US517987A - Ments - Google Patents

Description

NITE STATES ATENT F ICE.

JOHN H. STEVENS, OF NEWARK, NEW JERSEY, ASSIGN OR, BY MESNE ASSIGN- MENTS, TO THE OELLULOID COMPANY, OF SAME PLACE.

MANUFACTURE OF souo COMPOUNDS OF PYROXYLIN'.

SPECIFICATION forming part Of Letters Patent No. 517,987, dated April 10, 1894;

Applioationfiled June 9, 1890. Serial No. 354.786. (No specimens.)

T0 at whom it may concern:

Be it known that I, JOHN H. STEVENS, ofthe city of Newark, county of Essex, and

State of New Jersey, have invented certain new and useful Improvements in the Mannfacture of Solid or Massive Compounds of Pyroxylin, of which improvements the'following is a specification.

This invention relates to the manufacture or manipulation of those varieties of material designated as solid or massive compounds of pyroxyline, or those compounds in which the process of conversion is effected while the material is in a solid or massive condition, which, as is well known, have already been the subject of extensive investigation and numerous patents, and it has for its object the production of anew composition of matter, byb ringing together into new relations and with novel effects certain substances well known to chemistry, as hereinafter described.

The distinctive novelty of this improvement in the art of manufacture consists. in the employment, in combination with pyroxyline, of the solid substance known as phenyl acetamide (acetanilid), and in such a manner that the presence of the phenyl acetamide gives the property of plasticity to the compound and renders it susceptible of conver-.

sion into an amorphous condition, or permits its manipulation or change of shape by the ordinary means employed in connection with other solid pyroxyline compounds, and in addition furnishes a compound possessing entirely new and unique properties.

Wherever I use the word phenylacetamide, in this specification, I also include the substance having the name, acetanilid, the latter being the name of the commercial article. In Watts Dictionary of Chemistry, London, 1883, volume 4, page 114, acetanilid and phenylacetamide are described as identical, with a melting-point of 112 centigrade.

The two substances are also pronounced the same in Beilsteins Haridbuch, second edition, volume 2, page 264, and in Roscoe and Schorlemmers Treatise on Chemistry, Appletons edition of 1870, volume 3, page 210. Butin Beilsteins Handbuch der Orgdnischen Chemie, second edition, volume 2, page 268, acetanilid is described as a distinct substance, melting at 112 centigrade, and, in the same book, page 841, phenyl-acetamideis described as a distinct substance, melting at from 154 to seem to have been originally confounded with each other, I prefer the use of the acetan-ilid of commerce to the true acetanilid-pheny1- acetamide,-because it has a lower boiling point, and also because the true phenyl-acetamide is so difficult of production that it will probably never be of commercial importance.

My invention is based upon the fact that v phenyl acetamide when melted by heat is an active solvent of pyroxyline, the discovery of which fact I believe to be entirely original with me. v

The pyroxyline employed in this manufacture is, as is well understood, of the variety designated as soluble, to distinguish it from the highly explosive kind used in blasting and for military purposes. That is, it is soluble ina variety of substances known as solvents of pyroxyline, of which a mixture of ether and alcohol is the best known example. It is generally produced by the action of nitric and sulphuric acids upon some form of cellulose, such as cotton or paper. Hence its name, nitro-cellulose.

Com pounds of pyroxyline, as is well known, are made by combining or dissolving pyroxyline with one or more of its solvents. For the purpose of'imparting to the compound, opacity, color, hardness, flexibility, or other desired quality, pigments, colors, and other substances are sometimes combined with the dissolved pyroxyline, as is well understood. It is also known that these compounds vary from the condition of dense solids to thin liquids, depending on the proportion of fluid present in the compound.

