WO1999002046A1

WO1999002046A1 - Flavor enhancement process

Info

Publication number: WO1999002046A1
Application number: PCT/US1998/014116
Authority: WO
Inventors: Henry B. Schur
Original assignee: Individual
Current assignee: Individual
Priority date: 1997-07-08
Filing date: 1998-07-08
Publication date: 1999-01-21
Anticipated expiration: 2000-01-08
Also published as: AU8657798A

Abstract

The invention relates to the modification of flavorants by reaction of mers in the presence of flavorants to form products having significantly increased molecular weight.

Description

FLAVOR ENHANCEMENT PROCESS Field of the Invention

The present invention relates to the modification of flavorants by reaction of mers, i.e., a monomer, prepolymer and/or polymer (including mixtures of the foregoing) , in the presence of flavorants to form products of significantly increased molecular weight. Preferably, the invention relates to reactions of mers in the presence of flavorants in liquid systems to form products of substantially increased molecular weight, in which products the flavorants are distributed for performing their characteristic functions in a host medium outside the reaction product. Background of the Invention

Flavorants are any of a wide variety of materials which perform useful functions by distributing themselves via physical and/or chemical transport mechanisms, such as diffusion, evaporation of the like, throughout a host medium, such as a gas, liquid, solid or combination thereof. Some examples of flavorant materials which find wide use in industrial, commercial, domestic and medical applications are disinfectants, foods, pharmaceuticals, flavors, insecticides, insect repellents, cleansing and cleaning materials, preservatives, emollients, exipients, stabilizers, dyes, diluents, lotions, inhalants, fungicides, air fresheners, anti-static agents, corrosion inhibitors, fertilizer, enzymes, poisons and lures.

Also, this technology could achieve wider commercial utilization of it could be performed more economically with more effective and controllable polymer inclusion. Optionally, the technology could achieve wider utilization of it could be successfully applied to water-soluble of hydrophilic water- insoluble flavorants. Summary of the Invention

The present invention is a method of modifying a flavorant comprising forming a liquid system including a solution of a mer with a flavorant, reacting the mer in the presence of the flavorant in a portion of the liquid system which contains substantial amounts of both mer and flavorant for significantly increasing the molecular weight of the mer under conditions which substantially preserve at least one useful flavorant function of the flavorant, continuing the reaction under such conditions to a sufficient extent for substantially reducing the diffusion rate, volatility flammability, toxicity or susceptibility to oxidation or other form of environmental attack upon the flavorant, and recovering a product of reaction of said mer substantially without rearrangement the liquid system into separate phases and substantially without encapsulation of the flavorant and having a consistency ranging from a liquid to a non-self-supporting soft gel, from which product the flavorant may escape for performing its flavorant function in or on a host medium outside the reaction product. Products produced according to the foregoing method are also part of the invention.

Moreover, the invention includes certain further improvements, all of which can be used singly or in any operative combination in or with the above-described methods and products of the present invention. These further improvements are discussed below under the heading "Detailed Description of Preferred Embodiments". Among them are a number of particularly preferred embodiments of the invention, including recovery of the product of reaction as a liquid.

In the practice of the invention, the flavorant may include a flavor, pesticide, repellant, cleansing or cleaning material, preservative, emollient, excipient, stabilizer, dye diluent, lotion, anti-static agent, corrosion inhibitor fertilizer, enzyme or lure.

Among the applicable mers are polyvinylpyrrolidone, a cyclodextrin, algin, chitin or a monomer or derivative of any of them. Polyvinylpyrrolidone, is the preferred mer, especially with a molecular weight in the range of about 5,000 to about 200,000 and more preferably about 7,000 to about 160,000. A preferred cyclodextrin is betacyclodextrin having a molecular weight of at least about 1,000. Where the mer includes algin, the preferred reaction product includes an alginate. Chitosan is a preferred chitin derivative.

Valuable products can be produced by applying the reaction product of the method to a substrate, and the invention therefore includes the corresponding products.

The invention provides the opportunity for obtaining one or more of the following advantages with respect to the performance of the flavorant in its end-use application(s) , including, for example, reduction of diffusion rate, volatility, flammability, toxicity, and oxidation or other environmental attack. With certain flavorants, the invention provides opportunities for providing or enhancing one or more of the following properties in the resultant product, including longevity of the action of the flavorant, gloss, moldability, resiliency and miscibility with certain liquids. Because certain flavorants are not readily convertible to gel-form by other means, the invention opens up new applications for certain of these flavorants.

Since certain embodiments of the invention can be performed at room temperature and do not require major alterations of the pH in the liquid system, they can, where necessary or desirable, be readily applied to a wide variety of temperature- and pH- sensitive flavorants. Detailed Description of Preferred Embodiments

The present invention can be embodied in a wide variety of forms, some of which will be described below. According to the invention a reaction is conducted in a liquid system which comprises, or consists essentially of, or consists of, a mer and a flavorant and other liquid or non-liquid ingredients useful in forming certain reaction products. Specific examples of the process materials and descriptions of how to form the liquid system, conduct the reaction, recover the resultant reaction products and apply them industrially are set forth below. Flavorant

As indicated above, flavorants are materials which perform useful functions by distributing themselves via physical and/or chemical transport mechanisms, such as diffusion, evaporation or the like, throughout a host medium, such as a gas, liquid, solid or combination thereof . The desired materials have utility in performing a flavorant function in a host medium outside the reaction product. Thus, instead of treating the reaction product, the flavorant is transported into and treats or otherwise acts upon something in an adjoining or surrounding host medium, including the host medium itself.

Preferred categories of flavorants include flavors, medicaments and pesticides.

Useful flavors include for example those based on aldehydes, ketones or alcohols. Examples of aldehyde flavors include: acetaldehyde (apple) ; benzaldehyde (cherry, almond) ; anisic aldehyde (licorice, anise) ; cinnamic aldehyde (cinnamon) ; citral, i.e., alpha citral (lemon, lime); neral, i.e., beta citral (lemon, lime) ; decanal (orange, lemon) ; ethyl vanillin (vanilla, cream); heliotropine, i.e., piperonal (vanilla, cream); vanillin (vanilla, cream) ; a-amyl cinnamaldehyde (spicy fruity flavors) ; butyraldehyde (butter, cheese); valeraldehyde (butter, cheese); citronellal (modifies, many types) ; decenal (citrus fruits) ; aldehyde C-8 (citrus fruits) ; aldehyde C-9 (citrus fruits) ; aldehyde C-12 (citrus fruits) ; 2-ethyl butyraldehyde (berry fruits); hexenal, i.e., trans-2 (berry fruits); tolyl aldehyde (cherry, almond) ; veratraldehyde (vanilla) ; 2-6-dimethyl-5- heptenal, i.e., Melonal^t (melon); 2 , 6-dimethyloctanal (green fruit) ; and, 2-dodecenal (citrus, mandarin) . Examples of ketone flavors include: d-carvone (caraway) ; 1-carvone (spearmint) ; diacetyl (butter, cheese, "cream") ; benzophenone (fruity and spicy flavors, vanilla); methyl ethyl ketone (berry fruits); maltol (berry fruits) menthone (mints) , methyl amyl ketone, ethyl butyl ketone, dipropyl ketone, methyl hexyl ketone, ethyl amyl ketone (berry fruits, stone fruits) ; pyruvic acid (smokey, nutty flavors) ; acetanisole (hawthorn heliotrope) ; dihydrocarvone (spearmint) ; 2 , 4-dimethylacetophenone (peppermint) ; 1, 3-diphenyl- 2-propanone (almond); acetocumene (orris and basil, spicy); isojasmone (jasmine) ; d-isomethylionone (orris like, violet) ; isobutyl acetoacetate (brandy-like) ; zingerone (ginger) ; pulegone (peppermint-camphor) ; d-piperitone (minty) ; and 2-nonanone (rose and tea-like) .

