US3720660A - Synthetic smoking material - Google Patents

Synthetic smoking material Download PDF

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Publication number
US3720660A
US3720660A US00175901A US3720660DA US3720660A US 3720660 A US3720660 A US 3720660A US 00175901 A US00175901 A US 00175901A US 3720660D A US3720660D A US 3720660DA US 3720660 A US3720660 A US 3720660A
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US
United States
Prior art keywords
acid
oxidation
oxidized
cellulose
polysaccharide
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00175901A
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English (en)
Inventor
J Arendt
J Sachetto
J Carriere
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Gallaher Ltd
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Gallaher Ltd
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Publication date
Priority claimed from GB1421571*[A external-priority patent/GB1355785A/en
Application filed by Gallaher Ltd filed Critical Gallaher Ltd
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Publication of US3720660A publication Critical patent/US3720660A/en
Assigned to GALLAHER LIMITED reassignment GALLAHER LIMITED CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE JAN. 2, 1981 Assignors: WATLING FIFTY-ONE LIMITED
Assigned to GALLAHER LIMITED reassignment GALLAHER LIMITED ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HERGALL (1981) LIMITED
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/10—Chemical features of tobacco products or tobacco substitutes
    • A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
    • A24B15/165—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes comprising as heat source a carbon fuel or an oxidized or thermally degraded carbonaceous fuel, e.g. carbohydrates, cellulosic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0021—Dextran, i.e. (alpha-1,4)-D-glucan; Derivatives thereof, e.g. Sephadex, i.e. crosslinked dextran

