United States Patent Office 2,776,965 Patented Jan. 8, 1987 1 2,776,965 NITRIC ACID ESTERS OF CELLULOSE AND. ‘METHOD OF PREPARATION : ames L Bennett, Wilmington, Del, and Robert M. Brooks, Milliown, Sanies G, MeMilian, tr Red Bante nt ren 1, Ploley, Sayreville N” 3, aienors fo Hereales Powder Company, Wilmington, Daly cor poration of Delaware’ ra No Drawing, Application March 28, 1956, ‘Serial No. 874,388 17 Claims. (Cl, 260220) ‘This invention relates to new nitric acid esters of cellulose and their preparation; more particularly this in. vention relates to new nitric acid esters of cellulose free ‘of unstable sulfur compounds and to a method for prepar- ing these esters employing nitrating mixtures containing yy essentially nitric acid, magnesium ailrate and water. The Only commercial method for preparing nitric. acid esters of cellulose employs nitrating mixtures containing essentially nitric acid, sulfuric acid and water. During nitration small amounts of uastable sulfate esters are formed which must de subsequently destroyed by hy. olysis during lengthy stabilization treatment by boiling in diltte acid solutions. “Unless thus treated the ite Acid esters are extremely unstable and unfit tor use However, it is impossible to remove all sulfate groups yp without Causing considerable hydrolysis of the nitrate ‘roups; hence, even the stabilized nitrocellulose of ine Atustry still contains traces of unsiable sulfur compounds, ‘The stabilization treatment alms to Temove suficient un. stable sulfate esters so that the final product will meet y5 at least minimum heat stability requirements as meas. lured by the 134.5° C. heat test Moreover, nitrating mixtures containing nitric acid- sulfuric acidawater penetrate into the cellulose relatively slowly. ‘Therefore, itis necessary to prepare the cellulose gq for nitration with extreme care, Cotton linters must be thoroughly fluffed up and must be substantislly free of all closely packed aggregates of flbers such as balls, pills and the like. Wood pulp must be shredded completely to thoroughly opea up the fiber aggregates, Uniess this is very carefully and thoroughly done the nitration will be nonuniform and the final product will not dissolve completely ia solvents to form smooth, cleat solutions which are necessary to commercial utilization, Hence it is apparent that the present commercial proc: 38 for preparing nitrocellulose requires very careful con. twol and treatinent of the cellulose supply to insure uni. form producis and requires a tedious and lengthy sia bilization treatment to produce a stable produc Much effort has been devoted to develop a practical ‘and economical process for altrating cellulose which » would overcome the recognized disadvantages of the resent commercial process iavolving mixed niticaul. furie nitrating mixtures. Heretofore, all such proposed processes have deen neither practical’nor have they pro- sluced acceptable products of commercial utility due %0 nonuniform nitration resulting in products having poor solubility characteristics, Now in accordance with this invention novel nitric acid esters of cellulose are produced by reacting cellulose with 4 nitrating mixture containing essentially nitric acid, maze nesium nitrate and water, the ratio of magnesium nitrate to water being at least about 1.2:1 and not more than about 2.2:1 by weight and said nitric aeld being present jin an amount suficent to yield a nitric acid ester of ecl- Julose having a nitrogen content of from about 11% #9 7 about 13.5% by weight. 2 More particularly, novel nitric acid esters of cellulose are produced by reacting cellulose with @ nitrating mike tute containing essentially between about 45%% and about 2496 nitric acid, between about 3.3% and about 349% ‘magnesium nitrate, and between about 2.7% and about 21% water by weight, the ratio of magnesium nitrate fo water being at least about 1.2:1 and not more than about 2.221 ‘A more specific nitrating mixture suitable for prepar ing most types of nitrocellulose contains essentially be. tween about 459 and about 80% nitric acid, between bout 109% and about 345 magnesium nitrate, and be. teen about 7% and about 21% water by weight, the ratio of magnesium nitrate to water being at least bout 41.2:1 and not more than about 2.2:1, Since the nitrat. ing mixtures of this