Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Compositions and Articles Containing an Active Liquid in a Polymeric
Matrix and Methods of Making and Using the Same
FIELD
Compositions and articles containing an active liquid intermixed with a
polymer matrix,
as well as methods of making and using the same, are described herein.
BACKGROUND
The curing and/or cross-linking of polymeric systems, for example epoxy
systems, is
described in textbooks and industrial handbooks such as "Handbook of Epoxy
Resins" by Henry
Lee and Kris Neville (McGraw Hill, 1967), "The Epoxy Formulators Manual" by
the Society of
Plastics Industry, Inc. (1984), and the Encyclopedia of Science and Technology
(Kirk-Othmer,
John Wiley & Sons, 1994). Until recently, curing such systems and others
related thereto in a
manner capable of immobilizing active liquids, such as those having and/or
containing fragrance,
has been very difficult, especially when durability and performance under a
dynamic range of
operation conditions are required from such systems.
For example, JP 032558899A requires the use of a solid powder system, while
JP07145299 requires the use of a pre-formed urethane-containing epoxy resin
cross-linked in the
absence of a polyamine and/or an active liquid containing a perfume. Further,
the above-
mentioned JP references refer specifically and only to fragranced articles,
such as air fresheners.
Because of this narrow goal to make such articles, the reaction and reaction
products described
therein fail to have a dynamic range of performance capabilities. Moreover,
they fail to provide
a product that is durable in the absence of a support. Therefore, a need
arises for controllable
reaction conditions that yield dynamic reaction products containing durable
matrices capable of
immobilizing any and/or all types of active liquids therein.
Compositions such as fragrance objects, even more specifically air fresheners,
are well
known devices that release a fragrance into the air of a room of a house, area
of a public building
(e.g., a lavatory), or the interior of a car to render the air in that area
more pleasing to the
occupant. Only substantially non-aqueous gels, for example, the thermoplastic
polyamide-based
products described in US Patent Nos. 6,111,655 and 6,503,577 and the thermo-
set poly(amide-
acid)s of US Patent No. 5,780,527 and US Patent No. 6,846,491, are
homogeneous, transparent
solids that can be easily charged, when in liquid form, to a mold and thus
made into a visually
attractive solid shape without the use of a means of support. However, during
preparation of
thermoplastic gels, the components must be heated to a temperature above the
gelation
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temperature of the mixture, a process detrimental to the volatile and
sometimes temperature
sensitive active liquid such as fragrance, pesticide, or surfactant. During
storage or use, these
gels must not be exposed to low temperatures because they can turn
unattractively cloudy.
Furthermore, these gels must not be exposed to high temperatures because they
will turn liquid,
losing their shape or leaking from their container. These drawbacks are
serious for air fresheners
necessarily exposed to a dynamic range of temperatures, such as car interior
fresheners. The
latter are often exposed to low temperatures in winter and temperatures in
excess of 110 F on
summer days when the car is parked in direct sunlight. In addition,
thermoplastic gels are soft
solids that are easily deformed if scraped, dropped, poked, or wiped. Thus,
these conventional
gels do not provide compositions and/or articles that are readily durable and
capable of operating
at a wide range of operating parameters.
Air care articles can contain a variety of fragrances. Aldehydes are common
fragrance oil
ingredients and can react with primary amines and interfere with polymer
matrix setting times,
especially for polymer matrices based on isocyanate-polyamine curing systems.
It is not unusual
that compositions fail to form the desired articles because aldehydes consume
free primary
amine groups.
(Polymer-)-NH2 + 0=C(R)-H 4=4' (Polymer-)-N=C(R)H +1120
This drawback significantly limits a consumer's options to choose fragrances
and makes product
manufacture very difficult.
SUMMARY
Described herein are compositions and articles containing an active liquid
intermixed
with a polymeric matrix and methods of making and using the same. The
compositions include
a polymeric matrix comprising the reaction product of a polyamine and a
compound having at
least two functional groups and an active liquid intermixed with at least a
portion of the
polymeric matrix. The functional groups are selected from the group consisting
of epoxy groups,
isocyanate groups, anhydride groups, and acrylate groups. The polyamine and
the compound are
reacted in the presence of the active liquid. In some examples, the polyamine
is a polyamide
polyamine and/or a secondary amine terminated polyamine. The reactive amine
groups of the
polyamine can include amino groups derived from at least one of ortho-
aminobenzoic acid or
para-aminobenzoic acid. In some embodiments, the polyamine is a non-water
soluble polyamide
polyamine with a molecular weight in the range of 4,000 to 30,000 Daltons.
In some examples, the active liquid is present in an amount from 10 weight %
to 85
weight % based on the weight of the composition (e.g., from 50 weight % to 85
weight % based
on the weight of the composition). The active liquid can include, for example,
a therapeutic
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active liquid, a nutraceutical active liquid, a cosmeceutical active liquid, a
pesticidal active
liquid, a laundry care active liquid, a fragrance, or a mixture thereof. In
some examples, the
compound includes at least one non-aromatic isocyanate compound.
The composition described herein can be in the form of a gel. In other
examples, the
composition can be in the form of a particle and can be present in an aqueous
dispersion. The
particle size can be, for example, from 1 micron to 100 microns (e.g., from 2
microns to 15
microns). Also described herein are articles comprising a porous support
material and the
composition described herein.
Methods of preparing the compositions are also provided herein. The methods
can
include reacting a polyamine with a compound having at least two functional
groups, the
functional groups selected from the group consisting of epoxy groups,
isocyanate groups,
anhydride groups, and acrylate groups in the presence of an active liquid. In
some examples, the
polyamine is liquid at room temperature. In some examples, the polyamine has
an amine
number of from 10 meq KOH/g to 100 meq KOH/g. The polyamine can have a
viscosity of
500cP or less at 150 C. In some examples, the reacting step occurs at room
temperature.
The details of one or more embodiments are set forth in the described below.
Other
features, objects, and advantages will be apparent from the description and
the claims.
DETAILED DESCRIPTION
Compositions and/or articles containing an active liquid-intermixed polymeric
matrix and
methods for their preparation and use are described herein. The polymeric
matrix can be a
thermoset (i.e., a cross-linked) polymeric matrix that includes an active
liquid intermixed within
the matrix. In some embodiments, the active liquid is uniformly (i.e.,
homogenously) intermixed
within the matrix. The polymeric matrices described herein are durable and
stable over a wide
range of conditions.
The polymeric matrix is the reaction product of a polyamine and a compound
having at
least two functional groups selected from the group consisting of epoxy
groups, isocyanate
groups, anhydride groups, and acrylate groups. The polyamine can include a
polyamide
polyamine (PAPA) and/or a secondary amine terminated polyamine (SATPA). The
reaction is
carried out in the presence of the active liquid. A small amount of water can
be intermixed as a
part of the active liquid. In some examples, the composition can then be
dispersed in an aqueous
phase in the form of a particle dispersion.
The compound having at least two functional groups selected from the group
consisting
of epoxy groups, isocyanate groups, anhydride groups, and acrylate groups can
be, for example,
crosslinking agents. In some examples, the crosslinking agent is an epoxy
crosslinking agent
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(i.e., a compound having at least two functional groups that include an epoxy
group). The epoxy
crosslinking agent can be any epoxy. In some examples, the epoxy crosslinking
agent is in the
form of a liquid. Examples of liquid epoxy resins that can be used in the
compositions
described herein include diglycidyl ethers of bisphenol A and F, commercially
available as
EPON 828 and EPON 8620 from Resolution Performance Products (Houston, TX);
hydrogenated glycidyl ethers of bisphenol A, commercially available as EPALLOY
5000 and
EPALLOY 5001 from CVC Specialty Chemicals; Moorestown, NJ; and diglycidyl
ethers of
butanediol, cyclohexane dimethanol, neopentyl glycol, dimer acid, and
trimethylolpropane, all
commercially available from Resolution Performance Products in the HELOXY
Modifier
product line. Further examples of the epoxy containing compound described
herein can be
found in "Handbook of Epoxy Resins" by Henry Lee and Kris Neville (McGraw
Hill, 1967),
"The Epoxy Formulators Manual" by the Society of Plastics Industry, Inc.
(1984), and the
Encyclopedia of Science and Technology (Kirk-Othmer, John Wiley & Sons, 1994).
The above-
mentioned epoxy-containing compounds are merely representative and many
additional epoxy-
containing compounds are applicable.
In some examples, the compound having at least two functional groups described
herein
can be a compound including at least two anhydride functional groups (i.e., a
polyanhydride). In
some examples, the polyanhydride is in the form of a liquid. For example, the
anhydride can be
a solid polymer dissolved in a suitable carrier liquid. In some examples, the
polyanhydride is not
a maleated polyolefin rubber. Examples of polymers for the anhydrides include,
for example,
maleated olefin polymers other than a maleated rubber (e.g., a polybutadiene
or a
poly(isobutylene)), olefin-maleic anhydride co-polymers, and alpha-olefin-
maleic anhydride
alternating co-polymers. Specific examples of suitable anhydride-functional
polymers include
styrene-maleic anhydride copolymers such as DYLARK 232 and DYLARK 332,
available from
NOVA Chemicals (Moon Township, PA), and poly(I-octadecene-alt-maleic
anhydride),
commercially available from Chevron Corporation (San Ramon, CA). These
anhydride-
containing polymers are representative and many additional anhydride-
containing polymers are
applicable.
In some examples, the compound having at least two functional groups described
herein
can be a compound including at least two isocyanate functional groups (i.e., a
polyisocyanate).
In some examples, the polyisocyanate is in the form of a liquid. In some
examples, the
compound includes at least one non-aromatic isocyanate compound. Specific
examples of the
isocyanate-containing compounds include aliphatic difimctional isocyanate
materials such as
liquid diisocyanates (e.g., isophorone diisocyanate and bis(4-isocyanato
cyclohexyl) methane).
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The polyfimdional isocyanates can have low volatility and reduced toxicity.
Examples of these
isocyanates include the DESMODUR N-series aliphatic isocyanurates (e.g.,
DESMODUR N-
3300, DESMOD'UR N-3600, and DESMODUR N-3800), and the DESMODUR Z-series (e.g.,
DESMODUR Z4470), all commercially available from Bayer Corporation, Industrial
Chemicals
Division (Pittsburgh, PA). These isocyanate-containing compounds are
representative and
additional isocyanate-containing compounds are applicable. In some
embodiments, the
equivalent weight for the isocyanate-containing compounds is in the range of
180 to 500.
As discussed below, certain functional groups react with certain polyamines
faster than
other functional groups. For example, the isocyanate functional group reacts
with an amine
functional group significantly faster than does the epoxy functional group so
that polyamine
compounds suitable for the cross-linking reaction with isocyanates are not
necessarily
satisfactory for use with epoxies. A polyamine compound for reaction with
epoxy-functional
compounds can be a liquid at room temperature (e.g., 25 C); can dissolve in,
and can be
compatible with, many active liquids; can have a viscosity, measured at 100 C,
of no greater
than about 100 cP; and can have an amine number of from 100 to 1200 meq KOH/g.
For
example, the amine number can be 100, 200, 500, 750, 1000 and 1200 meq KOH/g,
including
any and all ranges and subranges there between. Suitable polyamines include,
for example, 1,2-
diaminocyclohexane, isophorone diamine, meta-xylene diamine, and 1,3-
bis(aminomethyl)cyclohexa.ne (1,3-BAC). In some examples, the polyamines can
be
poly(alkyleneoxy) polyamines (i.e., polyether amines) that are liquid at 25 C
and include
polyether segments such that greater than 50% by weight of the amine is
derived from a
polyether. For example, the polyether can be an oligomerized ethylene oxide,
propylene oxide,
butylenes oxide, tetrahydrofuran, or combinations of these supplied by, for
example, Huntsman
Corporation (The Woodlands, TX) and BASF Corporation (Florham Park, NJ).
Examples of
suitable polyamines include, for example, JEFFAMINE D-230, D-400, D-2000,1-
5000,1-403,
and XT J511 XTJ-511, all polyether diamines commercially available from
Huntsman
Corporation (The Woodlands, TX). Liquid polyamines can also be chosen from the
polyamido-
amine family, examples of which are the UNIREZ series of amidoamide-amine
curing agents
commercially available from Arizona Chemical (Jacksonville, FL). These
materials are known
to impart adhesion and have lowered skin sensitivity. In some examples, the
amines can be
mixtures of two or more amines blended to optimize viscosity, reaction rate
and product
performance.
In some examples, the polyamine compound suitable for reaction with isocyanate-
functional compounds can be a material having a polymeric backbone comprising
repeating
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monomer units terminated by amine groups that are different from the repeating
amine groups.
This polymeric polyamine can be a liquid at a temperature below 50 C, e.g., a
liquid or low melt
point amine. For example, the polyamine can be a liquid at normal room
temperature. In some
examples, the amine has a melting or softening point at or below 50 C, (e.g.,
45 C, 40 C, 30
C, 20 C, and 10 C, including any and all ranges and subranges there between).
In some
examples, the polyamine is a liquid and/or tacky and/or a semisolid at a
temperature below 10
C.
Further, in some examples, the polymeric polyamine dissolves in, and is
compatible with,
many active liquids; has a number-average molecular weight of greater than
1,000; has an amine
number of from 10 to 100 meq KOH/g; and has a viscosity, measured at 150 C, of
no greater
than about 500 cP. The amine number can be, for example, 10, 25, 50, 75, or
100 meq KOH/g,
including any and all ranges and subranges there between. Further, the
viscosity, measured at
150 C, of the polyamine can be 500 cP or less. For example, the viscosity,
measured at 150 *C,
of the polyamine can be about 450 cP, 350 cP, 250 cP, 150 cP, and 100 cP,
including any and all
ranges and subranges there between.
In some examples, the polymeric polyamine for reacting with isocyanate-
functional
compounds can be a polyamide polyamine (or "PAPA"). The polyamide polyamines
can be
polyamide polyether block copolymers resulting from the reaction of one or
more
polyalkyleneoxy polyamines with one or more aliphatic polyacids as further
described below.
Such ether-based polyamide polyamines can be made by reacting a polyacid or
mixture of
polyacids with a stoichiometric excess of polyether polyamine admixed with
optional lower
diamines including piperazine, ethylene diamine, isophorone diamine,
hexamethylene diamine,
2-methyl-1,5-pentane diamine, and the like. Suitable polyacids for the
preparation of PAPAs are
adipic acid, azeleic acid, sebacic acid, dodecandioic acid or other aliphatic
diacid or its ester
equivalent. Use of such diacids and a majority amount of poly(alkyleneoxy)
polyamine,
determined as >50% of all amine equivalents present, ensures that the
resulting polyamide will
have good solubility in a wide range of liquids including in certain cases,
water. In some
examples, the polyamide polyamine is not soluble in water. The amine number of
the PAPA can
be less than 100, as measured by titration with dilute alcoholic hydrochloric
acid and expressed
as mg KOH/g sample. In some examples, the amine number of the PAPA is less
than 80 mg
KOH/g or less than 70 mg KOH/g.