Definitions

  • the invention is concerned with a method of producing an oxidized polysaccharide for use in a synthetic smoking material, wherein the polysaccharide is treated in an oxidizing system containing at least stoichiometric quantities of nitrosonium ion for uronic oxidation.
  • a synthetic smoking material which can be smoked like tobacco, but which is readily reproducible with consistant properties, and which has a simple smoke chemistry, has long been desired.
  • oxidized cellulose produced by an oxidizing reaction using liquid nitrogen dioxide.
  • the oxidized cellulose produced in this way has certain disadvantages as a synthetic smoking material, particularly the tendency for its physical properties to change on ageing. For example, it tends to darken in colour and to gel, probably as a result of hydrolysis, into a rigid form which is difiicult to shred and handle on conventional tobacco handling machinery.
  • an oxidized polysaccharide for use in a synthetic smoking material by treating the polysaccharide in an oxidizing system containing at least stoichiometric quantities of nitrosonium ion for uronic oxidation.
  • This method results in predominantly uronic oxidation with little ring oxidation, a low degree of degradation of the polysaccharide molecule, and a low degree of cross linking, that is lactone formation, between chains or within individual chains.
  • the oxidation proceeds at a very high reaction rate and produces an oxidation of 95% (expressed as oxidation of anhydro-glucose units to anhydro-glucuronic acid units according to the calcium acetate method of analysis) in 6 hours or even less.
  • the process is much easier and less dangerous than other oxidation systems, particularly liquid nitrogen dioxide systems.
  • the oxidized product exhibits little or no adverse ageing characteristics and requires no subsequent reduction step, owing to the absence of ring carbonyls.
  • the properties of the oxidized material give a good smokeability, and good mechanical strength and flexibility so that it can readily be handled by conventional tobacco handling machinery.
  • the nitrosonium ion in the oxidation system may be provided by a combination of a strong acid and a nitrosonium ion releasing constituent such as a nitrite, any tetranitrato metal complex, nitrosyl sulphate, and nitrosyl nited States Patent ICC chloride.
  • a strong acid such as sodium nitrite
  • a nitrosonium ion releasing constituent such as a nitrite, any tetranitrato metal complex, nitrosyl sulphate, and nitrosyl nited States Patent ICC chloride.
  • nitrites which can be used include the alkali or alkali earth metal nitrites, particularly sodium nitrite owing to its cheapness.
  • strong acids which can be used are: inorganic acids such as phosphoric acid (not less than sulphuric acid (not less than 65%), and strong organic acids such as trifluoroacetic acid, trichloroacetic acid in acetic acid, benzene sulphonic acid, anthranilic acid, para-aminobenzoic acid these solid acids being dissolved in acetic acid.
  • inorganic acids such as phosphoric acid (not less than sulphuric acid (not less than 65%)
  • strong organic acids such as trifluoroacetic acid, trichloroacetic acid in acetic acid, benzene sulphonic acid, anthranilic acid, para-aminobenzoic acid these solid acids being dissolved in acetic acid.
  • Acetic acid itself cannot be used alone because of its weak acidity.
  • phosphoric acid is recommended owing to its dehydrating power which favours the formation of N0+ from the equilibrium H NO NO++H Q its low degrading effect on cellulose and polysaccharides compared to HNO or HCl, and its weak reactivity with polysaccharides (the P content of the oxidized material obtained is below 0.01%).
  • the solvents or diluents must be passive, that is they must not react permanently with the acid, with the nitrosonium ion, with the polysaccharide, or the oxidized polysaccharide.
  • suitable solvents or diluents are water, dioxane, ethyl acetate, dimethyl formamide, dimethyl sulphoxide, and cyclohexane, or mixtures of these.
  • nitrosonium salts may be used dissolved in a pure polar organic solvent.
  • the polar organic solvent should be free of any groups which can induce its nitrosation, such as hydroxyl amino, keto groups or activated aromatic rings, and may be for example nitromethane, nitrobenzene, dimethyl sulphoxide, or mixtures of such solvents.
  • the reaction temperature can be between 0 C. and 50 C. but a temperature in the region of 20 C. is believed to be preferable.
  • the pressure should be between 0 and 20 atmospheres, prefferably 1 atmosphere.
  • the atmosphere over the reaction mixture can be made of pure oxygen or pure nitric oxide but is preferably simply air.
  • the polysaccharide to be oxidized may be a cellulosic material, such as cotton linters, regenerated cellulose, paper cellulose, or highly purified wood pulp, or it may be a polysaccharide such as starch or dextran, or another polysaccharide with hexopyranose rings free of groups containing nitrogen or sulphur.
  • dialdehydrocellulose containing up to 20% of the theory of aldehydic groups in the chain, dicarboxycellulose (up to 20% of carboxyl) trialcohol cellulose (up to 20% of primary alcohol on the ring) ruthenium tetroxide oxycellulose, and all cellulose or polysaccharides pre-oxidized by various means, as long as their oxidation degree is not too high, preferably below 20% of the theory, and insofar as they do not contain troublesome impurities.
  • the oxidized material is treated with aqueous solutions of calcium or magnesium acetate or formate, the cations being thus exchanged with the carboxyl groups of the oxidized material, the acetic or formic acid formed being eliminated by washing with water. Then the material is treated with an aqueous solution of ortho-phosphoric, citric or oxalic acid which precipitates the corresponding salt within the fibres.
