Manufacture of Diamidodiphenylamine Disulphonic Acid and Azom dyestuffs therefrom.
Year: 1898

page_text: Date of Application, 17th Nov., 1898
Complete Specification Left, 3rd Aug., 1899-Accepted, 9th Sept., 1899
Manufacture of Diamidodiphenylamine Disulphonic Acid and Azom
dyestuffs therefrom.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to me from abroad by The Farbwerke
vormals: Meister Lucius and Brüning, of Hoechst a/Main, in the Empire of
5 Germany, Chemical Manufacturers,) to be as follows :-
My foreign correspondents have found that nitrochlorbenzene sulphonic acid of the
constitution
reacts under appropriate conditions with diamine sulphonic acid while splitting off
0 hydrochloric acid and that in this way new diphenylamine derivatives may be obtained
which are of great importance to industry.
E
If the said acid be allowed to act, for instance, upon p-phenylenediamine
sulphonic acid, amidonitrodiphenylamine disulphonic acid is first obtained and from
this the diamidodiphenylamine disulphonic acid.
The constitution of the new acid is:

page_text: vessel provided with an inverted condenser; the brown yellow solution thus obtained.
is acidified with hydrochloric acid, whereupon amidonitrodiphenylamine disulphonic
acid, at first formed, separates as a thick greyish yellow precipitate; it is filtered,
pressed and reduced in the usual manner with iron and acetic acid.
The liquid of reduction made alkaline with soda, having been filtered from the iron,
diamidodiphenylamine disulphonic acid is precipitated by an addition of mineral
acid; it separates as a greyish-white crystalline precipitate, which is insoluble in an
excess of hydrochloric acid.
The acid is soluble with difficulty in water, it is easily diazotised and forms a
yellow tetrazo compound, soluble with difficulty, which combines with the usual
components to form valuable azo dyestuffs characterized by their great solubility and
the fastness of their tints.

page_text: The tetrazo compound obtained from 35.9 kilos. of diamidodiphenylaminedisul-
phonic acid is poured, while stirring, into a solution of 22 kilos. of m-phenylene-
diamine at 40° C., in 500 litres of water; a brown precipitate is formed at once,
5 consisting of the free dyestuff acid. When treated with 20 kilos, of soda or 24 kilos.
of caustic soda-lye (40° Bé.) it dissolves with a red-brown colour and, on addition of
salt, is again precipitated as sodium salt easily soluble.
The dyestuff yields on unmordanted cotton in a weak alkaline bath red tints, which,
when treated with acids, become violet and with diazonitrobenzene a very fast deep
0 brown.
By employing m-toluylenediamine instead of m-phenylenediamine similar dye-
stuffs may be obtained.
Manufacture of Diamidodiphenylamine Disulphonic Acid and Azo-
dyestuffs therefrom.
I, OLIVER IMRAY, of Birkbeck. Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to ine from abroad by The Farbwerke
vormals: Meister Lucius and Brüning, of Hoechst a/Main, in the Empire of Germany,
Chemical Manufacturers,) and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement :—
My foreign correspondents have found that nitrochlorbenzenesulphonic acid of the
constitution:-
reacts under appropriate conditions with diamine-sulphonic acid while hydrochloric
acid is eliminated, and that in this way new diphenylamine derivatives may be
30 obtained which are of great importance to industry.
If the said acid be allowed to act, for instance, upon para-phenylenediamine-
sulphonic acid, amidonitrodiphenylaminedisulphonic acid is first obtained and from
his the diamidodiphenylaminedisulphonic acid.