The earliest known pyroxyline compounds were thin solutions made with liquid sdlvents, and were the subject of practical applications long before the solid compoundsw hose production awaited the discovery and perfection of intricate methods and mechanical appliances-were possible. The extreme simplicity of the liquid solutions,whose manufac- ICO ture merely involved dissolving the pyroxyline to a sufficiently fluid condition by ordinary means, permitted their being early brought to a state of comparative perfection, so far as method went, and, consequently no new important uses for these liquid compounds have been found in twenty years; although their manufacture has become more extended through the employment of new liquid solvents discovered from time to time, the simple nature of the methods employed permitting their adoption whenever their properties were such as to be desirable in the compound.

Although there is a wide difference between thenature and applications of the liquid and solid compounds, the preferred liquid compounds being of an extremely fluid nature, and the preferred solid compounds being comparatively hard and dense, to some extent, in certain limited applications, the dividing line between the two classes of compounds is not so distinctly marked. Generally speaking, and leaving out ofconsideration these minor distinctions, the fluid compounds are those in which the proportion of solvent is suiiiciently large to permit the solution to flow, or to be easily poured from one vessel into another, and without the'aid of mechanical pressure or elevated temperatures. On the other hand, the solid compounds are those in which the proportion of solvent is so small that the solution will not flow, but appears as a solid or thick pasty mass, which requires the aid of rollers or other masticating apparatus, or the additional influence of elevated temperatures, to render it capable of being altered in shape or mixed or otherwise manipulated. The simple character of the liquid compounds, and their limited application as compared with the solid compounds, is illustrated both in the history of the art and in the well known commercial uses of these compounds. Thus the liquid compounds are almost exclusively employed as simple transparent solutions to be spread or flowed upon surfaces, with the result of depositing thin films, as artificial cuticle, or protective coatings for paper, metals, 850.; or these films are used, without further manipulation, for photographic purposes. On the other hand, the solid compounds are made in large masses of dense homogeneous material, colored and formed to closely imitate natural and other substances; for instance, fine marbles, tortoise shell, ivory, amher, due. Further,these are so formed and of such a nature that they can be readily molded or otherwise shaped into perfectly uniform sheets of any thickness, or tubes, rods and fine wire of any length. These again by reason of their peculiar composition and perfectly homogeneous solidity, are manufactured into jewelry, cutlery, toilet articles, collars, piano keys, 85c.

It was not alone the application of mechanical methods, or ingenious processes of mixing, which brought about the comparative state of perfection of this manufacture, but, in common with the liquid compounds, the progress of the art has depended largely upon the discovery and application of new solvents or menstrua useful in this manufacture. The solvents can generally be classed under two headsliquids and solids. There is awide difference, however, between the action and applicability of the liquid and solid solvents. The liquid solvents being fluids, which, whenever used with pyroxyline, soften or render it fluid, according to the proportion employed and other conditions, while the solid solvent solution of pyroxyline is only made at elevated temperatures, whatever the proportion used, and always results in a hard compound due to the solid nature of both ingredients; thus confining the employment of such' solvcut, when used alone, to the solid variety of pyroxyline compounds. it is true that modified results are obtained by combining both classes of solvents, a small proportion of liquid permitting the solid solvent to act at sufficiently low'temperatures so that the solid compounds are workable in heated rolls, and a large proportion forming a fiuid,compound useful as a varnish, or spreading solution. WVhile solid solvents like camphor have been so employed, such is the nature of pyroxyline compounds, as hereinafter explained, that the camphor loses its distinguishing characteris tics and importance asa solvent in proportion as the liquids are increased in amount, though it still retains sufficient of its peculiar nature to modify the compound by its presence. Again, I have discovered that some solid solvents are so difierent in their nature from camphor that even this property disappears, and unless they are combined with camphor, their usefulness is exclusively confined to the solid compoundsor, at least, whatever there is of utilityin applying them to this manufacture manifests itselfso differently in the various compounds as to make a broad distinction between their application to liquids, as distinguished from solid compounds. In other words, liquid solvents are generally useful in all compounds of pyroxyline, while some solvents are more especially fitted for the compounds, and some, unlike camphor, which is more or less of universal application, are almost exclusively confined to the solid modification. Hence, the action of liquid solvents is more apparent and simpler, while the discovery and application of solid solvents, which only exhibit all of their useful action under peculiar conditions, is more difficult. It therefore follows, naturally, that there are fewer known solid solvents than liquid ones, although the solids are especially applicable to the most popular form of compound, and therefore their discovery is very important.

