Oxidized cellulose smoking product composition


A smoking product is disclosed which comprises a charge of oxidized cellulosic material in combination with a treating agent which is designed to enhance the aroma evolved from the burning of the oxidized cellulose by masking undesirable residual odors. The treating agents which have been found to be effective are long fatty aldehydes containing 9-18 carbon atoms, 3,7,-dimethyl2,6-octadienol, methylheptyne carbonate, ethyl glyoxalate, sandalwood oil and amyris oil.


2. A smokable product as defined in claim 1 which includes an ashing agent. 3. A smokable product as defined in claim 2 wherein said odor masking agent is present in an amount corresponding to 0.01 to 0.05 percent by weight of said cellulosic material.
United States Patent Briskin et al. [ Feb. 22, 1972 OXIDIZED CELLULOSE SMOKING PRODUCT COMPOSITION Theodore S. Brlsldn; Geoffrey ll. Ward, both of Beverly Hills, Calif. Sutton Research Corporation, Los Angeles, Calif. Filed: Aug. 12, 1969 Appl.No.: 849,497 Related US. Application Data Continuation-impart of Ser. No. 802,229, Feb. 25, 1969, Pat. No. 3,559,655, Continuation-impart of Ser. No. 595,622, Nov. 21, 1966, Pat. No. 3,447,539, Continuation-in-part of Ser. No. 674,994, Oct. 12, I967, abandoned. Inventors: Assignee: U.S.CI. ..l3l/2,131/144 Int.Cl. ..A24b 15/02 Fleld ofSearch ...I3l/2, 17, 140-144 [56] Relerences Cited UNITED STATES PATENTS 3,006,347 10/1961 Keaton I 31/1 5 3,461,879 8/1969 Kirkland ..l31/2 OTHER PUBLICATIONS Dangerous Properties of Industrial Materials" (Text) by N. Irving Sax pub. by Reinhold Book Corp. N.Y.C, l968- Third Edition p. 1006 cited Primary Examiner-Melvin D. Rein Attorney-McDougall, Hersh, Scott & Ladd ABSTRACT 3 Clalms, No Drawings OXIDIZED CELLULOSE SMOKING PRODUCT COMPOSITION This is a continuation-in-part of Ser. No. 802,229, filed Feb. 25, 1969, now US. Pat. No, 3,559,655, entitled Smoking Products which in turn is a continuation-in-part of Ser. No. 595,622, filed Nov. 2t, 1966, now US. Pat. No. 3,447,539, and continuation-in-part of Ser. No. 674,994, filed Oct. 12, 1967 now abandoned. This invention relates to new smoking products and a method for preparing them. As used herein, the term smoking products" is meant to refer to and to include filler material embodied in cigarettes, cigars and for use with pipes and the like, and mixtures thereof with various proportions of tobacco and including cigarette papers and wrappers used in the preparation of such cigars and cigarettes, and it includes cigarettes, cigars and the like products manufactured with such filler materials and wrap pers. In the aforementioned applications, description is made of the preparation of a smoking product suitable for use in cigarettes, cigars or with pipes wherein the smoking product is prepared of relatively pure cellulosic materials subjected to selective oxidation with liquid nitrogen dioxide to convert preferably more than 90 percent of the methylol groups in the cellulosic molecule to yield a product which can be referred to as an oxycellulose or polyuronic acid. The oxidation reaction product is further processed by removal of liquid nitrogen dioxide by vaporization and preferably by washing the oxidized cellulosic product with water and/or alcohol and/or acetone or other solvent for removal of solubilized foreign material, including oils, waxes, latices and the like, which contribute undesirably to the taste and aroma when used as a smoking product in accordance with the practice ofthis inventum. One method for effecting this oxidation is disclosed in copending application, Ser. No. 745,22 l, filed July 16, l968, now US Pat, No. 3,5l6,4l6, wherein description is made of the oxidation of a cellulosic material by suspension in liquid nitrogen dioxide in the ratio of one part by weight cellulosic material to 5 to l,000 parts by weight liquid nitrogen dioxide, and preferably one part by weight cellulosic material to 25 to 50 parts by weight of the liquid nitrogen dioxide. The reaction therein is carried out at a temperature within the range of to 65 C., and at autogenous pressure when the reaction temperature exceeds 21C., the boiling point of nitrogen dioxide. Another method for effecting this oxidation is disclosed in copending application Ser. No. 745,135, entitled Prepara tion of Smoking Products of Cellulose Derivatives and Process," filed July 16, I968, now U.S, Pat. No. 3,491,766, wherein the oxidation reaction, including reaction rate and amount of conversion, is materially improved by formulation ofthe oxidation reaction