page_text: 150 kilos. of paraphenylenediaminesulphonic acid
200 » paranitrochlorobenzenesulphonic acid
Foda and
100
"
"
"
""
1000 " water, are boiled for 6 hours in a vessel
provided with an inverted condenser; the brown yellow solution thus obtained is
acidified with hydrochloric acid, whereupon amidonitrodiphenylaminedisulphonic
acid, at first formed, separates as a thick greyish yellow precipitate; it is filtered, 1
pressed and reduced in the usual manner with iron and acetic acid.
The liquid of reduction made alkaline with soda, having been filtered from the
iron, diamidodiphenylaminedisulphonic acid is precipitated by an addition of mineral
acid; it separates as a greyish-white crystalline precipitate, which is insoluble in an
excess of hydrochloric acid.
The acid is soluble with difficulty in water, it is easily diazotised and forms a yellow
tetrazo-compound, soluble with difficulty, which combines with the usual components
to form valuable azo-dyestuffs characterized by their great solubility and the fastness

page_text: The yellow coloured tetrazo-compound, soluble with difficulty, which is at once
formed, is run into a solution of
48 kilos. of amidonaphtholsulphonic acid G in
40
"
soda and 1000 litres of water, when a violet dyestuff (diamidodiphenyl-
aminedisulphonic acid + 2 molecules of amidonaphtholsulphonic acid G) is obtained,
which remains dissolved in the liquid.
This dyestuff is again diazotised by first adding 70 kilos. of hydrochloric acid to the
violet solution, whereupon the colour becomes a pure blue; and then 13.8 kilos. of
sodium nitrite are added.
Finally 22 kilos. of metaphenylenediamine, dissolved in 500 litres of water, are
added so as to form the black dyestuff.
The dyestuff separates as a black precipitate; it is neutralized with soda, and
heated, whereupon the dyestuff dissolves, it is salted out, filtered, pressed and
dried.
The dyestuff is a powder of bronze lustre, soluble in boiling water with a black
violet colour, dyeing unmordanted cotton deep black in an alkaline bath.
The tetrazo-compound obtained from 35.9 kilos. of diamidodiphenylaminedisul-
phonic acid is poured into a solution of 22 kilos. of metaphenylenediamine at 40° C.
in 500 litres of water while the mixture is stirred; a brown precipitate is formed at
once, consisting of the free dyestuff acid. When treated with 20 kilos. of sodium
carbonate or 24 kilos. of caustic soda lye (40° Bé. specific gravity) it dissolves with a
red-brown colour and, on addition of salt, is again precipitated as sodium salt easily
soluble.
The dyestuff yields on unmordanted cotton in a weak alkaline bath, red tints,
which, when treated with acids, become violet and with diazonitrobenzene a very fast
deep brown.
By employing metatoluylenediamine instead of metaphenylenediamine similar
dyestuffs may be obtained,
Having now particularly described and ascertained the nature of this inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
1. The herein described manufacture of diamidodiphenylaminedisulphonic acid
by first producing, by the action of paraphenylenediaminesulphonic acid upon
paranitrochlorobenzenesulphonic acid, amidonitrodiphenylaminedisulphonic acid and
then reducing the latter to diamidodiphenylaminedisulphonic acid.
2. The herein described manufacture of a black azo-dyestuff, directly dying cotton,
by combining the tetrazo-compound of diamidodiphenylaminedisulphonic acid with 2
molecular proportions of amidonaphtholsulphonic acid G, then transforming the
resulting dyestuff into a tetrazo-compound and combining the latter with 2 molecular
proportions of metaphenylenediamine.
3. The herein described manufacture of a violet dyestuff, by allowing the tetrazo-
compound of diamidodiphenylaminedisulphonic acid to act upon 2 molecular
proportions of metaphenylenediamine or metatoluylenediamine,

page_text: 4. The diamidodiphenylaminedisulphonic acid manufactured as
Claim 1.
5. The black azo-dyestuff manufactured as set forth in Claim 2,
6. The violet dyestuff manufactured as set forth in Claim 3.
set forth in
ABEL & IMRAY,
Agents for the Applicant.

