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Патент USA US2111882

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Patented
2, 1938
2,111,882
UNITED STATES PATENT: OFFICE
3.111.883
METHOD OI‘ SULPHUBIZING narauas.
ABIE'I'YL COMPOUNDS, ITO.
Joseph N. Borglin. Wilmington, DeL, asslgnor
to Hercules Powder Company, Wilmington.
not, a corporation or Delaware
No mam. ‘Application May 1 1m.
Serial No. mm
'
22 Claims. (Cl. 280-17)
This invention relates to an improved method the absence of air or other oxidizing agents. More
I for sulphurlzing organic compounds such as, for
particularly, the method as applied to naval stores
example, lard oil, cottonseed oil, petroleum lu
products may involve the puri?cation oi.’ the naval
bricating oil, etc., and more particularly to a stores product by theyremoval oi’ oxidized com
‘ method for sulphurizing naval stores products, ponents therefrom followed by the sulphurization
1. e. products obtained from the southern pine and
derivatives thereof, such as pine oil, turpentine.
dipolymer, rosin, rosin esters, etc., or their chem
.ical constituents as various terpenes, for exam
10 ple, terpineol, anethol, pinene, dipentene, terpin
olene, terpinene, di- and poly-terpenes, etc., and
abietyl compounds, for example, abietic acid, a1
kyl abietates, abietyi alcohol, etc.
The term "suiphurizing” as used in this art
I, designates the process of combining a substance
with elemental sulphur. This combination is ef
fected by heating the organic compound, e. g. a
naval stores-product, such as pine oil, with the
desired quantity oi‘ sulphur, or with equivalent
amounts
oi’ sulphur compounds which readily give
20
up elemental sulphur under the conditions of the
reaction. Such processes involving the use oi’
various naval stores products and the resultant
products are described in U. S. Patent No.
1,844,400 to W. H. Kobbé and U. S. Patent No.
25 1,926,687 to R. C. Palmer and P. 0. Powers. Any
organic compound which contains unsaturated
linkages and/or replaceable hydrogen may be sul
phurized by similar procedures.
The products produced by the methods de
30 scribed in these patents, while useful for certain
purposes, are nevertheless unsuited for many uses
to which they might otherwise be adapted by
reason of their extremely dark color, which in
most cases is almost Jet black.
It has been discovered in accordance with this
invention that sulphurized organic compounds
may be produced which are very light in color
and are accordingly adapted for many uses for
‘o wtgich the previously known products are unsuit
a
e.
>
Accordingly, the method in accordance with
thk invention is directed to the production of
sulphurized organic compounds, such as, lard oil,
“ cottonseed oil, petroleum lubricating oil, etc.,
various naval stores, products, such as, pine oil,
turpentine, dipolymer, rosin, rosin esters, etc.,
or their chemical constituents as, various ter
penes, for example, terpineol, anethol, pinene,
5° dipentene, terpinolene, terpinene, di- and poly
terpenes, etc., and abietyl compounds, for exam
ple, abietic acid, alkyl abietates, abietyl alcohol,
etc. having a very light color. The method in
accordance with this invention involves broadly
u the sulphurlaation oi’ the organic compound in
of the puri?ed material in the absence oi’ air or
_ other oxidizing agents.
The puri?cation, ii’ desired, 01' the naval stores
products to be sulphurized may readily be ef
iected by distillation, preferably preceded, where
hydrocarbons such as pinene, dlpentene, terpin 10
olene, ierpinene, etc., and their polymers, are to
be suiphurized, by washing with aqueous caustic
solution. The distillation of these hydrocarbons
will also be preferably conducted in the presence 15
01' alkali, with or without the use of steam in the
distillation procedure. When the boiling point
of the'material to be puri?ed is high, the distil
lation will desirably be conducted under reduced
pressure. The distillation may also be conducted
in an atmosphere oi‘ inert gas to prevent oxida- 20
tion during the distillation. 0! course, in some
cases the naval stores products to be sulphurized,
having been freshly prepared or distilled, will
not contain oxidized bodies and hence will not
need to be further puri?ed before sulphurization. 25
The sulphurization oi’ the organic compound, as.
for example, a puri?ed naval stores product, will
be conducted in the presence of an inert gas such
as, for example, carbon dioxide, nitrogen, etc.
