IMPROVE- MENTS IN MAKING A NEW DERIVATIVE OF PHENOL, AND IN PRODUCING CERTAIN COLOURS THEREWITH UPON TEXTILE FABRICS AND YARNS
Year: 1869

page_text: LETTERS PATENT to Theodore Reissig, of the City of Manchester, in
the County of Lancaster, Chemist, for the Invention of "IMPROVE-
MENTS IN MAKING A NEW DERIVATIVE OF PHENOL, AND IN PRODUCING CERTAIN
COLOURS THEREWITH UPON TEXTILE FABRICS AND YARNS."
Sealed the 27th May 1870, and dated the 29th November 1869.
PROVISIONAL SPECIFICATION left by the said Theodore Reissig at the
Office of the Commissioners of Patents, with his Petition, on the
29th November 1869.
I, THEODORE REISSIG, of the City of Manchester, in the County of
Lancaster, Chemist, do hereby declare the nature of the said Invention
for "IMPROVEMENTS IN MAKING A NEW DERIVATIVE OF PHENOL, AND IN PRO-
DUCING CERTAIN COLOURS THEREWITH UPON TEXTILE FABRICS AND YARNE," to be
as follows:-
-
My improvements consist in making from carbolic acid a new amido
compound which by suitable oxidation can be made to produce various
shades from black to brown upon fabrics and yarns of various materials.
To a mixture of carbolic acid and water I gradually add nitric acid,
and when the action has ceased and the liquor cooled I obtain crystals
of a new nitro compound which I purify by solution in boiling water.
Price S

page_text: pour
and recrystallization therefrom. 1 then act on this nitro compound by
nascent hydrogen obtained by means of an acid and a metal, as is well
known to chemists. When the liquid has lost all or nearly all its colour
1 off from the excess of metal, and separate the metal dissolved by
a current of sulphuretted hydrogen, or in any other convenient manner,
and after filtration or subsidence evaporate the solution to a strength at
which the new substance crystallizes. The crystals when drained are
the new amido compound.
To produce black or brown shades upon fabrics I apply to them a
solution of the above crystals, either thickened or not, and when dry
expose them to ammonia in the form of gas or vapour, and afterwards
expose them to the air till the full oxidation has taken place; or I
imbue the fabric with a solution of the crystals, either thickened
or not, to which I previously add an alkaline or basic salt, and
after drying expose to the air for oxidation as before; or I add to the
solution a salt capable of giving up oxygen easily, and apply it to the
fabric as before, in some cases steaming the fabric or exposing it to
the air for complete oxidation. After any of these processes I wash
the fabric in water, to which a little alkali or chalk has been added,
or I pass it through water containing an oxidizing substance, such as
bi-chromate of potash or chloride of lime.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Theodore Reissig in the Great Seal Patent Office
on the 27th May 1870.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, THEODORE
REISSIG, of the City of Manchester, in the County of Lancaster, Chemist,
send greeting.
WHEREAS
Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twenty-ninth day of November, in the
year of our Lord One thousand eight hundred and sixty-nine, in the
thirty-third year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said Theodore Reissig, her special licence
that I, the said Theodore Reissig, my executors, administrators, and
assigns, or such others as I, the said Theodore Reissig, ny executors,
administrators, and assigns, should at any time agree with, and no others,

page_text: from time to time and at all times thereafter during the term therein
expressed, should and lawfully might make, use, exercise, and vend,
within the United Kingdom of Great Britain and Ireland, the Channel
Islands, and Isle of Man, an Invention for "IMPROVEMENTS IN MAKING A
NEW DERIVATIVE OF PHENOL, AND IN PRODUCING CERTAIN COLOURS THEREWITH
UPON TEXTILE FABRICS AND YARNS," upon the condition (amongst others)
that I, the said Theodore Reissig, my executors or administrators, by an
instrument in writing under my, or their, or one of their hands and
seals, should particularly describe and ascertain the nature of the said
Invention, and in what manner the same was to be performed, and
cause the same to be filed in the Great Seal Patent Office within six
calendar months next and immediately after the date of the said Letters
Patent.
NOW KNOW YE, that I, the said Theodore Reissig, do hereby declare
the nature of my said Invention, and in what manner the same is to be
performed, to be particularly described and ascertained in and by the
following statement (that is to say):-
My improvement consists in making from carbolic acid a new amido
compound, and by applying this to fibrous or textile materials, and
oxidizing in a suitable manner in producing various dyed or printed
shades of brown or black.
I make first the substance called binitrophenol, and then convert
this into the new amido compound by reduction with nascent hydrogen.
To make binitrophenol I mix 50 lbs. of crystallized carbolic acid with
600 lbs. of water, and add to the milky liquid gradually 275 lbs. of nitric
acid of specific gravity 138, stirring all the time. If the weather is
very cold the mixture may require warming to begin the decomposition,
but when it has once fairly begun a brisk evolution of red gas takes
place, and the reaction is soon terminated. When the liquor is cold the
binitrophenol crystallises out, and may be further purified by washing
with cold water, dissolving again in boiling water, and recrystallization
by cooling.
To make the amido compound, which I call diamidophenylic acid, I
put 900 lbs. of commercial hydrochloric acid containing 30 per cent. of
pure dry hydrochloric acid in a large stone or stoneware vessel, and add
to it 450 lbs. of granulated tin. I then warm the mixture until hydrogen
gas begins, to come off freely, and add gradually the binitrophenol made
as above, stirring all the time. When all action has ceased I decant the

