U.S. patent number 3,603,319 [Application Number 04/783,743] was granted by the patent office on 1971-09-07 for flavor-releasing smoking article and method of making the same.
This patent grant is currently assigned to Philip Morris Incorporated. Invention is credited to Charles E. Badgett, Jerome S. Osmalov.
United States Patent |
3,603,319 |
Badgett , et al. |
September 7, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
FLAVOR-RELEASING SMOKING ARTICLE AND METHOD OF MAKING THE SAME
Abstract
This disclosure relates to a flavor-releasing smoking article
and to methods of making the same. More particularly, the
disclosure 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.
Inventors: |
Badgett; Charles E. (Richmond,
VA), Osmalov; Jerome S. (Richmond, VA) |
Assignee: |
Philip Morris Incorporated (New
York, NY)
|
Family
ID: |
25130260 |
Appl.
No.: |
04/783,743 |
Filed: |
December 13, 1968 |
Current U.S.
Class: |
131/274; 131/332;
131/342 |
Current CPC
Class: |
A24D
3/14 (20130101) |
Current International
Class: |
A24D
3/14 (20060101); A24D 3/00 (20060101); A24b
015/02 (); A24d 001/06 (); A24f 025/00 () |
Field of
Search: |
;131/267,266,262A,269,10.7,10.9,9 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Leonard, Application Serial Number 781,712, filed December 4, 1968,
as a continuation of Application Serial Number 648,972, filed June
26, 1967, laid open to public inspection on July 29, 1969, a noted
at 864 O.G. 1405. Pages 5-7 of the specification are relied upon.
Classified in class 131, sub. 266..
|
Primary Examiner: Koren; Samuel
Assistant Examiner: Yahwak; G. M.
Claims
We claim:
1. 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.
2. 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.
3. The filter of claim 1, wherein said polymer is a copolymer of
ethylvinylbenzene and divinylbenzene.
4. The filter of claim 1 wherein said flavorant is anethole.
5. The filter of claim 1 wherein said flavorant is menthol.
6. The filter of claim 3, wherein said polymer is a copolymer of
ethylvinylbenzene and divinylbenzene and said flavorant is
anethole.
7. The filter of claim 3, wherein said polymer is a copolymer of
ethylvinylbenzene and divinylbenzene and said flavorant is menthol.
Description
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.
With the increasing effectiveness of filter materials for the
removal of undesired elements of tobacco smoke a different problem
has arisen in connection with tobacco smoke filtration. Many of the
more effective filter materials have been found to remove desirable
flavoring materials, such as menthol, from the tobacco smoke.
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.
In addition, materials have been suggested for filtration of
tobacco smoke. Among some of the 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.
The so-called open-cell foams, i.e., foams having an open-pore
structure through which smoke may be drawn for filtration, have
been found to possess variable pore sizes and a large distribution
of pore sizes. As a consequence, such foams have imparted variable
resistance-to-draw (RTD) and, thus, variable quality to the tobacco
products in which they have been employed. In addition, such foams
are often so open in structure that an inconveniently long filter
section must be employed to effect significant particle removal.
Moreover, so-called 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.
In contrast, when the pores of such adsorbents having uniform but
very small pore size, such as the zeolite type materials are used,
they do not take up certain additive molecules. For example, the
few zeolite type materials which have room for additives, are, due
to their strong hydrophilic properties, susceptible to premature
displacement of the additive by tobacco moisture.
We have discovered a novel filter material which provides selective
filtration and excellent control of the RTD of filters in which
they are employed and which provides for the proper retention and
delivery to the tobacco smoke of desirable volatile additives and
flavorants such as menthol and anethole.
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, e.g. 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.
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 80 to 180 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. For example, 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 sec-butylstyrene. Mixtures of two or more
polyvinyl monomers such as for example, divinyl benzene, driving
toluene, divinylxylene, diallyl phthalate, diallyl fumarate, or
ethylene glycol dimethacrylate, can also be used. 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.