Example of alcohol flavor include anisic alcohol or p- methoxybenzyl alcohol (fruit, peach) ; benzyl alcohol (fruity) ; carvacrol or 2-p-cymenol (pungent warm odor) ; carveol; cinnamyl alcohol (floral odor) ; citronellol (rose like) ; decanol; dihydrocarveol (spicy, peppery); tetrahydrogeraniol or 3,7- dimethyl-l-octanol (rose odor) ; eugenol (clove) ; and, p-mentha- l,8dien-7-0 or perillyl alcohol (floral-pine).

It should be understood that any of the flavorants, when they are incorporated into the liquid system, may be in the form of a precursor or derivative of the flavorant which can be converted or activated to perform its flavorant function at a later time, and the term flavorant should therefore be understood to include such precursors or derivatives. To illustrate, the flavorant may be converted or activated prior to or during the reaction herein, during use of a composition containing the reaction product or over a period of time that such a composition is in use. For example, the useful flavors include flavor acetals and flavor ketals which are converted by hydrolysis during use to corresponding alcoholic, aldehydic or ketonic flavor compounds as illustrated in United States Patents No. 3,140,184 to Robbins, issued July 7, 1964 and assigned on its face to General Foods Corporation, and No. 3,857,964 to Yolles, issued December 31, 1974 and assigned on its face (in part) to David E. Brook, as well as further publications listed in said patents, all of which are incorporated herein by reference.

The flavorant in its pure state may for example be a solid or a liquid under standard conditions of temperature (20°C) and pressure (1 standard atmosphere) . Solid materials should be convertible to liquid form, such as by melting or dissolving in a solvent. Liquid flavorants are particularly preferred for use in the invention.

One may employ any of the above-mentioned kinds of flavorants and others, provided the flavorants do not interfere with the reaction to the point of destroying its usefulness. The reaction employed herein is one which includes reaction of molecules of mer with other mer molecules and/or with other material present in the liquid system. Depending upon its chemistry, the flavorant may or may not participate chemically in the reaction, but it does participate in the reaction at least in the physical sense of becoming intimately distributed among or in the mer and/or mer molecules as the reaction proceeds. Mer

According to the invention, a synthetic or natural mer, that is a monomer, prepolymer and/or polymer (including mixtures of the foregoing) , is included or distributed in a liquid system comprising a flavorant (including mixtures thereof) and is reacted in the liquid system in such a manner as to significantly increase the molecular weight of the mer in the liquid system. Thus, the suitable mers are those which are capable of undergoing (with the aid of catalysts, promoters and/or other additives as required) significant increases in molecular weight in a liquid system comprising a selected flavorant. The liquid system may, for example, be a flavorant which is itself a liquid, or the flavorant may be distributed in a liquid, such as by solution. Preferably, the mer is reacted while dissolved in the liquid system, for example in the flavorant itself.

The mer can be a single material, such as a polyhydroxy polymer that complexes with the flavorant or a monomer which forms a homopolymer. However as employed herein, the singular term "mer" also refers to combinations of materials which perform the mer function. Thus, a mer may be composed of a blend of two materials that are each individually reactive, i.e., they will each react in the desired manner without the other, but the blend is useful for one or more reasons, such as contributing a particularly desired combination of physical and/or chemical properties to the resultant product. On the other hand, the mer may involve a combination of two or more dependent reactants, such as a monomer and co-monomer which react by copolymerization. Other applicable combinations include a polymer and an accompanying organic or inorganic cross -linker, coupler or coagulant.

Among the many mers which may be selected for use in the invention may be either natural or synthetic substances and include, without limitation, polyhydroxy compounds, acrylic resins, amides, and alkenyl aromatic monomers.

Examples of polyhydroxy compounds, which are preferred mers, include, without limitation, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, algin, agar, chitin derivatives, dextrose, cyclodextrin, cellulose and its derivatives and starch and its derivatives. Typical of the cellulose derivatives are methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellose, and carbomethyl cellose. Typical starch derivatives are amylose, amylopectin, glycogen, methyl starch and hydroxyethyl starch.

Examples of monomers of the acrylic resin type include, without limitation, the hydroxy lower alkyl acrylates and hydroxy lower alkyl methacrylates such as 2-hydroxyethyl acrylate, 2- hydroxy-propyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylene methacrylate, diethylene glycol onomethacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy-propyl methacrylate and dipropylene glycol monomethacrylate.

Cross-linking agents which may be used with the hydroxy lower alkyl acrylates and hydroxy lower alkyl methacrylates include without limitation ethylene glycol diacrylate, propyleneglycol diacrylate, ethylene glycol dimethacrylate, 1,2- butylene dimethacrylate, 1-3-butylene dimethacrylate, 1,4- butylene dimethacrylate, and propylene glycol dimethacrylate.

A large number of other acrylates and methacrylates which are useful in the present invention are disclosed in U.S. Patent No. 4,310,397 to Kaetsu et al on January 12, 1982 and assigned on its face to Japan Atomic Energy Research Institute, and the disclosure of polymerizerable monomers and other materials in Kaetsu et al is hereby incorporated by reference.

Example of amides which may be used include acrylamide, n- methylacrylamide, n-isopropyl ethacrylamide, n-methyl methacrylamide, n-12-hydroxyethyl acrylamide and n-(2- hydroxyethyl methacrylamide) . Various cross-linkers may be used with the polyamides, such as N,N methylene-bis-acrylamide, various persulfates and others. The acrylamides may also be cross-linked by irradiation with UV light.

Examples of alkenyl aromatic monomers include styrene, o-, m- and p-methylstyrene , ethyl sytrene, o-chlorostyrene, vinylbenxyl chloride and p-tert-butyl styrene.

Examples of additional useful mers include 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, vinylidene chloride acrylonitrile, vinyl acetate, divinyl benzene, butadiene, chloroprene, isoprene, itaconic acid, acrylonitrile, and acrylamides.

Example of useful copolymers include, without limitation aromatic diisocyanates together with mono- or dialkanolamines . Typical diisocyanates include 2 , 6-toluenediisocyanate, 4,4- diphenyldiisocyanate, and diphenylmethane diisocyanate. Typically useful alkanolamines for copolymerization with the diisocyanates include monoethanolamine, monoisopropanolamine, and cyclohexylethanolamine.

Particularly preferred mers include the polymers described as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, vinyl a ine copolymer, algin, agar, chitin, dextrans, cyclodextrins (cyclodextrin compounds, especially β- cyclodextrin) , and cellulose, including the monomers and the derivatives of all of the foregoing. Other suitable mers may also be employed.