invention costain no sulfuric acid, ‘here are no unstable sulfate esters 10 contend with, and ence the resulting nitric acid esters do not requice a long and tedious stabilization treatment following mitre: tion to produce stable producis, ‘The nitric acid esters formed, after removal of the spent nitraing mixture, are Stable for about 15 minutes in the standard 134.5° C, hheat test without the necessity of any subsequent stabil zation treatment. ‘Within the operative range set forth above there is a preferred range particularly well adapted for commer. cial practice witerein the ratio of magnesium aiteate to water is at least about 1.3:1 and not more than about 2:1, end wherein the nitrating mixture is free of undis. Solved magnesium nitrate. ‘A particular embodiment of this invention iavotves immersing cellulose in a bath of nitrating mixture con. twining essentially between about 45% and about 90% nilsic acid, between about 10% and about 34%. mag. Besium nitfate and between about 7% and about 21% Water by weight, the ratio of magnesium nitrate to water Being at Jeast about 1.3:1 and aot more than about 2:1, Said: nitrating mixture being free of undissolved ‘mag. nesiuum nitrate, the ratio of said nitrating mixture to celle. jose being at least about 20:1 by weight, nitrating the cellulose at a temperature between about 13° Ce and about 70° C. for at. least about $ minutes and’ unlll aitration is substantially complete, and recovering ‘Uni- ‘ormly substituted nitric acid esters of cellulose substan. tially completely soluble in acetone to form smooth, clear solutions, 4n a preferred embodiment of the invention, after nitre tion the spent nitraing mixture is removed from the te. sulting nitric acid esters, and stable nitric acid esters of cellulose are recovered directly, without subsequeat sta- Pilization treatment. Following nitration and removal of spent nitrating mixture, the nitric acid esters may be wuie jected to subsequent conventional and well-known teat, ‘ient for viscosity control, bleschiag, dehydration, aod the Tike as desired, ‘The process in accordance with this invention is par- tiewlarly well adapted for continuous operation bectuse the nitrating mixture penetrates even dease.aggresatee Of ‘fibers such as sheeted linters or sheeted wood ily Tapldiy and uniformly, and hence nitration is rapid“and uniform, This is in marked contrast to the present cou- mercial method of making nitrocelfulose employing sized nitricsulfurie acids, which has never been success, fully adapted to continuous operation, due principally to the necessity for having the cellulose thoroughly faffed ot completely shredded in order to obtain uniform nitra- tion, ‘The new products of this invention ore nitric acid ssters of cellulose containing between about 11% and about 13.5% nitrogen in the substituent nitrate groups. ‘They are tree of unstable sulfur compounds, «table. for2,776,808 about 15 minutes in the 134.5° C. heat test, and contain Getectable amounts of magnesium nitrate Tess than about 50 parts per million by Weight, based on the weight of the product. Preferred products are uniformly substi filed’ being substantially’ completely soluble in acetone to form smooth, clear solutions. “The following examples set forth some specific embodi- ments of this invention, but these are not to be con- Shred as limiting the invention. EXAMPLE 1 4 ‘yas found to be 11.62% by weight. The nitrocellulose Bad a stability of about 15 minutes in the 134.57 C. heat test and formed a clear, smooth solution in acetone. EXAMPLES 3-13, A series of nitrocelluloses was prepared following sub- stantially the procedure set forth in Example 1. Table 1 lists pertinent data for theie examples including com- position of the sitrating mixtures, nitration times and tem- to peratures, type cellvlose employed, ratio of nitrating mix. Eire (o celose, percent nitrogen, acetone solubility, and 1A nraing mire won prepared which contied Sayin te HLS" eat oe. Table 1 =aare Ix fem | hin, | Type Cstelon | Oss |Ricoae | way ata a sar eae |oo= = [= oe ESS | date pa ag) ae Eee tlememel fcc) @a| Ee Seago Nora Pu Hea [occ BE foc] Be] Be ‘sed Wak nie Hats [cca a ; Hae Sani Haro i Ee m1 Bat ae BB fcc Bt ‘be desiemtion 2 means 62.56% nitric acid, 22.52% magnesium nitrate, 14.919 ‘water, and 0.01% N2Os by weight. The NaOs