Examples of suitable PAPAs include the reaction products of polymerized fatty
acids,
also known as dimer acids (e.g., material produced by Arizona Chemical Company
under the
trade name "UNIDYME"; Unichema Corporation (Wilmington, DE) under the name
"PRIPOL";
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and Cognis Corporation (Cincinnati, OH) under the trade name "EMPOL") and a
stoichiometric
excess of one or more poly(alkyleneoxy) polyamines chosen from the group of
Huntsman
JEFFAMINE polyamines, including, for example, D-400, D-2000, T-403, and XTJ-
500. In
these examples, the resulting polymeric polyamines can be liquid at room
temperature, have an
acid value of less than about 5 and an amine value of from about 10 to about
70; and have a
viscosity of less than 500 cP measured at 150 C. In some examples, the PAPA
is liquid at room
temperature, has an acid value of less than 2 and an amine value of 20-60, and
has a viscosity of
less than 300 cP at 150 C. For example, a polymeric polyamine can be obtained
by reacting
29.5 weight % of PRIPOL 1009 hydrogenated dimer acid, 44.5 weight % of
JEFFAMINE D-
2000,22.5 weight % of JEFFAMINE D400, and 3.5 weight % of JEFFAMINE 1-403 at
215 C under a sweep of dry nitrogen until the acid number drops to about 1.0
and the amine
value is adjusted to be about 30-40. The resulting material can be, for
example, a viscous liquid
at room temperature with a viscosity of about 100 cP at 130 C and a weight
average molecular
weight of about 25,000 Daltons.
Reaction rates for forming the matrix vary with the type of terminal amine
present in the
polymeric polyamine component. The shortest cure times result from the use of
a compound
whose polymer chain terminates in an aliphatic primary or secondary amine.
Amines hindered
by substitution with a bulky group such as a tertiary butyl moiety react more
slowly. The longest
cure times result from the use of a polymeric polyamine terminated with a
certain type of
aromatic amine whose aromatic ring bears a carbonyl, particularly an ester or
amide group, or
other strong electron-withdrawing group. While it is believed that the
carbonyl-substituted
aromatic amines can be utilized for reaction with any of the functional groups
described herein,
they are particularly useful when the functional group is the highly-reactive
isocyanate group.
While any such terminal carbonyl-substituted aromatic amine can be used, non-
limiting
examples of polyamines are those derived from para-aminobenzoic acid and ortho-
aminobenzoic
acid. These compounds are readily incorporated onto the termini of polyamides
described herein
by reaction with the specified polyamines along with the specified diacids. A
PAPA can include,
for example, a polymer produced by reacting any of the above-described diacids
and ether
diamines in the presence of para-amino benzoic acid and/or ortho-amino benzoic
acid. For
example, a PAPA can be obtained by reacting 24.0 weight% PRIPOL 1009
hydrogenated dimer
acid, 5.0 weight % para-aminobenzoic acid, 54.0 weight % JEFFAMINE D-2000,
11.5 weight %
JEFFAMINE D-400, and 5.5 weight % JEFFAMINE01-403 at 215 C under a sweep of
dry
nitrogen until the acid number drops to about 1.0 and the amine value is
adjusted to 15 by non-
potentiometric titration and 30-35 by potentiometric titration. This material
is a viscous liquid at
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room temperature with a viscosity of about 250 cP at 130 C and a weight
average molecular
weight of about 13,000 Daltons.
In some examples, the weight-average molecular weight (Mw) and/or number-
average
molecular weight (Mn) of the PAPA can be as high as desired but can be limited
by the desired
amine value and viscosity. For example, the Mw can be in the range of 3000-
40,000 Daltons
and can be greater than 3000, 4000, 5000, 6000, 7000, 8000, 9000, or 10,000
and/or less than
40,000, 38,000, 36,000, 34,000, 32,000 or 30,000 Daltons. Accordingly, the
polydispersity can
be any value but is desirably greater than 1.5 and less than 6, or in the
range 2.0-4.0, including
any and all ranges and subranges there between.
Co-diacids and co-diamines can be used to prepare PAPAs described herein in an
amount
of less than 50% on an equivalents basis. Co-diacids can be, for example,
adipic acid and
similar linear aliphatic diacids. Co-diamines can include, for example,
ethylene diamine,
piperazine, 1,2-diaminocyclohexane, isophorone diamine, 1,3-
bis(aminomethyl)cyclohexane,
dimer diamine (e.g., VERSAMINE 551, commercially available from Cognis
Corporation
(Cincinnati, OH)), hexamethylene diamine, 2-methyl-1,5-pentane diamine, and
similar linear,
branched and cyclic aliphatic diamines. The polyamidification reaction can be
carried out in the
presence of catalysts known to increase the reaction rate such as acids,
particularly para-toluene
sulfonic, phosphoric and sulfuric acids, and with removal of water of reaction
via application of
a vacuum.
Suitable PAPAs further include those that are not liquid at room temperature.
In some
examples, the non-liquid PAPAs can be solid at room temperature (e.g., low
melting
polyamines). These PAPAs can result from the reaction of a major diacid
portion of 1,4-
cyclohexane dicarboxylic acid and a stoichiometric excess of polyamine, the
majority of which is
a poly(alkyleneoxy) polyamine chosen from the group of Huntsman JEFFAMINE0
polyamines,
including, for example, D-400, D-2000, T-403, and XTJ-500 such that, after the
reaction is
complete, the PAPA is a solid at 25 C, has an acid value of less than 5, has
an amine value of
from about 10 to about 70, and has a Ring & Ball softening point less than 50
C. For these
polyamides, the dimer acid can be used as a co-diacid along with other co-
diacids such as those
mentioned above. Co-diamines can also be used to prepare the PAPAs described
herein.
Further examples of polymeric polyamines for use in the compositions and
articles
described herein include those described in U.S. Patent Nos. 6,399,713,
6,870,011; and
6,956,099, which are incorporated, in their entireties, herein by reference.
In some examples, the polyamine is a secondary amine terminated polyamine
(SATPA).
The amine number of the SATPA can be 100 meq KOH/g or less. For example, the
SATPA can
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have an amine number from 10 to 100 meq KOH/g. The composition can be, for
example, a
reaction product of a secondary amine terminated polyamine (SATPA) and an
isocyanate cross-
linking agent in the presence of an active liquid to be intermixed. The gel
composition can be
prepared by blending the SATPA, the liquid actives, and the cross-linking
agent.
The form of the composition can depend on the reactants used to form the
polymeric
matrix. For example, the polymeric matrix can include the reaction product of
a secondary
amine terminated polyamine and a compound having at least two functional
groups selected
from the group consisting of epoxy groups, isocyanate groups, anhydride
groups, and acrylate
groups. In some embodiments, the polymeric matrix can include the reaction
product of a
secondary amine terminated polyamine and a compound having at least two
isocyanate
functional groups. In some examples, the compositions can be in the form of a
gel (e.g., a clear,
crosslinked polymeric gel). In other examples, the polymeric matrix can
include the reaction
product of a polyamide polyamine and the compound having the at least two
functional groups
as described above. In these examples, the resulting compositions can be in
the form of a
particle (e.g., a particle in an aqueous dispersion). The particle size of the
particles can be from
1 micron to 100 microns, for example, from 2 microns to 15 microns. For
example, the particle
size of the particles can be 3 microns, 4 microns, 5 microns, 6 microns, 7
microns, 8 microns, 9
microns, 10 microns, 11 microns, 12 microns, 13 microns, or 14 microns.
As described above, the reaction to produce the polymeric matrix is carried
out in the
presence of an active liquid. The resulting polymeric matrix includes the
active liquid
intermixed with at least a portion of the matrix and, in some embodiments,
throughout the
matrix. The active liquid can be any liquid that imparts a function upon the
resultant
composition and/or article a function. For example, the active liquid can be a
volatile or non-
volatile organic liquid. In some examples, the active liquid can be a semi-
solid or a solid
dissolved in a carrier liquid (e.g., a diluent). Examples of suitable active
liquids include
therapeutic active liquids, nutraceutical active liquids, cosmeceutical active
liquids, pesticidal
active liquids, laundry care active liquids, fragrance oils, surface treating
chemicals, radio-
tracers, surfactants, or a mixture of these.
In some examples, the active liquid can be a fragrance oil (i.e., a scent or
perfume). A
fragrance oil can be any blend of the large number of synthetic aroma
chemicals and aromatic
natural oils known to one of skill in the art. Examples of useful classes of
chemicals include
esters such as linalool acetate and butyl acetate (present in banana oil),
phenols such as methyl
salicylate (present in oil of wintergreen), ethers such as 1,8-cineole
(present in eucalyptus oil),
alcohols such as geraniol (present in rose oil), ketones such as menthone
(present in spearmint
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oil), and aldehydes such as cinnamaldehyde (present in cinnamon oil). Further
examples of
suitable aldehydes include citral, benzaldehyde, p-alkyl-substituted
benzaldehydes, anisaldehyde,
vanillin, heliotropin, and alkyl-substituted cinnamic aldehydes.
In some situations, aldehydes may react with primary amines and interfere with
polymer
matrix setting times, especially for polymer matrices based on isocyanate-
polyamine curing
systems. While not wishing to be limited to theory, it is believed that
secondary amines do not
react with aldehydes because they do not have a proton available. Thus, the
aldehydes in
fragrances do not interfere with secondary amine crosslinking agent in
preparation of the
compositions and articles described herein. The interference from aldehydes in
fragrances can
be eliminated, which also leads to more consistent products and efficient
manufacturing.
Additionally, a number of fragrance types can be used to prepare the
intermixed fragrance oils
with high fragrance loading (e.g., greater than 50%, greater than 55%, greater
than 60%, greater
than 65%, greater than 70%, greater than 75%, greater than 80%, or greater
than 85%).
Specific examples of the many hundreds of commercially available fragrance
oils useful
for the compositions described herein are Ocean, Country Wildflower, Spring
Meadow, and
Morning Rain, supplied by Continental Aromatics (Hawthorne, NJ); Macintosh
supplied by
Orlandi, Inc. (Farmingdale, NY); Evergreen, Green Apple, and Yankee Home
supplied by Belle
Aire Fragrances (Mundelein, IL); Cherry, Vanilla, Downey, and Mulberry
supplied by Aromatic
Fragrances and Flavors International (Marietta, GA); Garnet supplied by
International Fragrances
Technology, Inc. (Canton, GA); Crisp Breeze, Tropical Fragrance, and Oceanside
Mist supplied
by Atlas Products (Tinley Park, IL); and Orange Twist, Linen Fresh, and
Country Garden
supplied by Wessel Fragrances (Englewood Cliffs, NJ).
The active liquid can be used at a level so as to impart efficacy to the
composition for the
intended application. The active ingredient can be extremely potent and need
be present only in
a very low level, e.g., less than 0.1%. In such a case, the active liquid is
said to be the solution of
potent agent in carrier. In these examples, the active liquid (or potent agent
dissolved in carrier)
can be used in the compositions and/or articles at levels from I% for lightly-
loaded objects to
90% or more. The loading can depend on the function of the particular active
liquid, polymer
matrix, and any other compounds present. It can also depend upon the final
configuration of the
formed product, that is, whether it is free-standing, contained, or supported.
In some examples,
the active liquid can be present in an amount of from 10 weight % to 85 weight
% or from 50
weight % to 85 weight %. For example, the amount of active liquid can be 1%,
2%, 5%, 10%,
15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% inclusive of all ranges and
subranges there
between.
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In some examples, the fragrance oil level for air fresheners can he from 15-
75% (e.g.,
from 30-70%) by weight of the finished article not counting the weight of any
embedded objects.
The amount of fragrance oil can be 15%, 20%, 25%, 30%, 40%, 50%, 60% or 75% by
weight of
the composition (not counting the weight of any supports or embedded objects)
inclusive of all
ranges and subranges there between. Inactive diluent or plasticizer can be
present in an
additional amount such that the total liquid level can be from 20% to 90% by
weight of the
composition, for example, from 40% to 80% by weight of the composition.
Similarly, the mixture of reactive components, active liquid and optional
liquids, while
still uncured, can be dispersed in water or other aqueous medium and the
resulting oil-in-water
emulsion stabilized by means of a surfactant. Droplets of inventive
composition thus
emulsified cure to form a dispersion of solid immobilized active liquid
particles in water. The
surfactant can be anionic, cationic, or non-ionic in nature. Examples include
the anionic salt
sodium lauryl sulfate, the cationic quaternary ammonium salts di(hydrogenated
tallow) dimethyl
ammonium chloride, cocamido propyl betaine, and dibenzyl dimethyl ammonium
chloride, and
the non-ionic polyethoxylated sorbitan mono-oleate. Such an emulsion is a
milky liquid and
can, as such, be impregnated into a porous medium such as paper, cardboard,
cellulose pad,
cellulose pulp, felt, fabric, a porous synthetic foam, a porous ceramic,
activated carbon, soil,
diatomaceous earth, kieselguhr, charcoal, silica, clay, and the like or coated
onto a non-porous
substrate included but not limited to plastic films, metallic foils, rubber,
ceramics, wood, glass,
and leather.
Surfactant compounds can themselves be active compounds when used in excess of
the
amount needed to stabilize the gel dispersion. The surfactants can be used
with or without
water. Surfactants thus intermixed within the polymeric matrix are released
slowly into their
use environment along with the fragrance and other active components, and can
thus serve as,
for example, a toilet air freshener/cleaner, a pesticide/disinfectant, or a
fabric softener in a
laundry dryer either in the form of a liquid or, if impregnated into a porous
medium, a sheet.
In some examples, the active liquid can be a liquid pesticide or a solid
pesticide dissolved
in a carrier liquid. As used herein, pesticide refers to any substance or
mixture of substances
intended for preventing, destroying, repelling, or mitigating any organism
that causes or is able
to cause harm or annoyance to humans, valuable animals (e.g., livestock), or
valuable plants
(e.g., flowers, trees, and food crops). Pesticides include chemical substances
or biological agents
(such as viruses or bacteria) used to control insects, plant pathogens, weeds,
mollusks, birds,
mammals, fish, nematodes (roundworms) and microbes that compete with humans
for food,
destroy property, spread disease, or are a nuisance. Because many pesticides
are poisonous to
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humans, it is useful to control their application and release by, for example,
dissolving them in a
harmless carrier liquid and then intermixing and immobilizing them within the
polymeric matrix.
The pesticides can be naturally derived or synthetic. Examples of synthetic
pesticides include
organophosphates, carbamates, organochlorines, and pyrethroids.
Organophosphates and carbamates can affect the nervous system by disrupting
the
enzyme that regulates acetylcholine, a neurotransmitter. They usually are not
persistent in the
environment. Immobilization by intermixing, then, can help the
organophosphates to be
effective for a longer period of time without harming the environment.
Organochlorines (e.g.,
DDT and chlordane) were commonly used in the past, but many have been removed
from the
market due to their health and environmental effects and their persistence.