The most preferred mers at present are polyvinylpyrrolidone, alginates and chitosan, but j3-cyclodextrin is also believed to be of substantial interest. Polyvinylpyrrolidone, its chemical and physical propertied and its methods of manufacture and uses are described in Chapter 21 of the "Handbook of Water-Soluble Gums and Resins" by Robert L. Davidson, copyright 1980 by McGraw-Hall, Inc. , which is incorporated herein by reference. Algin, its sources, manufacture, structure, other properties and uses are described in a brochure entitled "Algin/Hydrophilic Derivatives of Alginic Acid for Scientific Water Control" by Kelco Division of Merck and Co., Inc., second edition, the contents of which are incorporated herein by reference. For information on cyclodextrins, see "Celdex (Cyclodextrins) " , a publication of Nihon Shokuhin Kako Co., Ltd. (13 pages), the contents of which are incorporated herein by reference. Also incorporated herein by reference is an article entitled "Entrapment of Microbial Cells in Chitosan", by K.D. Vorlop and J. Klein of the Institute of Technical Chemistry, T.U. Braunschweig, Hans Summer-Strausser 10, 330 Braunschweig, FRG, which describes chitosan, its properties and uses, as well as additional literature containing information in chitosan.

The mer currently considered best is polyvinylpyrrolidine. While the use of polyvinylpyrrolidone and its derivatives with average molecular weights in the range of about 5,000 to about 1,000,000 is contemplated, including quaternized polyvinylpyrrolidone with average molecular weights in the range of about 50,000 to about 1,000,000, best results have been obtained to date with an unmodified polyvinylpyrrolidone having an average molecular weight in the range of about 5,000 to about 200,000, and more preferably in the range of about 7,000 to about 160,000 with an average molecular weight of about 10,000 having produced the best results. This particular polymer can be readily dissolved in a wide variety if essential oils and reacted to yield products that can be readily used in a manner further described below. Liquid System One of the basic characteristics of the liquid system is that it constitutes a substantially homogeneous liquid mixture of liquid, and in certain circumstances non-liquid, components. The mer and flavorant, which are liquid components of this mixture, are present in forms which are substantially compatible and preferably substantially miscible with one another, most preferably constituting substantially a single phase as distinguished from an emulsion or mere mechanical dispersion. More particularly, it is preferable that the mer and flavorant constitute a solution, which in the present invention includes sols and true solutions. While substantially complete solution is preferred, it is contemplated that in certain circumstances a portion including preferably the bulk or major weight portion of the mer may be dissolved to the point of disappearance into the liquid system while a minor portion thereof may be in microscopically observable colloidal "solution" or suspension.

As previously indicated, liquid flavorants (e.g. , essential oils are preferred, and it is most preferred that the mer be dissolved in the flavorant in the liquid system. However, for those mers and flavorants which are not mutually soluble the preferred procedure involves a liquid system which is usually but not necessarily a solvent solution of the flavorant. Alternatively, the flavorant may be introduced into a solvent solution of the mer. Such solvent-based liquid systems are preferably based in solvent (including solvent mixtures) that is a co-solvent for mer and flavorant and which may be polar or non- polar, aqueous or hydrophobic, organic or inorganic, using stirring and solubility aids as necessary.

The present invention makes possible the production of controlled release flavorant concentrated which exhibit a high degree of uniformity from batch to batch and are, therefore, usable as intermediates, dependable blending components, for production of end products having lower overall concentrations of flavorant. In the liquid systems used to prepare such concentrated, the flavorant is present at a high weight concentration as compared to normal average concentrations in the end products, For example, in many food and beverage products, flavor essential oils are present on concentrations typically below about 1% or even below 0.1% by weight. In some polymer/perfume combinations used in products having severe deodorant requirements (e.g., animal litter), equal parts of olfactant and polymer have been used to impart a final olfactant/litter substrate ratio (solvent free basis) of about

1.25%, while the weight ratio of solvent - polymer - olfactant in the litter impregnating solutions have for example been 90:5:5.

However, in personal embodiments of the present invention, the weight percentage of flavorant in the liquid system, based on the weight of flavorant, mer and any solvent which may be present, is generally substantially above 5% typically about 10% or more and most preferably about 20% or more, with about 50% or more where possible and the use of uncut essential oils being considered best. Also, it is preferred that the weight of flavorant

(solvent free basis) exceed the weight of mer (solvent free basis) included in the liquid system; for example flavorant to mer weight ratios (solvent free basis) of about 1.05 or more, typically about 1.3 or more and frequently about 1.5 or about 2 or more are contemplated. For further discussion of principles for selecting proportions of mer and flavorant, see under the heading " Reaction", below.

While the flavorant and mer are essential ingredients of the liquid system, it may contain other ingredients, including components which are and are not chemically active in the reaction or final product. Included are additives which catalyze or promote polymerization and/or plasticize the resultant product, such as glycerol, carboxymethylcellulose, diethyl phthalate, sorbitol, tannic acid, persulfates, multivalent (preferably divalent) metal salts such as calcium, barium, aluminum, iron and the like, polyphosphates and other materials with similar utilities, as well as solvents, agents for adjusting or otherwise controlling the particle size of the reaction product, surfactants, bentonite, PEG, carbopols and other modifiers and additives.

Where the final product is intended for pharmaceutical use, or for ingestion as a foodstuff, or for use in a product constituting an indirect food additive, it may be necessary or desirable to use only ingredients which are USP listed or have GRAS status, and it is an advantage of the invention that it can be readily performed with such ingredients, whereby the products will be useful in the pharmaceutical, cosmetic and food industries.

The liquid system should be pourable at specified temperatures and pressures. The herein described reaction can be conducted at temperatures of about 60°C or less, and the liquid system should therefore constitute a pourable liquid at temperatures of about 60°C or below, more preferably about 50°C or below, and still more preferably at about 40°C or below. However, those liquid systems which are pourable at about room temperature (e.g. , 20°C) are particularly preferred. The foregoing temperatures are assumed to correspond with standard atmospheric pressure or with the vapor pressure of the liquid system, whichever is greater.

Consistent with the manner in which the reaction is to be conducted, the liquid system should be formulated for stability. More specifically, the liquid system should be stable, in the face of the reaction, the foregoing temperatures and such agitation as may be necessary, against coagulation, stratification and such other forms of undesired deterioration as may seriously interfere with performance of the process.

Given the present disclosure and the working examples set forth below, persons skilled in the art will readily select appropriate flavorants and mers to use in combination, based on experience or simple experiments. The identities of the materials and the relative proportions can both be selected in the foregoing manner and will be governed in par by the intended end-use of the product, with due regard as to whether it must be soluble or insoluble in a given solvent, whether it must be biologically safe, whether it will be a final product or an intermediate of another process or product, whether product life is a consideration, whether the volatility of the final product is important and to what degree, and whether the flavorant includes a fragrance whose scent must be faithfully reproduced in the final product. In the last-mentioned circumstances the mer and other non-fragrance materials are preferably selected to be substantially odor-free when reacted, and preferably also when in their unreacted state.

