close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2119149

код для вставки
awed may 31,1938
» ‘
a I
'
2,119,149
UNITED STATES PATENT-‘OFFICE
STABILIZED
AND METHOD
CHLORINATED
OF PRODUCING
PARAFFIN
'
William '1‘. Bishop, Wilmington, Del., assignor to
Hercules Powder Company, Wilmington, Del.,
a corporation of Delaware
No Drawing. Application April 9, 1935,
'
-
,
'
Serial No. 15.505
'15 Claims. ‘(01. zoo-162)
This invention relates to stabilized chlorinated
paramn wax and the alkaline liquid may be
para?in waxes and to methods for effecting such
‘used in accordance with this invention in any
stabilization.
,
Chlorinated paramn waxes, as prepared by
5 various known methods, slowly decompose, lib-
amounts and proportions convenient for thor
ough admixture and contact.
In order to insure thorough and complete con- '5
erating hydrogen chloride. This characteristic tact between the chlorinated paraffin wax and
renders them un?t for many uses for which the alkaline’ liquid it is desirable to agitate the
they would otherwise be well suited. The slow mixture vigorously during-the treatment. The
decomposition referred to and the hydrogen chlo- stabilization treatment may be carried out at
10 ride thereby produced are not ._to be confused any temperature, but desirably a temperature 10
with the hydrogen chloride present in impure of from about 50° C. to about 100°C.,' and pref
chlorinated paraffin waxes as taken from the erably of from about 70° C. to about 80° C.,
chlorinating apparatus. This latter hydrogen will be employed. The necessary duration of
chloride is a by-product of the chlorination and the treatment cannot be given exactly, for it
may be removed by known puri?cation treat- _.will vary widely for different products treated 15
ments, as, for example, by passing a stream of ‘ and for different alkaline materials. However,
air or carbon dioxide through 'the- agitated, . a period of from‘ 1/2 to 6 hours will usually su?ice
molten chlorinated paraffin wax.
The puri?ed ‘ for satisfactory stabilization.
chlorinated para?in wax so produced will never-
- Where the chlorinated paraffin wax or solu
20 theless, upon standing for a few hours, give off ' tion thereof and the alkaline liquid are im- 20
appreciable amounts of hydrogen chloride ; miscible, as will usually be the case, the agita- ’
through decomposition.
Now in accordance with this invention it has
tion employed during treatment forms anemul
sion.
The stabilized chlorinated paraffin wax
been found that chlorinated paraffin wax may ' may be separated from this emulsion by a va
25 be stabilized so that its decomposition is greatly 5 riety of methods. For ‘example, it may be re- 25
retarded by being thoroughly washed or admixed * covered by distillation of the alkaline liquid or
with an alkaline liquid, as, for example, an aqueous phase thereof, by centrifugation or set
aqueous solution of sodium hydroxide, sodium tling, and by extraction with a solvent therefor,
carbonate, potassium hydroxide, potassium car-,
30 bonate, calcium hydroxide, sodium bicarbonate,
as, for example, ether, toluene, naphtha, ben
zene, carbon tetrachloride, turpentine, etc. This '30
'
potassium bicarbonate, ammonia, amines, ete.,
last method of recovery, being most simple and
which is later separated from the chlorinated
e?icient, is preferred.
paraffin wax.
The alkaline liquid employed will preferably,
35 for greater ease of separation after treatment,
be immiscible with chlorinated parai?n wax.‘
Accordingly aqueous or alcoholic solutions are
the preferred alkaline liquids. Where an aque-ous solution of an alkali metal or alkaline earth
40 metal hydroxide or carbonate is used as the
alkaline liquid, the concentration of the solution
may vary within wide limits, but preferably 1
to 20% solutions of alkali metal hydroxides or
carbonates and/' saturated or nearly saturated
45 solutions of alkali earth metal hydroxides or
carbonates will be used.
'
The chlorinated paraf?n wax,‘ if liquid, will
be treated directly with the alkaline liquid.’ If
the chlorinated para?in wax is a solid, it will
50 preferably be melted or dissolved in a solvent
immiscible with the alkaline liquid to be used,
as, for example in aromatic hydrocarbons such
as toluene or benzene, carbon tetrachloride,
ether, etc., before treatment to insure better
65 contact with the alkaline liquid. The chlorinated
Surprisingly, it has been found in accordance
with this invention that the degree of stabiliza
tion effected is, to a large extent, dependent 35
upon the use of particular solvents in the re
covery of the chlorinated paraffin wax from the
emulsion above described. Thus, when ether or
toluene is used as a solvent in recovering chlo
rinated para?in wax from this emulsion, a-prod- 40
uct of much greater stability is obtained than
when the chlorinated para?in wax is recovered
by using other solvents or in any other manner.