was only Jan incidental ingredient in the nitrating mixture, being. present in the concentrated nitric acid employed, Tt is frell recognized in the art that concentrated nitric acid bfien contains small percentages of N:O:._ The mixture Wvas brought to 0" C. and 1 part by weight of shredded Wood pulp dried 1 hour at 100° C. was immersed or Uipped into 54 parts by weight of the nitrating mixture ‘with agitation to form a slurry. The slurry of cxllulose wis nitrated at about SO C. for 10 minutes while agt- tating, after which the slurry of nitrocellulose in the spent fitting mixture was run info a centrifuge. . As rruch fs possible of the spent nitrating mixture was separated From the fibrous nitrocellulose by centrifugal force, and the nitrocellvlose wae then drowned in a large excess fof water, about 60. paris water to 1 part, nitrocellulose. After draining off the drowning bath, the nitrocellose ‘was washed with fresh water ntl free of acid, The ater-wet nitrocellulose was then dried ina stream of air at about 60° C., and the resulting dried nitrocellulose ‘was found 1 be stable for about 15 minutes in the stand~ ard 145° C. beat fest. It dissolved substantially com- pletely in acetone 16 form a smooth, clear solution, ths Ecinonstrating that it was uniformly. substituted." The fnitrogen content determined by the standard. nitrometer method on a simple dried for 1 hour. at, 105° C. was ound to be 12.08%, by, weight EXAMPLE 2 ‘A. nitrating mixture was prepared which contained 65.26%6 nitric seid, 20.35% magnesium nitrate, 14.34% Water, and 0.05% 'NaOs, This mixture was brought to 50° G. and 1 part of air-dry sheeted wood pulp shout (0,0 inch thick! cut into 3-ineh squares was immersed or dipped: into 66 parts by weight of the nitrating mixture ‘with agitstion, The cellulose was nitrated at about 50° C. for 2 period of 20 miautes with agitation, after which the nitrating mixture was drained off, and the sheets of nitrocellulose Were drowned in a large excess of water, about 60 parts water (o I part nitroceliblose. After drain- ing off the drowning bath, the nitrocellulose was washed with fresh water Until free of acid and.was dried ina Stream of air_at about 60° C, The nitrogen content Tha opie was Hh wable af ed of 2 inate ad ho tnt was sloppod tis pot EXAMPLE 14 36 A seties of nitrocelluloses was prepared following the procedure in Example 4, varying the temperature of nitra- tion from 25° to 50° C. as illustrated in Table 2 following. Table 2 “ihe Niroveaios Gj EXAMPLE. 15 A series of nitrocelluloses was prepared following the procedure in Example 1, varying the temperature of nitra tion from 30° C. to 50° C. as illustrated in Table 3 Tollowing 55 ea S900 In cece EXAMPLE. 16 0 |A series of nitrocelluloges, was prepared following the procedure in Example 1, etiploying 1 nitrating mixture Containing’ 56.2% nitric acid, 27.2% magnesium nitrate, fand 16.6% water by weight, and varying the time of mitra. a from 2 miautes 10°20 minutes ay ilustrated in Table $ 6 Iollowing,2,776,008 5 Table 4 Poet Nite fetes "Time of Nitro in ets EXAMPLE 17 ‘The procedure in Example 1 was followed omploy- ing nitrating mixture containing 65.00% nitric acid, 20.42% magnesium nitrate, and 14.58% water by weight, and employing a ratio of 20 parts nitrating mixture for each part of cellulose by weight. ‘The cellulose was readi- Jy slurried in the nitrating mixture without any dificuty and the resulting slurry was readily and effectively stirred in the nftrating pot. ‘The resulting nitrocellulose had a nitrogen content of 12.10%, was stable for about 15 ‘minutes in the standard 134.$° C. heat test and dissolved substantially completely in acetone to form smooth, clear solutions. EXAMPLES 18-23 A series of nitrocelluloses was prepared following sub- stantially the procedure set forth in Example 1. Table § lists pertinent data for these examples including composi- tion of the nitrating mixtures, nitration times and tem- peratures, type of cellulose employed, ratio of nitrating ‘mixture fo cellulose, and percent nitrogen in the nitro- cellulose product. 