The 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 dissolve 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.degree. and 120.degree. C. and at atmospheric,
subatmospheric, or superatmospheric pressure.
In preparing the polymer, 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.degree. and 120.degree. C. until the
monomer is polymerized. The vessel is opened and the porous polymer
removed.
Other methods for making 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 included in the mixture to cross-link
the polymer before cooling and extraction of the surfactant.
U.S. Pat. No. 2,537,951 involves the manufacture of porous
cross-linked copolymers of vinyl aromatic compounds, such as a
mixture of styrene, ethylvinylbenzene and divinylbenzene, which may
be employed in accordance with the present invention.
The various cross-linked insoluble popcorn or proliferous polymers
such as are described by Kondakow (J. prakt Chim. [2] 64, p. 109
(1961)); carothers (J.A.C.S. 53, D. 4203 (1931)); Staudinger et al.
(Berichte 68 p. 1618 (1935)); Britton (U.S. Pat. No. 2,341,175 of
Feb. 8, 1944); Karasch et al. (Ind. Eng. Chem. 39, p. 830 (1947));
and mentioned in U.S. Pat. Nos. 2,597,437-8-9 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 5 and 500
microns.
The following examples are illustrative.
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.sub.3.sup. . Mg(OH).sub. 2.sup. .
3H.sub.2 0), as suspending agent, and 0.1 gram of potassium
dichromate. The mixture was stirred and heated under time and
temperature conditions as follows: 4 hours at 50.degree. C., 4
hours at 55.degree. C., and 16 hours at 65.degree. 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
liquid to a pH value between 3 and 4. The 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 119-165
microns; 150-196 microns; 173-238 microns and 192-288 microns. The
product having particles of sizes between 119 and 165 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.degree. and 80.degree. 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.sub.2
Cr.sub.2 O.sub.7 and 12 grams of methyl cellulose. The mixture was
stirred and heated at a temperature of 55.degree. C. for a period
of 5 hours, then was stirred and maintained at 65.degree. 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.
As set forth later in this specification, the polymers used in the
present invention are preferably ethylvinylbenzene-divinylbenzene
polymers in spherelike particles of 80.times.100 mesh size (which
are marketed as "Porapak Q" polymers). These polymers have a pore
size of 10.sup.4 Angstrom units (1 micron), a total surface area of
50 meters.sup.2 /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.
By contrast polymers of 45 Angstrom pore size sample were found to
be less effective, removing a small percentage of the total gas
phase and exhibiting less selectivity for any of the compounds
tested.
The "Porapak Q" type polymers were found to provide particularly
effective performance as flavor release agents. The particles were
found to easily retain up to their own weight of flavorants such as
anethole or menthol. After cigarettes containing "Porapak Q" type
polymers containing a flavorant were stored for several weeks they
were smoked and found to release to the smoke as much as 14 percent
of the flavor.
Example 6
A styrene-ethylvinylbenzene-divinylbenzene cross-linked polymer
("Porapak Q," Waters Associates, Inc., Framingham, Mass.) was
sieved to pass 150 mesh. This resin was applied to cellulose
acetate crimped tow, 8 denier/40,000, which had been air-opened.
The resin was applied at the rate of 10 grams per meter. This tow
was gathered and wrapped as a filter rod by commercial
filter-making machinery. Lengths of 1 cm. were cut from the rod and
attached to 65 mm. cigarette rods, together with an outer 1 cm.
filter of 5 denier/68,000 cellulose acetate tow. The combined
filters had a resistance-to-draw (RTD) of 2.2 to 2.8 inches of
water.
These cigarettes were smoked and the smoke was separated into
particulate and gas phases; the analysis of the gas phase by mass
spectrometry by the procedure of C. J. Varsel, F. A. Morrell, F. E.
