Classifications

• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
  • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
  • A24D3/06—Use of materials for tobacco smoke filters
  • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive

Definitions

• the polymeric material which is employed in accordance with the present invention comprises a normally solid, finely divided, microporous, organic polymer as hereinafter defined, e.g.
• a microporous copolymer of a divinyl aromatic hydrocarbon and a monovinyl aromatic hydrocarbon such as a copolymer of divinylbenzene and styrene, or a copolymer of divinylbenzene, ethylvinylbenzene and styrene, or a homopolymer of ethylene glycol dimethacrylate.
• Another problem which has long been present in connection with smoking products resides in the fact that it is difficult to incorporate smoke flavoring agents in smoking products in a manner whereby the tobacco products can be stored for relatively long periods of time without losing the flavorants due to volatilization and yet in such a manner that the flavorants will be released when the smoking product is smoked.
• materials have been suggested for filtration of tobacco smoke.
• materials which have been employed as tobacco smoke filters are certain open-pore sponge or foam materials, and porous activated adsorbent materials, such as charcoals.
• Such materials have been used by themselves and in conjunction with papers, fibers, and other known filter materials. Though such materials have been found to have some effectiveness in removing tobacco smoke components, their effectiveness in general, has been with regard to the removal of the less volatile components of the smoke. Such materials have been found relatively indiscriminate and/or ineffective with regard to the removal of undesirable smoke ingredients generally.
• open-cell foams i.e., foams having an openpore structure through which smoke may be drawn for filtration
• foams having an openpore structure through which smoke may be drawn for filtration have been found to possess variable pore sizes and a large distribution of pore sizes.
• such foams have imparted variable resistance-to-draw (RTD) and, thus, variable quality to the tobacco products in which they have been employed.
• RTD resistance-to-draw
• foams are often so open in structure that an inconveniently long filter section must be employed to effect significant particle removal.
• socalled open-cell foams have some pores which are blocked so that they form useless dead space which does not interconnect with both ends of the filter.
• Activated porous adsorbents in general, also have been found to have many disadvantages. For example, in addition to their function as gas phase removers, they also have been employed in the filter to carry flavorants or other additives to be transferred to the smoke stream. When such materials have pores of varying sizes, some of the additive is wasted in the small pores which retain it too firmly to permit transfer to the smoke.
• the present invention relates to a flavor-releasing smoking article and to methods of making the same. More particularly, the present invention relates to a smoking article embodying a filter for tobacco smoke, which filter contains, as an essential filtering element, a solid polymer having controlled pore size and containing therein a flavor for incorporation in tobacco smoke, said polymer being capable of removing undesirable elements from tobacco smoke while imparting desirable flavor thereto.
• the present invention involves use: in filters for tobacco smoke of solid polymers or resins of controlled pore size.
• a filter comprising a polymeric material of controlled pore size, in accordance with the present invention can be chosen to accommodate and retain undesirable smoke components and at the same time to permit ready egress to small molecules of the volatile and flavorful components of smoke such as isoprene, acetaldehyde, acetone, and the like.
• the polymers or resins employed in accordance with the present invention are, in general, not strongly hydrophilic, so that the problem of displacement by or interference by moisture is not encountered as it is with the zeolites.
• the resins can, in addition, be chosen to have a strongly nonpolar aromatic character and thus can be chosen to provide an affinity for aromatic and polynuclear hydrocarbons and not for polar alcohols and the like.
• the polymeric material which is employed in accordance with the present invention comprises a normally solid, finely divided, microporous, organic polymer as hereinafter defined, eg a microporous copolymer of a divinyl aromatic hydrocarbon and a monovinyl aromatic hydrocarbon, such as a copolymer of divinylbenzene and styrene, a copolymer of divinylbenzene and ethylbenzene or a polymer of divinylbenzene, ethylvinylbenzene and styrene, or a homopolymer of ethylene glycol dimethacrylate.
