Patented Aug.

3, 1948 2,446,233

UNITED STATES PATENT OFFICE

AND ALAL EARTH SETA, SALTS OF
HALOGENATE LOWER, FATTY ACDS
Sayard T. Lamborn, Satawaa, N. J., assign or tG
Hercules Powder Company, Wirmington, Del,
a corporation of Delaware
No Brawing. Application November 20, 1946,
Serial No. 1,209
9 Cairns. (C. 26-539)
2
This invention relates to the preparation of Eacample II
Salts of lower fatty acids and more particularly
to the preparation of alkali metal salts and alkali Sixteen and eight-tenths parts of substantially
earth metal salts of halogenated lower fatty dry sodium bicarbonate and 18.8 parts of crystal
acids. 5 line monochloroacetic acid were mixed together
Preparation of the alkali metal Salts and the as in Example I. The reaction proceeded with
alkali earth metal salts of halogenated lower a slight, cooling effect. The sodium chloroacetate
fatty acids has heretofore been carried out by formed was dry enough to handle but showed
reacting the necessary ingredients in aqueous a slight, tendency to cake.
solution. Such procedure requires long reaction O Eacample III
times and considerable reaction space due to
foaming but is normally satisfactory where it is Thirteen and eight-tenths parts of crystalline
feasible to use the product, formed without fur potassium carbonate and 18.8 parts of Crystal
ther processing. However, in some processes, it line monochloroacetic acid were mixed as in EX
is desirable to utilize the material in a substan 5 ample I. This reaction proceeded with a slight
tially dry powdery form. In such cases the ad ly greater evolution of heat than with SOdium
ditional processing required to recover the ma carbonate. The product was a dry powder con
terial in this form adds to the cost of the process prising potassium chloroacetate.
and is economically disadvantageous. Eacample IV
In accordance with the present invention it has 20
Forty-rine parts of crystalline magnesium car
been discovered that the alkali metal Salts and
the alkali earth metal salts of halogenated lower bonate (24.5% Mg), 106 parts of crystalline SO
fatty acids may be prepared by reacting the de dium carbonate and 280 parts of crystalline
sired ingredients in a substantially dry state and monochloroacetic acid were mixed as in Example
that a dry, powdery, easily handled salt results. I. The resulting product was a substantially
Generally described, the process of this in dry, powdery mixture of magnesium chloro
vention may be carried out by mixing in a sub acetae and sodiuli in chloroacetate.
stantially dry state a crystalline halogenated Eaccingle V
lower fatty acid, such as crystalline chloroacetic Twenty parts of B-chloropropionic acid cryS
acid, With a crystalline alkali metal sait or alkali 30 tals were crushed in a mortar and then inti
earth metal Salt, such as crystalline Sodium cal mately nixed in the same vessel, with 9.8 parts
bonate or magnesium carbonate. The reaction
which takes place in the case of crystalline of dry sodium carbonate. The mass became
chloroacetic acid and crystalline sodium carbon slightly pasty on reacting but within 30 minutes
ate is illustrated in the following equation, the changed to a dry, friable mass. The reaction was
product formed thereby consisting of approxi substantially complete since very few bubbles of
mately 93% sodium chloroacetate With 7%. Water. CO2 formed when the powder was dissolved in
Water.
2CICH3COOH+Na2CO3->
2ClCH2COONa-i-H2O.--CO2
In accordance with the novel process of the
present invention the alkali metal salts and al
188.96 gms.--106 gms.-->232.9 gms.--18 gms. 40 kali earth metal salts of halogenated lower fatty
acids are prepared by mixing in the dry Or CryS
Having described the invention in general talline state without solvent, substantially stoi
terms, the following examples are given to illus chiometrical amounts of a halogenated lower
trate specific embodiment, thereof. All parts are fatty acid and an alkali metal carbonate or alkali
by weight unless otherwise specified. earth. metal carbonate. Any suitable type of
Eacample I mixing and/or mixing and grinding device where
by the ingredients are intimately contacted and/
One hundred sixty-seven parts of dry soda, ash or ground inay be utilized for carrying out the
(Na2CO3) Were placed in a mixer and 294 parts process. For large scale batches, the neutraliza
of crystalline monochloroacetic acid mixed 50 tion of the acid by the carbonate can best be ac
therewith. Mixing was continued for 4 hour. complished in a reactor such as a Werner-Pfleid
The reaction proceeded substantially to coin erer, pony or ribbon mixer. However, for Small
pletion with very little evolution of heat, ihe amounts it may be done as simply as mixing the
Sodium chloroacetate formed Was in a dry, two ingredients together in a beaker with inter
powdery state. 55 mittent stirring.