Resnik, and A. Powell, Anal. Chem. 32, No. 2, 182-186 (1960) was
compared with the analysis of smoke gas phase delivered from the
same cigarette rods filtered by 2.0 cm., 5 denier/68,000 cellulose
acetate tow filters with the same range of RTD. It was found that
xylene, toluene, benzene, and methylfuran had been reduced
significantly (more than 20 percent by the porous resin filter)
while the concentrations of methanol, isoprene, butadiene,
acetaldehyde, among others, were not significantly affected.
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 50 mg. of "Porapak Q"
porous ethylvinylbenzene-divinylbenzene-styrene polymer, with pores
10.sup.4 Angstroms in diameter and particles 150 .times.200 mesh.
This dual plug had a total resistance-to-draw (RTD) of 3 inches of
water. The same combination of tows was made into a similar dual
plug without the addition of the "Porapak Q" to serve as a control;
this plug had a 1.6 inch RTD. Each was attached to an identical
commercial cigarette rod 65 mm. long having a 2.0 inch RTD. A
number of cigarettes of each type was smoked for analytical
purposes.
Comparative results are given in Tables 1 and 2. It will be seen
that removal of aromatic compounds above toluene in molecular
weight is excellent. Removal of toluene is very good, while removal
of nonaromatic, volatile compounds from the gas phase is
insignificant (i.e., less than 20 percent), except for 22 percent
HCN removal which is desirable. An activated charcoal filter which
removes benzene and toluene to this extent also removes appreciable
quantities of isoprene, ester, ketones, aldehydes, and like flavor
contributors. This is illustrated in Table 3 where the action of
the filters by themselves on a smokelike gas mixture is compared.
##SPC1## ##SPC2##
IR signifies analysis by infrared absorbance of the gas phase or
gas mixture; GC signifies analysis by gas chromatography. In the
analysis of smoke gas phase, 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 15 cm. by 1/8-inch stainless steel packed with
60-80 mesh acid-base washed "Chromsorb P," 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 anethole-resin per
cm. of length. Filters 1 cm. long were attached to commercial
cigarette rods 65 mm. long and 1 cm. backup filters of 8
denier/48,000 cellulose acetate were added. These were smoked by
machine, and the smoke was trapped on Cambridge filter pads and
analyzed. Some of these cigarettes were subjected to an accelerated
aging cycle, in packs, consisting of 7 days at 110 .degree.F., 15
percent R.H. and 4 days at 90.degree. F., 85 percent R.H. Results
of smoke analysis for these cigarettes are also given.
Fresh Aged
__________________________________________________________________________
TPM, mg. 32 33 Anethole in Smoke, mg. 0.46 0.38 % of Original
Anethole 13.9 11.5
__________________________________________________________________________
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 100.degree.C. for
61/2 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.+ 1 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 11 days each and were then smoked.
---------------------------------------------------------------------------
Fresh Aged 2 Cycles
__________________________________________________________________________
TPM, mg. 38 32 Menthol in Smoke, mg. 0.53 0.38 % of Original
Menthol 14.5 10.6
__________________________________________________________________________
A second sample of the beads was treated with a menthol-ethanol
solution, washed with ethanol, and dried 2 1/2 hours at 100.degree.
C. to nearly constant weight. Analysis showed 34 percent menthol of
total weight. Cigarettes prepared as above, with 8 mg. of flavored
beads in the filter, were smoked.
---------------------------------------------------------------------------
TPM, mg. 34 Menthol in Smoke, mg. 0.30 % of Original Menthol 11.1
__________________________________________________________________________
Example 10
Beads of "Porapak Q" were mixed with one-third their weight of
"Magna" lime oil (distilled natural Mexican, Magnus, Mabee &
Reynard Inc., N.Y., N.Y.), and applied to filter tow at the rate of
32 mg./cm. of filter length. Sections 5 mm. long were attached to
cigarette rods and backed by 15 mm. of conventional cellulose
acetate filter. Smokers found the cigarette to have a distinctive
flavor which most identified as lime or citruslike.