• a microporous copolymer of a divinyl aromatic hydrocarbon and a monovinyl aromatic hydrocarbon such as a copolymer of divinylbenzene and styrene, a copolymer of divinylbenzene and ethylbenzene or a polymer of divinylbenzene
• the microporous resinous polymer to be employed can be any rigid, cross-linked, insoluble organic polymer having a plurality of interconnecting pores therein, a surface area of at least 50 square meters per gram, a high porosity and is in the form of particles of sizes between about 5 and 850 microns. Best results are obtained when the polymer is used in the form of particles having a relatively narrow range of sizes or of substantially the same size, preferably within the range of to microns.
• the cross-linking must be sufficient to maintain a rigid structure, and to inhibit or prevent appreciable shrinking upon drying, which decreases the porosity of the polymer.
• the amount of cross-linking necessary is dependent in part both upon the cross-linking agent and the monomer being polymerized and the manner in which the polymer is made. in the instance where the monomer is difunctional it can act as a cross-linking agent.
• a polymer made of divinylbenzene alone will be highly cross-linked, as will a polymer prepared exclusively from ethylene glycol dimethacrylate.
• Either of these polyfunctional monomers can be used to make cross-linked homopolymers of copolymers with one another, or to cross-link polymers made from mixtures of such divinyl monomers and other copolymerizable vinyl monomers.
• Polymers useful in the process of the invention are: the homopolymers of divinylbenzene, divinyltoluene, divinylxylene, or ethylene glycol dimethacrylate; copolymers of any two or more of such divinyl monomers; or copolymers of at least 20 percent by weight of at least one such divinyl monomer and up to 80 percent by weight of a monovinyl aromatic hydrocarbon such as styrene, ethylvinylbenzene, vinyltoluene, vinylxylene, isopropylstyrene, t-butylstyrene, or seebutylstyrene.
• a monovinyl aromatic hydrocarbon such as styrene, ethylvinylbenzene, vinyltoluene, vinylxylene, isopropylstyrene, t-butylstyrene, or seebutylstyrene.
• polyvinyl monomers such as for example, divinyl benzene, driving toluene, divinylxylene, diallyl phthalate, diallyl fumarate, or ethylene glycol dimethacrylate
• these latter difunctional monomers can be used alone, or with the monovinyl aromatic hydrocarbon monomers, to give cross'linked homopolymers and copolymers, respectively.
• Other nonaromatic vinyl monomers useful in forming copolymers with the aforementioned divinyl monomers are: methyl methacrylate, ethylene glycol monomethacrylate, ethyl acrylate, propyl acrylate, butylacrylate, vinyl acetate, vinyl propionate and the like.
• Copolymers prepared from monomers such as N-vinyl pyrrolidone, 4-vinyl pyridine N-vinyl morpholinone and N- vinyl oxazolidinone and the difunctional monomers such as divinyl benzene, or ethylene glycol dimethacrylate, and/or one or more monovinyl aromatic hydrocarbons can also be used in the proportions hereinbefore stated.
• microporous copolymers can be prepared by polymerizing the monomers in admixture with from about 0.5 to 20 times their weight of a solvent that is miscible with the monomers, but exhibits or has limited solubility for the polymer.
• the solvent for the monomer or diluent must be nonpolymerizable with the monomers, and only swell, but not dis solve the polymer.
• the size of the pores in the polymer and its density is dependent in part upon the kind of solvent employed, e.g. whether an aromatic hydrocarbon such as toluene or ethylbenzene, or an aliphatic compound such as heptane or an alcohol such isoamyl alcohol, or a mixture of such compounds is employed.
• the polymerization can be carried out in mass or in aqueous suspension, at temperatures between 50 and 120 C. and at atmospheric, subatmospheric, or superatmospheric pressure.
• a reaction vessel is charged with suitable amounts of styrene, ethylvinylbenzene and divinylbenzene, or a desired amount of other suitable monomers or monomer, and an inert liquid such as diethylbenzene, octane, or isoamyl alcohol, or a mixture of diethyl benzene and isoamyl alcohol.