In the preparation of the liquid system, where one or more of its components is (are) solid material(s), it may be of assistance to grind either or both of them to a fine particle size before attempting to form the above described homogeneous mixture. Thus, for example, solid mer may be ground before being dissolved in liquid flavorant. Solid flavorant may be ground before being mixed with liquid mer. Solid mer and flavorant may both be ground to fine particle size and either premised dry for simultaneous solution in a co-solvent or may be dissolved sequentially. Sequential solution with the mer being added to liquid flavorant or flavorant solution is preferred and where possible it is preferred that the mer be dissolved directly in substantially undiluted flavorant. Mixing with gentle to moderate but not excessive agitation may be applied to fully dissolve the mer and flavorant. Extended mixing is some times necessary, e.g., 24 - 48 hours. Gentle heating may be used when necessary. These steps set the stage for conducting the desired reaction. Reaction

In general, the reaction contemplated by the present invention is a reaction of mer in the presence of flavorant with participation of the flavorant either chemically or at least in the sense of becoming intimately distributed among or in the mer and/or resultant polymer molecules as the reaction proceeds, including a significant increase in the molecular weight of the mer.

Thus , the reaction may be any chemical change which results in a significant increase in the molecular weight of the mer accompanied by a substantial reduction in the diffusion rate, volatility, flammability, toxicity or susceptibility to oxidation or other form of environmental attack, on the part of the flavorant. Among the contemplated reactions are:

Polymerization - forming chain-like (including branched) macro-molecules which are the result of combining many small molecules (i.e., monomers), including homo- and co-polymerization.

Crosslinking - forming inter-connected macro-molecular chains which are the result of: opening bonds (which may include opening rings) along and intermediate the ends of adjacent chains of 2 (or more) similar or dissimilar macro-molecules and connecting those bonds with one another- to connect the chains together. opening bonds (which may include opening rings) along and intermediate the ends of adjacent chains of 2 (or more) similar or dissimilar macro-molecules and connecting those bonds through the residue of a different molecule of low, medium or high molecular weight acting as a cross-linking agent, forming ionic bonds along and intermediate the ends of adjacent chains of two or more similar or dissimilar macro-molecules; see C.F. Vorlop et al, supra, page 2; see also "ionomer resins" in Condensed Chemical Dictionary, 10th Edition, Van Nostrand Reinhold Company, New York, 1981, page 568) . (include para. page 6, line 11 of existing case). Grafting - enlarging polymeric species by adding pendant side chains to a backbone polymer.

Coupling - forming macro-molecules by end-coupling two or more large molecule (e.g. , prepolymer) building blocks to each other directly or through a coupling agent in a linear or branched arrangement. Complexing - forming or enlarging molecules by combining them with other molecules (and optionally also with themselves) in a form of association which does not involve strong chemical bonding, including for example clathrating, hydrogen bonding and/or formation of adducts, inclusion compounds or inclusion complexes in which guest molecules are incorporated in receptacles in the structures of host molecules, and forms of association based on electrostatic and ionic charges.

The significant molecular weight increase employed in the present invention is in general an increase which sufficiently provides or enhances at least one beneficial characteristic of the flavorant and/or its performance in its end-use (s) to have practical application(s) . Examples of such beneficial characteristics are set forth herein in the discussions of advantages and uses of the invention under the headings Summary of the Invention and Industrial Applicability. It appears that increases in the molecular weight of the mer which are very small in numerical terms can be useful for particular flavorant applications, such as about one, two, three or five percent of more, ranging upwards to about fifty percent or more, based on the molecular weight of the mer prior to the reaction. Thus, the molecular weight increase may appear significant or insignificant in purely mathematical terms, but should be significant in terms of its effect (s) on one or more characteristics of the flavorant and/or its performance.

The course of the reaction and the nature of the reaction product can be controlled by making appropriate selections of proportions of mer and flavorant in the liquid system. Subject to the requirement of conducting the reaction in order to substantially preserve at least one flavorant function of the flavorant, the concentration of mer in the liquid system can be up to about the maximum amount of mer that is soluble in the liquid system or in the flavorant, but lesser amounts are preferred.

For example, relatively low mer concentrations may be preferred for certain applications, especially in the manufacture of long lasting medicaments, perfumes and similar personal care products in which an excessive amount of reacted mer might introduce excessive tackiness into the resultant reaction product, leading to an unpleasant "feel" when the reaction product is used as perfume. It has been found for instance that a concentration of about 0.1 to about 2 percent by weight of mer based on the weight of mer plus flavorant is quite adequate and effective for such applications.

On the other hand, relatively high mer concentrations will be preferred for certain flavor/food/medicament applications and in olfactant applications where tack or at least higher polymer loadings are useful. In such cases, it may be found desirable to employ an amount of mer sufficient to bind or complex the majority, preferably about 60 percent or more, more preferably about 80 percent or more and still more preferably substantially all of the flavorant, on a weight basis.

One convenient measure of relative proportions of reacted mer and fragrance in the reaction product in liquid, gel-type and paste-like compositions is the ratio of the weight of polymer, in grams, to the volume of the essential oil (uncut basis) in milliliters, expressed as a percentage. Useful products may for example be prepared in the range of about two or three to about eighty percent, and more preferably about eight to about thirty percent, with about fifteen percent being best for producing gels for encapsulation. By way of example, with the preferred mers described above, one can produce a variety of products ranging from longer - to very-long - lasting liquid fragrances for use as personal perfume or in aerosol air fresheners at a level of about two or three to about eight percent, liquid through gel-type products with particularly good fragrance retention properties for encapsulation within a sub-range of about eight to about thirty percent, and continuing up to exceptionally long-lasting pseudo-solid fragrances for applications such as shopping bag inserts at a level of about thirty to about eighty percent. The polymer to fragrance ratio may thus be varied to select the desired physical form and longevity of the fragrance.

Likewise, with respect to reaction products of mers and medicaments, a convenient measure of relative proportions of reacted mer and medicament in the reaction product in liquid, gel-type and paste-like compositions is the ratio of the weight of the medicament to the weight of polymer (solvent-free basis) expressed as a percentage. Useful products may for example be prepared in the range of about two or three to about eighty percent, and more preferably about eight to about thirty percent, with about fifteen percent being best for producing gels for encapsulation. By way of example, with the preferred mers described above, one can produce a variety of products ranging from longer - to very-long - lasting liquid medicaments at a level of about two or three to about eight percent, liquid through gel-type products with particularly good medicament retention properties for encapsulation within a sub-range of about eight to about thirty percent, and continuing up to exceptionally long-lasting pseudo-solid fragrances for applications such as shopping bag inserts at a level of about thirty to about eighty percent. The polymer to medicament ratio may thus be varied to select the desired physical form and longevity of the medicament.

It has been found for instance that a concentration of about 0.05 to about 5% by weight of flavor based on the weight of mer plus flavorant is quite adequate and effective for such applications .

On the other hand, relatively high mer concentrations will be preferred for certain flavor/food/medicament application s where tack or at least higher polymer loadings are useful. In such cases, it may be found desirable to employ an amount of mer sufficient to bind or complex the majority, preferably about 60 percent or more, more preferably about 80 percent or more and still more preferably substantially all of the flavorant, on a weight basis.