The following examples are also illustrative of the present
invention:
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.times.100 mesh size was confirmed by screening
as 99 percent passed through an 80 mesh U.S. Standard screen and
was held on a 100 mesh screen. Measurements were also taken from
enlarged photographs. At 160 power the particles averaged 140
microns with a range from 120 to 175. At 500 power the surface
pores could be discerned and their sizes ranged from 0.2 to 2
microns. This confirmed the stated 1 micron or 10.sup.4 Angstrom
units size. During the testing our initial supply of "Porapak Q"
was exhausted and a new supply received. The beads in this batch
were the same size but were irregular in shape, not spherical.
There was no indication that the change in shape affected the
performance of the material.
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.
Another polymer of the "Porapak Q" type had a particle size of 150
.times.200 mesh. In utilizing this material, the main problem was
one of filter configuration. Because of the small particle size a
space fill plug gave a high RTD even at low loadings. A 12.5 mm.
loosely compacted cellulose acetate section was pushed into a 20
mm. empty mouthpiece tube already attached to a cigarette rod. This
section was made by dividing 5 dpf/30,000 denier tow in half and
threading it through 80 mm. empty tubes. These tubes were cut into
12.5 mm. sections and the tow transferred to the tubes attached to
the cigarettes. A weighed amount of the polymer was then dropped
into this section and the filter completed by capping with a 7.5
mm. 8 dpf/48,000 machine-made filter section. By this method a good
dispersion of material could be presented to the smoke at a
reasonable RTD. The following cigarettes were prepared for
analytical testing:
---------------------------------------------------------------------------
Cigarette 1 65 mm. tobacco rod, CA mm. 5/15 Ca plus 50 mg. "Porapak
Q," 7.5 mm. 8/48 CA-- RTD 5.0 .+-.0.3" for B(a ) P, whole smoke
H.sub.2 O, I.R. Index, gas phase profile, TPM, nicotine, phenol.
Cigarette 2 Same as Cigarette 1 except no "Porapak" added-- 3.6
.+-.0.2 " for TPM, nicotine, phenol. Cigarette 3 65 mm. tobacco
rod, 20 mm. mouthpiece tube, 2.0 .+-.0.2" for Control I.R. Index,
whole smoke H.sub.2 O, TPM, nicotine, phenol. Cigarette 4 65 mm.
tobacco rod, 20 mm. Marlboro 4/49CA filter, 4.6.+-.0.2" for Whole
smoke H.sub.2 O. Cigarette 5 Filter only: 5 mm. 8/48CA, 10 mm. 5/15
CA plus 50 mg. "Porapak Q," 5 mm. 8/48 CA--2.2.+-.0.2" for
Synthetic gas phase.
__________________________________________________________________________
The results of the analyses are shown in Tables 4 and 5. The TPM,
nicotine and phenol values appear to be a function of RTD and not
of the Porapak. That is, the decrease in deliveries shown are the
result of a higher RTD filter. The whole smoke water delivery is
slightly higher than expected from a cellulose acetate (only)
filter of equal efficiency. The "Porapak Q" is somewhat
nonselective for water. The I.R. index and the synthetic gas index
indicate some general gas phase removal but the amount was not
considered significant. ##SPC3##
Table 5
__________________________________________________________________________
Cigarette 1: Results of Gas Phase Profile. Analytical Method: Ratio
comparison of the experimental cigarette gas phase delivery to that
of a Marlboro monitor control by gas chromatography.
Compounds Ratio
__________________________________________________________________________
Methane thru methyl chloride 1.0 Isoprene 0.97 Acetaldehyde 0.98
Acetone 1.0 Acrolein 0.82 Methyl vinyl Ketone* 0.87 Benzene* 0.77
Toluene 0.52 Limonene 0.13 Other possible aromatics 0.13
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Total of all gas phase 0.86
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*Compound identity not positive.
The gas phase profile as determined by gas chromatography pinpoints
the selective removal properties of this material. While this test
showed a general reduction level of 14 percent, certain components
(aromatics) were reduced up to 87 percent. Note the agreement of
the general 14 percent reduction to the I.R. smoke index of 13.
