benzene or toluene. These water
alkali aluminate, silicate or zincate,
insoluble organic solvents should be indifferent, i.e. they
solvents which take up at least small
should not react under the reaction conditions either with
amounts of water being used as diluents. This method
of working is also unsatisfactory because relatively large 35 the initial materials or with the end products.
of hydrogen halide
in acetone or with
for‘ example‘ solid
dioxane or organic
amounts of solvent are required to carry it out and the
* The dehydrohalogenation of the polyhalogenhydrin
separation of the solid inorganic salts makes necessary I -- ethers according to this invention is preferably effected
by introducing an amount of an aqueous concentrated.
a further working operation; 'moreover‘the quality of
solution of a strong inorganic base which is at least
The object of this invention is to providev a process 40 equivalent to that required for binding the amount of
the compounds prepared 'i‘s‘not‘ entirely Satisfactory.
for the production of polyepoxy ethers of polyhydric
hydrogen halide split off, preferably a somewhat larger
alcohols in which the above-mentioned disadvantages are
avoided and the poly-epoxy ethers are obtained in a good
of the halogenhydrin ether in the inonohydric alcohol
amount, as for example up to 20% excess, to a solution
serving as solvent at temperatures of —20° to +30°
A further object is a process according to which the 45 C., care being taken for a good and thorough mixing
until the end of the reaction. The amount of alcoholic
hydrin compounds of polyhydric aliphatic alcohols with
solvent is preferably chosen so high that a good and
a plurality of halogenhydrin ether groups are converted
thorough mixing of the solution with the aqueous alkali
into the corresponding epoxy ethers and the latter may
solution is ensured. This can readily be ascertained by
be separated from the reaction mixture in the simplest
a small preliminary test. In general solvent additions
50 of 33 to 66%, with reference tothe amount of halogen
Another‘object of the invention resides in the use of
hydrin ether used, are used.
a hitherto unemployed aqueous solution of an agent bind
As inorganic bases, which are used in aqueous solu
ing hydrogen halide for the dehydrohalogenation of
yield with a high epoxy value.
tion in concentrations of, for example, 25 to 60%, prefer
alcohols containing a plurality halogenhydrin ether groups 55 ably 35 to 55% there may be mentioned in particular
sodium hydroxide and potassium hydroxide. Surpris
and a new solvent for this reaction which dissolves both
ingly no hydrolysis or polymerization of the epoxy com
both the halogenhydrin ether and also the epoxy ether
pounds, once they have been formed, takes place. After
formed, but is itself immiscible with water or only partly
separation of the aqueous phase, the epoxy ethers are
miscible therewith.
We have now found that the said objects are achieved 60 obtained by distilling o?" the alcohol, if desired after
washing with water or saturated salt solution, as for
and polyepoxy ethers of polyhydric saturated aliphatic
example sodium chloride solution.
alcohols are obtained in good yields by carrying out the
The following examples will further illustrate this in
dehydrohalogenation of polyhalogenhydrin ethers espe
halogenhydrin ethers of polyhydric saturated aliphatic
cially polychlorhydrin ethers of aliphatic saturated poly
vention but the invention is not restricted to these ex
inorganic bases in the presence of an aliphatic mono
Example 1
hydric alcohols with aqueous concentrated solutions of 65 amples. The parts speci?ed are parts by weight.
hydric alcohol which is only moderately soluble or in
soluble in water but which dissolves the resultant epoxy
ether and the halogenhydrin ether used as initial ma
terial, at temperatures of -20° C. to +30° C. advanta
geously at --5° C. to +20“ 0., in particular at_—5° C.
to +10° C.