One convenient measure of relative proportions of mer and flavor in the reaction product in liquid, gel-type and paste-like compositions is the ratio of the volume of the essential oil(s) (uncut basis) , in milliliters, to the weight of polymer, in grams, expressed as a percentage. Useful products may for example be prepared in the range of about 0.05 or 0.5 to about 80%, and more preferably about 0.1 to about 5%, with about 0.5% being best for producing gels for edible strips. By way of example, with the preferred mers described above, one can produce a variety of products ranging from longer - to very-long - lasting liquid flavors for use as edible samplers or in drug delivery systems at a level of about 0.5 or 2 to about 10%, liquid through gel-type products with particularly good flavor retention properties for encapsulation within a sub-range of about 0.5 to about 30%, and continuing up to exceptionally long- lasting pseudo-solid flavors for applications such as shopping bag inserts at a level of about 30 to about 80%. The polymer to flavor ratio may thus be varied to select the desired physical form and longevity of the fragrance.

With particularly reactive mer combinations, the reaction may be commenced merely by combining and mixing the ingredients. However, as indicated above, initiators, catalysts, promoters and other reaction aids can be useful in practicing the invention. It has been found that the order of addition of such reaction aids can be varied. Preferably, modifiers, reaction aids and other additives are added to a mixture formed by mixing the mer thoroughly and very uniformly with the flavorant, preferably for a few or even many hours. See the examples set out below. However, the afore-mentioned mixture can also be added to the catalyst, such as to a liquid system containing the catalyst in solution. If plasticizers are used, they can be added slowly with constant stirring to the afore-mentioned mixture. In certain instances, addition of plasticizer will initiate or at least promote polymerization. Generally, agitation is continued during the reaction until the desired final product is obtained. However, agitation sufficiently vigorous to emulsify the contents of the liquid system should be avoided.

With certain mers and other reactants, the reaction will proceed readily with extended stirring at room temperature. Although the process clearly is not limited to room temperature operations, it is a particular advantage of the invention that it can be performed at room temperature and at temperatures of about 60°C or less, preferably about 50°C or less and still more preferably about 40°C or less, thereby permitting the use of temperature sensitive materials, including fragrances and other flavorants which are temperature sensitive, in the product.

Depending on the characteristics of the flavorant, it may be desirable to provide it with partial or complete protection from atmospheric, air, such as by using a sealed reactor or mixing under vacuum or an inert atmosphere. Superatmospheric pressure or vacuum may also be employed to control particle size in those circumstances where the reaction is conducted to produce a particulate product.

Similarly, although the process is not limited to substantially neutral conditions, e.g., a pH of about 6 to about 8 or about 6.5 to about 7.5, it is an advantage of the invention that at least certain of its embodiments can be carried out within one or both of these ranges, thus making it possible to readily entrap pH sensitive materials in the resultant reaction product.

The process can be conducted in such a manner that it is compatible with biologically sensitive materials, and such materials can be incorporated into various forms of reaction product. When using biological materials it may be necessary to take precautions to protect such materials from contamination and degradation.

The progress of the reaction may be monitored in any suitable manner. For example, viscosity and/or preferably specific gravity measurements can be used. In general, other conditions remaining the same, increasing viscosity and/or specific gravity signifies increasing molecular weight of the mer in the liquid system.

The minimum acceptable proportion of mer to flavorant and the minimum acceptable extent of reaction for any mer/flavorant combination will be that proportion and that extent of reaction which are sufficient to cause the reaction to proceed and to cause a substantial reduction in the diffusion rate, or volatility, or flammability, or toxicity or susceptibility to oxidation or other form of environmental attack, upon the flavorant. Persons skilled in the art can ascertain appropriate proportions and minimum extent of reaction for the potentially useful mer/flavorant combinations with the aid of simple experiments guided by the discussion which follows.

In general, the quantity of mer and extent of reaction should be sufficient to provide in the resultant reaction product an average molecular wight of about 1,000 or more. For example, some of the lower molecular weight cyclodextrins have an average molecular weight of about 1,000. More commonly, the reaction product will have an average molecular weight of about 2,000 or more. Preferred are "high" polymers, meaning macro-molecules having an average molecular weight of about 5,000 or about 6,000, such as for instance cellulosic polymers. Algin has been described as a natural high polymer. More preferred are those reaction products having an average molecular weight of about 7,000 or more, for example those based on polyvinylpyrrolidone, the polyvinylpyrrolidone/flavorant reaction product that is presently most preferred having an average molecular weight above about 10,000.

There is no fixed upper limit on the molecular weight range and average molecular weight of the reaction product, except that these molecular weight properties of the reaction product should be limited, in relation to the quantity and structure of the reaction product, for preserving at least one useful flavorant function of the flavorant and for providing acceptable levels of viscosity, flavorant volatility suppression, water/oil solubility, tack (if any) and other properties that may be desired in the final product.

In general, with increasing and decreasing average molecular weight and with increasing and decreasing relative abundance of branching, ring structures and polar functional groups in the molecular structure of the reaction product, the viscosity of the reaction product respectively increases and decreases. Thus, polymeric species containing relatively high proportions of hydroxyl groups per unit average molecular weight will in general produce reaction products of higher viscosity than species with lower proportions.

Those factors which tend to produce increased viscosity are also believed to suppress flavorant volatility and diffusion rate. Thus, given a polymeric specie having a predetermined degree of branching and a particular proportion of specified functional groups in its molecular structure, increasing or decreasing the average molecular weight will generally be expected to increase or decrease flavorant volatility and diffusion rates.

In general, increasing the average molecular weight and the relative proportions of branching and ring structures will tend to increase the oil solubility and reduce the water solubility of the reaction product and vice versa. Contrariwise, increasing the quantity of strong polar groups, especially carboxyl and/or hydroxyl groups, tends to increase water solubility while diminishing oil solubility.

If substantial tack would be objectionable in the final product, which could be the case in reaction product used in formulating personal perfume, then the quantity of mer and/or extent of reaction should be limited. By way of illustration, a substantial prolongation of the fragrance effects of an essential oil for personal perfume can be obtained with only about 0.75% of mer based on fragrance oil; but in the preparation of a paper coating in which tack is desirable the amount of mer can for example be about 33% based on fragrance oil.

With the aid of these explanations and information known to skilled polymer chemists, persons skilled in the art should have no difficulty selecting suitable proportions of mer and flavorant and a suitable extent of reaction that will preserve the extended function of the flavorant while meeting the basic requirement of sufficient proportions and sufficient reaction described above. One may select mers, modifiers and polymerization conditions to form polymeric reaction products that are soluble or insoluble in selected solvents such as water and/or alcohols. The liquid system can be polymerized to form reaction products characterized by a variety of physical properties, including the full range of viscosities of liquids that are pourable. In certain embodiments the range of products may include those ranging in viscosity from pourable liquids through soft gels. Thus, the reaction may be terminated while the liquid system is still substantially liquid or when it has progressed to a non-shape retaining soft gel, i.e., a gel which when formed into a 2 inch unreinforced and unsupported homogenous cube, does not spread more than 20% linearly in any dimension upon standing for 8 hours at about standard atmospheric pressure at 20°C. In those instances in which relative humidity is deemed to have an influence on the performance of the sample, a relative humidity of 50% is assumed. Industrial Applicability

The reaction products thus formed are useful as ingredients in controlled release compositions in which the flavorant is used for performing a flavorant function in a host medium outside the reaction product. In this connection, the flavorant may constitute either the main active ingredient or an auxiliary component of the composition. In general, utilization of the reaction product in such compositions will tend to stabilize the flavorant and/or enhance its effect in one or more of the ways described below and/or change the properties of the flavorant in a way that makes it more useful.