Pyrethroids were
developed as synthetic versions of the naturally occurring pyrethrin to
increase stability in the
environment and lower their cost.
Some pesticides are derived from such natural materials as animals, plants,
bacteria, an
example being the naturally-occurring material, pyrethrin, extracted from
chrysanthemums.
Biopesticides include microbial pesticides that consist of a microorganism
(e.g., a bacterium,
fungus, virus or protozoan) as the active ingredient. Microbial pesticides can
control many
different kinds of pests, although each separate active ingredient is
relatively specific for its
target pest. For example, there are fungi that control certain weeds, and
other fungi that kill
specific insects. The most widely used microbial pesticides are subspecies and
strains of
Bacillus thuringiensis, or Bt.
Pesticides can be classified according to the type of pest that they combat.
Examples of
useful pesticides include algicides that control algae in lakes, canals,
swimming pools, water
tanks, and other sites; antifouling agents that kill or repel organisms that
attach to underwater
surfaces, such as boat bottoms; antimicrobials that kill microorganisms (such
as bacteria and
viruses); attractants that attract pests (for example, to lure an insect or
rodent to a trap) including
foods such as sugar; biopestic ides that are active agents derived from
natural materials such as
animals, plants, bacteria, and certain minerals; biocides that kill
microorganisms, disinfectants
and sanitizers that kill or inactivate disease-producing microorganisms on
inanimate objects,
fungicides that kill fungi (including blights, mildews, molds, and rusts);
herbicides that kill
weeds and other plants that grow where they are not wanted; insecticides that
kill insects and
other arthropods, miticides (also called acaricides) that kill mites that feed
on plants and animals;
microbial pesticides that kill, inhibit, or outcompete pests, including
insects or other
microorganisms; molluscicides that kill snails and slugs; nematicides that
kill nematodes
(microscopic, worm-like organisms that feed on plant roots); ovicides that
kill eggs of insects
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and mites; pheromones that disrupt the mating behavior of insects; repellents
that are chemicals
that repel pests, including insects (such as mosquitoes) and birds from a
surface such as skin or
seeds; rodenticides that sicken, repel, or kill mice and other rodents; insect
growth regulators that
disrupt the molting, maturity from pupal stage to adult, or other life
processes of insects; and
plant growth regulators that are substances (excluding fertilizers or other
plant nutrients) that
alter the expected growth, flowering, or reproduction rate of plants.
Without meaning to be exhaustive, specific examples of pesticides that can be
used as the
active liquid include: 2,4-D, 2,4-DB, DCPA (chlorthal), MCPA, abamectin,
acephate (orthene),
acetochlor, acifluorfen, alachlor, aldicarb, allethrin, ametryn, amitraz,
atrazine, azadirachtin,
azinophos-methyl, Bacillus Thuringiensis, bendiocarb, benomyl, bensulide,
bentazon,
bifenthrin , bromacil, bromoxynil, butylate, cacodylic acid, captafol, captan,
carbaryl,
carbofuran, carbophenothion, carboxin, chloramben, chlordane, chlorobenzilate,
chloropicrin,
chlorothalonil, chlorpyrifos, chlropropham, Clethodim, clomazone, coumaphos,
cyanazine,
cyfluthrin, cypermethrin, dalapon, daminozide, DEET, DDT, deltamethrin,
demeton-S-
methyl, diazinon, dicamba, dichlorvos, diclofop-methyl, dicofol, dicrotophos,
dienchlor,
diflubenzuron, dimethoate, dimetomorph, dinocap, dinoseb, diphacinone, diquat
Dibromide,
disulfoton, diuron, dodine, ethylene dibromide, endosulfan, endothall, EPIC,
esfenvalerate ,
ethephon, ethion , fenamiphos, fenitrothion, fenoxycarb, fenthion, fluazifop-p-
butyl,
flucythrinate, fluometuron, fluvalinate, folpet, fonofos, forrnothion,
haloxyfop, heptachlor,
hexachlorobenzene, hexazinone, hydramethylnon, imazalil, imazaquin,
imazethapyr,
imidacloprid, iprodione, isofenphos, lactofen, lambda- cyhalothrin, lindane,
linuron,
malathion, mancozeb, maneb, mecoprop , metalaxyl , metaldehyde, methamidophos,
methidathion, methomyl, methoprene, methoxychlor, , methyl bromide, methyl
parathion,
metiram, metolachlor, metribuzin, metsulfuron-methyl , mevinphos, molinate,
monocrotophos, naled, napropamide, nicosulfuron, oryzalin, oxamyl,
oxyfluorfen, paraquat,
parathion, pendimethalin, pentachlorophenol, permethrin, phorate, phosalone,
phosmet,
picloram, primisulfuron-methyl, prometyn, pronamide, propanil, propazine,
propetamphos ,
propoxur, pyrethrins and pyrethroids, quintozene, quizalofop-p-ethyl,
resmethrin, rotenone,
ryania, scilliroside, sethoxydim, simazine, streptomycin, sulfometuron-methyl,
tebuthiuron,
temephos, terbacil, terbufos, terbutryn, thiabendazole, thiram, triadimefon,
triallate,
trichlorfon, triclopyr, trifluralin, triforine, validamycin, vemolate,
vinclozolin, warfarin,
zineb, and ziram.
Liquid pheromones or solid pheromones dissolved in a carrier liquid can also
be
intermixed with the polymeric matrixes described herein to produce, for
example, articles that
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can serve as baits or lures in insect traps, fishing lures, rodent traps, and
the like. Pheromones
are typically six-to-twenty carbon atom esters, aldehydes, alcohols and
ketones and for that
reason resemble fragrance compounds and can be immobilized as described
earlier for fragrance
compounds. There are many hundreds of such compounds identified for many
animal and insect
species, many of which are not considered pests. Representative examples that
can be used in
the articles described herein include, for example, E or Z-13-octadecenyl
acetate; E or Z-11-
hexadecenal; E or Z-9-hexadecenal; hexadecanal; E or Z-11 hexadecenyl acetate;
E or Z-9-
hexadecenyl acetate; E or Z-11-tetradecenal; E or Z-9-tetradecenal;
tetradecanal; E or Z-11-
tetradecenyl acetate; E or Z-9-tetradecenyl acetate; E or Z-7-tetradecenyl
acetate; E or Z-5-
tetradecenyl acetate; E or Z-4-tridecenyl acetate; E or Z-9-dodecenyl acetate;
E or Z-8 dodecenyl
acetate; E or Z-5-dodecenyl acetate; dodecenyl acetate; 11-dodecenyl acetate;
dodecyl acetate; E
or Z-7-decenyl acetate; E or Z-5-decenyl acetate; E or Z-3-decenyl acetate;
octadecanal, Z or E,
Z or E 3,13-octadecadienyl acetate; Z or E, Z or E 2,13-octadecdienyl acetate;
Z, Z or E-7,11-
hexadecadienyl acetate; Z, E 9,12-tetradecadienyl acetate; E, E-8,10-
dodecadienyl acetate; Z, E
6,8-heneicosadien-11-one; E, E 7,9-heneicosadien-11-one; Z-6-henicosen-11-one;
7,8-epoxy-2-
methyloctadecane; 2-methyl-7-octadecene, 7,8-epoxyoctadecane, Z,Z,Z-1,3,6, 9-
nonadecatetraene; 5,11-dimethylheptadecane; 2,5-dimethylheptadecane; 6-ethy1-
2,3-dihydro-2-
methy1-4H-pyran-4-one; methyl jasmonate; alpha-pinene; beta-pinene;
terpinolene; limonene; 3-
carene; p-cymene; ethyl crotonate; myrcene; camphene; camphor; 1,8-cineole;
alpha-cubebene;
ally' anisole; undecanal; nonanal; heptanal; E-2-hexenal; E-3-hexenal;
hexanal; verbenene;
verbenone; verbenol; 3-methyl-2-cyclohexenone; 3-methyl-3-cyclohexenone;
frontalin; exo and
endo brevicomin; lineatin; multistriatin; chalcogran; 7-methy1-1,6-
dioxaspiro(4.5-decane,4,8-
dimethy1-4(E),8(E)-decadienolide; 11-methy1-3(Z)-undecenolide; Z-3-dodecen-11-
olide; Z,Z-
3,6-dodecen-11-olide; Z-5-tetradecen-13-olide; Z,Z-5,8-tetradecen-13-olide; Z-
14-methy1-8-
hexadecenal; 4,8-dimethyldecanal; gamma-caprolactone; hexyl acetate; E-2-
hexenyl acetate;
butyl-2-methylbutanoate; propylhexanoate; hexylpropanoate; butylhexanoate;
hexylbutanoate;
butyl butyrate; E-crotylbutyrate; Z-9-tricosene; methyl eugenol; alpha-ionone;
4-(p-
hydroxypheny1)-2-butanone acetate; E-beta-famasene; nepetalactone; 3-methyl-6-
isopropeny1-9-
decenyl acetate; Z-3-methyl-6-isopropeny1-3,9-decadienyl acetate; E or Z-3,7-
dimethy1-2,7-
octadecadienyl propionate; 2,6-dimethy1-1,5-heptadien-3-ol acetate; Z-2,2-
dimethy1-3-
isopropenyl cyclobutanemethanol acetate; E-6-isopropyl-3,9-dimethy1-5,8-
decadienyl acetate; Z-
5-(1-decenyl)dihydro-2(3H)-fiiranone; 2-phenethylpropionate; 3-methylene-7-
methyl-7-octenyl
propionate; 3,11-dimethy1-2-nonacosanone; 8-methylene-5-(1-methylethyl)
spiro(11-oxabicyclo)
8.1.0-undecene-2,2-oxiran-3-one; 2-propylthietane; 3-propy1-1,2-dithiolane;
3,3-dimethy1-1,2-
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dithiolane; 2,2-dimethylthietane; E or Z-2,4, 5-trimethylthiazoline; 2-sec-
butyl-2-thiazoline; and
isopentenyl methyl sulfide. Specific pheromones include the following: 8-
methy1-2-decyl-
propionate; 14-methyl-1-octadecene; 9-tricosense; tridecenyl acetate; dodecyl
acetate; dodecenyl
acetate; tetradecenyl acetate; tetradecadienyl acetate; hexadecenyl acetate;
hexadecadienyl
acetate; hexadecatrienyl acetate; octadecenyl acetate; dodecadienyl acetate;
octadecadienyl
acetate; and Z,E-9,12-tetradecadiene-l-ol.
The active liquid can be a liquid form of the active ingredient, or can be a
solid, liquid or
gaseous form of the active ingredient that is dissolved (contained) and
diluted by a carrier liquid
(diluent). In some examples, the active liquid can include or consist of water
and an active
agent dissolved in the water. Alternatively, the active liquid can include or
consist of an
organic liquid and an active agent dissolved in the liquid.
Examples of active ingredients contained in the active liquid can be
therapeutically
active ingredients (for humans or animals) such as medicines, drugs,
pharmaceuticals,
bioceuticals which are optionally combined with a biologically-acceptable
carrier. Further,
examples of the active ingredient contained in the active liquid can be
biological compound
such as amino acids, vitamins, carbohydrates, and/or steroids. Examples of
biological
compounds include biopolymers, biocopolymers, or chimera comprising DNA, RNA,
oligonucleotides, modified DNA, modified RNA, proteins, polypeptides, and
modified
polypeptides.
Additional components for use in the polymeric matrixes include, for example,
plasticizers, diluents, accelerators, retardants, tackifiers, fillers, and
colorants. Phthalates,
benzoates, salicylates, and lactate esters, alcohols, polyols, poly(alkylene
glycol)s and alkyl and
aryl ethers of alcohols, polyols and poly(allcylene glycols) are examples of
useful
plasticizers/diluents. These increase product flexibility, improve active
release, and lower
product cost. Reactive diluents and inert diluents can also be used to lower
the initial blend
viscosity. Possible diluents include, but are not limited to, various mono-
and diglycidyl ethers,
glycols, and N-methyl pyrolidinone. Phenols, such as nonyl phenol and 2,4,6-
tris(dimethylaminomethyl) phenol, are examples of known accelerators of the
epoxy-amine
curing reaction that can shorten the time needed to cure the air fresheners
described herein.
Reaction accelerators include, for example, any alcohol-containing compound
and/or water
and/or mixtures thereof. Further, resins such as rosin esters and polyterpenes
can be dissolved in
the epoxy or the diluent/plasticizer to add tack to the final product.
Examples of suitable resins
include SYLVATAC, SYLVARES, and SYLVALITE, commercially available from Arizona
Chemical (Jacksonville, FL).
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The compositions and/or articles described herein can be made by reacting (for
example,
by contacting, mixing, or blending) a compound having at least two functional
groups selected
from epoxy, isocyanate, anhydride, and acrylate with a polyamine in the
presence of an active
liquid. The resultant mixture, prior to and after curing, can be homogeneous.
Such contacting,
mixing, and blending of the reactive components and active liquid (i.e., the
reacting step) can
occur at a temperature from 10-50 C. In some examples, the reacting step
occurs at room
temperature. In other examples, the reacting step can occur, for example, at
10 C, 15 C, 20 C,
25 C, 30 C, 35 C, 40 C, 45 C, or 50 C, inclusive of all ranges and
subranges there between.
The components and optional ingredients can be added in any order. In some
examples, the
active liquid is added before the matrix-forming reaction proceeds to a point
where its high
viscosity and increasing elasticity precludes a blending operation. When the
amine is a solid, it
can first be dissolved in diluent liquid, in the active liquid, or in a
mixture of both.
Temperature and blending conditions can be controlled so as to preclude
premature
curing, that is extensive curing during the contacting, mixing, or blending
step. The mixture can
become a homogeneous thermoset solid thereafter. Curing temperatures can
differ from
blending operation temperatures and can be in the range of from 10-100 C, for
example, 10 C,
C, 30 C, 40 C, 50 C, 60 C, 70 C, 80 C, 90 C, and 100 C, inclusive of all
ranges and
subranges there between.
Curing rate is a function of at least six factors: curing temperature,
functional group and
20 amine group concentrations, ratio of these, structure of the amine,
accelerator/retardant
concentration, and composition of the fragrance oil/diluent. Accordingly, cure
times can vary
widely.
Mixing and/or curing can occur within a mold. For example, a low temperature
procedure can include blending at room temperature, pouring the blend into a
mold, sealing it,
and allowing the blend to stand at room temperature. Such a procedure can take
from a few
minutes to a few days depending on the functional groups chosen and the
reaction conditions.
For example, the isocyanate-amine matrix reacts significantly faster than the
epoxy-amine
matrix. Another example is a pre-curing procedure useful more for the epoxy-
amine matrix,
which can include blending at room temperature, sealing tightly, heating to 70
C for 30-90
minutes to obtain a partial cure but not gelling the composition, then pouring
the resultant partial
cure into a mold, letting it cool and stand at room temperature. Such a
procedure can take from
an hour to two days. Finally, another example is a high temperature procedure
which can
include blending at room temperature, pouring into a pouch or mold, sealing it
tightly, and
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heating it to a temperature ranging from 6010 100 C. Such a procedure can
take from a few
minutes to a few hours.
