Manufacture of Solutions of Tetranitrocellulose (Collodion Pyroxyline).
Year: 1896

page_text: Date of Application, 28th Mar., 1896
Complete Specification Left, 10th Dec., 1896-Accepted, 27th Feb., 1897
VIDIONAL SI DUIFICATION.
[Communicated from abroad by Dr. EMILE BRONNERT, Chemist, of 2 Rue du
Brubach, Mulhouse, and THEODORE SCHLUMBERGER, Manufacturer, of
Mulhouse, Alsatia.]
Manufacture of Solutions of Tetranitrocellulose (Collodion
Pyroxyline).
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention to be as follows:-
As solvents for tetranitrocellulose (collodion pyroxyline) the following substances
are generally employed :-
Acetic ether, mixtures of ether, and alcobol, methylated spirits, acetone, nitro-
glycerine, nitrobenzene, glacial acetic acid, acetate of amyle and alcoholic or ethereal
solutions of camphor.
Binitrobenzene, nitronaphthaline, anilides such as benzanilide, acet-toluide, and
analogous substances have also been used for preparing the so-called "solid
solutions" in works for the manufacture of explosives.
Nevertheless the price of most of these, the explosive nature of the vapours of
the more volatile substances, the deleterious nature of the vapours of some amongst
them, and other serious inconveniences, rendered the discovery of cheaper and
more innocuous solvents very desirable for many technical purposes.
In the course of investigations my correspondents have found that alcohol, which
does not dissolve tetranitrocellulose (collodion pyroxyline) at all, can be converted
into a very good solvent, when there is added to it even small quantities-about
5 1er cent. or more-of organic and inorganic substances of which a very
considerable number are applicable for the purpose, such as:
1. Acids Acetic acid, xalic acid, citric acid, tartaric acid, lactic acid, levulic
acid, and hydrochloric acid.
Instead of the free acids, their salts with alkalies (potassium, sodium, ammonium)
such as acetate of potash, chloride of ammonium &c.) earth alkalies (magnesium,
calcium. barium, strontium, such as borocitrate of magnesium, chloride of calcium
&c.) earth metals (aluminium, such as chloride of aluminium) and zinc (chloride
of zinc &c.) can often be used very advantageously, when they are soluble in
alcohol.
Alcoholic solutions of alkylsulphates, (like ethylsulphate of sodium &c.) dissolve
also very large quantities of tetranitrocellulose (collodion pyroxyline).
2. Aldehydes Acetic aldehyde, benzoic aldehyde &c., and their compounds
with alcohols, like methylal, acetal &c.
3. Ethers The ethers of the above named acids, especially those of oxalic,
citric, tartric, levulic, and hydrochloric acid with monatomic alcohols (methylated,
ethylated, &c. spirits) and polvatomic alcohols (glycerine, glycol &c.).
4. Phenols Nitrophenols, an.idophenols, phenolcarboxylic acids such as carbolic
and pieric acid, para-amidophenol, salicylic acid &c.
5. Nitro compounds of the aromatic hydrocarbons: Such as nitrobenzene,
m-binitrobenzene, Litronaphthalene, trinitrotoluene &c.
6. Bases Such as quinoline, pyridine and their homologues.
7. Amides: Such as urea &c.
°
Ad

page_text: The solutions should be made with dried tetranitrocellulose (collodion pyroxy-
line) or at least with tetranitrocellulose which contains only a small percentage of
water.
The dissolving power of methylated spirits is still farther increased, when to the
same is added even small quantities of the above named solvents.
The danger connected with the drying operation of nitro compounds of cellulose
can easily be avoided in using for example the following method:
30 kilos. of tetranitrocellulose (collodion pyroxyline) wet as it comes from the
hydro extractor, are carefully impregnated with a concentrated solution of chloride
of calcium, squeezed and dried.
The tetranitrocellulose (collodion pyroxyline) impregnated in such a manner is
scarcely inflammable and is readily soluble in cold alcohol.
The risks of accidents from concussion and spontaneous decomposition are
minimised.
A choice can easily be made amongst the solvents enumerated for ascertaining
those most convenient for the various technical purposes, such as the manufacture
of celluloid, filaments for incandescent lamps, artificial silk, varnishes, and gun-
powders, to which the solution is to be applied.
Dated this 28th day of March 1896.
ABEL & IMKAI,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Solutions of Tetranitrocellulose (Collodion
Pyroxyline).
CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery
ne, in the County of London, Consulting Engineer and Chartered Patent Agent,
hereby declare the nature of this invention and in what manner the same is to
performed to be particularly described and ascertained in and by the following
tement:-
As solvents for collodion pyroxyline the following substances are generally
ployed:
Mixtures of alcohol and ether
Methylated spirits
Mixtures of methylated spirits and methylic ether
Acetic ether
Acetone
Acetic acid, either alone or in mixtures with alcohol or ether
Acetate of amyle
Formic esters dissolved in alcohols
Mixtures of alcohols with their oxidation products (aldehydes,
ketones &c.)
Mixtures of sulphuric acid with alcohols (alkyl sulphuric acids)
Camphor dissolved in alcohol, ether, hydrocarbons, bisulphide of carbon,
carbon tetrachloride, or sulphurous acid
Aniline
Nitroglycerine
Nitrobenzene
Binitrobenzene, binitrotoluol, binitroxylol, anilides (formanilide, acetani-
lide, acettoluide, acetxylide) have also been used for preparing the
so-called "solid pyroxyline compounds."
Nevertheless the price of most of the above named solvents, the explosibility of