For example, in may instances the formation of the reaction product will be found to reduce the differential diffusion of component parts of flavorants containing multiple components. This can be useful in lengthening the shelf life of the composition by preserving the entire composition for a longer period of time.

In compositions containing flavorants which do not have components which exhibit differential diffusion tendencies, incorporation of the reaction product in the composition will be found to reduce the overall diffusion rate of the flavorant as compared to otherwise similar compositions containing the unreacted flavorant. Here again, shelf life can be increased and absorption of the product into packaging can also be reduced. A reduction in overall diffusion rate can also impart more longevity to the composition while it is in use. An additional potential benefit is reducing wastage of the flavorant, enabling its diffusion rate to be matched to the need for the flavorant in the host medium into which it is released.

As flavorants diffuse, they typically display a rate of diffusion which decays rapidly and then more slowly as diffusion of the flavorant continues. Another of the potential benefits of the invention is that it can reduce the decay rate of the diffusion process, making possible a higher rate of diffusion during the later stages of the life of the controlled release composition.

One of the other potential stabilization benefits of incorporating these reaction products into controlled release compositions is safeguarding the flavorant against unwanted chemical change. This is useful, for example, where the manufacturing process for the composition tends to adversely affect the flavorant. Where the composition is a bread or cookie dough and the flavorant is a flavor to be incorporated in such dough prior to baking, substituting a er/flavor reaction product can retard chemical change in the flavor during baking. Where the composition is a packaging material and the flavorant is a olfactant, formation of a mer/olfactant reaction product and incorporation of that product into the packaging material can reduce the tendency for chemical change in the olfactant during hot processing of the packaging material. Also, formation of the reaction product can slow or stop environmental attack upon the flavorant by oxygen, water vapor, carbon dioxide, carbon monoxide, nitrogen and other environmental factors.

The advantage of enhancement of flavorant effect follows from the manner in which formation of the reaction product affects diffusion of the flavorant. Because of this stabilization, the same amount of flavorant can be made more potent (available in a higher concentration) at a given time interval after initial application of the composition. This can in turn lead to the further benefit that fewer applications of the composition may be required. As indicated above, formation of the reaction product can make the flavorant more useful in controlled release compositions, such as by making the flavorant available in altered forms. Potential physical improvements include increased viscosity, changing normally liquid materials into solids, increasing the iscibility of flavorants with other ingredients of controlled release compositions, increasing the gloss and moldability of the flavorant or increasing its resilience. Potential chemical changes which can be affected by converting the flavorant to a mer/flavorant reaction product include reducing the reactivity or toxicity of the flavorant. In other cases side effects can be controlled.

The product recovered from the above-described reaction may be ready for use, i.e., may be used in exactly the same form in which it is recovered from the reaction. On the other hand, many of the uses of the reaction product will involve its further modification prior to use, including changes in physical form, combining the reaction product with other materials, encapsulation and application to various substrates. For example, the viscosity of liquid reaction products may be adjusted to higher or lower levels and they may be converted into gels or incorporated, such as by absorption, into solid products. Moreover liquid or gel type products may be dispersed or emulsified in compatible and incompatible liquids. Gels may be converted to solids or liquids and solids may be converted to gels or liquids by heating and/or solvent action.

The reaction products may be treated, as necessary or desirable, with appropriate coupling or cross-linking agents, which may be applied for example during or subsequent to the reaction of the present invention. For example, certain types of irradiation will cause polyvinylpyrrolidone to cross-link with itself. After a reaction product is formed between a flavorant and either a soluble alginate or chitosan, the alginate or chitosan moieties in the reaction product may be coupled or cross-linked with suitable reagents. Exemplary reagents for the alginates include multivalent (preferably divalent) metal salts such as calcium, barium, aluminum, iron and the like. Exemplary reagents for chitosan are polyphosphates and others described by Varlop et al, supra. For example, after a biopolymer, such as alginate or chitosan, has been reacted with the flavorant in a liquid system in which the biopolymer is dissolved, the resultant reaction product can then be formed into droplets in a suitable solution containing the coupling or cross-linking reagent. This may be accomplished by means as simple as dropping the flavorant/mer solution dropwise into the reagent solution or by mechanically projecting droplets beneath the surface of the reagent solution. In certain circumstances it may be necessary to gently or vigorously agitate the reagent solution and even to continue agitation of that solution for a period of time after initial formation of the droplets, as illustrated in the accompanying examples. The final product can, for example, be resilient, hydrated gel-beads whose particle size may be varied by controlling the size of the droplets of flavorant/mer solution initially formed in the ionic solution.

With regard to combining the reaction product with other materials, they may be incorporated into carriers which may comprise active materials or may consist or consist essentially of physiologically inert materials. Gaseous, liquid and solid diluents, as well as propellants and/or preservatives may also be mixed with the reaction products. Prior to or during their incorporation into controlled release compositions, the reaction products of the present invention may be further reacted with other materials.

Still another possible modification of the reaction products is their application to substrates prior to or during release of the flavorant into the host medium in which it is intended to perform. The mode of application may comprise coating, including coating on the surface or absorption into the interior of the substrate. Thus porous and non-porous as well as permeable and non-permeable substrates are contemplated.

A wide range of potentially applicable substrates exist, including living and inanimate substrates. Among the living substrates are animate (animal, insect, reptile, marine or human) and plant life substrates. In the animate types, the reaction product or compositions containing the same may for example be applied to hair, skin, nails and internal parts. In plant life, the reaction products and compositions thereof may be applied to leaves, stems, fruits, vegetables, roots, seeds and the like.

There are so many potential inanimate substrates that a complete listing herein would be impractical. A number of applicable categories of inanimate substrates include large surfaces, such as the floors and walls of buildings and the surfaces of machinery and equipment, the surfaces of particular solids, both organic and inorganic, and the surfaces and interstices of fibrous webs. Thus, gel-beads are only one of a wide variety of physical forms in which useful reaction product may be manufactured. Liquid and paste-like reaction products which may or may not be in bead form can be useful for spreading on (including into) paper, cloth and other substrates and can, for example, be employed in the manufacture of the above- mentioned scented papers, scented clothing and other products. Other examples of applicable categories of substrates are non- fibrous webs, including polymeric films and metal sheeting.

A particularly useful form of substrate is the edible web which can be used to make valuable articles when coated with reaction products (encapsulated or non-encapsulated) of a mer which includes flavor, food or medicament. Since these coated webs are intended for oral ingestion or for preparing other materials for oral ingestion, they should be composed of hygienic materials and kept sanitary. Applicable edible webs include those of paper, cardboard, polymeric films and other forms. Some examples of the applicable chemical species for making these webs include for example, natural and chemically modified starches as, for example, dextrin, dextran, amylose, and amylose cross-linked with a polyol or polypeptide; cellulose derivaties such as sodium carboxymethylcellulose , hydroxypropylmethylcellulose, hydroxyethylcellulose and the like; animal proteins such as collagen and gelatin; vegetable proteins such as corn, wheat, peanut and bean proteins; and other polysaccharides such as pectin, acacia, xanthan gum, guar gum, algin and the like; and synthetics such as polyvinylpyrrolidone, polyvinyl alcohol and the like.