The steps of the methods described herein can be performed in any order and
additional
steps can be added. In addition, the curing time can range from 0.01 hour to
60 hours (e.g., from
5 minutes to 20 hours or from 10 minutes to 100 minutes). In some examples,
the curing time
can be 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours,
80 hours, 90 hours,
or 100 hours, inclusive of all ranges and subranges there between.
In some examples, the method includes blending an active liquid, a liquid
polyepoxy, and
a liquid polyamine to form a mixture. Blending the components can occur at 10-
40 C.
However, the blending can be performed so as not to cause a loss of any
temperature-sensitive
active component. The temperature of blending can be 10 *C, 15 C, 20 C, 25
C, 30 C, 35
C, or 40 C, inclusive of all ranges and subranges there between. When an
epoxy-containing
compound is used, the temperature of curing can be room temperature, i.e. 25
C, but can be
higher, depending on the temperature sensitivity of the active liquid
component and its volatility.
If the active liquid does not degrade readily and the curing is performed in a
sealed mold, the
curing temperature, for example, can be about 60 C. At this temperature,
curing for a typical
formulation takes place in about 3-6 hours, or less if an accelerator is used.
In some examples, the methods described herein include blending an active
liquid, a
liquid diluent, a liquid polyisocyanate, and a liquid polyamine to form a
mixture that cures to a
liquid-immobilized polyurea composition. Blending the components can occur,
for example, at
10-40 C. However, the blending can be performed so as not to cause a loss of
any temperature-
sensitive active component. The temperature of blending can be 10 C, 15 C,
20 C, 25 C, 30
C, 35 C, or 40 C, inclusive of all ranges and subranges there between.
In some embodiments, a catalyst is not present in the reaction between a
polyamine and
an isocyanate. However, even in the absence of a catalyst, the reaction
between the polyamine
and the isocyanate can be rapid at room temperature. In these examples, a rate
modifier (i.e., a
retardant) can be used to slow the reaction, allowing ample time for the
ingredients to be blended
and poured into a mold. Useful rate modifiers include, for example, aldehydes
such as those
normally present in common essential oils and fragrance oils. Other rate
modifiers include those
that are either bland in odor or those that can enhance the odor of the active
liquid. Examples of
useful retardants include aromatic aldehydes such as benzaldehyde, vanillin,
and salicylaldehyde;
a43 unsaturated aromatic aldehydes such as cinnamic aldehyde and methyl
cinnamic aldehyde;
terpenic aldehydes such as citral, cyclocitral, and citronellal; and C4-C18
aliphatic and
cycloaliphatic aldehydes such as isobutyraldehyde, lyral, 2-phenyl
propionaldehyde, and the like.
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While a retardant described above can be used when an isocyanate-containing
compound is used,
such a retardant can be optionally utilized in any of the methods described
herein.
An aldehyde rate modifier retards the rate of the reaction by reacting with
the polyamine
to form a "blocked" amine in the form of an imine. In some embodiments, this
reaction can be
performed at room temperature. The rate of this reaction depends on several
factors, such as the
concentration of the aldehyde; whether the aldehyde is aliphatic or aromatic,
or linear or
branched; the functionality of the side chain(s); the acidity/alkalinity of
the side chain(s); the
electron donating or accepting capacity of the side chain(s); steric factors;
and other factors. In
these reactions, the aldehyde and polyamine reactants are in equilibrium with
the imine and
water is the by-product. When less than a stoichiometric amount of aldehyde is
present, the
reaction that generates the imine can proceed until all of the available
aldehyde has interacted
with the amine. In these reactions, unreacted amine can be present due to the
reversible reaction
and the value of the equilibrium constant. Upon addition of the isocyanate,
the amine can react
with the isocyanate, thus driving the equilibrium towards generating more
amine. As the matrix-
forming reaction proceeds, there can be less amine in the system relative to
aldehyde, which
favors blockage. Thus, an effective level of amine can be less than a
stoichiometric amount.
The presence of water forces the reversal of the process, so water can be used
as an accelerator,
negating the effect of aldehyde. Shown below is a table displaying the
influence of the type and
use level of aldehydes on the set time for isocyanate-polyamine reactions.
- 19 -
Total
Aldehyde. Poly
Weight Time Aldehyde/Amine 0
Wt% Aldehyde Eq. Amine(g) Aldehyde. MIBK Solvent Polyisocyanate
(g) To Set (Eq. Ratio) N
ALDEHYDE On Total , Wt. , (g) (E)
(g) (min.) .
.
, tõ...'
Blank (no aldehyde) 0 156.22 4.7 0 4.7 0.49
9.9 Instant 0 Zi
. .
para-chlorobenzaldehyde 1.4 140.57 , 4.7 0.14 , 4.7
0.49 , 10 17 , 0.37 .-
ra
2,4-dichlorobenzaldehyde 1.74 175.01 4.7 , 0.175 , 4.7 0.49
10.1 23 0.37 c,
.-
,
.
Citral + p-anisaldehyde 3.83 , 152.24 4.7 ,
0.394 4.7 0.49 10.3 >400 0.30+0.65
p-anisaldehyde 2.68 136.15 4.7 , 0.272 4.7 0.49
10.2 50 0.75 .
p-anisaldehyde 3.02 136.15 , 4.7 0.308 4.7
0.49 10.2 400 0.85
,
.
p-anisaldehyde 5.24 136.15 4.7 0.547 , 4.7 0.49
10.4 ca. 800 1.5
. .
2,4-dichlorobenzaldehyde 1.74 , 175.01 , 4.7 0.175 4.7 0.49
10.1 23 0.37
,
2,4-dichlorobenzaldehyde 1.84 175.01 4.7 0.185 4.7 0.49
10.1 120 , 0.4
-4
2,4-dichlorobenzaldehyde 3.42 , 175.01 , 4.7 , 035 4.7 0.49 10.2
1110 0.75
0
Alpha-
o
hexylcinnamaldehyde , 5.54 216.33 , 4.7 0.58 , 4.7
0.49 , 10.5 , Instant 1
,
co"
Alpha-
...1
hexylcinnamaldehyde , 6.83 216.33 4.7 0.725 , 4.7 0.49
10.6 1 1.25
u,
'
Iv
Alpha-
hexylcinnamaldehyde 8.09 216.33 , 4.7 0.87 4.7
0.49 10.8 10 1.5 Iv
o
. - 1-.
Alpha-
w
i
hexylcinnamaldehyde 9.27 216.33 4.7 , 1.01 , 4.7 0.49 ,
10.9 19 1.75 o
Ln
Alpha-
i
o
hexylcinnamaldehyde , 10.46 , 216.33 , 4.7 1.155 4.7 0.49
11 28 2 cil
Cara! 1 152.24 4.7 0.1 4.7 0.49
, 10 Instant 0.25
. '
Citral 1.22 152.24 , 4.7 0.122 4.7
0.49 10 100 0.3
Citral 1.49 152.24 4.7 0.15 , 4.7
0.49 , 10 210 0.37
Citral 1.98 152.24 4.7 , 0.2 , 4.7
0.49 10.1 588 0.49
_
Citral 2.98152.24 4.7 0.304 4.7
0.49 , 10.2 1230 0.75
,
'
Benzaldehyde 1.06 106.12 4.7 , 0.106 , 4.7
0.49 1027 0.37 mo
,
A
Benzaldehyde 1.15 106.12 , 4.7 0.115 4.7
0.49 10 70 0.41 1-1
.
,
Benzaldehyde 1.3 , 106.12 4.7 0.13 , 4.7 0.49
10 360 0.46
cn
Benzaldehyde 1.62 , 106.12 4.7
0.163 , 4.7 0.49 10.1 695 0.57 r.>
c
Benzaldehyde 2.1 106.12 4.7 , 0.212 4.7
0.49 10.1 _ >700.0 0.75
a
0.,
-,
t..,
.i.
,,c.
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The reaction between a polyamine and an isocyanate can be rapid at room
temperature
even in the absence of a catalyst. In some examples, a catalyst is not
present. In these
examples, a rate modifier (i.e., retardant) can be used to slow the reaction,
allowing ample
time for the ingredients to be blended and poured into a mold. Useful rate
modifiers include,
for example, aldehydes such as those normally present in common essential oils
and fragrance
oils. Others include those that are either bland in odor or enhance the odor
of the active
liquid. Examples of useful retardants are aromatic aldehydes such as
benzaldehyde, vanillin,
and salicylaldehyde; 043 unsaturated aromatic aldehydes such as cinnamic
aldehyde and
methyl cinnamic aldehyde; terpenic aldehydes such as citral, cyclocitral, and
citronella!; and
C4-C18 aliphatic and cycloaliphatic aldehydes such as isobutyraldehyde, lyral,
2-phenyl
propionaldehyde and the like. While a retardant described above can be used
when an
isocyanate-containing compound is used, such a retardant can be optionally
utilized in any of
the methods described herein.
Another method for increasing cure times includes employing PAPA terminated
with
a carbonyl-substituted aromatic amine prepared according to the methods
described herein.
Shown below are the set times (i.e., the time from mixing to lack of flow) for
four
commercial fragrances immobilized at 50% concentration with matrix derived
from the
reaction of PAPA and DESMODUR N3300, the PAPA being terminated either by a non-
aromatic primary amine or by a carbonyl-substituted aromatic amine, i.e., the
PAPA
terminated by reaction with para-aminobenzoic acid.
TTME TO SET (minutes)
PAPA with Non-Aromatic PAPA with para-Amino-
Fragrance Oil
Primary Amine Benzoic Acid Termination
Outdoor Breeze ca. 0.2 400
Tropical Splash 34 420
Clean Citrus 39 ca. 20 hours
Cotton Fresh 54 ca. 30 hours
When an isocyanate-containing compound is utilized, the curing temperature can
be
room temperature, i.e. 25 C, but can be higher or lower, depending on the
cure time desired.
For example, if the active liquid does not degrade readily and a very rapid
cure is desired, the
curing can be carried out in a sealed mold, and at a curing temperature of
about 50 C. At
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room temperature, curing for a typical formulation based on PAPA terminated by
a primary
aliphatic amine and carried out in the presence of little or no retardant,
typical setting times
are from less than 1 second to about 30 minutes. The time can be 0.1 minute,
0.5 minute, 1
minute, 5 minutes, 10 minutes, 20 minutes, or 30 minutes, including any and
all ranges and
subranges there between. Curing at room temperature for a typical formulation
based on the
carbonyl-substituted aromatic amine terminated polyamine can take place in
from about 10
minutes to over 2 days when carried out in the presence of retardant but can
be in the range
20-600 minutes in the absence of retardant. The time can be 20 minutes, 50
minutes, 100
minutes, 200 minutes, 300 minutes, or 600 minutes, including any and all
ranges and
subranges there between.
Further described herein are articles including the compositions described
herein. In
some examples, the articles further include a support material that can
optionally be a porous
support material. The articles described herein can include the gelled
compositions.
Examples of such articles include, but are not limited to, medicinal devices
having an active
liquid that is medicinally active, pesticide devices having an active liquid
that is a pesticide,
laundry care devices having an active liquid for laundry care (i.e., softener,
fragrance,
conditioner, cleaner, anti-stain, surface treating, and the like), or air
freshener having an
active liquid that is a fragrance. In some examples, the articles described
herein can include
the compositions in the form of aqueous dispersions. Examples of these
articles include sun
care products, skin care products, air fresheners, laundry fragrance sheets,
laundry fabric
softener sheets, laundry anti-static sheets, storage fragrance articles,
pharmaceutical
distribution articles, nutraceutical distribution articles, bioceutical
distribution articles,
moldicide distribution articles, bactericide distribution articles, pesticide
distributions,
decorative articles, biomedical sensors, and/or analytical devices.
The articles described herein can be processed into any desired shape that is
appealing
to a potential consumer. Such shapes can be 3-D shapes formed in a mold or a
flat shape
stamp-cut from pre-formed thin sheets. Shapes can include those geometrical in
nature, e.g.,
triangular, square, circular, spherical, oval, regular geometric figure,
irregular geometric
figure, etc. For example, air care articles can have an immense variety of
geometric and
artistic shapes such as, but not limited to, disks, rings, cylinders, squares,
rectangles,
pentagons, hexagons, stars, hearts, hemispheres, spheres, cubes, flowers,
animals, letters,
numbers, logos, trademarks, and faces. Such shapes are limited only by methods
known to
make appropriate-shaped molds.
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These articles can be colored with soluble dyes or with pigments. These
colorants can
be dissolved or dispersed prior to final mixing of the reactive components.
These colorants
can be conventional, fluorescent, pearlescent, temperature-sensitive, light-
sensitive, pH-
sensitive, or moisture sensitive. The latter four colorants allow for the
preparation of novelty
products that change color as environmental conditions change or that signal
the depletion of
the active component in the article.
Because the composition prior to curing is fluid, it can be poured easily into
such
molds and thus take on exacting shapes such as dimples, curves, logos,
etchings, and any
other embossed or engraved image. This is especially advantageous if the
article is designed
to fit directly into a holder, to adhere to a surface of complex shape, for
example, a body part,
a curved surface such as a heated potpourri dish, light bulb, or the inside of
a package.
Prior to curing insoluble matter can be suspended in the reactive mixture so
that when
cross-linked, the system traps the suspended matter. Suspended matter can be
decorative
items such as icons, beads, glitter, gems, shards and the like; botanicals
such as leaves, seeds,
stems, needles, nuts, and the like; insoluble powdered materials such as wax,
sugar, coffee
grounds, bait particles, insoluble plain, colored or flavored salts, water,
glycerin, silicone
fluids, and aqueous solutions of dyes, active materials, acids, bases and the
like with or
without the aid of a surfactant to stabilize the dispersion thus formed; or
with air or other gas
by a whipping action or other deliberate mixing with the gas to form bubbles
in the matrix-
forming fluid. Alternatively, gas can be generated inside the matrix-forming
composition by
chemical means, such as, for example, thermal decomposition of a nitrogen-,
oxygen-, or
carbon dioxide-generating substance. Examples of such compounds are carboxylic
acids,
azobis(isobutyronitrile), hydrogen peroxide, and sodium carbonate or
bicarbonate. A
carboxylic acid that can be used in this way is polymerized fatty acid.
In some examples, the article described herein can include the fragrance oil
or other
active liquid and components selected from those listed above as immobilized
by the cross-
linked matrix. In other examples, the article can consist of the immobilized
liquid and a
support, be it a container, bracket, or holder into which the mixture of the
reactive
components, actives and other liquids and optional components are poured
before curing
takes place or fitted after curing takes place.