page_text: liquid from the excess of tin, dilute it with some water, and pass a
current of sulphuretted hydrogen through it until all the tin is pre-
cipitated, filter out the sulphide of tin, and rapidly concentrate the liquid
in stoneware vessels until a drop taken out crystallizes on cooling. I
then set the concentrated liquor aside to crystallize. The crystals are
the new amido compound, which is diamidophenylic acid combined with
hydrochloric acid, and which has the composition CH, (NH2)2 0,+2 Hcl
(oxygen being 8). The binitrophenol may be also decomposed by
metallic iron and acetic acid as in the manufacture of aniline, or by zinc
and hydrochloric acid, but I prefer to make it with tin and hydrochloric
acid as above, or instead of passing sulphuretted hydrogen through the
liquid containing tin I can precipitate the tin as sulphide by the
cautious addition of sulphide of ammonium, though in that case muriate
of ammonia crystallizes along with the diamidophenylic acid compound,
which mixture of salts has however very similar properties to the pure
crystals, differing of course in strength. When the diamidophenylic acid
in an aqueous solution of the salt is set free from combination with the
hydrochloric acid by addition of an alkali it oxidizes in the air with great
rapidity, and a brown powder precipitates. If cotton or linen cloth or
yarn is padded in the alkalized solution before the brown powder begins
to fall the precipitation will take place in the interior of the fibre, and
as the oxidized substance has a great affinity for the fibre the latter
remains dyed a brown colour, which is not removed by dilute acids or
alkalies. Addition of an alkaline acetate to the solution of the salt
produces the same effect, since the base of the acetate being taken up by
the hydrochloric acid the acetic acid has little or no effect in preventing
the oxidation of the diamidophenylic acid. Many other bases or salts of
bases with feeble acids produce the brown colour by the bases combining
with the hydrochloric acid, and in some cases the shades can be modified
by the oxidized diamidophenylic acid combining with some of the base.
Metallic acetates are very convenient for use in this manner; amongst
them may be mentioned the acetates of iron, chromium, copper, and
lead as being serviceable, and by padding the cloth or yarn in a mixed
solution of the new salt and a metallic acetate, drying and exposing to
the air, and subsequent washing in water or soaping, a variety of shades
are produced varying according to the materials and the proportions of
them used; or the two solutions can be applied separately to the fabric
or yarn, and exposure to the air given as before. Passing the dried and
padded cloth through solution of chromate or bi-chromate of potash,

page_text: especially when hot, still further modifies the shade of colour, and by
steaming the padded goods in the manner well known to calico printers
they are often made to assume a darker shade, or by steaming and
raising through a chromate of potash.
Another way of applying the diamidophenylic acid is to dissolve the
new salt in water, and add chromate of potash as long as any brown
precipitate falls. This precipitate, which is a compound of oxide of
chromium with oxidized diamidophenylic acid, is soluble in acetic acid,
and the brown solution thus made may be applied directly to the cloth
or other material by padding, or after being suitably thickened may be
used for printing on the material, the goods in either case being exposed
to the air to drive off acetic acid, or steamed or raised in an alkaline
solution on in chalky water.
I make colours for printing by dissolving in water the new salt along
with an alkaline earthy or metallic acetate either with or without
addition of an oxidizing substance, thicken in a suitable manner by gum
or starch, and apply to the fabric or yarn. After printing I treat as
above described for padded goods. Or I make a colour similar to the
aniline black used by calico printers, substituting the new salt for the
aniline hydrochlorate, and giving the same treatment as for aniline
black. By these means a great variety of shades may be produced.
I give the composition of several colours which I have found useful.
No. 1-1 gallon of water, 1 lb. of starch; boil and add 4 ounces of
chlorate of potash and 4 ounces nitrate of ammonia, and when cold
8 ounces of the new salt.
No. 2.1 gallon of acetate of chromium at 11° T., 1 lb. of starch;
hoil and add when nearly cold 8 ounces of the new salt.
No. 3. 3 quarts of water, 1 quart of pyrolignite of iron at 18° T.,
1 lb. of starch; boil and add when near cold 8 ounces of the new salt.
No. 4. 3 quarts of water, 10 fluid ounces of sulphate of chromium
solution (containing in 1 fluid ounce 70 grains of oxide of chromium),
1 lb. of starch; boil and add 5 ounces crystallized protosulphate of iron
and 14 ounces crystallized acetate of soda, and when cold 8 ounces of
the new salt.
No. 5.-7 pints of water, 1 lb. of starch, 1½ lbs. of tungstate of
chromium paste made by precipitating sulphate of chromium with
tungstate of soda, and after washing filtering to a paste weighing 12 lbs,

page_text: per gallon; boil and add 6 ounces of chlorate of potash, and when near
cold S ounces of the new salt.
No. 6. Made the same as No. 5, but with an addition of 4 ounces of
arseniate of copper paste (made by precipitating solution of sulphate of
copper by arseniate of soda, and after washing filtering to a paste
weighing 12 lbs per gallon). This paste is added at the same time as
the tungstate of chromium paste before the boiling.
These colours may all be steamed after printing, but No. 6 will oxidize
quickly enough, in the air without steaming. They give shades from
chocolate to brown, but by adding less water to 5 and 6 shades so dark
as to appear black may be produced.
Having now described the nature of my Invention, and the way in
which I carry it out, I do not confine myself to the exact details herein
set down, as such may be varied without departing from the spirit of
my Invention, nor do I claim the preparation of binitrophenol, sucli
substance being well known to chemists; but I claim,-
1st. The manufacture of diamidophenylic acid in combination with
an acid such as hydrochloric acid, such substance never having been
made before to the best of my belief.
And, 2nd. Its application in printing and dyeing to produce brown or
other shades upon textile fabrics and yarns by oxidation of the diamido-
phenylic acid, or by its oxidation and combination with bases.
In witness whereof, I, the said Theodor Reissig, have hereunto
set my hand and seal, this Fifth day of April, in the year of
our Lord One thousand eight hundred and seventy.
THEODOR REISSIG. (L.S.)