A basic characteristic of these edible webs is that they will readily disintegrate and preferably also dissolve in aqueous fluids, for example water, beverages, saliva and gastrointestinal fluids, including those of the stomach or intestines. Certain of these edible web products may also contain a binder which should preferably also readily disintegrate or preferably also dissolve in the above-described fluids. Such binder may for example be used in forming multiple layers of the edible web material, adhering protective material to the webs, and where applicable, securing to the web microcapsules containing reaction product of mer with food, flavor and/or medicament. When used, the binder should be physiologically acceptable, meaning that it is physiologically inert or therapeutic or at least free of effects which would bar any necessary government approval for its use. The coatings applied to these edible webs are preferably stable and distributed substantially uniformly over the surface of the web.

The following are a number of specific examples of end use products embodying the reaction product of the invention. These include complexes of olfactants in personal care products, other primarily odor emitting products, flavor substances, packaging materials, other shaped objects of polymeric material, candy and chewing gum, cleansing agents, pesticides, repeHants, medicaments and advertising samplers containing any of the foregoing.

Mer/flavor reaction products may for example be used in beverages, foods, cigarette/cigar, papers/wrappers, tobacco and medicaments. Illustrative beverages include soft drinks, coffee or tea and alcoholic beverages.

While only a few examples of the many applicable foods may be mentioned, those of principal interest at present include potato chips, pretzels, popcorn, cookies, cakes, bread and other baked goods. In candy and related products mer/flavor reaction products may for example provide the flavoring for chewing gum, cough drops and breath mints.

The invention can be used to make separate mer/flavor reaction products of two different flavors which can then be separately polymer inclusioned and then mingled in a coating on an edible strip. One example would be peanut butter and jelly flavor.

The introduction of flavors into cigarette papers is known and the use of a mer/flavor reaction product as the flavor in this type of application should result in a much longer shelf life for the product. Similarly, flavors can be introduced into tobacco itself.

Reaction products of mer and flavor are also useful in rendering medicaments more palatable, either by incorporation mer/flavor reaction product directly in a medicament composition, such as in a menthol inhaler or by incorporating the reaction product in an edible surrounding member for the medicament. An example would be a flavored aspirin pill having an aspirin core surrounded by an edible strip impregnated with the reaction product of mer and chocolate flavor. Another example would be a flavored capsule prepared from an otherwise conventional capsule formulation into which a reaction product of mer and flavor had been introduced prior to actual formation of the capsule wall.

Another significant example is incorporation of mer/flavorant reaction products in packaging materials, including such flavorants as olfactants, bacteriostats and the like. For example, a mer/olfactant reaction product may be applied to a product container or its label either on surface or within a web forming the label or within a wall defining the container. The controlled release properties of the reaction product may for example perform one or more of the stabilizing functions described above.

Reaction products of mers and flavorants in accordance with the invention also have application to other shaped objects of polymeric material, including both resinous and elastomeric materials. For example, mer/flavor reaction products may be applied to or incorporated within the surfaces of toys, edible book pages, baby pacifiers, baby bottle nipples, dental bridgework supports and athletic mouthpieces. Mer/olfactant reaction products can be applied to or molded into hair brushes, combs and other products.

Reaction products of mer and flavorant may be formed with the main and/or auxiliary ingredients of the various cleaning agents, including detergents, sanitizing agents, solvents, waxes and the like. For example, compositions of cleansing agents may contain reaction products of mers with olfactants or sanitizing agents.

In the pharmaceutical field, the invention meets several requirements, including suitable mechanical properties and biodegradation kinetics, tissue compatibility, drug compatibility, drug permeability and ease of processing.

The invention can be used with or without a water soluble strip which holds the reaction products of mer and biologically active substances. The reaction products are, depending on the needs, fully soluble in the liquids of the body, but without swelling therein, and dissolve slowly, to provide an extended period of action for a given drug in some special dosage form.

Reaction products in liquid or gel form, including those which have and have not been substrate that is edible and that is intended to be eaten or at least partly ingested orally by a prospective customer. For example, the edible substrate could carry or include a reaction product of mer and food, flavor, beverage, medicament or the like which was connected with advertising material and intended to be eaten or chewed by the prospective customer. Similarly, the reaction product could be coated as a dissolvable layer upon an edible or non-edible substrate, including insoluble substrates, and could be swished about in a liquid to form a drink containing flavor or medicament which the prospective customer could swallow. Associated advertising material could be printed upon the substrate itself or upon a flyer or brochure packed in a container with the substrate, or upon a protective outer member for the substrate. It should be understood however that the respect to edible strips and advertising samplers including the same, the reaction products of the present invention are but one example of many types of controlled-release means which can be utilized for controlling release of the flavor. Thus, any presently existing or future controlled release means may be applied to these strips and samplers.

Preferably, the sampling layers containing the reaction product are applied to a "continuous" travelling web by printing or draw down techniques using a draw down bar, doctor blade or the like or any other suitable technique. Webs printed in this manner can then be cut to the appropriate size for the sampler and, if desired, combined with a suitable protective covering.

In general, a protective covering can be any device which has sufficient structural integrity to withstand normal handling of the advertising sampler during production, shipment and distribution to the prospective customer and will at least partially enclose or fully surround the portion of the sampler containing the reaction product. Partial enclosures assist in preventing premature mechanical rubbing of sample layers and particularly microcapsules while also excluding dirt. Examples of such partial enclosure include self-folds formed in substrates and a cellophane or polymeric film flap covering one or both major surfaces of a sampler substrate. A fully surrounding protective covering provides and opportunity to exclude bacteria and further reduce the opportunity for oxygen, moisture and other environmental factors to attack the reaction product. Examples of fully surrounding protective coverings include substrates confined between impermeable protective layers having full edge seals, sealed envelopes and the like.

In an advertising sampler, the substrate bearing the sample is typically connected with graphic material, including print, art work and pictures, advertising the sampled product. The appropriate connection may be direct, i.e., a connection of the graphic material and sample through the substrate which bears the sample. Examples include samplers where the sample and graphic material are on the same web or on webs which are attached to each other. On the other hand, the connection may be provided by having the graphic material and sample within one or more envelopes, such as by placing both within a common envelope. However, two-envelope systems are also applicable in which a first envelope encloses the sample while a second envelope encloses the first envelope and the graphic material.

Claims

CLAIMS What is claimed is:

1. A method of modifying a flavorant comprising: forming a liquid system including a solution of a mer with a flavorant; reacting the mer in the presence of the flavorant in a portion of the liquid system; continuing the reaction under such conditions to a sufficient extent for substantially reducing at least one of the liquid system's properties including diffusion rate, volatility flammability, toxicity, susceptibility to oxidation, and other forms of environmental attack upon the flavorant; and recovering a reaction product of said mer substantially without rearrangement of the liquid system into separate phases and substantially without encapsulation of the flavorant.