mixture to contain up to 8 percent by weight of water in the liquid-nitrogen-dioxide system and by carrying out the reaction at elevated temperatures above 15 C., and preferably between the range of to 45 C., depending somewhat upon the amount of moisture present in the reaction medium, whereby the reaction medium is rendered relatively nonelectrically conductive so that the presence of water in the reaction medium will not result in attack or degradation of the cellulosic material to be oxidized, and wherein the formulation to include aqueous medium in the reaction of liquid nitrogen dioxide also operates to adjust the specific gravity of the reaction mixture in the direction towards the specific gravity of the cellulosic material whereby suspension ofthe cellulosic material in the reaction medium is easier to achieve and maintain. The result is a more rapid and uniform oxidation reaction of the cellulosic material to produce a better product at a more rapid rate. A further method for effecting the oxidation of cellulosic materials is disclosed in copending application, Ser. No 774,064, filed Nov, 7, [968. and entitled Method for Produc ing Smoking Product of Oxidized Cellulosic Material" wherein the cellulosic material is first wetted with liquid nitrogen dioxide and then is exposed to hot gaseous nitrogen dioxide and then is exposed to hot gaseous nitrogen dioxide. This particular method can be advantageously used in the form ofa continuous process for the production of large quan tities ofoxidized cellulosic materialsv The resulting smoking product is then formulated with mineralizing agents such as oxalates, glycolates, diglycolates, lactates, pivalates or tannates of such metals as calcium, magnesium, lithium, potassium, barium, strontium, preferably in troduced to form the salt internally in the cellulosic derivative for purposes of providing desired ashing characteristics. Instead of forming the described salts internally in the cellulosic derivative, limited beneficial characteristics can be achieved by external application of such mineralizing agents. As described, the desired internal introduction is achieved by first wetting the cellulosic derivative with metal cation in dilute solution for absorption into the cellulosic derivative followed by exposure to the acid anion in solution to precipitate the metal salt in situ in the cellulosic material. This application is addressed to a process of treating oxidized cellulosic material, independent of the method by which the cellulosic material is oxidized, with an agent which enhances the odor and aroma which accompanies the burning cellulosic material. It is an object of this invention to produce and to provide a method for producing a cellulosic material which is suitable for use in smoking and which finds wide acceptance as a smoking product from the standpoint of taste, aroma, ap pearance, burning characteristics and relative absence of undesirable reaction products. As the cellulosic raw material, use can be made of various forms of cellulose, such as wood pulp, straw, alpha-cellulose. flax, fibrous carbohydrates, seaweed carbohydrates, bamboo filaments, cotton filaments, hemp, refined paper, ricc paper, filamentous gums and even plants and plant leaves and the like fibrous materials from which noncarbohydrate components have been separated, all of which is hereinafter referred to as cellulosic material. It is preferred to make use of a purified cellulosic material from which various of the sugars, proteins, chlorophylls, fiavones, colors, lignins, oils, waxes, resins and lacticcs have been removed since these contribute undesirable odors and tastes to the smoking product. Purified cellulose is unsatisfactory for use as a smoking product from the standpoint of taste, aroma and burning characteristics. This is believed to stem from the acids and aldehydes that are evolved upon pyrolysis of the cellulose. it has been found that many of the defects of pure cellulose can be greatly alleviated by conversion of the methylol groups to carboxyl groups to produce a product which readily pyrolyzes with complete breakup of the cellulosic molecule into water vapor, and oxidation products of carbon such as carbon dioxide and low molecular weight compounds which readily volatilize off. However, residual odors persist in spite of the advantages gained through oxidation of cellulosic materials. It has been found that undesirable residual odors can virtually be eliminated and the taste of the cellulosic material vastly improved by treating oxidized cellulosic material