6 nitration at equilibrium being governed primarily by the ‘composition of the nitrating mixture. It has been further established that at any given nitric acid content within the limits set forth hereinabove the nitrogen content of the resulting nitrocellulose increases with decreasing water content, in general a decrease of 0.1% in the water content of the nitrating mixture causing a corresponding increase of about 0.05% nitrogen in the nitrocellulose, and vice versa. Obviously, of course, for each change in water content there will necessarily be @ correspond- ‘ing inverse change in the magnesium nitrate content of the nitrating mixture, Similarly, it has been found that at any given water content within the limits set forth hereinabove the nitrogen content of the resulting aitro- cellulose decreases with increasing nitric acid content, in general an increase of 1% in the nitric acid content of ‘the nitrating mixture causing a corresponding decrease of about 0.1% nitrogen in the nitrocellulose, and vice versa. Here, likewise, for each chango in nitric acid content there will necessarily be a corresponding inverse change in the magnesium. nitrate content of the nitrating mixture. Henee, it is obvious that there are numerous nitrating mixtures within the operating limits set forth for prepar= ing any patricular nitrocellulose having a preselected nitrogen content. ‘The particular nitrating mixture to be ‘employed will therefore be largely a matter of choice governed primarily by economic considerations. Preferred nitrating mixtures in accordance with this invention are free of undissolved magnesium nitrate at the nitrating temperature selected, and preferably such solutions should not be supersaturated with respect 10 ‘magnesium nitrate, Additionally, in preferred nitrating Table 5 [ttn east Few eae lst ae Example Toe ——— | Rempgre | “ine ‘Type Cette afew. | tsegen| Ie Pg wan] | | Fe a et er ae ge) tal tel es] 3 g) a8) og Si) HE By ag) g) Bee) Ba) dele) ag] g Be) ig Be) TREE) GR) 8 2) HB] ig "The sheeted word palptabista weve spororimataly Ms neh lon x 3s inch wide +008 teh sk ‘The nitrating mixtures jn accordance with this javen- sion contain three essential ingredients, namely, nitric ‘acid, magnesium nitrate and water, the ratio of magnesium nitrate to water being at least about 1.2:1 and not more than about 2.2:1, and the nitric acid being present in an amoust suficiest to yield a nitric acid ester of cellulose having a nitrogen content of from about 11% to about 13.5% by weight. It will be understood, of course, that the sum of the three essential components will constitute substantially 100% of the nitrating mixture, any NiOs being only an incidental ingredient in the nitrating tore, sinco itis well recognized that concentrated nitric acid often contains small percentages of NaOs, usually fn the order of 0.1% or les. Although for most purposes the nitrating mixtures of this invention will usually con- tween about 3.3% and about 34% magnesium nitrate, and between about 2.7% and about 21% water by welaht, it's to be Understood that the invention f not to bs constried as Timited in tis respect, soe the important feature s the rao of magnesium strate t0 water a8 set forth hereinabove, nitric cid being present an amount suficiont to yield a ntsc acid ester of cellulose having Allrogen content between about 119% and about 13.5% by weit. Tt has been found that nitration in accordance with this invention is an equilibrium reaction, the extent of 150 mixtures the ratio cf magnesium nitrate to water is at least about 1.3:1 and not more than about 2:1 by weitht. ‘A convenient method fer prepsting the nitrating mix- {res ofthis invention is as follows: magnesium carbonate is slurried with water to form a thick paste, nitsie acid of 9896-b strength is then added slowly atl the solution is just acid to litmus paper. The solution is then boiled to remove water ul the desired magnesium nitrate concen {ation is obiained, The magnesium nitrate solution is then weighed, cooied to about 80" C. and the requisite quantity of strong nitric acid, 989% +4 strength of known composition, is weighed in, additional water, if necessary, is added, anid the mixture is stirred until homogeneous, ‘Magnesium oxide or magnesium hydroxide can be substi tuted for the magnesium earbonate. Another convenient method consists in melting com- mercial crystals of magnesium nitrate —hexahydrate, Mg(NOs)2.6H20, and boiling unl the desired concentra: tion of magnesinm nitrate is obtained. The solution is then weighed, cocled to about 