If not poured into a container, the article after curing can be coated,
printed, or
otherwise decorated, wrapped or supported by a stand, plate, bowl, dish,
bracket, holder, or
other supporting device. If poured into a container, the container can be made
of glass,
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ceramic, metal, paper, plastic, or any other oil-impermeable material and be
in any convenient
shape such as a cylinder, tube, bowl, dish, etc. The container can itself be
shaped to fit into a
holder, chamber, or receptacle designed to fit into a fragrance dispensing
device that can be
fitted with a heater, fan, blower, or other mechanical aid. If the article is
intended to be
heated, the heater can be external to the cross-linked matrix-immobilized
active liquid or it
can be internal, that is, surrounded by or embedded in the cross-linked
article. An example of
such a device is a reactive composition poured into a container threaded with
resistive heating
wires that, after the matrix cures, can be electrified, thus heating the cross-
linked composition
from within.
Similarly, the composition while still fluid can be impregnated into a porous
material
such as paper, cardboard, cellulose pad, cellulose pulp, felt, fabric, a
porous synthetic foam, a
porous ceramic, activated carbon, soil, diatomaceous earth, kieselguhr, sand,
charcoal, silica,
clay, and the like or coated onto a non-porous substrate included but not
limited to plastic
films, metallic foils, rubber, ceramics, wood, glass, and leather.
Similarly, the mixture of reactive components, active liquid and optional
liquids,
while still uncured, can be dispersed in water or other aqueous medium and the
resulting
emulsion optionally stabilized by means of a surfactant. Droplets of the
composition
described herein, thus emulsified, can then cure, resulting in a dispersion of
solid gel
particles. This can be considered a process for preparing encapsulated active
oils in dispersed
form. Such a material is a milky liquid and can, as such, be impregnated into
a porous
medium such as paper, cardboard, cellulose pad, cellulose pulp, felt, fabric,
a porous synthetic
foam, a porous ceramic, activated carbon, soil, diatomaceous earth,
kieselguhr, sand,
charcoal, silica, clay, and the like or coated onto a non-porous substrate
included but not
limited to plastic films, metallic foils, rubber, ceramics, wood, glass, and
leather.
In some examples, a container can be nearly filled with a volatile active
liquid and can
then be filled up with and sealed by the composition described herein, thus
trapping the
volatile material behind a barrier or membrane of cross-linked matrix. Such an
arrangement
allows the reservoir of volatile liquid to be released very slowly and
continuously as it
diffuses through the barrier of liquid-impregnated matrix.
In some examples, the article components can be insoluble in water without
losing
any of the desired final properties (e.g., fragrance release, stability) so
that the water can
optionally serve some useful purpose if incorporated in the cross-linked
composition such as
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causing shrinkage to indicate end-of-use-life or introduction of a water-
soluble active
ingredient such as a dye or a salt.
In some examples, the articles can be prepared by (1) blending the polyamine,
the
active liquid and any desired optional components including diluents,
plasticizers, fillers,
stabilizers, and colorants; (2) blending this mixture with the polyepoxy or
polyisocyanate
component optionally diluted with further amounts of plasticizers, fillers,
stabilizers, and
colorants; (3) pouring out the final blend as a sheet or slab or into a
support, form, container,
or mold; (4) optionally covering or sealing the poured blend to protect it
from contaminants
and prevent volatile components from evaporating; (5) optionally storing it
until the blend
cures; and (6) optionally removing the cured immobilized liquid article from
the sheet, slab,
form, container, or mold and cutting it to another shape or using it as made
in the container.
When the article is an air freshener, it can be "active" and/or "passive".
Active air
fresheners encompass relatively complex devices having moving parts such as
heaters and
fans to dispense concentrated or diluted aroma compounds or spray cans charged
with aroma
chemical, carrier liquid, and propellant. Active air fresheners require the
occupant to
dispense the material into the area to be treated. Passive air fresheners are
available in many
forms, but are in essence "fixed" liquid chemicals: a multi-component article
including
fragrance oil immobilized in and/or a solid support. The support material can
be simple, e.g.,
a piece of cardboard, blotter paper, cotton, or other fibrous materials. The
support material
can be complex, e.g., an aqueous dispersion (gelatin) or a non-aqueous gel
(gelled, e.g., by
polyamide resin). The air fresheners can be transparent, but, in some
embodiments, can be
opaque.
In some examples, the article is a visually attractive solid air freshener, in
particular a
room, closet, drawer, bag, area, container, or car interior freshener, that is
both transparent or
nearly transparent (e.g. "frosted") and robust. In these examples, the active
liquid is an
aromatic composition (i.e. fragrance oil, scent, or perfume). As used herein,
the term
"robust" means that the article can be packaged inexpensively and handled
without being
deformed. The composition containing the aromatic material can be supported
(i.e., in a
container or holder) or free-standing. In particular, no special care is
needed when the air
freshener is taken out of its package or wrapper. Furthermore, the air
freshener can resist
changes in temperature, humidity, and exposure to light over the lifetime of
its use or, with
reasonable protection in a suitable package, over the lifetime of its storage
and handling. The
air care composition can also be free of syneresis (also known as "sweating").
The matrix
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material of the product is to be effectively non-toxic and not cause skin
irritation if handled
out of its storage wrapper. The air care composition lends itself readily to,
but does not
require the use of, porous powders, fabrics or fibers as a support for the
fragrance oil.
The examples below are intended to further illustrate certain aspects of the
methods
and compounds described herein, and are not intended to limit the scope of the
claims.
EXAMPLES
Example 1
Air freshener components (names and amounts listed below) including a small
amount of green dye, which were weighed into a glass vial and stirred together
at ambient
temperature by hand with a wooden stir stick. A portion of the mixture (8.0g)
was then
poured into a flat, rectangular, 2.50 inch x 3.25 inch uncoated polystyrene
mold:
= Epoxy Resin: EPALLOY(1D 5001, 10.00g; 55.1%
= Hardener: 1,3-BAC, 3.55g; 19.6%
= Fragrance Oil: Belle Aire "Evergreen", 4.55g; 25.1 %
= Dye: Green, 0.05g; 0.3%.
The next day the sample was firm, clear, tack-free, and flexible. It could be
removed from
the mold by hand with only a slight amount of sticking to the mold. Placed in
a polyethylene
"baggie" for storage at room temperature, it exhibited no syneresis, even
after a number of
weeks.
Example 2
These air freshener components totaling 100 parts by weight were treated
following
the procedure of Example 1: EPALLOY 5001 (53.6 parts), 1,3-BAC (19.0 parts),
Belle Aire
"Evergreen" fragrance oil (25.1 parts), nonyl phenol (2.2 parts). The
resulting article after
curing at room temperature for one day was transparent, firm, flexible and
tack-free.
Example 3
These air freshener components totaling 100 parts by weight were treated
following
the procedure of Example 1: Cyclohexane dimethanol diglycidyl ether (22.8
parts), EPON(11)
828 (22.8 parts), Huntsman 1-403 polyamine (24.2 parts), Continental Aromatics
"Country
Meadow" fragrance oil (30.0 parts), plastic glitter 0.1 parts) and a trace of
green dye. The
resulting article after curing at room temperature for three days was
transparent, firm,
flexible, tack-free and exhibited ability to cling lightly to a flat vertical
glass surface from
which it could be easily removed and re-applied without marring the surface.
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Example 4
A polyamide polyamine was prepared by charging adipic acid (20.0g, 274 meq
acid),
JEFFAM1NE T-403 polyamine (20g, 132 meq amine) and Huntsman XTJ-500 (80g, 254
meq. amine) to a 250 mL glass flask equipped with a stirrer and heating this
charge to 210-
220 C under a stream of dry nitrogen. After holding this mixture under these
conditions for 5
hours, the reaction mixture was discharged to a container. The product was a
clear, viscous,
nearly water-white liquid having an acid number of 1.4, an amine ntunber of
42.2, and a
Brookfield viscosity at 150 C of 340 cP. A portion of this product (11.63g)
was dissolved in
water (27.5g) and then blended with a polyethyleneglycol diglycidyl ether (EEW
of 195;
3.40g). To a portion of this mixture (20.0g) in a small plastic jar with a
screw cap was then
added fragrance oil ("Sunshine Fruits", Firmenich fragrance oil #190196) and a
few drops of
Tween 80 surfactant, forming a milky emulsion which, after being capped and
allowed to
stand, gelled to an immobile firm homogeneous white solid that emitted the
fragrance
gradually after being un-capped.
Example 5
To a commercial resealable polyethylene "baggie" was added components totaling
100 parts by weight: cyclohexane dimethanol diglycidyl ether (13.9 parts),
EPONS 826 (13.9
parts), Arizona proprietary liquid triethylenetetraamine-based amido-amine
#X54-327-004
(amine number of 349, acid number of 0.8, 22.2 parts), Atlas "Crisp Breeze"
fragrance oil
(50.0 parts), and a trace of blue dye. The "Ingle" was massaged to blend the
components for
a few minutes, the air bubbles pressed out and the fluid mixture then stored
lying flat at room
temperature for one week. At that time the material was cross-linked to the
point of being
immobile, transparent, and flexible.
Example 6
To a glass beaker containing a magnetic stir bar was charged Huntsman
SurfonicOL24-5, a liquid ethoxylated alcohol surfactant (12.0g), Atlas
Products "Crisp
Breeze" fragrance oil (8.0g), Huntsman T-403 polyamine (8.4g), FD&C #3 blue-
green dye
(0.4g) and HELOXY 48 epoxy resin (14.0g). This mixture was heated to 58 C for
about 3
hours with stirring to nearly cure it and then poured into a cylindrical mold
and allowed to
cool. After the material stood about three days at room temperature it was
removed from the
mold as a slightly rubbery, firm solid.
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Example 7
These air freshener components totaling 100 parts by weight were blended at
room
temperature: cyclohexane dimethanol diglycidyl ether (25.3 parts), EPON 828
(17.2 parts),
Arizona proprietary polyamido-amine hardener #X54-327-004 (34.5 parts),
Continental
Aromatics "Ocean" fragrance oil (23.0 parts), and a trace of green dye. This
blend was held
for about 45 minutes at about 67 C, at which time it was allowed to cool to
room temperature.
It was, at this stage, quite viscous, but could still be poured and stirred.
To this partially
cross-linked intermediate was added with gentle distribution through the mass
approximately
two dozen Vs" colored foil hearts. The resulting article after curing at room
temperature for
three days was firm, flexible, and tack-free with the foil hearts clearly
visible suspended
uniformly inside it.
Example 8
These components totaling 100 parts by weight were treated following the
procedure
of Example 1: poly(propylene glycol) diglycidyl ether (13.0 parts), EPON 828
(22.0 parts),
Arizona 'UNI-REZ 2801 amido-amine (14.0 parts), "Vanilla" fragrance oil from
Aromatic
Flavors and Fragrances, dipropyleneglycol benzoate (19.5 parts) and commercial
ground
coffee (29.5 parts). The resulting article after curing was firm, slightly
flexible, non-tacky.
The coffee grounds were uniformly distributed and gave the article a rich
brown, opaque
appearance, smooth at the bottom where the mold was smooth and rough on top
where the
grounds were allowed to settle freely.
In the following examples, abbreviations are as follows:
= CHDA is 1,4 cyclohexane dicarboxylic acid from Eastman Chemical;
= Empol is EMPOL 1008 dimer acid supplied by Cognis Corporation;
= Unidyme is UNIDYME 18 dimer acid supplied by Arizona Chemical Company;
= T-403 is JAFFAMINEll T-403 poly(alkyleneoxy) diamine supplied by Huntsman
Corporation;
= D-400 is JEFFAMINEOD-400 poly(alkyleneoxy) diamine also from Huntsman;
= D-2000 is JEFFAMINEOT-2000 poly(alkyleneoxy) diamine also from Huntsman;
= V-551 is VERSAMINE 551 dimer diamine supplied by Cognis Corporation;
= N-3300 is DESMODUR N-3300 or N-3300A, Bayer Corporation, Industrial
Chemicals Division;
= N-3800 is DESMODUR N-3800, also from Bayer;
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II Z-4470 is DESMODUR1) Z4470, also from Bayer.
Example 9
A polyamide polyamine was prepared by charging EMPOL01008 polymerized fatty
acid (63.0g, 219 meq acid), JEFFAMINEOT-403 polyamine (18g, 118 meq amine) and
JEFFAMINEOD-400 (45g, 205 meq. amine) to a 250 rnL glass flask equipped with a
stirrer
and heating this charge to 210-220 C under a stream of dry nitrogen. After
holding this
mixture under these conditions for 5 hours, the reaction mixture was
discharged to a
container. The product was a clear, viscous, nearly water-white liquid having
an acid number
of 0.3, an amine number of 41.8, a weight average molecular weight of 2,270,
and a
Brookfield viscosity at 150 C of 204 cP.
A solution was prepared by warming 10.0g of this polyarnide polyamine with
5.0g
FINSOLV TN benzoate ester and 10.0g fragrance oil ("Linen Fresh", Wessel
Fragrances),
cooled to room temperature and blended thoroughly with a mixture of DESMODUR
Z4470
and 5.1g additional fragrance oil. To the composition was then added a small
amount of red
dye and red glitter. A few minutes later about 25g of this final formulation
was poured into a
flat, circular rose-shaped silicone rubber mold and the remainder retained in
ajar. A total of
33 minutes after the component were blended, the retained material was set to
an immobile
gel. After standing at room temperature for 16 hours, the immobilized
fragrance oil article
was removed from the mold. It did not adhere to the mold, was non-tacky, had
the exact
flower shape of the mold, exhibited a uniform color and distribution of
glitter, and could be
handled without breaking up. It also exhibited excellent cling to a variety of
vertical surfaces
including glass and plastic film.
Examples 10-15
Polyamide polyamines were prepared according to the procedure of Example 9 by
charging acids and amines of the types listed in the TABLE A (below) in the
weight
percentages indicated to a reactor and heating the charge to 200-220 C under a
stream of dry
nitrogen for about 4-5 hours and discharging the product. Products properties
were then
measured and are also recorded in TABLE 1.
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Table 1
Example Example Example Example Example
EXAMPLE NUMBER Example 10
11 12 13 14 15
COMPONENTS
DiAcid Adipic Acid Empol Empol Empol CHDA Unidyme'
Diamine T-
5000 1-403 T-403 T-403 T-403 D-2000
Co-DiArnine D-400 D-400 XT.1-500 D-400 Piperazine
Third Diamine - D-2000 D-2000 - D-2000
COMPONENTS (Wt.%)
DiAcid 2.0%
41.2% 30.8% 43.3% 18.7% 82.3%
Diamine 98.0%
9.6% 4.2% 12.6% 17.8% 2.1%
Co-DiAmine 0.0%
24.6% 16.7% 44.1% 35.5% 15.6%
Third Diamine 0.0% 24.6% 48.3% 0.0% 28.0% 0.0%
PRODUCT PROPERTIES
Neutralization
194.4% 139.5% 141.5% 148.2% 141.1% 131.7%
Acid Number 0.4 0.5 0.4 0.4 1.4 0.6
Amine Number 12.2 27.1 22.6 42.4 44.6 14.1
Pale Pale Pale
Color Pale yellow Off-White
Amber
yellow yellow yellow
Softening Point (R&B, C) Liquid Liquid Liquid Liquid 128
Liquid
Viscosity At 150 C 770 391 141 190 290 481
1 Wt. Aver. Mol. Wt. 6,150 2,150 17,780 5,650
1,720 33,760
Immobilized fragrance oils were prepared by warming a mixture of 2.0 grams
PAPA
of the example and 2.0 grams fragrance oil to about 55 C and then blending the
warm
mixture by hand with a stir stick. Test fragrances were: "Ocean" (Continental
Aromatics),
"Linen Fresh" (Wessel Fragrances), and "Cherry" (Aromatic Flavors and
Fragrances). After
blending, one equivalent of isocyanate hardener dissolved in an equal weight
of oil was added
with manual stirring, a stopwatch was started, and the mixture monitored for
its consistency.
