US3612063A

US3612063A - Oxidized cellulose smoking product

Info

Publication number: US3612063A
Application number: US851104A
Authority: US
Inventors: Theodore S Briskin; Geoffrey R Ward
Original assignee: Sutton Research Corp
Current assignee: Gallaher Ltd; Sutton Research Corp
Priority date: 1969-08-18
Filing date: 1969-08-18
Publication date: 1971-10-12
Anticipated expiration: 1988-10-12

Abstract

Smoking products and process for their production wherein organic salts of potassium, lithium and copper, and titanium dioxide are incorporated into oxidized cellulosic materials for the purpose of controlling burning and for supporting glow between puffs. The potassium, lithium and copper organic acid salts employed are those of oxalic, lactic, glycolic, diglycolic, pivalic and tannic acid and in amounts less than 2 percent by weight.

Description

United States Patent- [72] Inventors Theodore S. Briskin;

Geoffrey R. Ward, both of Beverly Hills, Calif.

Aug. 18, 1969 Oct. 12, 1971 Sutton Research Corporation Los Angeles, Calif.

Continuation-impart of application Ser. No. 802,229, Feb. 25, 1969, which is a continuation-in-part of application Ser. No. 595,622, Nov. 21, 1966, now Patent No. 3,447,539, and a continuation-in-part of 674,994, Oct. 12, 1967, now abandoned.

[21 Appl. No. [22] Filed [45] Patented [73] Assignee 54] OXlDlZED CELLULOSE SMOKING PRODUCT 3 Claims, No Drawings [52] 11.8. CI 131/2 [5 l] Int. Cl ..A24b 15/00, A24d 01/ 1 8 Primary Examiner-Melvin D. Rein Attorney-McDougall, Hersh, Scott & Ladd ABSTRACT: Smoking products and process for their production wherein organic salts of potassium, lithium and copper, and titanium dioxide are incorporated into oxidized cellulosic materials for the purpose of controlling burning and for supporting glow between puffs. The potassium, lithium and copper organic acid salts employed are those of oxalic, lactic, glycolic, diglycolic, pivalic and tannic acid and in amounts less than 2 percent by weight.

OXIDIZED CELLULOSESMOKING PRODUCT This is a continuation-in-part of Ser. No. 802,229, filed Feb. 25, 1969, entitled Smoking Products which in turn is a continuation-in-part of Ser. No. 595,622, filed Nov. 21,. 1966, now U.S. 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.

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 wrappers.

In the aforementioned applications, description is made ofthe 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 andaroma when used as a smoking product in accordance with the practice of this invention. Y

One method for effecting this oxidationis disclosed in copending application Ser. No. 745,221, filed July 16, 1968, now U.S. Pat. No. 3,516,416, wherein description is made of the oxidation of a cellulosic material by suspension in liquid,

nitrogen dioxide in the ratio of lpart by weight cellulosic material 5 to 1000 parts 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 auto genous pressure when the reaction temperature exceeds 21 C., the boiling point of nitrogen dioxide.

Another method for effecting this oxidation is disclosed in copending application Ser. No. 745,135, entitled Preparation of Smoking Products of Cellulose Derivatives and Process," filed July 16, 1968, now U.S. Pat. No. 3,491,766, wherein the oxidation reaction, including reaction rate and amount of conversion, is materially improved by formulation of the 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 about 15 C., and preferably between the range of to 45C., 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 of the 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, I968, and entitled Method for Producing 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. This particular method can be advantageously used in the form of a continuous process for the production of large quantities of oxidized cellulosic materials.

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 introduced 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 characteristicscan 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 for the treatment of oxidized cellulosic material, independent of the method by which the cellulosic material is oxidized with an organic salt of potassium, lithium orcopper, or titanium dioxide to improve the burning characteristics of oxidized cellulosic material.

It is an object of the present 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, appearance, burning characteristics and relative absence of undesirable reaction products.

As the cellulosic raw materials, 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, rice 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, flavones, colors, lignins, oils, waxes, resins and lactices have been removed since these contribute undesirable odors and tastes to the smoking product.

It is known that various additives may be included in smoking products to insure proper burning and glow sustenance. However, in prior compositions potassium nitrate has been the primary additive in spite of the fact that the nitrate may be converted by polyanhydroglucuronic acid to the potassium salt with the liberation and loss of nitric acid.

In accordance with the present invention, oxidized cellulosic material is treated with a burning control agent which is believed to have a catalytic effect upon the burning of oxidized cellulose. The catalytic effect not only provides for glow sustenance and control of the rate of burning, but also serves to promote more complete combustion of the oxidized cellulose to carbon monoxide, carbon dioxide and water.