The smaller gel material was subjected to only limited testing. A
loading of 70 mg. of the gel on a loosely compacted cellulose
acetate (CA) inner filter showed no affinity for B(a)P or TPM. The
I.R. index was 5 which is indicative of almost no activity. A mass
spectrograph analysis of the smoke from this sample gave no
indication of selectivity or any adsorption.
The following examples are further illustrative of the flavor
transfer ability of the present materials.
Anethole was chosen as the flavor to be used with the "Porapak Q"
as a possible flavor transfer agent. The reasons for the choice of
anethole were the availability of analytical methods for the
quantitative determination of anethole and its ease of handling
(liquid at room temperature).
Technical grade anethole was slowly hand mixed (due to the heat of
adsorption) with the polymer in an approximate 1 anethole--2
polymer ratio. The mixture was then left in the flask and allowed
to equilibrate at room conditions (75.degree. F., 60 percent R.H.).
Equilibrium was reached in 2 days time as evidence by no further
weight loss on periodic weighings. A portion of the sample was
submitted for percent anethole analysis and the remainder utilized
in cigarette construction for smoke analysis. The cigarettes were
made by basically the same technique as described in the previous
section. Half of the cigarettes were smoked fresh and the others
were taken through one cycle of accelerated aging before smoking.
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Cigarette 6 65 mm. filter rod, 10 mm. 8/24 Ca plus 10 mg.
Porapak/Anethole, 10 mm. 8/48 CA outer filter. Cigarette 7
Porapak/Anethole sample.
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The results as shown in Table 6 were encouraging. The fresh
delivery is very good release from a filter. Although delivery
decreased after aging it still remained at a high level.
##SPC4##
A more comprehensive study was undertaken using menthol as the
flavor to give a comparison with an established flavor system.
The menthol employed was a conventional blend in an ethanol
solution.
The 80 percent menthol--20 percent ethanol solution was slowly
added to the polymer by hand mixing in an approximate 1 to 1 ratio.
The mixture was then placed in an air-circulating oven until
equilibrium was attained. The heating took 6 1/2 hours until no
further weight loss was noted. To check if the percent menthol in
the mixture could be calculated from the weight loss the following
computation was made:
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Weight of "Porapak Q" 20.205 g. Weight of menthol solution 18.458
Total weight as mixed 38.663 Final weight at equilibrium 35.048
Weight loss 3.615 Percent loss based on menthol solution 19.6 %
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The weight loss was assumed to represent the ethanol as it equaled
the amount in the initial solution. Then:
A sample cigarette 8 of the mixture was submitted for menthol
analysis to confirm the calculated value. Cigarettes were made for
smoke analysis in the same construction as before. A sample was
also constructed with an active carbon to test the delivery in the
presence of an active gas phase material.
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Cigt. 9 65 mm. filter rod, 10 mm. 8/24 Ca plus 8 mg.
Porapak/menthol, 10 mm. 8 148CA backup. Cigt. 10 65 mm. filter rod,
10 mm. 8 /24CA plus 8 mg. Porapak/menthol plus 50 mg. 50 .times.140
PCB carbon, 10 mm. 81 48 CA backup. Cigt. 11 65 mm. filter rod, 10
mm. 8/24 CA plus 50 mg. 50 .times.140 PCB, 10 mm. 8/48 CA backup.
Cigt. 12 65 mm. filter rod, 20 mm. mouthpiece tube control.
__________________________________________________________________________
These samples were analyzed fresh and after 2 cycles of accelerated
aging. The results are listed in Table 7.
The 45 percent menthol in the sample as analyzed agreed with the 42
percent calculated figure so that it appeared that very little of
the menthol was lost in the equilibrium process. The fresh delivery
of 14 percent was similar to that with the anethole and about the
same as if the menthol had been on the tobacco rod. However, the
delivery was reduced after aging and was almost completely stopped
by the active carbon. These results lead to the hypothesis that the
menthol is not held tightly by the Porapak. Although heat
(100.degree. C.) alone does not drive it off, it is released slowly
with time or rapidly in the presence of a highly active absorbent.