When the mixture no longer could flow under its own weight, the time (in
minutes) was noted
as the "gel time". TABLE 2 shows that all of these polyamide polyamines were
effective in
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immobilizing the target oils when cross-linked with polyisocyanates. Gel times
were short
but not so short as to preclude the preparation of useful articles and
followed the consistent
pattern: Ocean < Linen Fresh < Cherry.
Table 2
GEL COMPONENTS POLYAMIDE POLYAMTNE OF EXAMPLE
Fragrance Oil Type Hardener No. 9 No. 10 No. 11 No. 12 No. 13 No. 14 No.
15
Ocean N-3300 6.5 15 10 40 8.5 10 73
Linen Fresh N-3300 9 24 13 55 10 13 76
Linen Fresh Z-4470 33* 44 22 nd red rui nd
Cherry N-3300 75 170 95 335 87 red nd
*40% polyurea- see Example 9 for conditions
Examples 16-20
Polyamide polyamines (PAPA) were prepared according to the procedure of
Example
9 by charging acids and amines of the types listed in the TABLE C in the
weight percentages
indicated to a reactor and heating the charge to 200-220 C under a stream of
dry nitrogen for
about 5 hours and discharging the product. Products properties were then
measured and are
also recorded in TABLE 3.
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Table 3
EXAMPLE No. 16 No. 17 No. 18 No. 19 No. 20
COMPONENTS
DiAcid Empol Adipic Acid Adipic Acid Empol 1008 Unidyme
Triamine T-403 - 1-403 1-403 - - -
Diamine D-400 XT3-500 D-400 D-400 V-551
Third Amine D-2000 - D-2000 D-2000
WEIGHT %
DiAcid 30.6% 18.2% 15.2% 36.7% 41.7%
Triamine 5.0% 9.1% 7.6% - -
Diamine 16.5% 72.7% 38.6% 22.9% 58.3%
Third Amine 47.9% 38.6% 40.4%
PROPERTIES
Acid Number 0.6 2.2 0.7 0.7 1.1
Amine Number 27.0 28.9 29.9 13.1 33.2
Color
Colorless Colorless Colorless Colorless Amber
Viscosity [cP at 150 C] 106 393 198 1340 656
Weight Aver. MW 26380 12230 13490 31550 13180
Immobilized fragrance oils were prepared by warming a mixture of 2.0 grams
polyamide polyamine of the example and 2.0 gams fragrance oil to about 55 C
and then
blending the warm mixture by hand with a stir stick. Test fragrances were:
Oceanside Mist,
Tropical (Atlas Products), Spring Meadow, Country Wildflower, Ocean
(Continental
Aromatics), Linen Fresh (Wessel Fragrances), Yankee Home (Belle Aire),
Mulberry and
Cherry (Aromatic Flavors and Fragrances). After blending, one equivalent of
isocyanate
hardener dissolved in an equal weight of oil was added with manual stirring, a
stopwatch was
started, and the mixture monitored for its consistency. When the mixture no
longer could
flow under its own weight, the time (in minutes) was noted as the "gel time".
TABLE 4
shows that all of these polyamide polyamines were effective in immobilizing
the target oils
when cross-linked with polyisocyanates. Gel times were short but not so short
as to preclude
the preparation of useful articles and followed the consistent pattern:
Spring Meadow < Ocean < Tropical < Linen Fresh < Yankee Home < Mulberry <
Cherry
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Table 4
Polyamide Polyamine of Example
Fragrance Oil Type No. 16 No. 17 No. 18 No. 19 No. 20
Oceanside Mist Nd nd nd 41 Nd
Spring Meadow Nd nd nd 42 Nd
Country Wildflower Nd nd nd 75 nd
Ocean 32 14 18 >180 4
Tropical 38 nd 29 >180 nd
Linen Fresh 40 20 32 225 13
Yankee Home 80 27 51 >180 nd
Mulberry 315 185 250 nd nd
Cherry >420 360
>300 >180 240
Example 21
A number of batches of a PAPA were prepared by the method of Example 9 using a
charge (weight percentages in brackets) of either EMPOL 1008 or UNIDYME 12
(a low
trimer content, hydrogenated dimer acid obtained from Arizona Chemical)
[29.5%], T-403
[3.7%], D-400 [22.6%], and D-2000 [44.2%). This polymer, used in Examples #22-
35,
typically had an amine number of 30-35 (equivalent wt. of 1,800-1,600), a
weight-average
molecular weight of 10,700-12,100, a number-average molecular weight of 4,300-
4,900, and
a viscosity at 150 C of 40-70 cP.
Example 22
This example illustrates the preparation of an air freshener in a simple
geometric
shape. To a glass mixing jar was charged 13.1g of the Example 21 PAPA and 15g
of "Cotton
Fresh" fragrance oil (Symrise Corp.) and the mixture was stirred gently for 15
minutes at
ambient temperature. Blue dye (2 drops) was added to the mixture, turning the
solution light
blue. To this homogeneous mixture was then added 1.5g of DESMODURO N3300A.
This
mixture was then stirred until homogeneous, allowed to stand a few minutes to
allow any air
bubbles to dissipate, and 13g total was poured into a rectangular-shaped
flexible silicone
mold of uniform length of 1.87 inches, height of 0.3 inches, and width of 1.0
inches. The set
time was recorded at 28 minutes. The mixture was covered with polyethylene
film and
allowed to cure undisturbed for 24 hours. After this time the mold was
stripped away from
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the cross-linked air freshener object that was now firm, flexible, transparent
and non-tacky to
the touch.
Example 23
This example illustrates the preparation of an air freshener in a complex
shape. To a
glass mixing jar was charged 13.1g of the Example 21 polyamine and 15g of
"Snuggle Type"
fragrance oil (Alpha Aromatics) and the mixture was stirred gently for 15
minutes at ambient
temperature. Red dye (3 drops) was added to the mixture, turning the solution
light pink/red.
To this homogeneous mixture was then added 1.5g of DESMODURO N3300A. This
mixture was then stirred briefly (until homogeneous), allowed to stand a few
minutes to allow
any air bubbles to dissipate, lOg total was poured into a circular-shaped
briochette flexible
silicone mold of uniform top-width of 1.875 inches, height of 0.375 inches,
and bottom-width
of 1.625 inches. The set time was 6 minutes. The mixture was covered with
polyethylene
film and allowed to cure undisturbed for 24 hours. After this time the mold
was stripped
away from the cross-linked air freshener article that was now firm, flexible,
transparent, and
non-tacky to the touch.
Example 24
This example illustrates the preparation of an air freshener in a complex
shape. To a
glass mixing jar was charged 19g of the Example 21 polyamine and 20g of
"Tropical Splash"
fragrance oil (obtained from Symrise Corp.) and the mixture was stirred gently
for 15 minutes
at ambient temperature. Blue dye (3 drops) was added to the mixture, turning
the solution
light green. To this homogeneous mixture was then added 2.0g of DESMODURO
N3300A.
This mixture was then stirred briefly (until homogeneous), allowed to stand a
few minutes to
allow any air bubbles to dissipate, 20g total was poured into a scallop-shaped
flexible silicone
mold of uniform top-width of 2.375 inches, height of 0.125 inches, and bottom-
width of 2.25
inches. The set time was recorded at 24 minutes. The mixture was covered and
allowed to
cure undisturbed for 24 hours. After this time the mold was stripped away from
the cross-
linked air freshener article that was now firm, flexible, transparent, and non-
tacky to the
touch.
Example 25
This example illustrates the preparation of an air freshener containing
suspended
insoluble particles. To a glass mixing jar was charged 19g of the Example 21
polyamine and
20g of "Clean Citrus" fragrance oil (from Symrise Corp.) and the mixture was
stirred gently
for 15 minutes at ambient temperature. Yellow aluminum flake "glitter" (0.04g)
was added
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to the mixture. To this homogeneous mixture was then added 2.0g of DESMODURIO
N3300A. This mixture was then stirred briefly (until homogeneous), allowed to
stand a few
minutes to allow any air bubbles to dissipate, 18.0g total was poured into a
disk-shaped
flexible silicone mold of uniform circumference of 9.75 inches, height of 0.75
inches, and
width of 3.0 inches. The set time was recorded at 30 minutes. The mixture was
covered and
allowed to cure undisturbed for 24 hours. After this time the mold was
stripped away from
the cross-linked air freshener article that was now firm, flexible,
transparent, and non-tacky to
the touch and displayed a uniform distribution of glitter.
Example 26
To a glass mixing jar was charged 19g of the Example 21 polyamine and 20g of
"Sunshine Fruit" fragrance oil (Firmenich, Inc.) and the mixture was stirred
gently for 15
minutes at ambient temperature. Green "glitter" (0.03g) was added to the
mixture. To this
homogeneous mixture was then added 2.0g of DESMODURI1 N3300A. This mixture was
then stirred briefly (until homogeneous), allowed to stand a few minutes to
allow any air
bubbles to dissipate, 28.0g total was poured into a heart-shaped flexible
silicone mold of
uniform length of 2.5 inches, height of 0.3 inches, and width of 2.875 inches.
The set time
was recorded at 17 minutes. The mixture was covered and allowed to cure
undisturbed for 24
hours. After this time the mold was striped away from the cross-linked air
freshener object
that was now firm, flexible, transparent and non-tacky to the touch and
displayed a uniform
distribution of glitter.
Example 27
To a glass mixing jar was charged I9g of the Example 21 PAPA and 20g of
"Mandarin Grapefruit" fragrance oil (obtained from Givaudan Corp.) and the
mixture was
stirred gently for 15 minutes at ambient temperature. Blue dye (1 drop) was
added to the
mixture, turning the solution light yellow/men. To this homogeneous mixture
was then
added 2.0g of DESMODURO N3300A. This mixture was then stirred briefly (until
homogeneous), allowed to stand a few minutes to allow any air bubbles to
dissipate, 31.0g
total was poured into a Bundt cake-shaped flexible silicone mold of uniform
top-width of
1.75 inches, height of 0.75 inches, and bottom-width of 2.5 inches. The set
time was
recorded at 67 minutes. The mixture was covered and allowed to cure
undisturbed for 24
hours. After this time the mold was stripped away from the cross-linked air
freshener object
that was now firm, flexible, transparent and non-tacky to the touch.
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Example 28
This example illustrates the preparation of an immobilized phase-transfer
liquid. To a
glass mixing jar was charged 10.4g of the Example 21 polyamine and 18g of 1-
decanol
(freezing point, 5-7oC) as the active oil, 0.6g benzaldehyde as odorant and
cross-linking
reaction retardant and the mixture was stirred gently for 15 minutes at
ambient temperature.
To this homogeneous mixture was then added 1.5g of DESMODUR N3300A. This
mixture was then stirred briefly (until homogeneous), allowed to stand a few
minutes to allow
any air bubbles to dissipate and then 18.5g total was poured into a truncated
pyramid-shaped
flexible silicone mold of uniform top-width of 0.75 inches, height of 0.75
inches, and bottom-
width of 1.0 inches. The set time was recorded at 30 minutes. The mixture was
covered and
allowed to cure undisturbed for 24 hours. After this time the mold was
stripped away from
the cross-linked object that was now firm, flexible, transparent and non-tacky
to the touch.
When placed in a freezer. The object hardened but did not crack. When removed
from the
freezer and allowed to warm to room temperature, the object regained
flexibility but remained
a tough, firm clear, solid.
Example 29
This example illustrates the preparation of a small air freshener for use in a
purse or
other small enclosed space): To a glass mixing jar was charged 5g of the
Example 21
polyamine and 5g of "Ocean" fragrance oil (provided by Orlandi, Inc.) and the
mixture was
stirred gently for 15 minutes at ambient temperature. Blue dye (2 drops) was
added to the
mixture, turning the solution light blue. To this homogeneous mixture was then
added 0.6g
of DESMODURS N3300A. This mixture was then stirred briefly (until
homogeneous),
allowed to stand a few minutes to allow any air bubbles to dissipate, 5.0g
total was poured
into a lozenge-shape polyethylene bulb mold of uniform middle-circumference of
1.5 inches,
height of 1.625 inches, and top and bottom-width of 0.5 inches. The set time
was 7 minutes.
The mixture was sealed and allowed to cure undisturbed for 24 hours. After
this time the
mold was stripped away from the cross-linked air freshener object that was now
firm,
transparent, and non-tacky to the touch.
Example 30
To a glass mixing jar was charged 28g of the Example 21 polyamine and 30g of
"Country Garden" fragrance oil (Belle-Aire) and the mixture was stirred gently
for 15
minutes at ambient temperature. Green dye (3 drops) and yellow sprinkles
(0.02g) were
added to the mixture, turning the solution yellow/green. To this homogeneous
mixture was
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then added 3.0g of DESMODURO N3300A. This mixture was then stirred briefly
(until
homogeneous), allowed to stand a few minutes to allow any air bubbles to
dissipate, 50.0g
total was poured into a Half sphere-shaped flexible silicone mold of bottom-
circumference of
7.25 inches, height of 1.0 inches, and bottom-width of 3.75 inches. The set
time was 260
minutes. The mixture was covered and allowed to cure undisturbed for 24 hours.
After this
time the mold was stripped away from the cross-linked air freshener object
that was now
firm, flexible, transparent and non-tacky to the touch.
Example 31
To a glass mixing jar was charged 30g of the Example 21 polyamine and 30g of
"Cotton Fresh" fragrance oil (Symrise) and the mixture was stirred gently for
15 minutes at
ambient temperature. Autumn leaves foil confetti (6 leaves) were added to the
clear mixture.
To this homogeneous mixture was then added 3.5g of DESMODURC N3300A. This
mixture was then stirred briefly (until homogeneous), allowed to stand a few
minutes to allow
any air bubbles to dissipate, and 50g total was poured into a glass jar of
uniform
circumference of 7.25 inches, height of 1.25 inches, and top and bottom-width
of 2.25 inches.
The set time was recorded at 28 minutes. The mixture was capped and allowed to
cure
undisturbed for 24 hours. After this time the mold was now firm, transparent,
and smooth to
the touch.