A temperature of from so to about 200" 0. may. 3°
be employed for sulphurization, and if desired the
reaction may be carried out at superatmospheric
pressure. Deslrably, however, the temperature
‘of sulphurization will be kept below about 140"
C. in order to avoid substantial formation or
hydrogen sulphide. Sulphur will be used in
amount from about 1% to_i35% by weight of the
naval stores product, and the heating will be
carried out for a period of from 1 to/80 hours.
40
The following examples are illustrative of the
practical‘ embodiment oi’ the method in- accord
ance with this invention:
Emmple I
A dark-colored dipolymer (a diterpene) made 45
by dehydration of pine oil with fuller’s earth is
washed thoroughly with a ‘10% aqueous caustic
soda solution, separated from this solution, and
distilled under reduced pressure (1-30 mm. Hg). 50
Distillation is stopped when about 75-85% has ‘
distilled over, and the distillate is then heated
with 10-12% by weight of sulphur at 120-130“ C.
for about twenty hours. During the entire heat
ing period the reactants are blanketed with car
56
2
2,111,882
> bong dioxide gas to prevent oxidation. Carbon‘
dioxide gas is also passed through the cooling
copending application for Letters Patent, Serial
No. 723,330 filed May 1, 1934.
What I claim and desire to protect by Letters I
reaction product after the reaction is complete
to aid in the removal oi’ any slight amount of
Patent is:
‘
~ 1. A method for the production of sulphurized
H28 which may have been formed. The product
is a light colored liquid with a slight greenish products which includes reacting a compound
selected from the group consisting of terpene and
tinge, and contains about 10-12% sulphur.
abietyl compounds with sulphur in the absence of
Example II
4 an oxidizing material at a temperature oi’ from
800 parts by weight of a pine oil, purified by about 80° C. to about 200° C.
10
10
2. A method for the production of sulphurized
steam distillation from caustic soda solution, is
heated with 30 parts of sulphur for sixteen hours products which includes reacting a compound
at 130° C. in an atmosphere of carbon dioxide. selected from the group consisting of terpene and
abietyl compounds with sulphur in the absence
The product is a light-brown liquid. '
15
oi air at a temperature or from about 80° C. to 15
about 200° C.
' Example III
180 g. of freshly distilled methyl abietate and
20 g. of sulphur are heated for 48 hours at 130°
C. in an atmosphere of carbon dioxide. A light
agoa temperature of from about 80° C. to about
20 colored product is obtained.
2
Example IV
180 g. of I wood rosin and 20 g. of sulphur were
heated 50 hours at 130° C. in an atmosphere oi’
25 carbon dioxide.
A light-colored product is ob
tained.
.
Example V
85 parts by weight of a commercial grade oi.’
lard oil and 15 parts by weight of sulphur were
30 heated twenty-four hours at a temperature of
130-140” C., in an atmosphere of carbon dioxide.
The resulting product was lighter in color than
‘ a product similarly sulphurized in the presence
of air.
Example VI
15 parts by weight of sulphur and 185 parts by
35
weight of petroleum lubricating oil were heated
thirty-six hours in an atmosphere of carbon di
oxide at 130-1400 C. The resulting product was
40
lighter in color than a product similarly sulphur
ized in the presence of air.
Example VII
1'70 parts by weight of re?ned cottonseed oil
45 and 30 parts by weight of sulphur were heated
to reaction at 130-140° C., in an atmosphere oi‘
nitrogen gas. The resulting product was lighter
in color than when sulphurized in the presence
\
. of air.
so’
Example VIII
300 parts by weight of turpentine puri?ed by
steam distillation from alkali solution, 1700
parts by weight of alkali washed and distilled
dipolymer and 500 parts by weight of sulphur
55 were heated forty-eight hours at 130-140‘' C. in
an atmosphere of carbon dioxide.
The reaction
was then complete. This product contained
20-22% sulphur and was much lighter in color
than a‘ product similarly sulphurized in the
60
presence of air.
‘3. A method for the production of sulphurized
terpenes which includes reacting a terpene and
sulphur in the absence of an oxidizing material
~
The products of the method in accordance with
this invention will be characterized by a much
lighter color than similar products heretofore
prepared and will be resistant to i'urther dis
65
coloration upon use. They will consequently be
suitable for use in, for example, greases disin
fectant sprays, ?otation processes, etc., for which
purposes the dark-colored products heretofore
known cannot be readily sold.