The simple action of the liquids has rendered their discovery comparatively easy, but, doubtless, as in the case of camphor, solid solvents of great practical utility have IIO IIS

been employed in pyroxyline solutions, for the production of certain effects, in such a way that their usefulness has had no opportunity for sufficiently instructive demonstration; and what might have been valuable inventions, if followedup by a proper course of experimenting, have been lost to the art.

The simple use of asubstance'in connection with pyroxyline, or the mere discovery that certain menstruawilldissolvepyroxyline,does not necessarily involve the availability of such mens-trua as useful solvents in the manufacture of pyroxyline compounds, for some materials will dissolve in, or combine with pyroxyline solutions, but their presence adds no new and useful feature, and is more frequently detrimental, so that the solutions are better for theirabsence. Besides, somesolvcuts of pyroxyline are utterly useless ones and of no practical benefit to the art. Hence the mere discovery of solvent properties of a substance may be insufiicient to convey any instructive idea to the art, and it is only after a practical illustration of its utility such as to enable the user to say that it is a useful solvent that its applicabilityis proven beyond the necessity for further experiment. Thus while the use of ether and alcohol as the menstrua for the fluid compounds known as surgical and photographic collodion is perfectly practicable, it is well known that numerous attempts to utilize ether and alcohol in the production of solid compounds were attended by a large waste of capital and results' so discouraging that these solvents were abandoned as inapplicable to such manufacture, or, at least, unprofitable to use by reason of the uncertain character of the result. In

regard to solid solvents the same holds true,

but to a greater extent, and the mere fact that the presence of a solid substance in liquid compounds results beneficially is no de1non stration that it would also be useful in a solid compound, although the converse might be true. Thus, Cutting, in 1854, added camphor to ether-alcohol collodion to obtain effects beneficial in the evaporated solution when applied to photographic purposes, but Without the slighest intimation that camphor was to be the substance which, through the later experiments of Parkes and Hyatt was demonstrated to be of extraordinary utility in manufacturing solid compounds; and which, as a result of Hyatts discovery of its individual solvent powers when heated, became the foundation of the present method of manufacturing solid compoundsthat has resulted in such a remarkable commercial and financial success.

The fact that a solid body is a solvent of pyroxyline when, melted by heat so distinguishes it from all other substances, solid or liquid, that a proposed use of any such body in making solid compounds should invariably be based upon a knowledge of its solvent powers, or such description as would enable the operator in the art to use it understand roxyline solvents which, while enhancing the solvent action, exhibit a power to dissolve pyroxyline only when combined with other solvents, and when used alone are utterly valueless. This is also true of some liquids, asis well understood.

While it is true as before stated, that the solid compounds of pyroxyline have been brought to a state of comparative perfection,

these compounds are nevertheless, susceptible of greater improvement so that the range of their usefulness can be still further extended and their properties so modified as to remove a great many objections which the present state of the art can find no remedy for. Having, as an expert manufacturer of these compounds, appreciated the importance of these .facts, I have made a special study of the subject and believe that my experiments have resulted in such novel improvements as will producestill greater perfection in this art.

The present invention is exclusively confined to the manufacture of solid pyroxyline compounds, and is based upon the fact that phenyl acetamide, a substance known in commerce, is a solvent of pyroxyline when melted by heat. I believe that Iam the original discoverer of this fact, and I have applied it successfully to the production of a new and unique compound of pyroxyline having peculiar characteristics and differing from any of the compounds heretofore known, as hereinafter described.