The following examples are illustrative of pro
cedure in accordance with thisv invention'and 45
demonstrate the increase in stability of chlorin
ated para?in wax obtained by various procedures:
About 400 g. chlorinated para?in wax (Sample
A) Containing 46% combined chlorine and free
from uncombined chlorine or hydrogen chloride 50
was added ‘to 21/2 liters of a saturated solution
of calcium hydroxide, and ‘the mixture was Vig
orously agitated for about eight hours at a.
temperature of 75°-80° C. The emulsion so
formed was divided into two portions. One por- 55
2
2,119,149
80° C. ior several hours with an equal volume of
tion was extracted with ether‘ and the ether
evaporated for .the recovery of the chlorinated
para?ln wax. This material was designated
Sample‘ A2. The second portion was distilled
for the removal of the waterpresent, and the
mixture of chlorinated para?in wax and calcium
1.5% sodium hydroxide solution. The emulsion
formed was allowed to stand over night, where
upon the chlbrinated para?in' wax settled almost
completely. The alkali solution was decanted
of!’ and the chlorinated para?in wax washed
with distilled water. The wash became slightly
hydroxide thinned slightly with carbon tetra
chloride and ?ltered. The chlorinated paraffin alkaline and was neutralized ‘with hydrochloric
wax recovered from the filtrate was designated > acid. Further decantation and washing was car
ried out until neutral conditions were obtained. 1O
10 Sample A3. The stability of Samples A2 and A3
The chlorinated para?in wax was then trans
compared with each other and with the un
treated original Sample A are tabulated below: - ferred to a distilling ?ask and the water distilled
‘ The stability data are obtained by a test which out. The following stability tests were secured:
consisted in heating a l-gram sample of chlori
15 nated para?ln wax in a 6" x 1A" test tube, with
51%?“
Description of sample
Stability
a piece of Congo red test paper %"x 95" sus
pended by a wire so that the lower edge of the
paper is 4%’! from the surface of the sample.
The wire is held by a cork which tightly closes
20 the test tube. The test tube is then heated in a
A ....... __
About 300 g. of a chlorinated para?in wax
bility oi’ the sample under test.
A ....... _. Original sample
30
oi uncombined
Stabilit
100.,
washed entirely iree
chloride was agitated for about 4 hours at 80° C. 2.3
with 1 liter of saturated calcium hydroxide solu
at
tion'. The resulting emulsion, after cooling, was,
divided into three equal portions. The portions
were extracted with ether, naphtha and toluol,
Ominute.
respectively, and the chlorinated paramn wax Si)
recovered from each extract and tested for sta
l or H01).
A2 ...... -_ Sample aiter alkali treatment and ex-
20
(Sample B) containing 40.7% combined chlorine
and free from uncombined chlorine and hydrogen
25
'
Description
of sample
5 hours.
_________ __ Duplicate test on sample A6___.--_.--._ 4% hours.
at its lower edge recorded as a measure oi! sta
No_
0 minute.
solution.
bath at 100° C., and’ the time required for the
Congo red paper to change color from red to blue
Sample
Original sample ....................... ._
A6 ...... ._ Sample washed with sodium hydroxide
22hours.
traction with ether.
bility.
......... -. Duplicate test on Sample A2____...-____ 2056 hours.
A3 ______ __ Sample after alkali treatment and re- Shours.
The data obtained are tabulated below:
moval of water by distillation.
......... _- Duplicate test on Sample A3_.--_.-_____ 6% hours.
Duplicate test on Sample A3 .......... -. 4 hours.
. sample No,
08(03): w?lli?d recovered asttiligglmév'
35
It will be noted that Sample A3 which had been
subjected to the alkali treatment but not the
ether extraction was decidedly more stable than
the original sample. Sample'A2, however, which
40 had had the alkali treatment followed by the
,
'
Hours
B1
Ether
‘\
=
__
B2 --------------------- -.
‘
'
3
ether ‘extraction showed a stability test more
than four times that of Sample A3. The action
45
__
_
2%
Dunlimta
2
Dnnlimta
2%
Naphtha __________________ __
1%
Duplicat
1%
Toluol_.__.
2
'
oi’ the ether in improving the stability is obvious
' . Another 300 g. portion of chlorinated para?in
ly very great.
E_wax (Sample B) was similarly treated with a 2%
‘sodium hydroxide solution as the alkaline liquid.