It has been found that organic salts of potassium, lithium and copper, as well as titanium dioxide exhibit this catalytic effect. While the oxalate is the preferred salt, use may also be made of the lactate, glycolate, diglycolate, pivalate and tannate salts.

The treatment of the oxidized cellulosic materials is such that the burning control agent is incorporated into or associated with the cellulose. ln referring to incorporation" or assocation,"it will be understood that no specific limitation is intended. Diffusion within the fibers of the material being treated has been recognized, while presence of the material in particulate form on' the exterior of the fibers is also contemplated.

It is generally sufiicient to add the burning control agent in an amount corresponding to up to 2 percent by weight upon the oxidized cellulosic material. An amount in the range of 0.001 to 1 percent is preferred.

The burning control agents may be incorporated into the oxidized cellulosic material in a wide variety of ways. ln the case of the metal salts, it is possible to treat the oxidized cellulose with an aqueous or an aqueous alcoholic solution of the burning control agent. Any other inert solvent may also be used. Such solutions generally contain the burning control agent in an amount corresponding to 0.001 to percent by weight based upon the total weight of the solution. The oxidized cellulose is preferably treated with the solution by spraying the solution onto the cellulosic material in a conventional manner.

If desired, the cellulosic material may be washed after treatment to provide for removal of excess salt.

In the case of titanium dioxide, it is preferred to admix the titanium dioxide with the cellulosic material in dry form. The mixture is blended to insure uniform distribution of the titanium dioxide throughout the cellulosic material.

The following examples illustrate a typical process for the preparation of a smoking product in accordance with the invention.

EXAMPLE! A highly purified commercial grade of wood pulp is fabricated into a thin paper of a thickness comparable to commercial cigarette paper. This paper is shredded into strands of about 2 millimeters width and immersed in approximately one hundred times its weight of liquid nitrogen dioxide maintained at 20 C. Immersion continues for about five to ten days, or until testing indicates a carboxyl level of 92 to 100 percent expressed as polyanhydroglucuronic acid content. The testing involves washing in aqueous alcohol, drying, dissolving in ex cess standard alkali, and then back titrating with standard acid.

The shredded material is freed of excess nitrogen dioxide by means of a warm stream of dry air. Thereafter, a 0.01 percent aqueous solution of copper oxalate is sprayed over the surface of the oxidized cellulose. After the spraying operation is completed, the oxidized cellulosic materials are allowed to dry whereby the water evaporates leaving copper oxalate in the cellulosic material. The amount of copper oxalate present in the material constitutes about 0.001 percent by weight of the cellulosic material.

EXAMPLE [1 Oxidized cellulose prepared in the manner shown in example I is admixed with powdered titanium dioxide, and the mixture blended to insure uniform distribution of the titanium dioxide throughout the cellulosic material.

EXAMPLE Ill Oxidized cellulose prepared in the same manner shown in example 1 is sprayed with a 0.01 percent aqueous solution of lithium oxalate. The lithium oxalate constitutes a 0.0015 percent by weight of the cellulosic material.

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 menthol. 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.

It will be understood that various changes and modifications may be made in the above-described products which provide the characteristics of the invention without departing from the spirit thereof particularly as defined in the following claims.

1. A smokable product comprising a charge of oxidized cellulosic material and a compound selected from the group consisting of titanium dioxide and an organic acid salt of a metal selected from the group consisting of copper, potassium and lithium, wherein said organic acid is selected from the group consisting of oxalic, lactic, glycolic, diglycolic, pivalic and tannic acids.

2. A smokable product as defined in claim 1 wherein said compound is present in an amount corresponding to 0.001 to 2 percent by weight.

3. A smokable product as defined in claim 1 which includes an ashing agent.

Disclaimer and Dedication 3,612,063.-The0dm"e S. Brislcin and Geojfwey R. Ward, Beverly Hills, Calif. OXIDIZED CELLULOSE SMOLING PRODUCT. Patent dated Oct. 12, 1971. Disclaimer and dedication filed Apr. 8, 1971, by the assignee, Sutton Research Corporation. Hereby disclaims and dedicates to the Public the portion of the term of the patent subsequent to Feb. 2, 1988.

[Ofiicial Gazette April 18, 1972.]

Claims

2. A smokable product as defined in claim 1 wherein said compound is present in an amount corresponding to 0.001 to 2 percent by weight.
3. A smokable product as defined in claim 1 which includes an ashing agent.