 2,446,233
3 4.
The reaction may be carried out under any con sired, the invention may be utilized in prepar
ditions of temperature and pressure consistent ing mixed alkali metal and/or alkali earth metal
with maintaining the ingredients in powder or salts of the halogenated Iower fatty acids. Thus,
granular form. Thus the pressure may be at for example, mixed salts of sodium chloroacetate
mospheric, sub-atmospheric or superatmospheric, and calcium chloroacetate may be prepared by
depending on the conditions of reaction, mate reacting in a substantially dry state, chloroacetic
rials being reacted and the ends sought. Tem acid. With Sodium carbonate and calcium carbon
peratures may wary from about 0° C. to abouti. ate. Mixed salts of sodium chloroacetate and
65 C., depending on the pressure, time of treat- . magnesium chloroacetate may be prepared in a
ment, etc. Preferably, the temperature, will wary. 0. like manner from chloroacetic acid, sodium car
from about 20° C. to about 30° C. and the: pres-- bonate-and-magnesium carbonate.
Sure from slightly below to slightly above at It will thus be seen that the present inven
mospheric. It should be understood, of course, tion" provides a single, effective and economical
that these temperatures and pressuires are not : process for the preparation of the alkali metal
Critical and are given as illustrative of the pre 5 Salts and alkali earth metal salts of the halo
ferred operative range of the invention. gelated lower fatty acids. The process over
Time of treatment will vary with the type; : Comes the disadvantage of foaming encoun
amount and physical characteristics of the ma tered in prior art processes and thus requires a
terials being treated, the type of treating equip Shorter reaction time and less reaction space.
ment and other conditions of treatment. When 20 In addition the process avoids splitting of the
reacting about 42 pound of monochloroacetic acid chlorine atom since the reaction does not-gen
and 4 pound of sodium carbonate at atmos erate heat to any great extent. The product is
pheric temperature and pressure the time of re dry, powdery and easily handled and does not
action will wary from about 4 hour' to about 3 require further processing before use.
hours and Will usually be about 1 hour. When :25 What I claim and desire to protect by Letters
Operating With large batches of the order of Patentis:
about 470 pounds a minimum time of about 1 1. In the preparation of the alkali metal salts.,
hour will usually be required for the reaction and the alkali earth metal salts of halogenated:
to go to completion. Generally, it has been lower fatty acids the improvement which com-:
found that a more than 90% reaction takes place 30 prises inixing a Crystalline halogenated lower
in a few minutes While a more than 98% reac fatty acid having from 2 to 4 carbon atoms in
tion takes place in from 1 to 3 hours, depending the molecule with a carbonate selected from the
on the conditions of treatment. It will be un group consisting of alkali metal carbonates and
derstood, of course, that the time of reaction may alkali earth metal carbonates in a substantially
be varied over wide limits, depending upon the 35 dry state,
result Sought. Thus, for example, where partial 2. In the preparation of the alkali metal salts.
reaction of the ingredients is desired, for any and the alkali earth metal salts of halogenated
reason, the mixing may be terminated at any lower fatty acids the improvement which con- ;
suitable time interval . after initiation thereof. prises mixing a crystalline halogenated". lower :
The reaction, in accordance with the present 40 fatty acid having from 2 to 4 carbon atoms in
invention, is more readily accomplished when the molecule with at least one crystalline cars
both reagents are finely divided. Hence, it is bonate Selected from the group consisting of crys. .
preferred to utilize the reagents in a state of talline alkali metal carbonates and crystallineal
subdivision such that the individual particles kali earth metal carbonates.
vary from about 70 microns to about 700 mi 3. In the preparation of the alkali metal salts:
crons in diameter. However, this is not essen of halogenated lower fatty acids the improve
tial and the reaction will take place when the ment which comprises mixing- an alkali metal :
particles are of the size of 3000 microns and above Carbonate With a crystalline halogenated lower:
in diameter, though not quite as readily. fatty acid having from 2 to 4 carbon atoms in
Any of the alkali metal and alkali earthmetal 50 the molecule in a substantially dry state.
carbonates and bicarbonates may be utilized for 4. In the preparation of the alkali earth metal :
the purposes of this invention. However, the Salts of haiogenated lower fatty acids theim
carbonates and particularly the Substantially an provement: which comprises mixing in alkali
hydrous carbonates, are preferred since the re earth metal carbonate with a crystalline halo
sidual Water from neutralization is insufficient to 55 genated lower fatty acid having from 2 to 4 car.