• a catalyst e.g. 0.01 to 1 percent by weight of benzoyl peroxide, based on the total weight of the monomer is added.
• the vessel is purged with nitrogen to remove air, then sealed.
• the mixture is heated and stirred at temperatures between 50 and 120 C. until the monomer is polymerized.
• the vessel is opened and the porous polymer removed.
• porous cross-linked styrene polymers are described in British Pat. No. 980,299, wherein microporous hydrocarbon polymers are prepared by heating a mixture of a thermoplastic hydrocarbon polymer such as polystyrene and a water-soluble anionic surfactant to a temperature sufficient to render the polymer and surfactant mutually soluble. The resulting homogeneous mixture is cooled, after which the surfactant phase is removed by extraction with water or other liquid in which the surfactant is soluble and the polymer is not.
• a peroxide cross-linking agent may be in cluded in the mixture to cross-link the polymer before cooling and extraction of the surfactant.
• 2,597,43789 and 2,597,493 can also be used, as well as the microporous polymers used for the preparation ion-exchange resins described in British Pat. No. 889,304.
• Such cross-linked insoluble polymers should preferably have a surface area of at least 50 square meters per gram, and be in the form of particles of sizes between about and 500 microns.
• Example 1 A charge of 900 ml. of a liquid consisting of a mixture of 55 percent by weight of divinylbenzene, 43 percent by weight of ethylvinylbenzene and 2 percent by weight of diethylbenzene, and 600 ml. of diethylbenzene as solvent and reaction medium, together with 5.5 grams of azobisisobutyronitrile as catalyst, was suspended in 1500 ml. of water containing 100 grams of finely divided basic magnesium carbonate (3MgCO Mg(Ol-l) 3l-l 0), as suspending agent, and 0.1 gram of potassium dichromate.
• 3MgCO Mg(Ol-l) 3l-l 0 finely divided basic magnesium carbonate
• the mixture was stirred and heated under time and temperature conditions as follows: 4 hours at 50 C., 4 hours at 55 C., and 16 hours at 65 C., to polymerize the monomers in the mixture. Thereafter, concentrated hydrochloric acid was added to the mixture in the amount sufficient to neutralize the basic magnesium carbonate and bring the aqueous liquidto a pH value between 3 and 4.
• polymer was recovered by filtering and was washed with water, then with acetone, and finally with diethylbenzene.
• the product was in the form of small particles having a large surface area and a high porosity.
• the product was separated into fractions having particles of sizes between 1 19-165 microns; -196 microns; 173-238 microns and 192-288 microns.
• the product having particles of sizes between 119 and microns was separated from the main portion of the product and was washed with acetone, after which the washed product was dried by heating it at a temperature between 70 and 80 C. in vacuum oven at an absolute pressure of less than 1 millimeter, for a period of 16 hours.
• the surface area of the polymer was 700 square meters per gram.
• Example 2 A copolymer of 21.8 grams of styrene, 10 grams of divinylbenzene and 7.8 grams of ethylvinylbenzene, was prepared by polymerizing the monomers in an aqueous suspension containing basic magnesium carbonate as suspending agent, and a mixture of diethylbenzene and isoamyl alcohol, as diluent, employing procedure similar to that employed in Example 1.
• Example 3 A charge of 750 ml. of ethylene glycol dimethacrylate together with 750 ml. of methyl isobutyl ketone, and 5.5 grams of azobisisobutyronitrile as catalyst, were added to a 5 liter three-neck glass reaction vessel equipped with a reflux condenser and stirrer and containing 1500 ml. of water having dispersed therein 50 grams of basis magnesium carbonate, 0.1 gram of K Cr O and 12 grams of methyl cellulose. The mixture was stirred and heated at a temperature of 55 C. for a period of 5 hours, then was stirred and maintained at 65 C. for 20 hours longer. The polymer was recovered employing procedure similar to that employed in Example 1, washed with water and dried.