Example 32
To a glass mixing jar was charged 37g of the Example 21 polyamine and 40g of
"Lemon Citrus" fragrance oil (Alpha Aromatics) and the mixture was stirred
gently for 15
minutes at ambient temperature. Green sprinkles (0.02g) were added to the
mixture, turning
the solution yellow/green. To this homogeneous mixture was then added 4.0g of
DESMODUR N3300A. This mixture was then stirred briefly (until homogeneous),
allowed
to stand a few minutes to allow any air bubbles to dissipate, 60.0g total was
poured into a
lemon-shaped flexible silicone mold of uniform top and bottom-width of 0.75
inches, height
of 2.75 inches, and middle-circumference of 5.5 inches. The set time was
recorded at 42
minutes. The mixture was covered and allowed to cure undisturbed for 24 hours.
After this
time the mold was stripped away from the cross-linked air freshener object
that was now
firm, flexible, transparent and non-tacky to the touch.
Example 33
To a glass mixing jar was charged 36g of the Example 21 polyamine and 40g of
"Cherry Berry" fragrance oil (Belle-Aire) and the mixture was stirred gently
for 15 minutes at
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ambient temperature. Red dye (3 drops) was added to the mixture, turning the
solution red.
To this homogeneous mixture was then added 4.0g of DESMODUR N3300A. This
mixture was then stirred until homogeneous, allowed to stand a few minutes to
allow any air
bubbles to dissipate, 60.0g total was poured into a rose flower-shaped
flexible silicone mold
of uniform top and bottom- width of 3.75 inches, height of 0.75 inches, and
circumference of
12.25 inches. The set time was recorded at 155 minutes. The mixture was
covered and
allowed to cure undisturbed for 24 hours. After this time the mold was
stripped away from
the cross-linked air freshener object that was now firm, flexible,
transparent, and non-tacky to
the touch.
Example 34
To a glass mixing jar was charged 19g of the Example 21 polyamine and 20g of
"Cherry" fragrance (Atlas, Inc.) and the mixture was stirred gently for 15
minutes at ambient
temperature. Red dye (3 drops) was added to the mixture, turning the solution
red. To this
homogeneous mixture was then added 2.0g of DESMODUR N3300A. This mixture was
then stirred briefly (until homogeneous), allowed to stand a few minutes to
allow any air
bubbles to dissipate, 28.0g total was poured into a hollow polyethylene golf
ball mold of
uniform circumference 5.25 inches. The set time was recorded at 75 minutes.
The mixture
was covered and allowed to cure undisturbed for 24 hours. After this time the
mold was
stripped away from the cross-linked air freshener object that was now firm,
flexible,
transparent, and non-tacky to the touch.
Example 35
This example illustrates the preparation of a foamed article. To a glass
mixing jar was
charged 15g of the Example 21 polyamine, 15g of UNIDYME 60 polymerized fatty
acid
(from Arizona Chemical) and 30g of "Very Berry" fragrance oil (from Belmay
Corp.) and the
mixture was stirred gently for 15 minutes at ambient temperature, resulting in
a slightly hazy
solution. Red dye (3 drops) was added to the mixture, turning the solution
red. To this
homogeneous mixture was then added 4.0g of DESMODUR N3300A. This mixture was
then stirred briefly (until homogeneous), allowed to stand a few minutes to
allow any air
bubbles to dissipate, 40g total was poured into a baking cup paper mold of
uniform top and
bottom-width of 2.0 inches, height of 1.25 inches, and circumference of 7.5
inches. The set
time was 8 minutes. The mixture was allowed to cure undisturbed for an
additional 24 hours.
During this time the object became filled with trapped bubbles (foam) and
doubled in size,
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forming a rounded crown. This foam air freshener was now firm and non-tacky to
the touch.
When compressed (squeezed), it returned to its rounded shape.
Example 36
A number of batches of a polyamide polyamine terminated with a carbonyl-
substituted
aromatic amine were prepared by charging (weight percentages in brackets) of
PRIPOL
1009 hydrogenated dimer acid [24.0], para-aminobenzoic acid [5.0], JEFFAM1NEgi
D-2000
[54.0], JEFFAMINE6 D-400 [11.5], and JEFFAMINE0 T-403[5.5] to a 3L glass round-
bottomed reactor equipped with an overhead mechanical stirrer and heating this
charge to
215 C under a stream of dry nitrogen. After holding this mixture under these
conditions for
about 25 hours, the reaction mixture was discharged to a container. The
product was a clear,
viscous, slightly yellow liquid. This polymer had a titrated amine number in
the range 13-15
(non-potentiometric method, or 30-35 by potentiometric titration, amine
reactive equivalent
wt. of 1,800-1,600), a weight-average molecular weight of 13,000-14,000, a
number-average
molecular weight of 4,500-5,500, and a viscosity at 130 C of 250 cP. This
material was used
in a series of tests of immobilizing, at the 30 weight% use level, liquid test
media (70% by
weight), free of active, catalyst, or retardant. The results (TABLE, 5 below)
demonstrate that
set times can vary up to about 1 day for such a modified PAPA even in the
absence of
retardant aldehyde. The data also demonstrate the accelerating effect of the
use of an
alcoholic diluent, such as a polypropylene glycol or its alkyl ether, on the
cure rate.
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Table 5
Set Time Upon Curing Syneresis
Test Liquid Medium (Minutes) Appearance
(after 4 days)
Dipropylene Glycol 60 Hazy Slight syneresis
Isostearyl Alcohol 60 Hazy No syneresis
Significant
Tripropylene Glycol 66 Slight Haze
syneresis
Dipropylene Glycol Mono Methyl Ether 90 Clear No syneresis
Castor Oil 105 Slight Haze No
syneresis
Methyl Salicylate 400 Clear No syneresis
FINSOLV TN Benzoate Ester 440 Clear No syneresis
Dibutyl Adipate 1014 Clear No syneresis
Dipropylene Glycol Dimethyl Ether 1245 Clear No syneresis
Diethyl-m-toluamide (DEET) 1470 Clear No syneresis
Isophorone 1845 Clear, yellow i No syneresis
Example 37
This example illustrates the preparation of another type of polyamide
polya.mine
terminated with a carbonyl-substituted aromatic amine. The procedure of
Example 36 was
followed using a charge (weight percentages in brackets) of 1-5000 [92.9] and
para-
aminobenzoic acd [7.1]. This polymer, used in Examples #38-41, had an amine
equivalent
weight of 1.950.
Example 38
This example illustrates the preparation of an article containing liquid
fragrance
trapped behind a membrane of matrix. To a glass mixing jar was charged 5.0g of
the
Example 37 polyamine and 5.0g of FINSOLVO TN and the mixture was stirred
gently for 15
minutes at ambient temperature. To this homogeneous mixture was then added
0.6g of
DESMODURO N3300A. This mixture was then stirred briefly (until homogeneous),
allowed
to stand a few minutes to allow air bubbles to dissipate, and then a 1.0g
portion was poured
gently, without stirring, into a loz. glass vial containing lOg of "Lily of
the Valley" green
fragrance oil (Wellington Fragrances). The matrix solution floated on top of
the fragrance oil
and the oil remained as a separate reservoir below it. The set time for the
top (membrane)
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layer that gradually absorbed some of the fragrance oil, was 80 minutes. The
vial was capped
and allowed to cure for an additional 24 hours. After this time, the vial was
suspended
inverted. In this position, fragrance oil gradually permeated the membrane and
evaporated,
acting as a sustained release air freshener.
Example 39
This example illustrates the preparation of a article containing an aromatic
filler. To a
glass mixing jar was charged 15g of the Example 37 polyamine, 6g of castor
oil, and 9g of
commercial ground coffee and the mixture was stirred gently for 30 minutes at
ambient
temperature. To this viscous paste was then added 2.0g of DEMODUR N3300A.
This
mixture was then stirred briefly, allowed to stand a few minutes to allow any
air bubbles to
dissipate, poured (18.0g used) into a disk-shaped flexible mold of uniform
circumference of
8.25 inches, height of 0.25 inches, and top and bottom-width of 2.5 inches.
The set time was
recorded at 165 minutes. The mixture was covered and allowed to cure
undisturbed for 24
hours. After this time the mold was stripped away from the object that was now
fragrant
(coffee odor), firm, flexible, and non-tacky to the touch.
Example 40
This example illustrates the preparation of an article containing water. To a
glass
mixing jar was charged 20g of the Example 37 polyamine, 20g of "Snuggle Type"
fragrance
oil (from Alpha Aromatics), and 8g of de-ionized water, and the mixture was
stirred gently
for 15 minutes at ambient temperature, resulting in a milky suspension of
water in the matrix-
fragrance solution. Blue dye (2 drops) was added to the mixture. To this light
blue, milky
mixture was then added 2.5g of DESMODUR N3300A. This mixture was then stirred
briefly and allowed to stand a few minutes to allow any air bubbles to
dissipate. Then a 31.0g
portion was poured into a bunt cake-shaped flexible silicone mold of uniform
top-width of
1.75 inches, height of 0.75 inches, and bottom-width of 2.5 inches. The set
time was
recorded at 130 minutes. The mixture was covered and allowed to cure
undisturbed for 24
hours. After this time the mold was stripped away from the cross-linked air
freshener object
that was now firm, milky, flexible, and non-tacky to the touch. The article
gradually turned
clear (starting from the edges and moving toward the center) as the water
evaporated over a
period of one month.
Example 41
This example illustrates the preparation of a dispersion. Solution A: to a
glass mixing
jar was charged 8g of the Example 37 polyamine and 8g of FINSOLV TN and the
mixture
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was stirred gently for 15 minutes at ambient temperature. To this homogeneous
mixture was
then added 0.8g of DESMODURS N3300A. This mixture was then stirred briefly
(until
homogeneous), allowed to stand a few minutes to allow any air bubbles to
dissipate. Solution
B: to another glass mixing jar was charged 32g deionized water and 0.8g of
surfactant (1'-
DET A-136). This mixture was stirred (10 minutes). Solution A was then poured
into
Solution B with stirring for 10 minutes. This blend of mixture A+B mixture was
then poured
into a metal pan and the water allowed to evaporate (24 hours). This yielded a
white,
lubricious powder, insoluble in toluene, of immobilized oil particles.
Example 42
Representative of articles containing pesticide that can be prepared according
to the
present invention is the following controlled-release diethyl toluamide (DEET)
device. A
thorough mixture was made of DEET (20 parts), dimethyl adipate carrier (50
parts),
benzaldehyde as fragrance and retardant (1.6 parts), the polyamide polyamine
of Example 21
(26.8 parts) and a trace of orange dye. To this blend was then added with
stirring
DESMODUR N3300 polyisocyanate (3.2 parts) and the final mixture poured into
scallop-
shaped silicone molds. After this cured, the scallop medallion so formed was a
firm, non-
tacky, and flexible solid.
Example 43
Representative of articles containing pheromones that can be prepared
according to
the present invention is the following controlled-release device for the
pheromone
octadecanal. A thorough mixture was made of octadecanal (30 parts), F1NSOLVe
TN
benzoate ester as carrier (30 parts), and the polyamide polyamine of Example
21(35.5 parts).
To this blend was then added with stirring DESMODURe N3300 polyisocyanate (4.5
parts)
and the final mixture poured into a cylindrical mold. After curing, the
material formed was a
firm, non-tacky, and flexible solid that could be sliced into small disks for
use as lures.
Example 44
This example illustrates the use of a styrene-maleic anhydride copolymer as
the
reactive partner with a polyamide polyamine for preparation of a lightly-
scented disk-shaped
air freshener. To a glass mixing vial was charged 6.0g of a 25 wt% solution
FINSOLV TN
solution of the Example 21 polyamide polyamine, 7.5g of a 20 wt% solution of
DYLARK
232 poly(styrene-co-maleic anhydride, NOVA Chemicals), and ca. 2g of "Ocean"
fragrance
oil (provided by Wellington, Inc.). The mixture was stirred gently for a few
minutes at
ambient temperature and blue dye (4 drops) added. The mixture was initially
slightly turbid
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but cleared after a few more minutes and remained clear and apparently
homogeneous. The
mixture was then poured (about I I g was used) into a disk-shaped polyethylene
mold and
allowed to stand undisturbed. The mixture set to a sticky, elastic mass inside
about 2 hours
and after 24 hours could be stripped from the mold. After this time the mold
was stripped
away from the cross-linked air freshener object that was now firm,
transparent, and flexible
with a light tack to the touch.
Example 45
This example illustrates the use of a cationic surfactant to prepare an
immobilized
fragrance emulsion useful as a fabric softener. A blend of PAPA of Example 13
(4.0g),
"Cinnamon Char fragrance oil (3.0g), and VARIQUATO B1216 alkyl dimethyl benzyl
ammonium chloride (80% active, Degussa Corporation, 1.0g) was first prepared
by warming
and stirring the ingredients. To the blend was added water (9.0g) and then,
with stirring,
DESMODUR N3300A (0.65g). The mixture soon became viscous and uniformly
cloudy.
It was storage stable and was dilutable with water, indicating it was an oil-
in-water
dispersion. Light scattering particle size measurement on the material
determined the particle
size distribution to be bi-modal, with about 50% of the weight of particles
having a size
grouping around 0.4 microns and the other 50% grouping around 3.0 microns.
Example 46
This example illustrates the preparation of an immobilized cationic surfactant
useful
as a fabric softener. A blend of PAPA of Example 21 (3.0g), DOWANOL DPM
(1.0g) and
VARIQUAT B1216 alkyl dimethyl benzyl ammonium chloride (80% active, Degussa
Corporation, 6.0g) was first prepared by warming and stirring the ingredients
and then
cooling them to room temperature. A second blend was prepared of DOWANOL DPM
(4.2g) and DESMODURO N3300A (0.8g). The two clear mixtures were then mixed
together
and immediately poured into a mold. The blended components set almost
immediately and
were firm enough to pick up out of the mold in less than 30 minutes. The final
article
contained 32% by weight active quaternary compound.
Example 47
A secondary amine terminated polyamide polyamine (SATPP) was prepared by
charging PRIPOL 1006 polymerized fatty acid (48.8 g, 219 meg acid) (Croda,
Inc.; Edison,
NJ), JEFFAMINE D-2000 (54.9 g, 1000 meg amine) (Huntsman Corporation; The
Woodlands, TX), and JEFFAMINE D-403 (4.88 g, 146 meg amine) (Huntsman
Corporation;
The Woodlands, TX) to a 250 mL glass flask equipped with a magnetic stir bar.
The contents
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of the flask were heated to 100 C with stirring under a stream of dty
nitrogen and then 3-
cyclohexylamine propylamine (CHAPA) (11.59 g, 78 meq amine) was added. The
mixture
was heated to 210-220 C under a stream of dry nitrogen. Alter holding the
mixture under
these conditions for 4 hours, the reaction mixture was discharged to a
container. The product
was clear and viscous and had an acid number of 0.7, an amine number of 38.1,
and a weight
average molecular weight of 12,600 Daltons.