In combining phenyl acetamide with pyroxyline, I make use of the processes usually employed when camphor is the solid solvent; And'the results, to someextent, are similar, for the phenyl acetamide remains a part of the finished compound, and imparts to it the susceptibility of being readily molded under IIO heat and pressure. There are, however, the

following important differences. The high temperature at which camphor melts limits its practicalemployment as a solvent alone, or uncombined with a trace of alcohol, or its equivalent; for the use of great heat injures these compounds by its tendency to decompose the pyroxyline, or, at least, to discolor it. The usual practice has been to employ alcohol, or some similar solvent in connection -with the camphor, to so'lower its melting point that the compound could be manipulated at comparatively low temperatures in rolls, and the molding operation on the seasoned product be conducted at lower temperatures than are possible when camphor alone is the solvent. The effect of this has beento render the seasoning and molding of these compounds very delicate operations, requiring great skill and careful treatment; and hence it has been somewhat difficult to produce uniformly perfect results, and a certain percentage of the goods are of second quality, or have to be classed as scrap to be run over into cheaper grades of the product.

The compound made with phenyl acetamide can be thoroughly seasoned or dried without any impairment of its molding properties, the low melting point and non-volatile nature of the phenyl acetamide giving to the dry product the permanent quality of easy plasticity, as distinguished from camphor compound,from which the camphor is gradually evaporating. Another desirable effect obtained by the employment of this new solvent is that it renders the dry material much less liable to warp or shrink, or to loss of weight, which are very annoying features of the camphor process. The camphoraceous odor of the older compounds has also been a great objection, and has limited somewhat their usefulness in applications where the smell is undesirable. The inodorous character of phenyl acetamide does away with these objections also, and furnishes a compound more nearly resembling the natural substances it is intended to imitate.

In making an absolutely odorless, and permanent compound,l grind the pyroxyline and phenyl acetamide together to a fine pulp. This should be done in the presence of sufficient moisture to render the mixture non-inflammable but the particular mode of grinding or mixing is no part of my invention, and incorporate with it such coloring matters or pigments as are desired in the final compound, as is well understood. The grinding of all the ingredients can be done simultaneously, or the pyroxyline can be preliminarily reduced to pulp in a paper engine, or by any other well known means, and afterward mixed with the other ingredients, and further ground in any suitable apparatus, such as a Bogardus mill, as understood. For this compound good proportions are one hundred parts of pyroxyline and fifty parts of phenyl acetamide, by weight. After a very thorough grinding of the ingredients, I prefer to press the resultant mixture, if moisture is to be expelled, into thin cakes and submit them to pressure between blotting papers, in order to extract the water,in the well known manner, or in accordance with the process described in United States Letters Patent, No. 269,968, of April 15, 1884, issued to John W. Hyatt, W'illiam H. Wood and myself. The coloring ingredients vary with the properties desired in the final compound, as is well understood. Thus, for a plain white material, I employ about twenty to forty parts by weight of zinc oxide, modifying the whiteness, if necessary, by the addition of blue or other tint. Other plain colors, such as red or blue, are formed by combining with the pyroxyline and phenyl acetamide from one to five per cent. of Vermilion for the red, and ultramarine blue for the blue color. It is unnecessary to give further illustrations for the coloring of pyroxyline compounds is well understood by operators in this art, and all of the efiects necessary in the production of the various imitations of natural substances and the different applications of this material have long been produced.

In making the compound for rolling, the dried cakes produced by pressing the wet pulp, containing the solvents and coloring materials, between blotting papers, may be broken in small pieces and mixed with from about forty to fifty parts of wood alcohol or preferably a mixture of wood alcohol and grain alcohol (ethylic alcohol). This mixture should be inclosed in an air tight vessel and permitted to stand for several hours, generally over night, in order to allow the liquid solvent to become fairly welldiifused throughout the mass. After this, is done, the mixture is ready for mastication, which is performed in heated rollers at about 120, as is customary in manufacturing such solid compounds as this patent relates to. The effect of working the mixture in heated rolls is to transform it into a dough-like mass, and thoroughly combine the solvents with the pyroxyline. The heat generated by the friction of rolls, which at the commencement of the operation are entirely cold, will be sufficient it continued long enough, and even this will finally result in too high a temperature unless controlled by passing cold water through the rolls. After this operation has proceeded far enough, as is well understood,-

the material is removed from the rollers in a condition very much resembling the ordinary compound made with camphor; that is, in a rough porous condition which requires subsequent treatment in so-called stuffing machinery, or pressed, where heat and pressure can be applied, in order to solidify it and form it into the various shapes, such as tubes, rods, or sheets, required for the difierentpurposes to which these compounds are applied.