  • crystals of the salts are also formed on the surface of the material and this is unfavourable to the colouration of the material when after production it is impregnated with tobacco extracts, to produce a synthetic smoking product in its final form.
  • the material is treated with dilute aqueous acidic solution for a very short period, and washed carefully with water. After this treatment the material absorbed tobacco extracts quite well from their aqueous solution and after drying its appearance was acceptable.
  • the removal of the mineralizing agent was mainly localized on the surface of the fibres, and the salt content remained between 5-10% by weight. In addition, this led to the improvement of the smoking properties.
  • EXAMPLE 1 155 g. of cellulose in sheet form was impregnated with sodium nitrite by rapid soaking of the sheet into a saturated aqueous solution of sodium nitrite at room temperature followed by 10 seconds of hanging-out and then drying at room temperature until the moisture content was 8%. This process led in every case to a sodium nitrite content ranging between 1.5101 g. per g. of cellulose, and can be made in a continuous run.
  • the air dried impregnated product (473 g.) was then cut into strands and introduced into a 20 litre reaction flask A connected to a separating funnel B from one side and to a flask C (containing an aqueous solution of sodium hydroxide) fitted with a condenser D, through the trap E, in the other side.
  • 9 litres of 85% H PO were then displaced from the container F to B by applying vacuum.
  • the acid was then introduced into A by opening of the tap H, and the suspension homogenized with the mechanical stirrer G.
  • NO and N gases evolved are eliminated in the following manner. NO is converted into N0 by means of a current of air through the system, and the whole N0 is converted into sodium nitrite and nitrate by reaction with the sodium hydroxide solution of flask C.
  • the reaction is stopped by diluting the phosphoric acid with water, after a period depending on the required oxidation degree. After 70 minutes, an oxidation degree of 60% was obtained (carboxyl and lactone groups content included), after 80 minutes an oxidation degree of 75% and for higher oxidation levels (95%) 5 hours of reaction were required.
  • the process could be adapted to full commercial production by suitable upscaling of the apparatus.
  • EXAMPLE 2 As in Example 1, except that H PO is replaced by a mixture of H PO 40% aqueous dioxane in the respective proportion of 9 to 1 by volume. Under these conditions six hours are necessary to obtain an oxidized cellulose with a carboxyl content of 62% and the oxidized fibrous material has improved flexibility.
  • EXAMPLE 3 As in Example 1, except that the strands are not impregnated with sodium nitrite, nitrosyl sulphate being added to the suspension, in the proportion of 4 g. per gram of cellulose to be oxidized. The mixture is stirred for 10 hours and the degree of oxidation obtained is 70%. In this case also, addition of dioxane to the phosphoric acid (90% H PO 40% aqueous dioxane in the proportion 9:1 by volume) improved the flexibility of the material.
  • EXAMPLE 4 As in Example 3, but with tetranitratozincate (2NO+, Zn(NO replacing nitrosyl sulphate in the proportion of 6 g. per gram of cellulose to be oxidized. In this case 6 hours are necessary to obtain a degree of oxidation of 65%.
  • EXAMPLE 5 As in Example 1, except that 85% H PO is replaced by a mixture of CF COOH/dioXane in the ratio 10:1 by volume and in the proportion of 40 ml. per gram of pure cellulose.
  • the cellulose must be impregnated with NaNO or NaNO must be added to the suspension with stirring.
  • the sodium nitrite proportion to be used is 7 g. per gram of cellulose, and the reaction time must go from 15 to 20 hours. Careful washing with hot methanol and water has to be carried out until all the fluorine has been removed.
  • EXAMPLE 6 l0 grams of cellulose dried for 6 hours over P 0 at C., are suspended in 1000 ml. of nitromethane containing 98.1 g. of dissolved tetranitratozincate. The suspension is left for six days at 15 C., and then the liquid phase decanted. The cellulose is then washed on a funnel, first with pure nitromethane, then with ethanol and finally with water. The material thus obtained has a degree of oxidation of 65% and has very good physical properties.
  • a method of producing an oxidized polysaccharide for use in a synthetic smoking material wherein the polysaccharide is treated in an oxidizing system containing at least stoichiometric quantities of nitrosonium ion for uronic oxidation, said nitrosonium ion being provided by a combination of a nitrosonium ion releasing constituent and a strong acid selected from the group consisting of phosphoric acid, sulphuric acid, trifiuoroacetic acid, trichloroacetic acid, benzene sulphonic acid and paraaminobenzoic acid.
  • nitrosonium ion releasing constituent is selected from the group consisting of a nitrite, a tetranitrato metal complex, nitrosyl sulphate, and nitrosyl chloride.
  • said oxidation system includes a passive diluent to reduce hydrolysis and chain degradation resulting from the presence of the strong acid.
  • said passive diluent is one or more of water, dioxane, ethyl acetate, dimethyl formamide, dimethyl sulphoxide, or cyclohexane.
  • a method of producing an oxidized polysaccharide for use in a synthetic smoking material wherein the polysaccaride is treated in an oxidizing system containing at least stoichiometric quantities of nitrosonium ion for uronic oxidation, the nitrosonium ion in said oxidation system being-provided by a nitrosonium salt dissolved in a pure polar organic solvent.
  • said polar organic solvent is one or a mixture of more than one of nitromethane, nitrobenzene, or dimethyl sulphoxide.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US00175901A 1970-09-04 1971-08-30 Synthetic smoking material Expired - Lifetime US3720660A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1421571*[A GB1355785A (en) 1970-09-04 1970-09-04 Synthetic smoking material
GB1421571 1971-05-11