page_text: Date of Application, 17th Nov., 1898
Complete Specification Left, 31st July, 1899-Accepted, 16th Sept., 1899
PROVISIONAL SPECIFICATION.
Improvements in Packings for Pistons or the like.
I, ROBERT HEATON TAYLOR, Engineer, of 47, Norfolk Street, Sheffield, in the
County of York, do hereby declare the nature of this invention to be as follows;-
This invention relates to packings for pistons or the like. I roll a section of
metal, preferably steel, so as to form a spring ring and of such section as to
have suitable lateral angles.
The ends of this spring are formed so as to engage with each other and over-
lap, and are provided with lugs which enable the ends to be drawn together by
a bolt or screw.
Over the tightening bolt may be placed an easing spring, preferably coiled.
around the bolt.
Ordinary cast metallic rings may be used, having in each a strengthening ring,
corrugated or otherwise, either at the edge or at some suitable distance from the
edge of the ring so as to come in contact conveniently with the angles on the
spring.
Each ring has the usual saw-gates and stopping pieces.
I place one of the rings against the flange of the piston within the cylinder
and against it I place the spring ring, which is of such a diameter as to bear on
the inside diameter of the rings, the other ring is then added to and the junk ring
screwed up in place. Thus while the spring ring presses up against the inside
diameter of the rings, its angles are also pressing against the corrugated or
tightened rim in one with the rings thus obtaining both a vertical and lateral
pressure of the rings.
The spring ring is adjusted by the tightening or releasing of the bolt or screw,
thus giving greater pressure or less as required.
Dated this 17th day of November 1898.
Improvements in Packings for Pistons or the like.
I, ROBERT HEATON TAYLOR, Engineer, of 47, Norfolk Street, Sheffield, in the
County of York, do hereby declare the nature of this invention, and in what
manner the same is to be performed, to be particularly described and ascertained
in and by the following statement:-
This invention relates to packings for pistons or the like.
In carrying out my invention I provide a spring ring of angular cross section

page_text: and place the same between two packing rings secured between the piston flange
and the junk ring in the usual manner, the packing rings being so constructed
that the spring ring exerts both vertical and lateral pressure upon them, that is
to say presses them both against the cylinder surface and the faces of the piston
flange and junk ring.
In the accompanying drawings
Figure 1 is a cross section of my improved packing rings and spring ring in
operative position.
Figure 2 is a side clevation of part of a spring ring, and
Figure 3 is a side elevation of part of a packing ring.
Like letters indicate like parts in all figures.
In constructing my improved packing I roll or otherwise form of metal, prefer-
ably steel, a spring ring A, angular in cross section, so as to have two oblique
surfaces A¹ A as shown in Figure 1.
The ends of the spring A are formed so as to overlap, preferably by providing
on one end a lip As, which fits into the opposite end. Two lugs A' A³ may be
provided near each end of the ring to carry a tightening bolt B, having nuts
and lock nuts on each end, and with an easing spring B' preferably coiled
around it.
Conveniently the lip A³ and the lug A' may be formed in one and suitably
secured on the ring by brazing, rivetting, etc. The other lug A³ may also be
constructed with a flange A and similarly fixed within the ring.
Each packing ring C has a strengthening rim C¹ which may be lightened by
being corrugated or cut away as shown in Figure 3. Each ring is provided on
its inner side with surfaces CC, of an angle corresponding to that of the sur-
faces A¹ A of the spring ring, against which they bear when in operative
position as shown in Figure 1.
The packing rings are provided with the ordinary saw-gates and stopping
pieces.
When placed in position in the piston, the spring ring A pressing against the
angular surfaces CC of the packing rings, exerts a force in two directions
tending to press the packing rings C against the wall of the cylinder and also
against the piston flange and junk ring.
The degree of pressure exercised by the spring ring may be controlled by
the bolt B.
The degree of angle given to the cross section of the ring A and other details
of construction may be varied without departing from the spirit of the invention.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is: 1
1. In piston packings or the like the combination with two packing rings of a
spring ring angular in cross section arranged to put pressure on the packing
rings in two directions substantially as described.
2. In piston packings or the like the combination with two rings such as C
C2 C3 of a spring ring having oblique surfaces such as A¹ A substantially as
described.
3. The piston or like packing substantially as described or illustrated in the
accompanying drawings.”
DJ L
011
T 1
1000
ROBERT HEATON TAYLOR.
Boult & Wade,
Agents for the Applicant.