Stability data on three samples of chlorinated
A further portion of chlorinated para?in wax
(Sample A) was treated with calcium hydroxide
solution as described above and the emulsion pro
duced divided into two portions. One of these
was then extracted with ether, and the other
50 with naphtha for the recovery of the chlorinated
para?in wax. The two samples so obtained were
40
1%
paraiiin wax recovered in the same manner with
ether, naphtha and toluol, respectively, follow:
Stilbilii;
2% NaOH washed
Sample N°-
recovered from
at 100°
.
designated A4 and ASrespectively, and compara
tive data on their stability is tabulated below:
55
$11151“
Description 0! sample
13111A
Stability
Original sample ....................... __ 0 minute.
Ether extracted sample (test stopped
before iailure .
_
l0
Duplicate __________ _.'_ ____ __
13
A further portion of chlorinated paraffin wax
6 hours.
‘
55
1%
_
.
Naphtha extracted sample ............ _- 92-1 hour.
(Sample B) was similarly treated with a 5% 60
sodium hydroxide solution.v Two portions of the
It will be noted that naphtha does not give the - resultant emulsion were separately extracted
stabilization that ether does. In fact a compari-: with naphtha and ether, and stability data ob
son or the stability shown for Sample A5 in this tained on the chlorinated paraffin wax recovered,
65 table with that shown for Sample A3 above,
follow:
‘seems to indicate that the naphtha extraction
actually lowers the stability. It should be noted,
however, that these samples had had separate
alkali treatments, which probably account. for
70 this difference. It is believed, from a large num
‘ber of experiments, that the naphtha extraction
has no e?ect one way or the: other on the sta
bility.
'
Another 200 g. portion of chlorinated paramn
75 wax (Sample A) was vigorously agitated at
sample No‘
'
5
N 0H
11 d
grsecoeweredvg?osme
B7 ____________________ __ Naphtha __________________ __
65
h'l't
atSt 510601
(g.
mm_% 70
Dnnlimta
1%
Duplicate _________________ ..
1
51
No change
a t
hours.
.51
75
3
8,119,149
200 g. of chlorinated para?in wax (Sample B) -
were then similarly treated with a 2% sodium bi
carbonate solution. The emulsion produced was
separated into two portions, and the portions ex
paraiiln wax which includes admixing chlorinated
paraffin wax with an aqueous calcium hydroxide
solution, extracting the chlorinated paramn wax
tracted with ether and naphtha, respectively.‘
from the mixture with a solvent therefor selected
from the group consisting of ether and toluol,
The stability tests on the recovered chlorinated
parai’?n'wax are tabulated below:
wax from the extract.
and recovering a stabilized chlorinated‘para?ln
,
'
.
5. A method for the stabilization of chlorin
2% NsHCO; washed
Sample N°‘
recovered from
ated paraiiin wax which includes admixing chlo
Stabilit
at 100°
.
rinated paraffin wax with an alkaline liquid im
10
miscible therewith, extracting the chlorinated
-
Minutes
B9 __________________________ --
Ether _______________ ..
_____________________________ _-
Duplicate_____________
B10_
"
l7
20
“ Nnphi'hn
Dnnlimta
15
paraf?n wax from the mixture with ether, and
recovering a stabilized chlorinated paraf?n wax
5 '
from
7
6. A method for the stabilization of chlorin
ated para?in wax which includes admixing chlo
rinated para?ln wax with an alkaline liquid im
the
extract.
‘
'
Chlorinated paramn wax (Sample C) contain
ing 46% combined chlorine was treated with a 5% miscible therewith, . extracting the chlorinated
solution of sodium hydroxide in'thc manner here . para?in wax from the mixture with toluol, and
inbefore described. The emulsion formed was ex
recovering a'stabilized chlorinated paraffin wax 20
tracted with ether, and the extract evaporated
from the extract.
for recovery of the chlorinated para?in wax. Sta
bility data are tabulated below:
7. A method for the stabilization of chlorin
ated parai?n wax which includes admixing chlo
rinated para?in wax with an alkaline liquid im
miscible therewith, agitating the mixture, ex 25
tracting the chlorinated para?ln wax from the
mixture with a solvent therefor selected from
the group consisting of ether and toluol, and re
covering a stabilized chlorinated paramn wax
Sample No"
57 NaOH washed
Stabilit
ieecovered irom
at_l00°
.
Home
01 ........................... ._
Ether ______________ __-.
Duplicate
48
, 48%
-
‘from the extract.
200 g. of chlorinated paraf?n wax (36% Cl)
were given a water wash followed by a 5% alco
holic-sodium hydroxide. solution wash at room
temperature for three hours. The washed prod
uct was ether extracted and recovered.
‘
8. A method for the stabilization of‘ chlorin
ated paraf?n wax which includes admixing chlo
rinated parafiln wax with an alkaline‘ liquid im
miscible therewith, agitatingthe mixture at a
This ~ temperature of from about 50° C. to about 100° C.,
treatment produced a stability of one hour at , extracting the chlorinated paraf?n wax from the
a mixture with a solvent therefor selected from the
100° C.