As is well understood in the art some coloring materials or other substances desirable in the compound cannot be combined with the pyroxyline and solvent during the grinding, or mixing process, on account of their solubility in the water used to render the compound non -infiammablesome aniline dyes, for instance. I pursue the usual practice with such colors, &c., and add them to the compound either dissolved in the liquid part of the solvent, or by suitable means when the material is rolled.

When using camphor, it has been customary to employ mainly ethylic and methylic alcohols, although to a less extent, but just as effectively, other liquids have been used. I have found that phenyl acetamide is quite distinct from camphor in its solubility in various liquids, and the use of ethylic alcohol alcohol); itis more harmonious with methylic alcohol.

It is the practicein this art, in making or uslng compounds containing a solid solvent such as camphor, and a liquid solvent such as alcohol, to form the compound into various shapes such as sheets, rods, and tubes, and then to subject these to what is known as a seasoning process the object being to drive off the excess of liquid solvent, leaving behind practically the solid solvent. Thus, for instance, the most popular compound in commerce at present, .in its hard or seasoned state, consists essentially of pyroxyline and camphor with the usual coloring matters, &c., in combination. The presence of camphor imparts a valuable characteristic to such compound, for it enables it to be molded in heated dies into any desired shape, the application of heat and pressure softening or liquifying the camphor so that it acts on the pyroxyline in combination with it as a solvent, or to so dissolve or soften it that the compound flows, or can be manipulated at the pleasure of the operator. To some extent-,therefore, the employment of heat and pressure to effect a softening of the dried or hardened pyroxyline compound, containing a solid solvent, even though it has not been made originally in rollers, but has been made by the aid of liquid solvents, resembles the action which takes place when the solid solvent is intimately combined with the pyroxyline Without the presence of liquid solvents, and the mixture converted under heat and pressure in dies or other suitable apparatus. This resemblance is still more striking when employing the hence, the compound can be thoroughly deprived of all liquids before subjecting it to the final molding operations, and, in such a case, the phenyl acetamide is absolutely or practically the only solvent acting on the nitro cellulose. I mean to be distinctly understood, however, as claiming that even in the presence of a small proportion of liquid solvent, or of such proportion as wouldalone be ineffective for the purpose of usefully causing the pyroxyline to flow, under heat and pressure when molded the phenyl acetamide would be acting as a pyroxyline solvent when subjected to heat and pressure. In other words, my phenyl acetamide-pyroxyline compound, whether made by simply combining phenyl acetamide and pyroxyline, or formed with the aid of liquid solvents in heated rolls, or by dissolving the pyroxyline in a liquid solution of phenyl acetamide, or in anyequivalent manner, when in a dry or seasoned condition, or a comparatively hard state, due to the absence or removal of sufficient liquid to soften it, is in such a condition that when it is subjected to heat and pressure it depends for its plastic property, or susceptibilty of being flowed under heat and pressure, upon the solvent powers of the phenyl acetamide, and therefore any such heating, or the production of these conditions or efiects, is an employment of the phenyl acetamide, made efficient by heat, as a solvent of pyroxyline. The use of phenyl acetamide in solid or massive compounds of pyroxyline is not incompatible, however, with the employment of camphor. On the contrary, the use of phenyl acetamide in the camphor compounds imparts some of its novel properties to such compounds, namely, by enabling the camphor to melt at a much lower temperature by reason of its association therewith, and thus removing one of theobjectionable features associated with the employment of camphor alone, as asolid solvent. Consequently, compounds containing this combination solvent can be more readily molded at safe temperatures without the necessary presence of a residue of the alcoholic or other liquid solvent, thus rendering the manipulation of the camphor compound uniform and certain. In making such compound,I grind the camphor, phenyl acetamide, pyroxyline, and other necessary ingredients (preferably in the presence of water, and then dried in the regular manner). Ethylic 0r methylic alcohols or other suitable liquid, may then be added to the mixture, and the whole stirred together and left over night in an air tight vessel. The resultant mass is masticated in rolls and formed into shapes in the" usual and well known manner. The finished product will have the characteristics already described as pertaining to these compounds. Goodproportions for this latter compound are one hundred parts pyroxyline, forty parts camphor, ten parts phenyl acetamide, and about forty to forty-five parts of either of the alcohols mentioned, or acetone can be used in place of the alcohols.