Publications (1)

Publication Number Publication Date
US3720660A true US3720660A (en) 1973-03-13

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US00175901A Expired - Lifetime US3720660A (en) 1970-09-04 1971-08-30 Synthetic smoking material

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US (1) US3720660A (fr)
BE (1) BE772160A (fr)
CA (1) CA942610A (fr)
CH (1) CH528230A (fr)
DE (1) DE2144030A1 (fr)
DK (1) DK129900B (fr)
FR (1) FR2107211A5 (fr)
IE (1) IE35593B1 (fr)
IT (1) IT1050182B (fr)
NL (1) NL7112143A (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4034764A (en) * 1975-08-15 1977-07-12 Philip Morris Incorporated Smoking material and method for its preparation
US4090016A (en) * 1975-06-17 1978-05-16 Sumitomo Chemical Company, Limited Carboxylated pullulan and method for producing same
US4166847A (en) * 1976-03-22 1979-09-04 Miya Ozawa Anti-nicotine agent prepared from a saccharide and rosin or turpentine
US6627749B1 (en) * 1999-11-12 2003-09-30 University Of Iowa Research Foundation Powdered oxidized cellulose
US11206863B2 (en) 2010-12-07 2021-12-28 Steven R. Freeman Vegetable based tobacco alternatives and articles comprising same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE166362T1 (de) * 1991-11-14 1998-06-15 Procter & Gamble C6/c2-c3 oxidierte stärke als waschmittelbestandteil
CN107365627B (zh) * 2017-06-09 2020-09-22 广东中烟工业有限责任公司 一种用于延长烟用香料保质期的添加剂

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4090016A (en) * 1975-06-17 1978-05-16 Sumitomo Chemical Company, Limited Carboxylated pullulan and method for producing same
US4034764A (en) * 1975-08-15 1977-07-12 Philip Morris Incorporated Smoking material and method for its preparation
US4143666A (en) * 1975-08-15 1979-03-13 Philip Morris Incorporated Smoking material
US4166847A (en) * 1976-03-22 1979-09-04 Miya Ozawa Anti-nicotine agent prepared from a saccharide and rosin or turpentine
US6627749B1 (en) * 1999-11-12 2003-09-30 University Of Iowa Research Foundation Powdered oxidized cellulose
US11206863B2 (en) 2010-12-07 2021-12-28 Steven R. Freeman Vegetable based tobacco alternatives and articles comprising same

Also Published As

Publication number Publication date
IT1050182B (it) 1981-03-10
IE35593B1 (en) 1976-03-31
FR2107211A5 (fr) 1972-05-05
BE772160A (fr) 1972-03-03
DK129900B (da) 1974-12-02
CA942610A (en) 1974-02-26
DE2144030A1 (de) 1972-03-09
DK129900C (fr) 1975-05-20
IE35593L (en) 1972-03-04
CH528230A (fr) 1972-09-30
NL7112143A (fr) 1972-03-07

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Owner name: GALLAHER LIMITED, STATELESS

Free format text: CHANGE OF NAME;ASSIGNOR:WATLING FIFTY-ONE LIMITED;REEL/FRAME:003858/0227

Effective date: 19810220

Owner name: GALLAHER LIMITED, STATELESS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HERGALL (1981) LIMITED;REEL/FRAME:003858/0222

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Owner name: GALLAHER LIMITED

Free format text: CHANGE OF NAME;ASSIGNOR:WATLING FIFTY-ONE LIMITED;REEL/FRAME:003858/0227

Effective date: 19810220

Owner name: GALLAHER LIMITED

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HERGALL (1981) LIMITED;REEL/FRAME:003858/0222

Effective date: 19810306