"
'
The stability of the chlorinated paraffin waxes 1 group consisting of ether and toluol, and recover
produced in accordance with this invention may , ing a stabilized chlorinated paraffin wax from the
40
be ‘further increased by the incorporation therein
extract.
'
40
9. A method for the stabilization of chlorin
of organic bases, as for example, aniline, pyridine, ‘
etc., as is more fully disclosed in an application '; ated para?in waxwhich includes admixing chlo
Serial No. 19,468, ?led May 2, 1935 by me jointly i? rinated paramn wax with an alkaline liquid im
; miscible therewith, agitating the mixture for
with Emil Ott.
It will be understood that the details and ex L from about 1/2 to about 6 hours at a temperature 45
amples hereinbefore set forth are illustrative only, I of from about 50° C. to about 100° C., extracting
and are in no way in limitation of the invention .‘ the chlorinated para?ln wax from the mixture
with a solvent therefor selected from the group
as herein broadly described and claimed.
What I claim and desire to protect by Letters
1. A method for the stabilization of chlorinated
paraf?n wax whichincludes admixing chlorinated
para?in wax _with an alkaline liquid immiscible
therewith, extracting the chlorinated para?ln wax
from the mixture with a solvent therefor which
is substantially immiscible with the alkaline liquid,
and- recovering a stabilized chlorinated para?‘ln
wax from the extract.
consisting of ether and toluol, and recovering a
stabilized chlorinated parailin wax from the ex
50 Patent is:
'
.
2. A method for the stabilization of chlorinated
60 para?in wax which includes admixing chlorinated
paraf?n wax with an aqueous solution of an al
kalinelmaterial, extracting the. chlorinated paraf
tract.
50
.
10. A highly stabilized chlorinated para?in wax
characterized by the fact that it possesses very
little tendency to decompose with evolution of
hydrogen chloride and comprising a chlorinated 55
para?ln wax which has been admixed with an
alkaline liquid and recovered from such mixture
by extraction with a solvent therefor selected
from the group consisting of ether and toluol.
11. A method for the stabilization of chlorin 60
ated paraf?n wax which includes admixing chlo
rinated para?ln wax with an alkaline liquid im
?n wax from the mixture with a solvent therefor,
miscible therewith, extracting the chlorinated
which is substantially immiscible with the alkaline
para?in waxv from the mixture with a solvent
therefor selected from the group consisting of 65
ether and toluol, and recovering a stabilized chlo
rinated paramn wax from the extract.
12. A method for the stabilization of chlorin
ated para?in wax which includes admixing chlo
rinated paramn wax with an aqueous solution of 70
65 liquid, and recovering a stabilized chlorinated par
amn'wax from the extract.
_3. A method forthe stabilization of chlorinated
para?in wax which includes admixing chlorinated
paraffin wax with an aqueous sodium hydroxide
70 solution, extracting the chlorinated para?in wax
from the mixture with a solvent therefor selected
from the group consisting of ether and toluol, and
recovering a stabilized chlorinated para?ln wax
from the extract.
75 4. A method for the stabilization of chlorinated
an alkaline material, extracting the chlorinated
para?in wax from the mixture with a solvent
therefor selected from the group consisting of
ether and toluol, and recovering a stabilized
chlorinated parafiln wax from the extract.
75
9,119,149
13. A highly stabilized chlorinated para?ln wax para?in wax from the mixture with a solvent
characterized by having a stability to evolution of n which is substantially immiscible with the al
hydrogen chloride of not less than about six kaline liquid and recovering va. stabilized chlorin
hours when measured as the time required for
ated paramn wax from the extract.
the lower edge of a 1/2" x 1/2" piece of Congo red
test vpaper to turn from red to blue in the presence
15. A method for the stabilization of chlorin
ated para?ln wax which includes admixing chlo
of moisture when suspended 4%" from the sur
face .of a 1 gram sample of chlorinated para?ln
rinated para?ln wax with an aqueous calcium
in a’ closed 6" x 1/2" test tube when heated in a
~
hydroxide solution,'extracting ,the chlorinated
para?ln wax from the mixture with a solvent
10 bath at 100° C.
which is substantially immiscible with the al
kaline liquid and recovering a stabilized chlo
J . ated para?ln wax which includes admixing chlo
rinated para?in wax from the ‘extract.
1-1.v A method m the stabilization of chlorinl
rinated paramn wax with an aqueous sodium hy
~droxide solution, extracting the chlorinated
WILLIAM“: BiSHOP.
Документ
Категория
Без категории
Просмотров
0
Размер файла
493 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа