A New or Improved Process of Manufacturing Incombustible and Inodorous Celluloid.
Year: 1892

page_text: Date of Application, 25th N.v., 1892-Accepted, 6th May, 1893
COMPLETE SPECIFICATION.
A New or Improved Process of Manufacturing Incombustible
and Inodorous Celluloid.
We, EUGÈNE CADORET and EMIL DEGRAIDE, both of Deville, Republic of
France, Chemists, do hereby declare the nature of our invention and in what
manner the same is to be performed, to be particularly described and ascertained
in and by the following statement :—
Our invention relates to an improved process for producing incombustible and
inodorous celluloid of great purity and which we intend shall be commercially
known as "Cellulosine.' To attain this object the raw material is first subjected
to a preparatory treatment, for obtaining cellulose after which a compound or
mixture containing nitric acid is applied, the substance thus obtained being bleached
and dried.
The dinitrocellulose, after being bleached, and dried, is then treated with a
substance, which we call "camphogine," easily forming a solid compound with
dinitrocellulose and obtained in the manner hereinafter described. Finally, after
the treatment with said "camphogine," the incombustibility of the dinitrocellulose
is attained by adding the chloride of any suitable metal in combination with certain
organic animal substances, as will be more fully stated hereinafter.
We will now proceed to describe the specific manner in which we prefer to
perform our improved process.
The raw material which we make use of in this process is cotton, paper, straw,
wood, or a similar vegetable substance. This material is first washed in succession
with alkalies and with acids (for instance soda lye and diluted sulphuric acid)
and then treated with an acid solution composed and prepared in the following
manner:
About equal quantities of molasses and starch are partly dissolved in water, and
when the mixture has taken place, nitric acid of 36° Beaumé are added and the
liquid is heated. Fumes of nitrous acid are evolved, and the substances contained
in the mixture are gradually dissolved. The product obtained by the treatment of
the raw material by the above acid mixture is cellulose of great purity; this
substance is allowed to dry and then treated at a temperature of about 40-45° with
a double solution, obtained by dissolving a bisulphate (for instance bisulphate of
soda) in sulphuric acid of 66° Beaumé and a nitrate (for instance nitrate of soda)
in nitric acid of 42° Beaumé and by mixing these two solutions. The cellulose,
treated with this double solution is completely changed into dinitrocellulose.
The product is then thoroughly washed and bleached by means of a "double salt
of hyposulphites of soda and magnesia. The following is a suitable method of
preparing the bleaching liquid. In a vat containing 2000 L. of water we dissolve.
mechanically 144 kg. chloride of lime, 34 kg. sulphate of magnesium, and 20 kg.
soda. The salts which are precipitated are allowed to subside, and the clear liquid
is poured off. This liquid-a double solution of hyposulphite of soda and
hyposulphite of magnesia-is mixed with a quantity of a liquid containing
chlorine, in this case a chloro-metric degree, suitable for the bleaching operation.
We then add a small quantity of the above mentioned acid liquid which we call
Sacchooxalic acid and consists of 2 kg. molasses, 2 kg. starch, 10 L. water
and 6 L. nitric acid at 36°, whereby the dinitrocellulose is rapidly bleached, and all
traces of chlorine are removed.
50 kg. of the dinitrocellulose bleached in this manner, are then put into a vat
containing 2000 L. of 2% chloride of zinc solution. After some hours the
dinitrocellulose is removed and, after being mixed, whilst in a moist condition, that
is to say containing 40% of water, with oxide of zinc, is powdered by suitable
machines.

page_text: A substance, which we call camphogine, is added to the mass whilst still in a
moist condition, and gives it the necessary ductility and diminishes its combus-
tibility. Camphogine is similar to the camphor in its properties and forms easily an
intimate compound with dinitro-cellulose. The camphogine (not to be changed
with the so-named, artificial camphor or monochlorhydrate of turpentine CH16
HCI) is obtained by the decomposition of turpentine by means of hydrochloric-
acid gas with addition of any metal f.i. zinc. The formed hydrogen decomposes the
chlorhydrate of turpentine, thus producing a liquid mixture, which forms, after
boiling with any alkali, white crystals of camphogine. This camphogine with an
addition of an alcoholic solution of chloride of zinc is intimately mixed with the
dinitrocellulose, and certain organic animal substances as for instance, gelatinous
albumin, casein, etc. are further added to remove part of the moisture of the mass.
At the same time complete incombustibility is abtained.
The resulting mass is very plastic and can be either rolled, planed or otherwise
formed by suitable machines, at the same time, the mass may be coloured by the
admixture of suitable colouring matters. The finished product which we term
cellulosine is soluble in a mixture of alcohol and camphor, is very ductile, and can
be drawn out into fine silk-like threads, so that it is applicable to the manufacture
of yarn and textile fabrics etc. It can also be advantageously used for the
manufacture of silk.
The incombustibility of the fabrics prepared from this material is an especially
important and valuable property of the same.
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 :-
1. The process of manufacturing cellulosine, an inodorous and incombustible
material by bleaching celluloid by a double salt of. hyposulphites of soda and
magnesia, and sacchooxalic acid, and by then treating the mass with camphogine
and chloride of zinc, substantially as herein described.
2. As an inodorous and incombustible composition of matter, celluloid intimately
mixed with camphogine and chloride of zinc, substantially as herein described.
Dated this 23rd day of November 1892.
EUGÈNE CADORET and
EMIL DEGRAIDE.
By Geo. Thos. Hyde,
4, Moorfields, Fore Street, London, E.C., Agent for the Applicants.