Create a 'Wetness' or partial Solution of the Salt bon atoms in the molecule in a substantially dry
with a consequent tendency to cake. The re State.
suiting. salt is therefore dry and powdery. 5. In the preparation of the alkali metal salts of
Where caking is not objectionable and/or it is halogenated lower fatty acids the improvement
planned to dry the resulting product prior to use, 60: which comprises mixing a crystalline alkali metal
hydrated or partially hydrated carbonates and carbonate With a crystalline halogenated lower
bicarbonates may conveniently be used. It is de-, . fatty acid having from 2 to 4 carbon atoms in
sirable, however, that the resulting salt contain the molecule.
not more than about 10% residual Water. 6. In the preparation of the alkali earth metal. .
The invention is particularly applicable to the 65 Salts of halogenated lower fatty acids the im
preparation of the alkali metal salts and the al provement which comprises mixing a crystalline
kai earth, neta Salts of chloroacetic acid. In alkali earth metal carbonate with a crystalline
addition, it may, With advantage be applied to halogenated lower fatty acid having from 2 to 4
the preparation of the alkali metal salts and carbon atoms in the molecule.
alkali earth metal Salts of other crystalline halo 70 : 7. In the preparation of the sodium-salts of .
genated lower fatty acids such as dichloroacetic. halogenated lower fatty acids, the improvement
acid, trichloroacetic acid, B-chloropropionic acid, which comprises mixing crystalline sodium cara
a-brono-iso-butyric acid, and the similar. Sub bonate With a crystalline halogenated lower fatty.
Stitution products of acetic acid and propionic. acid having from 2 to 4 carbon-atoms in the
acid containing bromine and iodine,: "Also, if de 75: molecule,
 2,446,233
5 6
8. In the preparation of the potassium salts of metal carbonates with crystalline halogenated
halogenated lower fatty acids, the improvement acetic acid.
which comprises mixing crystalline potassium 16. In the manufacture of alkali earth metal
Carbonate With a crystalline halogenated lower Salts of halogenated acetic acid, the improvement
fatty acid having from 2 to 4 carbon atoms in which comprises mixing at least two crystalline
the molecule. alkali earth metal carbonates with crystalline
9. In the preparation of the magnesium salts halogenated acetic acid,
of halogenated lower fatty acids, the improve 17. In the manufacture of alkali metal salts
ment which comprises mixing crystalline mag and alkali earth metal salts of halogenated acetic
nesium carbonate with a crystalline halogenated O acid the improvement which comprises mixing
lower fatty acid having from 2 to 4 carbon atoms crystalline halogenated acetic acid with a crystal
in the molecule. line bicarbonate selected from the group consist
10. In the manufacture of alkali metal salts ing of alkali metal bicarbonates and alkali earth
and alkali earth metal salts of halogenated acetic metal bicarbonates.
acid the improvement which comprises mixing 5 18. In a preparation of the alkali metal Salts
Crystalline halogenated acetic acid with a crystal and the alkali earth metal salts of chlorinated
line carbonate Selected from the group consist lower fatty acids the improvement which com
ing of crystalline alkali metal carbonates and prises mixing a crystalline chlorinated lower fatty
Crystalline alkali earth metal carbonates. acid having from 2 to 4 carbon atoms in the mole
1. In the manufacture of sodium monochloro cule with a carbonate selected from the group
acetate, the improvement which comprises mix consisting of alkali metal carbonates and alkali
ing crystalline sodium carbonate with crystalline earth metal carbonates in a substantially dry
monochloroacetic acid. state.
12. In the manufacture of potassium mono 19. In the manufacture of alkali metal salts
chloroacetate, the improvement which comprises 25 and alkali earth metal salts of monochloroacetic
mixing crystalline potassium carbonate with crys acid the improvement which comprises mixing
talline monochloroacetic acid. crystalline monochloroacetic acid with a crystal
13. In the manufacture of magnesium mono line carbonate selected from the group consisting
chloroacetate, the improvement which comprises of Crystalline alkali metal carbonates and crys
mixing crystalline magnesium carbonate with 30 talline alkali earth metal carbonates.
Crystalline monochloroacetic acid.
14. In the manufacture of alkali metal salts BAYARD T. LAMBORN.
and alkali earth metal salts of halogenated acetic
acid, the improvement which comprises mixing REFERENCES CTED
Crystalline halogenated acetic acid with at east 35 The following references are of record in the
two crystalline carbonates selected from the file of this patent:
group consisting of alkali metal carbonates and UNITED STATES PATENTS
alkali earth metal carbonates.
15. In the manufacture of alkali metal salts of NuLinber Name Date
halogenated acetic acid, the improvement which 40 883,165 Blumenthal -------- Mar. 31, 1908
comprises mixing at least two crystalline alkali 2,396,115 Nicholls------------- Mar. 5, 1946