• Example 4 A polymer of about 46.75 percent by weight of divinylbenzene, 38.25 percent by weight ethylvinylbenzene and 15 percent by weight N-vinylpyrrolidone was prepared employing procedure similar to that used in Example 1 from a mixture of 75 parts by volume of commercial divinylbenzene consisting of about 55 percent divinylbenzene and about 45 percent ethylvinylbenzene and and 25 parts by volume of N-vinylpyrrolidone and with diethylbenzene as the diluent. The product was an insoluble microporous polymer.
• Example 5 A copolymer of about 51.15 percent by weight divinylbenzene, 41.85 percent by weight diethylbenzene and 7 percent by weight N-vinyl pyrrolidone was made by procedure similar to that used in Example 4.
• the polymers used in the present invention are preferably ethylvinylbenzenedivinylbenzene polymers in spherelike particles of 80 100 mesh size (which are marketed as Porapak Q polymers). These polymers have a pore size of 10" Angstrom units (1 micron), a total surface area of 50 meters /milliliter and a bulk density of 0.5 gram/ml.
• a filter containing 50 mg. of Porapak Q" polymer was found to remove approximately 15 percent of the total gas phase. It was found to selectively remove about 87 percent of the limonene and certain aromatics and, to a lesser degree, to selectively remove benzene and toluene.
• the Porapak type polymers were found to provide particularly effective performance as flavor release agents.
• the TABLE 1 particles were found to easily retain up to their own weight of u Commercial flavorants such as anethole or menthol.
• Filulwith h? N0 cellulose u Porapak Q" additive filter acetate filter taming Porapak Q type polymers containing a flavorant were stored for several weeks thev were smoked and found to Y 28 32 43 25 Total moisture, mg.. 11. 15. 2 8.8 release to the smoke as much as l4 percent of the flavor.
• Example 7 A filter plug was prepared for a cigarette consisting of an outer section 7.5 mm. long of crimped, fluffed cellulose acetate, 8 denier/48,000, plasticized with triacetin, and an inner section 12.5 mm. long of cellulose acetate tow approximately 5 denier/15,000 on which had been sprinkled mg. of Porapak Q" porous ethylvinylbenzene-divinylbenzenestyrene polymer, with pores lO Angstroms in diameter and particles 150x200 mesh. This dual plug had a total resistanceto-draw (RTD) of 3 inches of water.
• RTD resistanceto-draw
• IR signifies analysis by infrared absorbance of the gas phase or gas mixture
• GC signifies analysis by gas chromatography.
• the smoke delivered is passed through a Cambridge total removal filter pad (glass microfiber) to remove substantially :all the particulate matter.
• the gaseous portion is introduced into the cell of an infrared spectrometer and its absorbance spectrum is measured. The height of previously identified absorption peaks gives relative measurement of the concentrations of components in comparison with the concentrations when no active gas filter is used.
• the gas phase similarly separated from particulates, and suitably diluted, may be introduced into a gas chromatographic column.
• the column employed was l5 cm. by /s-inch stainless steel packed with 60-8O mesh acid-base washed Ch r5fnsorbl coated with 10 percent by weight Dow Corning 550 silicone oil.
• the carrier gas was nitrogen; the components were detected by a flame ionization detector and identified by previously determined retention times for known major components. The peak area gave a relative measure of concentrations in comparison with those when no gas filter was present.
• Example 8 Anethole, technical grade, was mixed with approximately twice its weight of Porapak Q porous polymer beads and left-exposed to air for 2 days, until no more weight loss was observed. Weight loss during exposure was 12 percent of the initial anethole weight. Anethole content of the total weight was 33.2 percent by extraction and analysis.