80° C. and the requisite quantity of strong nitric acid, 989% + strength of known composition, and additional water, if necessary, are added ‘and the mixture slirred uetil homogeneous. ‘A convenient method of analysis for checking the com- position of nitrating mixtures consists in determining total qs tidity by titration with sodium hydroxide, determining nitrogen trioxide by titration with potassium permanga+ os 02,778,008 7 nate, and determining magnesium nitrate by adding a known quantity of sulfuric acid, evaporating to remove the nitrie acid and the nitrate (as nitric acid), and titrating the exeess sulfuric acid with sodium hydroxide. Water is ‘computed by difference. Total acidity can be consistently checked within 0.08% and magnesium nitrate within 0.10% by this method. ‘Any-of the taal commercial forms of cellulose can bbe employed in this invention including cotton, cotton Tinters, wood pulp, regenerated cellulose, and the ik. ‘This can be in any form including fibers, siaple fibers, filaments, small shreds, chips, shredded linters, shredded ‘wod pulp, granules, shevts, finely ground, fffed bulk Fibers, and the like, It i presently preferred to employ Shredded or fluffed wood pulp or shredded or fffed fotton linters or mixtures of these since these forms of ‘Chemieal cellulose are particularly well adapted to present ‘commercial nitrocellulose facilities. ‘tis emphasized that celiulose can react with any quantity of the nitrating mixtures of this invention to form nitric seid esters of cellulose. However, in reacting cellulose. with the nitrating mixtures of this invention hitric seid is consumed and water is formed. From a practical consideration itis desirable to employ sn excess OF nitrating mixture aver the theoretical stoichiometric Fequirements. With the customary altrating equipment In common use in the industry 2nd employing the custo: ery forms of chemical eelluldse, it is presently preferred qo employ at least about 20 parts of nitrating mixture to 1 part of cellulose by weight so that the water formed i the reaction will not unduly dilute the nitrating mixture, bur it is to be understood that the invention is not limited in this respect, With other forms of cellulose and/or other conditions of nitration less than 20 paris nitrating Inixture fo 1 part cellulose ate quite feasible as illustrated by the examples, Tt will be apparent that larger quantities tan be employed, such as 30, 40, 50, 60, 70, or even more parts per part of cellulose, as desired. However, the Economies of the process will usually govern the ratto of fittating mixtare to cellulose, it being most economical Tornitrate with the lowest ratio that will give a high quality product. ‘A wide range of temperatures can be employed io practicing this invention. For practical reasons, how- ver, it i not desirable to employ temperatures below bout 15" C. or higher than about 70" G. Below about 15" C. the reaction becomes too slow to be economically attractive, and above about 70" C. the nitrocellulose tends fo erumbie so that mechanical losses ia the process be come excessive, A preferred range of temperatures lies Between about 40° C. and about 60" C, with tempera: ftres of about $0° C. being particularly suitabte. "The nitration resction In accordance with this inven- tion is very rapid, @ major portion of the substituent nitrate groups often being introduced within a matter of {two minutes oF less. However, 2 uniformly substituted nitrocelioiose in equilibrium with the nitrating mixture Tsually requires nitration for a Jonger period of time depending primarily upon the temperature of nitration fand the form of cellulose employed. Tn any case nitra- tion ‘will ordinarily be continued until nitration is sub- Stantally complete end tho resulting nitrocellulose is in Squilibeum with the nitrating mixture. With the cus- fomary shredded wood pulp-cor shredded Hinters at tem- peratures above about 30°C. it has been found that at Feast about 8 minutes is required to obtain a uniformly substituted nitroceliulose, Under similar conditions the Commercial process employing mixed nitrie-sulfuric acids Sequites at least about 18 minutes to obtain uniform nitra- Hon. Denser forms of cellulose such as sheets, granules ‘and the. like require longer sitration times to achieve @ uniformly substituted