The gas phase activity of the carbon was not reduced as expected,
perhaps since the 3.6 mg. of menthol available represents only a
small part of the material that this amount of carbon can absorb.
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TABLE 7
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ANALYSIS Sample Cigarettes Cigt. 8 -- "Porapak"/menthol only Cigt.
9 -- 8 mg. "Porapak"/menthol Cigt. 10 -- 8 mg. "Porapak" plus 50
mg. 50.times.140 PCB Cigt. 11 -- 50 mg. 50.times.140PCB Cigt.
12Empty tube control Percent Menthol in Cigarette 8 -- 45 % Aged(2
Fresh Cycles
__________________________________________________________________________
Cigt. 9 Cigt. 10 Cigt. 11 Cigt. 12
__________________________________________________________________________
Available menthol, 3.6 3.6 -- 3.6 mg. TPM, mg. 38 33 -- 32 Menthol
in smoke, mg. 0.53 0.04 -- 0.38 Percent menthol 14.5 1.1 -- 10.6
deliveryIR Index -- 27 25 --
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Two tests were attempted to determine the maximum retention level
of the polymer for menthol with nether being entirely
successful.
In the first test a sample of "Porapak Q" was treated with an
excess of menthol-ethanol, vacuum filtered washed with a small
amount of ethanol and dried in an air-circulating oven to nearly
constant weight. A sample (Cigarette 13) of this mixture analyzed
as only 34 percent menthol and from a cigarette (Cigarette 14)
delivered only 11 percent of the available menthol. Either the
Porapak was not left in contact with the menthol solution until
saturation was achieved or a portion of the adsorbed menthol was
removed by the alcohol wash.
In the second test a different approach was used. Additional
menthol-ethanol solution was added to the previously prepared
sample Cigarette 8 (45 percent menthol). From weight loss data it
was apparent that as more menthol was adsorbed, a higher percent of
that adsorbed was driven off in the equilibrating period. The point
at which the weight loss would equal the weight gain appeared to be
somewhat over 50 percent . The test was not run to conclusion as
the polymer was inadvertently exposed to 150.degree. C. temperature
during the latter stages and some unexpected degradation occurred.
Although a definite saturation point is still not known it has been
found that the "Porapak Q" can retain its own weight of
menthol.
A third flavor, lime oil, was tried with the polymer. The oil was
adsorbed on the "Porapak" in an approximately 1 oil to 3 polymer
ratio. As no analytical tests are were readily available cigarettes
were prepared from this sample and smoked for subjective taste. All
who smoked this cigarette (15) detected a definite different flavor
and in most cases identified the flavor as lime or citruslike.
Other 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 a variety of shapes and sizes and will be packed depending on
the particular flavor release, resistance-to-draw and filtering
characteristics desired.
The polymers used in the present invention are preferably
ethylvinylbenzene-divinylbenzene polymers in spherelike particles
of 80 .times.x 100 mesh size (which are marketed as "Porapak Q"
polymers). These polymers have a pore size of 10.sup.4 angstrom
units (1 micron ), a total surface area of 50 meters.sup.2
/milliliter and a bulk density of 0.5 gram/ml.
Generally, 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. For example, 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. Illustrative of 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, methyl nonyl
ketone, nerone, pulegone, piperine, and the like.
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.
As used herein, unless otherwise stated, all parts and percentages
are by weight.
The term TPM is defined as the total particulate material in
milligrams in the smoke from a cigarette as collected on a
Cambridge filter.
Resistance to draw, also referred to in this specification as RTD,
was determined as follows:
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.
Then the butt end of a cigarette or plug was inserted to a depth of
5 mm. in the dental dam of the cigarette holder. The pressure drop
behind this cigarette with 1050 cc./min. of air flow passing
through was read directly as RTD (inches water) from the inclined
water manometer.
* * * * *