• Filters were prepared by sprinkling this granular material uniformly on crimped, opened cellulose acetate filter tow, 8 denier/24,000 and making the composite into cigarette filter rods which were calculated to contain 10 mg. of the anetholeresin per cm. of length. Filters l cm. long were attached to Fresh Aged TPM, mg. 32 33 Anetholc in Smoke. mg. 0.46 0.38 "i of Original Anethole 13.9 1 L5
• Example 9 Granular Porapak Q was flavored by slowly adding with mixing a solution of menthol in one-fourth its weight of ethanol. The mixture was heated in an air-circulating oven at 100C. for 6 /2 hours until weight became nearly constant. The weights of porous beads and menthol were 20.2 and 14.8 g., respectively; the weight after heating was 35.0 g. Analysis by extraction and gas chromatography showed 45 percent menthol of total weight.
• Filters were prepared as in the preceding example, with a loading of flavored granules of 8 mg. per cm. of length, with the same filter tow and backup. These filters, 1 cm.+l cm., were attached as before to 65 mm. commercial cigarette rods. Smoking and analysis were carried out as in the preceding example; packs of cigarettes were aged for two cycles of l 1 days each and were then smoked.
• the Porapak Q polymer is in the form of small beads.
• the beads are quite spherical and similar in size when viewed under a stereo microscope.
• the 80 100 mesh size was confirmed by screening as 99 percent passed through an 80 mesh US. Standard screen and wa held on a 100 mesh screen.
• the polymer beads appeared to possess a static charge as they showed a definite affinity for each other and tended to form a one layer film on any surface upon which they were in contact.
• Cigarette l for Cigarette 2 for Cigarette 3 for Cigarette 4 for Cigarette S for TABLE 4.RESULTS OF ANALYSES FOR SELECTIY'E RE- MOVAL STUDY Cigarette Tub!e 5
• W menthol results of Gas Phase Profile. flavor system.
• the smaller gel material was subjected to only limited testing.
• a loading of 70 mg. of the gel on a loosely compacted celq Pompak X 100: percent menthol lulose acetate (CA) inner filter showed no affinity for B(a)P Equil. wt. or TPM.
• the IR. index was 5 which is indicative of almost no O48 20.205 activity.
• Anethole was chosen as the flavor to be used with the i
• a ample cigarette 8 of the mixture was submitted for menthol Porapak Q" as a possible flavor transfer agent.
• Cigarettes were made the choice of anethole were the availability of analytical i for smoke analysis in the same construction as before.
• a sammethods for the quantitative determination of anethole and its I ple was also constructed with an active carbon to test the ease of handling (liquid at room temperature). delivery in the presence of an active gas phase material.
• Porapak/menthol plus m for smoke analysis The cigarettes were made by basically the 50 soxmo PCB carbon. l0 mm. same technique as described in the previous section. Half of 8148CA p the cigarettes were smoked fresh and the others were taken 65 CA h h I f l d h f k. plus 50 mg. 50xl4
• Cigarette l2 aged sample was not run due to low fresh delivery.
• flavorants may also be effectively incorporated in cigarettes and other tobacco products in the same way.
• the polymeric materials used in the present invention may be utilized as components of the ultimate, or mouthpiece, section of a multicomponent filter system. They can then serve to replace flavors removed from the tobacco smoke by filter elements closer to the tobacco.
• the polymers may also be used as components of a single filter element or as components of any other filter combination.
• the polymer may comprise the only component of a filter section or may be employed with other filter material, such as tow or paper, with adhesives and the like and is, as set forth above, employed with flavorant materials to achieve the particularly beneficial results provided by the present invention.
• the amount of polymer present in the filter element of a smoking article may vary widely, but will generally comprise from about 1 to about 100 parts by weight based on the weight of the tobacco employed.
• the polymer may be in avariety of sheet sssizesasawll b ie qslss ss iassn t qparti yr teristics desired.
• the polymers used in the present invention are preferably ethylvinylbenzene-divinylbenzene polymers in spherelike particles of Xx mesh size (which are marketed as Porapak Q polymers). These polymers have a pore size of 10 angstrom units (1 micron a total surface area of 50 me ters /milliliter and a bulk density of 0.5 gram/ml.
• the polymers will contain or be loaded with from about 10 to 100 parts by weight of flavorant per 100 parts of polymer.