product, in some instances as much tas 43 miautes or more, under similar temperature condi fions 10 achieve uniform substitution. Since the rate of hltration is slower at lower temperatures it follows that Tonger nitration times are required at lower temperatures, 10 0 0 6 8 Agitation during the reaction hastens rapid and uniform wetting of all parts of the cellulose with the nitrating ‘mixture, and hence is preferred whenever possible. For ‘economic reasons nitration time will ordinarily be held to f minimum consistent. with obtaining a uniformly sub- Stituted produet, and for any particular case this can readily be established by the simple expedient of deter- Tnining. nitrogen content of the nitrocellolose and testing Solubility of the product in acetone. Following nitration itis necessary to remove the spent nitrating mixture fom the resulting nitrocellulose sub- stantially completely in order 0 recover a usable produ. ‘This can be accomplished by draining off as much as possible of the spent nitrating mixture by gravity dr fee, by suction, By centrifugation or similar means. This Teaves a cake or mat of nitrocellulose still wet with ad- hhering spent nitratiog mixture which must be removed. ‘The wet eake of mat of nitrocelfulose is then broken. up and drowned in & large excess of water with agitation. ‘The objective of this deownlng operation is to dilute very fapidly and substantially the adhering spent aitrating ixtufe remaining on the nitrocellulose and thus prevent hydrolytic damage to the nitrocellulose. Ordinarily 50 ‘oF more parts of water fo 1 patt nitrocellulose is employed Tor drowaing the nitrocellulose. The drowning bath is then drawn of by any stitable means and the nitro- cellulose is then washed with fresh water until tests for Seidity show that substantially all nitrating mixture has been removed. Washing can be accomplished by any of the wellknown methods for washing a solid with a i including displacement or spray washing with gra suction, or centrifugation, “decantation and the ike: ‘Washing is continued until substantially all of the adher- ing nitrating mixture has been washed out as determined by test on the wash liquor. ‘The resulting wasbed nitrocellulose is stable to heat and ‘does not require a subsequent stabilization treat meat sby boiling in dilute acid solution for lengthy periods such as is essential when mixed. nitrie-sulfurie eid is employed as the mitrating mixture. Hence the hitrocelluloses of this invention following water wash- ing are teady to be treated immediately as desired by ‘any of the well-known nd conventional methods for adjusting viscosity, bleaching, dehydration and the Tike For some purposes’ the water-Wwet nitrocellulose can be tused directly, However, as is well known, most soluble nitrocellulose of commerce is dehydrated sith a suitable Tiquid. stich as ethyl alcohol, for example, before use fin accordance ‘with this iavention novel nitric acid esters are prepared which contain between about 117% Gnd about, 15.5% nitrogen in the substituent nitrate groups. These nitrocelluloses are free of unstable sul- far compounds since there are no sulfur-containing com: ‘pounds employed in the nitrating mixtures, and they ore Frable for sbout 15 minutes in the standard and wel- known 134.5° C. heat test. These nitrocelluloses usual Ty contain detectable amounts of magnesium nitrate Tess than about 70 parts per million by weight based on the weight of the ‘nitrocellulose. Preferred nitrocelinloses in accordance with this invention are uniformly sub situted as-evidenced by the fact that they dissolve sub- Stantially completely in acetone to form clear, smooth solutions. ‘This invention bas several notable advantages over the well-known commercial process for producing nitro cellulose which employs mixed nitrie-ulfuric aciés. To begin with the nitrating mixtures of this invention pent trate and wet even relatively dense aggregates of ol fulose particles rapidly and uniformly in contrast to ‘mixed nitrie-sulfuric acid. which requites that the cel lose be very carefully shredded, fluffed and opened up tand-made free of closely packed aggregates of ‘fibers Such es pills, balls and the like. The nitratfon reaction Of ‘this invention is auch more rapid. than the. well Enown commercial process, |The process of this inven- (a