with an aldehydic or alcoholic agent. It is believed that the compounds utilized in accordance with the present invention become incorporated with the cellulosic material, and are preferentially sought out by the olfactory senses, thereby to dominate over any undesirable odors from the burning cellulosic materialv ln referring to the incorporation' or association" of the aldehydes or alcohols with the material being treated, it will be understood that no specific limitation is intended. Diffusion within the fibers of the material treated has been recognized while presence of the materials in particulate form on the exterior of the fibers is also contemplated. It has been found that aromatic compounds ofthe formulai wherein X is alkylene or methyLsubstituted alkylene having one to six carbon atoms; 2 is CHO or -CH,OH and, Y is a substituent selected from the group consisting of hydrogen, hydroxy, alkyl, such as methyl, ethyl, propyl, t-butyl, etc., having from one to six carbon atoms. and alkoxy, such as methoxy, ethoxy, butoxy, etc., having one to six carbon atoms, are suitable to enhance odor and aroma. Representative compounds falling within this definition include a-methyl-fl (partert-butyl phenyl) propionaldehyde, which is available commercially under the trademark Lilial" from Givaudan- Delawanna, Inc. of New York; phenyl propyl aldehyde; and phenyl ethanol. Another group of compounds which can be used as treating agents in the present invention is the C, to C long chain fatty aldehydes, having either branched or straight chains. Representative of this group is nonyl aldehyde (C,), capryl aldehyde (C undecylenyl aldehyde (C and lauryl aldehyde (C,,). It is important that the fatty acid aldehyde contain at least nine carbon atoms since the corresponding C through C aldehydes gave a strong burning odor upon pyrolysis, and are therefore apparently unsuitable. Various hydroxy compounds have also been found to be suitable as treating agents in the present invention. Such compounds include 3, 7 dimethyl2, fi-octadienol, more commonly known as geraniol. Also suitable are methyl heptyne carbonate, ethyl glyoxalate, sandalwood oil and amyris oil. East Indies sandalwood oil is available commercially, and may be derived by distillation of Santalum album of India. Australian sandalwood oil is similarly commercially available and is derived by distillation of wood of Eucarya spicata in Western Australia. The agents of the present invention may be incorporated with the oxidized cellulose by any of a wide variety of procedures. For example. it is possible to soak the oxycellu lose in a dilute solution of the agent in water, alcohol or a mixture thereof. Any inert solvent may be used. It is preferred to incorporate the agent in the cellulose by spraying a dilute solution of the agent in an inert solvent onto the cellulose. The amount of agent applied is not critical, and it is generally sufficient to apply an amount such that any unpleasant odors of the pyrolyzing cellulose are not detectable. An amount within the range ofOfll to 0.05 percent by weight of the cellulose is usually sufficient for this purpose. After treatment with the odor mask. the resulting oxidized cellulose may be, ifdesired, washed to remove excess agent. The odor of burning protein or paper is not noticeable during pyrolysis of the cellulosic material treated in accordance with the concepts of this invention. It has been found that of the foregoing agents, sandalwood, amyris oil, geraniol, phenyl ethanol, alpha-methyl-beta-(para-tertiary-butyl phenyl) propionaldehyde and methyl heptyne carbonate are the most effective. The odor evolved by the agent is not necessarily the same as that which is characteristic of the particular agent material. On the contrary, the odor produced is that which is characteristic of the particular agent during rapid pyrolysis with the oxidized cellulose. For this reason, agents should be selected upon the basis of the odors evolved upon pyrolysis, with the oxidized cellulose, and not upon the characteristic odor of the agent per se. The following examples illustrate a typical process for the preparation of a smokable material in accordance with the present invention. EXAMPLE I A highly purified commercial grade of wood pulp is fabricated into a thin paper of a thickness comparable to a commercial cigarette paper. This paper is shredded into strands of about 2 mm width and immersed in approximately lOO times its weight in liquid nitrogen dioxide maintained at C. Immersion is continued for about 5 to ID days, or until testing