In describing the practical manipulation of my new compounds, I have recommended processes which a practical experience in the manufacture of these compounds has demonstrated to be preferred, as giving exact and economical results. I do not limitmyself to such processes", because useful results can be secured by departing more or less widely from ration, and the mastication would necessarily have to be more thorough to compensate for the absence of an intimate mixture, or the superior conditions afforded by the pieces of pressed cake. The drying moisture from the wet pyroxyline need not necessarily be done by means of blotting paper, as a more exposure to the air would permit the evaporation of the water; and, in fact, a novel property of my mixture results from the non-volatile nature of phenyl acetamide which would permit such exposure to the air without loss of solvent, as when camphor is employed. In regard to proportions also, it has been the custom in making compounds by the solid or massive process to vary the proportion of solid or liquid, according to the effect it was desired to produce, and I might give numerous examples of changes in proportion differing from those which I have recommended as examples; but I regard this as unnecessary, and I simply state that the proportion of solid solvent can be reduced, or increased, or the liquid solvent can be used in greater or less amount. It is simply necessary to keep in mind that sufficient of the solid solvent must be employed to give to the finished result the necessary quality of plasticity under heat. If plasticity is not desired to any great extent, a very small amount of the solid solvent can be employed. On the other hand, too large a proportion would tend to make the compound flow too readily when heated, or would weaken it by reason of the consequent lessening of the amount of pyroxyline present, upon which, as is well understood, these compounds depend for their strength and other peculiar characteristics. The use of rolls or any other masticating machinery can also be dispensed with if found convenient, and replaced with dies or with stufiing machinery or similar apparatus, in which the compounds can be converted under heat and pressure, or the conversion may be eifected by forcing through nozzles into various desirable shapes. I would recommend the rolls, however, as furnishing the most convenient means .for a thorough mixing or masticating of the materials, although the converting processes can be performed in stuffing machinery with a less waste of solvent when using carefully ground mixtures.

Among the advantages I claim for this new compound of pyroxyline in which phenyl acetamide is the solid solvent are that the operations of mixing are carried on without the loss by evaporation incident to the use of camphor, thus permitting a freer use of drying methods, and also rendering the air of the work room more pleasant and healthful than when filled with camphor fumes. There is practically no loss of the solid solvent by evaporation, which is due to the non-volatile property. The comparatively unchangeable character of the compound due to the non-volatile nature of the solid solvent employed also enlarges the field for the application of compounds made in this manner. Many I difli culties, more or less connected with or due to the continual warping of the older materials containing camphor, will be remedied by the application of my new compound to such uses.-

I would mention drawing instruments, parts of machinery, playing cards, and other printed matter, and also articles requiring to be nicely fitted together, like boxes, as examples. My new compound will also be found much harder and more elastic than the compounds made with camphor. When used alone as the solvent, of course, it is limited to What is known as the solid or plastic process of conversion but this process may also be practiced as above shown by adding such small quantity of liquid solvents, as will not make the compounds flow or result in what is known as the fluid process of conversion.