• the present polymers are particularly effective for the incorporation of menthol, anethole and similar flavorants into tobacco products but may be employed to incorporate other flavorants as well.
• any flavorants may be employed which comprise molecules containing polar groups and/or possess some degree of polarity, whereby displacement of the flavorant by the smoke stream may be effected.
• suitable flavorants are the following materials:
• Aromatic acids such as: phenyl acetic acid, nonanoic acid, and the like.
• Aromatic aldehydes such as: benzaldehyde, tolylaldehyde cinnamaldehyde, anisic aldehyde, citral, ethyl vanillin, vanillin, phenyl acetaldehyde, and the like.
• Aromatic ketones such as: benzophenone (diphenyl ketone), acetophenone, dibenzylketone, ionones, menthone,
• Aromatic ethers such as: anisole, anethole, benzylisoamyl ether, dihydroanethole, dimethyl hydroquinone, estragole, methyl eugenol, safrole, and the like.
• Aromatic esters including: acetates, anisates, anthranilates, benzoates, butyrates, butyrates, caproates, cinnamates, formates, laurates, palmitates, propionates, and the like, for example, methyl anthranulate, ethyl anthranilate, dimethyl anthranilate, benzylisoamylacetate, p-cresyl acetate, cinnamyl acetate, benzyl acetate, eugenol acetate, benzyl phenyl acetate, and the like.
• Aromatic alcohols such as: menthol, eugenol, cinnamic alcohol, methyl eugenol, anisyl alcohol, citronellol', geraniol, farnesol, nerol, myristyl alcohol, and the like.
• TPM is defined as the total particulate material in milligrams in the smoke from a cigarette as collected on a Cambridge filter.
• RTD Resistance to draw
• a vacuum system was set to pull an air flow of 1050 cc./min. by inserting the tapered end of a standard capillary tube through the dental dam of the cigarette holder and adjusting the reading on the water manometer to correct RTD.
• the water level of the manometer was set at zero before inserting the standard capillary.
• a filter for tobacco smoke comprising a solid, finely divided, microporous organic polymer containing within the pores from about 10 to about 100 parts, by weight, of an adsorbed flavor for tobacco smoke, per 100 parts of polymer said polymer upon contact with tobacco smoke, being capable of removing undesirable components from said tobacco smoke.
• a smoking article comprising tobacco and a filter for tobacco smoke, said filter comprising a solid, finely divided, microporous organic polymer containing within the pores from about 10 to about 100 parts, by weight, of an adsorbed flavor for tobacco smoke, per 100 parts of polymer, upon contact with tobacco smoke, being capable of removing undesirable components from said tobacco smoke.
• Percent menthol delivery IR Index should be Percent menthol delivery I i b IR Index line 26, "nether” should be neither line 29, insert a comma after “filtered” line 55, "citruslike” should be citrus-like line 61, "multicomponent” should be multi-component Column 12, line 4, "spherel'ike” should be sphere-like line 5, remove the extra “x”; line 27, “piperine” should be piperitone line 32, remove the extra “butyrates”; line 34, "anthranulate” should be anthranilate Claim 2, line 5, insert said polymer' aft er "polymer,

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Cigarettes, Filters, And Manufacturing Of Filters (AREA)

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Cited By (21)

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Citations (5)

• 1968
  • 1968-12-13 US US783743A patent/US3603319A/en not_active Expired - Lifetime
• 1969
  • 1969-10-23 GB GB52070/69A patent/GB1286999A/en not_active Expired
  • 1969-11-20 FI FI693357A patent/FI51039C/fi active
  • 1969-12-09 FR FR6942498A patent/FR2026057A1/fr not_active Withdrawn
  • 1969-12-12 DE DE19691962452 patent/DE1962452A1/de active Pending
  • 1969-12-12 CH CH1855369A patent/CH526278A/de not_active IP Right Cessation

Patent Citations (5)

Non-Patent Citations (1)

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