Improvements in the Production of Dyes.
Year: 1896

page_text: Date of Application, 29th Sept., 1896
PROVISIONAL SPECIFICATION.
Improvements in the Production of Dyes.
We LEON PAUL MARCHLEWSKI of 25 Wellington Street Higher Broughton,
Manchester, in the County of Lancaster, Chemist; and EDGAR SIDDONS WILSON of
Arthog, Goddington Road, Strood, in the County of Kent, Chemist; and EBENEZER
STEWART of 94 Queen Victoria Street, in the City of London, Merchant, do hereby
declare the nature of this invention to be as follows:-
When crude Cotton-seed Oil is refined by means of weak alkaline solutions, the
solutions after separation from the oil, contain amongst other matters a substance
which after a series of crystallizations from Glacial Acetic Acid and from Alcohol,
can be obtained as yellow crystals easily soluble in alcohol, ether, and boiling acetic
The said substance may
acid, not soluble in water, and easily soluble in alkalies.
be isolated from other matters contained in the aforesaid solutions by treatment
in the manner specified by Edgar Siddons Wilson and Ebenezer Stewart under
the serial number 24418 of the year 1895. The said treatment consists essentially
in submitting the solutions to fractional precipitation with earthy salts such
as Ca: Cl, which convert the fatty acids contained in the said solutions into in-
soluble or not easily soluble soaps. The residual liquor is then treated with an
acid such as hydrochloric acid, which will decompose alkaline carbonates and the
like as well as the alkaline compound of the colouring matter. To the flocculent
precipitate thereby produced we have given the name of Gossypol, and will here-
inafter refer to it by that name.
We find that by treating Gossypol as follows, useful colouring matters are
produced:-
First. Take twenty parts of Gossypol, dissolve it in a solution of about fifteen
parts of NaOH in three hundred parts of water and pass through this a current
of air for several hours. The original brown solution gradually becomes brown
violet, and at the same time a colouring matter is produced which possesses marked
affinity for mordanted fibres. From time to time samples of the solution are
drawn and used for dying small weighed specimens of mordanted wool or cotton,
and as soon as it is found that the maximum of colouring matter is produced, the
Instead of
air current must be stopped, and the alkaline solution acidified.
Na: OH the corresponding quantity of KOH or alkaline carbonates may be
used and instead of passing a current of air through the alkaline solution, the
said alkaline solution may be agitated by agitators in the presence of air. This
colouring matter we propose to call Oxygosspol-brown.
Second. Ten parts of Gossypol are heated with from fifty to one hundred parts
of crystallized sodium sulphide with the addition of, or without, sulphur. The
heat is maintained for a short time at about one hundred and twenty degrees C,
and is then raised to about two hundred and fifty degrees C, for several hours.
There is produced a colouring matter which dyes unmordanted cotton, shades of
brown; it may be used direct in the crude state for dyeing or it may be pre-
cipitated from its solution in sodium sulphide with acids and afterwards re-dissolved
in sodium sulphide. The shades can be fixed by passing the dyed goods through

page_text: solutions of metallic salts, such as copper sulphate, bichromate of potassium and
the like. Instead of Gossypol oxygossypol brown or an oxidation product of the
latter may be used. The colouring matter can be used for printing cotton.
Dated this 28th day of September 1896.
Improvements in the Production of Dyes.
We, LEON PAUL MARCHLEWSKI of 25 Wellington Street Higher Broughton,
Manchester, in the County of Lancaster, Chemist; and EDGAR SIDDONS WILSON of
Arthog, Goddington Road, Strood, in the County of Kent, Chemist; and EBENEZER
STEWART of 94 Queen Victoria Street, in the City of London, Merchant, do hereby
declare the nature of this invention and in what manner the same is to be per
formed, to be particularly described and ascertained in and by the following
statement:-
-
When Crude Cotton Seed Oil is refined by means of weak alkaline solutions, the
solutions, after separation from the oil, contain amongst other matters a substance
which, after a series of crystallisations from glacial acetic acid and from alcohol,
can be obtained as yellow crystals, easily soluble in alcohol, ether, and boiling
acetic acid, not soluble in water and easily soluble in alkalies. The said substance
may be isolated from other matters contained in the aforesaid solutions by treat-
ment, in the manner specified by Edgar Siddons Wilson, and Ebenezer Stewart,
under the serial number 24418 of the year 1895. The said treatment consists
essentially in submitting the solutions to fractional precipitation with earthy salts
like CaCl, which convert the fatty acids contained in the said solutions into
insoluble or not easily soluble soaps. The residual liquor is then treated with an
acid such as hydrochloric acid, which will decompose alkaline carbonates and the
like as well as the alkaline compound of the coloring matter. To the flocculent
precipitate thereby produced we have given the name of Gossypol and will here-
inafter refer to it by that name.
We find that by treating 'Gossypol as follows useful coloring matters are
produced.
(1) Take 20 parts of Gossypol, dissolve it in a solution of about 15 parts of
NaOH in 300 parts of water and pass through this a current of air for several
hours. The original brown solution gradually becomes brown violet, and at the
same time a coloring matter is produced which possesses marked affinity for mor-
banted fibres. From time to time samples of the solution are drawn and used for
dyeing small weighed specimens of mordanted wool or cotton, and as soon as it is
found that the maximum of coloring matter is produced the air current must be
stopped and the alkaline solution acidified thereby precipitating the coloring
matter which may then be employed for dyeing in the usual manner. Instead of
NaOH the corresponding quantity of KOH or alkaline carbonates may be used,
and instead of passing a current of air through the alkaline solution, the said
alkaline solution may be agitated by agitators in the presence of air. This
coloring matter we propose to call Oxygossypol-brown.
(2) 10 parts of Gossypol are heated with from 50 to 100 parts of crystallised
sodium sulphide with the addition of, or without sulphur. The heat is maintained
for a short time at about 120° C. and is then raised to about 250° C., for several
hours. There is produced a coloring matter which dyes unmordanted cotton shades
of brown: it may be used direct in the crude state for dyeing or it may be precipi-

page_text: tated from its solution in sodium sulphide with acids and afterwards redissolved in
sodium sulphide. The shades can be fixed by passing the dyed goods through
solutions of metallic salts, such as copper sulphate, bi-chromate of potassium and
the like. Instead of Gossypol, the Oxy-gossypol-brown described under the first
head or an oxidation product of the latter may be used, or the Calcium Soap,
obtained during the above mentioned process specified under the serial number
24418 of the year 1895, which contains a quantity of coloring matter of the Cotton
Seed Oil. The coloring matter can be used also for printing cotton.
Having now particularly described and ascertained the nature of our said Inven-
tion and in what manner the same is to be performed we declare that what we
claim is :-
First. The process of converting the substance hereinbefore called Gossypol or
equivalent substance into a mordant coloring matter by a gentle oxidation process,
preferably by the action of air, in the presence of free alkalies, or alkaline car-
bonates, as hereinbefore stated.
Second. The process of converting the substance hereinbefore called Gossypol, or
its oxidation products (obtained by gentle oxidation) or equivalent substances into
coloring matters containing sulphur, by heating at a temperature from 250° C to
300° C., with alkaline sulphides or mixtures of alkaline sulphides and sulphur as
hereinbefore set forth.
Third. The coloring matters obtained by the processes substantially as set forth
under heads 1 and 2.
Dated this Twenty-eighth day of June 1897.
W. B. JOHNSON,
4 Clayton Square, Liverpool, Agent.