I have in conjunction with Frank (J. Axtell, filed another application, dated June 9, 1890, Serial No. 354,822,for the use of this ingredient in the fluid process of conversion because spe cial means are often required to render it effective in the fluid compounds, and to prevent it from injuring them by its presence, means of remedying which has been specified and claimed in said other application; and the use of the ingredient in the solid or plastic process is therefrom to be definitely distinguised. I have demonstrated its extraordinary utility in the solid varieties, as herein described, and the novelty of my present invcntion depends on such demonstration, according to the principles hereinbefore set forth.

I wish, it distinctly understood that even if pyroxyline be treated by the liquid mode of conversion and the liquid is then evaporated and then phenyl acetamide be present in proportions such as to produce, after evaporation of the liquid solvents, what is substantially a compound of pyroxyline and phenyl acetamide, any heating or treatment of the resulting solid which will develop the latent solvent power of the phenyl acetamide, so that it will soften, dissolve, or make plastic pyroxyline, is a use of the solvent powers of the phenyl acetamide as already explained, and such operation is within the invention herein set forth. a

It will be understood by those skilled in this art that the order in which the solvents or converting agents of pyroxyline, are introduced into the compound where a number of such solvents are used, does not necessarily affect the result. Thus, for instance, the pyroxyline may have been dissolved or converted by the use of one or more of the solvents,

solvents or converting agents, because they IIO are introduced after the original fibrous structure of the py'roxyline has been broken down, since their introduction does convert the compound finally procured, into a compound diiferent to that which would be obtained if they were not used. And it is with this understanding that I employ the words solvent and converting ag'enti'n this specification.

While, as above stated, I have divided the forms of pyroxyline compounds into the two classes of solid and fluid, nevertheless, as I believe myself to have been the first to use phenyl-acetamide (acetanilid) as a solvent or converting agent in pyroxyline compounds, I claim it broadly,'as such in this application.

Simultaneously herewith I file another application, Serial No. 354,785, (designated as Case 0,) for a similar invention relating to the use of dinitro-toluol in pyroXyline compounds, but the present invention differs from this in certain important particulars, as that/ the phenyl acetamide compound does not soften at so low a temperature, is not so inflammable, and is more colorless thamdinitrotoluol compounds.

This application is designated as Case A of June 2, 1890, to distinguish it from other applications to be filed simultaneously herewith.

What I claim, and desire to secure by Letters Patent, is-

1. In the art of manufacturing compounds of pyroxyline, the subjecting of such pyroxyline to the solvent or converting action of phenyl-acetamide (acetanilid).

2. A new composition of matter consisting of pyroxyline and acetanilid substantially as described.

3. The process of manufacturing solid or massive pyroxyline compounds which consists in mixing phenyl acetamide (acetanilid) and pyroxyline, and subsequently subjecting the resulting compound to heat and pressure sists in mixing pyroxyline, phenyl acetamide,

(acetanilid,) and a liquid menstruum or liq.- uid menstrua, and subsequently subjecting the resulting compound to heat and pressure suficient to render the composition plastic, substantially as described.

5. The process of manufacturing solid or massive pyroxyline compounds which consists in mixing pyroxyline, phenyl-acetamide (acetanilid) and camphor, and subsequently subjecting the resulting compound to heat and pressure suflicient to render the composition plastic, substantially as described.

6. The process of manufacturing solid or massive pyroxyline compounds which consists in'mixing pyroxyline, phenyl-acetamide (acetani1id);camphor and a liquid menstruum or liquid menstrua and subsequently subjectin g the resulting compound to heat and pressure sufficient to render the composition plastic, substantially as described.

7. As a new composition of matter, a solid or massive pyroxyline compound containing phenyl-acetamide (acetanilid) and pyroxyline, substantially as set forth.

8. As a new composition of matter, a solid or massive pyroxyline compound, containing pyroxyline, -pl1'enylacetamide (acetanilid) and camphor, substantially 'as described.

In testimony whereof I affix my signature, in presence of two witnesses, this'2d day of June, 1890.

JOHN H. STEVENS. r

Witnesses:

J AMES J. Oosenovn, WM. H. BERRIGAN, Jr.