370 parts of the chlorhydrin ether of glycerine, which
has been obtained from glycerine and epichlorhydron
in the mol ratio of 1:3 with boron tri?uoride as catalyst,
are dissolved in 150 parts of butanol, cooled to -5°
C. and while stirring vigorously 262 parts of a 45%
caustic soda solution are slowly added so that the tem
10° C. to 15° C. 700 parts of a 45% caustic soda solu
perature does not exceed 0° C. When all the caustic
tion are added during the course of an hour. When
soda solution has been run. in, the whole is stirred for
all the caustic soda solutionhas been run in, the Whole
about 3 hours further at 0° C. to —5° C; and then,
is stirred for another 2 hours. Then 425 parts of water
for more rapid phase separation, 50 parts of. toluene“ and:
are added and the aqueousmother liquor separated from
200 parts of water are added. The phases are separated.
the organic‘ liquids. The solvent is then removed in
and the aqueous layer is repeatedly‘ extracted with 100'
vacuo. There remain 670 parts. of apale yellow colored,
parts of a mixture of butanol and toluene. in equal pro—
liquid of low viscosity which has an epoxy value of 0.63
portions. From the non-aqueous phase combined with
and a chlorine content- of 10.6%,.
the extracts, the solvent is distilled o? in vacuo, ?nallyv 10
What we claim is:
in a boiling waterbath, and- as a residue 260 parts are
.In a method of producing polyepoxy- ethers from poly
obtained which after ?ltration is an almost colorless,
halogenhydrin ethers of saturated aliphatic polyhydric
clear, thin liquid. The ?ltratehas an epoxy value oi
alcohols selected from the group consisting of glycerine,
0.73. The substance still contains 10.5% of chlorine and?
butane-triol, and‘ pentaerythritol by dehydrohalogenation
has a mean molecular weight of 283 (ebullioscopically 15 of said polyhalogenhydrin ethers with a concentrated;
from dioxane) which corresponds to a content of some
aqueoussolution of an. alkali metal‘ hydroxide at a temwhat-more, than 2 epoxy groups per molecule. ,
perature of about ~20” C. to‘ about. +30° C., the im
Example 2
provement which comprises’carrying out, said dehydro-l
halogenation in the presence of a monohydric alcohol?
384 parts of the chlorhydrin ether of 1.2.4-butane-triol 20 selected from the’ group consisting oi n-butanol andi
which has been obtained from 1 mol of butane-triol and.
alkanols having fromS to 8 carbon‘ atoms, in the, molecule:
3 mols of epichlorhydrin with boron tri?uoride as cat
in an amount of about 33 to 66% by weight with refer
alyst, are, dissolved in 200 parts of a mixture. of equal.
ence to the amount of the halogenhydrin ether.
parts of butanol and toluene and while stirring vigor
ously at --5° C., 310 parts ofv a- 38.% caustic soda solu 25
References Cited in the?le of this patent
tion are slowly added so that the temperature. remains
between about --2° C..and,-6,° C. When all the caustic.
Groll‘ _______________ __ Nov. 17; 1936;
soda solution has been run in, the whole is stirred for
a further 3 hours at, 0° C. to —5‘’ 0., then 150 parts
Evans _______________ __ June 27,1939‘
of water are; added, the aqueous layer separated and 30
2,224,849 1
Groll __ _____________ .. Dec” 17,v 1940;
the solvent distilled off in vacuo from the non-aqueous.
Marple. et a1. ________ __ July 8,‘ 1941'
layer. There» remain behind 294 parts of a pale yellow
Evans ______________ _.. Mar. 16', 1943-‘
Kharasch ___________ __ Jan. 13, 1948‘
chlorine" content of 10.25%. The product obtained has
Zech _______________ __ Jan. 8, 1952.
a mean molecular weight of 350 corresponding to a. 35
Stevens ______________ __,._, June 1, 19541
colored liquid.
It has an epoxy value of’ 0.67 and a.
contentof 2.14‘epoxy groups per molecule.
Example 3
990'parts of a chlorhydrin ether which has. been. pre
pared in known manner from 46 parts of glycerine, 829. 40
parts of pentaerythritol and 2,128 parts of epichlorhydrin'
are dissolvedv in 600 parts of amyl alcohol and then at.
Canada, _______.._,_..__,_ May 31', 1955,‘
. .Fieser: “Org. Chemistry” (1944), page 117.
Cohen et aL: Jj.A.-C;S-,. 75:173.‘ (1953‘).
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