70
Where it is desired to use sulphurized organic
compounds in paints, varnishes, etc., the color of
the products in accordance with this invention
may be still further improved by re?ning them
in accordance with the method disclosed in my
20
° C.
4. A method i'or the production of sulphurized
terpenes which includes reacting a terpene and
sulphur in the absence of air at a temperature of
from about 80° C. to about 200" C.
25
5. A method for the production 01' sulphurized
abietyl compounds which includes reacting an
abietyl compound and sulphur in the absence of
an oxidizing material at a temperature of from
about 80° C. to about 200° C.
30
~
6. A method for the production of sulphurized
abietyl compounds which includes reacting an
abietyl compound and sulphur in the absence of
air at a temperature 01' from about 80° C. to about
200° C.
,
‘
7. A method for the production of sulphurized
products which includes treating a compound
selected from the group "consisting of terpene
and abietyl compounds for the removal of oxi
dized components therefrom and then reacting 40
the treated compound with sulphur in the absence
of an oxidizing material at a temperature of
from about 80° C. to about 200° C.
8. A method for the production of sulphuriz'ed
products ' which includes treating a compound 45
selected from the group consisting of terpene and
abietyl compounds for the removal of oxidized
components therefrom and then ‘reacting the
treated compound with sulphur in the absence of
air at a temperature of from about 80° to about
200° C.
9. A method for the production of sulphurized
terpenes which includes treating a terpene for
the removal of oxidized components therefrom,
and then reacting the treated terpene with 55
sulphur in the absence of an oxidizing material
gt a temperature of from about 80° C. to about
00° C.
_
10. A method for the production of sulphuriz‘ed
terpenes which includes treating a terpene for
the removal of oxidized components therefrom
and then reacting the treated terpene with
sulphur in the absence of air at a temperature of
from about 80° C. to about 200° C.
11. A method for the production of sulphurized 65
abietyl compounds which includes treating an
abietyl compound for the removal of oxidized
components therefrom‘ and then reacting the
treated abietyl compound with sulphur in the
absence of an oxidizing material at a tempera
ture of from about 80“ C. to about 200° C.
'
12. A method for the production of sulphurized
abietyl compounds which includes treating an
abietyl compound for the removal of oxidized
components therefrom and then reacting the
3
a,111,eea
treated abietyl compound with sulphur m the
absence of an oxidizing material at a temperature
absence of air at a temperature of from about oi‘ from about 80° C. to about 200° C‘.
80° C. to about 200° C.
17. A method for the production of sulphurized
13. A method for the production 01' sulphurized ‘ products which includes washing a compound
products which includes washing a compound selected from the group consisting of terpene
selected from the group consisting of terpene and and abietyl compounds with an aqueous caustic
abietyl compounds with an aqueous caustic solu
solution, distilling the washed compound, and
tion for the removal of oxidized components then reacting the treatedcompound with sulphur
therefrom and then reacting the treated com
in the absence of an oxidizing material at a tem
10 pound with sulphur in the absence of an oxidiz _ perature of from about 80° C. to about 200° C.
ing material at a temperature of from about 80°
18. A method for the production of sulphurized
C. to about 200° C‘.
products which includes reacting a compound
14. A method for. the production of sulphur
selected from the‘group consisting of terpene and
ized products which includes distilling a com
abietyl compounds with sulphur in an atmosphere
pound selected from the group consisting of of inert gas at a temperature of from about 80°
terpene and abietyl compounds for the removal C. to about 200° C.
'
of oxidized components therefrom and then re
19. A method for the production of sulphurized
acting the treated compound with sulphur in the products which includes reacting a compound
absence of an oxidizing material at a temperature selected from the group consisting of terpene
and abietyl compounds with sulphur in an at
of from about 80° C. to about 200° C.
v 15. A method for the production of sulphurized mosphere of carbon dioxide at a temperature of
from about 80° C. to about 200° C.
products which includes steam distilling a com
20. A method for the production of sulphurized
pound selected from the group consisting of
terpene and abietyl compounds for the removal turpentine oil, which includes reacting turpentine
oil and sulphur in the absence of air at a tem
of oxidized components therefrom and then re
\h‘
acting the treated compound with sulphur in perature from about 80° C. to about 200° C.