indicates a carboxyl level of 92-l00 percent, expressed as polyanhydroglucuronic acid content. The testing involves washing in aqueous alcohol, drying, dissolving in excess standard alkali, and then back titrating with standard acid. The shredded material is then substantially freed of excess NO, by means ofa warm stream of dry air. A solution of 0.03 percent by weight of phenyl propyl aldehyde is sprayed upon the shredded material, and the alcohol is allowed to evaporate. Analysis showed that the cellulose contained 0.037 percent by weight of phenyl propyl aldehyde. The shredded cellulose is wrapped in the form of a cigarette in cigarette paper which had been treated in the same manner with phenyl propyl aldehyde. It has been found that the residual odor can best be tested in a "drum" test, which is conducted in the following manner. A one-fourth inch of the above described cigarette is burned in a closed top drum. To avoid irritant affects, an interval of 3 minutes is allowed to elapse, and the odor in the drum is tested through an opening in the top. The drum test reveals no burnt paper odor, but yields a pleasant fernlike odor. When the drum test is repeated on the shredded cellulose used above, but not treated with phenyl propyl aldehyde, an acrid odor characteristic of burning paper is detected. Residual caramel odors are likewise detected. EXAMPLE II The shreaded cellulose produced in Example I is sprayed with a 0.4 percent alcoholic solution of "Lilial." which was substantially pure a-methyl-Btpara-tert-butyl phenyl] propionaldehyde. Analysis showed that the "Liliul" content was 0.015 percent by weight. Drum tests on cigarettes made from the treated cellulose reveal no unpleasant odor. The odor detected had a pleasant floral sent. EXAMPLEIII Oxidized cellulose in the form of shredded strands produced in the same manner as in Example I is sprayed with a dilute solution of lauryl aldehyde in alcohol until the cellulose contained 0.02 percent by weight of the aldehyde. Drum tests showed the absence of any unpleasant odors as only a mild soap odor was detected. EXAMPLES lV-lX Shredded cellulose produced in the manner shown in Example l is treated with C, to C C m and C fatty aldehydes. Drum tests conducted on each sample revealed the following: C. laundry soap odor C coconut odor C, snap odor C, nutodnrlpeach kernel) C scorched nul ndur The materials prepared in accordance with the practice of this invention find excellent use as a smoking product in cigarettes. pipes and like smoking devices. Use can be made of the treated material alone or in admixture, in various proportions with tobacco. A cigarette can be made by cylindrically wrapping the shredded material with cigarette paper. or preferably with paper treated in accordance with the instant invention, or better still with a paper made with pulp thus treated. A cigarette filter can then be attached, such a filter being treated with an appropriate flavor such as methol. lndividuals smoking the individual type product will experience a clean taste. and the smoke inhaled will prove to be extremely mild, and in no sense irritating. lt will be understood that various changes and modifications may be made in the above described products and processes which pro ide the characteristics of the invention without departing from the spirit thereof particularly as defined in the following claims. We claim: bonate, ethyl glyoxalate, sandalwood oil and amyris oil. I. A smokable product comprising a charge of oxidized cel- 2. A smokable product as defined in claim I which includes lulosic material and a minor amount of treating agent selected an ashlflg g f h group consisting of h pm m ni b l 3. A smokable product as defined in claim 2 wherein said phenyl) propionaldehyde, phenyl propy] aldehyde Pheny] 5 odor masking agent is present in an amount corresponding to ethanoL] long chain fatty aldehydes containing nine to [8 cap 0.01 to 0.05 percent by welght of said cellulosic material. bon atoms, 3,7-dimethy|-2,6-octadienol. methylheptyne car-



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Patent Citations (2)

    Publication numberPublication dateAssigneeTitle
    US-3006347-AOctober 31, 1961Reynolds Tobacco Co RAdditives for smoking tobacco products
    US-3461879-AAugust 19, 1969Celanese CorpOxidized cellulose tobacco substitute composition

NO-Patent Citations (1)

    Dangerous Properties of Industrial Materials (Text) by N. Irving Sax pub. by Reinhold Book Corp. N.Y.C. 1968 Third Edition p. 1006 cited

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