Improvements in the Manufacture of Blue Mordant-dyeing Colouring Matters.
Year: 1892

page_text: Date of Application, 15th July, 1892
Complete Specification Left, 15th May, 1893-Accepted, 30th Sept., 1893
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Blue Mordant-dyeing Colouring
Matters.
I, JAMES YATE JOHNSON, of 47 Lincoln's Inn Fields, in the County of Middlesex,
Gentleman, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by The Badische Anilin and Soda Fabrik of
Ludwigshafen on Rhine in the Empire of Germany) to be as follows:-
This invention relates to the processes for the production of colouring matters
described in the applications for Letters Patent Nos. 19588 and 19589 of 1891 and
has for its object to improve the same.
The said colouring matters are obtained by treatment of certain nitro-anthra-
quinones first with fuming sulphuric acid and then with strong sulphuric acid under
suitable conditions.
The first phase of this process that is the treatment of nitro-anthraquinones
with fuming sulphuric acid has been referred to in an indefinite manner in the
Patent No. 2177 of 1878.
The present invention relates in the first place to a modification in the first stage
of the process consisting in preparing partially reduced nitro-anthraquinones and
treating these with funning sulphuric acid instead of subjecting the nitro-anthra-
quinones to this said treatment as hereinbefore explained. In the second place the
process can be modified by substituting for the strong sulphuric acid in the second
phase thereof other acids or re-agents, suitably altering the conditions in each
case. The reagents which can be substituted are such as will eliminate sulpho-
groups from sulphonated bodies; for instance dilute sulphuric acid, strong hydro-
chloric acid and water alone. When using these it is preferable to employ a higher
temperature than that employed when using strong sulphuric acid, and when
necessary to heat under pressure.
The following examples will serve to illustrate tlic nature of the invention but I
do not bind myself to details as great variations can be made in the manner of
carrying the invention into practical effect.
PRODUCTION OF THE PARTIALLY REDUCED DINITROANTHRAQUINONES.
EXAMPLE A.
Treat about one molecular proportion of 1.4'-dinitroanthraquinone (or a similar
quantity of a suitable isomeric dinitroanthraquinone, or of the mixed product
obtained on strongly nitrating anthraquinone) with the quantity of the reducing
agent chosen (stannous chloride in acid or alkaline solution, ammonium sulphide
&c.) corresponding to from three to six atomic proportions of hydrogen. If an
excess of reducing agent be used, less satisfactory or useless results are
obtained.
The partially reduced product resulting is used as the initial material for
treatment with fuming sulphuric acid. If desired the reduction can be effected in
the fuming sulphuric acid mixture itself by adding a suitable reducing agent. The
treatment with sulphuric acid then is effected as described in the Provisional
Specifications of the Applications for Letters Patent Nos. 19588 and 19589
of 1891.

page_text: SUBSTITUTION OF OTHER REAGENTS FOR CONCENTRATED SULPHURIC ACID IN
THE SECOND STAGE OF THE PROCESSES DESCRIBED IN THE PROVISIONAL
SPECIFICATIONS OF THE APPLICATIONS FOR LETTERS PATENT NOS. 19588
AND 19589 OF 1891.
EXAMPLE B.
Mix about ten parts (by weight) of the colouring matter soluble in water,
obtainable as the result of the first stage in the processes described in the said
Provisional Specifications of the Applications for Letters Patent Nos. 19588 and
19589 of 1891 with about from one hundred to two hundred parts of concentrated
hydrochloric acid containing about thirty two per cent. of real acid (HCL) and
heat the mixture, under pressure, for from five to ten hours at a temperature of
about from one hundred and eighty to two hundred degrees centigrade. Allow the
mixture to cool, dilute with water, filter and wash, the colouring matter obtained.
In the above example dilute sulphuric acid (containing say about sixty two per
cent. H.SO) can be used instead of the hydrochloric acid; it is then unnecessary
to heat under pressure.
EXAMPLE C.
Mix about ten parts (by weight) of the colouring matter soluble in water
mentioned in the foregoing Example B with about one hundred parts of phosphoric
acid (containing say about eighty seven per cent. H,PO) and stir continuously.
Heat for some time at about one hundred and forty degrees centigrade, when the
mixture froths up owing to the evolution of steam. Afterwards raise the temperature
to about from two hundred to two hundred and forty degrees centigrade and maintain
this temperature for about half an hour, or until the desired colouring matter
comparatively insoluble in water is produced. Pour into water, filter, dissolve in
alkali, precipitate in hydrochloric acid, filter, and wash.
EXAMPLE D.
Mix or dissolve about fifteen parts of the aforesaid soluble colouring matter with
about one. hundred parts of water and heat the mixture in an autoclave at a tem-
perature of about one hundred and fifty to two hundred degrees centigrade for about
eight to ten hours. The same test to determine the completion of the reaction may
be used as in Example B; work up also in the same way as above described.
The modification of the process described in Part 2 can be applied to the
soluble colouring matters, in all cases, regardless of the manner in which they
may have been obtained.
Dated this 15th day of July 1892.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Blue Mordant-dyeing Colouring
Matters.
JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention (which has been com
municated to me from abroad by The Badische Anilin and Soda Fabrik of
Ludwigshafen on Rhine in the Empire of Germany) 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 the processes for the production of colouring matters