21. A method for the production of sulphurized
the absence of an oxidizing material at a tem
pine oil, which includes reacting pine oil and
perature of from about 80° C. to about 200° C.
sulphur in the absence of air at a temperature
16. A method for the production of sulphurized from about 80° C. to about 200° C.
30
products which includes distilling a compound
22. A method for the production 01? sulphurized
selected from the group consisting of terpene and diterpene, which includes reacting a diterpene
abietyl compounds from caustic tor the removal and sulphur in the absence of air at a temperature
of oxidized components therefrom and then re
from about 80" C. to about 200° C.
acting the treated compound with sulphur in the
JOSEPH N. BORGLIN.
,
D l 5CLA l M ER
2,111,882.—J0seph N. Borgl'in, Wilmington,v Del. METHOD or SULPHUinzmG TER
PENEB, ABIETYL COMPOUNDS, E'rc. Patent dated March 22, 1938. Die
claimer ?led October 31, 1942, by the assignee, Hercules Poreder ‘Company.
Hereby enters this disclaimer to claims 1, 2, 3, 4, 18, 19, and 20 m said patent. ‘
[O?mhl Gazette November 24, 1942.]
~
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10
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20'
80
3
a,111,eea
treated abietyl compound with sulphur m the
absence of an oxidizing material at a temperature
absence of air at a temperature of from about oi‘ from about 80° C. to about 200° C‘.
80° C. to about 200° C.
17. A method for the production of sulphurized
13. A method for the production 01' sulphurized ‘ products which includes washing a compound
products which includes washing a compound selected from the group consisting of terpene
selected from the group consisting of terpene and and abietyl compounds with an aqueous caustic
abietyl compounds with an aqueous caustic solu
solution, distilling the washed compound, and
tion for the removal of oxidized components then reacting the treatedcompound with sulphur
therefrom and then reacting the treated com
in the absence of an oxidizing material at a tem
10 pound with sulphur in the absence of an oxidiz _ perature of from about 80° C. to about 200° C.
ing material at a temperature of from about 80°
18. A method for the production of sulphurized
C. to about 200° C‘.
products which includes reacting a compound
14. A method for. the production of sulphur
selected from the‘group consisting of terpene and
ized products which includes distilling a com
abietyl compounds with sulphur in an atmosphere
pound selected from the group consisting of of inert gas at a temperature of from about 80°
terpene and abietyl compounds for the removal C. to about 200° C.
'
of oxidized components therefrom and then re
19. A method for the production of sulphurized
acting the treated compound with sulphur in the products which includes reacting a compound
absence of an oxidizing material at a temperature selected from the group consisting of terpene
and abietyl compounds with sulphur in an at
of from about 80° C. to about 200° C.
v 15. A method for the production of sulphurized mosphere of carbon dioxide at a temperature of
from about 80° C. to about 200° C.
products which includes steam distilling a com
20. A method for the production of sulphurized
pound selected from the group consisting of
terpene and abietyl compounds for the removal turpentine oil, which includes reacting turpentine
oil and sulphur in the absence of air at a tem
of oxidized components therefrom and then re
\h‘
acting the treated compound with sulphur in perature from about 80° C. to about 200° C.
21. A method for the production of sulphurized
the absence of an oxidizing material at a tem
pine oil, which includes reacting pine oil and
perature of from about 80° C. to about 200° C.
sulphur in the absence of air at a temperature
16. A method for the production of sulphurized from about 80° C. to about 200° C.
30
products which includes distilling a compound
22. A method for the production 01? sulphurized
selected from the group consisting of terpene and diterpene, which includes reacting a diterpene
abietyl compounds from caustic tor the removal and sulphur in the absence of air at a temperature
of oxidized components therefrom and then re
from about 80" C. to about 200° C.
acting the treated compound with sulphur in the
JOSEPH N. BORGLIN.
,
D l 5CLA l M ER
2,111,882.—J0seph N. Borgl'in, Wilmington,v Del. METHOD or SULPHUinzmG TER
PENEB, ABIETYL COMPOUNDS, E'rc. Patent dated March 22, 1938. Die
claimer ?led October 31, 1942, by the assignee, Hercules Poreder ‘Company.
Hereby enters this disclaimer to claims 1, 2, 3, 4, 18, 19, and 20 m said patent. ‘
[O?mhl Gazette November 24, 1942.]
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