Example 48
A secondary amine terminated polyamide polyamine (SATPP) was prepared by
charging PRIPOL 1006 polymerized fatty acid (48.8 g, 219 meq acid) (Croda,
Inc.; Edison,
NJ), JEFFAMINE D-2000 (54.9 g, 1000 meq amine) (Huntsman Corporation; The
Woodlands, TX), and JEFFAMINE D-403 (4.88 g, 146 meq amine) (Huntsman
Corporation;
The Woodlands, TX) to a 250 mL glass flask equipped with a magnetic stir bar.
The contents
of the flask were heated to 210-220 C with stirring under a stream of dry
nitrogen and held at
these conditions for 3 hours. The mixture was then cooled to 100 C and
aminoethylpiperazine (AEP) (9.5 g, 64.6 meq amine) was added. The resulting
mixture was
heated to 210-220 C and held at these conditions for 4 hours. The reaction
mixture was then
discharged to a container to provide a clear and viscous product having an
acid number of
1.5, an amine number of 32, and a weight average molecular weight of 36,700
Daltons.
Examples 49-78
For each of examples 49-78 (see Table 1), a secondary amine terminated
polyamide
polyamine (SATPP) (1.25 g) and fragrance oils (3.5g) were manually mixed in a
glass vessel
to obtain a homogenous solution. The fragrance oils were obtained from Belcan
Inc.
(Yonkers, NY), Givaudan (Vernier, Switzerland), or Orlandi, Inc. (Farmingdale,
NY), as
indicated in Table 6. The mixture was allowed to stand for 10 minutes. One
equivalent of
DESMODUR N 3300, an isocyanate hardener commercially available from Bayer
Corporation (Pittsburgh, PA), was then added with manual stirring. The gel
time was
measured by observing the amount of time lapsed to provide a mixture no longer
able to flow
under its own weight. As shown in Table 1, each of the formulations using a
SATPP
immobilized the target fragrance oils within 2 minutes, implying that the
SATPP amine
functional groups did not interfere with the aldehyde functional groups in the
fragrance oils.
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Table 6
Set Time
Example Fragrance Oil Type SATPP (minutes)
Belean Fragrances
49 Lemon Sage Example 48 <2
50 Lemon Sage Example 47 <2 ,
, --
51 Lemon Sage JEFFAMINE SD-2001 <2
51 Juicy Apple Example 48 <1
______________________________________________________________ -
53 Juicy Apple Example 47 <2
54 Juicy Apple JEFFAMINE SD-2001 <1
55 Applewood Example 48 <2
56 Applewood Example 47 <2
57 Applewood JEFFAMINE SD-
2001,.. --,
,
58 Strawberry Example 48 <2
59 Strawbeny Example 47 <2
60 Strawberry JEFFAMINE SD-2001 <2
61 Honeysuckle Example 48 <2
_________________________________ _ -----
62 Honeysuckle Example 47 <2
63 Honeysuckle JEFFAMINE SD-2001 <2
64 Apricot Mango Example 48 <2
65 Apricot Mango Example 47 <2
66 Apricot Mango JEFFAMINE SD-2001 <2
' 67 Fresh Rain Example 48 <1
__________________________________________________________________ 1
68 Fresh Rain Example 47 <2
69 Fresh Rain hEFFAMINE SD-2001 <2
. Givaudan Fragrances
70 Natalie Example 48 <2
71 Natalie Example 47 <2
72 Natalie JEFFAMINE SD-2001 f <2
(Mandl Fragrance
73 Garden Sage Example 48 <2
74 Garden Sage Example 47 <1
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75 Garden Sage JEFFAMINE SD-2001 <2
76 Lime Basil Example 48 <2
77 Lime Basil Example 47 <2
78 Lime Basil JEFFAMINE SD-2001 <2
Examples 79-90
Examples 79-90 illustrate the gel setting time differences between secondary
amine
terminated polyamide polyamine (SATPP) and primary amine terminated polyamide
polyamine (PATPP), as shown in Table 7. The formulations using PATPP showed
longer
and varying set times for different fragrance oils. On the contrary, all the
formulations using
SATPP had set times within 2 minutes. The immobilized and intermixed fragrance
oils were
prepared according to the procedure for Examples 49-78.
Table 7
SATPP Set Time
Fragrance Oil Type Hardener Polyamine PATPP (minutes)
Bayer
Ex. 79 Cherry N3300 Ex. 48 SATPP <2
Ex. 80 Cherry N3300 JEFFAM1NE SD-2001 SATPP <2
Ex. 81 Cherry N3300 JEFFAMINE D-2000 PATPP Never Set
Ex. 82 Cherry N3300 SYLVACLEAR 1M 700 PATPP Never Set
Ex. 83 Orange N3300 Ex. 48 SATPP <2
Ex. 84 Orange N3300 JEFFAMINE SD-2001 SATPP <2
Ex. 85 Orange N3300 JEFFAMINE D-2000 PATPP 30
Ex. 86 Orange N3300 SYLVACLEAR IM 700 PATPP 45
Ex. 87 Berry N3300 Ex. 48 SATPP <2
Ex. 88 Berry N3300 JEFFAMINE SD-2001 SATPP <2
Ex. 89 Berry N3300 JEFFAMINE D-2000 PATPP <2
Ex. 90 Berry N3300 SYLVACLEAR IM 700 PATPP <2
Examples 91-94
For each of examples 91-94, a secondary amine terminated polyamide polyamine
(SATPP), SYLVACLEAR 1M 800, a polyamide polyamine terminated with a carbonyl-
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substituted aromatic amine commercially available from Arizona Chemical
Company
(Jacksonville, FL), and fragrance oils were manually mixed in a glass vessel
to obtain a
homogenous solution. The mixture was allowed to stand for 10 minutes. One
equivalent of
isocyanate hardener DESMODUR N 3300 (Bayer Corporation; Pittsburgh, PA) was
then
added with manual stirring. The gel time was measured by observing the amount
of time
lapsed to provide a mixture no longer able to flow under its own weight. Table
8 illustrates
the gel setting time for the formulations with SATPP can be adjusted by
blending with
polyamide polyamines terminated with carbonyl-substituted aromatic amine.
Table 8
Components Ex. 91 Ex. 92 Ex. 93 Ex. 94
Ex. 48 0.75 0 0.43 0
JEFFAMINE SD-2001 0 0.71 0.0 0.41
SYLVACLEAR 1M 800 0.68 0.69 0.9 0.96
Orange fragrance 3.6 3.6 3.6 3.6
DESMODUR N3300 0.31 0.3 0.29 0.32
Set Time, minutes 310 198 355 243
Examples 95-104
For each of examples 95-104, immobilized fragrance oil dispersions were
prepared
according to the following generic process. Details on the individual
components for each of
the dispersions are described in Tables 9 and 10. To form Part A, the
indicated amounts of
water, 1% MF,THOCEL 311 cellulose water solution (Dow Chemical; Midland, MI),
FINSOLV-TN (an alkyl benzoate commercially available from Innospec Active
Chemicals
(Edison, NJ), and a surfactant ARQUAD 18-50 (Alczo Nobel Surface Chemistry
LLC;
Chicago, IL) were charged into a 100 mL plastic cup equipped with an impeller.
Part B was
prepared by pre-mixing the indicated amounts of fragrance Natalie (Givaudan;
Vernier,
Switzerland) and polyamide polyamine S'YLVACLEAR 1M 700 (Arizona Chemical
Company; Jacksonville, FL) to form a homogenous solution in 2 minutes. Part B
was
dispersed dropwise into Part A aqueous phase immediately at the indicated rpm.
Part B
addition was completed in 3 minutes. After addition, the mixture was agitated
at the
indicated rpm for 60 minutes and discharged to a container. The dispersions
were milky
solutions. For some batches, the indicated amount of additional surfactant
ARQUAD 18-50
was added and mixed for 5 minutes.
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Table 9
Ex, 95 Ex. 96 Ex. 97 Ex. 98 Ex. 99
Mixing speed (rpm) 600 600 700 700 700
1
- _____________________________________________________________
SYLVACLEARIM700 (grams) 2 4
.25 2.25 225 2.25
' -
Natalie (fragrance) (grams) 5 5 5 5 5
F1NSOLV4N (grams) 0 0 0 0 0
1% NETHOCEL 311 (grams) 6 6 6 6 6
Water (grams) 6 6 6 6 6
ARQUAD 18-50 (first addition) (grams) 0.7 0.7 03 0.7 13
DESMODUR N3300 (hardener) (grams) 0.35 0.35 0.35 0.35 0.35
'
ARQUAD 18-50 (second addition) (grams) 0 1 0 1 0
Total weight (grams) 20.3 213 20.3 21,3 2L3
Mean particle size (microns) 69A 58.02 45,2 45.4 25,9
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Table 10
Ex. 100 Ex. 101 Ex. 102 Ex. 103 Ex. 104
Mixing speed (rpm) 700 800 1000 1000 1000
SYLVACLEAR 1M700 (grams) 2.25 2.25 2.25 2.25 2.25
Natalie (fragrance) (gams) 5 5 5 5 5
F1NSOLV-TN (grams) 0 0 0.8 0 0.8
1% METHOCEL 311 Cellulose (grams) 6 6 4.5 6 4.5
Water (grams) 6 6 6 6 6
ARQUAD 18-50 (first addition) (grams) 2.3 1.7 1.7 1.7 1.7
DESMODUR N3300 (hardener) 0.35 0.35 0.35 0.35 0.35
ARQUAD 18-50 (second addition) (grams) 0 0 0 0 0
Total weight (grams) 21.9 21.3 20.6 21.3 20.6
Mean particle size (microns) 38.6 31.8 21.52 25.91 12.82
Example 105-107
For each of Examples 105-107, the fragrance oil dispersions were prepared
according
to the following generic process, with details regarding the individual
components shown in
Table 11. The indicated amounts of SYLVACLEAR1M700 (Arizona Chemical Company;
Jacksonville, FL) and the fragrance Berry (Belmay Fragrances Ltd.; Yonkers,
NY) were pre-
mixed to form a homogenous solution. The solution was added dropwise to an
aqueous
solution having the indicated amounts of water, 1% METHOCEL 311 (Dow Chemical;
Midland, MI) water solution, and surfactant ARQUAD 18-50 (Akzo Nobel Surface
Chemistry LLC; Chicago, IL) with mixing at the indicated rpm in a 100 mL
plastic cup. The
addition was completed within 3 minutes and the mixing was continued for 30
minutes. The
hardener DESMODUR N3300 (Bayer Corporation; Pittsburgh, PA) was added
dropwise,
mixing was allowed to continue for 60 minutes, and the resulting dispersion
was discharged
to a container. The dispersions were milky solutions.
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Table 11
Ex. 105 Ex. 106 Ex. 107
Agitation speed (rpm) 1500 700 700
SYLVACLEAR IM700 (grams) 2.34 2.24 2.24
Berry fragrance (grains) 7.22 7.2 7.2
1% METHOCEL 311 Cellulose (grams) 5.7 8 8
Water (grams) 5.7 5 5
ARQUAD 18-50 (grams) 0.66 0.69 1.37
DESMODUR N3300 (hardener) (grams) 0.39 0.41 0.41
Total weight (gams) 22.01 23.54 24.22
Mean particle size (microns) 4.29 22.37 5.67
Example 108
SYLVACLEAR 1M800 (4.50 g) (Arizona Chemical Company; Jacksonville, IL) and
10.50 g of the fragrance Natalie (Givaudan; Vernier, Switzerland) were mixed
to obtain a
homogenous solution. Then 0.58 g DESMODUR N3300 (Bayer Corporation;
Pittsburgh,
PA) was added to the solution and mixed well to form a homogenous solution in
5 minutes.
The solution was added dropwise to an aqueous solution having 12.50 g water,
5.0 g 1%
METHOCEL 311 water solution (Dow Chemical; Midland, MI), and 2.68 g surfactant
ARQUAD 16-50 (Akzo Nobel Surface Chemistry LLC; Chicago, IL) with mixing at
1200
rpm in a 100 mL plastic cup. The addition was completed within 3 minutes. The
mixing was
continued for 130 minutes and the resulting mixture was discharged to a
container. The
dispersions were milky solutions. The mean particle size was 10.5 microns.
Example 109
SYLVACLEAR IM800 (4.50 g) (Arizona Chemical Company), 5.5 g of solvent
FINSOLV-TN (a solvent commercially available from Innospec Active Chemicals
(Edison,
NJ)), and 5.0 g N,N-diethyl-meta-toluamide (DEET) were mixed to obtain a
homogenous
solution. Then 0.58 g DESMODUR N3300 (Bayer Corporation; Pittsburgh, PA) was
added
to the solution and mixed well to form a homogenous solution. The solution was
added
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dropwise to an aqueous solution having 12.50 g water, 5.0 g 1% METHOCEL 311
water
solution (Dow Chemical; Midland, MI), and 2.68 g ARQUAD16-50 (Alczo Nobel
Surface
Chemistry LLC; Chicago, IL) with mixing at 1200 rpm in a 100 mL plastic cup.
The addition
was completed within 3 minutes. The mixing was continued for 120 minutes and
the
resulting mixture was discharged to a container. The dispersions were milky
solutions.
Example 110
SYLVACLEAR IM800 (4.50 g) (Arizona Chemical Company; Jacksonville, FL), 5.5
g of F1NSOLV-1'N (a solvent commercially available from hmospec Active
Chemicals
(Edison, NJ)), and 5.0 g sumithrin were mixed to obtain a homogenous solution.
Then 0.58 g
DESMODUR N3300 (Bayer Corporation; Pittsburgh, PA) was added to the solution
and
mixed well to form a homogenous solution. The solution was added dropwise to
an aqueous
solution having 12.50 g water, 5.0 g 1% METHOCEL 311 water solution (Dow
Chemical;
Midland, Ml), and 2.68 g surfactant ARQUAD 16-50 (Alczo Nobel Surface
Chemistry LLC;
Chicago, IL) with mixing at 1200 rpm in a 100 mL plastic cup. The addition was
completed
within 3 minutes. The mixing was continued for 120 minutes and discharged to a
container.
The dispersions were milky solutions.
The compositions, methods, and apparatuses of the appended claims are not
limited in
scope by the specific compositions, methods, and articles described herein,
which are
intended as illustrations of a few aspects of the claims and any compositions,
methods, and
articles that are functionally equivalent are intended to fall within the
scope of the claims.
Various modifications of the compositions, methods, and articles in addition
to those shown
and described herein are intended to fall within the scope of the appended
claims. Further,
while only certain representative composition materials and method steps
disclosed herein are
specifically described, other combinations of the composition materials and
method steps also
are intended to fall within the scope of the appended claims, even if not
specifically recited.
Thus, a combination of steps, elements, components, or constituents can be
explicitly
mentioned herein; however, other combinations of steps, elements, components,
and
constituents are included, even though not explicitly stated. The term
"comprising" and
variations thereof as used herein is used synonymously with the term
"including" and
variations thereof and are open, non-limiting terms. Although the terms
"comprising" and
"including" have been used herein to describe various embodiments, the terms
"consisting
essentially of" and "consisting of' can be used in place of "comprising" and
"including" to
provide for more specific embodiments and are also disclosed.