page_text: the vapours of the more volatile ones, the toxic nature of the vapours of some
amongst them and other serious inconvenience rendered the discovery of cheaper
and more innocuous solvents very desirable for many technical purposes.
In the course of investigations my foreign correspondents have found that the
ethyl alcohol (95° Tralles) which does not dissolve collodion pyroxyline at all (see
Eder, Berichte d. deutschen chem. Ges. 1880 XIII p. 184) can be used as a very
good solvent, when it is added with even small quantities-about 5 per cent. or
more of certain organic or inorganic acids either a free state or in the form of
their ethers or salts which are soluble in alcohol
The acids they employ are the following :-Oxalic acid, citric acid, tartaric acid,
lactic acid and levulic acid (C'HO³ see Wurtz. Dictionnaire de Chemie Supple-
ment G.Z. page 981).
The salts of these acids and those of alkylsulphuric and hydrochloric acid with
alkalies (potassium, sodium, ammonium) earth alkalies (magnesium, calcium,
barium, strontium) earths (aluminium) and zinc, which are soluble in alcohol can
be used with the same result.
The ethers of the above named acids with mono- (nethyl, ethyl &c. alcohols)
or polyatomic alcohols (glycol, glycerine,) may also be substituted for the free
acids.
The known dissolving power of methylated spirits is highly increased, when to
the latter is added even small quantities of the above named substances.
The solutions should be made up with dried collodion pyroxyline or at least
with such an one, which contains only a small percentage of water.
The danger which resides in the drying operation of the pyroxyline can easily
be avoided in proceeding for example in the following manner
30 kilos. of wetted collodion pyroxyline are carefully impregnated with a solution
of chloride of calcium in water, squeezed and dried.
The thus impregnated and dried collodion pyroxyline is scarcely inflammable
and is readily soluble in ethylic alcohol.
The risks of accidents from concussion and spontaneous decomposition are
mininised.
A choice can easily be made amongst the enumerated substances to find out
those most convenient for various technical purposes, such as the manufacture of
celluloid, artificial silk and varnishes.
Having now particularly described and ascertained the nature of this inven
tion and in what manner the same is to be performed, 1 declare that what
I claim is :-
1. In the manufacture of solutions of collodion pyroxyline, the use as a solvent
of ethylic alcohol or methylated spirits to which are added small quantities of
certain acids or the salts or ethers thereof, substantially as set forth.
2. The manufacture of solutions of collodion pyroxyline by using together with
ethylic alcohol or methylated spirits the following substances:--
a) free oxalic, citric, tartaric, lactic or levulic acid.
b) the salts of the said acids or of hydrochloric or alkylsulphuric acid with
the alkalies (potassium, sodium, ammonium) the earth alkalies (magnesium,
barium, calcium, strontium; the earths (aluminium) and zinc.
c) the ethers of the said acids with mono- or polyatomic alcohols (methyl or
ethyl alcohol, glycol or glycerine).
3. The process of making up the solutions of collodion pyroxyline consisting in
impregnating the wetted pyroxyline with an aqueous solution of chloride of
calcium (CaCl2) or the like, squeezing and diying the so prepared collodion
pyroxyline and dissolving it in methyl or ethyl alcohols, substantially as
described.
4. As a new article of manufacture the solutions prepared as set forth in the
preceding claims.

page_text: 5. The employment of the said solutions to various technical purposes, substan-
tially as set forth.
Dated this 10th day of Dovember 1904
ABEL & IMRAY,
Agents for the Applicant.