page_text: .
parts of crystallized sodium sulphide (Na,S + 7Aq) in about two hundred parts
of water. Boil the mixture for from one to two hours. When all the sodium
sulphide has been used up and its presence cannot be detected in the mixture, filter
and wash and dry the residue.
The reduction product so obtained using the aforesaid quantities and under the
aforesaid conditions possesses the following properties but if the degree of reduction
be varied within the limits hereinbefore mentioned, products varying in character
are obtained, but these can still be used in the same way. It is a reddish powder
which is soluble in cold fuming sulphuric acid containing about twenty-three per
cent. free.anhydride yielding a solution of a brown-red colour. In cold fining acid
containing about seventy per cent. free anhydride it dissolves, the solution being
of a green-blue colour. In ordinary concentrated sulphuric acid, containing about
ninety five per cent. H₂SO, it dissolves with difficulty, the solution on warming
being of a green colour and the product is reprecipitated unchanged by the addition
of water.
To prepare the mordant dyeing colouring-inatters from this reduction product,
the process described in the examples of the master-patents can be used simply
replacing the dinitro-anthraquinone mentioned in each case by the same quantity
of the reduction product. The soluble colouring matters obtained as the result of
the first step of the process are the same or similar to those described as the result
of the first step in the master-patents and so also the comparatively insoluble dyes
ultimately obtained are practically, identical with those described in the said
master-patents.
EXAMPLE 2.
Production of the reduction product in the fuming sulphuric acid mixture.
Mix together about ten parts of 14 dinitro-anthraquinone (or other .dinitro-
anthraquinone as aforesaid) about one and a half parts of sulphur and about fifty to
one hundred parts of fuming sulphuric acid containing from about 12 per cent. to
about 40, per cent. free anhydride (see the examples given in the Specifications of the
master-patents). Heat the mixture for several hours at a temperature of about
one hundred or one hundred and thirty degrees centigrade and subsequently (either
with or without previous isolation of the soluble, colouring-matter formed) with
ordinary.concentrated sulphuric acid. The treatment in fact after mixing may be
exactly as described in the Specifications of the master-patents.
The reduction products formed in the melt are immediately converted into
colouring matter, which appears to be practically identical with the product
obtained by the corresponding treatment in the manner described in the Specifica-
tions of the master-patents.
The improved process as herein described yields the valuable mordant dyeing
colouring matters in larger quantity and of a purer quality than is the case with
the processes described in the Specifications of the master-patents so that by this
invention the cost of production is lessened.
SUBSTITUTION OF OTHER REAGENTS FOR CONCENTRATED SULPHURIC ACID
IN THE SECOND STAGE OF THE PROCESSES DESCRIBED IN THE SPECIFI-
CATIONS OF. THE LETTERS PATENT HEREINBEFORE REFERRED TO.
The following examples (the details of which are also capable of variation
without departing from the nature of this invention) will illustrate this part of the
invention.

page_text: Mix or dissolve, about fifteen parts of the aforesaid soluble colouring matter,
(as mentioned in the foregoing Example 3) with about one hundred parts of water
and beat the mixture in an autoclave at a temperature of about one hundred and
fifty to two hundred degrees centigrade for about eight hours or until the desired
colouring matter comparatively insoluble in water is produced, work up in the same
way as herein before described.
The modification of the process described in Part 2 can of course be applied to
the soluble colouring matters, in all cases, regardless of the manner in which they
may have been obtained.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The improvement in the manufacture of blue mordant dyeing colouring
matters consisting in the employment in a process such as is hereinbefore described
of nitro-anthraquinones which have been partially reduced by treating the dinitro-
anthraquinones hereinbefore referred to with the suitable reducing agents herein-
before set forth substantially in the proportionate quantities and manner described.
2. The manufacture of blue mordant dyeing colouring matters by treating
substantially in the manner hereinbefore explained nitroanthraquinones which have
been partially reduced by any suitable reducing agents first with fuming sulphuric
acid and then with concentrated sulphuric acid.
3. The improvement in the manufacture of blue mordant dyeing colouring
matters consisting in first preparing partially reduced nitro-anthraquinones substan-
tially as hereinbefore described and claimed in the first claiming clause then
treating them successively with fuming sulphuric acid, and with ordinary sulphuric
acid substantially as hereinbefore described and claimed in the foregoing second
claiming clause.
4. In the manufacture of blue mordant dyeing colouring matters the treatment
of the dinitro-anthraquinones herein before referred to in admixture with fuming
sulphuric acid, with a suitable reducing agent, substantially in the proportions and
manner hereinbefore described.
5. In the manufacture of blue mordant dyeing colouring matters the production

page_text: of the partially reduced nitro-anthraquinones by treating the dinitre-anthraquinones
herein before set forth with sodium sulphide as a reducing agent in the manner
described in the foregoing Example 1.
6. In the manufacture of blue mordant dycing colouring matters the treatment
of the dinitro-anthraquinones herein before set forth with fuming sulphuric acid
and sulphur as a reducing agent in the manner described in the foregoing
Example 2.
.7. The improvement in the manufacture of blue mordant dyeing colouring matters
consisting in the treatment of soluble colouring matters herein before defined with
suitable reagents for the elimination of sulpho groups substantially as hereinbefore
described.
8. The production of blue mordant dyeing colouring matters by treating the
soluble colouring matters herein before defined, with hydrochloric acid or dilute
sulphuric acid, with phosphoric acid or with water alone as described in the
foregoing Examples 3, 4 and 5.
Dated 15th day of M 1902
J. H. JOHNSON & Co.,
Agents.