2. The method of claim 1 in which the liquid system contains substantial amounts of both mer and flavorant for significantly increasing molecular weight of the mer under conditions which substantially preserve at least one useful flavorant function of the flavorant.

3. The method of claim 1 wherein the reaction product has a consistency ranging from a liquid to a non-self-supporting soft gel, from which reaction product the flavorant may escape for performing its flavorant function in or on a host medium outside the reaction product.

4. The method of claim 1 in which the mer is at least one of the class including polyvinylpyrrolidone, a cyclodextrin, algin, chitin, a monomer of any of the foregoing, and a derivative of any of the foregoing.

5. The method of claim 4 in which the polyvinylpyrrolidone has a molecular weight in a range of about 5,000 to about 200,000 and more preferably about 7,000 to about 160,000.

6. The method of claim 4 in which the preferred cyclodextrin is betacyclodextrin having a molecular weight of at least about 1,000.

7. The method of claim 4 where the mer includes algin and the preferred reaction product includes an alginate.

8. The method of claim 4 where the mer includes chitin and chitosan is a preferred chitin derivative.

9. The method of claim 1 which further comprises applying the reaction product of the method to a substrate.

10. The method of claim 9 in which the result of the method is an advertising sampler.

11. The method of claim 1 which includes enhancing at least one of the reaction product properties including longevity of the action of the flavorant, gloss, moldability, resiliency and miscibility with certain liquids.

12. The method of claim 1 in which the flavorants include flavors, medicaments and pesticides.

13. The method of claim 12 in which the flavors include those selected from the group of aldehydes, ketones and alcohols.

14. The method of claim 13 in which aldehyde flavors include acetaldehyde (apple) , benzaldehyde (cherry, almond) , anisic aldehyde (licorice, anise) , cinnamic aldehyde (cinnamon) , alpha citral (lemon, lime), beta citral (lemon, lime), decanal (orange, lemon) , ethyl vanillin (vanilla, cream) , piperonal (vanilla, cream) , vanillin (vanilla, cream) , a-amyl cinnamaldehyde (spicy fruity flavors) , butyraldehyde (butter, cheese) , valeraldehyde (butter, cheese) , citronellal (modifies, many types) , decenal (citrus fruits) , aldehyde C-8 (citrus fruits) , aldehyde C-9 (citrus fruits) , aldehyde C-12 (citrus fruits), 2-ethyl butyraldehyde (berry fruits), hexenal, i.e., trans-2 (berry fruits) , tolyl aldehyde (cherry, almond) , veratraldehyde (vanilla), 2-6-dimethyl-5-heptenal, i.e., Melonal tm (melon), 2 , 6-dimethyloctanal (green fruit), and, 2-dodecenal (citrus, mandarin) .

15. The method of claim 13 in which ketone flavors include d-carvone (caraway) , 1-carvone (spearmint) , diacetyl (butter, cheese, "cream") , benzophenone (fruity and spicy flavors, vanilla) , methyl ethyl ketone (berry fruits, maltol (berry fruits) menthone (mints) , methyl amyl ketone, ethyl butyl ketone, dipropyl ketone, methyl hexyl ketone, ethyl amyl ketone (berry fruits, stone fruits), pyruvic acid (smokey, nutty flavors), acetanisole (hawthorn heliotrope) , dihydrocarvone (spearmint) , 2,4-dimethylacetophenone (peppermint), 1, 3-diphenyl-2-propanone (almond) , acetocumene (orris and basil, spicy) , isojasmone (jasmine) , d-isomethylionone (orris like, violet) , isobutyl acetoacetate (brandy-like) , zingerone (ginger) , pulegone (peppermint-camphor) , d-piperitone (minty) , and 2-nonanone (rose and tea-like) .

16. The method of claim 13 in which the alcohol flavors include anisic alcohol or p-methoxybenzyl alcohol (fruit, peach) , benzyl alcohol (fruity) , carvacrol or 2-p-cymenol (pungent warm odor) , carveol, cinnamyl alcohol (floral odor) , citronellol (rose like) , decanol, dihydrocarveol (spicy, peppery) , tetrahydrogeraniol or 3,7-dimethyl-l-octanol (rose odor) , eugenol (clove) , and, p-mentha-l,8dien-7-0 or perillyl alcohol (floral- pine) .

17. The method of claim 1 in which the mer may be selected from the group comprising polyhydroxy compounds, acrylic resins, amides, and alkenyl aromatic monomers.

18. The method of claim 17 in which the polyhydroxy compounds include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, algin, agar, chitin derivatives, dextrose, cyclodextrin, cellulose and its derivatives and starch and its derivatives.

19. The method of claim 18 in which the cellulose derivatives include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellose, and carbomethyl cellose.

20. The method of claim 18 in which the starch derivatives include amylose, amylopectin, glycogen, methyl starch and hydroxyethyl starch.

21. The method of claim 17 in which the acrylic resin monomers include the hydroxy lower alkyl acrylates and hydroxy lower alkyl methacrylates such as 2-hydroxyethyl acrylate, 2- hydroxy-propyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylene methacrylate, diethylene glycol monomethacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy-propyl methacrylate and dipropylene glycol monomethacrylate.

22. The method of claim 21 in which the mer include a polymer and an accompanying organic or inorganic cross-linker, coupler or coagulant.

23. The method of claim 22 in which the cross-linker used with the hydroxy lower alkyl acrylates and hydroxy lower alkyl methacrylates include ethylene glycol diacrylate, propyleneglycol diacrylate, ethylene glycol dimethacrylate, 1,2-butylene dimethacrylate, 1-3-butylene dimethacrylate, 1,4-butylene dimethacrylate, and propylene glycol dimethacrylate.

24. The method of claim 17 in which the amides include acrylamide, n-methylacrγlamide, n-isopropyl methacr lamide, n- methyl methacrylamide, n-12-hydroxyethyl acrylamide and n-(2- hydroxyethyl methacrylamide) .

25. The method of claim 24 which further comprises cross- linking the acrylamides by irradiation with UV light.

26. The method of claim 24 which further comprises cross- linking polyamides with at least one of N,N methylene-bis- acrylamide, and persulfates.

27. The method of claim 17 in which the alkenyl aromatic monomers include styrene, o-, m- and p-methylstyrene, ethyl sytrene, o-chlorostyrene, vinylbenxyl chloride and p-tert-butyl styrene.

28. The method of claim 1 in which the mers include 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine vinylidene chloride acrylonitrile, vinyl acetate, divinyl benzene, butadiene, chloroprene, isoprene, itaconic acid, acrylonitrile, and acrylamides.

29. The method of claim 1 which further comprises placing one solution into another solution to initiate a polymerization process.

30. The method of claim 29 in which a result of the polymerization process is a solid.

31. The method of claim 30 which further comprises combining the solid with a further ingredient.

32. The method of claim 31 in which the further ingredient is a solid.

33. The method of claim 31 in which the further ingredient is a liquid.

34. The method of claim 1 in which flavor that results from the flavorant possesses enhanced endurance because the reaction is polymerization that results in polymer inclusion of the flavorant.